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32-3 (1984).
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CUles, 19. 750-4 (1986).
Analysis of Synthetic Polymers
Charles G. Smith,* Richard A. Nyquist, Nels H.Mahle, Patrick B. Smith, Steven J. Martin, and
Andrew J. Pasztor, Jr.
Dow Chemical U.S.A., Analytical Laboratories, 1897 Building, Midland, Michigan 48667
This paper reviews state-of-the-art techniques for the
characterization and analysis of synthetic polymers, co-
polymers, and blends. This review includes techniques for
structure determination, separation and quantitation of ad-
ditives and residual monomers, determination of molecular
weight, and the study of thermal properties including deg-
radation mechanisms. A majority of the cited references were
obtained from volumes of Chemical Abstracts or CA Selects
published between November 1984 and December 1986. For
the most part, this review contains references to journals
published in English.
GAS CHROMATOGRAPHY
Denig (A24) reviewed the applications of thin-layer chro-
matography (TLC), high-pressure liquid chromatography
(HPLC), size-exclusion chromatography (SEC), and gas
0003-270018710359-119R$06.5010
(177) Cooper, S. L.; Miller, J. A., Rubber Chem. Techno/, 5 8 , 899-912
(1985).
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27, 1211-18 (1986); Chem. Abstr., 704, 169884t.
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Abstr., 703, 7591x.
(180) Maconnachie, A., fo/ymer, 25, 1068-72 (1984).
(181) Vnukova, V. G.; Kiseiev, V. Ya.; Bukanov, A. M.; Proyanenkov, V. V.;
Tutorskii, I.A... Vysokomol, Sodin., Ser. 8,26. 739-41 (1984); Chem.
Abstr., 102, 8028k.
(182) Mutagahywa. B. M.; Hemsley, D. A., Piast. Rubb. Process. Apph., 5 ,
219-27 (1985).
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Abstr., 705, 1157671.
(184) Hamada. T.; Kohno, M., KamiPa Gikyoshi, 3 9 , 477-85 (1985); Chem.
Abstr., 702, 222387~.
(185) Tanaka, Y.; Sato, H.; Adachl, J., Rubber Chem. Technoi., 5 9 , 16-26
(1986).
(186) Steuer, W.; Jost, K.; Halasz, I., Chrometographia, 20, 13-19 (1985);
Chem. Abstr., 702, 1361 15x.
(187) Haeusier, K. 0.; Bischef, G. V., Schuffenhauer, C., Plaste Kautsch.,
37,332-4 (1984); Chem. Abstr., 702, 8013b.
(188) Grandi, F. 2.; Talamini, G., Chimica Ind., 6 6 , 400-5 (1984).
(189) Burfield, D. R.; Llm, K. L.; Law, K. S., Ng, S., Polymer, 2 5 , 995-8
(1984).
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Haberiand, N.; HeMe, R.; Huebei, R.; Clerniak, M., German Patent (East)
DD 214454, 1984, Chem. Abstr., 702, 114967a.
(191) Shah. R. D., Rubb. India, 3 6 , 9-19 (1984).
(192) Brimhail, S. L.; Myers, M. N.; Caidwell, K. D.; Giddings, J. C., ACS
folym. Mat. Sci. Engng., 5 0 , 48-52 (1984
(193) Share, S.; Baba, A., Sampa J . , 27, 7-11 (1985).
(194) Markert, J., Kautsch. Gummi, Kunstst., 38, 122-7 (1985); Chem.
Abstr., 702, 2052192.
(195) Grechanovskii. V. A.; Dmitrieva, I . P.; Zaitsev, N. B., Kauch. Rezina,
3, 15-18 (1985); Chem. Absfr., 702, 205204r.
(196) Aarts, A. J.; Baker, K. M., Kautsch, Gummi, Kunstst., 3 7 , 497-500
(1984); Chem. Abstr. 702, 221952~.
(197) Hill, R. G., Tomiins, P. E.; Hughes, J. S., Polymer, 26, 1708-12 (1985).
(198) Moore, E. R., U.S.Patent US 4591632; Chem. Abstf., 105, 61474r.
(199) Wetton, R. E., Dev. folym. Charact., 5 , 179-221 (1986); Chem.
Abstr ., 705, 982303.
(200) Lobo Fiiho, Eurico de Baros; Reyx, D.; Campistron, I.; Casals, P. F.,
Makromoi. Chem., 187, 1573-82 (1986); Chem. Absah., 105, 118303s.
(201) Hergenrother, W. L., J. Appl. Poly. Sci., 32, 3039-50 (1986); Chem.
Abstr., 705, 989760.
(202) Barquino, M.; RoquesGarmes, C., Rev. Gen. Caoutch. Piast., 667,
89-93 (1986); Chem. Abstr., 105, 135220d.
(203) Jurado, C. W.; Mayhan, K. G., Rubber Chem. Technoi., 5 9 , 84-102
(1986). Edited by: Touchstone, J. C.; Sherma, J., Wiley: New York.
(204) Dimonie, V. L.; El-Aasser; M. S.; Vanderhoff, J. W., Tech. Appl. Thin
Layer Chromatogr. (Proc.-Bienn. Symp. Thin Layer Chromatogr.), 3rd
Meeting 1982, 240-59. Edited by: Touchstone, J. C.; J. C.; Sherma, J.,
Wiiey: New York.
