Analysis of high polymers - Analytical Chemistry (ACS Publications)

Analysis of High Polymers John Mitchell, Jr., and Jen Chiu, Plastics Departmenf, E. 1. du font de Nemours & Co., Inc., Wilmington, Del. 7 9898

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covers significant developments in polymer analysis during the past two years. Stress is placed on techniques providing information on chemical and physical structure. No attempt was made to provide details of elastomers analysis, since these are reviewed in another section of this issue. However, reference is made to these materials where the techniques involved appear to provide useful background information on the more rigid polymers. References from Chemical Absfracts through November 1970 are noted. Advances in macromolecular chemistry were the subject of a book edited by Pasika (50). Volume 4 of “Reviews in 1Iacromolecular Chemistry” was published ( 9 ) , together with an extensive compilation of references to to the literature of polymers (52). The National Bureau of Standards issued a special publication on “Molecular Dynamics and Structure of Solids” (14). “Formation and Characterization of Addition Polymers” was edited by Smith (55) as a text for students majoring in polymer science. The second edition of Ferry’s book on “Viscoelastic Properties of Polymers” was published (24). Brun and Pellerin (8) reviewed items on definition, structure. classification, and preparation of plastics. Polymer microstructure was reviewed by Aubrey (1) and microtacticity by Krigbaum and Dawkins (58). Kavesh and Schulz (55) reviewed methods for determining crystallinity, including density, infrared, thermal, nuclear magnetic resonance, and x-ray procedures. Carroll ( I S ) edited a book on physical methods covering spectroscopy, electrical, and physical tests. “Polymer News,” edited by Immergut (SO), was started as a monthly report on business and scientific developments. The Japanese Society of Polymer Science launched a polymer journal for bimonthly issue. Several symposia dealt with new developments in polymer analysis. An international meeting on polymer characterization covered molecular weight methods, gel permeation chromatography, thermal, solution, and optical properties, microstructure, and morphology (3). Other symposia included one on interdisciplinary approaches to polymer characterization, sponsored jointly by the Divisions of Polymer Chemistry and Organic Coatings a t the 160th ACS Meeting in September 1970 and the 8th International Gel Permeation and Liquid ChromatogHIS REVIEW

raphy Seminar held in Prague in July 1970. “Introduction to the Chemical Analysis of Plastics” was the subject of a book authored by Kraus and Lange (97), while the first volume of a planned “Atlas of Plastics Analysis” was issued by Hummel and Scholl (29). Journal literature during 1968 on analysis and testing of plastics was reviewed by Ledwoch (40). Testing of plastics was reported by Lever and Rhys (41), Horowitz (28), and Brown (6). Solvents in polymer chemistry were reviewed by Davies (19). Values of constants for a diffusion curve relationship were modified by Kaneko et al.

(98). A computer program on the copolymerization equation for acrylics was devised by Tobolsky and Hopkins (57). A sequential index was defined as the basis for quantitative expression for homogeneity of copolymers (58). Instrumental methods for inorganic substances in polymers were reviewed by Narasaki (49). Oxidation of a variety of polymers was studied by electron spin resonance, chemiluminescence, chromatography, mass spectrometry, and chemical methods (10). Structure of copolymers was discussed by Makarevich and Nitikin (44). Zerbi (66) reviewed spectroscopic techniques in polymer structure analysis. Volume 6 of “Developments in Applied Spectroscopy” was published in 1968 (2) and “Spectroscopy of Polymers” in 1969 (61). Crztical Rewiews i n Analytical Chemistry included a report by Drushel on recent developments in polymer analysis by spectral methods (21). Volume 1 of “Applied Spectroscopy Reviews,” edited by Brame (4), covered techniques for elemental and chemical structure analysis. Apparatus was devised for measuring water vapor permeability by an electrical method (45). A simple technique for concentrating polymer solutions was reported by Ferguson (B),while Molyneux (46)described a vessel for isolating viscous sediments, such as in polymer fractionations. A separation procedure in plastics analysis was developed by Braun (5),involving partial separation by solubility with chemical, colorimetric, and chromatographic tests. A report on separation methods was made under the editorship of Gerritsen (26)*

Wheeler (66) reviewed methods for determining antioxidants in polymer systems. Other reviews on additives analysis appeared in a report by Schroder

and Hagen (54). Characterization of coatings by physical techniques was published (42, 48). Sampling and analysis of nonvolatile coatings components in aerosol containers were reported (16). Other reports on analysis of classes of polymeric materials included laminated composite structures (11) and films (27, 47, 52). I n the fibers field, Wakimoto and Yano (68) described quantitative analysis of mixed fibers; Majewski and Gregorowicz (49) reported on analysis of synthetic fiberforming polymers, and Krystufek (99) on amino acid composition of wool. Analysis of paper was reported in a book by Browning (7). Applications of physical, spectroscopic, and optical methods in pulp and paper research were reviewed by Jayme (51). Analytical methods in textile testing were reported ( l a , 16, 64). Textile testing was reported in detail (94) as well as analysis of synthetic resin finishes (59). Reports on analyses of polymer types included aromatic polyethers (%), epoxy resins (25), and ethylene-vinyl copolymers (56). Active centers in heterogeneous Ziegler-Natta polymerizations were established by end group analyses (59). ;Inalyses reported for poly(viny1 chloride) (PVC) included qualitative and quantitative measurements on plasticized resin (GO), PVC blends (22),and PVC copolymers (61). Analytical chemistry of polyurethanes was reported (18) and also analysis of rubberlike polymers (62). Structure studies were discussed on copolymers of polyacrylic acid grafted on ethylenepropylene elastomers (17) and on regular copolymers of butadiene and methylene (20). Specific references to techniques and polymer groups follow. CHEMICAL, ELECTROCHEMICAL

Titrimetry and polarography formed the basis for most analyses of polymers and additives. Harwood (C69) reviewed means for chemical modification of polymers for analytical purposes, including hydrogenation and cyclization reactions. I n characterizing polymer networks, Shultz (CldO) employed chemical analysis in estimations of branch points. For C and H determinations in polymers containing halogens, Bartels (C9) used a CeOntrap in the combustion train to remove halogens before they reached the CoaOd-pumice catalyst. The Kjeldahl method was modified to provide a controlled temperature for de-

ANALYTICAL CHEMISTRY, VOL. 43, NO. 5, APRIL 1971

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composing basic nitrogen-containing polymers (CQ2). Majewska (CQI) found the Schoniger combustion procedure better than wet oxidation in oxidation of polymers for subsequent sulfur determination; glucose was often mixed with the sample to aid combustion. Radioactivation analysis was used in determining inorganic ions in textile fibers (CIO8); as little as 10 ng of elements such as Ti, Rb, or M n was determined. Oxygen absorption by polymers was measured in apparatus with an electrolytic cell which generated oxygen in proportion to the amount adsorbed ((37). Ciampa et al. (C31) discussed nonaqueous titrimetry of acid functions in several polymers of pharmacological interest. Samples in DAIF-chlorobensene, pyridine-benzene, or acetoneacetonitrile solutions were titrated with potassium methoxide or tetrabutylammonium hydroxide. Acid-base equilibria of polyampholites with pyridine and phosphoric acid groups were established by potentiometric titration (C1.42). Hydroxyl groups in organic compounds were determined with tolylene diisocyanate reagent, with diethylamine and titration ((7141); to assure complete reaction in substances such as epoxy compounds, a n organometallic material was used as catalyst. I n attempts to determine valence state in Ziegler-Satta catalysts, Kollar and coworkers (C71) decomposed the sample with H2S04, added FeC13, and measured reduced Fe+Z by titration with KAfn04. Diester plasticizers were saponified, acidified with HC104, and titrated potentiometrically with KOH ((777); the first inflection was due to excess HC1O4, the second and in some cases the third were due to carboxyl groups. Wexler and Georgescu (ClSQ, ClYO) used a gravimetric procedure for determining plasticizers and lubricants in plastics stabilizers. Applications were described to dioctyl sebacate in a P b soap and diisooctyl phthalate in P b sulfate. Bezuglyi (C1.4) described uses of polarography in the chemistry and technology of polymers. Jura ( C S I ) reviewed basic principles of polarography with emphasis on application to polymer analysis. Helmstedt and coworkers (C56) discussed tensammetry, a variation of a x . polarography in analyses of emulsifiers, lubricants, and antistatic and textile additives. Minsker et al. (CIOO) reported halfwave potentials for several substituted phenols used as stabilizers for poly(vinyl chloride) (PVC). Polarographic procedures were used for determining oxygen in monomers and organic solvents (C172) and for measuring oxygen permeability of polymer films (CI36). Determination of 4,4’-isopropyli268R

denebis-2-aminophenol in polymers was based on reaction with benzaldehyde and polarographic reduction of the resulting Schiff base ((772). Acrylics. E n d group analysis of isolated PMMA from graft copolymers with wool involved HCl digestion, leaving amino acid residues on the end of the graft polymers, dinitrophenylation of the isolated polymer, and colorimetric analysis (CS). The -COONa groups in Na polymethacrylate and copolymers with kIMA were measured by chronoconductometric titration with HC1 (C69). Potentiometry was used in kinetic studies of copolymerization of MMA with LMA (CY). For characterization of MMA-MA or MMA-itaconic acid copolymers, Fontanyanes and GarciaBordas (C.46) used methylation and nuclear magnetic resonance; the former was quantitative and permitted determination of JI,. Poly(methacry1ic acid) (PMA) and copolymers with ATRIA were determined by oscillometric titration (130 Mc per second) with NaOH in methanol ( C I S ) . The abnormal behavior of PMA in water on potentiometric titration was explained from a change of conformation (CISS). Kawaguchi and Nagasawa (C65) observed a detectable difference in the potentiometric titration curves of isotactic and syndiotactic polyacrylic acids. Mandel (C95, CQS) studied potentiometric titration of weak polyacids, such as poly(acry1ic acid), and devised an empirical approach to the potentiometric titration curve. Potentiometric titration curves of 0chloroacrylic acid-lIMA copolymers in D M F solution and tetraethylammonium hydroxide titrant showed two inflections (C8). Oligoester acrylates were determined polarographically following removal of polyesters and inhibitors on an alumina column (CQO). Cellulose. Mixtures of cellulose with polyester, polyamide, acrylic, and PVA fibers were analyzed gravimetrically with separation of the cellulose by modified Cadoxene solution (5%) Cd, 28y0 ethylenediamine in 0.5M NaOH) ( C l ) . Nabar and Shenai ( C l o y ) compared alkali titration and a n iodometric procedure for estimating carboxyl groups in oxycellulose. Total acidity in cellulose triacetate was measured potentiometrically with 0.01N KOH in methanol (C78). Polarographic studies on cellulose acetate provided a means for estimation of molecular weight (C7.4). Titrimetric procedures were used for determining chlorine-containing rubber adhesive on cellulose-based cartons following evolution as HCl (CSS), small amounts of formaldehyde in paper by the sulfite method (CI25), and sulfonic


acid groups in unbleached sulfite pulps (C88). Nitrocellulose and poly(viny1 nitrate) (C118) and mercaptan or disulfide groups in modified cotton ( C l S l ) were determined by polarography. Iodometric titration of mercaptocellulose gave higher values than polarographic analysis. Polyethyleneimine used for waterproofing paper was determined by Kjeldahl or colorimetrically (Cas). For determining boron in cotton fabric, Liepins (C89) used electrodeless radiofrequency-discharged oxygen for removing organic matter, leaving Bz03for gravimetric determination, Polyacrylonitrile (PAN). I n studies of the pyrolysis of PAN, Watt (C167) used a titrimetric procedure to determine the HCN evolved. Acrylonitrile (AN) and methacrylonitrile (MAN) in the presence of acetonitrile and HCN were determined polarographically in the presence of tetramethylammonium iodide (CQQ). Half-wave potentials were -2.15 and -2.22 us. SCE for AN and MAN, respectively. ABS was degraded by treatment with tert-butyl hydroperoxide and osmic acid. AN was determined by Kjeldahl; butadiene and styrene by infrared spectrometry (CIS,$). Polyamides. Shtal and coworkers (C139) used a polarographic procedure for identifying polyamides based on acid hydrolysis and conversion of the diamine or amino acid to the Schiff base. Kreshkov and coworkers (C79) determined end groups in aromatic polyamides as follows: for carboxyl ends, potentiometric titration with KOH solution of the sample in D M F ; for amine ends, reaction with excess salicylaldehyde and potentiometric titration of the excess with KOH reagent. Kvasha et al. (C86) used a similar method for carboxyl ends in polyamides but added 5 to 10% LiCl to “increase the accuracy.’’ H e x a fluor o i s o p r o p a n o l served as a solvent for nylon in titrations for water with Karl Fischer reagent

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(C66)

I n a new method for R f W determinations on nylon 66, Head (C55) methylated the sample with diazomethane and analyzed for methoxyl content. -4mercurimetric method was proposed for determining total nitrogen in polycaprolactam and certain other polyamides (C178). Caprolactam and oligomers in nylon 6 were separated by boiling water extraction and gravimetric measurement of the evaporated residue ( C l d l ) . Water in nylon 6 was determined from Karl Fischer reagent (KFR) titration of a 2 to 1 phenol-methanol solution (CIZO). I n a variation of the KFR technique, Praeger and Dinse ( C I I Q ) removed moisture from nylon 6 in a flowing stream of Nz a t 170°,

absorbed the water in. methanol, and titrated with KFR (C119). The procedure was applied also to poly(ethy1ene terephthalate) (CS4,Ci19). Acetyl end groups in nylon 6 were determined via acid hydrolysis, azeotropic distillation of acetic acid, and titration with alkali (CSS). A means for determining type and degree of nylon 6 degradation in relation to gel formation involved conductometric impulse counting by the Coulter principle (C122). Formaldehyde bound to modified nylon 6 was determined by a distillation-sodium carbonate method or by the KCN procedure (C113). Polyesters. Hydroxyl groups in polyesters, such as poly(ethy1ene terephthalate) (PET), were determined by dissolving the polymer in a solvent such as nitrobenzene, reacting with a reagent such as o-sulfobenzoic anhydride, reprecipitating the polyester, and back-titrating the filtrate potentiometrically (Ci82). Polarographic procedures were used to study carbonyl-ester group interactions of polyesters and anthraquinone dyes (c175) and catalyst residues in polyesters (C41). Residual benzoyl peroxide in hardened polyester resins was determined polarographically (C70). Unsaturated bonds in polyesters were measured by a bromination procedure (CY). I n analyses of PET, hydroxyl end groups were determined by an acylation procedure employing 3,5-dinitrobenzoyl chloride (Cl81). For hydroxyl in poly(oxyethylene terephthalate), Zimmermann and Kolbig (Ci80)recommended o-sulfobenxoic acid anhydride. Karl Fischer reagent methods for water in PET involved distillation of water from phenol-CClr solution into methanol, followed by titration (C179), and evolution in nitrogen at 170" into a methanol scrubber and titration (CS4, (7119). Small amounts of sulfur in polyester acrylates were determined by combustion, oxidation, and titration of H2SOt (c50). Double bonds in polyester acrylates were estimated by microhydrogenation, using Pd on charcoal catalyst (C61). Polyesters from phthalates were analyzed gravimetrically for isophthalic acid (C148); free acids and anhydrides in unsaturated polyesters were extracted by methanol-water from a CHC13 solution of the polymer, followed by potentiometric titration (C146). Fumaric and maleic acids in polyester resins were determined by a complexometric method involving EDTA (C177). Volodina and coworkers (C164, C166) studied conditions for hydrolysis of polyesters involving fumarate and determined double bonds polarographically. Unsaturation in maleic acid esters was measured by bromination following saponification

(C20). Determination of sebacic and maleic acids in polyester resins involved complexometric titration involving EDTA (C176). Polyethers, Epoxides. Tetramethyldiphenoquinone in polyphenylene oxide was determined by reduction with acid KI, followed by iodometric titration (C44). Small amounts of boron in copolymers of propylene oxide and tetrahydrofuran were determined by potentiometric titration in the presence of mannitol following nitric acid oxidation and by direct titration (c42). Graft polymers of poly(ethy1ene oxide)starch were analyzed via periodic acid oxidation and NMR ("3). Bell ( C l l ) used analyses for primary amino and epoxy groups in structure studies of amine-cured epoxy resins. ,Methods for determining epoxy groups were critically evaluated by Dobinson and coworkers (CS6) and by Budyak et al. (C21). Specific methods were reported involving argentimetry ('226) and direct titration with HBr (Ci26). Epoxy and carbonyl groups in elastic epoxy-Novolak copolymers were titrated potentiometrically (C82). Hydroxyl groups in epoxy resins were determined by the Zerewitinoff technique for active hydrogen (Gila), by the lithium aluminum hydride gasometric procedure (CCO), and by acetylation (C67). Graphite fibers in epoxy, polyimide, and phenolic resin composites were determined gravimetrically after digestion of the sample in H&04 and HzOz (C64). Polyolefins. Giuffre (C62) described potentiometric and spectrophotometric methods for determining valence states of catalysts used in stereospecific polymerization of a-olefins. Szewczyk et al. (C149) in determining double bonds in polyolefin homo- and copolymers preferred bromination and determination of Br by combustion and titration against Hg(N0&. Carbonyl groups in polyethylene (PE) films were made to react with W-labeled 2,4-dinitrophenylhydrazine and measured from radioactivity or by extraction and titration with tetrabutylammonium hydroxide (C111). PE stabilizers based on 2-hydroxy-4alkoxybenzophenones were determined potentiometrically with sodium methoxide (C64). Azomethines as heat stabilizers in E-P copolymers were evaluated potentiometrically ((773). Unsaturation in E-P terpolymers was estimated by the pyridinium bromide perbromide method (C155). To separate PP of differing tacticities, Natta, Pino, and Mazzanti (C109) used ethyl ether for atactic, amorphous polymer, and boiling heptane for partiaIly crystalline PP, weighing the evaporated extracts. Studies of thermal degradation of atactic PP were aided by iodine value for unsaturation

and infrared analysis together with cryoscopic measurement of -MW (C116). Traces of C1 in PP were determined by combustion and potentiometric or spectrophotometric analysis (C9S). Turbidimetric titration was used in studies of solvent-nonsolvent fractionation of P-S copolymer (CS2). Hydroperoxide formation in oxidized poly-1butene was estimated with triphenylphosphine reagent (C39). Polystyrene (PS) and Copolymers. Thermal decomposition of peroxide bonds in PS was studied by conventional chemical methods and by infrared spectroscopy (C154). Peroxide groups (C115), and formaldehyde and benzaldehyde (Cii3) in S monomer, were determined polarographically. Conductometric procedures proved adequate for sulfate end groups formed during emulsion polymerization of S (C158, C159).

Composition and degree of grafting in high-impact PS were measured from fractions separated in benzene-gasoline mixtures (CS). Carroll (C24) determined inorganic halide impurities in 2-butanone solutions of PS by a coulometric procedure. Compounds such as a-methylstyrene, (r-3,5- and a-2,4trimethylstyrene, and 4-isopropyl-amethylstyrene were measured polarographically with a coefficient of variation of 2.75% ((216). An indirect potentiometric method was used to determine degree of unsaturation in s, vinylbiphenyl, and their polymers (C75); analysis was based on methoxymercuration. Polarographic procedures were used in analyses of a variety of copolymerse.g., for S and AN in food containers (C156), nitration products of S-butadiene rubbers (Ci66), copolymers of Sand p-substituted stilbenes (C17) and and for peroxide acenaphthylene (CfS), decomposition products of S-divinylbenzene copolymer (Ci14). Other Vinyl Polymers. Laczko (C86, C87) preferred automatic p H measurement to Congo Red indicator in following thermal decomposition of PVC. A similar method was used in following thermal degradation of poly(vinylidene chloride) homo- and copolymers (CW). Thermal degradation of PVC was accelerated by HC1 (C160); removal by inert gas stream or by addition of chloride complexing agents considerably reduced the rate. Organotin stabilizers in PVC were determined by an EDTA procedure (CIS), while stabilizers such as dibutyltin chloride (C162) and phenolic (2,6-ditert-butyl-p-cresol and 4,4'-isopropylidenediphenol) (C161) were estimated polarographically. To determine C1and Br- in PVC and related compounds, Cassani (C25) decomposed the sample and measured halide coulometrically. Peroxides in radiation-


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oxidized PVC were determined chemically (N260). For unsaturation in vinyl acetate (VAc) in an aqeous dispersion of PVAc, Kropivnitskaya and Pogosyan (C81) used coulometric bromometric titration. VA in polymerization media was measured by a polarographic method (C58). Total organic acids in VAvinyl butyrate or VA-butyl acrylate copolymer systems were determined potentiometrically, even in the presence of large amounts of salts (C6). Effects of hydrophobic bonding on macromolecular structure of copolymers of alkyl vinyl ethers and maleic acid were followed potentiometrically (C38). Polarographic procedures were used to follow anionic polymerization of vinyl monomers (C173), determine dissolved oxygen in vinyl monomers (C97), estimate vinyl compounds of the biphenyl series in monomers and polymer (CS), investigate acid-catalyzed polymerization of methyl vinyl ketone in methanol (C57), and analyze for N-phenylmaleimide during its polymerization with vinyl monomers (CS9). Miscellaneous. Fluorine in F-containing polymers was determined titrimetrically or colorimetrically following their decomposition in a stream of ammonia a t 600" to 700' (C163). Selig (C15.4)decomposed F-containing polymers in oxygen and measured Fgravimetrically as LiF. For chemical determination of formaldehyde in reactant resins, Bennewitz and Foth (C12) concluded that no one method was universally applicable; they showed that a distillation-bisulfite or iodometric method gave best results for free and combined HCHO in triazinone types of resins, while the hydrogen peroxide method appeared best suited for other types. Formaldehydeacetone resins were analyzed polarographically (CS2). Pyrolysis products from urea-formaldehyde resins were analyzed by chemical and infrared methods (C48). Free formaldehyde in urea resin adhesives was determined by the ammonium chloride procedure (C98). Acid character of p-hydroxybenzoic acid-formaldehyde copolymers was established by nonaqueous titrimetry (Car). Hexamethylenetetramine in phenolHCHO and urea-HCHO resins was determined by titration with HC104 in acetic acid potentiometrically ((710) or visually to methyl red (C171). Potentiometric titration with alkali served to measure phenol, formaldehyde, and acid in phenol-HCHO resins (C76). For methylol groups in these resins, Bulygin and coworkers (CS3) used alkaline iodination and potentiometric titration. The potentiometric bromide-bromate procedure was used to estimate brominatable groups in phenol-HCHO resin (C143). 270R

Potentiometric titrations were made on polyacids derived from cinnamic acid, ethyl cinnamate, ethyl a-ethyl acrylate, ethyl tiglate, N-vinylsuccinimide, and citraconic anhydride (C129) as well as poly-a-hydroxyacrylic acid, polyatropic acid, and polyglutaconic acid (CI28). Polarographic studies on polymers based on acrylamide were used to study kinetics of polymerization (C83), copolymerization (c106), and copolymerization with maleic acid (Clod) and citraconic acid (C106). Kinetics of polymerization of acrylic acid aminoesters were followed polarographically ((74). Free maleic anhydride in mixtures with dienes was determined by a polarographic procedure (C30). Potentiometric titrations were used in studies of maleic anhydride-olefin copolymers (C18, C174) and maleic acid-vinyl ester copolymers (C130).

A number of chemical tests were applied to elastomers. Specific reagents were used to indicate the presence of biuret or allophanate linkages in polyurethane foams (C35). Polarography was used to assess electrochemical initiation of phenyl isocyanate polymerization (C136). X,,of polyurethane having ether, urethane, and urea segments was estimated from elemental and volumetric analyses (C1.45). Peroxides formed on oxidative degradation of copolymers of tetrahydrofuran and propylene oxide were determined iodometrically ((794). Acidic impurities in polyurethane were measured potentiometrically (C117). Distribution of carboxyl groups in ethyl acrylate-acrylic acid copolymer latex particles was determined by conductometric titration ((7103). Carboxyl groups in latex were measured by acidimetric titration (C.45). Kurzmann and coworkers (C8.4) compared four methods for determining carbon black in vulcanizates and plastics, both wet chemical and pyrolysis; the accuracy of each method was dependent on the matrix. Polarographic methods were employed for traces of Cu, Mn, and F e (C32) and for Zn (C101) in elastomers. I n sulfur-cured vulcanizates C-C bonds were measured folIowing destruction of C-S bonds (C110) and sulfide bonds by a modified LiA1H4 procedure ((7144). Taubinger (C163) determined free acrylonitrile in AN-butadiene latexes by reaction with sodium suIfite and subsequent potentiometric titration of alkali released. Nitrile groups in soluble diene polymers were determined by chemical determination of end groups, by N determination, and by infrared (C167). m-Phenylenediamine was determined potentiometrically during synthesis of poly-m-phenyleneisopht halamide (C80). Saber and E l Din (Cld7) used polarographic, conductometric, and potentiometric methods in studies on poly-


ethyleneimine. Wetters and Smith (C168) found KOH better than NaOH for fusion of siloxane polymers in preparation for Si determination. End group analysis by chemical and NMR methods showed a zwitterion structure in polymer from propiolactone or pivalolactone and trimethylamine (C69). Polarography was used in studies of redox behavior of photochromic polymers (C63) and together with potentiometric titration in analyses of polymeric isothiuronium salts (C4O). I n studies on ion-exchange resins, various chemical methods were used to determine exchange capacity in sulfonated phenol-HCHO resins ( C l S l ) , to define complexing on vinylpyridinebased ion-exchange resins by potentiometry (C152), and to determine water by a Karl Fischer reagent (KFR) procedure in comparison with drying and magnetic resonance (CIS?', C138), and by KFR alone (CI51). Moisture in proteins, including wool, was calculated from results by automatic elemental analysis (Cl.47). Extraction and polarography were combined in studies of carbonyl groups in oligosaccharides (C150). High-frequency titrations were used in determining acid groups in lignin (CIOS) and in thiolignin (C49). Molecular structure of chain-extended polycaprolactone diols was established by determination of hydroxyl groups by phthalation and nitrogen by the Dumas method together with N M R (N176). A sublimation procedure was used to separate dimers and polymers from oxidized fats and oils (Y59). INFRARED AND RAMAN SPECTROMETRY

Zerbi (1426) presented an in-depth review of spectroscopic problems in polymer systems,. primarily from the standpoints of ideal molecular and crystalline states. Hummel and Scholl (1166) issued a compendium of infrared spectra, including 1454 of polymers, primarily covering the region from 2.5 to 19 microns. Elliott (198) covered structure determinations of organic longchain polymers, Chulanovskii ([YO) discussed polymers and auxiliary materials, and Zerbi (1.427) studied molecular conformation from analyses of vibrational spectra. Crister's review on infrared (ir) spectrometry (185)covered miscelIaneous publications from December 1967 to December 1969. Reviews of other applications of ir to polymer analysis included theory and techniques in polymer analysis by Mihaila and Costea (1260), monitoring of chemical changes in coating materials by Smith (1347), characterization of structural changes in poIymers by Luongo (1230), and structure analyses of graft

polymers by Moore and coworkers (1264)* Influence of defects on ir spectra of polymers was reported by Opaskar and Krimm (1284). Pyrolysis products from 15 fibers were characterized by Cassels (163). Applications to thermal degradation of polymers were illustrated from pyrolysis of isotactic polypropylene (1233) and of a variety of rubbers (1240) and elastomers (137). Gases from thermal decomposition of a polyurethane, urea-HCHO resin foam, nylon, and polyacrylonitrile were identified by ir, mass spectrometry, and colorimetry (146). Structure assignments on ladder polymers were made by ir, uv, N M R , and x-ray studies (1286). Internal reflection spectroscopy in the study of polymers was reviewed by Barr and Flournoy (131). Infrared dichroism and its application to orientation studies in polymers were reviewed by Asada ( I l Y ) , Chabert and Grollier (165), and Cornille (180). Infrared and Raman studies on molecular structure and motion in condensed phases, including polymers, were reported by Wilkinson (1411). Far-infrared and Raman spectroscopy of intermolecular vibrations in solids and liquids also was detailed by Wilkinson (1410). Schaufele (1324) reviewed laser-vibrational scattering by polymers. Sloane (1345) compared Raman to ir in use of the empirical group frequency approach. Application of laser Raman spectroscopy to characterizations of a variety of polymers was discussed by Cain and Harvey (154), Hendra (1145, 1146), and Ito and Yokoyama (1165). Technique development provided extensions of ir applications to polymer analysis. An ir spectrometric gage was reported for measuring thickness of films and thin polymeric coatings (1150). A kinetic device with a flowthrough cuvette for studying chemical reactions in the liquid phase was reported (1225). Chemical aging was followed through changing intensity of the C = O stretching vibration (1148) and internal reflection spectroscopy was used to study chemical changes during weatherometer exposures (166). ATR (attenuated total reflectance) spectroscopy was used in surface studies of films ( D o g ) , in analysis of surface coatings on textiles (1305), and in general polymer examinations (1371). High temperature ATR spectroscopy was applied to study of crosslinking reactions (1115). Pearson (1299) used KBr abrasion in studies of polymer surfaces. Gesner (1126) characterized polyblends by ir, electron microscopy, x-ray spectroscopy, solvent eIution, and precipitation techniques. Quantitative analysis of insoluble polymers in KBr disks was reported ( 1 9 7 ) . Studies were reported of strained chemi-

cal bonds in stressed polymers (1482, 1433). Wolfram and coworkers (1418) improved the ir method for measuring orientation in polymers by obtaining refractive index data from multiple measurements. Samuels (1320) reviewed methods for characterizing deformation mechanisms in polymers, including ir dichroism, birefringence, and x-ray diffraction. Included in Urbanski's review (1398) of methods for determining water in polymers were ir, NMR, drying, distillation, and Karl Fischer reagent titration. Application of ir in the coatings industry was described in a new issue of a popular pamphlet (1103). Low and Mark (1228, 1229) described the use of ir Fourier transform spectroscopy to examination of coatings, and Withers (Z417) of internal reflection spectroscopy. Paint materials were characterized by ATR (1326) and by ir spectra of pyrolysis products (1346). Fibers from polyamides, PVC, PAN, and polyesters were identified using KBr wafers (1359). Zimmer (1434) pressed films of fibrous materials for ir examination. Wilks and Cassels (1412) discussed use of internal reflection spectroscopy to fiber analysis, and Bouriot (146) described use of ir in following structural changes during heat treatment. Causes of textile damage were assessed through ir, chromatographic, x-ray, and colorimetric methods (1400). Structural changes on irradiation grafting and subsequent hydrolysis of synthetic fibers were followed by ir (1303). Determination of resins in fabrics (1.422) and analyses for textile finishing agents (1378) were reported. Quantitative analysis was developed for crosslinking agents in copolymers of styrene and divinylbenzene (1218). Other applications included identification of thermosetting resins in glass fiber-reinforced articles (I%), analyses of mastic by ir and gas chromatography (1310), and characterization of binder systems by ir and uv spectroscopy (1211). Mueller and Geiseler (1265) suggested that molality is often a better means than molarity for estimating monomer concentration in mixtures forming hydrogen bridges. Separation of additives from polymers by thermal means was reported (1358). Infrared techniques aided in studies of polymer strength in drawn polymer films through dichroism measurements ( I % l ) , polymer failure under loading (14OZ), and stresses near concentrators in polymers (IZO.4). The nature of bonds between polymers and disperse dyes was studied by Naumova and coworkers (1269). Acrylics. Kinetics of bulk polymerization of MMA a t high and low conversions was studied by ir (1142). Willis and coworkers (1414) made group assignments for laser Raman and ir spectra of PMMA. The ir spectra of

isotactic, atactic, and syndiotactic PMIMA, PMA, and W A C were obtained from 600 to 130 cm-' a t 77" to 295 OK (134). The structure of crystalline isotactic PMMA was analyzed from far-ir and x-ray diffraction data (1363). Comparison was made between ir spectra of head-to-head PMMA and conventional head-to-tail polymers (1285). Melt kinetics of crystallizing stereoregular PMMA were studied by ir, x-ray diffraction, and polarized light microscopy (1272). Acid hydrolysis products of isotactic and syndiotactic PMMA were examined by ir spectroscopy (1330). Structures of complexes of LIMA with metal halides were determined from ir spectra (1132). Tacticity of stereoregular polyacrylic acids and polyacrylates was measured by " I R and ir (N152). Aylward (L10) determined tacticity of stereoregular polymethacrylic acids by ir, NMR, x-ray diffraction, and DTA, while GPC was used for M W information. Laser Raman spectra were reported for PMA as solid, aqueous gel, and alkaline aqueous gel (1382). Koenig et al. (1192) reported similarly on laser Raman studies of syndiotactic PMA as a solid and in water solution as a function of degree of neutralization. Schmolke and Kimmer (I3W6) employed ir in assigning sequence distribution of copolymers of MMA-acrylonitrile, methacrylonitrile-acrylonitrile, and vinyl chloride-vinyIidene chloride. Guillot and coworkers (N73) used ir and NhIR in sequence distribution studies of >MA-acrylonitrile copolymers. Grassie and Torrance (1137) reported on thermal degradation of MMA-RIA copolymers from data obtained by ir, uv, and thermal volatilization analysis. Studies of extent of intersequence cyclization between MAMA and vinyl halide units in co- and terpolymers were aided by ir (1176). Characterizations of thermosetting water-soluble acrylic copolymers were made from ir and NRIR data (1215). Nitrile groups in soluble diene copolymers were determined by ir and chemical analysis (C157); the former utilized absorbance a t 2250 cm-l. Analyses by ir methods were made on acrylate or acrylonitrile-divinylbenzene-styrene terpolymers (1151),graft copolymers of wool and silk with hIMA (114, and reticular polymers of triethylene glycol dimethacrylate (1287)). Polyacrylonitrile (PAN) and Copolymers. Imai et al. (1158) characterized amorphous P A N by ir, NMR, and x-ray methods. Kinetics of conversion was studied of the C=N group in PAN during heating in vacuo to a conjugated structure with a ladder polymer (1209). Structure of PAN was examined by ir while heating films a t 230" to 250' (1208) and by multiple internal reflection analysis of fiber

