Analysis of high polymers - Analytical Chemistry (ACS Publications)

ANALYTICAL CHEMISTRY, VOL. 51, NO. 5, APRIL 1979 Chromatogr. 1977, 136(3), 391-399. (19K) High-pressure liquid-chromatographic determination of the 15-epimer of dinoprost [prostaglandin F Z a ] in bulk drug. Roseman, T. J.; Butler, S. S.; Douglas, S. L. J . Pharm. Sci. 1976, 65(5), 673-676. (20K) Determination of halothane in [the air of] operating theatres by chromatographic techniques. Schoentube, E.; Schaedlich, M. Ergeb. Exp. Med. 1975, 2 0 , 219-226. (21K) Recommendations to eliminate subjective olfactory methods from compendia1 identification tests. Schwartzmann, Gewge J . pharm. Sci. 1978, 67(4), 539-545. (22K) Determination of methyl methacrylate in surgical acrylic cement. Sheinin. Eric 6.: Benson. Walter R.: Brannon, Wilson L. J . Pharm. Sci. 1976, 65(2), 280-283. (23K) The analysis of iridoid drugs. Sticher. 0. pharm. Acta He&. 1977, 52(1-2). 20-32. (24K) Determination of cyclchexanone in intravenous solutions stored in poly(viny1 chloride) bags by gas chromatography. Ulsaker, G. A,; Korsnes, R. M. Analyst (London) 1977, 102(1220), 882-883. (25K) Determination of chamazulene and prochamazulenes in essential oils and crude drugs from yanow (Achillea spp.; Compositae). I. New colorimetric method for determination of chamazulene in essential oils. Verzar (nee Petri),

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G.; Cuong, Bhanh N. Sci. Pharm. 1977, 45(1),25-39. (26K) On the quantitative determination of chamazulene and prochamazulenes in essential oils and crude drugs from yarrow (Millefolii. Achillea genus, Compositae). 111. A discussion of colorimetric methods for chamazulene (and prochamazulene) determination. Characteristic features of our new method. Verzar-Petri. Gizella; Bhanh Nhu Cuong Sci. Pharm. 1977 45(3). 220-234. (27K) Persistence of dextran 70 in blood plasma following its infusion, during surgery, for prophylaxis against thromboembolism. [Determination of dextran.]; Walkley, J . W.; Tillman, J.; Bonnar. J. J . Pharm. Pharmacol. 1976 28(1), 29-3 1. (28K) Determination of aminobenzoic acid by room-temperature solid-surface phosphorescence. von Wandruszka, R . M. A ; Hurtubise, R. J. Anal. Chem. 1976, 48(12), 1787-1788. (29K) Gas-liquid chromatographic method for monitoring vinyl chloride in drugs and in poly(viny1 chloride) drug containers. Watson, J. R.: Lawrence. R C.; Lovering, E. G. Can. J . Pbarm. Sci. 1977, 72(4). 94-97. (30K) Quantitative analysis of trifluoroacetic acid in body fluids of patients treated with halothane. Witte, Ludger; Nau, Heinz: Fuhrhop, Juergen-Hinrich; Doenicke, Alfred; Grote, Bernhard J . Chromatogr. 1977, 743(4):Biomed. Appi. 1(4), 329-334

Analysis of High Polymers John G. Cobler" and Carl D. Chow The Dow Chemical Co., Midland, Michigan 48640

This review includes analytical methodology, related to the analysis and characterization of polymers, that has appeared in the literature between November 1976 and November 1978. This is a n update of the 1977 review. Van Krevelen (27) provided valuable information on polymer properties. The National Materials Advisory Board (18)defined the properties of organic polymers critical to their use in various applications and methodology to measure and control these properties. Urbanski et al. (21) published a handbook on the analysis of synthetic polymers. Czerwinski (12) discussed chemical methods of polymer analysis and D'Oyly-Watkins (13) reviewed instrumental methods useful for determining the quality of polymers. Bollinger (5)reviewed methods used to demonstrate the presence of block stuctures in copolymers. Garmon (14) reviewed the methods for determining end groups while Leca (16) discussed methods for determining structural isomerism and tacticity in polymers. T h e principles and applications of various methods for the fractionation of polymers were reviewed by Tung et al. (14). T h e determination of additives in polymers was reviewed by Crompton ( ] I ) , Coe (9, I O ) , and Kennett and Stanton (15). Urbanski discussed the analysis of polyacrylates and polyacrylonitrile (22), fluoroethylene polymers (25),polystyrene and copolymers (23),poly(viny1 alcohol) ( 2 4 ) ,and siloxanes (26). The analysis of polyamides was discussed by Majewska (17)while Park (19)discussed the determination of branching in poly(viny1 chloride). Specifications for plastics materials and test methods for analyzing commercial plastics and plastic products are covered in publications of the American Society for Testing and Materials (1-3). Recent additions to the ASTM Book of (Plastics) Standards (2) include D3016, gel permeation chromatography definitions and relationships; D3417, heats of fusion and crystallization of polymers by thermoanalysis; D3418, transition temperatures of polymers by thermoanalysis; D3536, molecular weight averages and molecular weight distribution of polystyrene by liquid size exclusion chromatography (gel permeation chromatography); D3591, logarithmic wscosity number of poly(viny1chloride) in formulated compounds; D3592. determination of molecular weight by vapor pressure osmometry; D3593, molecular weight averages 0003-2700/79/0351-287R$05,00/0

and molecular weight distributions of certain polymers by liquid size exclusion chromatography (gel permeation chromatography) using universal calibration; and D3594, copolymerized ethyl acrylate in ethylene-ethyl acrylate copolymers by infrared spectroscopy. General techniques and procedures for emission, molecular (infrared), and mass spectrometry, gas chromatography and microscopy are covered in part 42 of the Annual Book of ASTM Standards ( 4 ) . The Code of Federal Regulations (21 CFR 170.3) (6) defines a food additive as all substances, not specifically exempted, the intended use of which results or many reasonably be expected to result directly or indirectly in their becoming a component of food. The regulation further states that a material used in the production of containers and packages is subject to the definition if i t may reasonably be expected to become a component directly or indirectly of food packaged in the container. Components of a plastic packaging material (i.e., residual monomer, oligomers, plasticizers, stabilizers, etc.) are considered to be food additives if they migrate or diffuse into food in contact with the plastic. A food additive may not be used until its safety has been established and a regulation issued by the Food and Drug Administration defining the conditions of safe use. Requirements for a petition for a food additive regulation are outlined in 2 1 CFR 171.1 ( 7 ) . Regulations pertaining to the use of plastics for food contact applications (including specifications, use limitations, extractive limitations, and required methodology) are covered in 21 CFR, Parts 175-181 (8).

GENERAL Canji et al. ( A 5 ) determined the structures of 1,4-polybutadiene and butadiene-styrene copolymers by metathesis with 3-hexene. Reaction with 1.2 linkages produced 1-butene and with 1,4-1,4 sequences produced 3,7-decadiene. Ast et al. ( A I )and Hummel et al. (AI7) characterized polybutadienes by metathesis with 4-octene. Sobek and Dreyer (A381 fractionated copolymers of acrylonitrile and vinyl acetate according to molecular weight by titration of DMF solutions with B u 2 0 and according to chemical composition by titration with EtOH. Stejskal arid Kratochvil (A401 found that binary and ternary solvent (c: 1979 American Chemical Society

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mixtures were suitable for fractionation of copolymers according to molecular weight if the cloud points of the corresponding binary solutions did not differ significantly. Styrene monomer in polyester laminates, SBR, and acrylic polymer dispersions was determined polarographically after conversion to PhCH(NO)CH2N02and PhC(:NOH)CH2N02 by reaction with N a N 0 3 in AcOH (A30). Banthia and coworkers (A3) determined sulfate. sulfonate. and isothiouronium salt end groups in polystyrene by the dye-partition technique. Polymer polarity did not affect the results of the end group determination. Royol (A36) determined residual monomers in styreneacrylonitrile copolymers by extraction into CsHs followed by bromination of the styrene monomer and cyanoethylation of the acrylonitrile with dodecanethiol. Hall and Stevens (A15) developed a spectrophotometric method for the determination of acrylonitrile based on the absorbance a t 411 nm of the pyridine complex formed in the presence of basic hypochlorite. Nitrile groups incorporated in polystyrene by initiation or copolymerization were detected and estimated by dye-partition techniques after reduction with LiAlH, in T H F (A19). Vasil’yanova et al. (A43) found that a 1 : l O Et,O-EtOH solvent mixture did not dissolve low molecular weight PVC and allowed maximum extraction of plasticizers such as dibutyl phthalate and tricresyl phosphate. Kohman and Ciecierski (A20) determined the concentration of plasticizers in PVC from specific volume/concentration calibration curves. Labile chlorine in PVC was determined by LJV spectral analysis of the phenolysis reaction product (A34). Ruruiana et al. (A4) determined the allyl chlorine content of PVC by measurement of the 36Cl radioactivity of the PVC after exchange with S036C12in tetrachloroethane at 60 “C. Getmanenko and Perepletchikova ( A l l ) determined hydroperoxides in C6H6-MeOH-THFsolutions of PVC by oxidation of Fez+ of Mohr’s salt to Fe3+ and formation of the ophenanthroline colored complex. Butyl acrylate, butyl methacrylate, methyl methacrylate, and styrene monomers were determined in acrylic-styrene copolymers by polarography. Acrylic monomers in solutions of the copolymers in alcohol-benzene on a Bu,NI base gave a wave with E I l 2-2.2 to -2.3 V; Styrene formed a wave with Eli2 -2.5 to -2.6 (A94). Kalinin et al. (A18) discussed the PO arographic determination of methyl methacrylate monomer, oxidation products, inhibitors, and traces of copper and iron. Grant and McPhee (A22) titrated methacrylic acid in aqueous solution with electrogenerated bromine. Copolymers of vinyl esters and esters of acrylic acid were saponified in a sealed tube with 2 M NaOH. The free acids from the vinyl esters were determined by potentiometric titration or gas chromatography. The alcohols formed by the hydrolysis of the acrylate esters were determined by gas chromatography (-42). Morishima et al. (A26) found that a red-violet color for the poly(viny1 alcohol) (PVAL)-iodine complex began to appear a t 12-mer and that the typical blue color was not apparent even at 14-mer. Partially saponified poly(viny1 acetate) (PVAC) gave a red-violet color with iodine in the presence of boric acid attributed to long sequences of vinyl acetate units (A16). Leukroth (A22) found that the best method for determination of bound vinyl acetate in ethylene-vinyl acetate copolymers (E-VAC) was saponification with p-MeC6H,S03H and titration of the acetic acid. Mlejnek et al. (A24, A25) determined vinyl acetate in E-VAC copolymers thermogravimetrically when pyrolyzed a t 770 “C for 15 s or 550 “C for 10 min. Munteanu (A27) determined vinyl acetate in random and graft copolymers with ethylene by saponification in 1 N ethanolic KOH at 80 “C for 3 h. Citovicky et al. (A6)developed an iodometric method for the determination of hydroperoxides in powdered isotactic polypropylene. Guise and Zoch (A14) determined the functionality of aliphatic isocyanates by gel-point titration with amino-terminated polyethers; aromatic isocyanates by titration with water; and phenol- and ketoxime-blocked polyisocyanates by titration with polyamines. Low molecular weight polymer (LMWP) in poly(hexamethy1eneadipamide) was determined by an interferometric method based on the dependence of the refractive index on the LMWP content of a methanol extract (A29).

Greenhow and Shafi (A13) determined bound phenol and resorcinol in novolaks and resols by thermometric titration with alc. KOH in Me2SO- -CH,=CHCN. Methanol formed on the hydrolysis of urea resins was separated from HCHO by sorption on an anion-exchange resin and determined colorimetrically with chromotropic acid (‘432). Patek (A31) described methods for the determination of HCHO. CH20H, NHCONH, and urea in urea-formaldehyde resins. Low molecular weight components in urea-formaldehyde resins were determined by silylation with N,O-bis(trimethylsily1)trifluoroacetamide and gas chromatography of the resulting mixture (A7). Martynenko and Vinoslavskii determined furfurylideneacetone in ketone-formaldehyde oligomer mixture photometrically after reaction with o-nitrobenzaldeh~de~(A.23). Hvdrazides of carboxvlic acids used as cross-linking agents for epoxy resins were measured by oxidation with burcmine and amperometric titration (A44). Free phenolic hydroxyl groups in epoxy resins, dissolved in DMF containing H,S04 and MeOH, were titrated amperometrically against bromate bromide solution (A21). Gasan-Zade et al. (AIO) followed the conversion of phenolic hydroxyl groups in the polymerization of epichlorohydrin with bisphenol A by the change in refractive index. Fregert and Trulsson described a colorimetric test for the detection of bisphenol A epoxy resins (A9): low molecular weight oligomers were isolated by thin-layer chromatography. a-Glycol groups in epoxy resins were determined by oxidation with PhCH2N(Me3)+I04in CHC13;MeOH. The excess reagent was determined iodometrically (‘48). lirbanski (A42) measured small amounts of propylene oxide and epichlorohydrin in polyesters colorimetrically after reaction with a CHC13 solution of 2,4(02N),C6H3S01H.Myakukhina et al. (A28) discussed methods for the determination of epoxy, carboxvl, and hydroxyl groups and unsaturation in water-soluble epoxy resins and polyesters. Vinyl groups in siloxanes were determined by hrornination with electrogenerated bromine in AcOH: the extent of bromination depended on the ring size and substituent size at the Si atom ( A 4 1 ) . Trace amounts of SiH-groups in poly(organosi1oxanes) were determined by titration with N-bromosuccinimide; by spectrophotometric measurement at 450 nm of the Ag solution formed in the redox reaction with AgN03; by gas chromatography; or by IR measurement at 2160 cm (A35). SiCl groups were determined by potentiometric titration with methanolic KOH using a C1-selective electrode. Phthalic acid and (T,Br , I-, and NO2- containing isophthalic acids in polyesters were determined by conductometric titration with triethanolamine in isopropanol (A37). Pohorelsky and Heran ( A 3 3 determined 6-caprolactam in poly(ethy1ene terephthalate), after hydrolysis in 1 N HCI, colorimetrically with ninhydrin.