(205) Chaturvedi, Po. N.; Patel, C. K., Makromoi. Chem., 786, 2341-53
(1985).
chromatogra hy with and without pyrolysis for analysis of
plastics. Liegman and Levy (A29) provided an overview of
chromatogra hic approaches to polymer analysis while
Liebman anb3Wampler (A30) presented an in-depth review
of pyrolysis instrumentation, gas chromatography, and coupled
techniques such as GC/MS and GC/IR. Aspler (A31) re-
viewed the theory and applications of inverse gas chroma-
tography.
Horna and co-workers (A20, A211 used capillary gas chro-
matography to separate acrylate and methacrylate monomers.
These workers used OV-101,SE-54, and SP-1000phases to
determine the retention indices of 38 esters of acrylic and
methacrylic acids. Retention behavior of n-alkyl and isoalkyl
acrylate esters and their mono- and dihalogen derivatives were
examined by Horna et al. ( A 2 3 using several capillary col-
umns.
0 1987 American Chemical Society ll9R
ANALYSIS OF SYNTHETIC POLYMERS
DiPasquale and co-workers (A2) demonstrated the use of
high-resolution capillary gas chromatography for separation
of additives such as slip agents, stabilizers, and antioxidants
extracted from polyethylene. Hayashi and Matsuzawa (A9)
used methanol for transesterification of the hindered phenolic
antioxidant IRGANOX 1076 after extraction from poly-
propylene with hexane. The derivative was separated and
determined by gas chromatography.
Di(2-ethylhexyl) phthalate plasticizer can migrate from
poly(viny1 chloride) bags used to store blood. Teirlynck and
Rosseel ( A B ) described extraction and gas chromatographic
procedures for determination of this plasticizer in blood.
Rocchelli and Razzini (AB) described two vapor-phase in-
jection systems for the determination of residual solvents in
multilayer polymer films for food packages. The systems could
differentiate between thermal degradation products and the
inks or adhesives used in the packages. Smith and co-workers
( A I 7 ) described a simple procedure for determination of
solvents in polymers. A polymer sample, in a glass injection
port liner/sample tube, was placed into the GC/MS injection
port with a packed column at -50 "C. The injection port was
heated a t 275 "C to liberate the solvents and other volatiles
which were transferred to the chromatographic column for
separation and identification. A multiple headspace extraction
(MHE) technique, described by Kolb, Pospisil, and Auer
(A23), gave applications for the determination of residual
monomers in polymers or residual solvents in other solid
samples.
Hoppler ( A l 4 ) described an apparatus based on gas chro-
matography that could be used to determine gas emissions
from plastics. The system using flame ionization and thermal
conductivity detectors was used to analyze polycarbonate
products.
Schultz, Kaladas, and Schultz (AIO) evaluated GC, SEC,
and HPLC for separation and analysis of molecular weight,
composition, and the molecular weight distribution of acrylate-
and styrene-based polyether macromonomers. Fused silica
capillary gas chromatography was used to differentiate the
alcohol and acrylate distributions for phenoxy poly(ethy1-
eneoxy) acrylates. Styrene-based macromonomers gave
chromatograms including doublets for the polyether distri-
bution from meta and para isomers of vinylbenzyl chloride.
Vimalasiri, Haken, and Burford ( A l 2 ) used a mixed an-
hydride reagent to cleave polyether-based polyurethanes.
After liquid-liquid extraction, the diamine corresponding to
the polyether portion and the poly01 acetate were separated
by gas chromatography. The same workers (A26) reported
on the gas chromatographic analysis of cross-linked poly-
urethane foams containing tri- and tetrafunctional alcohols.
By use of alkali fusion, the polymer was cleaved to give
identifiable diamine, dicarboxylic acid, and polyol products.
Degradation products from an amine-cured epoxy powder
paint were extracted by Peltonen (A25). Nitrogen-containing
heterocyclics and phenols were identified by GC/MS. Vis-
cometry, titrimetry, and gas chromatography were used by
Severini and co-workers (A28) to study the alkaline degra-
dation of styrene-acrylonitrile copolymers.
Card and co-workers ( A I ) discussed the role of the inert
support for inverse gas chromatographic (IGC) studies. This
article, which included references to earlier inverse gas
chromatographic applications, reported on the effects of in-
jection volume for polar and nonpolar probes using uncoated
columns and columns coated with polyisobutylene and poly-
(methyl acrylate). Miltz (A41 used the technique to study
diffusion coefficients for styrene in polystyrene. Su and Fried
(A5) used IGC to study the miscibility of poly(2,6-di-
methyl-l,.i-phenylene oxide) with poly(4-methylstyrene) and
polystyrene.
Kontominas, Demertzis, and Gilbert (A6) compared inverse
gas chromatography and classical partition methods to study
the sorption of vinyl chloride monomer by PVC. Both tech-
niques indicated that temperature and the nature of the
contacting phase were more important than particle size.
Some of the same co-workers (A7) studied the effects of
monomer concentration, plasticizer content, and temperature
on the interaction of vinyl chloride with PVC. Increased
plasticizer content resulted in high retention of monomer in
the polymer, and vinyl chloride retention was favored at lower
monomer concentrations. Increased temperature, however,
caused interaction between monomer and polymer to decrease.
120R ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
Solubility of 14 polar and nonpolar solvents was determined
in copolymers of acrylonitrile and a-methylstyrene using in-
verse gas chromatography. Flory-Huggins interaction pa-
rameters, partial molar heats of mixing, and heats of solution
were calculated by Siow, Goh, and Yap (A3). Shijji and co-
workers ( A l 9 ) also used inverse gas chromatography to de-
termine glass transition temperatures for cholesteryl meth-
acrylate-methyl methacrylate copolymers. Gas chromatog-
raphy and differential thermal analysis were used by Beldie
and co-workers ( A B ) to determine the glass transition tem-
peratures for copolymers of styrene and methyl methacrylate.