ANALYTICAL CHEMISTRY, VOL. 43,

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(1551). Mechanical degradation of PAN during melting led to formation of rings having conjugated C=N bonds based on ir, uv, and visible spectral data (1202). Carbonyl formation during stereospecific polymerization of methacrylonitrile by diethylmagnesium was established by ir (1174). The technique aided in identifying thermal degradation products of poly-a-chloroacrylontrile (1135). Extensive studies were made on acrylonitrile co- and terpolymers. All'-acrylate, AN-vinyl acetate, AN-styrene, and other vinyl comonomers were examined by ir, pyrolysis-gas chromatography, and chemical procedures ( 1 9 ~ ) . Similar techniques were used on copolymer fibers (1270). For study of copolymers of AN with styrene derivatives having side chain nitrile groups, Ronel and Kohn (1312) used ir, uv, and thermal methods (1312). Copolymers of AN-hydroxyethyl methacrylate were examined by ir and x-ray diffraction (1189). Infrared methods provided structural information on AX-methylacrylate graft copolymers (1236), fibers of AS-a-methylstyrene-vinyl acetate terpolymer (122), AS-ethenesulfonyl fluoride copolymers (/213), and An'VAc copolymers for structure and shrinkage behavior (1219). Riess (C124) described methods for identifying and characterizing acrylonitrile-butadiene-styrene (ABS) terpolymers; B and S were determined by ir analysis and A was determined by the Kjeldahl procedure. As reported by Gesner (1127), ABS resins are primarily heterogeneous blends of A-S copolymers modified with B rubbers. He recommended ir methods for rapidly comparing commercial resins. Degradation of ABS resins from uv irradiation was studied through ir spectra (16, 1125). Cellulose. O'Connor (1276) reviewed ir techniques for identifying cellulose and cellulose derivatives in natural fibers and blends with synthetics. McCall (1249) reviewed applications, including ATR, in analyses of cotton. Crystallinity of various celluloses as measured by ir and x-ray diffraction was compared (1172). Crystallinity of cellulose fibers (cotton, ramie, viscous rayon) was measured via deuteration and ir spectroscopy (1207). Levdik and Nikitin (1222) used absorption at 1375 and 1325 cm-' t o show that mercerization of cotton causes a structural change from type 1 to type 2. MacKay (1231) reviewed in detail procedures for establishing the mechanism of thermal degradation of cellulose, including ir, chromatography, and thermal methods, while Shimizu and coworkers (1336~)used similar techniques in studies of thermal treatment 272 R

of hemicelluloses. Supramolecular structure of cellulose fibers was studied (1101). Analytical ir methods were described for identification of fibers from regenerated cellulose and acetylcellulose (1360), components such as xylan in wood fibers (1281), and inorganic and organic materials associated with the pulp and paper industry (1356). Hydroxyl groups were measured on cotton fibers, and related to degree of hydrogen bonding (1317). Near-ir was used to determine total OH in cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate (1168). Bound acids in highly substituted cellulose esters were calculated from absorbance at 3600 and 3480 cm-' for simple esters and a t 2880 cm-I for mixed esters (1255). Acyl groups in mixed esters were determined by ir and saponification methods (1254). Structural features of cellulose trinitrate were studied by polarized ir and x-ray analysis (1406). Panov and coworkers (1289, 1290) made analytical studies of hydrogen bonding between hydroxyl and nitrate groups in cellulose nitrate. Kitukhina and Zharkov (1187) use ir to determine plasticizers in cellulose acetate, measuring absorbance a t 750, 690, and 2260 cm-I for dialkyl phthalates, (Ph0)3PO, or adiponitrile, respectively. Spectra were recorded for a number of cellulose esters and graft copolymers having ion exchange, bactericidal, and flame-resistant properties (1244). Products from y-irradiation grafting of cotton by acrylonitrile were studied by ir, x-ray, and thermal methods ( 1 7 2 ~ ) . Studies were made of graft copolymers of cellulose with PMMA (137'5), methacrylic acid (14, groundwood grafted with MLIMA (1121), and carboxymethylcellulose with styrene (1178). Chow and Troughton (169) determined melamine-HCHO in wood and cellulose products from the absorbance ratio, 810 crn-'/2900 crn-'. Chow and Mukai (168) used a similar method for phenol-HCHO. McCall and coworkers (1248) used direct ir and KBr pellet and hydrolysis techniques in identifying nitrogenous crosslinking agents on cotton cellulose. .4TR and multiple internal reflectance procedures were used in studies of polymeric coatings on paper (1173). ATR also was used in a study of the interface between epoxy resin and wood (1275). Other ir studies included metal derivatives of cellulose with polyacrylohydroxamic and N-carboxy(alky1 or aryl) aminotriazinylcellulose (187), reaction products of cellulose and propylene oxide (15), and the structure of hydroxypropylcellulose in conjunction with a variety of other techniques (1819). Polyamides, Polyimides. B y multiple attenuated internal reflection ir, Baier and Zisman (124) showed that variable surface properties of poly-


amides may result from masking or exposure of hydrogen-bonding sites. The 1224 and 1323-cm-I conformation bands in nylon 66 were shown due to the nitrogen-methylene bond (1112). The 1329- and 1224-cm-I bands due to chain-folded conformations were used to indicate more extensive regular folding in negative nylon 66 spherulites than in positive (156). Factorsaffecting crystal structure of nylon from mechanical and thermal treatments were followed by ir (147). Transformations in nylon 66 resulting from treatment with phosphoric acid were studied by ir (1179). ATR aided in ir examinations of skin and core structures of nylon 66 fibers (1144). Transitions and relaxation phenomena in nylons 4, 6, 7, 9, 11, and 12 were studied by ir (1273). On nylon 6 surface studies were made by ATR and crystallinity was measured by transmission ir (1288). Volatile thermal decomposition products from unstabilized and stabilized nylon 6 were trapped a t -78' and analyzed by ir (1502). Thermal degradations of several secondary diamides were studied as models for nylon 66 using ir and gas chromatoggraphy (1221~). Spectroscopic studies were reported on fibers of nylon 6 directly and modified by crosslinking with formaldehyde (1183, 1 3 5 0 ~ ) . Polymorphism and crystalline structure features of nylon 3 were established by ir spectroscopy and x-ray diffraction (1245)* Pyrolysis products of nylon 6/66 copolymers included cyclopentanone and caprolactam based on characteristic bands a t 2920, 1750, and 1680 cm-I (1389). Structure information was obtained on polyamide-polyurethane systems (194). Unusual applications of ir included studies of relative basicities of a n N,N-disubstituted polyacrylamide and models (175), characterization of polyacrylamide graft on cellulose (1341a), and kinetics of H-D exchange in poly-N-vinylacetamide ( I 156). Hummel (1154) reported ir spectra of several materials to aid in identifying polyimide wire lacquers, including polyamidocarboxylic acids, polyamidoimides, polyesterimides, and polyimides. NcGowan (1250) found ATR helpful in determining the degree of cure of polyimide coating lacquer. Polyimide films, containing silver were examined (1306). The structure of polyglutarimide was suggested from ir and N M R data (1839). The ir spectra of dehydrocyclization products of polyamide acids from pyromellitic dianhydride and diaminodiphenyl ether were obtained to aid in assessing stepwise reactions to polyimide (1106). Polyesters. Schulz and coworkers (1329) in studies of hydrolytic sensitivity of linear polyesters followed the C=O band a t 1600 to 1800 cm-l to

show a relation due to the inductive effect of the C=O group. Effects of thermal treatment on the fine structure of polyester fibers were examined by ir spectroscopy and electron microscopy (1291); an increase in degree of disorientation was observed. Thermooxidative degradation of polyethylene adipate and polyethylene sebacate was followed by ir (1133). Polarized far ir spectra, up to 80 em-', of aliphatic polyesters were compared with that of nylon 6 (1354). From ir spectra polymers from radical and anionic polymerization of methyl isoprenecarboxylate were shown to have stereoregular 1,4trans structures (115). Residual unsaturation in unsaturated polyester resins crosslinked with styrene was measured quantitatively by ir (1221). The ir spectra from 3600 to 400 cm-l were obtained on polyester-polyether and polyester-polyurethane systems (1239). Kveder and Seke (1217) characterized polyethylene terephthalate (PET) from ir absorptivity data, and calculated amorphous content. Rlanley and Williams (1241, 1243) used polarized far-ir spectra in characterizing rotation of groups in crystalline phase of PET. I n chain-folding studies on PET, Koenig and Hannan (1198) assigned the 988-cm-l band to a fold conformation. Danzund and coworkers (185) studied orientation by ir. Effects of drawing of P E T on segmental motion were examined by ir dichroism, wide-line N M R , and dynamic viscoelasticity measurements (1163), while Schoenherr (1328) studied rotational isomerism based on C=O absorbance. Koenig and Cornel1 (1196) studied uniaxially drawn P E T by polarized ir. Change in crystallinity in P E T in relation to induction times from the melt was reported from ir data (1181). Low temperature transitions to 77°K were characterized by ir (1143). From ir studies Il'icheva and Slovokhotova (1157) showed formation of COz and increase in COOH groups from radiation degradation of PET. Structural changes from fusing P E T with nylon 6, 66, and 610 were established by ir analysis (1188). McGraw (1251) followed effects on structure of heat treatment of PET, using laser-Raman spectroscopy. Thermal decomposition products of aromatic polyesters were analyzed by ir and mass spectroscopy and chemical methods for elements (196). Polyethers, Epoxides, Glycols. Grassie and Roche (1136) followed photodegradation of polyoxymethylene by ir spectra. Dick and coworkers (LW, 189) determined M W of polyoxymethylene diacetates via end group analysis by ir and by osmometry, and LfWD by fractionation. iicid and base degradations of paraformaldehyde, polyoxymethylene, and copoly-

mers were characterized by ir and differential scanning calorimetry (1247). Laser Raman studies of polyoxymethylene were reported by Sugete and coworkers (1365). Quantitative analyses for free aldehyde groups and lactones in methacrolein polymers were made by a n ir method (110). Data supported a partial acetal (ladder) form for polymethacrolein made by radical initiation. The ir spectra were reported for amorphous and crystalline poly(propylene oxide) (1399); a band a t 1268 cm-l served to measure crystallinity, and bands a t 833 and 873 crn-', to estimate type of addition and degree of isotacticity. Valles (1.401) used a variety - techniques, including ir, chemical, of M,, and thermal methods, in studies of solution properties of polypropylene oxide. Polarized ir spectra aided in group assignments for the three crystalline modifications of polyoxacyclobutane (1238). Kinetics and mechanism of phase transitions in poly(ethy1ene oxide) and poly(tetramethy1ene oxide) were established by ir and NMR (1313, 1314). Chain folding in poly(ethy1ene oxide) was measured by ir (112). To estimate Znof poly(ethy1ene oxide) oligomers, Favretto and Stancher (1102) used the ratio between absorbances a t 1245 and 1105 cm-l. The degree of polymerization of low MW poly(oxyethy1ene glycols) was calculated from absorbancy a t 3485 and 3605 cm-l (1256). Perret and Skoulios (1294) characterized ethylene oxide-caprolactone block copolymers by ir, NMR, and x-ray analysis. Thermal degradation studies were reported for poly(pheny1ene oxides) and polyphenylenes (197) and poly(2,6dimethyl-l,4-phenylene oxide) (1236, 1344). Quantitative analysis of aroxyethylene copolymers by ir was proposed (1212). Other analytical studies were made on propylene oxide-tetrahydrofuran copolymers (199, 1296), propylene oxide-allyl glycidyl ether copolymer and rubbers (172),and ethylene oxide-epichlorohydrin copolymers (191). Analysis of epoxy resins by pyrolysis followed by ir and thin-layer chromatography was described by Gedemer (1123). Curing reactions in phenolicepoxy resins used for can coatings (1372), primary amine-epoxy resins (1321), and pyrolysis of aromatic aminewere characcured epoxy resins (1366~) terized by ir procedures. Curing of epoxy resin with BFB-ethylamine complex was followed by ir, NMR, and mass spectroscopic analysis (1164). Tanikawa et al. (1373) determined phenolic components in cured phenolic-epoxy resins based on absorbances a t 1500 to 1450,1150 to 1100, and 900 to 700 cm-1. Williams and Delatycki (1413) compared ir data with mechanical loss

measurements for transitions in epoxydiamine networks. Other ir studies on epoxy resins included effects on addition of an epoxy ring to a carboxyl group in polymers (1104), effects of time on nature of epoxy pyrolyzates (164, effects of ionizing radiation on epoxy resins (I%?), and curing reactions after the gel point of carboxyl-terminated polybutadiene-epoxide systems by ir transmittance and reflection techniques (1363). Brodskaya, et al. (T51, 152) obtained ir, Raman, uv, and NMR spectra on polymers of dimethyl vinylethynyl carbinol and its ethers. Characterization studies on polyether-methane elastomer include ir (1367). Characteristic ir bands were identified in molten poly(ethy1ene glycol) (1246). Liu and Parsons (1227) studied solvent effects on polytethylene glycols) by ir and NMR measurements, while Koenig and Angood (1191) obtained Raman spectra on these polymers in the solid and molten phases as well as in aqueous and chloroform solutions. Polyolefins. Far-ir spectra between 30 and 600 cm-' were reported for different polyethylenes (PE) , polyoxymethylene, and vitreous silica (116). Popov and Voropaeva (1300) reported on ir measurements of vinyl, vinylidene, and disubstituted trans-vinyl unsaturation plus methyl end groups in high density PE. End group analyses of narrow fractions served to estimate RfW. Molecular orientation studies of linear and branched P E mere reported by Suchkov and Kovak (1354). Spectra of PE, chain-folding state of P E crystals, and partially deuterated polymer were obtained by Tasumi (1376), while Bank and Krimm reported on mixed crystal studies of chainfolding (129) and chain segregation (130) in crystalline PE. Short-chain branching in low MW PE crystallized from solution was measured with reference to absorbance a t 1380 and 1460 cm-l (166). Polarized ir studies were made on drawn P E (1130) and of amorphous orientation in P E and some copolymers (1307). Studies of irradiated P E included effects of tin and iron chlorides by ir, ESR, x-ray, and DTA procedures (136a), free radicals by ir and uv examination (1407), determination of chemical aging from uv exposure from ir measurements of hydroxyl, carbonyl, and vinyl absorption (1149), influence of ?-radiation on structure and MW (1161), and structural features after irradiation a t - 180' (193). The amount of phthalocyanine blue in P E concentrate was determined by absorbance in the 1110 cm-1 region (1381). Olsen and Osteraas (1280) used frustrated multiple internal reRection spectroscopy to define the nature of sulfonated P E surfaces. Un-


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saturation in polyolefin terpolymers was determined successfully by ir, but bromo- and copolymers were analyzed by bromination and determination of Br following combustion (C149). Raman spectra of crystalline PE were reported by Boerio and Koenig (139) and by Frenzel and coworkers (1113). For stereoregular PP Miyazawa (1268) reviewed ir spectral assignments of isotactic and syndiotactic PP as well as the molten polymer. Peraldo (1293) used ir spectra for determining molecular structure of amorphous and isotactic PP. Effects of temperature between 5" and 70" on absorptivities were reported by Tanimoto and Tanaka (1390),who found changes between 20" and 30" probably due to T,. Isotacticity of PP between 90 and 100% was calculated from ratio of intensity of the 1000-cm-1 band to that a t 973 cm-l (1153). Structural correlations were made from band intensity ratios a t 973 and 1460 cm-l for PP and a t 720 and 1380 cm-l and 1155 and 1380 cm-l for copolymers (1186). Possible use was reported for determining the stereoregularity of PP from intensities a t 975 and 1156 cm-l (1232). Miyamoto and Inagaki (1257) determined the structural and steric isomerism of PP from ir, NMR spectra, and solution properties. Kinetics of autoxidation of atactic PP were followed by ir (1169, 1170). Studies of PP subjected to photooxidation included measurements of carbonyl and hydroxyl groups (128), effects on molecular order (1182), and determination of inhibition period (1284). ATR was used to study surface changes during photooxidation of PP (161) and during corona treatment (160). Adams reported on analysis of nonvolatile oxidation products of PP from thermal oxidation ( Z I ) , process degradation (IS), and photodegradation (12). Quantitative analysis of CCld-soluble stabilizers in PP involved ir spectroscopy and gas chromatography (1279a). Effects of adding poly-2-vinylpyridine to PP on structure were determined by ir (163). Zerbi and Hendra (1429) obtained laser Raman spectra on syndiotactic PP using an exciting line a t 6328 A. Cornel1 and Koenig (177') obtained Raman spectra on the three crystalline modifications of poly-1-butene; the Raman frequencies were in good agreement with infrared data. The ir spectra were reported for trans-polyalkenamers in the amorphous and crystalline states (171). Thermal degradation of poly-4-methyl-1-pentene from 291' to 341' was studied by ir, NMR, GC, and thermal methods (1308).

A review of ir analysis of E-P copolymers was reported by Kimmer and

274R

Schmolke (1184) and Simonazzi (1348). Applications of near-ir combination bands to analysis of E-P copolymers and physical blends of homopolymers were described by Takeuchi and coworkers (1369). Popov and Duvanova (1299) used a compensation procedure for determining methyl groups in E-P copolymers utilizing the CH, group absorption a t 1378 cm-1 corrected for the interfering CH2 group doublet a t 1369 to 1350 cm-l. Tosi et al. (1384) discussed general ir determination of sequence distribution in copolymers, emphasizing E-P copolymers. Pyrolysis-ir was used for analysis of E-P copolymers; absorbance ratio a t 1380 cm-'/1470 cm-l was nearly independent of pyrolysis temperature and a linear function of composition (1368). Propylene in E-P copolymers and terpolymers with dienes was measured from bands a t 1380 and 1355 cm-I with calibrations obtained from compressed films of the homopolymers (1362). Formation of conjugated double bonds in y-irradiated E-P and E-a-butene copolymers was studied by ir and uv spectroscopy (192). Tosi and coworkers (1385) described ir methods for quantitative analyses of E-1-butene, E4-methyl-l-pentene, and P-1-butene copolymers. Wegemer (1408) established methods for quantitative determination of 1-butene in copolymers with P and terpolymers with P and 1-octene. Fractions from column separations of E-P terpolymers were characterized by ir analyses for 1' content (L246). Ethylidenenorbornene in E-P terpolymers was determined from absorption a t 1700 cm-I (Z223), while determination of dicyclopentadiene in E-P terpolymers used absorbance a t 695 cm-l (1361). Conjugated double bonds from E-P terpolymers with fulvenes and acetylenes were measured by ir and uv analyses (1349). Alternating copolymers of P and butadiene were characterized by ir and NMR spectroscopy (1117). Polymers for E-butene-isobutene were analyzed by absorbance measurements a t 722, 770, and 1230 cm-' due to CzH4, CH&HCzHs, and CH2C(CH& units, respectively (1425). Effect of polymerization temperature branching in E-VAc copolymers was determined by ir and NMR (1416). Saito and coworkers (1518) determined alkyl side branching in E V A c by ir analysis of hydrocarbon polymer resulting from hydrolysis, iodation with HI, and reduction. Both ir and light scattering were used by Andrei et al. (111) to characterize E-VAc copolymers. Molecular structure was established from ir spectra (1221b). The microstructure of E-trifluoropropylene copolymers was established by spectroscopic studies (11S1). Structural and compositional information


on E-S copolymers was based on ir studies (184, 1171). E-SO2 copolymers was characterized by ir, x-ray, and thermal methods .of analysis (174). Band assignments on polyethylene sulfide were made for ir and Raman spectra (113). Polystyrene (PS) and Copolymers. Deshpande and coworkers (188) made an ir study of conformation of chain termination by Zn(C2H& in polymerization of s; they concluded that absorption a t 727 cm-' was due to the presence of three CH2 groups in the polymer. Terminal groups on PS prepared with difunctional diacyl peroxides were studied by ir (1321,1332). Structures of PS, PMMA, and poly-4vinylpyridine a t a liquid interface were determined from ir spectra (1380). Rubber in high-impact PS was determined from absorbance a t 967 cm-' (1124). Molecular orientation in amorphous PS was evaluated by ir dichroism and birefringence (1252). Mechanism of thermal degradation of PS was studied by ir and thermal methods (1143~). Ester groups resulting from thermal decomposition of peroxide bonds in PS were detected by ir and chemical methods (C154). Increase in CO groups and crosslinking on the surface of PS film subjected to ionization aging were followed by ir analysis (123). Bortnichuk and Shtyrkov (144) studied kinetics of bulk polymerization of S from intensity of the 622- and 1636cm-' bands. Cornell and Koenig (176) made depolarization measurements of oriented and unoriented PS by Raman and ir procedures. Kobayashi and coworkers (1190) measured sequence lengths in isotactic copolymers of normal and deuterated styrenes. Monomer distribution in styrenated acrylic copolymers was established by ir analyses of cesium iodide pellets from 4000 to 200 cm-I and by gel permeation chromatography (151.21). Giammarise (1129) determined styrene in S-acrylate copolymers by near-ir measurements a t 2.144 microns. Post (1801) described ir methods for analyses of S-acrylate and S-butadiene resins in paint. For analysis of S-AN copolymers, Takeuchi and coworkers (1370) used absorption from combination bands at 1.910 and 1.952 microns and from overtone bands near 1.68 and 1.75 microns, Gross (1158) analyzed S-AN copolymers by ir analyses of pyrolysis products. Quantitative ir methods were developed for analysis of residual S and 4-phenyl-1,3-dioxane in the copolymer (1409), and distribution of monomer units in S-VC copolymers (1316) and S-diketene copolymers (1114). Infrared spectroscopic studies were reported on analysis of (1162) and degree of crosslinking in S-divinylbenzene copolymers (1216), and on structure of chloromethylation of these CO-

polymers (1152). Copolymers of sunsaturated oligoesterurethanes were studied by ir (1282) and S-butadiene by ir and polarographic methods (C166). Gunder et al. (1140) studied polymers of a-methylstyrene homologs by ir, x-ray, and thermal methods. The a-methylstyrene content of copolymers in VAc was calculated from ratio of absorbance a t 705 (aromatic CH) and 1465 cm-I (aliphatic CH) (1352). Infrared methods were used to characterize a-methylstyrene-cyclopentadiene copolymers (Z159), -butadiene copolymers (1331), and -butadiene copolymer grafts with acrylonitrile and vinyltoluene (1107). Infrared spectroscopy served to follow the mechanism of hydration of polystyrenesulfonic acid (1435). Other Vinyl Polymers. Infrared and ESR methods were applied to study of graft polymerization of vinyl monomers on polymeric materials (N121). Chain structure and conformation of PVC were established by ir (1253). The degree of branching in PVC was studied by Baijal and coworkers (125, 132) and by Caraculacu and coworkers (157). Verdu (Z403) studied the stabilization of PVC by lead stearate. Ogura and Kawawata (1278) used ir in a systematic procedure for identifying plasticizers in PVC, and Fischer and Leukroth (Z109a) for their separation and identification by ir, pyrolysis, and chromatographic methods. Studies on mechanism of chlorination of PVC included ir analysis (19, 1377). Mechanism of dechlorination of PVC by Zn was established from ir and N M R data (1255). Dehydrochlorination studies on PVC included ir examination for changes in films (1134, formation of branch structure ( I @ ) , and mechanism of reduction by LiAlHI (148). Formation of oxygenated functional groups from oxidation of dehydrochlorinated products of PVC was established from ir spectra (1388). Soboe and coworkers (1348~)studied thermal degradation of PVC by ir and thermal analysis methods. Volatile combustion products were studied by ir, thermal, gas chromatographic, and mass spectrometric procedures (141). Infrared dichroism was used in studies of oriented PVC films (1337,1397). Raman spectra were reported on PVC of low crystallinity and on highly crystalline syndiotactic polymer (1197') and on powdered poly(viny1idene chloride) (Zl47'). Poly(viny1 alcohol) (PVA) was characterized by ir and thermal methods (16?'). Solid PVA and aqueous solutions were characterized from ir and N N R spectra (1386). Nikitin and Aslanyan (1272) studied crystallization of PVA from ir bands a t 920 and 1146 cm-'. Korodenko et al. (1203) determined effects of y-radiation on

order in PVA, while Kasatochkin and coworkers (1180) followed phase transitions by ir, x-ray, and thermal methods. Oxidative thermal degradation was studied by ir and uv spectroscopy (143) and structure of dehydrated PVA fibers was ascertained from ir spectra (1405). Both ir and uv spectra were made on PVA films treated with tetramethyldiacetoxydisiloxane (1334). Shifts in CO and OH absorption bands were followed in hydrogen-bonding studies of PVA-polyvinylpyrolidone and -polyvinylcaprolactam mixtures (ZS04). Shibatani and coworkers (1336) obtained ir and proton NMR spectra of polyvinyl formal and model compounds such as formals of pentane-2,4-diol and heptane-2,4,6-triol. K M R and ir studies were made of poly(methy1 vinyl ether) and model compounds (N142). Other reports on homopolymers included ir and thermal data on poly(vinylphthalic anhydride) (Z404),and ir spectra on isotactic polyvinylethylsilane (158) and vinylaromatic homoand copolymerse.g., polyvinylbiphenyl, polyvinylnaphthalene, and Svinylbiphenyl (Z141). Richards and coworkers (1311) studied ir and NMR spectra of copolymers from vinyl monomers with alkali metal in the presence of aliphatic dihalides. Broadskaya and coworkers (160) discussed ir spectra of copolymers from vinyl and acetylenic monomers with phenylene and azophenylene radicals. Analyses of VC-VAc and VCMMA copolymers and other vinyl copolymers were made by ir and uv spectroscopy (1110); the VC-LIMA copolymer analysis utilized ir bands at 1740 or 1725 ern-'. Copolymers from mastication of PVC in the presence of MMA and S monomers were studied by ir, NMR, and flash pyrolysis (1259). Johnsen and Lesch (1175) used ir to determine the over-all composition, concentration of diads, and sequence lengths in vinylidene chloride-isobutene copolymers. The ir spectra were reported and used for analysis of VAcmaleic acid diester copolymers (1268). VGVAc copolymers and PVC-PVAc blends were examined by ir and thermal methods (Z327'). Other ir studies of analytical value included VA-N-vinylpyrrolidinone copolymer (1322) and VA-hydroxymethylene copolymers (1210). From ir spectra Kusakov and Perekal'skaya (1214) concluded that chargetransfer complexes were formed in vinyl polymers containing aromatic groups. Polymers studied included polyvinyltoluene, polyvinylxylene, polyvinylpyridine, polystyrene, and polychlorostyrene. Fluorocarbon Polymers. Surface changes from electron bombardment of P T F E were examined by ir (1392). A white residue from irradiated P T F E

was shown to be shortened molecular chains based on ir absorption a t 1150 and 1210 cm-l for CF2 units and N M R spectra (1396). Raman spectra and band assignments were made by Koenig and Boerio (1193, 1194) on PTFE, including measurements as a function of temperature through the 19' transition. Thermooxidative degradation of polytrifluoroethylene was followed by ir measurements in the 1600 to 1800 cm-1 region (190). Zerbi and Cortili (Z428) made a vibrational analysis of poly(vinyl fluoride) (PVF) from polarized ir spectra; they proposed a primarily syndiotactic structure. From Raman and ir spectra Koenig and Boerio (1195) concluded that sequences of syndiotactic placement are short and in PVF of high crystallinity the chain is atactic. On poly(viny1idene fluoride) (PVFJ Tarutina (Z374) analyzed polarized ir spectra of stretched films. Similar studies were made by Makarevich and Sushko (1237). Gal'perin and coworkers (1120) related the structure of PVFz to polymerization conditions based on ir and x-ray diffraction data. Boerio and Koenig (140) obtained Raman data on the nonplanar form of PVFz and found unique Raman bands a t 2973, 1437, 1327, 1198, and 1059 cm-'. Miscellaneous. Products from polymerization of chloral and monoisocyanates were shown by ir and DTA to be copolymers and not mixtures of (1277). Absorptivity homopolymers measurements served to analyze fumaric diester polymers and copolymers with vinyl acetate (1298). Relations were observed between crystallization capacity and ir spectra of isotactic and atactic poly(methally1 alcohol) (1261). Thermal stabilities of polyamino acids were followed by ir, TGA, and x-ray diffraction (Z27'4). Shiskina (1338) reported ir spectra of polymers of 1-ethylenimino-2-hydroxybutene.Kagiya et al. (1177) used ir to determine the nature of products from y-ray-induced copolymerization of carbon monoxide with cyclic ethers. Polymerization products of acetylene were studied through Raman spectroscopy (1420). Tadokoro et al. (Z364) studied polyallene by polarized ir and N M R spectroscopy with x-ray diffraction. N-benzoylated poly-2-ethyleneimines were examined by ir spectroscopy and optical rotatory dispersion measurements (1387). Spell (1350) used a n ir method for determining piperazine rings in polyethyleneamine and polyethyleneimine. N-alkylated polyhydrazides from diesters and hydrazine were characterized by ir and thermal analyses (1167). Yukel'son and Glukhovskoi (1424) reviewed synthesis and properties of


275 R

polyarylenealkyls in which ir was used for polymer identification and characterization. They also obtained structural information of polyphenyleneethylene (1423). Yoshida and coworkers (1421) estimated crosslinking of diallyl phthalate prepolymer from a splitting of the C=C stretching band of the allyl group into two bands a t 1645 and 1651 cm-l. The ir spectra were reported for polyphenylene, polynaphthalene, polyanthracene, polybianthryl, naphthalene-benzene, and anthracene-benzene copolymers (136). Polytoluene was examined by ir, NMR, and uv methods (N118). Berry and Fox (136) made structural studies of heterocyclic condensation polymers such as that from naphthalene-l,4,5,8-tetracarboxylic acid and 3,3'-diaminobenzidine by ir, exclusion chromatography, light-sca ttering, and viscosity measurements. Oxidation products of bisphenol A polymers included ir studies (1128). Thermal decomposition of polyphenylene-ethyl hydroperoxide was followed by ir (1199). Characterizations of poly(dimethy1 pyromellitamates) (1273a), monomers and polymers with oxadiazole rings (1226), poly-2-oxazolidones (N86a),and thermally treated poly-p-oxybenzoyl (181) included ir studies. Gabe and coworkers (1118) obtained ir spectra of several polypyridazines, polytetrazines, and polytriazoles. Structure information was reported on polybibenzimidazoles and polybibenzimidazoles and polybibenzimidazolines (1106) and fiber-forming copolymers based on hexahydro-p-aminobenzoic acid lactam (Z&O6a). Effects of pyrolysis temperature on structure of some aromatic poly(amido and poly(aminoamido acids) were followed by ir, ESR, electron microscopy, and x-ray diffraction (1833). Fujisawa and Kakutani (1116) prepared poly(ary1ene sulfides), characterizing them by ir. Ehlers and coworkers (196) examined thermal degradation products of poly(p-phenylene sulfide), a poly(ary1ene sulfone), and a poly(ary1ene sulfonate) by ir and mass spectrometry plus elemental analysis. Evers and Ehlers (1100) determined thermal stability of piperazine polysulfonamides by ir, thermal, and chemical methods. Phenylmethylene polysulfone was studied by ir, NMR, chemical, and thermal methods (1383). Diene polysulfones were characterized by ir and N M R methods (133). Thermal degradation of polyphosphonylureas was followed by ir spectroscopy (162). Alkyd resin components were determined from characteristic ir absorption bands (1266). Pyrolysis products analyzed by ir and chemical methods aided in identifying urea-HCHO poly276 R

*

mers (C48). Characteristic ir absorption bands were used for study of the crosslinking of urea-HCHO oligomers (17)*

Thermal degradation of phenolic resins included ir studies (1122, 1220). Yamao and coworkers (1419) used ir to determine the mole ratio of resol-type phenol-HCHO resins, utilizing band intensities a t 1610, 1150, and 890 cm-l relative to that a t 1590 cm-l. I n thermal degradation or^ phenol-HCHO resins ir spectra showed a decrease in phenolic O H and increase in intensity of ether bonds (1348). Hardening and degradation of phenol-HCHO resins were followed through ir spectra (1200, 1201).

Composition and microstructure of rubber vulcanizates were established by ir and N M R methods (169). Oxidative stability of crude elastomers was studied by automatic ir analysis between 1500 and 1800 cm-1 (1109). Crosslinking of isoprene- and butadiene-based rubbers by alkylphenol-HCHO resins was established by ir analysis (142). Corne11 and Koenig (179) published Raman spectra of cis-1,4-, trans-1,4-, and 3,4polyisoprene. Among pyrolysis products of polyisoprene was a high proportion of a dipentene isomer, either 1,4dimethyl-4-vinylcyclohexene or 2,4these dimethyl - 4 - vinylcyclohexene; identifications were based on ir, ESR, and mass spectra (1119). Information on microstructure was obtained through ir and TC'RZR analyses on polyisoprene, polybutadiene, and copolymers (N200, 1341).

Clark and Granquist (173) described a rapid pyrolysis4 technique for identification of neoprene (polychloroprene resin). Ferguson (1108) described an improved high resolution ir method for polychloroprene isomers. Crystallinity and crystallization kinetics were studied by ir measurements a t 780 and 1225 cm-1 (119). Aslanyan and eoworkers (118) studied polychloroprene crystallization through ir absorption a t 1450 cm-1, while Kostrykina and coworkers (1206) used crystallinesensitive bands a t 955 and 755 cm-l. Continuous measurement was made of ir dichroism and stress in polychloroprene (1367). The 1,2- and 1,4-trans components in polybutadiene were calculated from absorbance a t 910 and 967 cm-l (121). Ruzicka (1316) described analysis of butadiene and B-S copolymers based on absorbance at 3080 and 6100 em-' for vinyl-1,2-, at 2840 and 550 cm-l for methylene in trans-1,4- plus cis-1,4-, a t 3010 cm-l for ethylenes unsaturatior in cis-1,4-, and a t 3030 cm-l for aromatic CH. Oikawa and Takahashi (1279) analyzed polybutadiene from absorbance at 915 cm-' due to trans double bond, and at 910 to vinyl and 800 to


630 cm-l to cis. Rotational isomerism and crystallization of trans-1,4-polybutadiene were studied (1263). Raman spectra were recorded for cis-1,4-, trans-l,4, and 1,2-polybutadiene (17'8). Other ir studies included structures of chlorinated trans- and cis-1,4-polybutadienes (1366), of polybutadiene, and a prepolymer diamine by ir, NRIR, and thermal analysis (NlOla), of copolymers of butadiene with diene monomers (1379), and of allyl rearrangement in poly-trans-I-phenylbutadiene and poly1-phenyl-4-methylbutadiene (18). Structure of poly-1,a-pentadiene was studied by ir and N M R (1160) and of poly-1,3-dimethylcyclopentadieneby ir (120). Chemical modifications of diphenylbutadiyne polymers were observed using ir, NMR, ESR, thermal, and chemical procedures (N29b) Fogg and coworkers (1111) used ir to identify polyurethanes such as those from tolylene diisocyanate and 4,4'diphenylmethane diisocyanate. Gudim (1139) reported ir spectra of crosslinked polyurethanes. Zharkov et al. (1430) described ir for analytical control of hardening of polyurethane elastomers. Quantitative determination of isocyanate groups in polyurethanes was made through absorbance a t 2275 and 2956 cm-1 (1343). A similar procedure was used for unreacted isocyanates in polyurethane films (1391). Spectroscopic determination of 2,4-tolylene diisocyanate (1166) and of allophanate groups (1431) was used during polyurethane synthesis. Dawson and coworkers (186, 187) used the infrared ATR technique to identify components in polyurethane foams. Nolecular configuration of stereoisomeric po!ymethallyl phenylurethanes was studied by ir (1262). Structural information based on ir spectra was obtained on copolymerization of oligoester maleate urethanes (1283), and on polyurethanes from polytetrahydrofuran, diphenylmethane-4,4'-diisocyanate, and ethylenediamine (1267). Both ir and thermal methods served to characterize polyurethanes based on acryloyl isocyanate (ICOSa) and copolymers of phenyl isocyanate and P-propiolactone (1143b). Both ir and ESR were employed in thermal studies of polymeric organosilicon films (N19a). Infrared studies were used in assigning group vibrations in cyclic polydimethylsiloxanes (1206), in determining alkoxy groups in polyarylalkoxysiloxanes (1340),and in identifying thermal oxidative products of polyorganosiloxane fluids a t metal surfaces (1415) and of organosilicon binders (1185). Tsyba and Egorov (1396) obtained ir spectra of monomers and polymers containing =Si(CHz)nSi= units. Tsyba also reported on ir studies of poly-l,l-dimethylsilacyclobutane (1393), and emission and ab-

sorption spectra of polydimethylsilaalkanes (1.394). Shetty and Fernando (1335) described a technique for obtaining spectra of insoluble metal chelate polymers employing electrodeposition. Cozzens and Harvey (182) obtained ir, Raman, and ESR spectra of polyselenacyclobutane. Manley and Williams (1242) obtained ir spectra from 5000 to 20 em-1 and made band assignments for poly(phosphonitri1ic chloride). Raman spectra were recorded for some biological polymers, including polypeptides and polynucleotides (1295). Lindeman (1224) obtained ir spectra of linear and crosslinked polyelectrolytes from eopolymers of styrene-divinylbenxene and derivatives. ULTRAVIOLET-VISIBLE

Hatano ( C Y . 4 ) reviewed applications of uv-visible spectroscopy for molecular structure determinations, reaction mechanisms, and analysis of polymer residues. Recent advances in instrumentation for determining color in plastics were reported by Ingle (U28). Antioxidants synthesized from reactions of polybutadiene with N-phenyl-pphenylenediamine and 2-naphthylamine were determined a t 293 and 350 nm, respectively (U34). Schiff's base formed from reaction of 2-hydroxy-1naphthaldehyde with amino groups in polymers was measured a t 420 nm ( U l 7 ) . Carbonyl functions in polymers, such as certain polybutadienes, were estimated spectrophotometrically as the 2,4-dinitrophenylhydrazones ( U 4 ) . The K3[Fe(CN)6] procedure was used to determine aromatic antioxidants such as butylated hydroxytoluene and substituted butylphenols (L788). Direct uv measurement on extracts from polymers also was reported for phenolic stabilizers ( W f ) . Colorimetric procedures were reported for disperse dyes on synthetic fibers (U29). O'Connor ( U 5 f ) reviewed a variety of methods for elemental analysis of textiles and textile fibers, including uv-visible spectrometry, emission spectroscopy, x-ray fluorescence, and atomic absorption. Pentachlorophenyl laurate in textile and paper materials was removed by saponification, isolated, and reacted with CuS04-C6H6iY reagent for measurement of 450 nm ( U Y O ) . Reducible sulfur in paper and paperboard was measured by the methylene blue procedure (U9). Onari ( U S 4 obtained vacuum uv spectra from 2500 to 1100 A on polymers such as PVC, PS and modified PS, PMMA, PAN, polyvinylcarbazole, poly(ethy1ene glycols), polybutadiene, and paraffin. Acrylics. Dawson and Haken ( U f 4 ) described a colorimetric reaction for methacrylate monomer and polymer.

Acrylate polymers in aqueous solutions were estimated turbidimetrically following reaction with Cuf2 (U77). The uv absorption spectrum between 245 and 450 nm was studied on yirradiated PMhIA ( U f8). PMMA isolated from wool was identified following dinitrophenylation (CS). Cellulose. Phosphorus in fireproofed cellulose fabrics was recovered by acid digestion and determined by the vanadomolybdate method ( U S ) . Bound sulfuric acid in cellulose esters was measured by a colorimetric methylene blue procedure (U37). I n kinetic studies on the bond-formation activation energy of polymerization of phenol-HCHO resins in the presence of cellulose, Chow ( U f1 ) relied on correlation between absorbance a t 287 nm and curing time. Absorbance a t 280 to 320 nm was used to determine degree of esterification of cellulose xanthate in rayon (US6). Tunc and coworkers (U78) used a rapid uv method for simultaneous determination of xanthate, by-product, and total S in viscose (U78). Williams ( LT82) found uv absorption helpful in relating delignification rate to pulp uniformity in paper making. Polyamides, Polyimide. The degree of oxidation of polyamides was determined from absorbance a t 530 nm following reaction of aldehyde groups with guaiacol (liS9). I n vacuum uv studies of nylons 3, 4, 6, 66, and 610 a peak due to NV, transition of the amide bond was observed near 190 nm, while no absorption was found for N V 2 (C'63). Optical rotatory properties of asymmetric polyamides were studied in the uv region. Praeger and eoworkers (U67) developed colorimetric, complexometric, and turbidimetric methods for lactam content in suspensions of TiOz and dull polyamide. Determination of primary aliphatic amino end groups in polyamides was based on their conversion to pyrrol groups and measurement a t 560 nm (U68). Apparatus was designed for measuring uv dichroism in nylon 6 and polyester filaments (CSS). The Ti02 content of nylon 6 was determined colorimetrically as H4TiOs following wet oxidation ( U 4 f ) . Caprolactam in nylon 6 was estimated by photometry ( U 8 f ) . Amine impurities in caprolactame.g., NH3 and HzN(CH?)&OOH-were found by studying uv behavior as a function of p H (U86); polarography also was employed. Pyromellitic acid in the dianhydride was determined by uv absorption with a sensitivity of 0.03% ( U 2 ) . Polyesters, Epoxy Resins. Carboxyl end groups in polyethylene terephthalate (PET) were monitored a t 602 nm during titration with KOH with bromophenol blue indicator (U80). ,Metals such as P, Sb, Co, Mn, Mg, and

Zn were determined in PET by colorimetric procedures (Lr87). Visible dichroism was followed in studies of the behavior of P E T film dyed a t 70" with Disperse Red 17 or Disperse Yellow 7

(U.47, U48). Epoxy groups in polymers were measured a t 390 nm based on reaction with 2,4-dinitrobenzene sulfonic acid and piperazine (U79). Spectrophotometric procedures measured phenol in epoxy and HCHO resins in containers ( U75). Polyolefins. The mechanism of polymerization of ethylene with eoordination catalyst was studied by uv and ESR spectroscopy (C52, U66). Light attenuated by PE film aided in studies of surface and bulk optical properties ( U f S ) . Both uv and fluorescence spectra were used in studies of effects of phases of a PE matrix during photocrosslinking ( U 6 ) . An improved ASTM spectrophotometric method for C in P E film was described by Howard (U2Y). Juskeviciute et al. ( U S f , L'S2) described uv and infrared methods for determining stabilizers and antioxidants in PE. The rate of photopolymerization of ethylene in the presence of oxygen was followed by uv absorption spectra showing peaks in the 270 to 350-nm region ( l i 2 S ) . Photodegradation of PE containing trapped allylic free radicals was investigated using uv and ESR measurements together with viscosity for MW ( U7.4). Richters (C69) reported on a color reaction for early detection of oxidative degradation of PP. Hydrogen peroxide decomposition was used in a spectrophotometric method for Ti02 in PP based on reaction with diantipyrylmethane (C84). The presence of diene, triene, and polyene free radicals in ?-irradiated PP mas indicated by uv spectra (US6). E-P terpolymers were identified by nitration, reduction, and reaction with p-Me2KCsH4CHO to form a colored complex (1158). Traces of C1 in PP were determined by spectrometry and potentiometry following combustion (C93). Polystyrene (PS) and Copolymers. Brussau and Stein (lis) showed that uv absorption in styrene copolymers depended on length of S sequences. Free rubber in high-impact PS was determined by turbidimetric titration (UY6). The uv spectra showed a hyperchromism in random S-vinylpyridine copolymers (U60). Effects of isotactic and atactic poly(styrenesulfonic acids) on proflavine absorption were observed (CSO). Compositions of S, halo-substituted S, and diene copolymers were determinined by uv absorption a t 240 to 280 nm ( U 2 f ) . S-butadiene latex caoating on papers was determined colorimetrically as a Schiff's base

(UfO).