GEL PERMEATION CHROMATOGRAPHY There are several publications on the general technique of gel permeation chromatography (GPC). “GPC of Polymers” by Tung and Moore (C32); “GPC” by Boni (C7) and by Ouano et al. (C22); “Characterization of High Polymers by GPC” by Billingham ( C 4 ) ; “Size Exclusion Chromatography in the Characterization of Polymers” by Abbott ((‘2); and “Application of Liquid Chromatography to the Solution of Polymer Problems” by Cazes and Fallick (C9). A density measuring device based on a mechanical oscillator method was used as a universal detector in GPC. The linear relation between the density difference of polymer and solvent and polymer concentration was demonstrated for solutions of poly(propy1ene oxide) in dimethyl forniamide and chloroform (C19). Francois and co-workers used an automatic digital densimeter as a GPC detector when the refractive index increment was near zero and when there was an appreciable density difference between solvent and solute ( C 2 2 ) . A quantitative treatment of infrared detector response in terms of transmittance was given and verified experimentally ((‘5). GPC combined with viscometry was used to analyze branching in polyethylene ((‘22, C26, (’34) and in polybutadiene, styrene divinyl benzene copolymer and poly(v1nyl acetate) (C.29). Ilamielec and Ouano used a low angle laser light scattering coupled with GPC for the characterization of branched poly(viny1 acetate) (C16). GPC was used to determine the chemical composition of butadiene -styrene co-

ANALYTICAL CHEMISTRY, VOL. 51, NO. 5, APRIL 1979 John 0 . Cobler is an associate scientist with the Health and Environmental Research Department, Dow Chemical U S A A graduate of the College of Wooster, where he received a B.S in 1940, he d d two years graduate study at Purdue University before joining the Pharmacology Division of the Manhattan Project. H s Dow career w n in 1949 in the AnaMical Laboratones I n 1953, when he was promoted to g-cup leader, he started the Polymer Anabsis Laboratory and supervised its operation until 1969 He was named an associate scientist in 1969 and acted as a consultant in polymer analytical chemistry until 1975 when he transferred to the Health and Environmental Research Department He is currently responsibl activities relating to the health safety of plastics materials He has published 38 articles on polymer charactermbon and subjects related to the use of matenak for food and drug packaging applications He IS a member of the of Polymer Chemistry and the Division of Rubber Chemistry of the American Chemical Society, the Scientific Research Society of America, and the American Society for Testing Materials At the present time he is chairman of the Methods Subcommittee of ASTM F-2 on Flexible Barrier Materials and chairman of the Analykal Methods Subcommittee of ASTM 1320on Plastics He has been actwe in technical subcommittees of the Society of Plastics Industry and the Manufacturing Chemists Association Carl D. Chow s a research specialist with the Polymer Analysis Group of the Analytical LaDoratories. Mich,gan Division The Dow Chemical ComDanv He receive0 his B S in oraanic chemistrv .from the National Taiwan University and his M.S. in polymer chemistry from North Dakota State University. He joined the Physical Research Laboratory of Dow in 1965 and worked on polymerization kinetics, foam technology, and reinforced plastics. He transferred to the Polymer Analysis Group in 1967. His specialities are molecular weight measurements, gel permeation chromatography (GPC), and thermal analysis. He has published in these areas and has lectured on GPC at iocai ACS sections and universities.

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polymer and butadiene-a-methylstyrene copolymer with considerations of the refractive index and extinction coefficient, etc. The results agreed well with those obtained from IR and NMR spectroscopy (C30). GPC was also used to determine the oligomer composition in polymerization mixture of terephthalic acid and ethylene glycol (C20). Chemical compositions and structures of hydrocarbon resins and epoxy resins were analyzed by IR and NMR ( C l O ) and high-resolution mass spectroscopv _ - (C271, respectivelv, after fractionation by GPC. Molecular weight distribution was determined bv GPC of oligomeric si1aza;les ( ~ 3 1isotactic , fraction of polypropylene (C33),ethylene-propylene copolymers (C211, copolymers of styrene or a-methylstyrene and butadiene (C29), vinyl acetate-vinyl chloride copolymers (C1 7), poly(organosi1oxanes) (C2),poly(ethy1ene terephthalate) in a nitrobenzene-tetrachloroethane mixture at room temperature (C24),thermosetting resins (C31), poly(tetramethy1ene terephthalate) (C28), diallyl phthalate prepolymers (C6), and isotactic polystyrene using the universal calibration (C14). Hamielec and Ouano have claimed (C15) that the universal calibration parameter, expressed as intrinsic viscosity multiplied by the weight average molecular weight is incorrect, and the number average molecular weight should be used instead. Kat0 and co-workers (C18) have used a high speed aqueous GPC to demonstrate good resolution of polyethylene glycol oligomers and small molecules on TSK-Gel type PW packing. T h e resolution was comparable to that in GPC with organic solvent system. Detection of anionic polyacrylamide by GPC was accomplished by addition of a salt to the eluent which caused a large increase in the elution volume of the partially hydrolyzed polymer (C13). Glycerine-coated controlled-pore glass column packings were evaluated for high speed GPC of water-soluble polymers ( C 2 5 ) . A chemically unmodified porous silica packing could

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be used to determine the molecular weight distribution of various polyelectrolytes and neutral water-soluble polymers ('28).Adsorption on the SiOz surface of nonionic and cationic polymers was prevented by using a tetramethylammonium salt as a modifier.

THERMAL ANALYSIS (TA) Thermogravimetric (TG) and differential thermal analyses (DTA) of polymers were reviewed by Flynn ( 0 1 4 ) . The use of TA to evaluate and select polymer additives was shown by Cassel (06, 0 7 ) , Riga ( 0 2 5 ) ,and Chan ( 0 9 ) . Some applications of TA for the analysis of polymers were demonstrated by Brennan ( 0 3 ) and Barton et al. ( 0 2 ) . Brennen also discussed the use of thermal analysis (TA) for quality control of thermoplastics ( 0 4 ) . Levy gave examples of TA as a technique for quality assurance and product reliability in polymer, automotive, electronics, and foodstuffs industries (021). T A of high polymers coupled with thin-layer chromatography was discussed by Bruederle ( 0 5 ) . DTA combined with infrared provided a powerful analytical means to identify and solve problems for flexible packaging materials ( 0 1 2 ) . Laine used differential scanning calorimetry (DSC) to analyze multilayer films (020). The effectiveness of TA in determining safety hazards was reviewed by Hassel ( 0 1 9 ) in the area of flammability and explosiveness. DTA as a rapid and simple method for studying the stabilization of poly(viny1 chloride) was discussed ( 0 1 0 ) and reviewed ( 0 2 4 ) . A new, thermal mechanical analyzer was developed to determine the effects of thermal relaxation in films and fiber ( 0 2 2 ) . Measurement can be made in a solvent or liquid. Gillen used thermal mechanical analysis to estimate the tensile compliance for polymers ranging from hard plastics to rubbers. The results correlated well with tensile modulus obtained by conventional techniques ( 0 1 5 ) . T G was used to analyze the decomposition of fireproofed polystyrene. The effect of blowing agents on the efficiency of fire retardant was also examined (028). The determination of antioxidants volatility by T G was reported by Cech and Gomory ( 0 8 ) . DTA and T G were used to analyze the hardening of various phenolic plastics. Thev could be used to determine the bptimum compression tkmperature of the materials ( 0 1 3 ) . Stabilizers for poly(ethy1ene terephthalate) were investigated by Angelova and co-workers using both dynamic and isothermal DTA ( 0 1 ) . Wight used the quantitative DTA to determine the effectiveness of antioxidant in polyethylene stabilization by comparison of oxidative induction times on copper and aluminum pans ( 0 2 7 ) . A combination of DSC and dynamic dielectric analysis was shown to be useful in the study of rheological changes, curing rate, and degree of cure ( 0 2 3 ) . Relative number average molecular weight of poly(tetrafluoroethy1ene) was calculated from the heat of crystallization measured by DSC using the equations of Sperati and Starkweather or Osten ( 0 2 6 ) . Compatibility in polymer blends can be investigated by DSC for glass transition temperature changes. Example for poly(viny1 chloride) and ethylene-vinyl acetate copolymer was given ( 0 1 2 ) .

TORSIONAL BRAID ANALYSIS ( T B A ) The TBA approach to polymer characterization and its application to specific polymer systems were discussed by Gillham ( 0 1 6 ) . Gillham also used TBA to characterize thermosetting epoxy systems ( 0 17) and to investigate relaxation in homopolymers and block copolymers of styrene ( 0 1 8 ) . Evaluation of the thermomechanical behavior of poly(viny1 chloride) using TBA showed changes of relative rigidity due to structural changes in the process of degradation ( 0 2 9 ) .

ELECTRON SPECTROSCOPY FOR CHEMICAL ANALYSIS (ESCA) Clark described the application of ESCA to polymer chemistry in a series of publications (E5-EII) and reviewed its application to studies of structure and bonding in polymers ( E1-E3).

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Possible applications of ESCA in the identification and quantitative examination of polymers was discussed by Holm et al. (E23). Structural changes, such as ring formation in polyacrylonitrile and dehydrochlorination in poly(2-chloroacrylonitrile) due to heat, ultraviolet light and electron impact could be shown by ESCA (E22). Surface changes between original and plasma-treated ethylene-tetrafloroethylene copolymers were studied by comparing ESCA spectra in a multichannel analyzer and producing the different spectra by direct, in-store subtraction (E4).

INFRAREDSPECTROSCOPY General reviews of infrared spectroscopy (IR) for the characterization of polymeric materials were written by Koenig (F32),Nagasawa (F47),Wiles (F73),and Willis (F75). Fourier transform infrared studies of polymeric materials were published by Coleman et al. (F24),D'Esposito and Koenig ( F I 6 ) ,and by Koenig and Antoon (F33). Janicka (F30) reviewed the use of IR and UV absorption spectroscopy for the analysis of polymers and Brown and Harvey (F22) reviewed IR and Raman spectroscopy. Truett (F72) discussed the pyrolysis-IR analysis of polymers. Haering reviewed the IR analysis of polymeric packaging materials and presented IR spectra of polymers, plasticizers, and mineral fillers (F23-F2.5). IR absorption spectra of the surface layers and of the bulk of low density polyethylene (PE) showed a smaller content of crystallites in the surface layers compared to the polymer bulk (F67). Painter et al. (F56, F.57) assigned an infrared absorption band a t 716 cm-' in the spectrum of P E to a monoclinic arrangement of chains and an absorption band at 1346 cm-' to a regular tight fold chain structure. McRae et al. (F42) followed changes in the relative concentrations of methylene groups in crystalline regions, in gauche conformations, and in tie chains in amorphous regions of cold drawn high density P E by unpolarized and polarized IR spectroscopy. A regression analysis of IR, DTA, and X-ray diffraction data (F38)for low pressure PE showed that, as synthesis conditions varied, the number of methyl groups varied from 0 to 15 per 1000 carbon atoms and the degree of crystallinity varied from 84 to 61 %. LePoidevin (F39) showed that the oxidation of stabilized PE in aqueous solution occurred in four steps; the first involving the formation of aldehydes and/or acids followed by a decarbonylation-decarboxylation reaction; the third step involved ester formation and was confined to short polymer chains; the final step involved the rapid formation of acids and ketones. Gamma radiation (sterilization dosages and higher) of high pressure PE gave predominantly ketones at dosages equal to or less than 40 Mrad, and alcohols, ketones, and acids a t dosages 40 to 100 Mrad (F35). T h e far IR spectrum of P E was found by Frank (F20) to consist of a broad background absorption attributable to the amorphous regions of the sam le and a relatively sharp absorption band centered at 73 cm- Pcaused by a lattice vibration of neighboring chains within the crystalline area. Chen (F12) determined the isotacticity of polypropylene (PP) from the ratios of the optical densities of peaks at 1170 998, 973, and 841 cm-' to that of the peak a t 1460 cm-{ (internal standard). Painter e t al. (F58) isolated IR bands characteristic of isotactic PP in the preferred helical conformation and in the irregular conformation of the amorphous phase using the absorbance subtraction technique. Yur'eva et al. (F77) developed a method for the determination of the composition of 1-buteneethylene-propylene copolymers using mechanical mixtures of 1-butene--propylene copolymers and ethylene-propylene copolymers for calibration. Siryuk (F64) determined the absolute content of vinyl acetate blocks in ethylene-vinyl acetate copolymers using absorptivities at 1743 and 1245 cm-'. The absorptivity at 1378 cm-l did not give satisfactory results for the determination of the degree of branching. Munteanu et al. (F46) determined the degree of grafting of vinyl acetate onto PE and the content of vinyl acetate in linear ethylene-vinyl acetate copolymers from the absorptivities of the peaks a t 3455 and 3420 cm The IR spectra of ethylene-vinyl acetate random copolymers, graft copolymers, and blends of PE and polyvinyl acetate (PVAC) exhibit characteristic bands of acetoxy groups (3455, 1739,1241, 1022,947,794 cm-') and of CH, CH2, CH3 groups