Inverse gas chromatography was used by Gozdz and We-
igmann ( A l l ) to determine adsorption isotherms and surface
areas for textile fibers. The technique was also used by Nandi
and co-workers (A13)to explain the solution incompatibility
of poly(methy1 acrylate) and poly(viny1acetate) and to study
the thermodynamic interactions between these polymers.
Equiazabal and co-workers ( A l 5 ) used the inverse gas
chromatographic technique to determine solubility parameters
for polyacrylates, while Sanetra, Lolarz, and Wlochowicz (AI6)
used the technique to determine the glass transition tem-
perature of styrene-divinylbenzene copolymers (5-20% DVB).
These workers also studied the interactions of these co-
polymers with C1 to C6 alcohols.
PYROLYSIS TECHNIQUES
The Proceedings of the Sixth International Symposium on
Analytical and Applied Pyrolysis (B35) included papers on
instrument and method developments including cryofocusing,
photoionization mass spectrometry, and the effects of various
pyrolysis parameters. Applications included mechanisms of
thermal degradation, thermal recycling, plus forensic uses and
application of pyrolysis techniques to food chemistry, med-
icine, biochemistry, and the study of fossil fuels and biomass.
Ahlstrom (B55) reviewed the application of pyrolysis tech-
niques to study polymer microstructure. Examples were
presented for polyolefins, vinyl polymers, and condensation
polymers including polyesters, polyamides, and polyethers.
Jones (B4) presented an overview of fingerprint identifi-
cation, structure elucidation, and compositional analysis ap-
plications of pyrolysis- as chromatography. Levy and Wam-
pler (Bl6)also reviewecf applications of pyrolysis capillary gas
chromatography for the identification and differentiation of
synthetic polymers.
Whiton and Morgan (B2) described the modification of a
capillary gas chromatographic injection port to accommodate
a pyrolysis probe. Lloyd (BIZ)described an instrument for
the automated thermal desorption of cryogenically trapped
pyrolysis products. The system was used to determine de-
sorbable compounds (e.g., limonene) from substrates such as
packaging materials. Whiting and Langvardt (€64) described
a sampling device for combining thermogravimetry, gas
chromatography, and mass spectrometry. The device per-
mitted on-column trapping with a fused-silica capillary col-
umn.
Venema and Veurink (B3I) described a method for ap-
plication of soluble and insoluble samples to ferromagnetic
wires without using solvents. Samples were pressed on to the
wires. The authors also described techniques for coating these
wires with a porous polymer (i.e., Tenax) and depositing liquid
samples for pyrolysis without affecting the porous polymer
substrate. The effects of sample layer thickness and tem-
perature rise time were studied by van der Kaaden, Hoo-
gerbrugge, and Kistemaker (B36). Cellulose was used as a
model to study the effect of these variables on the pyrolysis
temperature using Curie point wires.
Cold trapping, heartcutting, and back flush techniques were
used by Wright and co-workers (BI8) to profile narrow re-
tention windows from complex pyrograms of synthetic poly-
mers. Kogerman ( B l 9 ) compared thermal analysis and
stepwise pyrolysis-gas chromatography for studying the
degradation of cellulose derivatives. This study showed the
importance of pyrolysis data to supplement the thermal data
from degradation of cellulose and an acrylonitrile-cellulose
copolymer.
McMinn, Carlson, and Munson (B3) proposed the use of
pyrolysis and capillary GC/MS to analyze automotive paints
and prepare a searchable data base for identification of these
materials. Burke et al. (B5) comDared wrolvsis-mass met-
trometry, pyrolysis-gas chromatographi, and infrared spec-

Char*. 0. Smlh is a Research A S S O C ~ I W
win m e Polymer c Materials Refearch Cen
10, DOI Cnemcal U S A He rece~vean8'
~~
0,s. dearee from Alleghanv College and hi:
M.S. inchemistry from ihe Unberslty 0
Michigan. Following graduation. he work-
3 years with the Chemical Division 01 PP(
Industries before Fining Dow in 1967. Alte.
4 years Of methods development in the Or-
ganic and Agricultural Products Groups. he
transferred to his Current assignment. His
exoertise has been concentrated on
ch;omatographic separations and applica-
M;thods Sub-Commmee 01 ASTM D-20OhPlastlCs
Rlohard A. Nyqul.1 is a Senior Associate
Scientist in the Instrumental Group 01 the
Analflical LabOmtorie% DOW Chemical
U.S.A. He received his 0. A. degree in
chemistry from Augustans College. Rock Is-
land. IL. and his M.S. from Oklahoma State
University. He joined The Daw Chemical
Company in 1953, and his career has been
mainly in the field of I R and Raman spec-
troscopy. He utilizes I R and Raman spec-
troscopy for solving chemical problems. for
the elucidation of molecular structure. and
for qualitative and quantitative analyses.
Nyquist Is the auihor or coauthor Of over 90
scientific articles Including books. chapters
in books, and patents. He Is a member 01 the American.Chemica1 Society.
The Coblentr Society. The Society fw Applied Spectroscopy. and ASTM E13
on molecular ~ p e ~ h o s ~ o pI ny .1965 he received the Williams-Wright Award
lor his contributions to inlrared ~pe~troscopy.