277 R

Vinyl Polymers. Thermal elimination reactions of vinyl polymers were studied through development of conjugated diene structures in the residues as measured by uv (U20). Formation of a chromophoric enolethylene compound served to identify PVC (U61). Effects of various conditions were studied during thermal degradation of PVC through uv spectra (U5, U40, U43, C4.4). Carbon black in PVC was measured by absorbance in a cyclohexanone system (U16). Both uv and visible spectra were obtained on irradiated PVC to follow polyene formation ( U r d , U7S). Poly(viny1 acetate) (PVAc) was determined through formation of the redviolet iodine complex measured a t 510 nm (U25). Thermal degradation of VC-VAc copolymers was studied through uv spectroscopy (U22). Reactions of polyacrylonitrile (PAN) during pyrolysis in air were studied via visible luminescence spectra (U19). Polyene sequences formed on thermal decomposition of PAN and poly-achloroacrylonitrile were identified by their electronic spectra ( U 7 ) . Color formation was followed during degradation of PAN and AN-methyl acrylate copolymers in alkaline D M F solutions (C.42). Formation of polyvinylcyclohexane from hydrogenation of PS was followed by uv ( U l ) . Ultraviolet spectra were used in studies of polyvinylpyridine (U49) and poly(viny1pyridine oxides) ( U26). Miscellaneous. Photodegradation of polycarbonate film and extruded samples was compared in the uv; the results supported a stepwise degradation process (U46). Determination of 3,3’,5,5’-tetramethyldiphenoquinone in poly(pheny1ene oxide) was based on absorptivity a t 420 nm (U52). Drefahl and coworkers (U15) studied the uv spectra of a series of oligoxylylidenes in solution (Cf 5). Onari (U55) compared far-uv spectra of poly-~-leucine and nylon 6, which indicated recurrence in the former of hypochromism near 190 nm and hyperchromism near 225 and 165 nm. The uv was used to determine isotruxene in admixture with indene polymers (L‘85). The degree of cure of phenolHCHO resin was established from ratio of absorbance a t 287 and 302 nm ( U f2 ) . Analyses of rubbers included Zn in halogenated butyl rubber by the dithiazine method (US@, and isoprene in charges for butyl rubber production a t 220, 223.5, and 230 nm (U45). Panagoulias devised colorimetric tests for natural rubber and polyisoprene ( V 6 4 ), isobutylene rubber (U65), and butadiene-vinylpyridine copolymers (U59). Panagoulias also developed qualitative tests for polybutadiene elastomer 278R

0

(U57), polyurethane elastomer ( U W ), neoprene (U60), and nitrile elastomers (U6.3). Yatsimirskii et al. (U85) made a spectrophotometric study of complex formation between Co bis(acety1acetonate) and chloral during its copolymerization with phenyl isocyanate. I n studies of polymerization of toluene Kovacic and Ramsey ( N f 1 8 ) determined structural features by uv, infrared, and NMR. Polyethylenimine used to waterproof paper was determined by Kjeldahl analysis and as its Cu chelate at 620 nm (C28). MAGNETIC RESONANCE

Recent books providing general information on the theory and practice of N M R included a second edition of Jackman’s treatise on applications of N M R in organic chemistry ( N 1 0 fb ) , together with books by Becker ( N f O a ) , novey ( N 1re), Diehl (N45a), Mavel (NlAda), Strehlow (LV204a),and Lynden-Bell and Harris (NlSSb). Progress in N M R was reported by Waugh (N2S4a) and Emsley, Feeney, and Sutcliffe (N54a). Reported 19FT\J?\.fR chemical shifts from 1951 to mid-1967 were compiled by Dungan and Van Wazer (N49a). Mooney acted as editor of an “Annual Review of NRlR Spectroscopy,” Volumes 1 to 3 of which have been published ( N f5%). Discussions on polymer spectra were included. Books on specific applications to structure of polymers were written by Bovey (N17a) and Slonin and Lyubinov (N200c). The latter stressed broad-line N h l R and was out of date relative to high resolution NhIR. Lucken (NlS5a) published a book on nuclear quadrupole coupling constants and Maksyutin and coworkers (NlS9a) a review on NQR through 1968. A large number of reviews of magnetic resonance were published in journals throughout the world. Heeschen’s biannual review in Analytical Chemistry (N84a) covered the period from July 1967 to July 1969 and included 1149 references. General reviews of high resolution N M R were prepared by Feeney (N54c, N54d) and Yamamoto (N244a). Other reviews were devoted to proton magnetic resonance (N14a), 1lB (N84b), 13C ( N f 5 2 c ) , 14N and 15N (N152b),and 31P( ( N f 5 6 d ) . Reviewsof applications of NLIR to polymer structure were published by Sewell (NlSSa), Allen ( N l a ) ,Bovey ( N f7b, N f 7 c ,N l r d ) , Niculescu ( N f55b), Chierico (NS4a), Khachaturov ( N f 0 9 a , N f 0 9 b ) , and Woodbrey (N238a). Georgescu discussed N M R of polymers in solution relative to structure of the fundamental unit (N66a) and stereochemical configuration (N65b), while Yamashita (N246c) discussed determination of microtacticity in polymers such as poly-


(methyl methacrylate) and poly(viny1 chloride). N M R of irradiated polymers, using polyethylene as an example, were reported by Chierico and coworkers (NS4) Principles involved in studies of molecular motion in solids were given by Richards ( N f 8 0 a ) and Chachaty (N29a). Specific studies of molecular motion in solid polymers were reviewed by Slichter (NdOOa, NZOOb), Lenk (N127a), Stejskal (NdOSb), and Niculescu and Georgescu ( N f56). McCall and coworkers (Nl45a) reviewed relaxation data in studies of side-group and main-chain orientations and glasstransition phenomena in polymers such as poly(viny1 acetate), PNlMA, PTFE, PTFE - hexafluoropropylene (HFP) copolymer, and poly-1-butene. Relaxation and solvation dynamics were measured for deuterium in polystyrene (PS) and polyvinylpyrolidionone (N199a). Standley and Vaughan (N203a) described electron spin relaxation phenomenon in solids. Electron spin resonance (ESR) was reviewed generally by Symons (NbfOa), Carrington and Luckhurst (N26a), and Horsfield (N90a). For polymers, Campbell’s report (N2S) included studies of macroradicals of acrylics, polyolefins, perfluorinated polymers, vinyls, polyamides, polyethers, polystyrene, and polyesters, while Butyagin and coworkers (N20) stressed the vinyl series, polyoxides, and polyamides. Among new developments in the technique of magnetic resonance having potential applicability in polymer chemistry were design of a liquid cell cryostat (N235), purity control via N M R cryoscopy (N86), a flow probe for continuous determination of liquid composition by NLIR ( N f 4 6 ) ,and use of hexafluoroacetone adducts of alcohols, mercaptans, and amines for characterizations via 19Fspectra ( N f 2 6 ) . Telomers involving allylic compounds or olefins ( N 7 ) or vinyl compounds ( N 6 ) were studied by Asahara and Wu. Monomer reactivity ratios in the copolymerization of methyl acrylate and vinyl acetate were calculated fromNA1R spectra peak areas by Ibonai and Kuramochi (N9S). Johnson and coworkers ( N fOS) found that direct spectra of l3C provide useful information on tacticity of vinyl polymers. Sudol (N207) compared proton resonance spectra a t 60, 100, and 220 MHz on a variety of polymers, including polycarbonate, polyamide, poly(viny1 chloride) and copolymer. Applications of NMR in the coatings industry were discussed by Afremow ( N l ) and in analysis of rubber vulcanizates by Carlson and Altenau (N25). Applications to direct measurement of stereochemical configuration were reported further by Bovey ( N l 7 ) and micro-

structure broadly by Fischer (N69). Svegliado and Zilio-Grandi (N208) used N M R in determining the structure of postchlorinated poly(viny1 chloride) (PVC) and stereoregularity of PAN, PVC, and PMMA. Wide-line and pulsed N M R techniques were applied to studies of crystallization of polymers from second moment of absorption lines (N186),and orientation in polymers (N181). Relaxation times served in studies of plasticization of vinyl polymers by certain esters (N32) and aqueous polymer dispersions (N106). Measurements of Tz,TI,and TI,were reported for natural rubber, poly-1-butene, polyethylene, poly(viny1 chloride), polychlorotrifluoroethylene, poly(ethy1ene terephthalate), and polycarbonate ( N l 4 6 ) . A rotating frame method was used by Connor (N36) in relaxation time studies on polyethers, poly(methy1 methacrylate), and starch (N36). NQR was proposed by Hewitt and coworkers (N88) in nondestructive inspection of reinforced plastic structures. The technique was based on use of trace quantities of inert fillers which respond to NQR. For ESR spectroscopy Ohno and Sohma (N161) described coupling with a computer for rapid scanning (several milliseconds) and recording of spectra. Radicals obtained during cobalt yirradiation during polymerizations were followed by ESR (N178). Free radicals produced from high-dose, nanosecond pulses of electrons on several polymers were identified ( N l 2 9 ) . Reactions between organic nitroxides dissolved in a variety of host polymers were the basis for spin-probe studies (N173). Macromolecular segment mobility in several polymers was studied by the ESRprobe method using radical-forming species (N229). Uses of ESR in polymer fracture studies were reported by Devries and coworkers (N44) and by Backman ( N 9 ) . Spectra from polymerizations of conjugated dienes were reported by Hirai and coworkers (N89) and from polymers having conjugated double bonds by Lapitskii et al. ( N l 2 6 ) . Polymer radicals from mechanical rupture of rubber were examined by Razgon and Drozdovskii (N177a). Effects of cold drawing of several polymers were studied by ESR (N131), with the conclusion that orientational drawing caused significant chemical modifications in fibers of poly(viny1 chloride), polycaprolactam, poly(ethylene terephthalate), and poly(m-phenyleneisophthalamide). Bond breakage induced by uniaxial tension was studied in a number of polymers, including drawn polycaprolactam (N182a). ESR studies of several grades of Tic13 were made and applied in rate studies on olefin polymerizations (N168a).

Acrylics. Precise measurement of stereoregularity in poly(methy1 methacrylate) (PMMA) was made in a 100-MHz spectrometer ( N 4 ) . Ferguson (N65) identified resonances of tetrad and pentad configurational sequences in PMMA using chlorobenzene solutions at 120' in a 220-MHz spectrometer. Insertion P h l M A formed from a monolayer of monomer absorbed on clay was shown to be composed on short sequences of predominantly isotactic diads (N16). Dixit and coworkers (N47') used N M R to confirm the mechanism of polymerization and stability of active sites responsible for isotacticity of PMMA in a VCl4-AI(CZH& catalyst system. N M R spectra from partial acid hydrolysis of isotactic and syndiotactic PMMA indicated random sequence distribution (N19S). I n studies designed to provide a better understanding of microstructures and tacticities in polymers, Lee and coworkers ( N l 2 7 ) examined fluorinated methacrylate polymers having bulky side groups. Configurational peaks in poly(methacrylic mid) (PMA) were assigned by comparing with PMMA in deuterated dimethylformamide (N116) Tacticity of PMA and poly(isopropy1 acrylate) from photochemical or radiochemical radical polymerizations was established by high resolution N M R and by infrared spectroscopy (N152). From studies of ten acrylic homopolymers a t 100 MHz, Yeagle and Scott (N249) devised a means for analysis of several copolymers; quantitative data were obtained from 4 C H z and -0CHa resonances from 10% solutions of the polymers in deuterochloroform. Compositional and configurational parameters, including assignment of diads and isotactic, syndiotactic, and heterotactic triads, were reported by Klesper and coworkers on MMA-MA copolymers (N113, N l l 4 ) ; N M R measurements were made a t 100 and 220 MHz. Sequence distributions in MMA-acrylonitrile (AN) copolymers were determined by Guillot, Tho, and Guyot (N73, N222). For low percentages of MMA, quantitative analyses for triad sequences were made from methoxyl group proton resonances (N222). The fine structures of MMA-styrene (S) copolymer were established for N M R as well as the mechanism of the propagation step of the copolymerization in the presence of ZnCh (N244). Harwood et al. (N76) examined methoxy resonances in several MMA copolymers to determine relationship with microstructure; comonomers were p-chlorostyrene, 2vinylpyridine, and 4-vinylpyridine. Chemical and configurational sequences in MMA-dimethyl methylenemalonate copolymers were derived from proton resonances a t 220 M H z (N101). Solvent chemical shift and temperature I

effects on acrylic copolymers were measured in o-dichlorobenzene, bromoform, tetrachloroethylene, and tetrabromoethane solutions (N156a); bromoform was the best solvent, giving wellresolved spectra a t 102' suitable for analysis for comonomers. LMMA-MA and itaconic acid copolymers were studied ((746). Wide-line N M R was used by Solomko and coworkers (Nd03) to determine the influence of certain fillers on transition temperatures of PMMA. Methyl group relaxations in the glassy phase of polymethacrylate esters and polypropylene were observed by Tanabe and coworkers (N217). ESR was used by Golubev et al. (N68) in studies of complexes of PMMA radicals with GaCL, AlC13, AlBr3, and 67ZnCl~. Iwasaki and Sakai (N99a) observed the conventional nine-line ESR spectrum between - 196' and +25 OC of P M M A and PML4y-irradiated a t room temperature; they interpreted the spectrum by introducing the concept of the distribution of the conformational angle in the irregular polymer matrix. Further elucidation of the structure of MA radicals trapped in solid M A 7irradiated at -196 "C was provided by Sakai and Iwasaki (N188); the ordinary nine-line spectrum was observed below -80 "C, which changed reversibly to a 13-line spectrum a t higher temperatures. Wide-line N M R showed a n unusual crystalline transition around -30" (N188). Decay of free radicals in irradiated PMMA a t high pressures was studied by Szocs (N211a). I n ESR studies of thermal polymerization of MMA, Sagitova and coworkers (N187) found that small amounts of manganous methacrylate react with the monomer and are included in the polymer chain. Paramagnetic centers in y-irradiated polyacrylamide were determined by Milinchuk and Dudarev (N148). ESR studies of y-irradiated octadecyl methacrylate were reported by Bowden and O'Donnell (N18); three radicals were observed. Decay of free radicals in crosslinked irradiated polyglycol methacrylate was studied by Szocs and Lazar (N212). Radical formation with intramolecular energy transfer from yirradiation was examined in PMhIA, PS, and MMA-S copolymers (Nd38). Kovarskii and coworkers (N119) used the paramagnetic probe method in studies of crosslinking during addition of triethylene glycol dimethacrylate to butadiene-AN rubber in the presence of cumene peroxide. The ESR spectrum of polymethacrylamide, formed by ?-irradiation solidstate polymerization a t - 196', indicated initiation by the C(CONH2)(CH3)Z radical (N54b). Cellulose. High resolution N M R was used by Ogiwara et al. (N160) in


279 R

studies of bound water in cellulose; they found that accuracy in determining the amount of bound water could be improved by measurements a t low temperature and that the boundary temperature, T,,could be established a t which water molecules are bound to the cellulose. Two regions were observed in N M R studies of water in cellulose (N169); in one the width a t half value decreased rapidly with increasing water content and, in the other, the width slowly decreased. Rapid estimates of the degree of acetylation of cellulose acetate gave values somewhat higher than those by a saponification method (N64). N M R evidence was presented for sites of attack of a reactive dye on cellulose ( N l S a ) . Cellulose formed ether linkages with reactive dyes of the vinylsulfone type and ester linkages with dyes of the monochloro- and dichlorotriazine types, based on NMR data ( N 1 J ) . Sterling andMasuzawa (N804)studied gel-water relationships in hydrophilic polymers (carboxymethylcellulose, gelatin, starch, agar). Changes in N M R signal areas were interpreted in terms of ‘‘solid,” “bound,” and “free water.” Line widths, second moments, and relaxation times on some celluloses provided data on crystalline fractions and water-cellulose proton exchange ( N I 7 8 ) . hlacroradicals formed by 7-irradiation of cellulose were studied by ESR (NlOgc, N184). Effects of crystalline modifications of cellulose and of free water on ESR spectra of trapped free radicals in ?-irradiated specimens were investigated ( N 6 ) . ESR and infrared spectra were obtained on charred cellulose (N149). ESR spectra were obtained of ethyl acrylate graft-copolymerized with 7-irradiated cotton cellulose (N166). Polyacrylonitrile (PAN). Relative parameters for isotactic and syndiotactic methylene groups in bulk-polymerized P-4N mere calculated from N M R spectra at 100 MHz (NdOSa); spectra of dimethyl sulfoxide solutions of the polymer were obtained a t 150’. NMR spectra of PAN were obtained by Murano (N16Sa) and compared with spectra of the model compounds, 2,4dicyanopentane and 2,4,6-tricyanoheptane (N16Sa);tacticity of PAN was determined. Spectra a t 60 MHz were obtained on copolymers of AN and of methacrylonitrile with vinylidene chloride t o determine sequence distributions (N97). Patnaik and coworkers (A‘l67) used N M R in studies of variable compositions, random and equimolar, and alternating copolymers of AN with S, isoprene, and butadiene. Evidence points to alternating copolymerization of AN and 1,a-butadiene by alkylaluminum halides (N63). ESR spectra of PAN heated above 600 “ C in the presence or absence of 280 R

oxygen provided information of concentration of unpaired electrons; g values varied with temperature of the heat treatment (N76). Polywtero, Polyamides. Yeagle (N848a) determined the compositions of unknown polyesters by comparing their N M R spectra with known polyols, poly(carboxy1ic acids), and polyester resins. Qualitative and quantitative analyses were made from proton resonance assignments for each monomer. Sequence distribution of polyesterurethane block copolymers were established by NMR (NBOTa). These copolymers were prepared from reactions of ethyleneterephthalate oligomers and/or ethylene glycol with hexamethylene diisocyanste or methylene bis(4phenylisocyanate). End groups analysis by N M R aided in assigning a Zwitterion structure to amine-initiated polymerization of plactones ((769). An ESR probe method was used to obtain crystallization rates of poly(ethylene terephthalate) (PET); 4hydroxy - 2,2,6,6-tetramethylpiperidinooxy served as the paramagnetic probe (N180). The same radical was used by Stryukov et a1. (NZO6) in studies of changes in the amorphous regions of elongated P E T , nylon 6, and polypropylene fibers. Verma and Peterlin (N8J1) found that stretched nylon 6 fibers in vacuum gave a well resolved ESR spectrum attributed to the secondary radical -CO-NH-CH-CH2-. Two types of spectra were observed following 7-irradiation of linear aliphatic polyesters (N168). Free radicals formed on photodegradation of nylon 6 were studied by Heuvel and Lind ( N 8 7 ) , while Taranukha and coworkers (N880) measured spatial distribution of radicals formed from 7irradiation of nylon 6. An ESR study of radical formation during washing and drying of nylon 66 fibers was made by Verma and Peterlin ( N M 8 ) . Michel and Chapman (N147) reported on ESR and electrical conductivity measurements on polypropiolamide. The ESR signal was associated with the conjugated bond system along the polymer backbone. Polyethers, Epoxides, Polycarbonates. Tacticities of polymers of ethyl, isopropyl, isobutyl, and tertbutyl vinyl ethers were assigned from 60- and 100-MHs N M R spectra (N174). Yuki and coworkers studied products from copolymerization of n-butyl vinyl ether with other vinyl ethers. Close correlations were found between N M R spectral characteristics and relative reactivity of the vinyl ether used as comonomer (NP66). Natural abundance N M R spectra on whole and fractionated polypropylene oxide were interpreted in terms of structural, stereo-regularities, and


defects in the chain backbone (N189). Tani and Oguni (NW18) found nearly equal content of isotactic and syndiotactic diads in poly(tert-butylethylene oxide) prepared with potassium tert-butoxide catalyst. Gibson and Quick (N66) prepared trifluoroacetyl derivatives of basecatalyzed low-molecular-weight adducts of propylene oxide to glycerol. Proton N M R analysis distinguished between internal isopropoxy units and terminal isopropoxy units. Structural information was obtained on poly(ethylene oxide)-starch graft copolymers by N M R and periodate oxidation data ( N b l S ) . Schaefer and coworkers (N190) obtained structural isomer distributions from 220-MHz spectra of linear copolymers of propylene oxide with maleic and citraconic anhydrides. All four kinds of diad sequences were measured in copolymers of 3,3-bis(chloromethy1)oxacyclobutane and 6-propiolactone initiated with BF, etherate and SnC14 (N246). Quantitative analyses of polyoxyphenylenepolystyrene blends were made by NMR; Penczek and Bialy (N168) observed relative errors of +2.0 to -1.0% of blends ranging from 1 : 9 to 9: 1. Relaxations of polymer protons in poly(ethy1ene oxide)-salt solutions were studied by Liu and Anderson ( N l S S ) . N M R line width measurements on poly(2,6-dimethyl-p-phenylene oxide) provided information on relaxation processes ( N 2 b ) . N M R studies were made on the nature of the active center on polymerization of formaldehyde with triethylphosphine ( N l 4 0 ) . Both slP and lH spectra showed that a quaternary P compound containing a -CH20 group was formed. Chen and coworkers (NJO, N31) investigated mechanisms of cationic trioxane homopolymerization and copolymerization with ethylene oxide with BF3.Bu20 and C ~ C ~ H ~ N Z P F ~ as catalysts. Sequence distributions of formal and ethylene oxide units were determined by Yamashita and coworkers (N846) in trioxane-1,3-dioxolane copolymers. Yamashita and coworkers (NW48)also determined sequence distributions in copolymers of p,fl-dimethyl-@-propiolactone with 1,3-dioxolane, 3,3-bis(chloromethyl)oxycyclobutane, and styrene. NMR provided information on microstructure of copolymers of isobutylene oxide and cyclic formals (N846a). Anisotropy and motional narrowing of the NMR absorption line were measured on highly oriented, crystalline polyoxymethylene (N100). Effects of temperature, degree of order, drawing, and correlation frequency with temperature on polyformaldehyde were studied by Sobottka and Keller (NIO1) using wide-line NMR. Molecular structures of chain-ex-

tended polycaprolactone diols were established by N M R together with chemical analysis (N176). Page and Bresler (N166) determined end gIoups and calculated number average molecular weights of polyoxyalkylene glycols and glycol polyesters by NMR. They measured selectively methylene and methylidyne groups attached to a hydroxyl group, permitting differentiation from these attached to ether groups. Activation energies and correlation frequencies of rotational motion of methyl groups of polycarbonates and poly(a-methylstyrene) were determined from line widths and second moments given by wide-line N M R spectra (N117). Spin-lattice relaxation measurements on poly(ethy1ene oxides), particularly TI, values, showed discontinuities a t the melting or softening points (N38). ESR spectra recorded radical intermediates during ultraviolet photolysis of polyoxymethylene ( N Q 2 ) . Haser and Roth ( N 7 7 ) , investigating free radicals from x-radiation of polyformaldehyde, found that the unpaired electrons of the radicals in the polymer are strongly delocalized. During degradation, short-chain end group radicals, CH30CH2, were observed ( N 7 7 ) . Morphological features of polyformaldehyde were studied by a spin probe method (N206); comparison of ESR spectra showed more compact amorphous regions in polymer prepared by cationic polymerization of trioxane than that from anionic polymerization of formaldehyde. The ESR spectrum of irradiated isotactic polypropylene oxide showed two radical species: CH2CH(CHa)0 and CH(OH)CHCH3 (N14). Mechanisms were established of radical formation from electron and ultraviolet irradiation of poly [3,3-bis(chlorornethyl)oxetane] (Ndd6). A dimethylphenoxyradical was found to be the only major species in the ESR spectra of ultraviolet and y-irradiated poly(2,6-dimethylphenylene oxide) ( N d l l ) . The oxidative coupling polynierization of 2,6dimethylphenol was studied in the presence of a copper complex of pyridine (N179). I n ESR studies of polycarbonate Hama and Shinohara (N74) observed scissions of carbonate groups upon yirradiation. Ultraviolet irradiation appeared to lead to crosslinking of phenyl groups on the surface of polycarbonate ( N 7 4 ) . The decomposition rate constant of, isopropyl peroxydicarbonate was determined by Rathke (N177), using diphenylpicrylhydrazyl to monitor formation of free radicals. Polyolefins, Polydienes. Detailed 220-MHz N M R studies of isotactic polypropylene showed about 2% of racemic diads which occurred randomly

a t junctions of isotactic sequences of opposite configurations (N80, N81). Assignments for tetrad resonances in polypropylene were made by Heatley and Zambelli (N8W). N M R studies of isobutene polymerization in the trialkylaluminum-methyl chloride system showed that methyl exchange was very rapid and provided some insight on the theory of polymerization initiation with these catalysts (N109). Benedetti and coworkers ( N 1 1 ) compared three conformations proposed for crystalline polyisobutene with observations on the aliphatic portion of 2,2,4,4-tetramethyladipic acid. A new 1 to 1 block copolymer was prepared from polybutadiene and a prepolymer diamine (from reaction of trimellitic anhydride acid chloride with 4,4'-diaminophenylmethane) ( N l O l a ) . The integrated ratio of total aromatic to aliphatic protons, as determined by NMR, was in g o d agreement with calculations for a 1 to 1 copolymer, while the integrated ratio of total aliphatic versus olefinic protons indicated that pendent vinyl groups remain essentially intact during polymerization. Infrared data also were used to confirm structure. I n 60and 220-MHz studies of polyisoprene Carman ( N d 6 ) showed that the latter can be used to detect as little as 0.5% trans in a high cis-polymer; the practical limit of detection a t 60 MHz appeared to be above 1 to 2%. Duch and Grant ( N @ ) made assignments for all resonance peaks in the lacNMR spectra of cis- and trans-polyisoprene. The microstructure of poly-l,&pentadiene was studied by 60- and 100MHz N M R plus infrared spectroscopy

(N94).

N M R analyses of ethylene-propylene (E-P) copolymers agreed well with those by infrared (N111). Studies by Chierico and coworkers (NS6) showed that chain mobility of polyalkenamers depends on the number of methylene groups located between double bonds; a similar dependance for E-P copolymers was found based on comonomer ratio. Weight per cent termonomer (1,4hexadiene, dicyclopentadiene, ethylidene norbornene) in E-P terpolymers was determined by a time-averaging N M R method ( N 3 ) . An N M R was devised for E-vinyl acetate (E-VA) and E-acrylate copolymers based on areas under peaks corresponding to ester C H a groups, chain CHt groups, and terminal CHa groups (N108). Wu studied sequence distribution (N9.43) and solvent effects on proton spectra of E-VA copolymers. The microstructure of Evinyl formate copolymers was studied by 220-MHz N M R ; Wu (N839, NW.41) found that monomer distribution in the copolymer was blockier than would be

predicted from statistically random comonomer sequence distribution. Sequence distribution of E-vinyl chloride (VC) copolymers was established by N M R (N297) and structural features were observed for a-alkyl-a-olefin-SOz copolymers ( N l O ) . Both lH and 19F nuclei were studied for isobutylenechlorotrifluoroethylene copolymers polymerized by y-irradiation (N96a). It was concluded that the copolymers have a completely alternating structure, Wide-line and relaxation studies were made on several polyolefins. Moldovan and Ionescu (N161a) reviewed spectra of polyethylene with emphasis on determination of degree of crystallinity and effects of irradiation. Crist and Peterlin ( N d l ) studied proton spinlattice relaxation times of linear PE of varying morphology as a function of temperature, while Crist (N4O) made similar observations on P E single crystals; effect of adsorbed molecular oxygen on the crystals was elucidated. I n studies of molecular motion in oriented long-chain alkanes Olf and Peterlin (N162) discussed theory on oriented mats of P E single crystals, and oriented n-C32&8. Wide-line studies were made on stretched and unoriented PE (N21 , NQ6,N136, N14.4). Proton relaxation time was measured on isotactic PP (N110). Physical structure and properties were studied on 3methyl-1-pentene polymer and fiber and copolymers of low 1-olefin content. A major transition between 50" and 100" was interpreted as a crystal-crystal transition from N M R , dilatometric, and density data (N17da). Configuration of amorphous and crystalline polydichloropropylene was established by N M R and electron microscopy ( N 1 1 6 ) . Wide-line studies on E-lithium acrylate copolymers indicated two transitions in support of the assumption that the salt groups are uniformly distributed in the amorphorus phase (N163). Calleja (N2d) used magnetic susceptibility measurements in studies of orderdisorder phenomena in PE. HenriciOlive and Olive (N86) used magnetic measurements (susceptibility, ESR) and polymer kinetics in research designed to elucidate valency and ligands in homogeneous Ziegler-Xatta type catalyst systems. A linear relationship was reported between rate of polymerization of ethylene and concentration of TiIV in a titanium dichlorideethylaluminum dichloride environment. Dole and coworkers (N48) used ESR to study mechanisms and kinetics of radical reactions of PE, including rate of conversion of alkyl to allyl free radicals. Campbell ( N d 4 ) reported on positive ions from irradiation of P E a t 77 O K . Trapped allylic free radicals were observed in 7-irradiated PE subsequently subjected to ultraviolet irradiation (N196). ESR spectra and


281 R

spin-lattice relaxation times were observed on irradiated PE ( N 5 0 ) . Sohma (N202) reported on ESR spectra from free radicals produced by 7-irradiation of PE, PP, polybutadiene, and polyoxymethylene. Nishimina and coworkers made ESR studies of y-radiation-induced solid-state polymerizations via a matrix-isolation technique of ethylene (N156a), propylene (N156c), and isobutylene (N156a). Kusumoto (N122) studied ESR spectra of isotactic, syndiotactic, and atactic PP subjected t o ?-irradiation, while Eda and coworkers (N52) examined the behavior of peroxy radicals. Other studies on PP included graft copolymerization of gaseous styrene on preirradiated PP in the presence of oxygen ( N 5 3 ) and development of radical sites on irradiated PP from nitric acid etching (N123). Kinetic studies were made on free radicals produced in E-VA by x-ray irradiation ( N 5 8 ) ; the ESR spectrum after a short period a t room temperature was similar t o the alkyl radical spectrum of PE. The effect of oxygen contact during storage was to oxidize the alkyl radicals. nousted (N16) reported on further use of thermoluminescence in studies of low- and high-density P E after low temperature 7-radiolysis. One of the three glow peaks was thought due t o electron trapping on molecular oxygen. Polystyrene (PS). Using 60- and 1003IHz NMR measurements, Noel and Platzer (N157) studied chain movements in PS; studies were made of the width a t half peak height of the atertiary proton peak in a solution of atactic (CHPhCD2)n. Similar measurements were made on poly-a-methylstyrene (N164). Ramey and coworkers (N175) made assignments for a-methyl and P-proton triads and tetrads in the 100- and 220-MHz spectra of poly-amethylstyrene. Stereoregularity of poly-o-methoxy styrene prepared by anionic initiators was established by X M R (N257), Products from thermal degradation of dehydrogenated polystyrene and polyphenylacetylene were found to contain cyclic trimers (N33). Kinstle and Harwood (N11.9) prepared polymers and copolymers of 3,4,5-trideuteriostyrene and studied their N M R spectra a t 100 RIHz; they found three signals assignable to syndiotactic, heterotactic, and isotactic triads, affording for the first time a reliable method for characterizing the stereoregularity of conventional polystyrene. %lochel (N151) described an N X R method for determining "block styrene" in copolymers, using an analog computer to resolve overlapping peaks; the method was applied t o a variety of copolymers, including emulsion styrene @)-butadiene copolymers. Yamashita and Ito (N346b) used 60-MHz spectra 282 R