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independently of the mode of bonding of vinyl acetate in the polymer (F45). Tamura et al. (F70)developed a pyrolysis-molecular weight chromatography-vapor phase infrared spectrophotometric method for the analyses of polymers. When applied to the analysis of l,4-polybutadiene, the main pyrolysis products were -i-vinyl-l-cyclohexene, 1,3-butadiene, cyclopentene, and 1,3-cyclohexadiene, the relative amounts of which depend upon the cis-trans configurations in the polymer. Allara (F4) used internal reflection IR to study the oxidation of polybutadiene-1 cast on copper or gold. Only carboxylate ion was formed a t the copper interface whereas bands typical of carbonyl, carboxylic acids, aldehydes, and ketones appear a t the gold interface. Spells et al. (F65)described the Raman spectrum at 5-560 cm of amorphous and partially crystalline isotactic polystyrene (PS). IR absorption data for the fluoro, chloro, and bromo substituted P S derivatives are given over the same frequency range. Schmolke et al. (F62)used IR spectroscopy to determine the types and quantities of rubber components in rubber-modified styrene polymers and for the determination of the type and content of ethylene-vinyl acetate copolymers in impact resistant blends with poly(viny1 chloride) (PVC). Oehme et al. (F52) studied the structure of styrene-divinylbenzene copolymers substituted with functional groups (e.g., -CH2CN, -CH20Et, -CH2Bu) in the para position by a combination of pyrolysis-IR, pyrolysis-GC-IR, and pyrolysis-GC-MS. Jasse and Monnerie (F29)used the vibrational spectra of PS model compounds to demonstrate the effects of alkyl chain conformation on the wave number of the 16b and 10b out of plane vibrations of the benzene ring. The 16b mode was influenced only by the local conformation of the alkyl chain whereas the 10b mode is sensitive to the length of the alkyl chain conformation. Aliev et al. (F3) determined the composition of styreneglycidyl p-isopropenylphenyl ether copolymers using the optical density ratios of the IR absorption bands a t 1250 and 1490 cm-'. Balard and hleybeck ( F S ) studied the alkaline yellowing of polyacrylonitrile by the use of model compounds and showed that the yellowing proceeded with the formation of an anion conjugated with a series of conjugated C=N bonds followed by intramolecular cyclization of CN groups. Annealing of highly syndiotactic PVC a t a series of increasing temperatures, above 180 "C, caused the crystallinity to increase steadily as indicated by X-ray diffraction measurements. However the IR spectra did not change indicating that C-C1 bands cannot be used as a measure of crystallinity (F7). Comparison of the Fourier transform IR spectra of poly(viny1idene fluoride) (PVDF) and poly(methy1 methacrylate) with the spectrum of a 1:l molar blend demonstrated that a chemical interaction had occurred when the two polymers were blended (F25). The IR spectra of graft copo1q;mers of Nylon 66 with P V P F showed bands at 840- 885 cm corresponding to rocking vibrations of CH2 groups in PVDF and broken bands a t 1000-1300 cm-' resulting from super position of stretching vibrations of C-N bonds in secondary amide groups with C-F stretching vibrations (F74). Asamov et al. (F2) determined that the content of poly(viny1 fluoride) (PVF) grafted onto PE was linearly related to the ratio of the absorbance of the bands a t 1100 cm-' (stretching vibrations of the C-F bonds) and 1400 cm-' (deformation vibrations of the CH2 groups). Grafting was found to occur on the surface and in the amorphous regions of the PE. The grafting of vinyl fluoride onto Nylon 66 was followed using the 830 cm-' absorption band, the intensity of which increased with increasing amounts of PVF (F76). Dichroism of spectral lines in the multiple attenuated total internal reflectance of poly(tetrafluoroethy1ene) was found to be related to the molecular orientation in the surface layer. An increased intensity of dichroism of the spectral lines a t 1150 and 553 cm suggested a high degree of ordering of the polymer molecules in the surface layer (F37). Copolymers obtained by grafting tetrafluoroethylene onto P E exhibited IR absorption bands a t 515-60,640, and 1115-1225 cm-' assigned to rocking and deformation, wagging, and symmetrical and asymmetrical stretching vibrations of C-F2 groups, respectively, as well as a new band at 820 cm-' absent in the respective homopolymers. The content of tetrafluoroethylene was determined from the ratio of the absorbance at 1170 cm-' to that at 1470 cm-' (deformation vibration of CH2) ( F I ) .


A wide structureless band covering the 5&250 cm-' region with a maxima at 185 cm-' in the spectrum of poly(methacr lic acid) and a band with maxima a t 97, 113, and 136 cm-Y in methacrylic acid was assigned to the fundamental vibrations of hydrogen. Methacrylic acid was shown to exist as cyclic dimers with three IR-active normal modes (F9). Tomescu et al. (F7I) characterized the structures of a series of acrylonitrile-maleic anhydride copolymers from IR spectra. The block structure of polyamides obtained by the two stage polycondensation of p,p'-diphenylenediamine first with terephthaloyl chloride and then with adipoyl chloride was confirmed by extraction and characterization of the fractions by IR, UV, and NMR (FIO). Okamoto et al. (F53) dehydrochlorinated poly(cu-chloroacrylonitrile) and found that the absorbance of the polymer a t 2200 cm-' was directly proportional to the degree of dehydrochlorination and that absorption bands near 1500 cm-' shifted to lower wave number with increasing sequence length of CH=C(CN) units. Structural transitions and relaxation phenomena of polycarbonates were followed by plotting the absorbances at 1230 cm-' (stretching vibration of C-0-C groups) and 940 cm ( P a - C group) against temperature (F5). Stas'kov (F68, F69) used polarization IR to determine the character of molecular orientation in subsurface layers of rigid polymers. The dichroism of the line at 1020 cm-' in the spectra of poly(ethy1ene terephthalate) ( P E T P ) was characteristic for the orientation of CsH6 rings with respect to the film plane. The IR absorbance subtraction technique was used to isolate bands, in composite samples of annealed melt-quenched and solution case samples of PETP, according to their crystalline or amorphous character (F17). The amorphous trans bands were found to shift approximately 1 to 3 cm-' from their positions in the crystalline trans spectrum. Sprouse (F66) used Fourier transform IR to characterize epoxy resin cure processes and internal reflection spectroscopy to study the weathering and oxidation of epoxy-glass fiber composites. Antoon et al. (F6) used Fourier transform IK to study the curing of epoxy resins, to determine the degree of cross-linking and to characterize the chemical processes occurring during various stages of cross-linking. Examination of the IR spectra of the reaction products of glycidyl phenyl ether and bisphenol A diglycidyl ether with secondary alcohols indicated that epoxy cross-linking occurs via interaction between secondary alcohol groups arising from glycidyl ring cleavage and the epoxy groups of the starting chains (F49). Rate constant activation energies and entropies of activation for reactions of diglycidyl ethers with diols were determined by followin changes in the intensity of the absorption band a t 917 cm- (stretching vibration of the epoxy ring) (F60). Gasan-Zade et al. ( F 2 I ) used multiple attenuated total internal reflection IR to follow the reaction of epichlorohydrin and diphenylolpropane. As the reaction proceeded, the intensity of the 1040 cm-' absorption band (ether bonds) increased while the intensity of the 1520 cm-' absorption band (benzene rings) remained constant. T h e composition of epoxy resins reinforced with polyamide fibers was determined from the ratio of the absorbance a t 1660 cm-l (fiber) and 1042 cm (resin) ( F I 8 ) . Noskov (F48)studied the reaction of glycidyl ethers with resorcinol using the IR absorption peaks a t 917 cm (epoxide ring) and 965 cm-' (phenyl ring of resorcinol). Morimoto and Enomoto (F44) determined the major components of cured epoxy resins and polyester resins by IR analysis of gaseous components generated on pyrolysis of the cured resins. Ishida and Koenig (F27, F28) used Fourier transform IR to study glass surfaces modified by silane coupling agents and showed the existence of covalent bonds at the glass-coupling agent interface.. T h e microstructure of trioxane- 1,3-dioxolane copolymers was studied by Opitz (F54, F55). Changes in distribution of OCH2 and OCH2CH20CH2units in the copolymers were explained in terms of transacetalization reactions. IR spectra of samples from the condensation of phenol with urea and formaldehyde showed the presence of secondary and tertiary amine groups indicating the formation of dimers and trimers (F36). A mechanism involving formation of methylolated (hydroxybenzyl) ureas was proposed. Ortho and para substituted benzene rings and intramolecular hydrogen bonding between OH groups of adjacent phenolic rings were observed in t h e IR spectra of wood containing phenol-

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formaldehyde oligomer (F34). Chow (F13)observed that the curing of formaldehyde-phenol- resorcinol copolymers takes place in two stages. A characteristic band a t 960 cm-' was useful for determining resin cure and estimating the resorcinol content of the copolymers. Rocmiak et al. (F60) identified multisubstituted benzene rings, OH attached directly to benzene rings, CH,OH, and CH2 in phenol-formaldehyde resins. Peppas (F59) related the intensity of the 1141 cm-' band to the degree of crystallinity of semicrystalline cross-linked poly(viny1 alcohol). Bound acetic acid in partially hydrolyzed cellulose acetate was determined from the intensity ratios of the absor tion bands at 1740 cm and 890 cm-' (F60). The 1740 cm- absorption band corresponds to the stretching vibrations of the C=O groups. The band at 890 cm-' was used as a measure of thickness of the samples. Jansson and Yannas ( F 3 1 ) measured the IR dichroism of polycarbonates at different strain levels. Below 0.6% strain, the IR dichroism is negligible while above this level the dichroism increases linearly. Gritsenko and Kutsenko (F22)compared the IR spectra of polyurethanes differing only in the distribution of urethane groups along the polymer chains and showed that the urethane group distribution had a significant influence on the distribution of hydrogen bonds along the chain. The absence of intramolecular hydrogen bonding in polyurethane solutions was demonstrated. Disorder in the packing of polyurethane molecules was studied by Semenovich et al. (F62). The highest disorder in molecular packing was observed for polyurethanes prepared by compression molding of the polymer. The presence of 1,2,4-substitutedC6Hs rings in carboxylated styrene--divinylbenzene cation-exchange resins was confirmed by IR analysis iFe?5). A method for determining the water absorption isotherms in styrene sulfonate-Teflon-perfluoro(ethy1ene-propylene) graft copolymer cation-exchange membranes was developed by Le\y et al. (F40). An IR method for the determination of the degree of sulfonation of cation-exchange resins and for determining the chelate complexes formed from carboxylic acids and metals is discussed by Hlavav et al. (F26). The photodegradation of hardened epoxy oligomers was followed by Noskov and Novikov (F51) from the IR spectra of 20 to 30 pm films. Cross-linking and thermal degradation of hydroxymethylated norbornane bisphenol polymers were studied over the temperature range from 20 to 300 "C by Papava et al. (E'63). CH#H groups underwent condensation at lo& 130 "C to the ethers. The ethers decomposed between 130 and 180 "C giving CHO- and methyl-substituted bisphenols. Extensive oxidation was observed a t 250 to 300 "C giving mainly carboxylic groups. An IR rnethod for the determination of the concentration of double honds in unsaturated oligoesters and for estimation of the size of oligomeric blocks between neighboring double bonds was discussed by Faizi and Chikin (Fly).

r:

'

GAS CHROMATOGRAPHY General. The general aspects of the gas chromatography (GC) of polymers were reviewed by Berezkin et al. (G6) and by Epton (G13). Matkovskii et al. (G.Y4) developed a GC method for the determination of the molecular weight distribution of ethylene oligomers and the fractional composition of products of disproportionation of higher olefins. Residual butyl acrylate, methyl acrylate, and methacrylic acid were determined in acrylic polymers after solution in isopropanol (G35). Methods for the determination of unreacted styrene, diallyl phthalate, and methyl methacrylate in polyester resin moldings were proposed by Holtmann and Souren (G25)and by Yamaoka et al. ( G 5 4 ) . Yoshita ((255) extracted plasticizers from poly(viny1 chloride) (PVC) and determined the composition by GC. Barla (G5) hydrolyzed plasticizers extracted from PVC and analyzed the resulting alcohols by GC. Schroeder and Byrdy (G43) converted PVC to polyethylene (PE) by treatment with LiAIHI and determined the short chain branching by GC of the radiolytic splitting reaction products. A GC/MS method was developed by Gilbert et al. (G21) for the determination of ppm quantities of vinyl chloride in plasticized and unplasticized PVC. Reaction products of phenol and formaldehyde were si-

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lylated and separated by GC to give peaks corresponding to methylolated phenols, dihydroxydiphenylmethanes, and monomethyloldihydroxydiphenylmethanes (G32). Krasnova et al. (G28) developed a method for the GC determination of 2,2'-, 2,4'-, and 4,4'-isomers of (H2NC6HJ2 CH2 in aniline-formaldehyde copolymers. Imide monomers and aromatic polyimides, polyamides and poly(amide-imides) were analyzed using alkali fusion reaction-GC (G39). Plasticizers were extracted from cellulose 2,4-diacetate film with ethyl ether and subsequently subjected to GC analysis ( C I S ) . Allen and co-workers (G2) hydrolyzed polyesters and converted the product acids and glycols to the corresponding trimethylsilyl esters and ethers which were then analyzed by gas chromatography. DiPasquale et al. (GI2) developed a head space technique for the determination of trace amounts of dichloromethane in polycarbonates. Schlueter and Siggia ((240) determined alkyl and aryl hydrocarbon groups in polysiloxanes by GC analysis of the alkali fusion reaction products. Pyrolysis-Gas Chromatography. Polymer characterization by pyrolysis-gas chromatography (PGC) and pyrolysis-gas chromatography equipment were reviewed by Brown and Hall ( G 8 ) , Koltai and Barla (G27), Kullik et al. (G30), and by Tsuge and Takeuchi (G52). Zizin et al. (G56) determined the composition of styrene, a-methyl styrene, and butadiene-styrene-a-methyl styrene block copolymers by PGC using mixtures of the corresponding homopolymers for standardization. A PGC method was developed for the quantitative determination of the composition of multicomponent polymer systems and applied to t h e analysis of polyisoprene-poly(methy1 methacrylate)polystyrene mixtures and isoprene-methyl methacrylatestyrene block copolymers ( G I ) . Combined methyl methacrylate in methyl methacrylate-butadiene-styrene copolymers was determined by PGC (G33). PGC analysis of polypropylene showed a characteristic peak of 2,4-dimethyl-l-heptene which was absent in a similar chromatogram of EPDM rubber ( G I 5 ) . Sugimura et al. ((348) found that the thermal stability of ethylene-methyl methacrylate copolymers was related to the degree of branching and the localized distribution of methyl methacrylate units in the polymer chain. Seeger et al. (G44) observed that films, oils, and powders of polyethylene, polybutylene, polybutadiene, polyacetylene, and polybenzene obtained by plasma polymerization did not resemble their commercial analogues when characterized by PGC. Degradation activation energies were calculated and decomposition mechanisms discussed for the thermal degradation of polytetrafluoroethylene and hexafluoropropylene-tetrafluoroethylene copolymers (G38). Fluoroethylene polymers were identified by PGC employing styrene monomer formed bv the decomposition of r>olvstvrene as an internal standard-(G29). Shimono et al. (G45) used PGC to evaluate the seauence distribution in butadiene copolymers with acrylorhrile, methacrylonitrile, methyl methacrylate, methyl acrylate, and methyl vinyl ketone. T h e yield of vinylcyclohexene formed from successive butadiene units in the copolymer showed the different sequential structures. Bound styrene in butadiene-styrene copolymers was determined using PGC with a pyrolysis temperature of 610 "C ((247). Sokolowska e t al. ((246) determined the chemical composition of butadiene-methyl methacrylate-styrene copolymers by PGC with a pyrolysis temperature of 610 "C. Evans and coworkers ( G 1 4 ) analyzed methyl methacrylatestyrene copolymers and butyl methacrylate-styrene copolymers by PGC. Haken et al. (G24) found that copolymers and homopolymer mixtures from styrene, methyl acrylate, 0-methyl styrene, and methyl methacrylate behaved differently when analyzed by PGC. Haeusler and co-workers (G23) determined the microstructure of styrene-butadiene copolymers by PGC. Tsuge and Takeuchi (G53) designed a furnace pyrolyzer stated to yield highly specific quantitation and reproducible pyrograms for any form of polymer sample. The concept was applied to the characterization of diad sequence distribution in acrylonitrile-rn-chlorostyrene copolymer, acrylonitrilep-chlorostyrene copolymer, rn-chlorostyrene-styrene copolymer, methyl acrylate-styrene copolymer, and acrylonitrile-styrene copolymer. Milina and Pankova (G36) de-