Nds H. Mahk is a Projen Leader wkh the
Instrumental Group 01 the Analytical
Laboratories. Dow Chemical U.S.A.. Mid-
land. MI. He received his FhD. in anawical
chemistry from Northern Illinois University.
He was a postdoctoral associate with L. E.
R a p r s SIPUrdw Universky for 2 years p r l a
to joining The DOWChemical Company in
1974. He is the author or coauthor 01 21
publications and one U.S. patent. His re-
search interests include polymer characteri-
m i o n . mass spectrometry. separation sci-
ence, trace organic m a l y ~ b .environmental
American ASSociatbn lor IlkAdvan<ment of Science, the American Socie-
ty lor Mass Spectrometry. and Sigma Xi.
Palrlck B. Smlh is a member 01 Me Poly-
meric Materials Research Center. Dow
Chemical U.S.A.. Mdland. MI. Ha ,ecaived
a B.S. degree from Michigan State Universi-
ty in 1972. a M.S. in 1974. and a PhD. de-
gree in physical chemistry Com Michigan
State University in 1978. Dr. Smith's re
search interests are Largely concerned wit1
the ~ t r ~ c l ~charanerizatlon
ral 01 synthetim
polymers by NMR spectroscopy. both higl
resolution and solid state. Dr. Smith ha
lectured at a number Of universkies on thi
topic 01 pOlymer characterization by NMI
P Y is the authar or cwutho
S ~ C ~ ~ O S C Oand
of 10 publications. He is a member 01 thb
American Chemical Society. Polymer Science Division
6Iw.n J. Martln lo a ReDearch A s ~ ~ ~ l a t e
Unh lhe Polymeric Materas ReSearCh Ceh
ter. Dow Chemical U S A , Mdlana. M I He
is also Adjunct Professor at Central Michi-
gan University. He received his B.S. (1973)
at Michigan State Univerrky and his Ph.D.
119771 at the UniversiN Of Illinois under h
birectikn of H. V. M a l k d t . His research
interests are in the development of polymer
characterizatbn techniques and the appllca-
lion of new and nadtional techniques to the
characterization of novel polymers. Current
emphasis includes the use of Size-BxcIusion
chromatography. liquid chromatography.
light rcanering. and combined technique$ to
Characterize heterogeneous polymers.
ANALYSIS OF SYNTHETIC POLYMERS
And,** J. P8UIW. Jr.. )sa ReMarm Lead-
BI n me Polymeric Materals Research Ccn-
tor 01 Dou Cnamcal U S A , Modland. M I
-. He received his Ph.D. in physical chemistry '
from the University 01 Miami (Florida) in
1976. He bined Dow in that Same year and
worked in the HaloOeN Research LBboratO-
ry and the Sty& Molding Polymers
Laboratory before taking his present assign-
ment. His research interests include the
cornpatability of polymer blends and the en-
ergy and Orientation in formed polymers
I I parts. He is a member 01 the North Ameri-
can Theimal Analysis Society and holds
three U.S. patents.
.. .
troscopy for analysis of paint resins. Data suggested that best
results were achieved by using a combination of these tech-
niques. A forensic application of pyrolysis-gas chromatog-
raphy involved the identification of automobile paint. Fukuda
(825) categorized the pyrograms from 78 topcoat materials
used by major Japanese manufacturers based on the height
of four major peaks.
Neubecker and Schultz (81)used pyrolysis-gas chroma-
toeraDhv to studv the comDosition of random 2-iso-
propenylnaphthalene-n-butyl' methacrylate copolymers.
Monomer yields were correlated with mole fraction of the
corresponding homopolymers in mixtures. Dhal and Babu
(86)reported mechanisms for the pyrolytic decomposition of
glycidyl methacrylate-alkyl acrylate copolymers using gas
chromatography and mass spectrometry.
Ohtani, Asai, and Tsuge (814) used pyrolysis-GC/MS and
pyrolysis-hydrogenation GC/MS to identify products from
pyrolysis of alkyl methacrylate copolymers used as viscosity
index improvers. The hydrogenation runs gave simplified
pyrograms containing n-paraffin and isoparaffin peaks. These
latter peaks resulted from &branch points in the polymeth-
acrylate. Sequence distribution of acrylate-methacrylate
-
copolymers was determined by Yamaguchi and co-workers
'.
(828). Diad sequence distributions were studied for an ethyl
.G acrylatebutyl acrylate copolymer and an ethyl acrylate-hutyl
acrylate-butyl methacrylate terpolymer. Brooks and Bates
(87) used Curie point pyrolysis-gas chromatography to
characterize acrylate and methacrylate copolymers used in
dental applications.
Styrene-divinylbenzene (DVB) copolymers with varying
levels of DVB were studied by Nakagawa and Tsuge (810)
using a high-resolution fused-silica capillary column to sep-
arate the pyrolysis products. Compounds up to styrene
trimers and hybrid trimers were resolved within 80 min and
correlations were established to permit calculation of the
ethylstyrene and DVB contents of these copolymers. Phe-
nylpropionic acid and propiophenone derivatives of poly-
styrene were pyrolyzed by Venema and Sukkel ( / ? I S ) . Iden-
tification of substituted styrenes from the Curie point ex-
periments gave information about substitution and the for-
mation of byproducts.