*

for assignment of triad distributions of S-MMA copolymers. Sequence distributions in S-methacrylonitrile copolymers were made from measurements of methine and a-methyl proton resonances (N153). The microstructure of S-polyisoprene copolymers was established by N M R (N66). I n N M R spectra of S-itaconate ester copolymers, CHIO- and PhChzO absorptions were sufficiently resolved to permit structure assignment (N250). Connor (N37') made nuclear relaxation studies on atactic polystyrenes, measuring T, and T l p from 90' to 500" K; TIvalues in the low temperature region permitted calculation of approximate molecular weight. Different splittings for two sets of amethylene protons of ?-irradiated PS were observed in the ESR spectra (N230). Two types of radicals were observed from ESR studies of mechanically degraded PS (N.2.23). ESR spectra were observed on Mn** ions on sulfonated PS crosslinked with mor p-divinylbenzene (N.236). Other Vinyl Polymers. Tishkov et al. (N224) used NhIR to control the change of O2 concentration during the induction period of bulk polymerization of vinyl monomers. Conformations of tetrads (N60) and pentads (N62) in vinyl polymers were studied. The 220-MHz proton spectrum of PVC was studied and interpreted in terms of pentads for a-protons and tetrads for @-protons(N79). PVC, chlorinated by different suspension techniques, was studied and sequence lengths for chlorinated and unchlorinated units were established (N.210). Tho (N2.21) studied tacticity of PVC by high resolution NMR. N M R analysis of low molecular weight PVC polymerized in THF with tert-BuMgC1 initiator suggested that the tert-butyl remained as an end group in the polymer chain (N2.2.2~).Similar studies were made by Pham and coworkers (N171) of chain ends in PVC prepared using a Ti(OBu)4-alkylaluminum system in CC14. Horsma (N91) measured the relaxation modulus from 150' to 220' of two samples of PVC having different molecular weights, permitting calculation of approximate activation energies. The rate of degradation of poly(vinylidene chloride) was measured in two solvents a t five temperatures by a NhIR technique (N43u). Differences in rate were determined by stereochemical considerations. Yoshino ( N 2 5 . 4 ~ used ) partially deuterated vinyl monomers in NMR studies of structure of PVC, PAN, and polyacrylate. High resolution N M R spectra were reported a t 60 and 100 MHz for PVC-p,p-ds in o-dichlorobenzene, pyridine, and pentachloroethane (N29). Ratios of CH2 to CHCl


protons in PVC and 2,4-dichloropentanes (model compounds) were established after photooxidation (N1.24). Vinyl acetate (VA) oligomers with degrees of polymerization from 2.5 t o 30 were studied by N M R (N198). Comonomer content in VA copolymers was determined by high resolution N M R ; included were dibutyl fumarate, dibutyl maleate, dioctyl maleate, and 2-ethylhexyl acrylate (N46). N M R proton and infrared spectra were obtained on polyvinyl formal and model compounds, permitting estimates of cis- and trans- configurations (N195). Sequence distributions were established for copolymers of vinyl acetate with acrylic, fumaric, and maleic esters (N152d). A conformational study was made of models of poly(methy1 vinyl ether) and coupling constants compared to those from the polymer (N142). High resolution N M R spectra were studied further b y Goodman (N69) and by Goodman and F a n (N70). Structures were studied of polymers of dimethyl (vinylethynyl) carbinol and several derivatives (N104) and on poly(N-vinylcarbazole) (N254). N M R spectra were obtained on polyvinylthiazoles and derivatives (N191). Proton resonance studies of polyvinylpyridine solutions were made a t several temperatures (N157a) ; the width a t half height of peaks assigned to aromatic protons decreased rapidly between 0' and 50'. Holt and Lindsay (U26) studied tacticity of poly(-2-vinylpyridine oxide) and copolymers. Diad and tetrad (N247) and pentad and hexad (NlOd) sequences were established in vinylidene chloride-vinyl vinyl acetate copolymers, respectively. 19F resonance studies were used to assign structure to a,P-difluoro-substituted p-divinylbenzenes and their copolymers with styrene; distribution of cis- and trans-isomers was deduced (N233). Compatibility of PVC-butadiene-AN terpolymers was established from wideline N M R studies together with determination of changes in mechanical loss angle ( N 2 ) . ESR studies were made of initial processes in copolymerization of vinyl monomers in aqueous solution (N216) and of radiation-induced ionic polymerizations (N262). Initial reactions of vinyl esters with redox systems in aqueous systems also were studied (NZ14, N216). ESR and infrared procedures assisted in following graft polymerization of vinyl monomers on polymeric materials-e.g., styrene on polypropylene fibers and films (N1.21). Zeppenfeld and Bart1 (N260) combined ESR with chemical methods t o determine quantitatively hydroperoxides and peroxyradicals in radiationoxidized PVC (N.260). Residual poly-

mer from low temperature pyrolysis of PVC (in vacuum a t 160" to 230") was examined by ESR, N M R , and magnetic susceptibility (N138). Thermal dehydrochlorination of PVC and poly(viny1idene chloride) was studied by Hay ( N 7 8 ) , giving evidence of radical elimination of HCI. y-Resonance spectroscopy was used to study structure and reactivity of organotin derivatives of PVC (N67). Fluorocarbon Polymers. Chemical shifts in TFE copolymers were measured by Ellett and coworkers (N54). Analysis of N M R spectra indicated the mode of addition polymerization of vinylidene fluoride and of TFE-vinylidene fluoride copolymers (N139). 19F spectra were used in studies of tacticities of poly(viny1 trifluoroacetate) ( N 6 1 ) . Both 60- and 100-MHz 'H and '9F spectra were obtained on TFE-isobutylene copolymers obtained by yirradiation ( N 9 6 ) ; both methyl and methylene resonances were interpreted in terms of triads and fluorine resonances, in terms of tetrads. Line width measurements aided in studies of transitions in irradiated PTFE (N226,N22Y). Wide-line N M R was used by Romanov (N182) to determine monomer unit ratios in the following copolymers: CH-CH2CF-CFZ, CHFCHz-CFFCFCl, CFFCHZ-CFICF=CF~, CF-CHZ -CF-CFCl; experimental error was about 2% as compared to about 1% by high resolution N M R . Relaxation times (T2, TI,Tip) were reported for TFE-hexafluoropropylene (HFP) copolymers in both bulk and drawn fiber from -200' to +250° (N143). Iwasaki ( N 9 9 ) reported on ESR spectra of P T F E , TFE-HEP copolymer, and P T F E oxide. A mechanism for radiation degradation of P T F E was proposed by Hedvig (N8.9) based on formation of peroxy radicals being transformed into chain-end fluorocarbon radicals and then into chain-side radicals. Only one type of radical was observed in the ESR spectrum of irradiated P T F E (irradiated with 23 megarads a t 293') ( N 8 ) . Hedvig (N84) studied structure, stability and transformations of free radicals in P T F E irradiated by x-rays, y-rays, and accelerated electrons. Irradiation of P T F E by y-rays produced peroxy radicals of the types, CFzCFzOO and CF~CF (06)CF, ( ~1614 . Miscellaneous. Liu (N13.8) reported on near-neighbor effects on N M R spectra of polydimethylsiloxanes as a function of chain length. Spectra of poly(propene-2-d sulfide) showed the methylene protons gave two overlapping A B quartets where relative intensities depended on the polymerization catalyst ( N 9 8 ) . and proton magnetic resonance spectra aided in

determining nature of a n active center during polymerization of P-propiolactone on triethylphosphine (N141). Poly-2-oxazolidones were prepared and characterized by N M R , infrared, x-ray, and thermal methods (N86a). Structure of toluene polymerized with aluminum chloride-cupric chloride was studied by N M R , infrared, and ultraviolet spectroscopy (N118). N M R peaks of a-carbon protons in poly-y-benzyl-bglutamates suggested that behavioral differences are due to differing molecular weights and polydispersities (N19). Separate helix and random coil peaks were observed for the a-CH and peptide N H backbone proton resonances in poly-y-benzyl-~glutamate (N67). Ferretti (N56) also reported on N M R studies of several poly-a-amino acids. Conformations in polypeptides in solution were reported by Rydon (N183) and Ullman (NbZ8). Bradbury and Crane-Robinson (N18a) reviewed high resolution studies on biopolymers. A quantitative analysis scheme was developed based on intensity of the N M R peaks for OH protons in starchderived products ( N 2 8 ) . Proton N M R studies of GPC fractions of a petroleum residue provided data in "unit sheet" weights (N46).N M R spectra were applied to characterization of lignin (N128, N251) and to so-called polywater (N166, N170). Characterization of ion exchange resins was discussed by Darickova and coworkers (N42) and effects of counter ion were discussed by Howery and Kittay (N91a). N M R studies on polymers having conjugated double bonds included polyphenylacetylenes (N105, N136, N137), allyl-substituted cyclopentadienes ( N 150), polyisoprene (N19Z), polyiso( N Z O O ) , butadiene prene-butadiene (N167a),

1,l-diphenylethylene-2,3-

dimethylbutadiene copolymer (Nb55), interactions of SBR with carbon black (N234), polyurethanes (N71, NY2, N180), oil-modified alkyds (N180), phenol-formaldehyde Kovolak resins (N199, Nb53), and block copolymers of polyvinylenes with maleic anhydride and benzoquinone (N258). Chemical structures were established for diphenylbutadiyne polymers after hydrogenation, bromination, and nitration, employing N M R , ESR, and infrared spectroscopy and differential thermal analysis (N29b). Relaxation studies were reported on polydimethylsiloxanes (N134): T1 was found to be independent of concentration, while TZ was dependent. Wideline N M R studies indicated noncoplanar structure of oligoarylenes which increased on passing from polyphenylene to polynaphthalene to polyanthracene (Nib). Degree of polymerization and number of breaks in the conjugate bond

were evaluated for poly(propio1ic acid), polyacetylene, and polydiphenyldiacetylene (N19.4). Crystallization behavior and molecular motion in transpolychloroprene were investigated by wide-line N M R (N164). Molecular mobilities were established by wideline studies of several natural, synthetic, polar, and nonpolar rubbers having various molar interactions (Nb69). A relationship between spin-lattice relaxation time and fraction of mobile protons was observed for l,2-dinitrile polymers (N130). This effect was used to determine degree of polymerization of polyfumaronitrile and permitted calculation of number average molecular weight for this and other polymers which may be insoluble or infusible but not crosslinked. Formation and structure of polyselenacyclobutane were studied by ESR (N39) as well as polymers with indolquinoxaline basic units (N197). Crosslinking of poly-Cvinylpyridine was studied (N43). Intermolecular charge transfers in CZ-a polyenes and phenylacetylene oligomers were reported (N169). ESR studies of conjugated systems included polymerization of butadiene with homogeneous catalysts ( N 9 0 ) and free radicals from ultraviolet irradiation of cis-1,Cpolyisoprene ( N b 7 ) . For polyurethanes Tarakanov and coworkers (NZ19) reported on photooxidative destruction and Safonov and coworkers (N185) on structure and reactivity of several crosslinked systems. Eaton and Keighley (N61) examined solvent and heat-treated wool by ESR, while Keighley (NlO7) studied wool keratin by ESR, some of which was modified by exposure to 50-kv x-rays. Natural wool irradiated by ultraviolet and visible light was studied by ESR, which provided data on effects of dose, time, and atmosphere (NlC93a). Bushin et al. (N19a) obtained ESR and infrared spectra of several organosilicon polymer films a t various temperatures. Included were films prepared from hexamethyldisiloxane, octamethyltrisiloxane, and hexadecamethylheptasiloxane. No structural changes were observed between 20' and 150'; crosslinking occurred between 250" and 300', and degradation above 380'. MASS SPECTROMETRY

DeJongh (M21)has recently reviewed the fundamentals of mass spectrometry (MS) in this journal. Other books on general principles and applications of MS have been written or edited by Roboz (M81), Benz ( M 6 ) , and Burlingame (M15). Proceedings published include the 18th Annual Conference on MS and Related Topics, held in San Francisco, June 1970 ( M 4 ) , M S Con-


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ference, held in Berlin, September 1967 (M59), and European Symposia on Time-of-Flight RlS, held at the University of Salford, England, July 1967 ( M 7 7 ) and July 1969 (M78). An atlas of >IS data, edited by Stenhagen, Abrahamsson, and RIcLafferty (M88), consists of low resolution spectra contributed by a large number of organizations and individual workers. A comprehensive index of approximately 8000 mass spectra contained in the informal spectra program of ASThI Committee E-14 on blS is now available ( M 5 ) . Reviews on the use of M S for polymer studies have been written by Hiramatsu (1M5O), Osawa (M75), and Shulman (M85). The use of computer techniques for N S data acquisition and handling has been growing steadily (XI, X 9 , M.20, ME?, M46, M54, X 5 6 , 11167, Jf8O). Although these techniques may not be designed specifically for polymer studies, the procedures are generally applicable. Of particular importance is the development of combined GC-MS-computer systems (M7, M 5 f ) . Such systems have been used effectively for polymer characterization ( X S S , M72). The various interfacial systems used in M S analysis of GC effluence have been reviewed by Rees (M79). Merritt, Bazinet, and Yeomans (M69) discussed the parameters for GC-AIS coupling, and described the utilization of support-coated open tubular columns for such purposes. A patent issued to Llewellin ( N 6 6 ) describes a two-step separator with permeable membranes to control the gas volume-ratio entering LIS. Other improvements on molecular separators used for GC-XIS interfaces include membrane separators ( M I 0 , ;M48), porous stainless steel (M6S), improved glass frit ( X S S ) , and palladium-silver tubing ( X 8 6 ) . Based on a consideration of the physical processes involved in thermal fragmentation and electron impact fragmentation, Kelly and Wolf (M58) believe that a general technique, probably, cannot be developed to use existing 1IS data to interpret pyrograms obtained by pyrolysis GC. However, a combined use of pyrolysis-GC3IS seems to be increasingly popular. The pyrolysis products can be separated and then subjected to GC-AIS (Jf44, Jf57, i1189), or the pyrolyzer can be coupled to the GC injection port (M3.2, M 7 4 ) . Cohen and Karabek ( J l l 7 ) described a new technique using the Plasma ChromatographTM, a positive and negative ion-molecule reactor with a n ion drift spectrometer, as a n ion interface to GC-AIS in which principally molecular ions are formed. Many organic molecule types may be observed a t ultratrace concentration levels down to mole fraction. Other analytical techniques have been 284R

coupled to M S to solve particular problems. Applications of carbon-13 labeling to the study of mechanisms in electron-impact of organic molecules have been discussed by Meyerson and Fields (M7O). Coupling of thin-layer chromatography with GC and hIS for detecting trace impurities, especially in the plastics industry, was discussed by Kaiser (M56). Combination of &IST G (M9.S) or ,\.IS-DTA (M52) is effective in studying polymer degradations. Mass spectrometric studies of the kinetics of thermal degradation of polymers were reported ( M S , M34, MS5). I n particular, the kinetics of thermal degradation and composition of the degradation products of poly(methy1 methacrylate) were studied by using three different types of mass spectrometers: the time-of-flight mass spectrometer, a magnetic, static mass spectrometer, and the latter mass spectrometer with heated chamber (W.2). The resolution of the mass spectrometers, and the spectra of the degradation products obtained on the different instruments, were discussed. The kinetics of evolution of volatile products during mechanical degradation of polystyrene was studied mass spectrometrically (M76). Cornu, Xlassot, et al. ( J f f 9 )discussed the theory, apparatus, and techniques of trace analysis by XIS.. Spark source LIS appears to allow a general survey analysis of all trace impurities in a sample with sensitivity to a few parts per billion. Eustache (M.Iw9) reported h4S analysis of traces of gases and volatile liquids in polystyrene, vinyl chloride-vinylidene chloride copolymers, and poly(viny1 chloride). The type of catalyst and llionomer impurities could be identified rapidly. Hays and hltenau ( N 4 9 ) also reported rapid analysis of volatile antioxidants in rubbers and oil masterbatches a t concentrations of 1 part per 100 parts of polymer without prior sample treatment. Three types of plastics, including ethylene-vinyl acetate copolymer, crosslinked ethylenevinyl acetate copolymer, and crosslinked polyethylene, intended for satellite applications, were given overdoses of 7-irradiation, the amount of outgassing was measured, and the gas composition was analyzed by AIS (M91). Because of its high sensitivity in gas analysis, JIS continued to show applications in permeability studies of polymer films. The gas permeability of poly(viny1 chloride) wine bottles to oxygen and COz was determined by AIS (;MSO). The method was simple, fast, and accurate, with errors principally due to nonuniformity in the sample thickness, water bath temperature variations, and the velocity through the mass spectrometer. Kirilyuk, Belyaev, et al. (M60) measured the helium permeability of various commercial and experimental films, includ-


ing polyamides, laminates of polyamides, A1 foil coated with polyamide, tetrafluoroethylene-hexafluoropropylene copolymer, polyethylenes, A1 foil coated with polyethylene, a mixture of butyl rubber with ethylene-propylene copolymer, cotton cloth calendered to butyl rubber, and -41 foil coated with rubber. Although XIS has been a powerful tool in polymer studies, its utility is restricted to analysis of existing volatiles in a polymer sample or volatile segments produced by pyrolysis or other means. Direct >IS analysis of the polymer itself is most difficult, mainly because of its extremely low vapor pressure. However, a new dimension in LIS may have been opened by Dole and coworkers (M.23). I n their recent work, gas-phase macroions were produced and formed into a molecular beam by a n electrospray-nozzle-skimmer system. Thus, polymers such as polystyrene could be directly analyzed. Bott, Firth, et al. ( M I I ) studied evolution of toxic gases from heated plastics, including polyurethane, urea-HCHO resin, nylon, and polyacrylonitriie. Product gases were analyzed by LIS, ir, and colorimetry, and consisted mainly of HCN, SHa, CO, N oxides, COz, and H20. The threshold temperatures for evolution of each gas from each polymer were given, and the activation energies for HCN and CO evolution were determined. Hamano and Hiramatsu (M46) used M S to analyze combustion gases and smoke from open flame pyrolysis of commercial resinlaminated boards containing phenolic resins, melamine resin, or urea resin adhesives, and finished with poly(viny1 acetate) resin, urea resin, paper, aminoalkyd resin, polyacrylates, polyphthalates, melamine resins, etc. -4 modified time-of-flight mass spectrometer equipped with analog output was used for mass spectrometric thermal analysis (JITA), and applied to study degradation of an aromatic polyamide (MS6). Goldstein ( M 4 S ) described hITA techniques to analyze pyrolysis products from polymer samples contained in notches machined in graphite filaments. The samples were heated either linearly at 200" to 2000" per second from room temperature to 1000" or rapidly to constant temperature in the range 300" to 1000" and so maintained. Laser heating followed by h9S analysis was used to study decomposition of coal (M5S), phenolic resin ( M 4 O ) , poly(tetrafluoroethylene), and silicone rubber ( M 4 1 ) . Lincoln (M64) reported improved instrumentation for recording time-resolved mass spectra to permit more quantitative measurements of short-lived species and application to AIS analysis of transient events in the submicrosecond time domain. One

type of time resolution gave the duration of all the mass peaks within a designated range, and another type presented the intensity of any six preselected mass peaks as a function of time for each laser pulse. This combination of a pulsed laser with a time-of-flight mass spectrometer can be used to pyrolyze polymers or refractories directly in the ion source of the spectrometer. The main portion of lclS applications to polymers continued to be analysis of volatile products generated from thermal degradation. Thus, the structure of a pyrolysis product of polyisoprene was determined by L I S in conjunction with ir and N M R (MS8). Numerous studies were made on pyrolysis of polystyrene (MS, M16, M4.2, M71, M 8 9 ) , methylsubstituted styrene polymers (M42), and styrene copolymers with acrylonitrile (M44), vinyl chloride (M82), and divinylbenzene (M89). Vinyl polymers studied included poly(viny1 alcohol) ( X 2 4 ) and poly(viny1 chloride) ( M 7 4 , M82). Of interest was the study of mixtures of polystyrene and poly(vinyl chloride) in comparison with the corresponding copolymers (X82). While the mixtures produced fragments with the same mass peaks as obtained by pyrolysis of the homopolymers, the copolymers yielded additional fragments. Phenyl-butadiene (mass number 130) was formed from adjacent units of styrene and vinyl chloride. The intensity of this mass peak provided a measure of the block character of the copolymers. Degradation of poly(tetrafluoroethy1ene) was investigated by pyrolysis-AIS and pyrolysis-GC-AIS ( X I 8 , M S 3 ) . Oksent’evich and Pravednikov (M7S) studied hydrogen atom cleavage reactions in fluorohydrocarbon systems by pyrolyzing mixtures of deuterated polyxylylene with a copolymer of CH2=CF2 with CF3CF=CF2 in sealed ampoules and examining the products by MS and GC. Dymshits et al. (M25) described rapid continuous analysis of mixtures of perfluorohydrocarbons using a time-of-flight mass spectrometer, which could be useful in studying fluorocarbon polymers. A modified ion source and electron multiplier provided better resolution and resistance to the F compounds. Ehlers, Fisch, and Powell studied thermal degradation of polyphenylenes and poly(pheny1ene oxides) (MM26), aromatic polyesters (M28), and sulfur-containing polyarylenes (MZ7), using LIS, ir, and elemental analysis to identify volatile and solid degradation products. Wiley investigated the mass spectral characteristics of pivalolactone and poly(pivalolactone) (iM91) and poly(2,6dimethyl-l,4-phenylene ether) ( M 9 0 ) , whereas Factor (X31) studied thermal degradation of poly(2,6-dimethyl-1,4phenylene ether) with MS along with

other techniques such as GC, ir, TG, DSC, and x-ray diffraction. The structure of a phenol-formaldehyde resin was investigated using M S and N M R ( M l 2 ) , and the carbonization reaction of a series of phenol-formaldehyde resins containing various amounts of phenol was studied using MS, GC, DTA, ir, and x-ray data ( M 8 ) . AIS was mainly used in studying thermal degradation of epoxy resins ( M S 3 , M S 7 ) . MS studies were made of thermal degradations of polyurethanes ( M 6 S ) , polyimides ( M l 4 , M52), polysuccinamides (1M84), poly(bisbenzimidazobenzophenanthroline) ( M S 9 ) ,and a Cu(I1)bis(8-hydroxy-5-quinolyl)met liane coordination polymer ( M I S ) . Thermal degradation products of polyorganosiloxanes were identified with the aid of >IS (M83, M87). Pyrolysis of untreated :tnd flame-retardant-treated cellulose was investigated by GC and 11s ( X 6 5 , M94). Qualitative structural determination of water-soluble cellulose ethers was made from their >IS degradation profiles ( M 4 7 ) . Differences in the profiles of methyl, hydroxyethyl, and hydroxypropyl celluloses were evident. The pyrolytic behavior of silk treated with tin complex was examined by T G and MS, and compared with untreated silk and silk treated with other solutions (M61). X-RAY METHODS

X-ray spectroscopy or fluorescence and x-ray diffraction with small-angle x-ray measurements continued to provide direct analyses for elements and physical structure. X-Ray Spectroscopy. Books on x-ray spectrochemical analysis included the second edition of Birks’ treatise ( X 9 ) , Bertin’s principles and practice of the technique ( X 8 ) , and Bernstein’s comparison of methods of standardization of x-ray data ( X 7 ) . Barbier ( X 6 ) discussed relation of x-ray fluorescence intensity with concentration. Analysis of small samples in borax disks was described by Schneider ( X 7 Z ) , who gave the following detection limits on a 2-mg sample: Ca 4 pg, Ti 0.4, V 3, Cr 2.5, Fe 5.5, Ni 8, Zn 6, Nb 3, and hfo 5. Mege ( X 5 4 ) discussed a standardized dilution method, while Gunn ( X 2 6 ) devised a means of determining Zn, Fe, and Si in diatomaceous earth dispersed in hydrocarbon. I n studies of surface roughness, using trans-l,4polyisoprene as specimen, Gianelos and Wilkes ( X 2 3 ) found that a t A > lA, loss of x-ray intensity increased with increasing roughness. Indicator elements were employed by Hoffmann ( X 3 4 ) in a method for dyes on fabrics; suitable indicators were S, C1, Co, Ni, Cu, and Br. Simplified operation is reported with nondispersive x-ray

spectrometers applicable to elements having atomic numbers >12 ( X I @ . X-ray absorption methods were used for determining elements with atomic numbers 2 14 in synthetic fibers (U51, X86, X 8 7 ) . X-ray emission analysis of paints by a thin-film method was reported ( X b S ) . Application in the coatings industry was described by Scott (X75). Regester and Riggs ( X 6 7 ) devised a method for determining depth of chemical penetration into reinforced plastics exposed to corrosive environments. X-ray fluorescence methods were used to determine P, S, and C1 used in chemical treatment of cotton fabrics ( X 6 4 ) and P b in cellulose ( X S ) . Phifer ( X 6 S ) developed a procedure for determining s, Ca, Fe, Cu, Mn, and C1 in viscose. From poly(ethy1ene oxide) prepared with bromophenol initiator, Haftka ( X 2 8 ) determined degree of polymerization by determining Br. Among the elements determined in polyethylene by x-ray fluorescence were Cu, Ti, Cr (XSO), Al, C1, Ti, Fe ( X S Z ) , All and C1 (XS1). X-Ray Diffraction. References were chosen to provide insight on applicability to physical structure studies on polymers. X-ray diffraction in polymer science was the subject of a new book by Alexander ( X I ) . A review of x-ray diffraction with discussions of PMMA and poly(ethy1ene sulfide) was given by Tadokoro and Takahashi ( X 8 1 ) . I n his review of intramolecular rotation in high polymers Shimanouchi ( X 7 6 ) discussed x-ray diffraction studies of the helical structure of polymer chains. Dynamic x-ray diffractometry was described for measuring the rheo-optical behavior of crystals subjected to mechanical strain (XS9, X4O). A review on dynamic x-ray diffraction and lightscattering studies referred to PE, PP, P E T , microscopic phase separation, texture of graft and block copolymers, and stretching-induced crystallization of rubber ( X d l ) . X-ray reflection and transmission diffractometric techniques were discussed by Zannetti and coworkers ( X 9 3 ) . Electron diffraction studies of polymer melt structures were applied to PE, gutta-percha, polytrifluorochloroethylene, poly(ethy1ene sebacate), and polydimethylsiloxane (X61). Broad applications of the x-ray diffraction technique were described for crystallographic studies of synthetic fibers ( X 7 9 ) , the paint industry (X73, X 7 4 ) , the pulp and paper industry ( X 8 0 ) , and determining degree of crystallinity in drawn polymers by smalland wide-angle x-ray scattering and density (Xl7‘). A structural model was proposed for poly(alky1 acrylates) and poly(alky1


0

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methacrylates) based on x-ray data (X95). Microstructure of blockPRlMA was brought out using laser irradiation, although the polymer remained amorphous by x-ray structural analysis (X58). Degree of crystallinity was determined in cellulose ( X 6 8 ) and cellulose fibers (X90). The two forms of cellulose triacetate and form-regenerated cellulose were examined by Watanabe and coworkers ( X 9 1 ) . X-ray studies were made without positive results on cellophane ( X 8 5 ) . Both x-ray diffraction and electron microscopy were used in studies of graft copolymers of cellulose acetate and acrylonitrile ( X 5 7 ) . X-ray diffraction studies of nylon 6 , and y forms, crystals, showing were reviewed by llohobe and Kawaguchi (X55). Crystallization behavior of linear and cyclic oligomers of nylon 6 was studied ( X 2 9 ) . I n nylon 3 four polymeric forms were observed ( X 6 2 ) and the crystal structure of drawn fiber was established ( X 5 1 ) . Guseinzade et al. ( X 2 7 ) used x-ray diffractometry in studies of the valence state of Cr in CrO catalysts for ethylene polymerization. Hosemann and Wilke ( X S 6 ) described a method for calculating crystallite size and lattice distortions in branched PE. Molecular motion in PE crystals was studied between -90' and 110' ( X 4 ) . Desper et al. ( X 1 4 ) discussed orientation and structure of PE crystallized in a pressure capillary viscometer. Wilson and Longworth ( X 9 1 ) described x-ray studies of PE crystallinity in copolymers and ionomers. A procedure was developed for indexing x-ray wide-angle reflexes for PE and PE-PP copolymer ( X 9 6 ) . Relative crystallinities of linear PE and isotactic PP were established from x-ray photographs ( X 6 9 ) . A Fourier method was applied for absolute degree of crystallinity in PP ( X 8 2 ) . Ciystalline modifications in thermally decomposed PP were studied (XS7). Samuels ( X 7 1 ) developed a method for quantitatively characterizing morphological changes in PP fibers using wide-angle and smallangle x-ray, birefringence, light scattering] etc. Crystalline properties of several polyolefins were established ( X 7 0 ) , including unit cell parameters for poly-5-methyl-1-hexene and poly5-methyl-1-heptene ( X 1 1 ) . Among copolymers studied were E-P and Ebutene ( X S 5 ) , E-P block ( X 5 0 ) , and E-vinyl acetate ( X 6 ) . PE-polyisobutene mixtures were subjected to x-ray analysis ( X 2 2 ) . The microstructure of S-polyisoprene copolymers was established by x-ray diffraction; a lamellar structure was indicated (N65). Poly-o-methylstyrene polymerized with anionic initiators was crystalline and highly isotactic, based on x-ray and N M R data (N257). X-ray diffraction measurements showed CY]

286R

that temperature had a negligible effect on the structure of styrene-vinylpyridine sequence copolymers ( X 2 6 ) . The degree of crystallinity was measured in PVC ( X 1 2 ) and in poly(viny1idene fluoride) ( X 2 0 ) . Effects of E°Coirradiation on the crystal structure of PVA derivatives were followed ( X 1 6 ) while the kinetics of crystallization of vinyl chloride-vinylidene chloride copolymer were studied by low temperature x-ray diffraction ( X 6 0 ) . X-ray diffraction patterns and thermomechanical measurements were made on oligomeric acid esters and polyesters ( X 2 ) . Unit cell dimensions were obtained on poly-0-hydroxybutyrates ( X 5 9 ) . X-ray and infrared studies were made on products from photopolymerization of maleimide and N-substituted derivatives ( X 9 S )and on metalcontaining pyromellitimides (X46). Studies on pyromellitimides included calculations of spatial lattice parameters ( X 4 2 ) . The change in structure of polyformaldehyde fiber during elongation was follob-ed ( X 2 4 ) . Crystalline formaldehyde polymers were examined in detail ( X 4 9 ) . X-ray examinations were made of poly(trimethy1ene oxide) ( X 3 3 ) , poly(oxacyc1obutane hydrate) ( X S 9 ) poly(p-phenylene oxide) ( X I @ , poly-3,3,3-trifluoro - 1,2 - epoxypropane ( X 4 6 ) ,and a n epoxy resin after reaction with m-phenylenediamine (X44). Miscellaneous x-ray diffraction studies were reported on the crystal structure of poly(chloromethy1 ethylene oxide) ( X 6 2 ) poly(N-butyl isocyanate) ( X 7 7 ) , polytetrahydrofuran ( X 8 4 ) , polysiloxanes ( X I S , X56) trans-1,Ppolyisoprene ( X 4 7 ) ,poly-2-oxazolidenes (N86a), and polyepiclilorohydrin (863). X-ray small-angle scattering was reviewed by Wada ( X 8 8 ) including measurements on polymer solutions ( X 8 9 ) . Scattering of cellulose nitrate in acetone solution was studied ( X 9 4 ) . Geil and Burmester ( X 2 1 ) described small-angle x-ray and electron microscopical examinations of PE and polyoxyethylene. Maeda and coworkers ( X 4 8 ) measured changes in small-angle diffraction patterns with temperature of low and high density PE, PP, nylon 6, and poly(ethylene terephthalate). Small-angle studies were reported on PE having molecular weight of 1.2 X lo4 to 1.3 X 108 ( X 4 S ) , on drawn PE (XI??), and reversible long period variations with the temperature of single crystals of branched PE ( X I S ) . Tordella and Dunion ( X 8 3 ) studied isomorphic interactions in blends of E-vinyl acetate copolymers with paraffin wax. Smallangle x-ray diffraction and electron microscopical measurements were made on S-butadiene solvent-cast and compression-molded block copolymers ( X 6 6 ) . Other applications of small-angle x-ray methods were made to bulk-crystallized


]

and annealed oriented films of poly(tetramethyl-p-silphenylene) siloxane fractions ( X 6 5 ) , and nitrated keratin fibers (X78). THERMAL METHODS

The use of thermal methods for polymer characterization continues to increase a t a fast pace. New techniques and applications have appeared during the past few years. Recent developments in the two well established techniques, differential thermal analysis (DTA) and thermogravimetry (TG), are reviewed in the next two sections. Differential scanning calorimetry (DSC) or dynamic differential calorimetry (DDC) is included in the DT.4 section. Classical calorimetry] dilatometry, and physical testing are not included in the present review. Thermal techniques associated with other major analytical methods are discussed under the headings of those methods. Murphy (T7S) continued his biennial review on fundamental developments in thermal analysis, including DTA, TG, pyrolysis, electrothermal analysis, microscopy, and dilatometry. -4 pocket book on thermal analysis by Harmelin (TS4) was published. Other reviews on thermal techniques were written by McLaughlin (T61) and Redfern (T79). Basic thermochemical data were reported for various organic compounds (2'77, T91). Two new journals devoted to thermal analysis, Journal of Thermal Analysis (T.40) and Thermochimica Acta (2'101), appeared during this biennium. The proceedings of the second International Conference on Thermal Analysis, held in Worcester, Mass., August 1968, were published (T85). Other proceedings published include those of the third Toronto Symposium on Thermal Analysis (T54) and the second Symposium on Analytical Calorimetry (0188). Papers presented a t a n International Symposium on Recent Advances in Thermal Analysis, held February 22 to 27, 1970, at the American Chemical Society meeting, Houston, Tex., were published in various issues of Thermochimica Acta in 1970. A symposium on Methods and Applications of Thermal Analysis was held at the Polytechnic, Wolverhampton, U.K., on October 31, 1969. McAdie (T66) reviewed the experimental program leading to issuance of thermal analysis standards, and current activities of various international organizations on standardization] including the International Confederation for Thermal Analysis (ICTA). Mackenzie (2'59) reported recommendations in nomenclature used in thermal analysis on behalf of the Nomenclature Committee of ICTA. Proper use of abbreviations in thermal analysis was also suggested by this committee (2'60).

Thermal properties of plastics were reviewed, including thermal expansion coefficient, specific heat, thermal conductivity, dimensional stability with heating, and temperature dependence of mechanical properties (2'47). Heats of polymerization and their structural and mechanistic implications were discussed (2'39). Reviews on thermal properties and methods for their measurement were presented (T41, 2'4.9). A third literature survey on thermal degradation, thermal oxidation, ' and thermal analysis of high polymers appeared, including 1836 references for a period from about March 1965 to January 1969 (V116). A book on thermal characterization of polymers edited by Slade and Jenkins (T92) included techniques such as DSC, pyrolysis-GC, stress-strain temperature relations, torsional braid analysis, thermal conductivity, and electrothermal analysis. Reviews on thermal analysis of polymers in general appeared (T23, T68, T7.4). Other reviews were devoted to thermal analysis of elastomers (T66),organic coatings (TSY),vinyl polymers (T19), and wood coniponents (T10). More recent thermal techniques besides DTA and T G are reviewed in the following. For convenience, the nomenclature and abbreviations used are adhered to those adopted by the authors, and are not necessarily accepted by most workers. Thermomechanical analysis (TMA) is a name coined by many authors to describe a thermal technique which follows the dimensional changes of a sample as a function of temperature. The information obtained by TMA correlates with important mechanical properties of the sample, such as softening, tensile modulus, compression modulus, shrinkage, glass transition, and expansion coefficients. Commercial TMA units with expansion, compression, flexure, and extension modes are now widely used in the United States. Other devices were recently reported (TI1, T2.4, T89, 2'99). Miller ("69) compared the thermal behavior of inorganic and organic glasses using TMA, DTA, and stress-strain curves. Machin (2'58) compared the kinetics of penetration of a polymer by a spherical indenter with tensile creep measurements, and a simple semi-empirical relation was described. Other TMA studies on polymers included phase transitions of polyesters (T66),structural effects on molecular interactions in segmented polyurethanes (T70, T71), kinetics of polystyrene swelling and dissolution (T57'), curing of polyimides (T29),and curing of epoxy resins (TS8). Torsional braid analysis (TBA), recently reviewed by Gillham (T26), is an extension of the torsion pendulum method for materials characterization. A multifilament glass braid substrate,

impregnated with a solution of the material under investigation, is subjected to free torsional oscillations under programmed temperature conditions. The frequency and decay of the freely oscillating pendulum provide information on the modulus and mechanical damping of the sample, and polymer transitions, resin curing, and degradation are studied. The use of a single glass fiber impregnated with a plastic binder was reported in studies of various epoxy, phenolic, and imide resins (T2). TBA was applied to study relaxations and stability of a n aromatic polysulfone (T27'), polymerization of carboxy-terminated polybutadiene with tris(methyl aziridinyl) phosphine oxide (TI), crosslinking of reactive acrylic polymer containing N-butoxymethylamide and amide functional groups ( T S S ) , thermal transitions in laminated circuit board materials in relation to punchability (T4S), and antioxidant activity in elastomer systems (2'106). Electrothermal analysis (ETA) can be broadly defined as a thermoanalytical technique for studying the nature and behavior of a material by monitoring its resistivity or dielectric loss automatically and continuously as a function of temperature, or as a function of time a t a maintained constant temperature. The use of a rapid dynamic ETA technique for polymer characterization is still in the developing stage. However, potential applications to polymers include detection of physical transitions, analysis of additives and contaminations, elucidation of structures, identification of polymer blends and copolymers, and study of polymerization, curing, and degradation reactions. Principles and applications of direct current (d.c.) ETA or resistivity measurements were reviewed by Warfield (2'105) and Seanor (T87). A method was developed for simultaneous scanning calorimetry and conductivity measurement, while the temperature of the sample is changed a t a programmed rate (T15). Concurrent D T B and ETA were reported (2'20). A technique for simultaneous TG, DTG, DTA, and ETA was described (T17). A patent was granted for a test cell for ETA, which also provides simultaneous DTA capability (T18). An apparatus for determination of the temperature dependence of resistivity a t 300' to 2500 O K was described, using specimens 6 to 10 mm in diameter and 15 to 30 mm high, heated directly by the measuring current (d.c. or ax.) (T53). A device for conductivity measurements was reported, employing a small, thin disk of sample held between flat platinum electrodes to minimize thermal inertia and temperature gradient (TIO4). Conductivity and temperature were measured periodically and punched on a paper tape for com-

puter processing of the experimental data. Studies were made of polymer electrets such as PE, PTFE, and poly(viny1idene fluoride), formed under a high static field at a high temperature (2'96). Depolarization current changes observed upon temperature variation were consistent with thermal molecular motions or physical transitions in the polymer structure. Conductivity of nylon 66 was studied as a function of temperature, and a mechanism involving both electronic and ionic conduction was postulated (T86). Resistivity measurements were effectively applied to study polymerization kinetics of allyl isopropenyl ethyl phosphonate and aryl curing of polyesters phosphonates (TM), (T52), and cross-linking in thermosetting resins (2'51). The conductivity of PVC, used for the manufacture of cables, was investigated under programmed heating to simulate aging (T46). The electrical conductivity of stabilized and unstabilized plasticized PVC samples was measured during heat treatment (2'45). For stabilized samples, the conductivity increased linearly with time a t a rate determined by the stabilizer used. The conductivity of unstabilized samples reached a saturation value after an approximately linear increase. Electrical conductivity us. temperature curves were used to follow changes in coal and PVC during carbonization processes (T78). Dielectric measurements of acrylic polymers were made a t 60 Hz over a temperature range of -40' to 200 OC (T94). The method showed promise in elucidation of structure and stereoregularity. Sacher (T83)used a continuously nulling capacitance bridge to obtain dissipation factor vs. temperature curves for poly(ethy1ene terephthalate), and was able to resolve the fine structure of its p-relaxation. Galand (2'25) measured permittivity and dielectric loss angle of PVC automatically as a function of temperature and frequency. Wrasidlo and Augl (T108) determined glass transition temperatures of aromatic polyimide-amides by a dielectric measuring apparatus. Dielectric relaxation effects in polyquinoxalines were investigated by dielectric measurements as a function of temperature (TlO7). Thermal degradation of PVC was studied by an a.c. conductometric technique that permitted separation and continuous recording of the resistive part of the a.c. flowing through the sample during aging (2'35). The capacitative and resistive parts of the current were separated by a phase-sensitive lock-in detector and recorded continuously as a function of temperature. The increase in the electrical conductivity of PVC during thermal degradation was shown to be caused by dehydrochlorination and conjugation


NO. 5,

APRIL 1971

0

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of the polymer chains. Other studies using dielectric measurements included determination of glass transition temperatures of poly(pheny1-as-triazines) (T36), study of crystallization kinetics of polychloroprene (2'90), detection of crosslinking in unsaturated polyester resins (T60),study of structural effects on setting of epoxy resins (TlS), and following thermal degradation of aminecured epoxy resins (2'76). Thermal depolarization analysis (TDA), depolarized light intensity analysis, (DLI), and thermo-optical analysis (TOA) are names used to describe a thermal technique recently introduced as a complement to existing modes of thermal analysis (2'8, 2'9, 2'42, 2'67, 2'98, 2'100). Basically, the technique measures the changes in depolarized light transmission as a function of temperature or time. Results obtained by the optical technique correlate well with DTA, ThIA, and x-ray measurements, and, in many cases, provide unique information on partial melting, premelting, and recrystallization phenomena not readily observed by other techniques. The use of changes in optical properties for studying fusion phenomena was discussed by Vaughan (2'103). Simultaneous thermomicroscopy and DTA was reported, providing visual observation during thermal analysis (T72, T102). Thermoparticulate analysis (TPA), a means for studying degradation of polymers through the detection of condensation nuclei evolved during the process, was described (2'7%). Apart from indicating the decomposition temperature of the sample, this technique also shows the evolution of particulate material as well as molecular species. The use of radioactive isotopes in polymer analysis was reviewed, including techniques for degradation studies (2'6, T12). Radiothermal analysis (RTA) was used to study thermal degradation of epoxy resins (TIC). Thermal stability of various groups in the resin was determined by following the evolution of radioactive materials upon heating the 14C-labeled sample. Importance of an intermolecular chain transfer reaction in the thermal degradation of polystyrene was established by a radiochemical method using Wlabeling (2'81). The mechanism of thermal degradation of PVC was studied using positronium lifetime measurements (2'44) and both T- and 14C-incorporation (2'7). Pyrolysis of polyethylene was characterized by RTA using ***Thand 224R,showing four maxima on the radioactive curve: 120" f 2', 230' f 4 O , 320 f loo, and 520' f 10' due to melting, formation of oxygen crosslinks, degradation of macromolecular bonds, and oxidation and sublimation of pyrolysis products, respectively (2'109). Curves showing the characteristics of 288 R

radioactivity in crystallization of PE were also discussed. A study was made of degradation of chlorinated polyisobutenes labeled with a8C1, and evolution of volatiles was followed radiochemically (2'66).

