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Analysis of High Polymers Charles G. Smith," Nels H. Mahle, and Carl D. Chow Analytical Laboratories, Dow Chemical U.S.A., Midland, Michigan 48640
This review includes techniques for the analysis and characterization of synthetic polymers, copolymers, and blends. Included are techniques for structure determinations, separation and quantitation of residual volatiles and additives, 156 R
determination of molecular weight, and studies of thermal properties and degradation products. The majority of references cited in this review were obtained from volumes of Chemical Abstracts and C A Selects published between No-
0003-2700/83/0355-156R$01.50/00 1983 American Chemical Society
ANALYSIS OF HIGH POLYMERS
C o w and his M S in-chemistry fro; & Universiiy of Mkhlgsn Following graduation. he wwked 3 years wlih the Chemical Dwisbn 01 PPG lndustrter belme l k l n l ~Dow in 1967 Alter 4 years of memobs ~ e i o p m m lIn me Organic and A g r k ~ t l ~ r a l PICducts CIOUPI. he transferred to me polymer Analysis Croup HIS expen& has been concentrated on chomalqpaphk ~eparalions and application to polymer systems Wnh last 4 years devoted Io davebping PYrOlySlS lechniqm He IS chairman Of the ChromalOgraphic Section of the AnaWlcal Memods SubCommmee 01 ASTM D-20 on Plaslics
de-
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c Neb H. Y.M.
b a poJe.3 leader w h the
PcWnev A n a W s C r w p 01 AnalyUml LabOlatmbs. Daw Chemical U.S.A.. Mlb land. MI. He recshed his R.D. In anawlcal chemistry f r m NoRhern Illin& Unhersity. He was a poStdOCtMBI associate wnh L. 0. R ~ g e r sat Rrdue University lor 2 years to loinlng me Dow Chemical CO. in 1974. He is me aumOr m coaumot 01 17 publicatianr and one U.S. patent. HIS research int e r m s include polymer characterization. -55 ?ipeclromehy. Leparalio" SCia"Ce. trace mganr analysb. environmemai c h e m
(AZ5).
m
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Chemical Socbhl (InCIUding the AnaWical Chemistry D#v#sm).Ihe American Asw)ciaf!m lor me Advancemen1 01 Science. the Amer~canSociety for Mars spectrometry. and SQgma XI
E *1 worked on polymerization kinetics. loam technology. and reinforced plasllcs. He nanslerred to the Polvmer Anahsls Grwo in
In
chloride) powders was measured by Pausch et al. (A15) using mom temperature headspace gas chromatography. Headspace gas chromatography was also used by Gilbert and Shepherd (AIS) to determine vinyl chloride, vinylidene chloride, styene, and acrylonitrile in packaging materials and food. Volatile components such as xylene, vinylcyclohexene. cumene, and styrene were determined in styrene-butadiene latex by using headspace gas chromatography with cyclohexanone as the solvent (A27).Ioffe and Reznik (A30) reveiwed the applicatinn of headspace gas chromatography for the determination of volatile impurities in polymers. Buckley and Augostini (A191 used gas chromatography to determine reactivity ratios for a styrene-p-decylstyrene copolymer. Solubility parameters and solubilities were determined by Lipson and Guillet (A221 using the inverse gas chromatographic technique for ethylene-vinyl acetate copolymers. Fernanda-Berridi et al. (A%) determined solubility parameters for poly(ethy1ene oxide) by using gas chromatography. Solubility parameters were also determined for poly(viny1acetate) and vinyl acetatevinyl chloride copolymers using 15 polar and nonpolar solvents a t two temperatures
areas and has lsctured ohGPC at lacs1 ACS sections and unaeral-
tier
vember 1980 and November 1982.