Cascaval and Poinescu (821) pyrolyzed a divinylbenzene-
ethylstyrene-vinyl acetate copolymer a t 200-800 "C with
subsequent gas chromatography. Thermogravimetric analysis
was also used to study degradation of this material. Costa
and co-workers (850)prepared anionic polystyrene samples
end-capped with different functionalities. These polymers
were degraded in nitrogen and products were analyzed by
combined thermogravimetry and gas chromatography.
Perlstein and Orme (826) used pyrolysis-gas chromatog-
raphy to differentiate between polyeste~polyetherrubber and
poly(1,lbutanediol terephthalate). Pyrolysis of poly(hexa-
~- methyleneadipamide) at 220 "C gave a number of products
generated during elimination and chain end reactions.
MacKerron and Gordon (824) used gas chromatography and
mass spectrometry to separate and identify lactams and cy-
-r. clopentanone derivatives.
T_ Noel, Cole, and Hechler (B38)used a pulse mode pyrolyzer
(Chemical Data Systems) to characterize epoxy-based com-
posites or prepregs. Samples were pyrolyzed for 10 s a t 650
V
OC using the nonlinear heating rate, then products were
F;;, separated by capillary gas chromatography. The GC column
was interfaced with Fourier transform IR via a gold-coated
light pipe to identify some of the major pyrolysis products.
ANALYTICAL CHEMISTRY, VOL. 59. NO. 12,JUNE 15, 1987 121 R
ANALYSIS OF SYNTHETIC POLYMERS
The amount of dicyandiamide hardener was calculated by
ratioing the aniline (hardener) and phenol peak responses. In
another study, Peltonen (B40) pyrolyzed an amine-cured
epoxy paint at 350 "C and trapped the products with dry ice
and acetone. The trap was washed with acetone and diethyl
ether, then the combined organic extract was shaken with HCl
and aqueous NaOH. Analysis of extracts by GC/MS showed
phenol, cresols, and bisphenol A as the main acidic products
while pyridine and 2,3-dimethylpyrazine were the primary
basic degradation products.
Alexeeva and Solomatina (B43)used stepwise pyrolysis and
gas chromatography to analyze composite samples. Initial
heating of the pyrolysis cell to a temperature close to the
boiling points of the additives resulted in evolution of these
stabilizers and plasticizers. Subsequent 700-770 "C pyrolysis
and gas chromatography gave information on the polymer
composition.
Materials such as poly(methy1 methacrylate) and poly-
ethylene are used in prosthetic devices. Henkel and
Luderwald (B45)used Curie point pyrolysis to qualitatively
and quantitatively determine these polymers in human tissue
samples.
In a unique application of pyrolysis technology, Sotnikov
and Volkov (B44) collected aerosols on powdered materials
such as crushed silica then pyrolyzed the adsorbents. The
aerosol products were separated by gas chromatography and
detected using flame ionization and flame photometry.
Photocopies from different manufacturer's machines were
pyrolyzed by Levy and Wampler (B27). Different pyrolysis
products were dependent on the toner material used in the
photocopying process.
Barford and co-workers (B52) studied the degree of me-
thylation of pectin by using pyrolysis-gas chromatography.
A peak identified as methanol gave the best correlation with
the degree of methylation. Polymeric hindered-amine light
stabilizers and other commercial additives were also deter-
mined by Perlstein and Orme (BI3) using pyrolysis-gas
chromatography.
Leijenaar, van den Heuvel, and Huysmans (B9)degraded
poly(viny1 chloride) a t 180 "C in helium. Size exclusion
chromatography with refractive index and a photodiode array
UV-visible detector were used to confirm polyene formation
from the dehydrochlorination reaction.
Pyrolysis-hydrogenation-gas chromatography was used by
Tulisalo and co-workers (BI 7 ) to determine branching in
1-butene-1-decene-ethylene, 1-butene-1-dodecene-ethylene,
and 1-butene-1-hexadecene-ethylenecopolymers. Ohtani,
Tsuge, and Usami (B57) reported the use of this technique
to study short-chain branching up to hexyl in low-density
polyethylene. Some of these same workers (B17) used pyro-
lysis and capillary gas chromatography to determine the
composition of block copolymers prepared from styrene and
deuteriated styrene.
Kaljurand and Kullik (B20) described the application of
correlation chromatography to a study of degradation kinetics
for a polyamide. The technique was based on sample intro-
duction to a chromatographic column using a pseudo random
binary sequence. Montaudo and co-workers (B22)used flash
pyrolysis followed by gas chromatography and mass spec-
trometry to study the thermal degradation of polyethers.
Pyrolysis products such as aldehydes, phenols, ethers, and
hydrocarbons resulted from thermal rearrangement of polymer
chains and their subsequent decomposition.
Mitera and Michal (B23) utilized GC/MS to study the
formation of toxic compounds from combustion of poly-
ethylene, polypropylene, polystyrene, and a polyamide.
Nonflaming combustion of these polymers gave products
similar to those obtained from pyrolysis in an inert atmo-
sphere.
Silica, zeolites, alumina, and silica-alumina blends were
used as catalysts by Audisio and Silvani (B30)to study po-
lypropylene degradation between 200 and 600 OC. Experi-
ments were performed in a glass apparatus heated with a
furnace and degradation products were collected with liquid
nitrogen traps. The trapped products were separated on a
capillary column and identified by mass spectrometry. A
silica-alumina catalyst gave much lower yields of C,-CZ7 hy-
drocarbons than polypropylene without the catalyst. Some
of the same workers ( B I I ) used pyrolysis-GC/MS to study
the thermal degradation of polypropylene mixed with a
122R 0 ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
chloroparaffin and a bismuth salt. Presence of the flame
retardant additive resulted in a decrease in the amount of low
boiling decomposition products and a change in the ratio of
isomers resulting from hydrogen transfer reactions.