termined the acrylonitrile in copolymers with styrene and methyl methacrylate with an error of approximately 2.2% by PGC. Araki ((33)discussed a method for the determination of butadiene in acrvlonitrile-butadiene-stvrene resins bv quantitative PGC. Takada (G49, G50) discussed the PGC determination of dibutylphthalate, diisobutylphthalate, bis(2-ethylhexylphthalate) and di-n-octylphthalate in plasticized PVC. Zorina et al. ((257) described a PGC method for the identification of' glycols and e-caprolactone in urethane polymers such as 1,4-butanediol-diphenylmethane diisocyanate-polypropylene glycol copolymer and e-caprolactone-diphenylmethane diisocyanate-ethylene glycol copolymer. Lesiak et al. ((231) obtained partial qualitative characterization of polyurethanes prepared from 4,4'-dihydroxydibutyl thioether by PGC. The ethylene oxide and propylene oxide content of ethylene oxide--propylene oxide copolymers was calculated from the ethene and propene formed on pyrolysis of the copolymer a t 700-800 "C (G22). Inverse Phase Gas Chromatography, Measurements of polymer structure and interactions by inverse phase or molecular probe gas chromatography were reviewed by Gray ( G I 7 ) . Partial molar free energies of mixing of hydrocarbons in polystyrene, polyethylene, polypropylene, and polybutene-1 were reported by DiPaola-Baranyi et al. (GIO, G I I ) . Galin and Rupprecht (G4j studied the thermodynamic interactions between supported branched and linear polystyrene and nonsolvents at 140-200 "C. The thermodynamic interactions between polydimethylsiloxane or polydiethylsiloxane and various aliphatic and aromatic hydrocarbons over the range 60-180 "C were investigated by Galin ((316). Millen and Hawkes (G37) calculated the diffusion coefficients for various solutes in low density polyethylene from inverse chromatography data. Diffusivities of vapors of glutaraldehyde, formaldehyde, and methanol in poly(methy1 methacrylate) and low density polyethylene were determined by Tock (G51). Hudec (G26) determined the crystallinity of polyethylene powder by inverse chromatography. Braun and Guillet (G7) found that crystallinity as determined by inverse GC could vary by approximately 50% depending upon the experimental conditions and the temperature. T h e discrepancy should be alleviated by a curvilinear extrapolation of retention data. Deshpande and Tyagi (G9) used inverse GC to determine the T g of poly(viny1 acetate). The T g was related to the first deviation in the retention diagram but its accuracy was dependent on the specific probe used. Schneider and Calugaru (G41) discussed the use of inverse GC to determine T g and T m of poly-€-caprolactam, Inverse phase GC was also used to determine the compatibility of polymer mixtures such as PVC-PS mixtures and PVC-polyacrylonitrile mixtures (G42). Grozdov et al. ( C I 9 , G20) used inverse GC to follow the changes in the physical chemical properties of epoxy resins during cross-linking reactions. THIN-LAYER CHROMATOGRAPHY General reviews on polymer separation and characterization by thin-layer chromatography (TLC) were prepared by Belenkii and Gankina ( K I ) ,Inagaki (K5,K6), and by May (K12). Inagaki e t al. (K7, K 8 ) discussed the use of thin-layer chromatography for the separation and characterization of block copolymers. Gankina et al. (K3)used TLC to determine the polydispersity, composition, and stereoregularity of polymers. 2,4- and 2,6-diaminotoluene were determined in polyurethane foam by extraction with methanol, separation of the amines by TLC, and fluorimetric assay (K4). Tinuvin 320, Tinuvin 327, Tinuvin 326, and Tinuvin P were determined in polyethylene by extraction with ethyl ether and TLC on silica gel with cyclohexane-ethyl acetate as the eluent and 5% FeC1, as the developer ( K I I ) . Kalamar et al. (K9) used TLC to determine the purity of plasticizers based on dialkylene glycol dibenzoates. Brinkman et al. (K2) analyzed 2hydroxyethyl methacrylate by TLC on SiOz gel with hexane-ethyl ether or hexaneMIBKoctano1 saturated with 25% HNOBas the mobile phase. Raudsepp et al. (KI3) used TLC to determine 5-methylresorcinol and caprolactam reaction products in polycondensates of 5-methylresorcinol with N-hydroxymethyl-E-caprolactam and formaldehyde. Poly-

ANALYTICAL CHEMISTRY, VOL. 51,

urethanes were hydrolyzed by heating a t 60 "C in nitrogen in an alcoholic KOH solution and the tolylene diamine isomers were separated and characterized by TLC (K10).

LIQUID CHROMATOGRAPHY T h e principles of liquid chromatography (LC) as applied to polymers were reviewed by Cazes (L3)and by Zowall (L18). Fallick and Cazes (157)discussed the application of LC to the characterization of polymer additives and oligomers. Eisenbeiss et al. (L5) reviewed the use of adsorption and partition chromatography for the separation and determination of monomers and oligomers and for the determination of polymer additives such as surfactants. Gross and Strauss (L8) used LC for the analysis of plasticizer mixtures and claimed that the method was superior to gas chromatography and thin-layer chromatography. 2-Ethylhexanol was determined in polymer samples by LC of the corresponding urethane formed by treatment of the alcohol with phenyl isocyanate (L2). Antioxidants in polyethylene were determined by gradient elution high performance LC. More than 20 thermal and photochemical transformation products from 2,6-di-tertbutyl-p-creso! were isolated (L12). Dengreville (L4)described a rapid routine LC method for the determination of UV absorbers and antioxidants in low density polyethylene. Klesper and Hartmann (LIO) described an apparatus for chromatography with supercritical dense gases comprising a pressure cascade of three consecutive levels of decreasing pressure. Separations of styrene oligomers were carried out on analytical and preparative scales. Antioxidants such as Santonox, hydroquinone methyl ether, and hydroquinone were determined in tetraethylene glycoldimethacrylate by high pressure LC (L14). Impurities in bisphenol A were determined by a reverse phase liquid chromatography with a gradient elution system (L15). VanderMaeden and co-workers (L16)used a gradient elution high performance LC to analyze oligomeric mixtures of low molecular weight resins, prepolymers and polymer extracts. T h e separation of epoxy resins, novolaks, poly(ethy1ene terephthalate), and nonionic surfactants are described. Bagon and Hardy ( L I )described a high performance LC method for the determination of monomeric toluenediisocyanate and 4,4'-diisocyanatodiphenylmethane in T D I and MDI prepolymers. Kumlin and Simonson (L11) separated the low molecular weight components of urea-formaldehyde copolymers on the lithium form of cation-exchange resins. A high performance LC procedure for the determination of poly(ethy1ene terephthalate) prepolymer oligomers containing from 1-7 terephthaloyl repeat units was described by Zaborsky (L17). Eremeeva et al. ( L 6 ) used absorption chromatography to determine the molecular weight distribution and the functionality of oligomeric adipic acid-trimethylol propane copolymer and adipic acid-diethylene glycol-trimethylol propane copolymer. Ludwig and Besand (L13) determined unreacted acrylamide in aqueous solutions for oil extended emulsion homo- or copolymers by high performance LC. Husser et al. (L9) determined residual acrylamide monomer in aqueous and nonaqueous dispersed phase polymeric systems by high performance LC with UV detection.

MASS SPECTROSCOPY Brodskii et al. ( M Z ) ,Hughes et al. ( M 6 ) ,Hummel ( M 7 ) ,

Luederwald et al. ( M I 7 ) Mischer (M21),and Mitera (M22) reviewed the pyrolysis of polymers and subsequent mass spectrometric (MS) analysis of the volatile degradation products. Baba ( M I ) determined residual vinyl chloride monomer from 0.02 to 0.1 ppm in PVC by GC/MS monitoring m l e 62. Tantsyrev et al. ( M 2 6 )determined the microstructure of perfluoroethylene-vinylidene fluoride copolymers and chlorotrifluoroethylene-vinylidene fluoride copolymers from the relative intensities of the lines for CF +, CC13+and CH3+. Thermogravimetric-MS and pyrolysis-&C studies of polytetrafluoroethylene and hexafluoropropylene-tetrafluoroethylene copolymer showed that COFz, CF,, and CO, are the main decomposition products in air ( M 2 4 ) . Chaigneau ( M 3 ) found that the main gas phase pyrolysis products from polyacrylonitrile, acrylonitrile-styrene co-

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polymer, and acrylonitrile-butadiene-styrene copolymer are HCN, Hz, and methane. Mitera et al. (M23) found that polystyrene started to decompose in air a t about 290 "C with the main products being COP,benzene, alkylbenzenes, styrene, phenol, indane, styrene oxide, acetophenol, vinylbenzaldehyde, dimer, diphenylpropane, and diphenylpropene. Fewell ( M 4 ) found that p-polyphenylene thermally decomposed in two stages, the first being dehydrohalogenation and the second dehydrogenation. Leuderwald et al. (M19)volatilized cyclic oligomers present in poly-t-caprolactams by pyrolysis at 100 "C in the ion source of a mass spectrometer; polymer degradation with the formation of cyclic oligomers begins a t 390 "C. Luederwald e t al. ( M 1 8 ) differentiated between the isomeric polyamides of truxillic and truxinic acid and piperazine by direct pyrolysis in the ion source of a mass spectrometer. The composition of adipic acid-piperazine-truxillic acid copolymers was determined by the same method. The sequence distribution of copolyamides such as p-aminobenzoic acid-6-aminohexanoic acid copolymers was determined by pyrolysis in the ion source of a MS (M16). Mumford et al. (M25) analyzed the hydrolysis products of rigid polyurethane foams using chemical ionization MS and high-pressure liquid chromatography. Koscielecka (M13) showed that the thermal degradation of polyurethanes occurred by depolymerization. Leuderwald and Urrutia (M20)established the degradation mechanisms of aliphatic and aromatic polyesters by direct pyrolysis in the ion probe of a MS. Cyclic trimers were determined without previous isolation. Kricheldorf and Leuderwald ( M 1 4 ) determined the structure of poly(@propiolactone), poly(@-pivalolactone), and poly(a-propiolactone) by pyrolysis-MS. Direct pyrolysis of polyesters and copolyesters of lactic acid and glycolic acid yielded cyclic oligomers which were further degraded by an electron impact induced mechanism with the elimination of HCHO or MeCHO and C 0 2 ( M 6 ) . Gilland and Lewis ( M 5 ) found that cyclic trimer, tetramer, pentamer, and hexamer were produced when terephthalate polyesters were heated at 240, 280, 330, and 360 "C, respectively. Iyoda et al. ( M 8 , M 9 ) prepared a siloxane mass map for interpreting the structure of linear and cyclic siloxanes. Pyrolysis-MS was used for the determination of low molecular weight components in solid and liquid epoxy resins ( M 1 2 ) . Kalinkevich et al. ( M I I ) used pyrolysis-MS to determine epoxy and hydroxyl groups and the number of phenylene rings between epoxy groups in epichlorohydrindiphenylolpropane copolymers. Lee and Sedgwick ( M 1 5 ) found that the mass spectra of linear copolymers of ethylene and propylene oxides showed features characteristic of the two monomers permitting identification of random and block structures.

NUCLEAR MAGNETIC RESONANCE General reviews of the principles of nuclear magnetic resonace (NMR) spectroscopy and its use for the characterization of polymers were published by Harwood, ( N 3 3 ) , Heatley ( N 3 7 ) , Chung ( N 4 2 ) , Levy (N62), Moniz (N68), Nishioka ( N 7 3 ) ,Poranski et al. ( N 8 4 ,Roth et al. (N95),and Urbanski (NII0). Nishioka et al. ( N 7 4 ) determined the degree of chain branching in low density polyethylene (PE) using proton continuous wave NMR, Fourier transform NMR a t 100 MHz and 13CFourier transform NMR at 25 MHz with concentrated solutions at approximately 100 "C. The methyl concentrations agreed well with those of IR based on the absorbance a t 1378 cm-'. Cutler et al. (N20)determined the distribution of side chains in branched P E by 13C NMR of the HNOBdegradation product. Ethyl and butyl side chains were found to be excluded from the crystalline zones. Amyl and hexyl branches were identified from the I3C NMR spectra as short chain branches in low density P E (N88). Multiple-pulse NMR was used by Pembleton et al. (N80)to determine the amorphous fraction of PE. NMR investigations of solution crystallized PE showed that the lamellar crystallites are composed of approximately 80% crystalline material with a noncrystalline overlayer of about 15%. The phase structure exists independent of molecular weight (N40). Proton NMR studies of low molecular weight PE confirmed that it is predominantly composed of lamellar crystalline regions with a minor amount