Evaporation rate analysis (ERA) involves deposition of a monolayer of I4C-labeled, high boiling material on the surface of the sample, and measurement of the desorption rate of the radioactive material. From this rate, information is obtained of the state of the surface and the effect of test variables on the surface. Two symposia were sponsored by the American Chemical Society, Division of Organic Coatings and Plastics Chemistry, to discuss this technique (2'3, 2'4). Studies were reported of degree of cure of thermosetting resins, adhesion, sorption and desorption, determination of nonvolatile residue, drying of coatings, surface changes caused by aging, and other surface properties. Application of ERA to coatings evaluation was discussed by Anderson (2'6). Cerceo (2'16) reported an economical, simple ERA method by which the rate of cure of polymeric materials may be followed as a function of pressure, temperature, and time. Sanders (2'84) compared various methods for polyurethane cure measurement, including ERA, DSC, ir, and hardness determination, and found good agreement. The cure parameters of can coatings and enamels were studied by ERA (T8OlT82). The ERA method used for determining best cure conditions for water-thinnable baking resins was reported to agree with the acetone resistance and hardness test (2'95). Techniques have been developed in studying thermal degradation by monitoring the changes in pressure in a n evacuated system while the sample is heated under controlled conditions (2'62, 2'88, 2'93). Such a technique has been referred to as thermal volatilization analysis (TVA), and applied to studies of thermal degradation of styrene-acrylonitrile copolymers (TSO),vinyl chloridevinyl acetate copolymers ( T S l ) , and PVC-Ph4MA mixtures (2'63, T64). A technique using flame ionization detection to follow evolution of volatile materials upon heating a sample was reported (2'21, 2'22). Essential features of apparatus design were close coupling of the detector to the sample furnace and provision for operating the detector at high temperatures to avoid condensation. Similarly, Nematollahi, et al. (2'76) employed programmed pyrolysis in connection with flame ionization detection to characterize plastics such as PVC and polyacrylonitrile. An automatic recording microcalorimetric apparatus for the study of thermal processes during mechanical deformation of polymer films and fibers was described (2'28). The thermal be-


havior of polystyrene and polyethylene during elastic deformation was studied. A processing temperature indexer was reported, which followed changes in apparent viscosity of polymers with temperature (T32). The data obtained correlated well with data obtained isothermally, and allowed prediction of polymer decomposition temperature and minimum processing temperature. Data were presented for polycarbonate, polyethylene, polypropylene, and nylon 6. Construction and operation of a continuous-flow enthalpimetric analyzer were reported (2'97). The apparatus is useful for slow sample-reagent reaction, and especially suitable for measuring large temperature changes associated with the determination of reactants a t high concentrations. Monomeric acrylonitrile in aqueous acrylonitrile-butadiene copolymer latexes was determined by reaction with sodium bisulfite. The solution temperature rise after mixing was monitored by a thermistor bridge circuit and recorded continuously. DIFFERENTIAL THERMAL ANALYSIS

Several books and review articles on general principles and applications of DTA and DSC have appeared since the last review ( 0 1 2 , DIS, D27, D60, 0167, D169, D21U, 0212). The proceedings of the second symposium on analytical calorimetry a t the 160th meeting of the American Chemical Society, held in Chicago, Ill., September 13, 1970, include many papers on DTA and DSC (0288). Reviews devoted to polymers have been written by Kanetsuna (Dl26) Mihaila (D166), and Wunderlich (0230). More specific reviews on applications of DTA and DSC include those on biological macromolecules (D168),rubbers (D9),film-forming polymers (D96), and coating resins (D219). Applications of DTh and DSC to studying melting and crystallization of polymers have been reviewed (D64, 0 2 2 5 ) . The meaning and measurement of crystallinity in polymers by various methods, including density, ir, thermal, NMR, and x-ray techniques, have been discussed in the light of modern theory on the structure of semicrystalline polymers (Dl28). A review has also been presented on recent DTA studies of polymer degradation (0194). Progress towaids establishment of DTA standards was reported by hIcAdie (0166) and Einhorn ( 0 6 8 ) . Based on interlaboratory evaluations involving a large number of industrial and government laboratories as well as academic institutions, a suitable temperature standard for DTA seems to be a pure inorganic solid which undergoes a reversible transition in the solid phase: Two standards of this type, potassium nitrate and quartz, have now

been issued by the National Bureau of Standards. A similar study in Japan (D181), using crystalline polyolefins, crystalline ethylene-vinyl acetate copolymer, and crystalline ethylene-ethyl acrylate copolymer, showed wide variations in both temperature and heat of fusion measurements among the participating institutions. Several analytical standards were evaluated using both DTA and DSC ( 0 6 9 ) . New DTA techniques pertinent to polymer studies have been reported. Simultaneous DSC and electrical conductivity measurements were made on several polymers using a modified commercial instrument (D88). High-frequency heating was employed for DTA of polymers and elastomers (D.2.27'). A scanning microcalorimetric cell based on a thermoelectric disk was reported and applied to polymer studies ( D f7 ) . Thermal analysis under high pressure has aroused great interest of polymer chemists. A system for obtaining DSC data under reduced (to 10microns) or elevated (to 1000 psi) pressure (D1.49) has become commercially available. Crystallization and melting of polyethylene and other polyolefins were studied under pressure, and the design of the DTA apparatus was described (0.48,D.49). A dynamic differential microcalorimetric technique for measuring heats of polymerization was reported, which employed sealed sample ampoules to prevent loss of volatile monomers and to recover reaction product for other analyses (DSS). Informative results were obtained in studying curing behavior of thermosetting resins using highpressure DTA apparatus (D4l , DlS8) or sealed sample cells to generate pressure within the cell (D61). Under normal conditions, volatilization of some constituents would dominate the thermogram and obscure the curing exotherm. A stirred reaction vessel was added to a commercial scanning calorimeter to allow direct and continuous measurement of changes in the thermal energy of a chemical reaction such as emulsion polymerization of methyl methacrylate (D1.4). A technique was devised for determination of thermal diffusivity of polymers by DTA ( 0 8 2 ) . Polymer deformation was studied by a calorimeter based on a DSC control circuit (066). Combined DSC-MS was used to study thermal and oxidative decompositions ( 0 6 2 ) . Computer techniques were used to reduce DSC data for rapid calculation of rate constants of solid-state decompositions (D50), or obtaining cure parameters of thermosetting reactions (D190). hililler (D167) used an isothermal preconditioning technique for quantitative thermal analysis, and applied it to the crystallization of poly(ethy1ene terephthalate) and pyrolysis of cellulose. Strella and Erhardt (0.218) demon-

-

strated heating rate effects in the measurement of polymer transition temperatures by DSC, and attributed this rate dependence to a lag in the heat path to the sample and lag in heat transfer within the sample. The effect of environment on quantitative measurements by DSC was studied by David (D46), and the effect of packing modes on DTA was reported by Yamashita and Waki (DZSS). The use of a quenched polymer as reference material has been shown to magnify small energy differences (D67). New methods for analyzing DSC curves were based on procedures for obtaining the true heat capacity base line for a system undergoing a thermal event, allowing enthalpy changes to be isolated from heat capacity contributions ( 0 2 1, D78a). Glass transitions in certain polymers have been frequently detected as endothermic peaks by DTA. Ali and Sheldon (DS) described results obtained from DTA and DSC on annealing a number of glassy polymers which have been rapidly cooled from the glass temperature and on slowly cooled samples. I n every case, evidence of structural reorganization was observed, and the rate a t which this took place was reported. Roberts and Sherliker (0800) proposed, however, that such a step change in a DTA scan in the exothermic sense could be explained as a manifestation of the volume relaxation occurring a t the glass transition in internally strained samples. The dependence of glass transition temperatures on heating rate was studied by Barton ( 0 1 6 ) . I n studies of plasticized butyl rubber systems, Maurer ( D l63) demonstrated the utility of DTA and DSC for evaluation of low temperature dynamic behavior, polymer-plasticizer compatibility, and quality control analysis. Unique applications of DTA were obtained without much modification of existing equipment. For instance, Mahr (0161) employed DTA methods to measure surface energy of amorphous, synthetic latices of polystyrene and various vinylidene chloride copolymers. Heskins and Guillet (096) used a modified sample pan for DSC measurement of heat of phase separation in poly(N-isopropylacrylamide) solutions. With additional amplification to existing equipment, DTA was used to study aqueous and nonaqueous thermally reversible polymeric gels, including gelatin (HzO), polyacrylylglycinamide (HzO), vinyl alcohol-vinyl fluoride copolymer (HzO), poly(viny1 chloride) (dibutyl phthalate), nylon 66 (5 to 1 m-cresol :DMF), and poly-y-benzyl-lglutamate (xylene) ( 0 8 5 , 0186). The effect of various initiators on the polymerization rate of vinyl acetate was studied by DTA (DS.2). The use of DSC to study polymer crystallization

kinetics was compared with dilatometry by Booth and Hay (D20),and applied to PE fractions (D20, D6.2).The principal advantages of the DSC method were microsample requirement and obtaining quantitative kinetic isotherms rapidly over a range of temperatures. Friedman (D69) discussed new methods for evaluating kinetic parameters from thermal analysis data including DTA and DSC by which all kinetic parameters were obtainable from two or three points on a thermogram. Polyethylene. The thermal properties of n-hectane, CIWH~OZ, were measured by DSC as a model compound for crystalline polyethylene (PE) ( 0 9 2 ) . The heat of fusion values obtained compared favorably with the data available for other normal paraffins. Results were presented of calorimetric and dilatometric experiments on meltcrystallized PE's with various thermal histories ( 0 8 ) . The derived heat of fusion of perfectly crystalline PE a t the melting point was 307 js per gram, and the temperature dependence of the free energy of fusion indicated an extended chain melting point of 141' & 1'. Rijke and Mandelkern (D195) made DSC and dilatometric studies of the melting behavior of linear PE crystals precipitated by high speed stirring from solution, and produced a small fraction of material with a melting temperature of 146.0' + 0.5' by proper annealing. This increased melting temperature was attributed to either an increase in the crystallite size or a reduced interfacial free energy. DSC and x-ray studies (D171) showed changes in lamellar thickness of PE single crystals during isothermal annealing in bulk, which could be explained by assuming mechanisms of partial melting followed by recrystallization a t the initial stage, and subsequently, of thickening nucleus formation and longitudinal translation of chains within the crystal. The effect of annealing on low density PE was also investigated by DSC and dilatometric techniques (D178). Jackson and Johnson ( 0 1 1 1 ) employed crosslinking by high energy radiation to suppress the multiple melting peaks due to recrystallization of metastable crystals in their DSC studies of dilute solution crystallized PE. Calorimetric data were used to derive information on the nature of fold surfaces of PE single crystals (020.2). The surface free energy value was determined either from a plot of melting temperature us. reciprocal lamellar thickness or from the free energy of formation of crystals calculated from observed specific heat values. The surface enthalpy value was determined from the plot of heat of fusion us. reciprocal lamella thickness. Prime (D191) used DTA, dilatometry, and electron


0

289R

microscopy to study the melting of PE's of different molecular weight distribution, and PE fractions crystallized to extended-chain crystals. I n all samples, eutectic separation occurred up to a molecular weight of 10,000. Multiple peaks before the final melting peak were assumed to be caused by low molecular weight fractions, which possibly formed narrowdistribution mixed crystals. DTA and DSC techniques have been extensively used to study P E with modified morphology. Illers (0106) observed that the melting behavior of drawn P E was strongly affected by the shrinkage occurring simultaneously, and that the melting point measurement could be falsified by superheating if heating rates larger than 0.5' per minute were used. Illers (0107) also studied melt-crystallized linear and branched PE's with amorphous regions destroyed to various degrees by nitric acid. The influence of acid concentration, reaction temperature, and reaction time on heat of fusion, melting point, molecular weight and molecular weight distribution, x-ray crystallinity, etc., was discussed. Peterlin and Meinel (0186) made DSC studies of nitric acid-treated drawn and rolled PE of low and high crystallinity. The heat of fusion data as function of draw ratio, temperature, and thermal history were consistent with the molecular model of plastic deformation-Le., of the transformation of the original microspherulitic into the new fiber structure. DSC studies of drawn films from P E single crystal mats by Maeda et al. (0160) showed different melting behavior from ordinary drawn bulk polymer. Extended-chain crystals of P E crystallized from the melt under high pressure were conveniently studied by DSC in conjunction with other techniques (026, 0 6 6 , 081, 0192). Melting peaks on the low temperature side of the main melting peak were due to narrowly distributed, low molecular weight poIymer segregated in extendedchain crystals. The amount of extended-chain crystals could be estimated from heat of fusion. DSC and x-ray techniques were used to investigate the structure and properties of high-density PE crystallized under the orientation and pressure effects of a pressure capillary viscometer (0216). Such a sample was found to have a high degree of crystal perfection and crystal orientation in combination with the usual pioperty of transmitting visible light. Evidence was presented to show presence of an extended chain component in the crystal structure. Melting behavior of stress-crystallized P E was studied by DSC (040, 084). I n addition to the major melting peak, a separate higher-temperature endotherm was observed, due to two-phase 290R

crystal morphology. Harrison and Baer ( 0 8 6 ) used a bromination technique to study the fold surfaces of polymers, and found the reaction to be mild and nondestructive of the fold. The effect of bromination on melting point and heat of fusion of PE single crystals was investigated by means of DSC. Gee and Melia (073) reported the use of DSC to measure heat capacities, melting temperatures, heats, and entropies of fusion of PE single crystals and melt-crystallized samples of PE and isotactic PP, which had been subjected to direrent doses of gamma radiation. Changes in these parameters with radiation dose were interpreted in terms of ordering processes resulted from radiation-induced formation of intermolecular crosslinks. Free radicals in irradiated PE were detected calorimetrically (043). The sample was heated in a DSC apparatus to undergo simultaneous fusion and free radical reactions. The exothermic heat of the free radical reactions was calculated as the difference between the heat of fusion of an irradiated and oxidized sample and a n irradiated one. Natov and Peeva ( 0 1 7 3 ) used DTA to determine the phase transitions of a binary high-pressure PE-low-pressure P E system a t different compositions of the system and a t different molecular weights of the components. Both plane and three-dimensional phase diagrams were constructed and used to explain the changes in the mechanical properties with composition. DTA and DSC studies of the melting and crystallization behavior of blends of high- and lowpressure PE's revealed three endotherms (0137, 0207). The nature of the intermediate temperature peak was discussed in relation to thermal treatment, blend composition, and blending conditions. Polypropylene and Other Polyolefins. Gee and Melia ( 0 7 0 ) measured the heat capacity of both melt and solution crystallized isotactic polypropylene (PP) from 200' to 500 OK. A glass transition occurred a t about 265 OK in both samples, and a value of 207 =t5 joules,/gram was obtained for the heat of fusion of isotactic PP. The heat capacity of syndiotactic PP was also measured ( 0 7 2 ) . A glass transition a t 265 O K , an unknown first-order transition a t 386' to 406 OK, and a melting transition a t 404' to 417 'K were observed. Kamide (0121) studied recrystallization of unoriented isotactic PP film during annealing by DSC, ir, electron microscopy, and density measurements. The multiple peaks observed were interpreted in terms of partial melting, followed by recrystallization resulting in thicker lamellae. Such an interpretation was also used by Maeda and Kanetsuna (0158) for peaks other than the major melting


peak in their DTA studies of effects of stereoregularity on crystallinity of PP. The equilibrium melting temperature of a sharp fraction of isotactic PP was determined to be 187.5" (0123). This contrasted with an equilibrium melting point of 232" A 2' obtained from a toluene- and xylene-insoluble fraction of PP (0169). Isotactic PP crystallized under high pressure was studied by DSC, x-ray diffraction, and electron microscopy (0208). All pressure-crystallized samples were found in the y, or triclinic, modification, and their melting temperatures were in the range of 157' to 182', dependent on the degree of supercooling. DTA and x-ray diffraction measurements on the p-form crystal of isotactic PP showed that the @-form crystals were transformed to the aform on recrystallization, and the melting of p-form was time-dependent (0122). The equilibrium melting point and heat of fusion were 147' and 24 cal. per gram, respectively. Duswalt and Cox (066) reported a reliable p-form nucleator, a quinacridone dyePermanent Red E3B, enabling detailed study of 0-form properties. Some interesting PP melting curves were obtained showing two exothermic recrystallization steps and three separate melting endotherms. Examination of PP samples crystallized under shear stress via DSC, x-ray diffraction, and optical and electron microscopy indicated the presence of various degree of order, and a rheological phase transition probably occurred in the range of 195' to 215 'C (0211). The physical interaction of low molecular weight compounds with isotactic PP was studied by DSC ( 0 4 ) , and the interaction energies determined were used satisfactorily for comparison of compatibility. The efficiency of nucleating additives in PP was evaluated by DTA and microscopy (0204). A strong dependence of nucleating efficiency on the mixing method was observed by DSC and by measuring the nucleation density by means of polarization microscopy (0116). Gordon ( 0 7 8 ) made a comparative study of various test methods for evaluation of antioxidants in PP, including DTA, oven-aging, oxygen uptake, water extraction resistance, carbonyl formation, re-extrusion, injection spiral molds, U-tube, melt flow drifts, and the torque rheometer. Only a fair correlation was found between the methods, and none was ideal as a simulated test for measuring oxidative and/or processing stabilities. DSC studies were made on the melting behavior of isotactic poly-4methyl-1-pentene single crystals ( 0 1 7 2 ) . Depending on the method of growing the crystal, various endothermic effects were observed. The crystals grown

from Decalin showed a n endotherm a t ca. 80 'C attributable to a solid-solid transition between two crystalline modifications. All cryst& grown in various solvents showed a small endotherm in the vicinity of 125 'C, the origin of which could not be determined. I n the high temperature region, two inseparable endotherms corresponded to the melting of the original single crystals and to the melting of crystals with thicker lamellae formed in bulk during heating by partial melting and recrystallization. The melting transitions of both crystalline forms of trans-1,4-polyisoprene, as detected by DTA, were identified by studies with optical microscopy and x-ray diffraction (0164, 0165). The melting temperatures of the two forms were found dependent on the crystallization temperature. Their equilibrium melting points were determined to be 78" and 87 'C, respectively. Conversion from one form to another occurred only by fusion and recrystallization. No evidence of a solid-solid transition was found. Ethylene and Other Olefin Copolymers. Precision adiabatic calorimetry and DSC were used to measure the heat capacity of ethylene-propylene block copolymers over the temperature range 80' to 500 'K (D34). Two first-order transitions a t 399" f 3' and 435' 1 'K were observed and attributed to the melting of ethylene and isotactic propylene blocks. Values for the heat of fusion of the copolymers were listed. Results of heat capacity measurements on ethylene-isotactic propylene block copolymers after gamma radiation were also reported ( D 7 l ) . After irradiation, a single endotherm replaced the two observed with the unirradiated sample. A DSC method of characterizing ethylene-propylene copolymers (035) provided information on comonomer distribution, tacticity, and crystallinity of the sample. The effect of fuming nitric acid on single crystals of random ethylene-propylene and ethylenebutene copolymers was investigated using DSC, GPC, and x-ray methods (D99, DlOO). A qualitative correlation between the changes in molecular weight distribution and changes in melting behavior of degraded polymer crystals was described. Results obtained from I4C-labeled samples with branches removed by nitric acid suggested that the branches were contained within the crystalline cores of the lamellar crystals. DSC and DTA studies on ethylene copolymers and branched polyethylenes showed that methyl side groups caused less diffuse melting and less melting point depression than either ethyl groups or polyethylene branches (D23,0 8 0 ) . Enthalpy and entropy of fusion data were

reported for ethylene copolymers and branched polyethylenes. Good agreement was found between crystallinities determined independently by DTA and x-ray analysis. Thermal degradation kinetics of ethylene-propylene copolymers and terpolymers was investigated using both DTA and T G ( 0 6 1 ) , and effects of vulcanization and ablative fillers were studied. Heat capacity measurements were made on ethylene-1-butene block copolymers by DSC and precision adiabatic calorimetry (DS6). A glass transition a t 200 O K , a transition of unknown origin a t 335 O K , and a melting transition a t 400 'K were observed. DSC and dilatometric studies on 1butene-propylene copolymers indicated that the phase transitions of these had the peculiar trend of 1-polybutene, whereas remarkable changes were observed in the kinetic parameters (076). I n contrast to the homopolymer, these copolymers crystallized from the melt directly in a low-melting form. Polymers, obtained from ethylene with Ziegler catalysts which also accelerate formation of 1-butene from ethylene, were studied by DTA, ir, and x-ray diffraction (0223). The structure of these polymers was essentially the same as that of ethylene-1-butene random copolymers containing a small amount of I-butene. Ethylene-vinyl acetate copolymers of varying compositions were examined by DTA and x-ray analysis from -80' to 140' (DflQ). Copolymers containing less than 40% ethylene were amorphous. I n partially crystalline copolymers containing less than 60% vinyl acetate, the glass transition temperature was independent of composition and was lower than that in the amorphous copolymer. The melting point of the partially crystalline copolymers increased with ethylene content and was described by a modified Flory equation. The degree of crystallinity also increased with ethylene content. Melting behavior of ethylene-vinylene carbonate copolymers was studied by DTA and compared with that of ethylene-vinyl acetate copolymers (D206). The melting point and crystallization temperature of ethylene-vinylene carbonate copolymers were considerably higher than those of ethylene-vinyl acetate copolymers a t the same molar compositions. The difference was attributed to the higher dipole moment of the vinyl carbonate links in comparison with that of vinyl acetate. The isothermal crystallization from the melt of ethylene-vinyl acetate copolymers with different compositions and different molecular weights was investigated by means of DSC (0115). It was observed that the crystallization kinetics as well as the maximum degree of crystallinity depend on both composi-

tion and molecular weight. DSC and x-ray studies were made on partially hydrolyzed ethylene-vinyl acetate copolymers (0222). The glass transition temperatures were found to be increasing functions of vinyl alcohol content and the terpolymers became crystalline a t concentrations of vinyl acetate below 12 mole %. Acrylics and Vinyl Polymers. T h e phase diagram of acrylic acid-acrylamide system was determined by DTA and x-ray diffraction data (D18S), showing the formation of a 1 to 1 addition compound and one eutectic point a t 67 mole % acrylic acid. Kuznetsov and Shakhmina (01.40) observed a single endothermic effect a t 185' to 226' for poly(methacry1ic acid), corresponding to dehydration and decarboxylation. For methacrylic acidcaprolactam copolymers, endothermic effects were noted a t 164-80' for acylation and a t 206-18' corresponding to dehydration and decarboxylation, and for methacrylic acid-diethylamine copolymers, a t 160-84' corresponding to acylation and a t 205-36' corresponding to dehydration and decarboxylation. Slade (D2IS) determined the melting point of polyacrylonitrile to be 322 'C from melting point measurements of a series of acrylonitrile-vinyl acetate copolymers by DTA. Heat of fusion of polyacrylonitrile was also determined. Dunn and Ennis (064) obtained a melting point value of 326°C for polyacrylonitrile by direct DTA measurement with a fast heating rate of 100' per minute. Two glass transitions were observed for butadieneacrylonitrile copolymers having less than 36% acrylonitrile, and were interpreted as the result of incompatible phases differing in butadiene and acrylonitrile ratio (DSO). -4transition observed above the main glass transition of butadiene-acrylonitrile copolymers was attributed to the melting of paracrystalline regions primarily consisting of 1,Ccis-polybutadiene sequences ( 0 3 1 ) . A DSC study of first-order transitions in poly(viny1 chloride) (PVC) was reported (0119). Various commercial PVC's exhibited a melting range starting a t about 150 "C and extending into the thermal decomposition region, and a heat of fusion of 750 cal per mole was obtained. However, a similar melting range starting a t 180 'C was found in PVC polymerized a t -30 OC. Secondary crystallinity could also be produced by annealing above the glass transition. Illers ( 0 1 0 8 ) studied the effect of annealing on the physical state of PVC. Depending on the relation between heating and cooling rate, either an endothermic peak was superimposed on the glass transition step, or a peak or minimum was found below the glass transition.


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Similarly, Foltz and McKinney (068) observed normal DTA or DSC curves for the glass transition of PVC quenched from above glass temperature. If cooled slowly or annealed near the glass temperature, PVC displayed a peak a t the glass transition. Quantitative studies of the time and temperature effects on the production of this endothermic peak during annealing of PVC and an acetate copolymer were presented. Hatakeyama and Kanetsuna (087) also produced double peaks on the DSC thermogram by thermal treatment of PVC below its glass temperature, and interpreted these peaks as a result of coexistence of different glassy states in the amorphous region. The low temperature transition was due to movement of a mobile or unstable structure having a short relaxation time, and the high temperature transition due to closely packed rigid chains. The dependence of glass transition temperature of PVC on molecular weight was described (0187). The effect of simple organic solvents of different molecular size, flexibility, and polarity on glass transition temperature of PVC was studied (0186). DTA was also the technique used for investigation of plasticization of PVC by various liquid and solid materials by another school of workers (0150-153). DSC was used to determine the effect of additives on glass transition of poly(vinyl acetate), and to correlate glass transition temperature with the minimum temperature a t which the polymer particles coalesced to form a continuous film (0209). A quantitative thermal technique was described for analysis of polyblends of PVC, polystyrene, polybutadiene, and poly(pheny1ene oxide) (010, 011). A particular component in the blend was detected by its glass transition, and the amount of the component was measured from the magnitude of the increase in specific heat a t the glass transition. Sequence distribution effects on glass transition temperatures of butyl methacrylate-vinyl chloride copolymers were studied using DSC (0117). A relationship was thus developed for correct prediction of glass transitions in such copolymers. DTA was mainly used for a study of thermal decomposition of compounded PVC (065). Effects of plasticizers and additives were discussed. Under isothermal conditions, the induction period was used to estimate the activation energy for dehydrochlorination of PVC and the effectiveness of thermal stabilizers. A combined use of DTA, ir, and chemical analysis effectively established the mechanism of PVC stabilization by lead salts (0236). Polystyrene and Copolymers. Specific heats of amorphous samples of atactic and isotactic polystyrene (PS) 292 R

were determined using an improved DSC instrument (044). A study was made on the thermal behavior of isotactic PS crystallized under different conditions (089). For a sample quenched from the melt, the melting peak was located a t 226", the cold crystallization exotherm a t 150-90",and the glass transition a t 83". Lambert (01.43) used DSC to study the effect of thermal history, sample form, and scan rate on glass transition of PS, and showed a clear endotherm of about 0.92 cal per gram during the glass transition. Two glass transitions were observed by dynamic loss modulus, DSC, and broad-line NMR measurements on either heat-treated or meltpressed PS samples (091). Presumably, these were due to mobile and rigid groups of molecules having different relaxation times. Thermal behavior near the glass transition of mixtures of monodisperse PS fractions was investigated using DSC (090). A single endothermic peak was observed for homogeneous blends, and double peaks appeared for inhomogeneous blends, depending on their thermal histories. When samples initially showing a two-phase nature were quenched from the melt, a one-phase structure was formed by treatment a t the intermediate temperature of glass temperature of each component. For samples with one phase in the quenched state, a two-phase structure was formed by treatment below the glass temperature. Multiple melting was created in PS fibrillar crystals when the samples were annealed in a certain temperature range, and also in unoriented PS crystallized under proper conditions (0184). The phenomenon of multiple melting was studied in PS, and nylon 66 as a function of sample treatment by annealing and drawing (018). Results obtained from a variety of techniques, including DTA, x-ray diffraction, electron microscopy, and mechanical testing, showed that double endotherms were not caused by a bimodal crystal size distribution, by recrystallization, by orientation changes, or by phasechanges. It was proposed that one endotherm was caused by the melting of folded chain crystals, while the other due to melting of less perfect bundle crystals. Multiple glass transitions were observed in styrene-butadiene block copolymers (0206). The two glass transitions, one near 0 "C for the 1,2-p0lybutadiene segment and the other near 100 "C for the PS segment, provided a method of determining the copolymer composition from the relationship between the magnitudes of the transition inflections and monomer mole fractions. A method was described for the determination of the amount of block styrene in butadiene-styrene copolymers ( 0 5 ) . By using the total styrene


content of the copolymer, determined by refractive index, and the nonblock segment composition, determined from DTA measureq-ts using a graph of glass transition ,,temperature us. composition, the amount of block styrene was obtained by difference. A quantitative thermal technique was reported for analysis of polyblends of acrylonitrile-butadiene-styrene (ABS) copolymer and Noryl-type resins (011). A DTA study of ABS resins and related copolymers was reported (0232). Polymer blends and grafted polymers showed characteristic DTA peaks of each homopolymer. The catalytical effects of metals on the oxidation of styrene-butadiene rubber with or without the presence of an antioxidant were evaluated by DTA (0166). Excellent correlation was reported between highpressure DTA data and conventional tensile strength and ultimate elongation values used for evaluation of antioxidant activity in styrene-butadiene and natural rubber samples (0164). Two glass transition temperatures were reported for styrene-isoprene block copolymers (0201), which were dependent on both the block sequence and block length, indicating some compatibility between the two phases. DSC was used to characterize the thermal transition behavior of styreneethylene oxide block copolymers (0179). Melting transition of polyoxyethylene and glass transition of polystyrene were observed over the composition range studied. Heat of fusion measurements indicated that the crystalline fraction of polyoxyethylene is composition-dependent. The concentration-temperature phase diagram of a styrene-oxyethylene block copolymer-diethyl phthalate system was established by simultaneous DTA and x-ray diffraction studies ( 0 7 6 ) . DTA and TG were employed to study the effect on thermal degradation of the molecular weight of poly(m-aminostyrene) homopolymers and copolymers with styrene (0217). Related substituted styrene polymers and copolymers with styrene were also studied in order to assess the effect of introduction of amino, substituted amino, and hydroxy groupings into a polystyrene main chain. The inherent antioxidant characteristics of the substituent groups seemed to play a major role in stabilization. Fluorine-Containing Polymers. Transitions and nature of high-pressure phases in poly(tetrafluoroethy1ene) were studied using DTA, x-ray diffraction, thermal expansion, and ultrasonic methods (097). A phase diagram was established in a pressure range from 1 atm to 6500 kg per cm*, and in a temperature range from room temperature to 165". Three phases were found; phase I above 30", phase I1 below 20" (both a t 1 atm), and phase 111 above

5000 kg per cm2. The triple point was located a t 75" and 5000 kg per cm2. The high-pressure phase, 111, may be a closely packed but disordered phase. The glass transition temperatures of several F-containing polymers were determined by use of DSC (022). I n polymers of a-olefins, T , increases with the F content of the backbone and the length of the n-perfluoroalkyl branch. I n styrene polymers, T , is also higher if the backbone contains fluorine, but nearly the same T i s are found for polymers with phenyl and pentafluorophenyl groups. Saturated polymers of perfluoro-a,w-dienes have lower T i s than perfluoro-a-olefins. Glass transition temperatures were determined for a series of perfluoroalkylene-linked aromatic polyimides by DSC and dilatometry (016, 042). The values obtained appeared to be appreciably lower than those of the polyimides containing no such perfluoroalkyl groups. The values provided a simple molar additive relationship between T , and copolyimide composition which could be used to predict T , of polyimides difficult to observe experimentally. The effect of F in aliphatic polyurethanes on their ability to crystallize was studied by DTA (0131). F decreases the mobility compared to the unfluorinated polymers. Their very low melting points were explained by the low degree of crystallinity and by the decrease in the entropy of melting of the crystalline phase. These F-containing polymers may form two types of crystalline structures. Polyesters. Heats of fusion were measured by DSC of linear aliphatic polyesters, and extrapolated to 100% crystallinity by using measured amorphous densities and redetermined crystalline densities (098). The melting process of poly(ethy1ene terephthalate) (PET) was described in terms of initial temperature, melting point, and height of DTA peaks (0228). The temperature a t which P E T began melting increased with increasing annealing temperature. The width of the melting range decreased with increasing pretreatment temperature. Roberts ( 0 1 9 8 ) reviewed literature values for the heat of fusion of P E T , and compared with values obtained using DSC and from melting point depression produced by dibutyl phthalate diluent. Roberts (0199) also observed an additional melting endotherm a t a temperature intermediate between the annealing temperature and the melting temperature. The magnitude of this endotherm increased with both annealing time and temperature and was found to be associated with decrease in the original melting endotherm and not with crystallization of amorphous material. Ikeda (0104) showed from DSC studies that the thermal behavior

of PET crystallized isothermally from the melt depends on the crystallization time. I n the initial phase of the secondary crystallization, the thermogram showed two or three peaks, and in the region of long crystallization time, it showed one or two peaks. Equations relating crystallization time, melting temperature, crystallization temperature, and lamellar thickness were obtained. Roberts (0197) ascribed the double melting peaks of P E T to lowmelting crystals melting and recrystallizing to ordered high-melting ones. Bell and others (018, 019, D l 7 4 ) , however, believed these t o be due to two morphological forms, I and 11, associated with folded-chain crystals and less perfect bundle crystals, respectively. The @relaxation a t -40" to - 60 "C, observed in form I only, was thus attributed to motions in the chain folds. DSC was employed to study the kinetics of crystallization processes of P E T over a wide temperature range (063). The rates of crystallization were found in agreement with earlier dilatometric measurements. P E T samples, crystallized under molecular orientation, mere examined by D T h and electron microscopy as a function of shear rate (0125). To avoid rearrangement during DTA measurements, the crystallized films were treated with 70% aqueous ethylamjne. Crystallization of amorphous unoriented P E T was induced by various organic liquids, and crystallinity was measured by DSC and ir (0144). It was reported that the crystallinity of polyester fibers determined by DTA method was 1 to 3y0 lower than that determined by x-ray diffraction (0113). PETsamples, amorphous by x-ray and density standards, showed a local order of ca. 1% crystallinity in the glass transition region as observed by DTA, when the samples were slowly cooled from above the glass temperature ( 0 1 2 7 ) . This order was presumed to be due to the formation of stable structures from individual chain segments through local alignment of chains similar to the concept of small crystallites in a fringed-micelle model. The helix-coil transition of poly-7benzyl-cglutamate in a mixed solvent system was studied by a modified DSC instrument (0120). The sensitivity was enhanced by additional amplification, and the sample was placed in sealable containers. The heat of transition was found to decrease substantially with decreasing molecular weight. DTA was used to control molding of polycarbonate (0129). Glass transition temperatures were determined rapidly and reproducibly. Relative molecular weight was determined in less than 20 minutes. The technique was also used t o monitor crystallinity, water

or zinc stearate contamination, and internal stresses. The adhesion of polyester hot-melt adhesives to epoxy resin coatings was affected by factors including T,, melting point, and crystallinity which were conveniently measured by DSC (0112). The bulk copolymerization of diethyl fumarate with styrene was investigated using DSC operated isothermally (0102). The heat of copolymerization decreased almost linearly with the increase in diethyl fumarate content in the copolymer. The curing reaction of polyester fumarate with styrene was also studied (0103). The change in rate of cure was followed over the entire range of conversion. The heat of polymerization of cold-curing plastics was measured by a DTA apparatus, which permits rapid comparison of new resins, fillers, and initiators with those in use for dental cements (0162). Curing of a polyester with rutile or anatase white filler in the presence of varying amounts of a peroxide catalyst was illustrated. Reactions during fusion of mixtures of polyesters and polyamides were studied by DTX ( D l 3 3 ) . Polyester-polyamide block copolymers may form by an ester-amide interchange reaction. A thermoanalytical study of crosslinked polyesters containing isocyanuric rings was reported ( 0 2 ) . Formation of additional cross bonds through vinyl groups in the preliminarily cured polymers was observed as exothermic effects. More extensive crosslinking was achieved by the use of an initiating system consisting of two peroxides and an activator. Polyacetals and Polyethers. The heat capacity, entropy, enthalpy, and free energy of tetroxan were measured using DSC, and the results were used to evaluate the entropy changes occurring in the system formaldehyde-trioxantetroxan-polyoxymethylene ( 0 3 7 ) . The heat capacity, entropy, and enthalpy of 1,3-dioxolan, 1,3-dioxepan, and their polymers were also reported (038,0 3 9 ) . An attempt was made to study the controversial polywater by DTA ( 0 4 7 ) . Glass transition temperatures were determined of a series of poly(o1efin oxide) and poly(o1efin sulfide) samples using DTA and dilatometry (0142). I n the poly(o1efin oxide) series, T, remained practically unchanged as the length of the pendent alkyl group was increased from methyl to n-hexyl. I n the poly(o1efin sulfide) series, T , decreased as the pendent alkyl group changed from methyl to ethyl. Replacement of ether oxygen in the polymer main chain by sulfide sulfur increased the T , value. Crystallization kinetics of poly(ethy1ene oxide) samples, fractionated and unfractionated, was studied using DSC (093). The effect of molecular weight was discussed.