Day and Wiles (B29)studied the thermal degradation of
poly(ethy1ene terephthalate) with and without the tris(2,3-
dibromopropy1)phosphate flame retardant. Under the con-
ditions of the experiment, oxygen did not play a significant
role in the degradation mechanism between 450 and 700 "C.
Major products obtained in air and helium included CO, CO,,
hydrocarbons, acetaldehyde, benzene, benzoic acid, vinyl
benzoate, and divinyl terephthalate.
Alajbeg and Stipak (B33)studied the thermal degradation
of polystyrene foam with and without the flame retardant
tetrabromovinylcyclohexene. Degradation products in air,
nitrogen, and mixtures were trapped in n-hexane at 260 K and
subsequently analyzed by GC/MS. The quantity and identity
of degradation products were influenced by temperature, but
not by the test atmosphere. An increase in pyrolysis tem-
perature in the presence of the flame retardant decreased the
amount of volatile products less than samples without the
flame retardant.
One of these workers (B34) used the same apparatus to
study the decomposition of phenol-formaldehyde foam under
nonflaming combustion conditions. The material was heated
at 823, 1023, and 1223 K in atmospheres of air, nitrogen, and
1/1 airlnitrogen. Volatiles, trapped in hexane and identified
by GC/MS, included phenol, cresols, xylenols, other substi-
tuted phenols, benzene, substituted benzenes, and fused-ring
compounds. Phenols were predominant in nitrogen, but ox-
ygen appeared to further degrade them to aromatics. In an
attempt to study the decomposition of methylene bridges and
aromatic methyl groups in a phenol-formaldehyde polycon-
densate, BlazsB (B39)pyrolyzed samples at 650 "C. The yields
of alkylbenzenes and alkylphenols in capillary pyrograms were
correlated to the structure of the polycondensate.
Pyrolysis-electron impact mass spectrometry was used by
Pidduck (B32)to identify commercial halogenated polymers.
Samples of vinyl polymers, hydrocarbon polymers, and
polyethers were heated a t 50-100 "C/min over the range of
50-650 "C. Mass spectra from the vinyl and hydrocarbon
polymers were dominated by ions attributed to HCl, although
cross-linked polyene structures were evident for the higher
pyrolysis temperatures. The chlorinated polyethers showed
chlorine-containing ions throughout the entire mass range.
Statheropoulos (B41) degraded poly(viny1 chloride) film a t
160-280 "C for 30 min in the ion source of a mass spectrom-
eter. Products identified by direct inlet mass spectrometry
included HC1, benzene, toluene, substituted benzenes, and
fused-ring compounds. These latter compounds were pre-
dominant a t temperatures above 240 "C.
Lonfei and co-workers (B42)used pyrolysis-GC/MS and
direct pyrolysis-mass spectrometry to study the mechanism
for degradation of fluoropolymers. Depolymerization of
perfluoropolymers and chlorine-containing fluoropolymers was
the predominant mechanism, but the presence of OCF, groups
altered this mechanism. For these latter polymers, random
cleavage and fluorine transfer reactions were important.
Using pyrolysis-gas chromatography and thermogravimetric
analysis, Radhakrishnan and Rao (B37)studied the mecha-
nism and kinetics of thermal degradation of a thiol-terminated
polysulfide polymer cured with ammonium dichromate. Major
products from pyrolysis of liquid and cured polymers a t 420
and 470 "C included 1,3-oxathiolane, dioxa-6-thiocane, 2-
mercaptomethyloxirane, and 1,3-dioxa-6,7-dithionane.
Product yields were similar suggesting the same degradation
mechanism for the cured and uncured polymers.
Grassie (B46)reviewed the application of thermal analysis,
infrared spectroscopy, and GC/MS to polymer degradation
studies. In more definitive studies, Grassie and co-workers
reported on the thermal degradation of epoxy polymers de-
rived from bisphenol-A and epichlorhydrin (B47),bisphenol-A
diglycidyl ether cured with ethylenediamine (B48), and
polyether-urethanes prepared from methylene bis(4-
phenylisccyanate) and poly(ethy1eneglycols) (B49). One study
(B53) proposed mechanisms for the formation of 15 products
from the degradation of bisphenol-A diglycidyl ether homo-
polymer.
Polyolefins, polystyrene, poly(viny1 chloride), polyamide,
arid some copolymers were studied by Pacakova et al. (B51)

using a combustion chamber designed to simulate fire con-
ditions. The volatile decomposition products were analyzed
by GC/MS using a combination of packed and capillary
columns.
LIQUID CHROMATOGRAPHY (LC)
Gur'yanova and Pavlov ( C l ) analyzed oligomers of poly-
(butylene terephthalate), polysulfone, and polycarbonate by
adsorption LC. Careful selection of mobile phase enabled
separation either by molecular weight or by the structure of
terminating groups. Lai and Sangermano (C4) determined
the molecular weight distribution of epoxy novolac resins using
LC with a phenyl-bondedphase. No61 et al. (C6) characterized
epoxy resin formulations using reversed-phase LC. Men and
Rogers (C5) studied the LC separation of isomers of poly-
styrene trimers on derivatized silica. Jandera and Rozkognl
(C7) and Lai et al. (C19) separated oligomers of polystyrene
by LC. Alexander et al. (C2) investigated the separation of
poly(ethy1ene glycol) oligomers by normal-phase and re-
versed-phaseLC. Lai (C8) characterized the molecular weight
distribution of poly(ethy1ene glycol) oligomers by using
open-tubing LC-mass spectrometry. Burford et al. (C3) used
reversed-phase LC to analyze polyester-based polyurethane
elastomers after alkali fusion.