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of interfacial regions and no liquid-like interzonal regions (N56). High-field I3C Fourier transform NMR spectra indicated -40 "C as the upper limit to the T g of linear P E (N5). Pulsed NMR measurements of ultra high molecular weight linear PE indicated a second transition of longer relaxation time appearing at the temperature characteristic of the gamma relaxation. The gamma relaxation meets most criteria for assignment of T g (N7). Asakura and co-workers ( N 3 )observed several new peaks in the 13CNMR spectra of polypropylene (PP)prepared with VC14-Et2A1Cl catalyst and assigned the peaks t o isolated head-to-head or tail-to-tail units. Randall (N87) developed a 13C NMR method for the determination of the ethylene/ propylene mole fractions and the number average sequence length of CH2 units in the ethylene-propylene copolymers. Natural abundance I3C NMR a t 22.6 and 37.9 MHz and nuclear Overhauser enhancements were used to study the stereochemical configuration in a low ethylene content ethylene-propylene copolymer. No evidence was found for a mixture of meso and racemic configurations in the PP chain across an inserted ethylene unit (N98). Comonomer content in isotactic ethylenepropylene copolymers, complete diad and triad content as well as partial tetrad and pentad distributions were determined by Ray and co-workers (N93) using "C NMR. An analytical method was developed for determining the composition of CZF4- C3F, copolymers based on the 19FNMR spectral peaks for CF3 and CF, ( N 2 ) . A peak assigned to the acetate methyl protons wm split into a triplet and the peak assigned to the methine proton was split into a quintet and a broad peak in the high resolution proton NMR spectra of ethylene-vinyl acetate copolymers measured in the presence of a shift reagent. The split peaks were assigned tentatively to the acetate methyl and methine protons of the central vinyl acetate unit in triad sequences, respectively (N77). Elmqvist (N27) investigated the compatibility of blends of PVC and ethylene-vinyl acetate copolymers by NMR. Keller and Muegge (N53, iV54) and Schwind and Keller (N99) determined the microstructure of chlorinated PE based on high resolution proton and 13C NMR studies. The microstructure of polychloroprene was characterized by I3C WMR (N18)and by high resolution NMR (N76). Lines associated with diad and triad sequences involving trans-1,4-; cis-1,4-; 1,2-; isomerized 1,2-; and 3,4-structural irregularities were identified and assigned. Brame and Khan (NIO)used proton NMR to determine the composition of 2-chlorobutadiene-l,3 and 2,3-dichlorobutadiene-1,3 copolymers and 13C NMR to characterize the sequencing in the polymers and copolymers. T h e diad distribution of cis-1,4 and trans-1,4 units in low molecular weight 1,4-polyisoprene was determine from the 13C NMR spectra a t 350 K by Morese-Seguela et al. (N69). Beebe ( N 8 ) and Dolinskaya et al. (iV24) studied the sequence structure of polyisoprene with 3,4- and cis,trans-1.4 structural units by 13C NMR. Mauzac and co-workers ( N 6 7 ) determined the overall isotactic content of crude polybutene-1 by "C NMR. The C3Hs content of 1-butene-propylene copolymers was determined from the area of the C3H6-C4H8diad in the NMR spectra ( N 2 8 ) . T h e stereosequence distribution in 1,4poly(2,3-dimethyl-l,3-butadiene) as determined by "C NMR was evaluated (N94). Quack and Fetters (N85) showed the presence of a vinylcyclopentane structure in polybutadiene apparently resulting from intramolecular cyclization during propagation a t low monomer concentration. Shibata and co-workers (N100) determined the vinyl content in 1,2polybutadiene by pulse Fourier transform 13C NMR using acetonitrile as a n internal standard. T h e microstructure of polyperfluorobutadiene as determined by 13C NMR complemented and confirmed the "F NMR data which showed mainly 1,4 moieties ( N I 0 9 ) . T h e Composition and diad, triad, and tetrad sequences of isotactic 1-butene-propylene copolymers were determined by I3C NMR ( N 9 0 ) . The tetrad was the longest sequence detected a t 25.2 MHz. Proton NMR signals for olefinic end groups, --CH2C(CH3)=CH2, -CH=C(MeI2, and --CH&(=CH2)CH2- were observed in high molecular weight polyisobutylenes (N65). Ivin and co-workers ( N 4 3 ) determined the fraction of cis double bonds in cyclopentene polymer and in bicyclo(2,2,l)hept-2-enzpolymer with 13C NMR. The

spectra of polycyclopentene showed a cis and trans peak for each =CH and n-CH2 but only 1 peak for the P-CH,. Jasse and co-workers (N45) compared the I3C NMR chemical shifts of various structural sequences of model compounds with the chemical shifts of polystyrene (PSI and concluded that methyl, methylene, and carbon atoms attached to the backbone chain are sensitive to tacticity. The degree of cross-linking and residual monomer and oligomer content of PS films formed by glow discharge polymerization of styrene was determined (N70). Morita and co-workers (N71) used broadline NMR to study plasma polymerized PS. Two types of NMR line shapes were observed: a broad component attributed to cross-linked P S and a narrow component attributed to low molecular weight species. Conti and co-workers ( N I 9 ) concluded that the off-resunance 13C NMR data on butadiene-styrene copolymers were consistent with that for atactic polystyrene. The composition of butadiene-styrene copolymer latexes as determined by I3C NMR is reported by Cunliffe and Pace (N21). Randall (N89) described a general method for the characterization of terpolymers using 13C NMR. The method as applied to hydrogenated butadiene-styrene copolymers shows how the number average sequence length can be obtained from diad, triad, and higher order monomer distributions. T h e sequence length of sterochemical additions in amorphous and semicrystalline olymers such as PP and PS were accurately measured using f:C NMR (N91). The method has some limitations for addition polymers having predominantly isotactic sequences. Comonomer composition of random and alternating copolymers of styrene with butyl methacrylate, ethyl methacrylate, butyl methacrylate, or octyl methacrylate was calculated from proton NMR spectra (N82). T h e stereoregularity of polymers such as polyacrylates, poly(alkylviny1 ether), polymethacrylonitrile, rolystyrene, and poly(propy1ene oxide) was determined from C NMR spectra (N61). W-ang and co-workers (N114)studied the 300 MHz proton NMR spectra of methacrylic acid-styrene copolymers and found that the spectra contained sufficiently well resolved methine proton resonances that could be used directly for sequence distribution characterization. The monomer sequence distribution in styrene-sulfur dioxide copolymers was determined from I3C NMR spectra. The spectra showed that 1:1 alternating sequences were not formed above approximately 40 "C. Triad monomer sequences were resolved and assigned from the multiple resonances observed for the methine, methylene, and quaternary carbons. The sequence distribution in acrylonitrile-methyl methacrylate copolymers was determined by analyzing the complex pattern of the (w-CH3peaks in the NMR spectra (N48). A 13C NMR technique was developed for the direct estimation of the relative concentrations of different acrylonitrile oligomer isomers (N6).The technique was used to determine the tacticity of polyacrylonitrile and acrylonitrile dimer, trimer, and tetramer. Fourier transform proton NMR studies of poly(viny1 chloride) (PVC) indicated that the unsaturated end groups contained allylic chlorine atoms. The presence of the unsaturated end groups would partially explain the PVC degradation ( N 1 4 ) . Petiaud (N81) observed that very low molecular weight PVC contained l-chloro-2-pentene groups which can be hydrochlorinated to form 1,2-dichloroethylene. The polymer also contained 2 to 3 double bonds per 10o0 mer units. Lukas and coworkers (N63) suggested that the chlorination of PVC involves a dehydrochlorination-chlorine addition mechanism. The 13C NMR spectra of chlorinated P V C was used to determine the fraction of vinyl chloride units in unchlorinated sequences. Keller and co-workers (N51,N55) interpreted the 13CNMR spectra of chlorinated PVC in terms of structure and the fraction of vinyl chloride units in unchlorinated sequences. Copolymers of vinyl chloride and trichloroethylene were prepared and used as models for the NMR determination of the structures of chlorinated P E and chlorinated PVC (N30). An NMR technique was developed by U'ilks (N115) to determine the average block length in copolymers. The technique was illustrated by a monomer sequence study of stereoregular butadiene-vinyl chloride copolymers. Kubik et al. (N60) developed a proton NMR method for determining the ratios of vinyl chloride and propylene in vinyl chloride-propylene copolymers. Kubik and cu-workers ( N b ' f )


showed that the NMR spectrometry of propylene-vinyl chloride copolymers a t 160 "C is improved when oxygen has been removed beforehand by blowing helium over the copolymer at a temperature of liquid nitrogen. Keller (N50) proposed introducing corrections, relating to the interactions of vicinal chlorine atoms within the chain, through the increment system proposed for calculating the chemical shift of 13C: NMR of chlorine-containing polymers. The deviations of 13C chemical shifts to higher fields caused by the steric hinderance of vicinal carbons were 7 ppm for chlorinated P E , 1 2 ppm for chlorinated PVC, and 7-15 (depending on the possible arrangement of chlorine) for trichloroethylene-vinyl chloride copolymers (N571. NMR spectra, 300 MHz and 220 MHz, were obtained for poly(methy1 methacrylate) (PMMA). The methylene proton resonances in the 300-MHz spectra were better resolved and defined. Tetrad, pentad, and hexad resonances are recognizable in the 300-MHz spectra (N107). Strasilla and Klesper (N106)showed that in syndiotactic PMMA only the units once removed are responsible for resolving the methoxy resonance into three peaks. Roussel and Galin (N96) determined the sequence distribution in methacrylophenone-methyl methacrylate copolymers by 13C [proton] NMR. The sequence distribution of chloroprene-methyl methacrylate copolymers was studied using proton NMR (N78). The 13C relaxation times a t 38 and 100 "C were longer for isotactic PMMA than for syndiotactic PMMA indicating more segmental motion in the isotactic chain backbone (N116). Keller et al. (N52) stated that the overall composition of ethylene-2-chloroacrylate copolymers and ethylene-glycidyl acrylate copolymers could be determined easily and cheaply by proton NMR; however, 13C NMR was a more accurate technique for sequence distribution determination. Configurational pentads and compositional triads in the 13C NMR of atactic methacrylic acid-methyl methacrylate copolymers were assigned based on known chemical shifts and analysis of syndiotactic and isotactic copolymers and atactic homopolymers ( N 4 6 ) . Johnson et al. (N47) calculated the composition of methacrylic acid -methyl methacrylate copolymers from the I3C Fourier transform NMR spectra in pyridine employing the resonances arising from COzH and ester CO groups. Heublein and coworkers (Ar38) determined the composition, tacticity, average sequence length, and degree of cross-linking of poly(ally1 methacrylate) and allyl methacrylate-methyl methacrylate copolymers by proton NMR. T h e tacticities of poly(alky1 methacrylates) were determined by using the large difference in the spin-relaxation times of protons in a-methyl and ester groups t o eliminate the ester group resonance overlap with the tu-methyl signal (''36). The spin-lattice relaxation of the ct-methyl protons in isotactic PMMA and syndiotactic PMMA arise mainly from dipolar interactions between the protons in the methyl group itself (N34)and the relaxation times of carbon atoms in isotactic polymers are consistently longer than those of comparable carbon atoms in syndiotactic polymers (X35). NMR spectra, 220 MHz, for copolymers of methyl methacrylate, acrylonitrile, or methacrylonitrile with isoprene or chloroprene showed that a linkage was always formed between the alpha-position of the acrylic monomer and the one-position of the 1,3-diolefin (N31). Adelman and Ferguson ( N I ) determined the concentration of 1,2-glycol and side HOCH2CH2groups in poly(viny1 alcohol) (I'VAL) by NaIO, cleavage and 220-MHz proton NMR. The methine carbon resonances in I3C Fourier transform NMK of P V A L were resolved into a triplet of triplets which was assignable to pentad tacticity. Analysis of the methine NMR showed that radical polymerization of vinyl acetate is atactic while poly(viny1 acetate) prepared by cationic polymerization is isotactic ( N 1 1 8 ) . 13C resonances of head-to-head and tail-to-tail sequences in poly(viny1idene chloride) were assigned by Bovey and co-workers ( N 9 ) . Proton and 19F NMR relaxation data of hexatluoroisobutylenevinylidene chloride copolymers showed an tu-relaxation associated with the glass transition (N30). The proton spin-spin relaxation times were deconvoiuted into crystalline and amorphous components above the glass transition temperature. DeMember et al. iN23) measured the relative intensities of I3C NMR signals for carbon atoms in hydroxyethyl cellulose and computed the average chain length of the poiy(ethy1ene oxide) side chain, the degree of substitution of ethylene oxide,

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and the relative degree of substitution of the alcohol groups on the anhydroglucose ring. The isomerization of maleic to fumaric during polymerization of maleic acid with polyols was determined from NMR signals at 3.26 and 3.67 corresponding to trans and cis hydrogen respectively (N112,N113). A I3C NMR and proton NMR study of the distribution of monomer units in copolyesters such as ethylene glycol--sebacic acidterephthalic copolymers was reported by Urman et al. (N111). Sharper resonance signals and slightly greater differences in chemical shifts were observed when trimethylsilyl ethers of polyhydric alcohols were used instead of the alcohols in NMR analysis ( N 4 4 ) . The cross-linking of unsaturated polyesters with styrene was determined by NMR from the aromatic proton band width of free styrene ( N I I i . Pulsed NMR was used by Rutenberg et al. (N97)to measure the Tg of cured epoxy resins. Paladini (N79)used a 60-MHz proton NMR technique to measure the average number of repeating units, number average molecular weight, and hydroxyl number of both liquid and solid epoxy resins. A rapid proton NMR method was described by Dorsey and co-workers (N25) for the determination of epoxide equivalent weight of epoxy resins. Poranski (N83) used I3C Fourier transform NMR to identify solvents and reactive diluents in epoxide resin systems without separation. Pulsed NMR was used by Assink and Wilkes ( N 4 )to show that segmented polyurethanes as well as block copolymers segregate into domains with distinct mobilities. Nikolaev et al. ("2) studied the rate of reactions and chain mobilty of polymeric systems based on 2,4-tolylene diisocynate from spin-spin relaxation times. Yeager and Becker ( N I 1 9 ) determined the composition of polyester urethanes and the number average molecular weight of the polyester units by high resolution proton NMR. Willsch et al. (!VI171 used 60-MHz pulse proton NMR to distinguish between the three different t>-pes of carbon bonded protons in rolyamides. Kricheldorf and Hull (NS8) used 90.5-MHz C NMR to determine the sequence distribution and the ratio of monomer units in ternary copolyamides. Thermal analysis and NMR studies indicated that Nylon 66 was composed of folded chain lamellae with large amounts of less perfect crystalline regions ( N 4 1 ) . Kricheidorf et al. (X59) used 13C NMR to show that the ratio of different amide groups present in polyamides depended on the monomer properties. Ratov et al. (X92) determined the content of end NCO groups, number of isocyanurate rings per unit of polymer chain, and the number of bridging groups between isocyanurate rings in polyisocyanurate. C NMR. 25.03 MHz, studies of poly(N-vinyl carbazole) indicated the presence of syndiotactic rich structures or isotactic rich structures depending upon the catalyst system employed in the polymerization. Griffiths ( N 3 2 ) concluded that NMR st,udies of poly(N-vinyl carbazole) indicated an atactic backbone. Williams and co-workers ( N Z I 6 ) used 29Siand NMR to determine the number average block lengths and total polymer composition of polycarbonate-polydimethylsiloxane block copolymers. Proton NMR was used by Raigorodskii et al. (r\iS6) to determine the block structure of copolymeric siloxane-urethane polymers. Pulsed NMR techniques were used by Charlesby et al. (lV15, ,V16, N29j to evaluate cross-links and entanglements in polydimethylsiloxanes. Carbonyl 13C NMR resonances were assigned to monomer sequence pentads and configurational sequence diads and triads in acryamide- sulfur dioxide copolymers (N13). The content of methylol, methylene, and oxymethylene formaldehyde and of nonsubstituted, monosubstituted, and disubstituted amino groups in melamine-formaldehyde condensates was determined using NMR and chemical analysis ( N I 7 ) . Tomita ( N 1 0 8 )used NMR and high speed liquid chromatography to follow the formation of methylol derivatives of melamine in polymerization with formaldehyde. Nine methylol melaniiries including isomers of di-, tri-, and tetramethylolmelamine were identified and quantitated. T h e formation of monomethylol urea, symmetrical arid asymmetrical diniethylol urea, trimethylol urea, and hemiformals in the first stage of polymerization of urea-formaldehyde resins was confirmed by proton NMR studies (N102). Slonim et al. (N101.N103, N 1 0 4 ) and Ebdon and Heaton (N26) used NMR t.o determine the composition of urea-formaldehyde resins.