0

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Thermally stable and chemically resistant epoxy polymers derived from phenylene oxides were studied by DTA and T G (0175). D T A showed significant differences in thermal behavior in catalyzed and uncatalyzed monomers. The uncatalyzed monomer showed fusion, thermal rearrangement, and degradation, whereas the catalyzed monomer showed only curing reaction. The effect of isothermal crystallization conditions on melting behavior of polyoxymethylene was studied by D T A (0205). Two melting regions were observed. The premelting region was attributed to a transition from ordered t o disordered spherulite structure. The effect of the previous history of a melt on crystallization kinetics of polyoxymethylene was studied by a modified DTA apparatus (D203). The over-all crystallization rate was inversely proportional to the melting temperature up to 210-20' or higher. The dependence of crystallization rate on melting temperature was attributed to seed formation. DTA was used to study the effect of plasticizers on thermal behavior of polyoxymethylene (0224). I n general, the addition of 30% or less of plasticizers did not increase the rate of melting, although the crystallization rate was reduced. Oxymethylene copolymers containing pendent ionic groups were examined by DSC and x-ray diffraction (D229). The introduction of ionic groups reduced crystalline order and thus increased transparency and ductility of the copolymer. Epoxy and Phenolic Resins. D T A was used as a simple, rapid method for determining the degree of hardening (crosslinking) of epoxy, phenolic, urea, and unsaturated polyester resins (0170). Uses of DSC were described for characterization of epoxy resins at various stages of fabrication (01). Studies of cure rate, extent of cure, softening point of the cured resin, and thermal stability of finished laminates were discussed. Apparent activation energy of the curing of glycidyl epoxy resins was obtained from DTA measurements (0124). ,4 DTA method for determining relative rates of different chemical reactions was outlined and applied to reactions between an epoxy resin and a series of rtromatic diamines (0221). Kinetics of the curing reactions of epoxy resin with aliphatic diamines and the reaction of phenyl glycidyl ether with butylamine as a model for the curing reaction was investigated by DSC under isothermal conditions (0101). The effect of graphite and kaolin fillers on thermal properties of hardened epoxy resins was investigated by DTA and ir spectroscopy (0216). Chemical reaction between the hydroxy groups of kaolin and the reactive groups of epoxy resin was observed during heating. Thermal degradation of phenolic 294 R

resins made from phenol, p-cresol, and bisphenol A was investigated by DTA, TG, and other techniques (0145). The methylene bridge was found stronger under nonoxidative conditions than the isopropylidene linkage. The result was somewhat affected by the degree of crosslinking. D T A and TG, combined with x-ray diffraction and GC results, were used to obtain detailed information on the reactions between phenol and hexamine, and Novolak resins and hexamine (0180). A twostage crosslinking reaction occurred when resins were cured with hexamine. Polyamides, Polyimides, and Other %Containing Polymers. The effects of drawing conditions and wet heat treatment on melting behavior of nylon 66 were studied by DSC and x-ray diffraction (0220). Double melting peaks were observed in a sample drawn below the glass transition temperature, whereas one broad peak, corresponding to the lower peak, was observed in the sample drawn a t higher temperatures. When the samples were annealed, the lower melting peak also appeared in the sample drawn a t higher temperatures. From the temperature shift of the lower melting peak upon annealing, the equilibrium melting point of nylon 66 was estimated a t 294'. According to Bell et al. (018, D19), the double melting peak in nylon 66 and other polymers could be explained by assuming two morphological forms, I and 11. Only nylon 66 films exhibiting form I melting behavior showed ymechanical relaxation a t -140'. Form I was converted to form I1 by annealing or by cold drawing. DSC was used to measure heat capacities of nylon 6 samples, which had been subjected to gamma radiation ( 0 7 4 ) . At doses up t o 200 Mrads the melting temperature decreased steadily with dose, while heat and entropy of fusion steadily increased. The equilibrium melting point of nylon 6 was estimated a t 250' f 2' from DSC measurements (0110). A crystalline transition from a to y phase by iodine treatment and a biaxial orientation in the drawn and heattreated samples were also observed. DSC and x-ray diffraction studies were made of drawn nylon 6 filaments annealed a t various temperatures and then methoxymethylated to various degrees ( 0 7 ) . The melting point inherent to the morphology of the polymer was obtained from samples in which the reorganization of defect crystallites during the course of thermal analysis was prevented by methoxymethylation of amorphous regions. The melting point thus obtained was in linear relation with the reciprocal crystallite size in the direction of fiber axis obtained from x-ray data and crystallinity. The extrapolation and the slope of this


linear relation gave a n equilibrium melting point of 245' for nylon 6. D T A of polycaprolactam modified by monourethanes showed a n inflection near the melting peak, but the melting point was the same as that of the unmodified polymer, indicating grafting occurring on the surface only (01%). The effect of mineral fillers on the degree of crystallinity of polycaprolactam was studied by D T A (0130). The decomposition of a cured polyimide resin was studied using simultaneous D T A and mass spectral analysis (0118). Decomposition kinetics and mechanisms were discussed for the polymer and selected model imides. D T A and T G results were presented for benzheterocycle-imide and -amide copolymers of limited order (0189). Copolymers based on salts ofunsaturated lactam compounds were studied by DTA and T G (D141). The chain propagation mechanisms of radiationinduced polymerization in the solid state were studied by DTA of the postpolymerizations of tetroxocane and acrylamide (0176). A polyurethane adhesive was studied by D T A a t cryogenic temperatures (0196). Aglass transition temperature at 235 O K was obtained. Thermal stabilities of polyazines and derived polystilbenes were studied by DTA, TG, and ir (045). Calorimetric and kinetic data on the decomposition of polyazines were discussed. A mechanism for the condensation of urea-HCHO resins was developed by DTA and T G studies (029). DTA curves showed a peak a t 80' or 90' to loo', corresponding to partial liquefaction and melting of the monomers with a n irreversible chemical modification, and a second peak a t 120' corresponding t o condensation with the loss of water and formaldehyde. Cellulose, Silk, and Related Materials. Linter, gel, and amorphous cellulose were studied by DSC and ir (088). Glass transition temperatures were observed in the range of 55' to 85', depending on the type of cellulose and relative humidity. Exothermic peaks observed in the range of 80' to 180' for gel and amorphous cellulose were attributed to the increase of Hbonding. Thermal degradation of cellulose, hemicellulose, and lignin was investigated by DTA and TG, and activation energies for the decompositions were calculated ( 0 1 9 3 ) . DSC was used to determine the specific heat of wood and bark (0194). The variability due to position in the tree and geographic location was presumed to be due to variation in the proportions of cellulose, lignin, and extractives in the wood. The effect of wood preservatives on thermal decomposition of wood mas studied by D T A (D139). The water-borne preservatives had a n accelerated action on thermal decom-

position of wood. The peak temperatures in the oil-borne preservatives containing organic chlorine compounds were increased markedly compared with the untreated wood. D T A studies, made on various types of regenerated cellulose, showed a weak endotherm a t 110-25" due t o evaporation of moisture, an endotherm a t ca. 312" due to dehydration of cellulose, and in some fibers an exotherm due to formation of crosslinks ( 0 6 ) . Above350°, the shapes of the D T A curves were all different and dependent on the structure of the fibers. DTA and T G studies of flame-retardant rayon fibers indicated that thermal degradation of these fibers began a t a lower temperature than that of the untreated control, evolved smaller amounts of flammable volatile materials, and left larger amounts of residue (D77). The exothermic peak area was smaller for the flame-retardant fibers than for the control. Phase transitions of cellulose, cellulose diacetate, and cellulose triacetate were studied by DTA (02.4). Endothermic and exothermic effects were used to study the separation of water, heat of fusion, and transition temperatures for these materials. DSC determined the main melting temperature of cellulose acetate to be 230" f 2", and also showed a secondary peak a t 217" (0136). Heat of fusion values were determined for various sample forms. Thermal stability of cellulose acetate was determined by D T A ( 0 2 5 ) . I t s decomposition temperature was decreased by acid treatment, and increased by introduction of metal cations. The glass transition temperature of cellulose nitrate cannot be determined, since it is higher than the decomposition point. However, addition of nitroglycerin as a plasticizer allowed determination of T, of cellulose nitrate over a wide composition by DTA (Dal.4). When the amount of nitroglycerin in the mixture exceeded 30 mole yo,its compatibility limit, a second transition point appeared. DTA of silk fibers showed a n initial endotherm a t ca. 100" due to evaporation of adsorbed water and a second endotherm a t 305" to 350" due to destruction of @-configuration (D109). The effect of tin salt or complex treatment on silk was reported (0156). Other DTA studies were made on keratin fibers ( 0 6 7 ) , synthetic polypeptides ( 0 7 9 ) , oxystarch ( 0 1 7 7 ) , and collagen (086). Miscellaneous Polymers. T h e effect of high pressure on melting and polymerization of sulfur was investigated using DTA, x-ray, and optical methods ( 0 2 2 6 ) . At least four different liquid fields were identified. Thermal properties of organic polysulfide polymers with uniform repeating units

were studied by D T A (D66). The glass transition temperatures decrease as the sulfide portion increases from disulfide to tetrasulfide. The melting point of the polymers decreases as the polysulfide chain length increases. There is a trend in the temperature a t which rapid decomposition starts in the direction of lower temperatures with higher sulfur ranks. The kinetics of thermal degradation of polysulfone was studied using DSC (D147). Phase transitions of poly(dimethy1siloxane) were studied by DSC (01.46), which showed glass transition a t - 123", cold crystallization a t -95" to -65", and two melting peaks a t -37" and -45". The heat of fusion was 325 cal per mole. The two melting peaks were attributed to two crystalline forms ( D I S I ) . A decrease in crystallization temperature increased the proportion of the high-melting form. DSC was used to study the effect of interfacial energy on heterogeneous nucleation in the crystallization of poly(dimethylsiloxane) (023.4). The quenching rate necessary to supercool poly(dimethylsiloxane) was determined using DTA techniques ( 0 9 4 ) . No supercooling was observed for a cooling rate of 1.6" per second, and 85% supercooling was found for a 52" per second cooling rate. Evidence was also presented that the crystals in poly(dimethylsiloxane) consist of two forms. The polymerization of crystalline benzyl tosylate to polybenzyl was investigated using DSC, ir, photomicrography, and molecular weight measurement (01.48). DSC was effective in measuring induction periods and rates of polymerization. THERMOGRAVIMETRY

Reviews on the use of thermogravimetry (TG) for analysis of polymers have appeared (V109, V128). Methods of characterizing polymers by degradation were reviewed by Smith (Vf12). Teetsel and Levi ( V 1 f 6 )presented their third literature survey on thermal degradation, thermal oxidation, and thermal analysis of high polymers covering a period from about March 1965 to January 1969. Since thermogravimetry is mainly applied to study of thermal stability of polymers, recent books and reviews on thermally stable polymers are useful for background information (VS9, V65, V69, V72, V98, V99, V127).

Relation of thermal stability and polymer structure has been discussed (V23, V27, V6.4, V 7 1 ) . The mechanisms of pyrolysis, oxidation, and burning of organic materials were the topics of a recent symposium ( V 8 9 ) . Degradation of high polymers was reviewed by Nakamura ( V 8 7 ) and Jellinek ( V 6 2 ) . Other reviews on deg-

radation of polymers were devoted to polyolefins (VIOW), halogenated polymers ( V S I ) , poly(viny1 chloride) ( V 9 4 , sulfone polymers ( V I @ , siloxane polymers (7r7), and cellulosic materials (V107). Reviews on stabilization and aging of polymers have appeared (V.47, V90, V106, V118). Recent advances in the development of flame-retardant polymers were described ( V 2 8 ) . Smilek (V110) characterized the thermal stability of polymers by the temperature corresponding to half of the weight loss in a given degradation process. For more detailed characterization, the temperatures of start and end of the degradation and of the inflection point were used. Danilova et al. ( V 9 5 ) demonstrated the autocatalytic nature of thermo-oxidative breakdown of elastomers. Substituents and molecular configuration showed a remarkable influence on the degradation curves. Davtyan et al. ( V 2 6 ) derived the relation between thermal stability and the average degree of polymerization of a copolymer composed of a thermally seable and a thermally unstable polymer section for the most probable distribution of links in the copolymer chain. King and Corbett (V68) used a quartz cryst,al microbalance to study relative oxygen absorption and volatility properties of submicron films of asphalt. Isothermal and dynamic T G methods for kinetic studies of polymer degradation were compared by several workers (V4, V79, V 8 f ) . Seemingly, the dynamic methods provide more rapid measurements over a wide temperature range, whereas the isobhermal technique is more reliable and versatile. Difficulties encountered in use of T G methods for kinetic studies were discussed by Farre-Rius et al. (V35). T G can be used to determine the activation energy and the rate constant of a degradation reaction, when only one mechanism is involved or several mechanisms occur simultaneously with a relative extent which does not depend much on the temperature. Smith and Youren ( V l IS) indicated that, t o obtain meaningful kinetic parameters from T G results, strict control of environmental conditions is required. Experimental results were given for ethylene-propylene copolymers, PVC and neoprene in admixture with ferric oxide, and other materials. Audebert and Aubineau (VS, V 5 ) found that results obtained by most proposed dynamic T G methods in the literature for determining activation energy of polymer degradation depended to a large extent on the mode of polymer degradation, and only those based on the shift of thermogram obtained a t different heating rates were independent of pyrolysis mechanism. Schneider (Vf0.4)discussed the inter-


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dependence between observed effects of degree of conversion and heat,ing rate on the apparent a ~ t ~ i v a t i oenergy n of polymer degradations occurring under dynamic T G conditions. It is possible to deduce the activation energy of initiation by extrapolation of the obtained apparent activation energies. A simple, relative method for thermal stability evaluation of polymers was developed on the basis of slope measurements of the T G curves. Broido (VIS) described a simple, sensitive graphical procedure of treating T G data. A ratio method was reported of analyzing T G results for which the power-model kinetic equation was assumed to hold (V85). New methods for evaluation of kinetic parameters obtained by a n y thermal technique were described by Friedman (D69), whereby all kinetic parameters were obtained from two or three points 011 a single thermogram. Digit,al comput'ers have been used for kinetic analysis of T G data obtained either from isothermal or programmed heating conditions (VS4, V41, V4S, V44, V53, V56, V9S). Not only kinetic parameters are computed, but thermograms are const.ructed from computer codes for comparison wit,h the experiment'al. Siniult'aneous TG-DTA measurements in connection with gas analysis by G C or %IS Ji-ere discussed, and demonstrated with inorganic materials (8124). Possibilities of different t,ypes of instruments for simultaneous TG-GC were discussed (G18). A coupler for TG-GC was reported, and used for characterizat'ion of several polymer systems (821). A technique combining T G with 11s provided rapid and quantitative results for the parameters of thermal degradat,ion of polymeric materials (NQS). T G is now being used routinely in polymer research laboratories for evaluation of new products and for characterization of polymer st,ructures and formulations. T G d a h reported in the lit'erature are in such a vast amount that it is impractical even t'o tabulate them. In t,he following sections only unique applications are selected for review according to polymer types. Polyolefins and Fluorocarbon Polymers. The mechanism of bond format,ion between polyethylene (PE) and iron and between PE and talc was studied by T G (V67). Thermal oxidation of P E was activated by the surface of iron particles. A strong interaction of adsorption or chemisorption nature between PE and metal was suggested. -1multiple isothermal degradation method for determination of vinyl acetate content of ethylenevinyl acetate copolymers was essentially a modified T G procedure to handle a large number of samples simultaneously (V66). The thermal stability of et'hyl296 R

ene-N-vinylcarbazole copolymers was determined by T G and D T A (VI). The copolymers showed no crystallinity, and the thermal stability increased with N-vinylcarbazole content. The amount of oil, polymer, carbon black, mineral filler, and ash present in a vulcanizate such as butyl rubber, and the type of carbon present, were determined by T G procedures (V82, V8S). The thermal stabilities of a series of hydrocarbon condensation polymers made by the Richards synthesis were examined using TG, and the stabilities of specific interunit linkages were discussed (V80). The thermal stability of copolymers of TFE and perfluoroalkenes was assessed by T G and copolymer compositions were determined by pyrolysis-GC (GS5). For a particular copolymer, the thermal stability decreased with increasing number of side chains. Copolymers containing the same proportion of side chains of different lengths showed a marked decrease in thermal stability on going from CF3 to C2F5,but further increase in size had relatively little effect. Copolymers of tetrafluoroethylene (TFE) and 3,3,4,4,5,5,5-heptafluoro-lpentene were studied by TG, DSC, and ir (Vf5). The glass transition temperature of the copolymers decreased and thermal stability increased as the TFE content increased. Copolymers of TFE and perfluoro(methy1 vinyl ether) were studied by TG, DTA, dilatometry, and ir (V8). These copolymers showed both glass temperature and thermal stability increasing with increasing TFE content. PTFE was selected for kinetic studies by T G in many cases (VS, V5, V.43). Appreciable heat transfer effects were observed in T G studies of PTFE degradation (VIOO). Vinyl a n d Acrylic Polymers. The thermal degradation of poly(viny1 chloride) (PVC) was investigated by TG, DTX, and dehydrochlorination measurements (V52). The degradationrate decreased with increasing degree of polymerization and chlorine content. The activation energies of the degradation of PVC and of chlorinated PVC were determined. PVC samples containing structural defects were studied by TG, ESR, and conductivity measurement of HC1 evolution (V.49). Orders of thermal stability related to the structural entities, such as end groups, branches, olefins, and oxygenated segments, for the initiation of decomposition and for the chain lengths of HC1 evolution were established. The effect of stereoregularity of PVC on its thermal stability was determined by T G analysis of samples with varying degrees of syndiotacticity (V86). PVC with the highest syndiotacticity had the highest activation energy forthermal


degradation. A new macromolecular model compound for branched PVC was synthesized by copolymerization of vinyl chloride with 2,4-dichloro-1pentene, and its composition and properties were studied by derivative T G (DTG), ir, and phenolysis reaction (V17). It was concluded from this study that there were no chlorine atoms a t the branching sites in PVC. T G studies of decomposition of PVC below 155°C showed that degradation was enhanced by irradiation with 1-Mev electrons (VIOS). Later stages of isothermal weight loss for thermal and radiolytic decomposition followed 3/2order kinetics, suggesting a similar reaction scheme. A free radical mechanism for dehydrochlorination involving allyl and polyenyl radicals was postulated. Mastication of PVC in presence of other monomers such as styrene, acrylic esters caused important changes in thermal stability of the polymer as shown by TG, DTA, and ir studies (V84). The improved stability was attributed to a n improved crystalline organization. When mastication caused polymerization of the monomer such as methyl methacrylate, degradation of the PVC part and depolymerization of the grafted part occurred simultaneously, supporting a radical mechanism for the thermal degradation of PVC. Schneider and Vasile (Vf05) investigated the dependence of thermal stability and size of the dispersed particles as a function of composition of binary and ternary mixtures of PVC, poly(viny1 acetate) (PVAc), and a copolymer of PVC and PVhc, using T G and polarized light examination. It was possible to distinguish two or more regions of optimum compatibility, characteristic of different compositions of a mixture of polymers. Chifor (V20) characterized PVhc samples obtained by suspension polymerization by T G and DTA. Three stages of decomposition were observed, and the activation energy of the first stage of decomposition was obtained. A T G study of the dehydration of poly(acry1ic acid) was reported (V22). Loss of adsorbed water, dehydration, and decarboxylation were observed a t temperatures below thedepolymerization temperature. The thermal degradation of polyacrylonitrile (PAN) was studied using T G , DTA, and thermal volatilization analysis (V.48). The effect of experimental conditions on the results was examined. The very sharp exothermic reaction below 300°, corresponding to the thermal polymerization of nitrile groups, was removed completely by isothermal aging below ZOO", during which treatment there was negligible weight loss. Oxygen was shown to have marked inhibiting effect on the exothermic reaction. The development of color, in relation to the

thermal analysis curves, and the reactions occurring a t higher temperatures were discussed. Effects of molecular weight and degree of elongation on pyrolysis and carbonization of PAN were investigated by T G and D T A (VI 15). An increase in molecular weight of P A N shifted the maximum gas evolution region to lower temperatures, and decreased the total amount of volatiles and the heat of reaction. On the other hand, oriented P A N fibers had higher gas evolution temperatures but approximately the same heat of reaction as the unoriented fibers. Polyacetals, Polyethers, and Polyesters. Thermal degradation of polyformaldehyde diol, polytrioxane, polyformaldehyde diacetate, a trioxanedioxolane copolymer, and several model compounds of the type MeO(CHZO),Me was studied b y T G and DTA (Till). Effects of molecular weight and structure of the polymer on degradation kinetic parameters were discussed. The kinetics of the thermal decomposition of poly(oxymethy1ene) dihydrate was investigated by TG, ir, and viscosity measurements (V18). The polymer decomposed in two steps in the presence of oxygen or in a n inert atmosphere, owing to a real scission of the initial macroradical. This scission led to a more thermally stable polymer with a lower molecular weight, in which the original terminal O H groups were replaced by CHO groups. Ingraham and Fraser ( V 6 l ) reported that the most significant factors in determining the rate of unzipping polyoxymethylene were particle size, temperature, and the partial pressure of the product gas in the sweeping atmosphere. When pelletized samples of polyoxymethylene were depolymerized, it was necessary to introduce a surface roughness factor into data normalization procedure t o obtain a correct resolution of the data. A series of polymers based on the reaction products of bis-(a-chloro-ptolyl) ether, formaldehyde, and phenols was studied by TG, and the char yields of these polymers were determined (Vl2S). The results indicate t h a t the char yield is influenced by the degree of crosslinking, and t8hat the char structure still possesses the phenyl ether unit. The high char yield and char stability of these systems suggest potential ablative applications. T G procedures were used to obtain kinetic parameters of intermolecular polymerization of aldohexoses ( V 7 8 ) . The initial 60% of the reaction, the loss of reducing end groups, was bifunctional and self-catalyzed, and followed a t hird-order kinetics. The thermal decomposition of poly(ethylene terephthalate) was studied by T G , and the activation energy was obtained in both air and nitrogen ( V l 2 6 ) . The various parameters used

to characterize the decomposition were found t o be independent of polymer molecular weight and preparation method. Golfarb and McGuchan (V@) studied thermal degradation of aromatic and semiaromatic polyesters. Poly(hexamethylene terephthalate) decomposes by the mechanism observed for aliphatic polymers-via., random scission and subsequent reaction of the olefinic and acid end groups. When the acid part is aliphatic as in poly(p-phenylene succinate), etc., the polymers are less thermally stable initially than comparable aliphatic polyesters. The degradation mechanism is complex and involves crosslinking. Fully aromatic systems such as poly(p-phenylene terephthalate), etc., are more thermally stable, especially the all-para systems. Features such as initial low activation energy processes, complex rate curves with several components, and char formation at higher temperatures imposed difficulties in kinetic analysis of the degradations by dynamic T G methods. Learmonth et al. (V76) described the effects of halogenated additives on the pyrolytic decomposition of polyesters in his series of publications on flammability of plastics. The polyesters were subjected to candleburning test, ignition test, DTA, and T G analysis. The thermograms indicated five separate zones. Use of an additive decreased the total loss in weight, and the difference occurred by the end of t h e 2nd stage of pyrolysis. The addition of a flame-retardant also increased ignition temperature above that of the standard resin. Reactions between antimony trioxide and organic halogenated flame retardants with reference to their performance jn a crosslinked polyester resin were described (V76). Epoxy and Phenolic Resins. T h e effect of curing temperature on thermal degradation of an epoxy resin was investigated by both isothermal and dynamic T G ( V 7 7 ) . The stability increased with increasing curing temperature as a result of higher degree of crosslinking. The thermal properties of a number of nitro-substituted and analogous nonnitro-substituted epoxide polymers were investigated by T G ( V S S ) . Dramatic increases in char yield and decreases in maximum rate of weight loss were observed for the nitrosubstituted systems compared to their nonnitrated analogs. The sample size and heating rate employed had pronounced effects on the amount of char formed during thermal degradation. Polymers derived from resorcinol diglycidyl ether cured with several bicyclo Diels-Alder anhydride adducts were investigated (V37). Increased char yields and decreased rates of weight loss were observed for these systems as compared to polymers

cured by Diels-Alder adducts from acyclic dienes. The unique capabilities of derivative T G (DTG) were demonstrated in studies of an epoxy resin and a phenolic-silica prepreg (V46). The ratio of curing agent to epoxy in a cured epoxy adhesive and thus the mixing ratio throughout the material were determined. D T G also showed differences in phenolic-silica prepregs having similar volatile and resin contents. The degradation of phenolic resins was studied by T G and continuous ir analysis of the gaseous product's during pyrolysis ( V 4 0 ) . The T G curves distinguished the resins as a function of their chemical composition, nature of the cat,alyst, and crosslinking. Learmonth el al. (V74) compared several D T A techniques for studying osidative and nonoxidative thermal degradation of phenol-HCHO resins, and found T G more useful than DTA for such st.udies. Parker et al. (VYS) esplained the char formation of phenolic resins and related polymers in terms of a general pyrolysis mechanism. Based on this mechanism, an analysis was developed which predicts, from molecular structure, the observed T G char yields accurately over a range from 11 to 65% yield. T G studies were made of t,he stabilities of resins made from diphenylolpropaae and HCHO (V7S). These resins were shown to be less thermally stable than phenol-HCHO resins. However, the stability of t h e resin was greatly improved, when t'he aliphatic H atoms of dipheii~-lol~)ropane were ent,irely replaced by F atoms. The addition of PTFE to phenolic resins inhibited degradation to a significant extent. Kinetic studies were reported of phenolic-carbon, -graphite, -glass, and -nylon composites, and computers were used to process the T G data (116, VS4, V45, V S S , V 1 2 l ) . Polyamides, Polyimides, and Other N-Containing Polymers. Goldstein (V45) postulated a multistep kinetic process to describe the pyrolysis of nylon 66, a phenolic resin, and their composites, and derived the kinetic coefficients from T G data using three correlation techniques. Hender (V53) described T G data reduction methods using digital computers for simulation of degradation of plast,ics such as nylon 66 fabric and nylon-phenolic composites. Goldfarb et al. (V4S) reported a method of obt,aining kinetic parameters from dynamic TG, and handling T G data by computer, and demonstrated t,he technique with degradation studies of nyln 610, PTFE, and poly( 1,4-phenylene sebacate). Olson (V9S) reported a computer method for T G of ablative plastic materials, and illust,rated t,he technique with analysis of a polyimide resin. The empirical Arrhenius parameters

ANALYTICAL CHEMISTRY, VOL. 43, NO, 5, APRIL 1971

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were derived from a computer program using the experimental thermogram, and a magnetic tape-plotter was used to reconstruct the thermogram. T G and DSC studies of poly(amide-imides) showed that the cyclization temperature of aromatic poly(amide-amic acidesters) was the same as that of poly(pyrome1litamic acid ester) and was independent of the amount of amide component. I n general, the stability of poly(amideimides) increases with increasing imide content (V92, V f f 7 ) . The thermal stabilities of imide-pyrrone copolymers in air also improve with increasing pyrrone content ( V f 0 ) . As shown by T G and DT.4, a polyimide devoid of hydrogen and other pendent groups exhibited extraordinary high temperature oxidative stability ( V 5 5 ) . The thermal stability of piperazine copolyamides was studied using TG, DTA, and DSC ( V f 6 ) . Rates of volatilization were found dependent of molecular weights of the block copolymers. A comparative T G study of polyimidazopyrrolones showed the thermal stability of the polymers increasing with increasing carbonyl groups within the polymer repeating unit (V68). T G studies of alicyclic polybenzoxazinones showed higher thermal stability for polymers from the trans-1,4-isomer than polymers from the cis-1,4-isomer (V60). The correlation of molecular structure and geometry of dibenzoylbenzenediamine polymers with their thermal stability and solubility was discussed on the basis of T G data (V122). The thermal degradation of nine structurally related polyquinoxalines was systematically investigated, using simultaneous TG-DTG-DTA and thermobarometric analysis in conjunction with mass spectrometry and pyrolysisgas chromatography ( V I % ) . The relative oxidation resistance of these polymers was controlled by two opposing structural effects. Phenyl side group substitution in the heterocycle improved oxidative stability, while the introduction of the ether-oxygen into the main polymer chain produced a negative effect of equal magnitude. Investigation of the thermal degradation of poly( 1,4-phenylenephthalidylidene-1,4phenylene - 1,3,4 - oxadiazole - 2,5diyl) by TG, DTA, ir, viscosity, and molecular weight measurements showed that crosslinking occurred, and thermal decomposition began with homolytic cleavage of the lactone ring and subsequent decomposition of the oxadiazole ring ( V f O f ) . The kinetics of degradation of poly(bisbenzimidazobenzophenanthroline-dione) was studied by TG, and experimental data were processed by a computer ( V 4 1 ) . A number of polymeric azomethines were investigated to determine the effect of char yields by deliberate 298R

introduction of crosslinks in their structures (V.24). The yield of char as determined by T G a t various temperatures increased with the introduction of crosslinks. Relation of chemical structure of polycyanurates to thermal stability was reported (V88). The thermal characteristics of ten rigid urethane foam formulations were determined using TG, DTA, TMA, and long-term heat-aging tests ( V f11). The results indicate that the polymeric isocyanate foams have better thermal stability than the toluene diisocyanate materials. T G and DTA were used to study flame-retardant properties of flexible urethane foams ( V 9 S ) . Thermal degradation of phosphorus-containing polyurethanes was shown to occur by an initial first-order process, releasing mainly carbon dioxide (V3.2). The activation energies for the maximum rates of weight loss were determined. Cellulose. The decomposition of cellulose, in the absence and presence of additives, was studied by simultaneous TG-DTA (Vbf). The over-all process was endothermic in untreated cellulose and i n the presence of acidic catalysts, but changed to an exothermic process in the presence of strong bases. A T G study of the isothermal kinetics of cellulose pyrolysis showed a pseudozero-order followed by a pseudo-firstorder (V19). Kinetics of pyrolysis of cotton cellulose and cellulose acetate with different degrees of substitution was studied by T G and DTA (V97). The range of decomposition temperature of cellulose decreased and the stability of the polymer increased with increase in degree of substitution. The thermal degradation kinetics was examined for several celluloses, including cotton, a-cellulose, viscose rayon, and cellulose, using dynamic T G (VS7). The degradation mechanism was apparently the same for all four types, although some effect of the structure of cellulose on the mechanism was observed. The thermal stability was lower for the amino celluloses than for the parent celluloses ( V 6 8 ) . Pyrolytic degradation of mercerized cotton treated with acrylonitrile and HCHO showed that the thermal stability of cotton below 500' was not improved by cyanoethylation and crosslinking ( V 9 ) . This was better illustrated by combined TGDTA than by ir spectroscopy. Cellulose decrystallized by swelling in liquid ammonia gave a simpler T G curve than that obtained from untreated cellulose as a result of a decrease in the intermolecular char-forming reactions (Vf 4). A graphical procedure was used to make a linear plot of the thermogram which resolved the over-all curve into two components. T G and DSC investigations were


made on cotton cellulose in the presence of both flame-retarding and non-flameretarding compounds, and evaluated quantitatively for enthalpy, activation energy, and char formation (V114). Activation energy generally decreased with increasing flame retardance. The ability of phosphorus-containing and nitrogen-containing compounds to act as flame retardants for cotton cellulose was investigated using TG, DTA, and flame tests ( V 5 4 ) . The effectiveness of either organo-phosphorus compounds or nitrogen-containing compounds correlated with the changes in decomposition behavior observed by DT-4. However, the presence of both nitrogen compounds and organo-phosphorus systems enhanced their ability to retard flame propagation but did not produce significant changes in the pyrolytic thermogram obtained by DTA. I n this respect, more conclusive evidence for a chemically based phosphorusnitrogen synergism was obtained by the use of TG. Thermal degradation of cellulose phosphate and ammonium phosphate-containing cellulose was studied (V59, V6O). Analysis of T G data indicated a different kinetics of degradation in the two systems. Miscellaneous. T G studies of poly(dimethylsiloxane) degradation in vacuo indicated a two-stage process ( V 8 ) . The first stage mechanism was explained as the destruction of the S i 0 bond and as the stepwise depolymerization of siloxane chains from their ends by the action of the OH groups with crosslinking occurring simultaneously. The second stage was accompanied by a series of side reactions and was dependent on the crosslinking extent. Kinetic studies of thermal degradation of poly(dimethylsi1oxanes) and polysiloxanes were reported ( V I f 9, V l d 0 ) . The degradation products were identified by GC and ir, and molecular weight distribution studies were made of the residues by GPC. Effects of different substituents on silicon and in the main siloxane chain on degradation were discussed. Thermal stability was studied of poly(dimethylsi1oxanes) containing P, Ai, Ti, or B and P in the chain ( V 9 I ) . The hetero atoms reduced weight loss of the polymer on heating in vacuo in the following order: B and P = Ti > ill > P. The kinetics of decomposition of the polymer was discussed. The presence of hetero atoms decreased the rate of Si-0 bond breaking. The oxidative thermal degradation of poly(pheny1butox.y-siloxanes), containing various numbers of bound OBU groups, was studied by T G and DTA ( V f08). The degradation occurred in three stages: the initial stage involved vigorous exothermic oxidation, breakdown of OBu, and formation of OH groups bound to the Si atom; the second

stage involved thermal condensation of OH groups to give new siloxane bonds available for further crosslinking; and finally, the phenyl groups bound to the Si atom were oxidized and the entire siloxane system was converted to SiOp. Comparative tests on the thermal stability of a large number of openchain and cyclic silazanes and silylamines showed that only the small fourmembered cyclodisilazanes were stable up to 500 O C (VS6). Accordingly, linear Si-N polymers and oligomers with cyclodisilazane units built into the chain were synthesized and their thermal stabilities determined. T G , DTA, and ir studies were made to determine the thermal behavior of structurally related polymers having a carborane nucleus in the repeating unit, some of which also contained phthalocyanine rings (VSO). A polymer with dimethylsiloxane units exhibited higher thermal stability than similar products having urethane groups in their molecules. The urethane polymers derived from tolylene diisocyanate were less thermally stable than analogous materials synthesized from methylenebis(p-phenyl isocyanate). The relative order of thermal stability of these materials followed that of more conventional polyurethane elastomers. The thermal behavior of poly(p-xyly1ene-mcarborane) was also studied by TG, DTA, ir, MS, and GPC (V29). The process of degradation was found to parallel closely the thermal oxidation of polybenzyl and other polymers with readily activated methylene groups. The preparation of boron nitride fibers by heating boric oxide in an ammonia environment was readily followed by T G ( V S S ) . The boric oxide fibers and ammonia reacted initially to form an addition compound, (B2O3).NHJ, probably consisting of boroxine rings coordinated with ammonia. Factors affecting the nitride-forming reaction included fiber diameter, ammonia concentration, time, and temperature. The thermal degradation of coordination polymers with a basic inorganic chain was studied by dynamic T G (V70). The metal poly (diphenylarsenates) showed the following order of decreasing stability: Cr > Fe > Mo > W > Mn. The poly(dipheny1 phosphinates) were more stable than the poly(dipheny1 arsenates). The most stable coordination polymer was M n poly(p-toluene sulfonate), stable to 520’. GAS CHROMATOGRAPHY

General books on gas chromatography (GC) published during this biennium include comprehensive texts written by Littlewood (G95), Schupp (GlSg), and Szepesy (G144), and those edited by Harbourn and Stock (G60) and Sakodynskii (GlSS). Several less compre-

hensive books (G71, GlOS, G125, G151) have also appeared, mainly devoted to teaching and training purposes. This journal continues to present comprehensive biennial reviews on fundamentals of GC (G75). The G C Discussion Group of the British Institute of Petroleum (G81, G82a) continues to edit excellent annual volumes of G C abstracts, which began with the 1958 issue. Meanwhile, the Preston Technical Abstracts Co. (G128a) has changed its G C abstracts from a pucnhed card system to booklet and microfilm forms. A useful directory of manufacturers and sources of G C instruments and accessories has been published annually (G74). A computer-based retrieval system of the GC literature has been updated through 1969 (GlOla). Books and reviews devoted to specific topics in GC include those on interfacing GC with other techniques (GCO), identification techniques in GC (G89), analysis by reaction GC ( G l d ) , gas adsorption GC (G78, G79, GlSra), GC instrumentation (G86), programmed temperature (G60a), choice of detectors (G29), $election of stationary phases (GlZsb),performances of columns (G56), and process control by GC (G104). Beroza (G15) discussed determination of chemical sturcture of organic compounds a t the microgram level by GC, covering C-skeleton techniques, instantaneous hydrogenation, locating double-bond positions, reaction loops, etc. The use of GC for analysis of polymers was briefly discussed by Mlejnek (G108). A comprehensive review of the same subject was presented by Stevens (G1S9) in his book on “Characterization and Analysis of Polymers by Gas Chromatography,’’ which includes chapters on characterization of polymers by thermal degradation and chemical degradation, analysis of volatiles in polymers, analysis of monomer purity, and various other techniques. A GC method has been reported (G2) for evaluation of thermal stability of polymers by concentrating the volatile degradation products formed during a certain period of time, followed by batch analysis. The method was tested with acetylated polyformaldehyde and polyesters. Water-absorption isotherms of textile fibers were obtained by using a GC technique with intermittent injection (GS7). The method was applied to poly(ethy1ene terephthalate), poly(vinyl chloride), and nylon 66. Guillet and coworkers (GSSa, G54, G88, G1S7) used a GC technique to study polymersolute interactions, and obtained information on glass transition temperatures and crystallinity variations with temperature. The technique involves sending a pulse of solute molecules or “molecular probes” along a narrow tube containing the polymer to be investi-

gated as the stationary phase. An interaction with the polymer affects the forward motion of the probe molecules to an extent depending on the nature of the interaction and the structure of the polymer. The molecular weight distribution of poly(ethy1ene glycol) products was determined by fractionation of their volatile derivatives by GC (G23, G24). A new GC technique for determining molecular weight up to 400 was reported (G125a), utilizing two gas density balances with two different carrier gases. An instrument based on this principle has been revealed (G25a). GC techniques were also used to determine permeability of various polymeric films to permanent gases or volatile organic compounds (G50, Glad, Gl28). A GC method was reported of determining the active centers in cationic polymerization, and applied to polymerization of dioxolane, trioxane, and formaldehyde (G66). I n this method, polymerization was terminated by adding sodium alkoxide to form alkoxy end groups which, after acid hydrolysis of the isolated and purified polymer, were determined by GC analysis of the produced alcohols. Kinetics of polymerization of propylene sulfide (G6S) and copolymerization of acrylonitrile with styrene or methyl methacrylate (G55) was examined by GC. Many workers used GC to obtain reactivity ratios of the monomers in their copolymerization studies (G72, G94, G98, G I O I , G167).