Fujimoto et al. (C9) analyzed oligomers of polystyrene and
methylphenylpolysiloxane using supercritical fluid chroma-
tography-infrared spectroscopy. Schmitz et al. (C10) used
supercritical fluid chromatography to separate oligomers of
poly(vinylbiphenyl), poly(vinylnaphthalene), and poly(vi-
nylcarbazole).
Vargo and Olson ( C l l , C12) used coupled ultraviolet and
mass spectrometric detection to identify and quantify anti-
oxidants and ultraviolet light stabilizing additives in plastic
materials which were separated by LC. Sreenivasan ((213)
used LC to determine epoxidized soyabean oil, di(Bethylhexy1)
phthalate, and tris(nonylpheny1) phosphite in poly(viny1
chloride).
Glockner (C14) reviewed the analysis of compositional and
structural heterogeneities of polymers by nonexclusion LC.
Sato et al. ((216) and Glockner et al. (C17)separated poly-
(styrene-co-methyl.methacrylate) copolymers according to
their chemical composition by gradient-elution LC. Under
the selected conditions, retention was essentially independent
of the polymer molecular weight. Mori et al. (C15) used
adsorption LC to fractionate poly(styrene-co-methylmeth-
acrylate) according to chemical composition and subsequently
determined the molecular weight distribution of the fractions
by size-exclusionchromatography. Mourey (C18) separated
poly(alky1 acrylate) and poly(alky1 methacrylate) homo-
polymers and copolymers by gradient-elution adsorption LC
and monitored the elution with evaporative light-scattering
detection. Solute retention was dependent on polymer
chemical composition and independent of polymer molecular
weight.
SIZE-EXCLUSION CHROMATOGRAPHY (SEC)
Lesec (01) reviewed the preparative applications of size-
exclusion chromatography (SEC). Unger and Janzen ( 0 2 )
provided a survey of commercial packings available for
preparative liquid chromatography, and discussed criteria for
selection of appropriate phase systems.
SEC procedures were developed for the molecular weight
characterization of polyacrylonitrile (052),polycarbonate
( 0 2 5 , 0 3 3 ) , polycaprolactone ( 0 2 6 ) , cellulose ( 0 3 2 ) , coal
derivatives ( 0 4 3 ) , polyethylene ( 0 4 5 , 057),dextran ( 0 4 1 ,
044)poly(ethy1
, methacrylate) (056),fluorescent-dye-labeled
poly(ethy1ene oxide) ( 0 17), lignin (042),poly(methy1meth-
acrylate) ( 0 5 9 , 0 6 2 ) , nitrocellulose ( 0 2 5 ) ,nylon ( 0 1 2 , 0 1 5 ,
D16), sodium poly(styrenesu1fonate) ( 0 3 ) , phenol-form-
aldehyde resins ( 0 2 1 ) ,poly(pheny1ene sulfide) (022), poly-
propylene (024,034,057,D60),polyurethane ( 0 1 3 , 0 3 0 , 0 3 1 ,
036-039), poly(viny1 acetate) (D61), poly(n-vinyl-3,6-di-
bromocarbazole) (018,0 5 8 ) ,xylan sulfate (023),poly(ethy1ene
terephthalate-methylene isophthalate) (019),polystyrene-
cellulose acetate graft (035),and poly(norbornene-methylene)
(020).
Kato et al. (049) evaluated the commercially available TSK
gel GMPW column and presented example SEC separations
of 24 water-soluble polymers. The mixed-pore-size column
exhibited a poly(ethy1ene glycol) molecular weight calibration
ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
ANALYSIS OF SYNTHETIC POLYMERS
curve which was almost linear over the range lo2-lo6. Wada
et al. (051) evaluated commercially available columns packed
with rigid poly(viny1alcohol) gels for use in SEC of water-
soluble polymers. Hatano (050) reviewed the liquid chro-
matography packing materials and detectors which are com-
mercially available in Japan.
Mori ( 0 6 3 , 0 6 4 ) used semimicro SEC columns for the
separation of oligomers of oligostyrene, epoxy resin, meth-
ylated melamine-formaldehyde resin, and phenol-form-
aldehyde resin. Chiantore and Guaita ( 0 6 5 ) applied SEC to
the analysis of n-alkanes and oligomers of polystyrene,
poly(styrene-co-acrylonitrile),poly(p-methylstyrene), and
phenol-formaldehyde resin. Ponnuswamy et al. (07)devel-
oped an automated SEC to monitor the molecular weight
distribution in a batch polymerization reactor.
SEC with a coupled low-angle laser light scattering detector
(SEC-LALLS) was used to determine the absolute molecular
weight distributions of polycarbonate (0331,polyethylene
( 0 4 5 ) , polyisobutylene (0461, lignite ( 0 2 9 ) ,polypropylene
( 0 3 4 ) ,polyquinolines ( 0 2 8 ) ,and poly(viny1alcohol) (027).
Lederer et al. ( 0 4 6 ) described a method for simultaneous
calibration of separation and axial dispersion in SEC-LALLS.