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T h e structures of formaldehyde copolymers with phenols, urea, and melamine were elucidated by 13C NMR studies (N22). Smejkal and Pop1 (NIO5)separated the condensation products of 2,6-xylenol and formaldehyde and characterized the various products by NMR and mass spectrometry. Nowlin a n d Boyd (N75) determined monomer, dimer, trimer, and tetramer in tert-butylphenol-formaldehyde resins after direct silylation.

LUMINESCENCE Nathan and co-workers ( P I 2 ) reported on the use of chemiluminescence for characterization of the degradation processes in polymeric materials. Chemiluminescence studies provided information on the nature of the thermodegradation of polyethylene and on the activity of antioxidants and oxidants (P8). Suzuoki et al. ( P I 6 ) reported on the effect of oxidation of polyethylene on the decay rate of the thermoluminescence peaks. Nakamura et al. ( P I I ) attributed the appearance of an anomalous thermoluminescence peak in oxidized polyethylene to the presence of oxides. Allan et ai. (P4) assigned the phosphorescence emission from low density polyethylene, prepared using oxygen as an initiator, to the presence of a dienone impurity chromaphore. Traps responsible for three lower temperature thermoluminescence peaks in high density polyethylene were located in the amorphous area and lamellar surfaces while the higher temperature peak was assigned to oxidation products in the crystalline or crystalline-amorphous boundary areas (PI 7). Changes in the phosphorescence spectra of oxidized polypropylene were attributed to carbonyl group formation and to subsequent onset of the photochemical decomposition (PI). Pender and Fleming ( P I 4 ) and Radhakrishna et al. ( P I 5 ) reported on thermoluminescence studies of polystyrene. The primary source of chemiluminescence in poly(tetrafluoroethylene) was attributed to oxidizable additives or contaminants (PIO). Matisova-Rychla et al. ( P 9 ) used chemiluminescence of ozonized PVC to determine the type of peroxide groups formed. Allen e t al. (P3,P5) elucidated the thermal and photochemical oxidation processes of nylon polymers by luminescence spectroscopy. Coisson et al. (P6) found electroluminescence useful as a probe for studying the breakdown mechanisms in triethylenetetramine-cured epoxy resins. Fedosyuk et al. (P7) established a dependence between polymer luminescence and the. degree of cross-linking of glass fiber reinforced epoxy resins. Allen et al. (P2)found that the fluorescence excitation and emission spectra of poly(ethy1ene terephthalate) did not match those of dimethyl terephthalate indicating that fluorescence emission is not due to monomeric units. The phosphorescence excitation emission spectra was observed to originate from the monomer unit. Padhye et al. (PI3) confirmed that the fluorescence emission spectrum of poly(ethy1ene terephthalate) did not arise from the basic terephthalate units.

ELECTRON SPIN RESONANCE The theory of electron spin resonance spectroscopy (ESR) and methods used in the study of polymers were reviewed by Hodgeman (Q2). Mizuno ( Q I O ) reviewed the principles of ESR and its application in polymer studies. Tsuji ( Q I 3 )and Windle and Freedman ( Q I 4 ) discussed the use of ESR for studying the photodegradation of polymers. Windle and Freedman observed that additives served as photosensitizers rather than as primary sources for free radicals in promoting photochemical degradation. Hori et al. (Q3,Q 4 ) used ESR to study radicals in polyethylene. ESR studies of polymer transitions were recorded by Kumler et al. (Q7,Q9) and Boyer et al. ( Q 1 ) . Keinath et al. (Q6) found the T g of the soft phases of block copolymers to be in approximate agreement with those of the respective high molecular weight homopolymers while the T g of the hard phases deviated widely from those of the corresponding homopolymers. Time-dependent ESR spectra were found to be sensitive to the number average rather than weight average molecular weight and were useful for determining Tg values in polydispersed materials ( Q S ) . Huron and Meybeck ( 9 5 ) determined the kinetic and thermodynamic parameters of the dehydrogenation of polyacrylonitrile (PAN) and of the reaction of oxygen with PAN pyrolysates by ESR. Sakaguchi et al. (Q12) used ESR to

determine free radicals produced at chain ends of poly(tetrafluoroethylene) by mechanical scission. O'Donnell et al. ( Q I I ) used ESR to study the degradation of polymers.

RAMAN SPECTROSCOPY The applications of Raman spectroscopy for structural studies of polymers were reviewed by Koenig (R8),Shepherd ( R I 4 ) ,and Zerbi (RI8). Andrews and Hart ( R I )discussed the potential applications of laser Raman spectroscopy to the study of polymers. Painter and Koenig ( R I 2 )reviewed the applications of computerized Raman spectroscopy to the analysis of polymer molecular structure using trans-1,4polychloroprene, neoprene rubber, and butadiene rubber as models. The longitudinal acoustical mode of Raman spectroscopy was found to have a frequency sensitive t o chain length and therefore related to lamellar thickness of crystalline polymers ( R 4 ) . Strobl and Hagedorn ( R I 6 )developed a Raman method for determining the crystallinity of polyethylene. Maxfield et al. (RIO) used polarized Raman to study the crystallinity and amorphous orientation in polyethylene. Assignments in the vibrational spectra of linear crystalline polyethylene are reported by Hendra et al. (R6). Chalmers (R2) discussed the laser Raman spectrum of helical syndiotactic polypropylene. Raman and IR spectra of melt crystallized and solution crystallized isotactic poly1-docosene showed that the second endothermic peak (328 K) in the DTA curve of melt crystallized polymer was due to a change of the polyethylene-like side-chain order (R7). Maddams (R9) used Raman to characterize polyene sequences in degraded PVC samples and made assignments of the C-C1 stretching modes. Methyl methacrylate monomer was determined in poly(methyl methacrylate) (PMMA) based on measurement of the intensity of the C=C vibration at approximately 1640 cm-' (RI7). Low frequency Raman spectra (less than 100 cm-') of solid amorphous PMMA and polystyrene showed two previously unresolved broad bands attributed to changes in the density of states function for skeletal normal modes ( R I 5 ) . The longitudinal acoustic mode fundamental and the 3rd harmonic in the Raman spectrum of poly(ethy1ene oxide) was observed to be a function of the oligomer (molecular weight -200) content (R5). Purvis and Bower ( R I 3 ) studied molecular orientation in poly(ethy1ene terephthalate) by means of laser Raman spectroscopy. Coleman et al. (R3)used Raman to identify the crystalline and amorphous regions of trans-1,4-polychloroprene. Mukherjee ( R I I ) developed a laser Raman method for the determination of terminal mercapto groups in polythiol ether prepolymers using ethyl acetate as an internal standard.

NEUTRON SCATTERING The theory of small angle neutron scattering and applications to the study of polymers were reviewed by Allen and Wright ( S I ) ,Hamada (S5,S6) and Jahshan (S12). Ballard et al. (S3) examined the chain configuration of pressure crystallized polyethylene and interpreted the results in terms of a chain folding mechanism in which a molecule was bounded by the surfaces of a lamellar block. King et al. ( S 8 ) discussed small angle neutron scattering on poly(deuteroethylene) dissolved in polyethylene. T h e factors governing molecular aggregation in polyethylene-d,-po!yethylene blends were studied by small angle neutron scattering

(SII).

Picot et al. (S9)discussed neutron small angle scattering experiments on hot-stretched and annealed tagged polyethylene films in terms of coil deformation. Benoit et al. ( S 4 ) used small angle neutron scattering to study the structure of networks formed by anionic block copolymerization of styrene with divinyl benzene. Small angle neutron scattering and light scattering studies of styrene-methyl methacrylate diblock copolymers indicated that the poly(methy1 methacrylate) block forms an interior core from which the polystyrene block radiates outwardly as an expanded chain (S7). Ruland (SIO) used neutron small angle scattering and X-ray small angle scattering to study the molecular conformation and disorder of molecular packing of amorphous polymers. Ballard et al. ( S 2 )studied the relationship between morphology and chain conformation of molten and crystalline isotactic polypropylene by small angle neutron scattering using samples containing

ANALYTICAL CHEMISTRY, VOL 51, NO. 5, APRIL 1979

small amounts of polypropylene-d, in a protonated polypropylene matrix.

MICROSCOPY Techniques for investigation of high polymers with scanning electron microscopy (SEM) was reviewed by Holm (T6, T7). The use of SEM and transmission electron microscopy (TEM) to characterize the morphology of multiphase polymers was studied and reviewed by Thomas ( T I 8 , T!9). Hobbs showed that the rubber particle size, as well as the size and density of the inclusions, in rubber modified polystyrene which couldn't be resolved by T E M with lengthy exposure of the sample to OsOI could be accurately resolved by S E M without staining ( T 4 ) . Morphology of polyethylene (PE) was extensively studied by numerous workers using various electron microscopies (EM) ( T S , T14-Tl7). A chlorosulfonation staining procedure was described by Hodge et al.; it was considered a major aid to the E M studv of PE and was used to examine the lamella growth in PE (p5). Cevnowa (T2)used T E M to investigate the distribution of small" ionogenic group concentratio; and morphology of various fluorinated polymeric and poly(styrenesu1fonic acid) containing cation-exchange membranes. T h e effect of spherulite on size fracture processes and mechanical properties of isotactic polypropylene was examined by Friedrich and Wittkamp (T3, T21). Koszterszitz and co-workers described in detail t h e freeze-drying sample preparation and shadowing techniques of EM to determine the molecular weight distribution of noncrystallizable polymers (T9-TI2). E M was used to study microstructure of synthetic latex particles ( T I ) ,latex particle size ( T I 3 ) ,and the kinetics and mechanism of polymerization of the latex ( T 2 0 ) .

ACOUSTIC Ultrasonic studies of solid polymers was reviewed by Phillips with 122 references ( U 4 ) . Ultrasonic attenuation and velocity could be followed to study relaxation process in polycarbonate, polysulfone (Cr3), poly(alky1 methacrylates) ( U 2 ) ,and structural transformation in polyamido imide films ( U 6 ) . Roeder and Crostack demonstrated that sound emission analysis could be used to distinguish between crazes and cracks in poly(methy1 methacrylate) (U5). Fisher used a rapid and simple ultrasonic method to determine the kinematic viscosity on dilute polymer solutions which was directly proportional t o the average molecular weight. The molecular weight of a polycarbonate sample determined by this method was the same as t h a t determined by means of intrinsic viscosity to within *170 ( U 1 ) .

TURBIDIMETRIC TITRATION The characterization of polymeric systems by turbidimetric titration was reviewed by Seymour et al. The use of turbidimetry for determining molecular weight distribution, separating and identifying the component mixtures, and estimating solubility parameters of homopolymers was described and illustrated (V3). A turbidimetric titration method was developed to determine the content of residual free oligomer which was related t o the deviation of the titration curve from its extrapolated linear portion (V2). T h e distribution of chemical compositions of butadienestyrene block copolymer molecules in a gel permeation chromatographic elute was derived from the increase of turbidity with volume a t different points of the turbidimetric titration curve. By plotting such a distribution perpendicularly over the curve representing constant elution volume a t the molecular weight-composition plane, a three-dimensional surface was obtained which characterized completely the molecular and compositional distribution of the polymer ( V I ) .

MOLECULAR WEIGHT A N D VISCOSITY T h e effect of solute volatility, drop size, and calibration factor constancy on t h e accuracy of molecular weight determination by vapor pressure osmometry was examined (W7,

W8).

A thermal precipitation method has shown that molecular weight distribution of low density polyethylene could be

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deduced from the precipitation curves using simple calculations ( W I ) . Sedimentation equilibrium in a density gradient gave accurate composition analysis of butadiene-styrene copolymers ( WIO). The design of an automatic recording capillary viscometer and its application to the study of polymeric reactions were described by Kilp et al. (W5). A new representation of viscosity data was proposed. A straight line plot was possible even when the exponent a in the Mark-Houwink-Sakurada (MHS) plot was not constant (W2). Accurate molecular weight determinations were possible in the range where the MHS equation is least applicable (W3). Solution viscosity of small poly(ethy1ene terephthalate) (PET) samples could be derived from viscosity of the mixture of the sample and a standard PET of known viscosity ( W I I ) . Viscometric determination of the molecular weight of polyethylene was reviewed by Lanikova et al. (W6). The values of constant K and 01 in the MHS equation were reported for both the number and weight average molecular weights of polystyrene in ethyl acetate ( W 4 ) . Viscosimetry was used to study the adsorption complex formation between anionic surfactants and water-soluble polymers such as poly(viny1 alcohol), methyl cellulose, and pol acrylamide. No complexes between cationic surfactants andiwater-soluble polymers were detected ("12). Viscosity measurement of powdered thermosetting resin, e.g., polyphenyls, melamine resins, and polyamides, was determined using a small specimen parallel-plate plastometer. The effects of specimens compaction pressure and reduction of adhesion between specimen and parallel plates were examined ( W 9 ) .