GAS C H R O M A T O G R A P H Y The 'CRC Handbook of Chromatography of Polymers" edited by Smith, Skelly, Solomon. and Chow (A31) presents tables of chromatographic data and practical information on gas chromatography. pyrolysis%as chromatography, size-exclusion chromatography, liquid chromatography, and thinlayer chromatography. Gilbert et al. ( A I ) presented a headspace procedure for determination of vinylidene chloride monomer in packaging films and foods, using a mNi detector. Lattimer and Pausch (AZ) described solid headspace procedures for determination of residual volatiles in polymers such as poly(acrylic acid). Gilbert and Startin (A61 determined styrene monomer in food samples by using automated headspace gas chromatography coupled with single-ion monitoring mass spectrometry. The detection threshold was reported at 0.001-0.015 mg of styrene/kg. McNeal and Breder (A91 described a manual headspace technique for determination of residual acrylonitrile in acrylonitrile-based polymers. The detection limit was reported at 70 pph (parts per billion) based on polymer. Kaminski et al. ( A 1 4 used headspace gas chromatography, adsorbent concentration prior to gas chromatography. and steam distillation to isolate and determine volatile compounds in packaging materials. Adsorption of octane on poly(viny1
The molecular probe technique was used by Leca and Surmeian (A3) to study polymer transitions for polystyrene and poly(ethy1ene glycol). Thermodynamic parameters and solubility properties of polystyrene were studied in 42 solvents by Gunduz and Dincer (A5). Data from inverse gas chromatographic experiments are useful to estimate the extent of migration of an impurity from a polymer container. Senich and Sanchez (AS) used the technique to establish specific retention volumes which were used to calculate polymermigrant interaction parameters and equilibrium partition coefficients. Douhe and Walsh ( A l l ) studied the interactions of poly(viny1chloride) and solution-chlorinated polyethylene with 10 solvents by using inverse gas chromatography. The technique was also used by Orr et al. (A161 to study the interaction between acrylonitrile and an acrylonitrilestyrene copolymer. Ward et al. ( A I 7) used inverse gas chromatography to obtain specific retention volumes for a series nf volatile probes on phases composed of dimethyl siloxane, bisphenol A polycarbonate or copolymers and blends of these substances. Polymer-surface structure of a blend of poly(ethylene oxide) and polystyrene was studied by means of inverse gas chromatography. Suzuki et al. (AZ3) demonstrated that phase separation occurred at about 30% poly(ethy1ene oxide). Llorente et al. ( A 2 4 described techniques for determination of glass transition temperature (T) by gas chromatography. Retention volume as a function of probe concentration was studied to optimize inverse gas chromatographic conditions to determine the T,for poly(cyclohexy1 methacrylate). Inui et al. ( A B ) discussed the principal factors involved in the preparation of columns for inverse gas chromatography. Silane-treated supports of relatively large surface areas were favorable with poly(ethy1ene oxide) and poly(methy1 methacrylate). Water a t part-per-million (ppm) level was determined in 1,3-butadiene by Wang et al. ( A 4 ) . Hawn and Talley (A7) determined ppm levels of polyacrylamide by caustic hydrolysis followed by gas chromatography of the derivatized ammonia. Rygle (AIO) reported the use of capillary gas chromatography for determination of trace levels of residual monomers in coatings. Impurities in caprolactam, a Nylon precursor, were determined on a poly(ethy1ene glycol) 4000 packed column by Czenvinski et al. (A12). Gas chromatography w&cused by lrvine and Sones (A13) for qualitative and quantitative determination of components in fog caused by vinyl plasticizers. Stein and Narang (AZO) utilized photoionization detectinn to improve sensitivity for vinyl chloride monomer in water. Rapid identification of polyamides based on dimer acids and polyamines was achieved by alkali fusion cleavage followed by gas chromatography. Haken and Ohita (A2J) used methyl esters and CF,CO derivatives of acids and amines obtained by cleavage. Gnauck and Habisch (A29)discussed silylation orocedures for determinations of olieomer structures in phen~,l-f,,rmald~hyderesins by gas rhrnmatngraphy mass spectrometry \G(: MS). ~~
~~
~~~~~
~
~
PYROLYSIS TECHNIQUES Most references cited in this section involve pyrolysis-gas ANALYTICAL CHEMISTRY. VOL. 55, NO. 5. APRIL 1983
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ANALYSIS OF H I G H POLYMERS