The coupling of GC to M S has become increasingly popular. Various interfacial systems used in ills analysis of GC effluence were reviewed ( M 7 9 ) . Improved molecular separators were reported (G52, G96, G97, X10, M48, M62, M66, ,2168, M86). An ion interface between GC and MS, the Plasma ChromatographTJI, was described ( M 1 7 ) . Bergstedt and Widmark (GlS) used repetitive scanning of a small range of the mass spectrum to improve sensitivity. Coupled GC-MS and a computer for data processing constitutes a powerful tool for analysis of polymer systems ( M 7 , MSS, M51, M 7 2 ) . I n most applications the polymer is first pyrolyzed, and the volatile products are analyzed by GC-MS (G76, X 3 2 , X 4 4 , M57, M74, M89). X technique using controlled thermolytic dissociation has been described for identification of G C effluence, by characterization of small molecules present in the thermolysis products of the parent molecule (G63, G91a). An instrument based on this principle has been marketed (G255b). Combination of paper or thin-layer chromatography with GC (G69, X 5 6 ) has shown unique applications in detecting trace impurities, especially in the plastics industry. A coupler for TG-GC has been reported, and applied

ANALYTICAL CHEMISTRY, VOL. 43, NO. 5 , APRIL 1971

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to characterization of complex polymer systems (G26). The possibilities of different types of instruments for simultaneous T G and G C has been discussed (Gf8 ) . Microsampling techniques for combined GC and high-resolution K M R have been described, and the spectra of less than 1-pl samples can be routinely recorded with the reported microcell and a spectrometer operating in the internal lock mode and a t 100 MHz without time averaging (Gf06). The increasing demand for accuracy, reliability, and time and labor saving has led t o the rapid growth of GCcomputer systems. Recent developments can be best summarized in a series of papers presented at the Symposium on Computer Automation of Analytical Gas Chromatography, held during the 158th American Chemical Society meeting in New York City, September 8 to 12, 1969, and later published in the Journal of Chromatographic Science (G9, G22, G51, G f f7,G f 29, G f49, G f 5 0 , G f 7 2 ) . Similar papers have appeared in other sources (G8, G f 0 , G f66). Existing Volatiles in Polymer Systems. G C procedures have been reported for determination of residual monomers in various polymers. Reichle and Tengler (Gf3O) compared three different GC procedures for quantitative determination of residual acrylonitrile in polyacrylonitrile-namely, releasing the monomer by heating the sample in a sealed ampoule, dissolving the sample in D b l F , and extracting the monomer with ether. While the heating method showed better detection limit, results of all three methods agreed with one another. Most workers used suitable solvents to dissolve the polymer samples before G C analysis of the monomers in solution, including polystyrene, a-methylstyrene-acrylonitrile copolymers, and a-methylstyrene-acrylonitrile-methyl methacrylate copolymers (G80), nylon 6 ( G f 7 3 ) ,and polyesters (Gl07, G f 0 9 ) . The individual contents of cycljc monomer and oligomers in polyamides were determined by reducing them to the corresponding cyclic amines followed by GC ( G f f 2 ) . Free diphenyl oxide in resins was also determined (GI%). A simple GC technique, with the sample contained in a disposable glass tube and heated in a closed loop before injection, was used to determine moisture content in vinyl, acrylic, and polyolefin homopolymers and copolymers (G7O). A rapid G C method was developed for quantitative determination of small amounts of water present in plasticizer-pigment and epoxy resinpigment dispersion used in polyurethane formulations ( G f 3 6 ) . Traces of water and hydrocarbons in polypropylene were determined by removing water from the molten polymer in vacuo, mea300R

0

suring water with Fischer reagent, and then dissolving the polymer in m-xylene for G C analysis of the hydrocarbons (Gf00).The D M F content of polyacrylonitrile fibers was determined in the range of 0.03 to 0.5% by extraction of the fibers with water or by heating the fibers a t 200" and trapping D M F in water, followed by GC of the aqueous solution (GI16). Vakhonin and Krest'yan ( G f 6 5 ) determined 1,5,9-cyclododecatriene from cis-polybutadiene solution by GC. Perepletchikova et al. (Gf26) reported procedures for determination of residual initiators-e.g., Bz2O2, azobisisobutyronitrile, lauroyl peroxide, etc.-in suspension poly(viny1 chloride) by GC and polarography. Polypropylene was rapidly analyzed for thermally stable antioxidants and ultraviolet stabilizers by a G C technique in which polymer samples as small as 200 mg were used (G87). More complex but carbon tetrafluoride-soluble stabilizers in commercial polypropylene pellets were identified and determined by a combined use of G C and ir (Gf18). A GC method was reported for determining a number of commercial antioxidants in oil-extended synthetic polymers such as polybutadiene or styrenebutadiene rubber (G47). Proper choice of solvents for the antioxidants and G C conditions prevented the extender oil from having a n effect on the elution of these materials. Bisphenol A, a n important monomer used in producing polymers such as epoxy and phenoxy resins, polycarbonates, and polysulfones, and the major, high-boiling impurities in bisphenol h were determined by GC of their trimethylsilyl ether derivatives (GZO). Trimethylsilyl ether derivatives were also used for GC analysis of polyols used in rigid polyurethane foam production (G28). Volatile Products from Polymer Reactions. Michajlov and Harwood (GI06) reported a unique G C method for characterization of diene polymer microstructure by olefin-polymer metathesis in the presence of a suitable catalyst. For instance, polybutadienes and styrene-butadiene copolymers metathesized with 2-butene to yield 2,6octadiene, 4-phenylcyclohexene, 5phenyl-2,8-decadiene and other fragments, which were analyzed by GC after hydrogenation. The amount of 2,6-octadiene provided a measure of 1,4-butadiene-1,4-butadiene linkages, whereas the amounts of 4-phenylcyclohexene and 5-phenyl-2,8-decadiene provided a measure of 1,4-butadiene-styrene-1,4-butadiene triads. Oxyethylene-oxypropylene copolymers were analyzed by a modified chemical fission-GC method, using HBr-acetic acid reagent to produce ethylene and 1,2-propylene dibromides


(G138). Ethanediol in formaldehydeethanediol polymers was converted into its diacetate by adding acetic anhydride and 70% HClOd to the powdered sample and chromatographed (G42). Alcohols and acids used in compositions of mixed polyesters of terephthalic acid were determined both qualitatively and quantitatively by GC and paper chromatography after saponification of the polymer (G82, GSS). Poly(ethy1ene terephthalate), however, was decomposed in refluxing 85% NzHd.H20 to prepare a sample for determination of diethylene glycol content by GC (GS4). Aminolysis was still a favored method to release the polyols from alkyd resins, which were then converted to their trimethylsilyl ether derivatives (GS8, GS9) or acetates (GS2) for GC analysis. Components of all types of polyamides, diamines, dibasic acids, and w-amino acids were determined in a single sample and on the same chromatogram after esterification and trifluoroacetylation of the hydrolyzates (Gf11). Alternatively, a one-step trimethylsilylation could be used to provide volatile derivatives for GC analysis of these components with triethylamine added as a hydrochloric acid scavenger and a catalyst for silylation ( G f f S ) . Constituents of polyurethanes (GSf), polyurethanes of polyesters, and unmodified polyesters (GQ2) were determined by hydrolyzing the polymer and analyzing the separated components by GC, uv, ir, NMR, and thin-layer chromatography. Reactive G C was used for determination of vinyl groups in siloxane and arylenesiloxane polymers by reaction with P206and water (G85). The results thus obtained agreed with the Br-I determinations of vinyl groups. -4simple rapid method for saponification of partial esters of cotton and quantitative G C analysis of the resulting soaps was developed for use in studies to elucidate the mechanism by which monobasic acid chlorides impart wrinkle recovery to cotton fabrics ( G f 4 ) . Hydroxyl groups in lignin were determined by transesterification with alkyl borates, followed by GC analysis of the B(OMe)3-MeOH or B(OPr)a-PrOH mixtures produced (G99). The ethoxyl content in ethylcellulose and ethylhydroxyethylcellulose was determined by oxidizing the ethoxyl group to acetic acid with chromium trioxide, and determining the acetic acid formed gas chromatographically (G67). Volatile Products from Pyrolysis. Brauer (Gf9) discussed recent developments in the use of pyrolysis GC techniques for polymer identification in a n excellent review. Other reviews on qualitative and quantitative analysis of polymers by pyrolysis G C appeared (GL, G42, G49, G f 15, G f27, G f47). Progress of cooperative work to

establish the precision of pyrolysis GC of polymers was reported (GSO). Results from “fingerprint” studies were encouraging, but reproducibility of quantitative results on polymer composition was disappointing. A comparative study was made of three different pyrolyzers for G C using two model compounds, 2,6,10-and 2,6,ll-trimethyldodecane(G169). The instrumental features and applications of a commercial accessory to GC for use in Curie-point pyrolysis were discussed (G43). Thompson (G148) reported the use of a Ni-Fe alloy coil for Curie-point pyrolysis of insoluble rubber vulcanizates. Buhler and Simon (G21) observed that, in Curie-point pyrolysis, the optimum wire diameter for a rapid warm-up was a function of the oscillator frequency. I n order t o have a fast temperature drop after cutting the rf field, small wire diameters were preferable. Several authors (G46, G57, G84, Gl7O) reported the use of a laser fragmentation source for GC, and a patent was issued (G5). The pyrolysis products of various polymers in the presence of air a t ea. 580’ were determined by GC, paper chromatography, thin-layer chromatography, and specific chemical tests, and their toxicity hazards were discussed (G58). Polymers studied in this work included PVC, polyamide, polyurethane, urea foam, phenolic, poly(methy1 methacrylate), polystyrene, polyacrylonitrile, and unsaturated polyester resins. A large group of elastomers were identified by G C of pyrolysis products a t various given temperatures (G27). Resin additives in polychloroprene adhesives were extracted with acetone and identified by pyrolysis GC (G45). Resins differentiated by this method were phenolic, alkyl phenolic, terpene phenolic, coumarone, hydrocarbon, glycerol, pentaerythritol, polyterpene, and root resins. Some mixtures of these resins were analyzed by pyrolysis GC, and others by combining pyrolysis GC with ir spectroscopy. Numerous studies were reported on the use of pyrolysis GC for polymer characterization, and a few selected references were listed according to polymer types in the following paragraphs. Willmott (G171) employed Curiepoint pyrolysis to study the effect of polymer microstructure upon pyrolysis products by pyrolyzing polyolefins having known degrees and types of branching and unsaturation. Deur-Siftar and Svob (G33) reported a pyrolysis GC method for determination of polypropylene tacticity. The ratio established for (iso-C4 - n-C4)/iso-C4 in the pyrolyzate was found to correlate with the isotactic polymer content. Structure of chlorinated 1,4-polybutadienes and poly(viny1 chloride) was elucidated by GC analysis of such characteristic

pyrolysis products as 0-, m-, and p dichlorobenzenes, and vinylidene chloride (G65). The amount of polyisobutylene in mixtures of polyisobutylene and polyethylene was determined by pyrolysis GC (G59, G61). The vinyl acetate content in ethylene-vinyl acetate eopolymers obtained by chemical analysis was correlated with the amount of acetic acid evolved and determined by pyrolysis GC (G121). The mechanism of decomposition of polypropylene (G153) and polyisobutylene (G152) was examined by GC analysis of their decomposition products. A comparative study was made on thermal degradation of polyethylene, isotactic polypropylene, and polyisobutylene a t various heating rates, and their degradation products were identified by GC (G62). The effect of degradation rates on thermal cracking and depolymerization patterns was observed. Pyrolysis G C studies on thermal degradation of different polystyrenes showed the mechanism of the degradation to be complex and not simple depolymerization (G25). The kinetic parameters of the reaction depended as well on the molecular weight as on the nature of the polystyrene and the degree of conversion. Other studies on fractionated polystyrenes found the monomer yield to increase with increase of molecular weight of polystyrene and to decrease with the elevation of pyrolysis temperature (G159). The effect of molecular weight and pyrolysis temperature on degradation of poly(maminostyrene) was also reported and compared with that on degradation of polystyrene (GldO). Seymour and Anderson (G135) reported the effect of derivatives of 2-mercaptobenzothiazole on pyrolysis of polystyrenes. The ratio of monomer to the corresponding unsaturated alkylbenzene in the products obtained from closed-tube pyrolysis decreased linearly as the concentration of 2-mercaptobenzothiazole derivatives was increased. Using a filament pyrolyzer and a specially constructed control unit, MeCormick (G102) examined the depolymerization behavior of acrylates, methacrylates, and styrene homopolymers and copolymers by both stepwise and “one-shot” pyrolysis under controlled conditions. The possibility of using pyrolysis GC for distinguishing mixtures of homopolymers from copolymers was discussed. Jones and Reynolds (G73) discussed the use of pyrolysis GC for polymer sequence analysis and illustrated the method with a range of styrene copolymers. Block and random butadiene-styrene copolymers were also distinguished by the method. The amount of propionitrile produced from pyrolysis GC was utilized to distinguish random styrene-acrylonitrile copolymer

from the homopolymer blend, and to obtain information on the molecular structure of the copolymer (G168). Other styrene copolymers investigated by pyrolysis GC included styreneacrylonitrile (GS, G48, M44),styrenebutadiene ( G l , G l l 4 , G121, G156), styrene-divinylbenzene (iIf89), styrene-ethylene oxide ( G l l ) ,and styrenemethyl methacrylate (Gl64) copolymers. Pyrolysis GC and ir spectrophotometry were used for qualitative analysis of polyacrylonitrile and acrylonitrile copolymers with methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate, acrylic acid, methacrylic acid, acrylamide, vinylpyridine, vinylpyrrolidinone, and styrene (GS). Acrylonitrile-butadiene copolymers were analyzed by GC of their pyrolysis products which were also produced from the homopolymers (G120). Pyrolysis of acrylonitrile-methyl methacrylate and acrylonitrile-styrene copolymers was investigated over the whole range of compositions, and yields of the respective monomers were determined (G48). Kinetic measurements were made on thermal degradation of poly(methy1 methacrylate) possessing lauryl-mercaptyl end groups (G6). The sample was fractionated by gel permeation chromatography and degradation of the fractions studied by pyrolysis GC. Results showed end initiation to be the predominating mechanism a t low temperatures, but random scission t o become important a t higher temperatures. Pyrolysis GC was used to analyze acrylic acid and methacrylic acid ester copolymers (GS6), or more complex multicomponent copolymers of CI-,S alkyl methacrylate monomers commonly used as viscosity index improvers (G142). Homopolymers and copolymers of vinylidene chloride and methyl methacrylate were studied by pyrolysis GC (Gl46). The relation between the yield of each monomer and the composition of the copolymers was linear. Tsuge et al. (G158, G160, G161, G162) made intensive pyrolysis GC studies on chlorine-containing synthetic polymers, including poly(viny1 chloride), poly(vinylidene chloride), vinyl chloridevinylidene chloride copolymers, and chlorinated poly(viny1 chloride). The chlorine content of the polymers was determined from the relative yield of the organic degradation products after elimination of evolved HCl by a NaOH precut column. The distribution of C1 atoms in the polymer chain was studied. The same authors also studied vinyl chloride-vinyl acetate copolymers by pyrolysis GC (G119). The analysis was based on the yields of acetic acid and benzene, with the former coming from vinyl acetate and the latter formed mainly from successive vinyl chloride units. I n some cases, pyrolysis GC


301 R

was employed for identification and determination of plasticizers in poly(vinyl chloride), preferably with the aid of other analytical techniques (G44, G68, M74).

Thermal decomposition products of poly(viny1 alcohol) were analyzed by GC (G154), and found to be mainly water, aldehydes, and methyl ketones during the first stage of decomposition. The degree of formalization of partially formalized poly(viny1 alcohol) was determined by measuring the relative peak height of HCHO in a pyrogram obtained by pyrolysis G C (G146). The compositions of copolymers of TFE and perfluoroalkenes were determined by pyrolysis GC, and their thermal stabilities assessed by thermogravimetry (G35). Better results were reported with boat-type than with filament-type pyrolyzer. Coupled TGG C was found effective in identification of a TFE spray (G26),and coupled GC&IS was useful in studying pyrolysis products of PTFE (MS3). Hydrogen atom cleavage reactions in fluorohydrocarbon systems were studied by heating mixtures of a copolymer of CH2=CFz with CF3CF=CF2 and deuterated polyxylylene in sealed ampoules and the products were examined by GC and M S (M?3). The fluorocarbon polymer lost CF3 radicals with H capture at noticeable rates. Radiolysis of tetrafluoroethylene, obtained by vacuum pyrolysis of PTFE, was studied by GC and ir (G7). Irradiation with ?-rays from a 6oCo source produced perfluorocyclopropane, hexafluoropropylene, perfluorocyclobutane, perfluoro-1-butene, and a low molecular weight compound. Comparison of ethylene and tetrafluoroethylene radiolyses indicated a specific character and high polymerizability of the latter. Oxyethylene and oxypropylene groups in ethylene oxide-propylene oxide copolymers were determined by pyrolysis followed by GC of the pyrolysis products, viz,, AcH and PrCHO (G110). The monomeric aromatic products formed on pyrolysis of poly(2,6-dimethyl-l,4-phenylene ether), poly(2,6-dimethoxy-lj4-phenylene ether), 3,3,5,5-tetramethoxydiphenoquiand none were investigated by using GC (G9S). Pyrolysis GC investigation of fractionated polycarbonates was reported (G157). The identification of the polymer and the estimation of molecular weight of the fractions were performed by measuring the yields of characteristic products originated from the end groups: p-fert-butylphenol from solution polymerization and phenol from melt polymerization. The thermal degradation of a bisphenol A-based epoxy resin was studied using a radiochemical pyrolysis G C technique (G16). Conclusive evidence for some of the degradation mechanisms 302 R

was obtained by pyrolyzing samples containing various 14C-labeled groups. Other studies on thermal degradation of epoxy resins cured by various amines were also reported (G91, G141). The hardeners used were identified by pyrolysis G C (G64). The phenol content of a phenolic Novolak-asbestos composite was determined by pyrolysis GC; the values obtained were in good agreement with those obtained by standard ashing techniques (G123). Pyrolysis GC also distinguished phenol- and cresol-formaldehyde resins (GIGS). Ross (G131) reported the use of pyrolysis GC to locate the degradation front in pieces of phenolic ablative materials. The technique provided quantitative results for per cent phenolic resin us. distance normal to the surface. Sykes (G143) generated pyrolysis products by flash pyrolysis of phenolic-nylon heat-shield material in front of a heated char, and analyzed these products by GC. The change in composition of the pyrolysis products after passing through the char showed that the high molecular weight products cracked to low molecular weight products, beginning a t about 700". The low molecular weight products increased with increasing char temperature, and, a t char temperatures approaching 1000°, the pyrolysis gases were composed of mainly COZ, CO, water, CHI, Hz, C2H2, benzene and cyclopentanone. The thermal degradation mechanisms of several secondary diamides as models for nylon 66 were examined in the presence of O2by GC and ir (G90). Coupled TG-GC was used to distinguish nylons 6, 66, and 610 (G26). The thermal degradation of aromatic polyimides was studied using pyrolysis GC, ir, and radiochemical techniques (GI") Degradation mechanisms were postulated to explain variations in the ratio of CO to CO2. Various types of polyurethane elastomer fibers were differentiated by GC analysis of their pyrolysis products using several columns (G77). Thermal degradation of polyurethanes was also studied by G C and MS analyses of the evolved gases and ir analysis of the solid residues (M63). Thermal degradation products of untreated and flame-retardant-treated cellulose were analyzed by GC and MS by several authors to further the understanding of the mechanism of flame retardancy (G156, M65, X 9 4 ) . MOLECULAR WEIGHT (MW)

I n his review of polymers Mark (W33) provided definition, classification, M W determination, and general properties. Livingston ( W S I ) characterized monodisperse polymers which are homogeneous with respect to MW. Definition and determination of average MW


were reviewed by Blackley (W9) who discussed osmometry, vapor pressure differential, ebulliometry, cryoscopy, light scattering, viscometry, and end group analysis. Similar coverage was given by Cantow and Johnson ( W l b ) . I n his report on recent advances in determining MW and sizes of polymers, Billmeyer (W6) referred to membrane and vapor pressure osmometry, light scattering, ultracentrifugation, and viscometry. Xature and molecular characterization of polymers were reviewed by Billmeyer (W7, W 8 ) referring to number average molecular weight (Jv,J,weight average molecular dimensions, and molecular weight distribution. Existing techniques were studied for RIW determinations by combining data from sedimentation, diffusion, and viscosity and tested on narrow fractions of polyarylates (Tt'47). The distribution of MW in free-radical polymerizations with branching was subjected to theoretical analysis (W43). In studies of solution properties of copolymers Kinoshita (L140) employed light scattering and viscometry. Copolymers examined included S-RIMA, E-P, S-AN, and S-isobutene. A review of ultracentrifugation for determining MW of polymers was published by Ion and coworkers (If7%$). Estimation of MW was reported employing sedimentation velocity and viscosity number ( WSO). The light-scattering method including history and theory was reviewed by Wlochowicz (W50a). Lechner and Schulz (W29a) reported measurements of the second virial coefficient and radius of gyration of polystyrene by light scattering a t pressures up to 750 atm and temperatures between 15" and 50". Continuous means was reported for following change in MW during some polymerizations ( W l d a ) . Average MW was obtained on 0.1 to 1-mg samples by a turbidimetric method which permitted measurement of absorbance of the sample solution as a function of temperature ( W S 8 a ) . A similar technique employing fractionation by cloud-point titration was used in estimates of M W of graft copolymers, such as propylene-styrene (C62). Budtov ( W10) derived a n expression for concentration dependence of viscosity from concentrated solutions of polymers with flexible chains. Rudin and Bennett ( 1 ~ 4 2 )described variations in the viscosity average molecular weight in calculating M w . Maron and Reznik (W%) deduced an equation to permit unambiguous intrinsic viscosity calculations. An automatic capillary viscometer was described (It'32). Azeotropes, such as provided by mixtures of cyclohexane-acetone, carbon tetrachloride-acetone, and benzenemethanol, eliminated effects of noise and drift in ebulliometer operation

(;vu),

(W48). Daniels and Lehrle (W15) recommended a three-thermistor ebulliometer for MW measurements. Osmometry was reviewed by Weissberg and Brown (W50) and by Armstrong ( L 9 ) . A discussion of osmotic membranes was published for R, measurements and a method devised for use of untreated membranes in analysis of polymers such as polystyrene and polybutadiene (W28) Modified apparatus was described for so-called vapor pressure osmometry (W36). Molecular weights of some coordination polymers were determined from radioactivity provided by *2Br tagging ( W 3 8 ) . Use of critical concentration for ternary systems containing two polymers, one of known MW, was devised and evaluated with a PS-PP-toluene system (W5). Acrylics. Behavior of k , during photopolymerization of methyl methacrylate was determined from lightscattering measurements (H’27). A similar technique was used in studies of swollen polymeric methacrylate and styrene gels ( W II). LV, of poly(ethy1ene glycol methacrylate) was determined by light scattering (LSO). The effect was studied of concentration, degree of neutralization, and counterions on viscosity of aqueous solutions of poly(methacrylic acid), poly(acry1ic acid), and their copolymers ( W S 4 ) . Viscosity and light-scattering data were obtained on chemically homogeneous random copolymers of MMA and butyl acrylate (W51),on PMMA (TVdGa), and MMAMA copolymers (W40a). Polyamides. Effects were studied of dissolution temperature and time on viscosity of high MW polyamides in formic acid (W44). Aggregation was found t o be a problem, and Simek and coworkers (U’44) did not recommend formic acid for precise hIW determinations. Viscometry of branched nylon 6 was studied in formic acid and mcresol ( W 1 8 ) . M W of nylon 66 was calculated from methoxyl content following methylation with ethereal diazomethane (W23). Polyolefins. During studies of properties of plastics, Salovey (L211 ) determined of PE by membrane osmometry. The morphology of PE single crystals prepared isothermally in solution was independent of MW, covering a range from 20,000 to 2,000,000 (lV3). Melt flow rate-intrinsic viscosity correlation was obtained for PP (V2). JTn of PP in the range 40,000 to 300,000 was determined by high temperature osmometry (W25) and by ultracentrifugation (L188). I n fractionation studies on P-S graft and bloc- copolymers both light scattering and osmometry were used for MW measurements (L84). Polystyrene (PS). Alliet ( L 4 ) made a comparative study of light scattering,

-v,,

osmometry, and GPC on PS of narrow and broad MWD, while Keijzers el al. (W25a) studied PS and PP. R, and R, data on PS assisted in defining polymerization of S by cationic initia; Enon PS standards u p to tion (WW) a t least 400,000 were measured by vapor pressure osmometry ( W 4 9 ) . The 10% solution viscosity was used for MW determinations on commercial PS; however, a t lower concentrations, such as 0.2%, the log-log plot of viscosity us. M W was linear (W41). Dautaenberg (WIG) used light scattering to investigate PS fractions having M, from 1.3 to 7.1 X 105. During crosslinking studies of PS, % . ?, was measured by light scattering and LV,,by osmometry

(Wl).

I n studies of styrene-polyisoprene block copolymers Cramond and Urwin obtained molecular dimensions by viscosity and light scattering (WI3) and thermodynamic properties from osmotic data (W14). M W of a standard 705 PS was determined from the intensity ratio of the Brillouin zone spectra coupled with light-scattering data (W37). Miscellaneous. Hayduk and Kelly (L104) developed an improved block osmometer in determinations of MW and MWD in commercial PVC. I n characterizations of PVC, Baijal ( L I I , L12) employed viscosity and osmometry for M W determinations. Light scattering was used for M W of PVC (TV21a). Rate constants for branching in poly(vinyl acetate) were established from variation of J i n and with extent of conversion (W21). MW of polytetrafluoroethylene was determined by the standard specific gravity method (71’19, W20). Dilute solution properties of bisphenol A polycarbonate were established in several solvents by osmometry, light scattering, and viscosity (T.1’39). R, of polycarbonate fractions in the range from 5000 to 22,000 were determined by vapor pressure osmometry ( JV40). Molecular weight measurements on fractions from polysulfone separations were made by viscometry and light scattering (L241). Viscometry and osmometry were employed in MWD studies of poly(2,6-dimethoxy-l,4-phenylene ether) (L161). Other polymers studied included polycarboxylic acids by vapor pressure osmometry (W22), amine-cured epoxy resin based on stoichiometry of the curing reaction and amount of amino and epoxy groups in the polymer ( W 4 ) , polypropylene sulfide by turbidity measurements (W’46), poly(ybenzy1-L-glutamate) by light scattering (W29), natural rubber and cis-polyisoprene by diffusion sedimentation, osmometry, and light scattering (W46), cyclic polyisoprenes by ebulliometry and light

*u,

scattering (L29),lignin by cryoscopy in dioxane, formamide, and ethylene carbonate ( W 1 7 ) , and alkyd resins by cryoscopy and viscometry (L187). On poly(oxyalky1ene glycols) and glycol polyesters end group analysis by NMR permitted calculation of (N165). A polarographic method was applied to determination of MW of cellulose acetate ( 0 ‘ 4 ) .

Av,,

MOLECULAR WEIGHT DISTRIBUTION (MWD)

Separation methods for polymers was covered in a book edited by Gerritson (L91). Research on methods for MWD and MW was facilitated by preparation of polymer standards. Two new P E standards were added to the National Bureau of Standards series of reference materials: a linear one (SRM 1475) for use in calibrating gel permeation chromatographs and a branched one (SRM 1476) for use in dilute solution studies and rheology. Various methods of determining MWD were compared by Yamamoto and coworkers (L261), including GPC, precipitation chromatography, and sedimentation. Effects of h l W D on mechanical properties of linear polymers were reviewed (L191). Rudin (L207) described the use of moments in deriving the average, breadth ,and skewness of MWD, while Kells and Guillet ( L I S 8 ) developed a simple, practical calculation procedure for predicting changes in M W D of a polymer undergoing crosslinking or degradation. h theoretical analysis of M W D in a realistic free-radical polymerization with branching was made by Saito and coworkers (LZ10). MWD measurements were reported for polydioxolanes (L200) and polyarylates (L75). Major literature on M W D continued to be devoted to gel permeation chromatography with emphasis on theory and technique. Gel Permeation Chromatography (GPC). The rapidly expanding technique of G P C was the subject of numerous reviews. Determann (L69) published the first book devoted exclusively to gel chromatography. A new mechanism for separation in GPC was proposed, assuming that flow occurs through the gel phase. Verhoff and Sylvester (L2.40) proposed the name “hydrodynamic fractionation” for this process. Discussions of principles and apparatus with examples of applications were published in reviews by Determann ( U S ) , Matsuura ( U r d ) , Kranz ( L l S Z ) , and Bly (L28). Cazes (L45) reviewed methodology in discussing instrument calibration, estimation of MWD, and fractionation of low molecular weight substances. Separation mechanism bringing in the concept of molecular size was the subject of a report by Bill-


*

303 R

meyer and Altgelt (LWW). Applications to polymer separations were reviewed by Armonas (L8) for resins such as urea-formaldehyde and phenol-formaldehyde, and by Flodin (L82) and Tung (L234). The last also discussed other methods for determining polydispersity, including ultracentrifugation and viscometry. Specific aspects of G P C were reviewed by Harmon (LIOS) on types and physical characteristics of column packings, by Coll (L49) on use of the universal parameter in relating M W and intrinsic viscosity, by Barrall (L16) on basic instrumentation with detectors for GPC effluents, and by Xmundson (L6) on methods for computation of MWD. Peak resolution and means for correcting for band broadening were reported by Harmon (L102), Kelley and Billmeyer (LfW), and Duerksen (L76). S e w developments in GPC were reported a t a n international seminar (Ld42). Boni and Sliemers (L36) pointed out that molecular weight averages calculated from G P C traces can differ markedly from values obtained by classical procedures. Such differences could be due to failure to predict the appearance volume-MW relation esisting during sample analysis, and to neglect of or insufficient correction for zone broadening of each NIW species in the polymer sample. From use of well-characterized polystyrene Iwama and Tagata (L124) determined reproducibility and concentration dependence of the GPC curve, and effect,s of column combination and column resolving power. Fuge and Hummel (L88) discussed a model for separations by G P C by analogy to mass transfer between liquid and gel phase in the theory of inst'ationary heat conduction. Theoretical aspects of determination of polymer branching by GPC were discussed by Drot,t and Mendelson (L73). Hamielec (1,100) provided a n analyt'ical solution to Tung's axial dispersion equation, while Lindhe (L162) showed t,hat shear stability is a function of the whole MWD. Dawkins (L64) obtained G P C molecular weight calibrations for PS, PE, and polyisoprene in o-dichlorobenzene a t 135" and found that experimental curves for t,he last, t.wo polymers agreed with those predicted from the PS calibratmion. An analysis of M W D of copolymers was report'ed by Terry (L227). Applications were reported to separations of low molecular weight polymers, such as PS, poly(buty1 methacrylate), poly(ethy1ene oxide), and polyepoxides (L105). Extension of GPC bo analysis of low molecular compounds, including monomers, oligomers, plasticizers, and other additives, was reported by Larsen (L168). Resins and gels studied for chromatography included copolymers of sty304R

rene with p - or m-divinylbenzene (L169), crosslinked copolymers of vinyl acetate with divinyl adipate and butanediol1,4-divinyl ether (L106),and gels from PMMA-glycol dimethacrylate (L108). Meyerhoff (L176) investigated the ability of several organic and inorganic gels to separate anionic PS, atactic PMMA, cellulose, and cellulose nitrate. 'A search technique and computer program was developed to assign a calibration curve from data provided by broad M W D standards (L14). Weiss and Cohn-Ginsberg (L244) calibrated GPC columns with unfractionated polymers having M W D approximating a generalized, two-parameter single peak distribution function. Ishida and coworkers (L122) obtained linear calibration curves from G P C columns packed with a mixture of four kind6 of gels of differing permeabilities; they obtained good results on tetrahydrofuran solutions of PS having molecular weights from lo2 to lo6. Iwama and coworkers (L123) found that the universal calibration curve was suitable only for linear polymers. Coll and Gilding (L50) provided theoretical justification for use of a universal calibration in GPC based on PS standards into calibration curves for poly-CYmethylstyrene, PPI and linear PE. To correct for instrument spreading, Tung (L233) used a Fourier analysis technique suitable for correcting nonGaussian instrument spreading or a fourth-degree polynomial for a Gaussian spreading function. Biesenberger and Ouano (L21) discussed three sources of zone broadening in a theoretical paper: packed columns, empty tubing between pump and columns, and detection system. Experimental data supported the theory (L192). Iwama and coworkers ( L I 2 5 ) found that zone broadening was affected directly by flow rate, due t o flow in t3he injection-detection system and due to interstitial flow in the column; they proposed a new correction method using a nonpermeating solute. Smith and Feldman (L220) proposed the relation, log (RI) = aTV, to define a resolution index for G P C columns ( R l is refractive index, CY is slope of calibration curve of log % ' M W us. peak position for narrow polymer fractions, and W is width of GPC curves for narrow fractions). A graphical method was presented by Schrager and Ward (L216), while Waters (L243) proposed a recycle procedure for extrapolating to infinite resolution. Tung and Runyon (L236) used the leading halves of chromatograms from several PS standards to calibrate instrument spreading. A new method of interpreting GPC chromatograms accounts for skewing and symmetrical axis dispersion ( L I S ) . Kelley and Billmeyer (L136) reported that peak broadening (dispersion) arising from permeation was a


NO. 5, APRIL 1971

linear function of flow rate. Little and coworkers (L163,L164) showed that peak spreading with increasing flow rate was less than predicted from the Van Deemter equation. B y optimizing operating parameters, these investigators achieved fast GPC analyses. High resolution chromatography was reported by Bombaugh and coworkers (L33) on a column yielding 180,000 theoretical plates. Applicability of the GPC technique was extended to polymer adsorption studies-Le., following M W D of polymers both in solution and on the adsorbed layer (L80). Insight on separation mechanism was obtained by Yau and Malone (L263) in studies of flexible polymers chromatographed on unpacked columns and columns packed with glass beads. Chang and Huang (L47) proposed a new method for calculating and correcting M W D of polymers, using a n integral equation relating true M W D of the sample to the chromatogram. Bly (L27) noted that M W D of any two polymers, one being a standard, can be compared, provided both GPC curves fall on linear portions of their calibrations. Lambert (L154) described a procedure to eliminate overload effects, based on extrapolating GPC data to zero injected weight. Tung (L233) devised a computer procedure for interpreting chromatograms having inseparable peak components. I n general applications of GPC Isakson and Anderson (L121) described analysis for monomer distribution in copolymers in conjunction with infrared analysis of fractions. Armstrong ( L 9 ) mentioned detectors other than differential refractometers and ultraviolet spectrometers, such as flame and infrared units, which could improve the technique. Cooper and coworkers (L54) interrupted solvent flow temporarily to permit infrared analysis of fractions. Coll et al. (L51, L52) described a belt detector for quantitative GPC and discussed application to PE, PPI and PS. Continuous recording of density variations in flowing liquids could find use in GPC (L86). Similarly, automated viscometry was adapted to G P C monitoring (L95, L176) and applied to PVA, PVC, and PS. For determining branching distribution in polydisperse samples, Tung (L232) employed concurrent GPC and sedimentation velocity measurements with application to styrene-divinylbenzene copolymer. Heitz and Ullner (LI07) devised a recycling technique for continuous concentration of eluate and illustrated its uses in separating oligomers of styrene, butyl methacrylate, and ethylene oxide. Instrumentation was described which combined two or more columns having differing packing permeabilities to resolve polymers having a wide M W D

(L204). Treatment of porous glass packings with hexamethyldisilazane improved fractionation capability and provided a means for infrared analysis of effluents (L66). Comparative data were obtained between G P C and column elution on a polysulfone, carboxy-terminated polybutadiene, and low M W PS (L216). When GPC was properly calibrated, there was good agreement between the two techniques. Acrylics, Polyacrylonitrile (PAN). Berger and Schulz (LIO) reported that G P C chromatograms of PMMA tended to contain broad peaks. They recommended that fractions be analyzed for M , and M , by osmometry, light scattering, and viscometry. MWD measurements of acrylic automotive lacquers showed a correlation of cracking failure with G P C peak position and ratio of height to area (L81). Stereoregular poly(methacry1ic acids) were fractionated on a preparative scale by GPC (L10). MWD of PAN and copolymers of AN and a sulfonate-containing vinyl monomer were estimated from GPC experiments (L46). Cellulose. M W D of wood cellulose was determined from GPC data (L116). Changes produced in cellulose by chemical modification were observed via GPC ( L l 7 g ) . Included were cellulose crosslinked in the swollen state as well as monofunctional substitution. Polydispersity of nitrated cellulose (L206, L217) and of enzymic-degraded cellulose was established (L206). Brewer and coworkers (L39) fractionated hydrolyzed cellulose esters from acetate through heptanoate. A prehump observed on the high end of GPC chromatograms of cellulose acetate from wood pulp was found to be enriched in mannose and xylose (L226). A comparison was made of structures of decrystallized cotton crosslinked with formaldehyde (L171). Polyamides, Polyesters. Panaris and Pallis (L193) fractionated nylons 6, 11, and 12 from hexamethylphosphorotriamide solutions; M , and M , data compared favorably with results by osmometry and light scattering. Mori and Takeuchi used GPC for characterizing linear monomers and oligomers in nylons 6, 66, and 12 (L182) and cyclic monomers and oligomers in nylons 6 and 66 (L181). For the former the aqueous ethanol extractables reacted with 2,4-dinitrofluorobenzene and absorbance of fractions was measured a t 370 to 450 nm Ethanol extracts containing the cyclic monomers were treated with 0.1N HC1 and absorbance of fractions was measured a t 210 nm; linear oligomers did not interfere. I n GPC studies of linear aliphatic polyesters-e.g., poly(ethy1ene adipate)-Billmeyer and Katz (L23)found M , / M , ratios from 2.0 to 4.9: 1.