X-RAY DIFFRACTION The use of high pressure X-ray diffraction for the study of linear polyethylene (PE) was discussed by Rozkuszka ( X I 4 ) . Pae and co-workers ( X 1 2 )found that P E with an initial chain folded morphology and orthorhombic crystal structure did not transform to any other phase prior to melting; however, a reversible orthorhombic and hexagonal phase transition is possible in an extended chain morphology formed on crystallization at high pressures. Small angle X-ray scattering and Raman characterization of the lamellar structure in solution crystallized P E indicated that the lamellae consisted of a crystal center and disoriented and disordered surface layers of thickness approximately 12 A ( X I S ) . Baczek ( X I )described small angle X-ray scattering studies of the deformation of PE. Kissin and Fridman ( X 5 )reviewed the use of X-ray diffraction for the determination of orientation of polymer crystals. A systematic error was observed for X-ray diffraction and transmission measurements on blends of polyethylene with amorphous atactic polystyrene unless the background incoherent scattering from the amorphous component over a wide Bragg angle range was defined ( X 7 ) . Kurilenko et al. ( X 6 ) found that the formation of fibrillar structures in polyethylene-acrylonitrile graft copolymers was not affected by the grafting before or after the orientation of the fibers. Munteanu and Masala ( X 8 ) found that the morphology of P E was not altered by grafting with low levels of vinyl acetate because the side chain in the graft copolymer was inserted perfectly in the crystal lattice of the P E backbone. Wignall and Longman ( X I 7 ) reported on short range order in amorphous polymers based on radical distribution functions derived from X-ray diffraction. Wendorff et al. (XI61correlated the effects of side chain flexibility of a series of methacrylic acid polymers with thermal and X-ray diffraction properties. The crystal density of semicrystalline polymers such as poly(ethy1ene terephthalate) was calculated from unit cell dimensions obtained by X-ray diffraction ( X 1 1 ) . A high pressure X-ray study of Nylon 11 indicated a crystal transition a t 95" from the triclinic ( a phase) to a pseudo hexagonal structure ( X I O ) . T h e morphology of poly(viny1 acetate) and atactic polystyrene was studied by small angle X-ray diffraction ( X 9 ) . Gaidarova et al. ( X 3 ) used small angle X-ray diffraction to determine the packing density of the super molecular structure of polymers and the microporosity of polymer films such as poly(viny1 acetate), poly(viny1 alcohol) and PVC. T h e structural parameters of crystalline polymers such as Nylon 6 were evaluated from small angle X-ray scattering ( X 2 ) .

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Solvent cast films of blends of poly-e-caprolactone with poly(viny1 chloride) were shown t o consist, by small angle X-ray and light scattering studies, of poly-e-caprolactone lamellae separated by amorphous regions containing both polymers ( X 4 ) . X-ray studies indicated that isotactic poly(2-vinypyridine) exists as a threefold helix with three chains passing through a hexagonal unit cell ( X 1 3 ) . LITERATURE CITED (1) Plastic Pipe, ASTM Annual Standards, American Society for Testing and Materials, Voi. 34, 1978. (2) Plastics-%eneral Test Methods and Nomenclature, ASTM Annual Standards, America1 Society for Testing and Materials, Vol. 35, 1978. (3) Plastics-Materials, Film, Reinforced and Cellular Plastics; Fiber Composites, ASTM Annual Standards, American Society for Testing and Materials, Vol. 36, 1978. (4) Emission, Molecular, and Mass Specboscopy; Chromatography; Resinography; Microscopy; Computerized Laboratory Systems. 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Thln-Layer Chromatography ( K l ) Belenkii, B. G.; Gankina, E. S. J . Chromatogr. 1977, 141(1), 13-90. (K2) Brinkman, U. A. T.; Van Schaik, T. A. M.; DeVries, G.; DeVisser, A. C. ACS Synp. Ser. 1976, 31(Kydrogels Med. Reht. Appl., Symp. 1975), 105-18. (K3) Gankina, E. S.; Belen'kii, B. G.; Kever, E. E. Met& Anal. Kontrolya Kach. Prod. Khim. Prom-sti. 1978(2), 19-21; Chem. Abstr. 1978, 89, 147351m. (K4) Guthrie, J. L.; McKinney. R. W. Anal. Chem. 1977, 49(12), 1676-80. (K5) Inagaki, H. Adv. Polym. Sci. 1977, 24, 189-237. (K6) Inagaki, H. Fractionation Synth. Polym. 1977, 649-712; Tung, L. H. Ed.; Dekker: New York. (K7) Inagaki, H. Pure Appl. Chem. 1976, 46(1), 61-70. (K8) Inagaki, H.; Kotaka, T.; Miyamoto, T. Kyoto Daigaku Nippon Kagakuseni Kenkyusho Koenshu 1976, 33, 43-7; Chem. Abstr. 1977, 86, 121796~. (K9) Kahmar. J.; Mravec, D. Zb. Pr. Chemickotechnol. Fak. SVST1973-1974 (Pub. 1977), 177-81; Chem. Abstr. 1978, 89. 147533~. (K10) Lesiak, T.; Orlikowska, H. Chem. Anal. (Warwaw) 1978. 23(1), 111-18; Chem. Abstr. 1978. 88, 170842k. (K11) Lewandowska, I. Rocz. Panstw Zakl. Hg,1976, 27(5), 525-33; Chem. Abstr 1977. 86. 908000. (K12)May, C.A. Crii. Rev. fech. Charact. Polym. Mater. 1976, ADA 036082. 195-6; Chem. Abstr. 1978, 88, 1061232. (K13) Raudsepp, H.; Kaps, T.; Christjanson, P. Tr. Taliin. Poiitekh. Inst. 1977, 427, 67-72; Chem. Abstr. 1978, 89, 1 1 0 8 8 6 ~ . Llquld Chromatography (L1) Bagon, D. A,; Hardy, H. L. J . Chromatogr. 1978, 152(2), 560-4. (L2) Bjorkqvist, B.; Toivonen, H. J . Chromatogr. 1978, 753(1), 265-70. iL3) . , Cazes. J. "Liauid ChromatoaraDhv of Polvmers and Related Materials", Marcel Dekker: ' New York, 1677. . (L4) Dengreville, M. Analusis 1977, 5(4), 195-202; Chem. Abstr. 1977, 87, 24 107n. (L5) Eisenbeiss, F.; Dumont. E.; Henke, H. Angew. Makromoi. Chem. 1978, 71, 67-89. (L6) Eremeeva, T. V.; Eweinov, V. V.; Davydova. E. V.; Karyakina. M. I.; Sarynina. L. I.; Entelis, S. G. Plaste Kautsch. 1978, 25(3), 192-4. (L7) Fallick, G.; Cazes, J. Tech. Charact. Polym.. Mater. 1976, ADA 036082, 159-75: Chem. Abstr. 1978, 88, 1059242. (L8) Gross, D.; Strauss, K. Kunststoffe 1977, 67(8), 426-8. (L9) Husser, E. R.; Stehi, R. H.; Price, 0. R.; DeLap, R. A. Anal. Chem. 1977, 49(1). 154-8. (L10) Klesper, E.; Hartmann. W. Eur. Polym. J . 1978, 14(2). 77-88. (L11) Kumlin. K.; Simonson, R. Angew. Makroml. Chem. 1978, 68(l), 175-84. (L12) Lichtenthaler, R . G.; Ranfeit, F. J , Chromatogr. 1978, 149, 553-60. (L13) Ludwig, F. J.; Besand, M. F. Anal. Chem. 1978, 50(1), 185-7. (L14) Pasteur, G. A. Anal. Chem. 1977, 49(3), 363-4. (L15) Szap, P.; Kesse, I.; Klapp, J. J , Liq. Chromatogr. 1978. 1(1), 89-96. IL161 Van der Maeden, F. P. B.; Biemond, M. E. F.; Janssen, P. C. G. M. J . Chromatogr. 1978, 149. 539-52. (L17) Zaborsky. L. M. Anal. Chem. 1977, 49(8). 1166-8. (LIB) Zowall. H. Chromatwr. Handb. Anal. Svnth. Potvm. Pbst. 1977. 101-28: Ellis Horwood. Ltd Ctkhester, England' 1-

Mass Spectrometry ( M l ) Baba. T Shokuhm Dsergaku Zasshr 1977, 18(6). 500-3, Chem Abstr 1978. 88, 153342e

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(N82) Podesva, J.; Doskocilova. D. Makromol. Chem. 1977, 778(8), 2382-92. (N83) Poranski, C. F.; M o n k W. B. J . Coat. Technol. 1977, 49(632), 57-61. (N84) Poranski, C. F.; Sojka, S. A.; Monk, W. B. Natl. SAMPESymp. Exhib. 1976, 27, 755-70: Chem. Abstr. 1977, 87, 69082s. (N85) Quack, G.; Fetters, L. J. Macromolecules 1978, 7 7(2), 369-73. (N86) Raigorcdskii, I. M.; Urman, Y. G.; Gol'dberg, E. S.; Alekseeva, S. G.; Savin, V. A.; Sbnim, I.Y. Vysokomol. Soedin.. Ser. A 1978. 20(7), 1486-90; Chem. Abstr. 1978, 89, 9 0 3 0 7 ~ . (N87) Randall, J. C. Macromolecules 1978. 1 7 ( 1 ) , 33-6. (N88) Randall, J. C. J . Appl. Polym. Sci. 1978, 22(2), 585-8. (N89) Randall, J. C. J . Polym. Sci., Polym. Phys. Ed. 1977, 75(8). 1451-73. (N90) Randall, J. C. Macromolecules 1978. 11(3), 592-7 (N91) Randall, J. C. J . Polym. Sci., Polym. Phys. Ed. 1976, 74(11), 283-94. (N92) Ratov, A. N.; Postnikova, V. A.; Vytnova. L. A.; Blagonravova, A. A,; Uvarov, A. V . Lakokras. Mater. Ikh Primen. 1978(2), 53-6; Cbem. Abstr. 1978, 89, 6882y. (N93) Ray, G. J.; Johnson, P. E.; Knox, J. R. Macromlecules 1977, 70(4), 773-8. (N94) Ritter, W.; Elgert, K. F.; Cantow, H. J. Makromol. Chem. 1977, 778(2), 557-fi0 (N95) Roth, H. K.; Geschke. D.; Keller, F. Faserforsch. Textiltech. 1978, 29(2). 119-32: Chem. Abstr. 1978. 88. 1 7 0 5 1 2 ~ . (N96) Rou&el, R.; Galin, J. C. J . & c r o m l . Sci., Chem. 1977, A 7 7(2), 347-77. (N97) Rutenberg A. C.; Dorsey, G. F.; Peck, C. G. Rep. 1976, Y-2015; Chem. Absfr. 1977, 86, 17493m. (N98) Sanders, J. M.; Komoroski. R. A. Macromolecules 1977, 70(6), 1214-16. (N99) Schwind, H.; Keiler, F. Faserforsch. Texfiltech. 1978, 29(2), 135-41; Chem. Abstr. 1978, 88, 1 7 0 6 7 0 ~ . (N100) Shibata, C.; Yamazaki, M.; Takeuchi, T. Bull. Chem. Soc. Jpn. 1977, 50(1) 311-12; Chem. Abstr. 1977, 86, 905404. (N 10 1) Sionim, I.Y .; Aiekseeva, S. G.; Urman, Y, G.; Arshava, 8. M.; Aksel'rod, B. Y. Vysokomol. Soedln., Ser. A 1977, 19(4), 793-807; Chem. Abstr. 1977, 87. 1 6 8 6 8 4 ~ . (N102) Slonim, I . Y.; Alekseeva, S.G.; Urman, Y. G.; Arshava, E. M.; Aksei'rcd, B. Y. Vysokomol. Soedin., Ser. A 1978, 20(6), 1418-26; Chem. Abstr. 1978, 89, 1 1 0 9 9 3 ~ . (N103) Slonim, I.Y.; Alekseeva, S. G.; Urman, Y. G.; Arshava, B. M.; Aksel'rcd, B. Y.; Gurman, I. M. Vysokomol. Soedln,., Ser. A (1977), 79(4), 776-84; Chem. Abstr. 1977, 86. 190728q. (N104) Slonim, I. Y.; Aiekseeva, S. G.; Urman, Y. G.; Arshava, B. M.; Aksel'rod, B. Y . ; Gurman, I.M.; Smirnova, L. N. Vysokomol. Soedln., Ser. B 1977, 79(3), 163-5; Chem. Abstr. 1977, 86, 1 7 2 2 3 5 ~ . (N105) Smejkal. F.; Popl, M. Angew, Makromol. Chem. 1978, 67(1), 175-92. (N106) Strasilla, D.; Klesper, E. J . Polym. Sci., Polym. Left. Ed. 1977, 15(4), 199-206. (N107) Suzuki, T.; Harwccd. H. J. Polymn. Repr.. Am. Chem. Soc.,Div. Polym. Cbem. 1975, 76(1), 638-43. (N108) Tomita, B. J . Polym. Sci., Polym. Chem. Ed. 1977, 15(10), 2347-65. (N109) Toy, M. S.; Stringham, R. S. J . Polym. Sci.. Polym. Left. Ed. 1976, 74(12), 717-21. (N110) Urbanski, J.; Handb. Anal. Synth. Polym. Plast. 1977, 142-61; Ellis Horwood Ltd.: Chichester, England. (N111) Urman, Y. G.; Alekseeva, S. G.; Slonim. I. Y. Vysokomol. Soedin., Ser. A 1977, 79(2), 299-303; Chem. Absfr. 1977, 86, 140576t. (N112) Vecera, M.; Machacek, V.; Mleziva, J. Chem. Rum. 1977, 27(1), 29-32; Chem. Abstr. 1977, 86. 9 0 2 8 8 ~ . (N113) Vecera, M.; Machacek, V.; Mleziva, J. Sb. Prednasek, Makrotest, Celosfatni Knof., 4th 1976, 2 , 93-6; Chem. Abstr. 1977, 86, 56015b. (N114) Wang. A.; Suzuki, T.; Hatwood. H. J. Polyrn. Prepr., Am. Chem. Soc., Div. Polym. Chem. 1975, 76(1), 644-8. (N115) Wilkes, C. E. J. Polym. Sci., Polym. Symp. 1977, 60, 161-74; Chern. Abstr. 1978, 89, 24952a. (N116) Williams, E. A.; Cargioli, J. D.; Hobbs, S. Y. Macromolecules 1977, 70(4), 782-5. (N117) Willsch, R.; Schnabel, B.; Scheler, G.; Mueller, R. Pbste Kautsch. 1976, 23(10), 735-7; Chem. Abstr. 1976, 85, 1 9 3 2 5 3 ~ . (N118) Wu, T. K.; Sheer, M. L. Macromolecules 1977, 70(3), 529-31. (N119) Yeager, F. W.; Becker, J. W. Anal. Chem. 1977, 49(6), 722-4.