chromatography or pyrolysis-GC/MS. Additional references to direct pyrolysis-mass spectrometry techniques are cited in the section entitled Mass Spectrometry. Chemically bonded phases for reversed-phase high-performance liquid chromatography were characterized by pyrolysis-gas chromatography and evaluated by Hansson and Trojer (B9). Lyle and Tehrani (B20)described a microfurnace for pyrolysis of 0.1-10 pg of samples taken from thin-layer plates. Examples included the separation of poly(viny1 chloride) and poly(viny1 acetate). The technique of focused cryogenic trapping to maximize peak resolution on fused silica capillary columns was described by Moncur et al. (B21)for dynamic headspace and pyrolysis/GC applications. Hu (B22) discussed the technique of chromatopyrography for analysis of compounded polymeric materials. By use of a two-step approach, compound volatiles were liberated in the injection port and polymeric species were subsequently pyrolyzed to leave a residue of inorganic fillers. Gargus (B23)described the application of a CDS-320 Concentrator for the analysis of trace organics in polymer articles and composites. Jacques and Morgan (B24) reported the use of an in-line, postpyrolysis precolumn cold trap, and rapid injection system to improve resolution on glass capillary columns. Anderson and Ericsson (B31) used polystyrene, polybutadiene, and poly(methy1 methacrylate) to study the effects of sample size on yields of pyrolysis fragments. In a related study of pyrolysis variables, these same researchers (B37) examined the effects of various metals as pyrolysis filaments. Hu (B6) discussed the application of pyrolysis-gas chromatography for the identification of natural, silicone, nitrile, and neoprene rubbers. Pyrolysis-gas chromatography and mass spectrometrywere used by Jin and Li (B15)to determine cross-link density of vulcanized polyisoprenes. Amounts of monomer and dimer decreased with increasing cross-link density. A high-resolution glass capillary column was suggested by Naveau and Dieu ( B I )for improved reproducibility of pyrolysis-gas chromatography for cis-1,4-polyisoprenes. Haeusler et al. (B2)discussed Curie point pyrolysis of polybutadiene with varying 1,4- and 1,2-microstructure. Relative isoprene, yields of cis- and trans-1,2-dimethylcyclopropane, and trans-piperylenewere related to microstructure. Thermal degradation of cis-l,4-, trans-l,4-, and 1,2-polybutadieneswas studied by Radhakrishnan and Rama (B17).The cis-l,4 and trans-1,4 polymers were distinguished from the l,%-polybutadiene by the low yields of 4-vinylcyclohexene. Milina (B18) used pyrolysis-gas chromatography to determine an antioxidant in synthetic rubber. The antioxidant was extracted and then pyrolyzed with 2-phenyl-2-(4-hydroxypheny1)propane observed as the major degradation product. Pyrolysis-hydrogenation glass capillary chromatography was used by Sugimura et al. (B16) to study short-chain branching in low density polyethylene. Characteristic isoalkane peaks in the Cll region were correlated with short-chain branches by comparison with reference model compounds of known short branch contents. Naveau and Dieu (B30)used high-resolution capillary gas chromatography to improve the reproducibility of separation for cis-1,4-polyisoprenepyrolysis fragments. Cross-link density of vulcanized polyisoprene was determined by Xigao and Huiming (B38) using pyrolysisGC/MS. Monomer, dimer, and trimer pyrolysis products from styrene-acrylonitrile copolymers varied with copolymer composition. Using these oligomer yields in a mathematical model, Blazso et al. (B4)obtained rate constants and sequence distribution for copolymers. Tanaka et al. (B5) showed that monomer yields were lower from head-to-head polystyrene and poly(a-methylstyrene)polymers than those of head-to-tail polymers. Additional studies on pyrolysis of head-to-head polystyrene were also reported by Sugimura et al. (BIZ). Braun and Steffan determined phenols, cresols, xylenols, and non-phenolic pyrolysis products of cross-linked or cured phenolic resins (B13). Sahraoui et al. (B19) described the pyrolysis of poly(a-acetoxystyrene)which was prepared from polystyrene and poly(viny1 acetate). Haeusler and Schroeder (B27)presented data on the microstructure and determination of cross-link density for butadiene, styrene, a-methylstyrene, and divinylbenzene polymers. Mori (B28)fractionated a styrene-acrylonitrile @AN) copolymer by preparative scale size exclusion chromatography and determined the composition of each fraction by pyroly158R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
sis-gas chromatography. Compositional analysis of poly(2,6-dimethyl-l,I-phenylene oxide)-polystyrene blends by infrared spectroscopy (IR) and pyrolysis techniques was reported by Mukherji et al. (B29). Ohtani et al. (B36)used the trimer peaks to determine the composition of block copolymers from normal and deuterated styrene with a relative standard deviation of