Oligomers of linear, nonlinear, and oil-modified polyesters were studied by G P C (L213). Included were oligomers of the type: diol-monool-diacid, -acrylic acid, -methyl acrylate, AN. Results were compared with those from column and thin-layer chromatography. Polyolefins. Polydispersity of PE was established by GPC with M , determined by osmometry (L211). Concurrent G P C and sedimentation velocity measurements permitted estimation of branching distribution in low density PE (L236). Alternately, Drott and Mendelson (L74) characterized branching in PE from GPC and intrinsic viscosity data. M W D of extendedchain crystals of PE was determined by GPC (Lf301). M W spread of narrow peaks in the GPC chromatograms of nitric aciddegraded P E was found due to formation of polar end groups added to the polymer during chain scission (L247). Nitric acid degradation of annealed single crystals of PE was studied by G P C (L209); peaks due to chain folding were found, as was the case with unannealed crystals. MWD of PP samples were made by GPC and gradient elution with calibration by fractions of PP or narrow MWD prepared by large-scale column fractionation (L68). M , and M , calculated from GPC curves showed good agreement with those calculated from column fractionation curves. A fractionation method was reported for obtaining larger than usual fractions from isotactic PP (L156a). Oxidative degradation of molten PP was studied by GPC (L2). With the aid of infrared analysis it was established that there is only one functional group per chain scission as opposed to two groups found from thermal oxidation of solid PP. Decreases in PP molecular weights during photodegradation were followed by GPC; in conjunction with infrared spectra there appeared to be one functional group formed per chain scission (L1). Polyethers, Epoxides. M W D of poly(2,6 - dimethoxy - 1,4 - phenylene ether) and of poly(2,6-dimethyl-l,4phenylene ether) were obtained by GPC, viscometry, and osmometry (L166). Kinetics of oxidative coupling polymerization of 2,6-dimethylphenol was established via GPC (L203). GPC on styrene oxide-propylene oxide copolymer indicated presence of low M W by-product identified as trans2,5-diphenyl-1 ,4-dioxane (L149). Products from cationic copolymerization of tetrahydrofuran with epoxides were isolated by GPC (L101). Rate of adhesive aging and curing in oneshot epoxy tapes was measured, as well as identification of components of adhesive systems (L110).

Polystyrene (PS). To investigate efficiency of the G P C process, Peaker and Pate1 (L194) used PS samples with l*C-labeled end groups. On mixing with inactive polymer of differing MW they obtained the expected twin-peaked chromatograms. Alliet (L4) made a comparative study of GPC, light scattering, and osmometry on PS having narrow and broad M W D ; M W results showed fairly good agreement among the methods over the range of M , = 10,000 to 250,000 with M,/M, of 1.05 to 2.50. GPC data consistently indicated greater polydispersity than those from the other methods. Dawkins and coworkers (L65) demonstrated applicability of the unperturbed dimensions GPC calibration procedure for determining M W of PS and polyisoprene. MWD studies on product from y-ray-induced polymerization of S showed two distinct peaks, indicative of two propagating species (L116). Changes in M W D during degradation of PS by ultrasonics and benzoyl peroxide were followed as a function of time (L218). G P C assisted in establishing the magnitude and mechanism of shear degradation of a narrow MWDhigh M W PS (L7). GPC studies of copolymers of S and isoprene indicated that fractionation was achieved according to chain length (L57). I n comparative studies of PS and S-butadiene block copolymers, Hadeball and Seide (L97) observed differences in the distribution functions. Use of a narrow M W D PS and polybutadiene as models provided a means for determining MWD and composition of S-butadiene copolymers (L4O). Runyon et al. (L208) used a dual detector system for ultraviolet absorption and differential refractometry for obtaining improved composition and MWD data of S-butadiene copolymers. Other Vinyl Polymers. Baijal (L11) obtained correlations between M W D of PVC by GPC and viscosity. M , estimated from GPC experiments on commercial PVC was in fair agreement with results by osmometry and light scattering (L196). A universal calibration was obtained for suspensiontype commercial PVC using tetrahydrofuran and water (L12). Felter (L79a) utilized G P C effectively in adsorption studies of PVC from chlorobenzene solution onto calcium carbonate a t room temperature. Adsorption of both high M , (114,000) and low M , (42,800) was studied. Bombaugh and coworkers (LS4) fractionated poly(viny1 alcohol) samples on deactivated porous silica beads; dextran calibration standards exhibited skewed distribution. Block copolymers of 4-vinylbiphenylisoprene were quantitatively analyzed by GPC from information on ratio of


305 R

refractive index increments of the two homopolymers and over-all composition (L109). Miscellaneous. For several thermosetting resins Aldersley et aZ. (LS) determined M W D using PS gels and tetrahydrofuran solvent for phenolic and melamine resins and a Sephadex G gel and LiCl for urea resins. GPC and thin-layer chromatography were used to estimate M W D in phenolformaldehyde resins used in plywood and hardboard production (Lb39). Reliable MWD measurements by G P C were obtained on commercial silicones-e.g., DC-200 fluids-using PS standards (L157). GPC gave a good indication of monomer consumption during polymerization of organocyclosiloxanes (L6). GPC, gas-liquid chromatography, and precipitation fractionation were used in determining MWD of polydimethylsiloxanes. After correction for band spreading, GPC data agreed closely with theoretical MWD calculated from polymerization kinetics (L1.39). Dawkins and coworkers (L66) studied various procedures for universal calibration in G P C with PS gels for polydimethylsiloxane and PS, using o-dichlorobenzene a t 138' and utilizing hydrodynamic volume and unperturbed dimensions in correcting for experimental errors. GPC served in a quantitative analysis of a moisture-cure polyurethane coating (L161). Diels-Alder reactions and thermal polymerization of chloroprene were followed by gel chromatography using column filled with styrene-divinylbenzene copolymer (L56). Cyclic polyisoprenes were fractionated by GPC and column precipitation (Ld9). Effect .of mastication on M W and MWD was established on E P D M and SBR polymers ( L I S ) . . Miscellaneous applications of GPC to polymer fractionation were reported for glucose sirup (LdSO), phenyl- and benzo-substituted aromatic compounds (Ldd8), poly-N-vinylcarbaaole (L11I ) , thermal polymeric fatty acids, methyl esters, and alcohols (L119), crude oil fractions ( L 4 8 ) , low temperature coal tar (L114),and asphalt (Ldbb). Column Chromatography. Several variations of liquid and solid phase column chromatography were described. Although most developments in instrumentation were described for use with low molecular weight materials, they also could be applicable broadly to separations of polymers, intermediates, and additives. Dobrescu and Diaconescu ( L 7 l ) reviewed continuous and discontinuous column elution methods for polymer fractionation, employing solvent gradients and temperature gradients. Bombaugh (LS.2) discussed an analytical liquid chromatograph employing linear elution and solvent pro306R

gramming. High speed, liquid-liquid chromatography employing controlled surface porosity supports was discussed by Kirkland (L141, L14.8). Huber (15117) also devised a high efficiency] high speed system. Techniques for high performance liquid-liquid and ion exchange chromatography were described by Kirkland (L14S). Column design in high pressure liquid chromatography was discussed by Horvath and Lipsky (L113), while Felton (L81) covered a 3000-psi system which employed an ultraviolet detector. Davis ( U S ) and Hills et al. (L112) described constant-head devices for column chromatography. A variety of detectors has been employed in column chromatography, several of which were reviewed by Conlon ( L 5 S ) , Huber (L118), and Munk (L184). More selective descriptions of detectors were reported by Ohzeki and coworkers (L190) based on thermisters, Jaynes and Maggs (L128) on polarographic electrodes, and Davenport (L6.8) and Smuts and coworkers (Lbdl) on heat of adsorption. Direct coupling of column chromatography and thin-layer chromatography was made by Van Dij k (L238). A new gradient elution liquid chromatograph was developed using dual columns with both differential refractometer and ultraviolet detectors (LS5). Fractionation of amorphous polymers in a liquid system was reported by Donkai and Kotaka (L7b). Chromatography of polymers on glass powderfilled columns was reported (L.26). Beau and coworkers (L18) discussed retention and separation processes occurring in liquid-phase exclusion chromatography through columns packed with porous silica beads in applications to PS, PVC, poly(butene sulfone), dextran, and serum proteins. Giddings et al. (L94) developed a statistical theory in formulating a general expression for partitioning of molecules between the bulk fluid and inert, porous solids. Factors affecting resolution in gel filtration and permeation chromatography were discussed by Giddings (L93). Column and extracolumn variables in gel chromatography were analyzed by Carmichael (L41), while Neddermeyer and Rogers (L18Q)studied column efficiency and electrolyte effects of inorganic salts in aqueous gel chromatography. Measurements were made for preparative fractionation on short columns of dextran gels (L166). Preparation chromatography theory for polymer fractionation (BakerWilliams fractionation) was discussed by Smith (Lb19). Vacancy permeation chromatography was reported by Malone and coworkers (15170) and illustrated in separation of PS having a broad MWD. Carr and Keller (L4.2)


in correlating self-seeding phenomena and epitaxial crystal growth in polymers proposed a novel kind of chromatography for separation of the highest M W end of a distribution. PMMA was fractionated by precipitation chromatography (L67) and by the Baker-Williams technique (L99). A modified method of precipitation column chromatography employing temperature programming was described by PolAEek (L1Q9)and applied to PMMA. Large scale fractionation (3 to 150 grams) of PMMA was carried out by column elution a t constant temperature (L18S). Chain-length distribution of regenerated cellulose was studied by gel filtration chromatography (L198) and of nitrocellulose by elution chromatography (Lb48). Bisphenol A diglycidyl ether was quantitatively separated from an epoxide resin by column chromatography (L9.9). Polyformaldehyde samples were fractionated on a Francis-Cook-Elliott (1958) column loaded with sea sand and hexanol-dimethylformamide solventprecipitant system (L77). Morelli and coworkers (L180) fractionated polyformaldehyde by a column elution procedure. Antioxidants and plasticizers were determined in polyacetal and polyethylene by liquid-solid column chromatography (L168). Oil-modified polyester oligomers of the type diol-monool-diacid were separated by column chromatography and other fractionation procedures (Ld12, Lb1.9). Linear and cyclic oligomers of poly(ethy1ene terephthalate) were isolated and identified by chromatographic methods (L197). Elution chromatography was adapted to analysis for oligomeric poly(diethy1ene glycol adipates) of M , = 300 to 2300 (L7Q). Column fractionation of polyolefins was applied to high pressure PE, where Murata and Kobayashi studied crystallization temperature of PE fractions in p-xylene and effects of number, length, and distribution of branches] and M W on crystallization temperature (L185) and effects of branches and M W on fractionation using p-xylene-ethyl Cellosolve mixtures (L186). MWD of PP was estimated by the column elution method (L.2449). Fractionations of P-S graft copolymers were made through a modified Baker-Williams apparatus and results evaluated with the aid of the Tung function (L8S). Johnson and coworkers (Llb7) studied effects of temperature gradient on fractionation of polyisobutene. MWD of E-P terpolymers was determined from fractionation by the Francis-Cook-Elliott method using a diatomaceous earth column with ethylbenzene-methanolbutanol or ethylene glycol monoethyl ether as eluents a t 55' to 75' (La.&). Yamaguchi and Saeda (Ld50) fractionated PS during an evaluation of the

nature of column fractionation using a methyl ethyl ketone-methanol system. Phase-distribution chromatography of PS was described involving a stationary phase of a very high M W PS fraction on glass beads (L43). Styrene oligomers were fractionated on a column of MMA-ethanediol dimethacrylate copolymer (L38). A commercial “monodisperse” PS was separated by supercritical fluid chromatography; 17 oligomers were isolated (L126). S-p-iodostyrene copolymers were fractionated by the Baker-Williams procedure (L37) and S-isobutene copolymers by thermal gradient and precipitation fractionation column methods ( L 6 f ) . MN7D of PVC and polyisoprene was measured via column chromatography involving a liquid column, countercurrent precipitation cell, and cell for determining absorbancy (L96). AXvinyl acetate copolymers were separated by a modified Krigbaum-Kurz method (1959) and fractions analyzed by viscosity, infrared, and for nitrogen (L237). Miscellaneous studies included fractionation of pyrolytic products of polydienes by column precipitation chromatography and mass spectrometer analysis (L60), polybutadienes by column elution (L254), cyclic polyisoprenes by column chromatography (Lag), resin-maleic anhydrate systems (L2.23), Xovolaks (L98), and nucleotides and nucleic acid bases by high speed separations using controlled porosity ion exchangers (L144). Precipitation, Fractionation, Extraction. Polymer fractionation covering theory, analysis, and preparative aspects was reviewed by Koningsveld (L150). Blackley (L.24)and Cazes (L44)also reviewed the various methods dependent on solubility differences, such as fractional precipitation, fractional extraction, gradient elution chromatography, and turbidimetric titration. Kamide et al. ( L l 2 9 , L13f , ,5130) made a mathematical model for successive precipitation fractionation of polymers from dilute solution, utilizing a computer. Experimental verification involved effects of initial concentration and amount of fraction on the MWD of atactic PS in methylcyclohexane (L132). Raynor (LbOla) gave theoretical evidence in support of MWD based on turbidimetric titration. Fractionation and light scattering of copolymers-e.g., S-RIMA, E-P, S-AN, and S-isobutene-were reviewed by Kinoshita (L140). Blair (L25) designed an automatic endless belt fractionator, employing a thin coating of polymer on a slow-moving belt passing through a series of solvent-nonsolvent mixtures. Applications to fractionating poly(tetramethy1ene ether glycol) and neoprene were given. Effects of seeding behavior from addition of well characterized fractions were studied t o assess

reliability of measurement on high M W fractions (L134) and examined experimentally in MWD experiments on PE ( L f 3 6 ) . Phase separation behavior of dilute polydisperse polymer solutions was studied to optimize conditions for polymer fractionation (L1.45). Turbidimetric titration of “calibration” fractions was used to assist in constructing a solubility diagram. Theoretical aspects of MWD from less than 1 mg of polymer by turbidimetric titration were discussed by Molyneux ( L f 7 9 ) . A technique for determining MWD in polymers by turbidimetric titration was described by Kleinin and Uglanova (L148). Comparative studies were made of separating efficiency from discontinuous and continuous fractionation (L147). Fractionation technique for polymers by subjecting solutions to pressure differential to force M W fractions through a pressure-sensitive, anisotropic membrane was invented by Michaels and Baker (L178). Polymer fractionation by repeated extraction via a multistage technique was described by Klein and Friedel (L146). Fractional precipitation and fractional dissolution of polyoxymethylene diacetate were used in MWD studies with infrared end-group analysis and viscosity measurements on the fractions (L70). Acetate-capped polyformaldehyde was fractionated by thermal precipitation (L224). Comparison was made of fractionation behavior of linear and branched nylon 6 (L175) by coacervate extraction. Polyimines and polyamines were separated into high and low M W fractions by treatment with aqueous H2S04 a t 10” to 50” ( L f7 ) . Concentration dependence in quantitative fractionation of poly(ethy1ene terephthalate) (PET) was established by Reinisch and coworkers (L202). Lovric (L167) used coacervate extraction of phenol-tetrachloroethylene solutions of P E T in M W D studies with -Ifn obtained from intrinsic viscosity data on fractions. MWD on thermostabiliaed P E T was obtained from precipitation fractionation (L89). A similar procedure was used for MWD studies of poly(ethy1ene glycol methacrylate) by precipitation from methanol solution by diethyl ether (LSO). MWD of high M W P E was obtained by successive dissolving ( L f 6 6 ) and of PP oligomers by fractionation (LwO6). Fractionation of P-S graft and block copolymers, together with light-scattering and osmometry data, permitted MWD measurements (L84). Direct examination of fractions from PS solutions was made by light scattering (L195). A thermal precipitation technique was employed in MWD studies of products from the thermooxidative degradation of PS ( L f9 ) . Fractionations of S-acrylonitrile copolymers

were made by successive precipitation (L166, Lb26) and by coacervate extraction or column elution (L165). MWD of polyacrylonitrile was obtained from turbidimetric titration (L90). Crugnola (L59) reviewed fractionation procedures for PVC in characterizations for MWD, MW, and physical properties. Precipitation fractionation was made on PVC with M , of fractions obtained by osmometry ( L f O 4 ) . PVA was fractionated by precipitation from aqueous solution (L252) and poly(viny1 phenyl ether) from acetone solution with methanol (Lf53).

Fractional studies were also made on polyperfluorobutadiene (L229), polysulfones ( L Z d f ) , polydimethylsiloxanes by precipitation, GPC, and gas chromatography ( L f39), and alkyd resins by a film extraction method using viscosity and cryoscopy for analysis of the fractions (L187). Other Methods. Ultracentrifugation for M W D was reviewed by Ion and coworkers (L120). Lee (L159) discussed MWD measurements from sedimentation-diffusion equilibrium data a t a single rotor speed. Effects of concentration dependence of the diffusion coefficient of a polymer solutione.g., PS in benzene and cyclohexaneon M W D were discussed by Matsuda and coworkers ( L f 7 3 ) . MWD data by ultracentrifuge were obtained for PS (L194)and PP (L188). Fractionation of MMA-methacrylic acid copolymers was achieved by foaming (L31); PS and poly-a-methylstyrene by diffusion ( L 7 8 ) ; polypropylene glycols in the 1200 to 2400-MW range by molecular distillation (L86). The aqueous polymer two-phase (APTP) method utilizing phase partition was reviewed by Katou ( L f 3 3 ) . MWD measurements on polymer were claimed by means of extrusion through a capillary die and measuring cross section or swell of the extrudate (L246). OTHER CHROMATOGRAPHIC METHODS, ELECTROPHORESIS

These techniques are used principally for determinations of low M W impurities and additives in resins. Thinlayer (TLC) and paper chromatography (PC) continued to be most widely applied to these analyses. Among the general books published were “Advances in Chromatography,” Vol. 8 ( Y b g ) ,Vol. 9 ( Y 3 0 ) , and Vol. 10 ( Y 3 1 ) , proceedings of the Fifth International Symposium on Advances in Chromatography ( Y 9 4 ) , “Progress in Separation and Purification” ( Y 6 4 ) , “Chromatography” ( Y 9 ) , and chromatography and electrophoresis ( Y 5 , Y78). hnalytical and preparative chromatography were reviewed by Stahl (Y8I) ; developments in T L C and column


0

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chromatography by DeLange (Y19) and Lederer ( Y 5 f ) . Column Chromatography. Principles of adsorption chromatography were covered by Snyder ( Y 7 9 ) , while books on ion exchange were published by Marinsky (1’66) and Rieman and Walton ( Y 7 f ) . An extensive review on analytical applications of ion exchange resins was given by Egorov et al. (Y24). GaspariE (Y26) discussed chromatographic procedures for identifying organic compounds after decomposition and pyrolysis. Direct coupling of column chromatography and TLC was achieved by Van Dijk (L238). Column chromatography was applied to polymer analysis primarily for molecular weight distribution studies. Among applications for other purposes were oligomers of phenylpropiolonitrile by elution chromatography on calcium hydroxide (Y43), polyether polyols by dry column chromatography and TLC (Y49),diglycidyl ether in epoxide resins by column chromatography with over-all composition established by T L C ( Y 2 8 ) , rosin acids and rosinmaleic anhydride adduct (L223), and dimers and polymers in heated fats and oils by chromatography and sublimation (Y39), oligomers of polyesters of the type alkanediol-alkanol-dicarboxylic acid by columns, ion exchange, TLC, and liquid-liquid extraction by the Craig technique (L2lS). Thin-Layer Chromatography (TLC). Books on TLC and P C included those by Hesse ( Y 3 7 ) and Shellard ( Y 7 5 ) . A bibliography of P C and T L C for the period 1961 to 1965 was published (Y54). A new edition of Stahl’s TLC handbook was published ( Y 8 1 ) . Haywood (Y36) published a bibliography on TLC for 1964 t o 1968. Advances in TLC were reported by Niederwieser and Pataki (Y63). New developments in TLC systems were made in matrix materials and in detectors. Dah1 and Deveraux (Y13a) devised a novel versatile system employing an inorganic adsorbent embedded in polytetrafluoroethylene matrix. Other matrix materials included glass fibers (Y33),P T F E layers ( Y 6 8 ) , and poly(ethy1ene terephthalate) ( Y 7 7 ) . Polyamides were proposed as sorbents ( Y 3 8 ) . Vapor-programmed TLC was described (Y92, Y93). Quantitative TLC was described employing a flame ionization detector ( Y S f , Y86). TLC densitometry was described by Lefar and Lewis (Y62), utilizing ultraviolet and visible photometers. Electrical conductivity was employed for automatic detection in TLC and thinfilm chromatography (Y13). Combined pyrolysis-TLC was described by Rogers and Smith (Y73) for use in chemical kinetics studies. Broad applications of TLC included preliminary pyrolysis for high polymers 308 R

(Y68), miscellaneous polymers and intermediates ( Y 6 5 , Y 7 0 ) , fractionation of polymers (YSO), plasticizers ( Y 8 5 ) , antioxidants (Y11, Y l d , Y16),inhibitors (YS8), accelerators, antioxidants and stabilizers ( Y 4 7 ) , and hydrophilic components in est,er emulsions by TLC and P C (Y74a). Acrylics, Polyamides, Polyesters. TLC was used in studies of specific interactions between stereoisomeric chains of PMMA (Y42, Y68). Methyl acrylate, MMA-styrene copolymers were examined by T L C for compositional homogeneity (YS, Y41). Aqueous hydrolyzates and alcoholic extracts of nylons 6, 66, and 610 were examined by TLC (Y69, L160). Edel and Etienne (Y22) used TLC in studies of thermal degradation products from nylon 66 in nitrogen below 300’. N-acrylamide derivatives were employed to detect crosslinking of cotton and TLC was used in separations of acid-dissolved reaction products and hydrolysis products ( Y 8 7 ) . The course of reaction in poly(ethy1ene terephthalate) synthesis was followed by TLC ( Y 6 7 ) . Wuntke ( Y 9 f )used TLC in separation and determination of monomeric and oligomeric terephthalic acid esters. Oil-modified polyester oligomers were separated by TLC, column, and gel permeation chromatography (L212). Epoxides, Polyols, Polyolefins. Amine hardeners and amine-cured epoxy resin pyrolyzates were characterized by Gedemer ( Y 2 7 ) . Diglycidyl ether in epoxide resins was estimated by TLC (L92).

Mameniskis (Y65) determined polyoxypropylenediol in the triol. Salvage ( Y 7 4 ) identified poly(ethy1ene glycols) and poly(propy1ene glycols), while Favretto and coworkers (Y25) used TLC in MWD studies of poly(ethylene glycols). Diethylene glycol units incorporated in poly(ethy1ene terephthalate) were determined conveniently following saponification ( Y 4 4 ) . Dallas and Stewart ( Y f 4 )synthesized polyglycerols and used TLC for separating higher linear polyglycerols and for separating nonlinear compounds from linear isomers of the lower compounds ( Y f 4 ) . Antioxidants in polyethylene and polypropylene were identified by TLC (YIO, Y80). Vinyl Polymers. Heterogeneity of S-MMA copolymers was followed by chemical composition data from a TLC technique ( Y 4 6 ) . Braun and Nixdorf ( Y 8 ) used TLC in identifications of Sand a-methylstyrene-containing polymers. Analyses for additives in PVC included lubricants in molding powder ( Y S 4 ) , lubricant and stabilizer ( Y 4 0 ) , and a variety of plasticizers ( Y f O ,Y 2 l ) . Miscellaneous. Partition coef-


ficients of disperse dyes between cellulose triacetate and methanol were determined ( Y 4 6 ) . Reaction mixtures and condensation products in phenolformaldehyde polymerizations were analyzed by TLC and P C ( Y 1 ) . TLC was used in conjunction with GPC in studies of MWD in phenolformaldehyde resins (L239). Miscellaneous applications of TLC were in thermal degradation products of butylphenol-amine resins ( Y6S), qualitative detection of aminoplasts ( Y 6 ) , identification of lacquers ( Y 4 8 ) , amino resins in paint binders (Y9O), polymethanes ( Y 7 ) , rubber compounding ingredients (Y50),and antioxidants and accelerators in natural rubber (Y17, Y18).

Paper Chromatography (PC). Weaver ( Y 8 8 ) reviewed the history of PC. Its use in determining polydispersity of polymers was reported by Siling and coworkers (Y76). Applications to synthetic resin analysis in the industrial textile laboratory were reviewed by Egginger (I’M). Specific applications to polymer analysis included identification of polyethylene oxides and derivatives by P C and TLC (Y15), separation of epoxy resins with a listing of R, values for 58 compounds ( Y 8 9 ) , detection and separation of aminoplasts ( Y 6 6 ) , approximate MW and polydispersity of silicon organic polymers ( Y 5 7 ) ,analyses for inorganic pigments and fillers in paints ( Y 8 4 ) , and studies of thermal degradation of sugars ( Y 8 3 ) . Electrophoresis. A theoretical discussion of gel electrophoresis and gel filtration was presented by Rodbard and Chrambach ( Y 7 2 ) . Haywood (Y35) reviewed applications of electrophoresis and provided a bibliography. Proceedings of the Belgian symposium on electrophoresis were published (Y4). Electrophoretic identification of nylons 6, 11, and 66 was described by Bauters ( Y 2 ) . OTHER INSTRUMENTAL AND PHYSICAL METHODS

Tosi (Sf 09) derived mathematical expressions in examining the problem of sequence distribution in terpolymers. Optical properties of black P E were measured from 3 to 4000 cm-l ( 8 7 ) ; an empirical fit of absorption coefficient appeared to demonstrate Rayleigh absorption. Standardization was made of an earlier optical method for determining low M W solid particles in nylon 6 (SS). Rates of crystallization of nylon 66/6 copolymers were measured photometrically, using a hot-stage microscope (837). Kinetics of isothermal crystallization of PP were determined by depolarization measurements or dilatometry (85); a double heating stage was employed. Thermo-

optical and thermomechanical studies aided in explaining range of transparency in optically isotropic materials, including certain polymethanes (812). Determination of nylon 6 extract by interferometry was found to be more accurate than a refractometric method (823). Chiklis and Grasshoff (818) devised a simple optical microscope arrangement for measuring swelling of thin films of polymers. Unit cell dimensions of polyepichlorohydrin were determined by electron microscope study of single crystals (S63). Polydichloroprene was studied by electron microscopy and N M R (N116). Optical activity in stereoregular synthetic polymers was reviewed by Pino and coworkers (882). Zand (8123) surveyed optical rotatory dispersion (ORD) and circular dichroism of polymers covering theory and practice with instrumentation. Abe (S1, 82) and Pieroni et al. (881) studied ORD properties of several vinyl homo- and copolymers such as optically active polyolefins and alkyl vinyl ketones. Other polymer systems on which ORD studies were made included poly-pbenzyl (or p-methyl)+aspartate (81O ) , asymmetric polythiol esters ( 8 7 7 ) ,polyGproline (S86),and poly(alky1 glutamates) (8105). A comprehensive survey of the Kerr electrooptic effect of polymers was made by O'Konski ( 8 7 5 ) , while Stein (#IO$) reviewed use of optical studies in determining orientation and morphology of polymer films, including birefringence, dichroism, and light scattering. Shindo and Stein (8101) discussed birefringence and dichroism of oriented polymers containing polyene segments. Flow birefringence of elasticoviscous polymer systems was discussed in detail by Janeschitz-Kriegl (843). Flow birefringence of real polymer chains was described in theory and in application to n-alkanes (867). Graft copolymers of MMA and S, and of diphenylpropene and S, were investigated by streaming birefringence and viscometry (SS6). Instruments were reported for making flow and circular dichroism measurements (874). Partial specific volumes of dissolved macromolecules were derived from specific refractive index (RI) increments (886). R I measurements on polyacrylates as a function of temperature showed a discontinuity a t the glass transition temperature (887). Compositions of acrylic copolymers were established by differential refractometry in mixed solvents (8111). Partial specific refractions for PMMA were determined in a variety of solvents based on the Lorentz-Lorenz, Gladstone-Dale, and Eykman formulas ( 8 8 ) . The technique also was applied to end group analysis of PMMA and PS (89). Chiang (817) interpreted specific refrac-

tive index of PE in hydrocarbon solutions by the Gladstone-Dale formula; he modified the Brice-Phoenix differential refractometer for use a t elevated temperatures. R I increments were determined on eleven poly(di-n-alkyl itaconate) polymers in seven organic solvents for use in light scattering and other solution property measurements (S114). Water in ion-exchange resins was determined through R I measurement of D M F extracts (8124). Light-scattering measurements served to measure particle sizes as well as molecular weight distribution. Photometers were discussed by Utiyama et al. (S112) and by Schulz and Lechner (S98) for use a t pressures to 1000 atm. Isaksen et al. (841) described low-angle light-scattering instrumentation using a laser source for measuring state of agglomeration of dispersed systems (841). New instrumentation for lowangle light scattering to study of particle sizes from 0.2 to 100 microns was reported by Livesey and Billmeyer (854). Electric field light scattering was described by Jennings (844). Statistical theory for light scattering from oriented polymer films was developed in terms of angularly dependent generalized correlation functions (S104). Clark (819) described a method, based on the Mie theory, for analyzing light-scattering data in measurements of particle size and distribution. Particle size and MWD of polystyrene emulsions were investigated by Krackeler and Naidus (850), while Maron and Pierce (855) reported on a forward angle ratio method for determining latex particle size. Ruland (888) showed the need for use of Fourier transform and convolution theory to interpret scattering of amorphorus materials. Effects of optical rotation on light-scattering patterns were examined (880). M W of PS was determined from intensity ratio of the Brillouin spectra (861). Turbidimetric titrations served to estimate particle size as well as MWD. Vilim and Novak (8116) measured both properties on nylon 6 and S-butadiene rubber. Maxim et al. (857) used turbidimetry for rapid estimate of particle size distribution of latexes. Lange (852) determined particle sizes of latexes through specific turbidity and refractive index data; results were in good agreement with those by electron microscopy. Turbidimetric titrations were used in assessing optimum conditions for fractional precipitation (892) and for determining phase equilibria in dilute polymer solutions (829). Applications of fluorescence measurements in polymer research was reviewed by Nishijima (873). Other reviews of fluorescence techniques were given for studying molecular motion in polymer systems (870,871,872) and for polymer

solutions (853). Principle and apparatus were described for estimating molecular orientation in cotton, and polyacrylonitrile and polyimide fibers and polyethylene film by fluorescence (899). Orientation studies also were reported for poly(ethy1ene terephthalate) (858) and isotatic polypropylene fibers (8122). Other fluorometric measurements were used to determine inorganic materials in PE (SS2, 863), to find the ratio of excimer to monomer fluorescence intensity bands in PS ( S 6 9 ) ,to study PS excited by 0-rays and ultraviolet light (8119), and to characterize polybenzyl (825). Fluorescence intensity of polytetrafluoroethylene was studied as II function of synthesis conditions (S32). Urethane-modified alkyd coating on wood was examined to determine the nature of the interaction (S20). Fluorescence and phosphorescence studies were made of aromatic hydrocarbons in PMMA as a function of temperature (851) and of commonly used antioxidants and uv absorbers (848). For low temperature (77 OK) phosphorimetry of nylon the only satisfactory solvents were concentrated phosphoric acid and formic acid-ethyl alcohol (845). Phosphorescence studies mere reported on the thermal cleavage product of N-(2-naphthylamino) crotonamide in PVC and biuret (864) and S-vinylnaphthalene copolymers (827). Luminescence spectroscopy in polymer science was reviewed with reference to PE, 1-vinylnaphthalene-S and -MMA copolymers (828). dpplications to polymer analysis were reviewed by Smith (8102). Prolonged luminescence in P E , PP, polyformaldehyde, nylon 6, nylon 66, and PMMA was studied after initiation by a Hg lamp having maxima a t 480 and 580 nm (834). Luminescence accompanying mechanical deformation and failure in polymers was studied (813); among polymers studied were PTFE, PET, PE, PP, E-P copolymer, and PVC. Spectra were obtained on monomers, oligomers, and polymer chains during crosslinking reactions (831), and dehydrogenation of polyacenaphthylene (890). Studies were reported on chemiluminescence produced by oxidation of hydrocarbon polymers (SllS), by ozonolysis of polymers (SSS), and by decomposition of initiators in polymers (879). The significance of oxyluminescence measurements on polymers was reviewed by Schroeder and coworkers (897), Hol and DeKock (840), and Montamat (865), who referred to several classes of polymers. Thermoluminescence of irradiated PE, PMMA, and PS (826) and of P T F E (8108) was investigated. Radiothermoluminescence and its applications for studies of molecular motion and structural changes related to crosslinking were studied by Buben and


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Nikol’skii for butadiene rubbers ( S l l ) , by Mozisek for PE and PP (866), and by Nikol’skii et al. for block copolymers (868). Radiothermoluminescence and photothermoluminescence studies were reported for styrene trapped in a methylcyclohexane glass a t 90’ to 95 “ K (838). An interferometric method was preferred over gravimetry for determining low MJV components in nylon 6 (884). Auger and photoelectron spectroscopy were applied to analyses of solid surfaces. For example, surface absorption by polypeptide films was studied by Auger emission (86). Atomic absorption ( A A ) was used to an increasing extent for elemental analysis. A device was described for feeding powders directly into the flame (821). Trace levels of metals were determined by AA in all types of polymers (876). Small amounts of Fe, Zn, and M g were determined in PS following decomposition by HzS04 and HNOa-HClOd (8107). The oxygen bomb method was used to decompose ABS resins in preparation for AA determination of Ca, Mg, Na, and K (856), while the oxygen flask method was used in determining C1 in PVC (8110). AA also was employed in determining silicone fluid surfactants in polyether-polymethane blends (824) and Cu and M n in crude rubber (836). I n a study of flame spectroscopy of powders Woods (8120) found detection limits of 1 mg for BrClZ,CaF2, and KC1 and 0.1 mg for NaCl and NiF. The electron beam microanalyzer was used in a n applied study of seeding particles and structure of coatings (891). Emission spectrographic procedures were used for determining trace metals in nylon 6 (860), PET ( S l S ) , polybutadiene (847), and raw and cured rubbers (8106). .A laser was used for microspectral analyses of hardened epoxy resins (878). Unsaturation in cyclic oxide polymers was determined by formation of the vicinal methoxy-14C-acetoxymercury derivative and measurement of radioactivity (814). Both F and C1 were determined in polymers by a gammaactivation procedure involving formation of positron-active ’*Fand a*Clwith half lives of 112 and 33 minutes, respectively (815). Dielectric relaxation provided information on structural features of the amorphous phase in polymers (84.2) , such as copolymers of vinylidene fluoride and hexafluoropropylene (849). Venkateswaran (8115) compared the dielectric method with density, moisture regain, and x-ray diffraction in studies of fine structure of cellulosic materials. Diffusion of water through polymer films was followed by electrical conductance (8100). Magnetic susceptibility aided in studies of order-disorder phenomena 310R

in PE undergoing mechanical and thermal manipulation (84). Particle analysis on nylon 6 solutions utilized conductometric impulse counting according to the Coulter principle (C122). I n physical studies, the nature of water vapor transport through polymers was discussed by Yasuda and Stannett (8121),Williams and coworkers (Sl18), Schneider and Dusablon (896), and Schneider and Allen (894). A technique using the resonating quartz crystal was described by Kennerley (846) for measuring water vapor adsorption by films. Schmalz (893) used a manometric procedure for determining water in polymers, demonstrating applicability in analyses for about 0.007% water in nylon 6 and PET. Illing and Hobe (839) devised a similar method for small amounts of water (> 0.01%) in polymers. Specific gravimetry of powdered PTFE was determined by a n air comparison type-specific gravimeter which measured volume of gas excluded by the solid (830). Microgel in polymers was determined by a procedure combining centrifugation and ultrafiltration (883). Meluch and Blizard (859) recommended a gradient density method rather than gravimetry to determine quantity of solvent imbibed by a crosslinked polymeric system. Solvents for poly(viny1idene chloride) in decreasing order of activity were hexamethylphosphoramide, tetramethylenesulfoxide, N-acetylpiperidine, iVmethylpyrrolidone, N-formylhexamethyleneimine, and trimethylene sulfide (8117). Solution in benzyl acetate was used to determine polyester fibers in mixed textiles also containing acrylic fibers or cotton (889). Relative hydrogen-bonding capabilities of several liquids on paper mere determined by sonic velocity techniques (822). Linear oligomers formed from ethylene glycol, octadecanol, and adipic acid quantitatively formed urea adducts, while branched-chain oligomers and polyesters added in a nonquantitative way (896). LITERATURE CITED

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