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~~~

Luminescence

Neutron Scattering

( P l ) Ailen. N. S.; Homer, J.; McKeller, J. F. J . Appl. Po/ym. Sci. 1976, 20(9), 2553-8. (P2) Allen, N. S.; McKeiler, J. F. Makromol. Chem. 1978, 779(2). 523-6. (P3) Allen, N. S.; McKelier, J. F.: Wilson, D. J . Polym. Sci., Polym. Chem. Ed. 1977, 75(11), 2793-5. (P4) Allen, N. S.; Homer, J.; McKeller, J. F.; Wood, D. G. M. J . Appl. Polym. SCi. 1977, 27(11). 3147-52. (P5) Alien, N. S.; McKeller, J. F.; Wilson. D. J . Phofochem. 1977, 6(5), 337-48. (P6) Coisson, R.; Paracchini, C.; Schianchi, G. J . Nectrochem. SOC. 1978, 125(4), 581-3. (P7) Fedosyuk. M. I . ; Zelichenko, Z. K.; Chernobia, A. V.; Shevchenko, E. A,: Bodganova, L. I.; Vinetskaya, Y.M. Zh. Wkl. Spekfrosk. 1976. 25(3), 542-4; Chem. Abstr. 1977, 86. 60742. (Pa) Krinitsyna, N. A.; Boyarskii, G. Y.; Kachna, A. A.; Shrubovich, V. A. Vysokomol, Soedln., Ser. B 1977, 79(6), 449-52. (P9) MatlsovaRvchh. L.: Rvchlv. ~. J.: Michel. A,: Ambrovic. P.: Paska, I. J. Lumin. 1978, 77(1),' 73-81. (P10) Mendenhall. G. D.; Hassell, J. A,; Nathan, R. A. J . Poiym. S o . , Polym. Chem. Ed. 1977, 75(1), 99-106. ( P l l ) Nakamura, S.; Sawa, G.; Leda, M. J . Appl. Phys. 1977, 48(8), 3626-7. IP121 . . Nathan. R. A.: Mendenhall. G. D.: Hassell. J. A. Crk. Rev. Tech. Charact. PoWm. Mater., 1976, ADA 036082, 123-4; Chem. Abstr. 1978, 88, 1059728. (P13) Padhye, M. R.; Tamhane, P. S. Angew. h k r o m o l . Chem. 1978, 69(1), 33-45. (P14) Pender, L. F.; Fleming, R. J. J . Phys. C 1977, 70(9), 1571-86. (P15) Radhakrishna, S.; Murthy M. R. K. J . Polym. Scl., Polym. Phys. Ed. 1977, 15(7), 1261-6.

(SI) Allen, G.; Wright, C. J. Int. Rev. Sci.: Phys. Chem., Ser. Two 1975, 8, 223-51; Brawn, C. E., Ed.; Butterworth, London (S2) Ballard, D. G. H.; Cheshire, P.; Longman, G. W.; Schetten, J. Polymer 1978. 79(4\. 379-85. (53) Ballard, D. G. H.; Cunningham, A.; Scheken, J. Pokmer 1977, 78(3), 259-61. (S4) Benoit, H.; Decker, D.; Duplessix, R.; Picot, C.; Rempp, P.; Cotton, J. P.; Farnoux, B.; Jannink. G . ; Ober, R. J . Polym. Sci.. Polym. Phys. Ed. 1976, 74(12), 2119-28. (S5) Hamada, F. Kobunshi 1976, 25( 11). 743-9. 6' 6 6 ) 6Hamada. , 3 0 0 9 0 F. ~ . Kaoaku1Kvofo) ,~ . 1976. 37(11). . . 903-6; Cbem. Abstr. 1977,

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I.

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1

(S7) Han, C. C.; Mozer, 8 . Macromolecules 1977, 70(1), 44-51. (S8) King, J. S.; Summerfieid, G. C.; Ullman, R. Pclym. Prepr., A m . Chem. SOC.. Chem. 1975, 7612). 410-12, _.. , Div. Polvm. -, (S9) Picot, C.; Dupiessix, R.; Decker, d.;'Benoit, H.; Boue, F.; Cotton, J. P.; Daoud, M.; Farnoux. B.; Jannink. G. Macromolecules 1977, 70(2), 436-42. (S10) Ruland, W. Strukt. Polym.-Syst.. Vortr. Diskuss. Haupfversamml. Kolloid-Ges., 26th 1973 (Pub. 1975), 192-205; Chem. Abstr. 1977, 86, 17229e. (S11) Schelten, J.; Wignall, G. D.; Ballard, D. G. H.; Longman, G. W. Polymer 1977, 18( 1l), 1111-20. (S12) Jahshan, S. N. Diss. Abstr. I n t . B(Univ. Michigan, Ann Arbor) 1977, 38(3). 1366; Chem. Abstr. 1977, 87, 185147r. ~

Microscopy ( T l ) Bradford, E. B.; Morford, L. E. Colloid Interface Sci., (Proc. I n t . Conf.) 50th 1976, 4 183-95.

ANALYTICAL CHEMISTRY, VOL. 51, NO. 5, APRIL 1979 (T2) Ceynowa, J. Polymer 1978, 79(1), 73-6. (T3) Friedrich, K.; Wittkamp, I. Prakt. Metallogr.. Sonderb, 1978, 9 (Metallogr. Keramogr.-Fortschr Praeparationstech.), 197-204. (T4) Hobbs, S. Y. J . Polym. Sci., Polym. Pbys. Ed. 1978, 76(7), 1321-3. (T5) Hodge, A. M.; Bassett, D. C. J . Mater. Sci. 1977, 12(10), 2065-75. (T6) Holm, R. Scanning Electron Microsc. 1975, 8 , 433-40. (T7) Holm, R.; Reinfandt, B. Z . Werkstofftech, 1978, 9(5), 153-64. (T8) Kanig, G. Strukt. Polym.-Syst., Vorir. Diskuss. Haupfversmml. Kolbid-Ges., 26th 1973 (Pub. 1975), 176-91. (T9) Kosztersz~z.G.; Barnikol, W. K. R.; Schulz, G. V. Makromoi. Chem. 1977, f78(4), 1133--48. (T10) Koszterszitz, G.; Schulz, G. V. Makroml. Chem. 1977, 178(4). 1149-68. (T11) Koszterszitz, G.; Schulz, G. V. M a k r o m l . Chem. 1977, 778(4), 1169-85. F 1 2 ) Koszterszitz, G.; Schulz, G. V. Makroml. Chem. 1977, 178(8), 2437-50. (T13) Liegeois, J. M. Angew. Makromol. Chem. 1976, 56(1), 115-20. iT14) Low, A.; Allan, P.; Vesely, D.; Bevis, M. Conf. Ser.-Insf. Phys. 1977, 36 (Dev. Electron Microsc. Anal.), 395-8. (T15) Sandilands, G. J.; White, J. R. J . Mater. Sci. 1977, 72(7). 1496-7. (116) Schaper. A.; Kupfer, R . Faserforsch. Textiltech. 1978, 29(4), 245-8. (T17) Tarin. P. M.; Thomas, E. L. Polym. Eng. Sci. 1978. 78(6), 472-6. (T18) Thomas. D. A. Polym. News 1978, 4 ( 5 ) . 200-3. Cr19) Thomas, D. A. J. Polym. S c i , Polym. Symp. 1977, 60(Adv. Prep. Charact. Multiphase Poiym. Syst.) 189-200. r 2 0 ) Wilkinsoa, M. C.; Cox, R. A. Pokm. Preor., Am. Chem. Soc., Div. Pokm. Chem. 1975, 76(1), 781-8. . (T21) Wittkamp, I.; Friedrich, K. Prakt. Metallogr. 1978, 75(7). 321-41

(W4) Khan, H. U.; Rao, K. V. C. Indian J . Techno/. 1977, 75(5),215-16. (W5) Kiip. T.; Houvenaghel-Defoort, B.; Panning, W.; Guillet, J. E. Rev. Scl. Instrum. 1976, 47(12), 1496-502. (W6) Lanikova, J.; Hlousek, M. Chem. Prum. 1977, 27(12), 628-9. (W7) Morris, C. E . M. J . Polym. Sci.; Polym. Symp. 1976, 55(Proc. Aust. Polym. Symp.. 8th, 1975), 11-16. (W8) Morris, C. E. M. U.S.Army Mater. Mech. Res. Cent., (Rep.) AMMRC MS 1977, AMMRC MS-77-2, Proc. TCP-3 Crii. Rev.: Tech. Charact. Polym. Mater., 1976; ADA 036082, 373-9. (W9) Price, H. L.; Burks, H. D.; Dalal, S. K. Proc., Annu. Conf., Reinf. Plasf./Compos. Insf., Soc. Plast. I n d . 1978. 33, Sec. 16-A. 1-6. (W10) Stacy, C. J. J Appl. Polym. Sci. 1977, 27(8), 2231-40. (W11) Steinke, J.; Vogel. I. Fresenius' Z . Anal. Chem. 1977, 285(3), 268-9. (W12) Wolf, F.; Koch, U. Faserforsch. Textiltech. 1978, 29(6), 402-6. X-Ray Diffraction ( X l ) Baczek, S. K . Diss. Abstr. Int. B(Univ. Michigan: Ann Arbor) 1977, 38(6), 2697; Chem. Abstr. 1978. 88, 5 1 3 0 0 ~ . (X2) Baldrian, J.; Plestil, J. Sb. Prednasek, Makrotest. Celostatni. Konf., 4th 1976, 1 , 303-10; Chem. Abstr. 1977, 86, 55834f. (X3) Gaidarova. L. L.; Polyakova, K. A. Izv. Vyssh. Uchebn. Zaved., Tekhnol. Legk. Prom-sti. 1978(2), 43-6; Chen). Abstr. 1978. 89, 444959. (X4) Khambatta, F. B.; Warner. F.; Russel. T.; Stein, R. S. J . Polym. Sci.. Polym. Phys. Ed. 1976, 74(8), 1391-424. (X5) Kissin, Y. V.; Fridman. M. L. Mekh. Polim. 1977(1), 143-55: Chem. Abstr 1977, 8 6 , 140483k. (X6) Kurilenko. A. I.; Krul, L. P.; Gerasimov, V. I.; Zubov, Y . A,; Shchirets, V. S.; Bakeev, N. F. Vvsdtomol. S d i n . , Ser. A 1976, 78(12),2712-17; Chem. Abstr. 1977, 86, 5 5 8 9 0 ~ . (X7) McRae, M. A.; Maddams, W. F. Polymer 1977, 78(5).524-5. (X8) Munteanu, D.; Masaia, F. Mater. Plast. (Bucharest) 1977, 14(1), 12-15; Chem. Absfr. 1977. 87. 102797d. (X9) Nadezhin, Y . S.; Sidorovich, A. V.; Asherov, B. A. Vysokomol. Soedin., Ser. A 1976, 78(12), 2628-30; Cnem. Abstr. 1977, 86, 90416t. (X10) Newman. B. A.; Sham, T. P.; Pae. Y. D. J . Appl. Phys. 1977, & ( l o ) , 4092-8. ( X l l ) Northolt, M. G.; Stuut, H. A. J . Polym. Sci., Poiym. Phys. Ed. 1978, 76(5), 939-43. (X12) Pae, K. D.; Newman, 13. A.; Sham, T. P. J . Mater. Sci. 1977, 72(9). 1793-7. (X13) Puterman, M.: Kolpak, F. J.: Blackwell, J.: Lando, J. B. J , Polym. S o . . Polym. Phys. Ed. 1977, 15(5), 805--19. (X14) Rozkuszka, K. P. Diss. Abstr. Int. B(Univ. Michigan: Ann Arbor). 1978, 3 9 j l ) . 258. (X15) Strobl, G. R.; Eckel, R. Prog. Colloid Polym. Sci. 1977, 62. 9-15. (X16) Wendorff. J. H.; Finkelmann. H.: Ringsdorf, H. ACS Synip. Ser. 1978. 74(Mesomwphic Order Pobm. Liq. Cryst. Media), 12-21; Chem. Abstr. 1978, 89, 755639. (X17) Wignall, C. D.: Longman, G. W. d . Macromol. Sct , Phys. 1978. 812(1). 99-123.

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303 R

Akutin, M. S.; Goidberg, V. M.; Lavrushin, F. G. Vvsokomol. Soedin., Ser. 1977, 79(5),11 13-26, Dondos, A , Benoit, H Polymer 1977, 7 8 ( l l ) , 1161-2. Dondos. A Polymer 1977, 78(12), 1250-2

Rubber' Coe W. Wadelin" and Marion C. Morris' Nastomer & Chemical Research Division, The Goodyear Tire & Rubber Co., Akron, Ohio 443 76 _

This review covers chemical analysis of rubber and characterization of rubber by physical, chemical, and spectroscopic means. Methods for the identification, characterization, and determination of rubber and materials in rubber are included, but the analysis of rubber additives when they are not contained in rubber is not included. Polymers other than rubber are covered in another review in this issue (33). T h e literature which became available to the authors between September 1976, the end of the period covered by the last review in the series (148),and September 1978, is covered. Abbreviations recommended in ASTM Designation D1418-77 have been used (7). They are listed in Table I.

GENERAL INFORMATION

~ ~

microscopy are used (138). T h e use of microscopy in the rubber industry was reviewed (95). A comprehensive book on analysis of rubbers and plastics has been published but, unfortunately, it is a translation of a Polish edition which was first written in 1972 and is, therefore, not up-to-date (143).

A review article summarized methods which use very small samples. A relatively complete characterization of a compounded, cured sample can be done with less than 20 mg of material. Thermal ana!ysis, pyrolysis, chromatography, and

POLYMER IDENTIFICATION

lCoritribution No. 606 from the Goodyear Tire and Rubber Co.. Research Laboratory, Akron, Ohio 44316. Present address, Kimber1:;-Clark Corp., Neenah. 'Ct-is. 51956. 0003-2700/79/035 1-303R$01.00/0

_

Table 1, Abbreviations ~ ~ ~ by ~ AS'rM ~ ( 7~) EPDM Terpolymer of ethylene, propylene, and a diene with the residual unsaturated portion of the diene in the side chain EPM Copolymer of ethylene a n d propylene BR Butadiene rubber CK Chloroprene r u b b e r IIR Isobutene-isop~enerubher IR Isoprene synthetic rubber NBR Nitrile-butadiene rubber NR Natural rubber SBK St v re n e - h u t a di eiie r u h be r

c w 1,4-Polyisoprene is recognized by many techniques but interest continues in differentiating NR and IR. Thermal

C

1979 American Chemica! Society

~

,

Analysis of high polymers - Analytical Chemistry (ACS Publications)

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