The method assumed a linear log (molecular weight)-retention
volume calibration and a Gaussian axial dispersion but was
not restricted to samples with logarithmic normal molecular
weight distributions. Prochazka and Kratochvil ( 0 4 7 ) ana-
lyzed the effect of concentration and light scattering detector
signal-to-noise ratios on the degree of uncertainty in the
molecular weight distributions determined by SEC-LALLS.
Berkowitz (048) described a computer data acquisition system
capable of extracting undistorted light scattering data from
chromatograms heavily contaminated with spike noise.
Schorn et al. ( 0 3 3 ) used SEC-LALLS to investigate the
formation of polycarbonate microcrystallites in tetrahydro-
furan. Grinshpun and Rudin ( 0 3 4 ) observed aggregates of
polypropylene in trichlorobenzene solutions at 145 "C, and
used SEC-LALLS to study the effects of solution storage time
on dissolution of aggregates and polymer degradation.
Grinshpun et al. (045)analyzed copolymers of ethylene and
1-alkenes by SEC-LALLS and discussed the implications of
their results to the calculation of long-chain branching from
SEC of polyethylene. Coleman and Dawkins ( 0 6 1 ) investi-
gated the long-chain branching in poly(viny1 acetate) by SEC
and off-line measurement of the intrinsic viscosity of polymers
and polymer fractions. MrkviEkovB and JanEa ( 0 6 2 ) char-
acterized tetrafunctionally branched poly(methy1 meth-
acrylate) by SEC and off-line viscometry.
Haney ( 0 5 3 , 0 5 4 ) described a commercially available
differential viscosity detector for SEC. The differential vis-
cometer used a balanced capillary bridge and exhibits a sig-
nal-to-noise ratio superior to that obtained with single capillary
viscometers. Lundy and Hester ( 0 5 5 ) combined a precision
syringe pump, Sephacryl packing, and a capillary pressure
detector to characterize large water-soluble polymers. Stacy
( 0 2 2 ) characterized poly(pheny1ene sulfide) using a high-
temperature SEC equipped with a capillary viscometer.
Deniz and Guven (056) investigated the effect of uncer-
tainties in Mark-Houwink constants on the average molecular
weights and molecular weight distributions of poly(ethy1
methacrylate) determined by SEC.
Mahabadi (059) determined the Mark-Houwink constants
of poly(methy1methacrylate)in tetrahydrofuran from the SEC
universal calibration curve obtained with polystyrene and
measurement of intrinsic viscosity and SEC chromatogram
of polydisperse samples. Horta et al. ( 0 5 8 ) determined the
Mark-Houwink parameters of poly(n-vinyl-3,6-dibromo-
carbazole) in tetrahydrofuran. The method required the in-
trinsic viscosity, one average molecular weight, and SEC
chromatogram for each of several polydisperse samples.
Grinshpun and Rudin ( 0 5 7 ) calculated the Mark-Houwink
constants of polypropylene and h e a r low-density polyethylene
from SEC-LALLS data.
Parks et al. (010, 066) characterized the molecular weight
distributions of poly(tributy1tin methacrylate-co-methyl me-
thacrylate) and poly((4-vinylpheny1)triphenyllead-co-octadecyl
methacrylate) using SEC with coupled differential refractive
index, ultraviolet, and element-specific atomic absorption
spectroscopy detectors. Harrison et al. (D11) used SEC with
coupled ultraviolet and differential refractive index detectors
(SEC-UV-DRI) to investigate the oxidative chain scission of
123R
ANALYSIS OF SYNTHETIC POLYMERS
polyisoprene in styrene-isoprene-styrene block copolymers.
Ogawa and Sakai (012) used SEC-UV-DRI to characterize
the molecular weight distribution and compositional hete-
rogeneity of polyamide copolymers derivatized with tri-
fluoroacetylene. Manolova et al. (026) used SEC-UV-DRI
to characterize mixtures of linear and cyclic caprolactone
oligomers. Linear oligomer hydroxyl end groups were labeled
with isocyanate.
Lee et al. (013) determined the molecular weight distri-
bution and Mark-Houwink parameters of linear polyurethane
block copolymers by SEC with coupled differential refractive
index, ultraviolet, and low-angle laser light scattering detectors.
The average segmental composition and specific refractive
index increment used in the light scattering calculations were
calculated at each retention increment from the multidetector
data. Grinshpun and Rudin (014) characterized the molecular
weight distributions of ethylene-propylene and ethylene-
propylene-diene copolymers using a SEC equipped with an
evaporative mass, differential refractive index, and low-angle
laser light scattering detectors. The average weight-fraction
diene and s ecific refractive index increment were calculated
at each S E 8 retention increment. Dumelow et al. (040) de-
termined the molecular weight and composition heterogeneity
of styrene-dimethylsiloxane block copolymers using SEC
coupled with infrared, differential refractive index, and low-
angle laser light scattering detectors.
Beazley (04) determined partially hydrolyzed polyacryl-
amide polymers in oil field production water with a detection
limit of 10 ppb. Gharfeh and Moradi-Araghi (D5) determined
proprietary anionic high-molecular-weight water-soluble
polymers in oil field brines by SEC. Sreenivasan (06) used
S&C to determine jasticizers in poly(viny1chloride).
SpaEek and Kugin (08, 0 9 ) investigated polystyrene
block-poly(ethene-co-butene)-block-polystyrenemicellization
by SEC in a mixed solvent dioxan-heptane. The association
equilibrium was shifted from pure unimer to pure micelles
by changing the mobile phase composition or the temperature.
MASS SPECTROMETRY
Montaudo ( E l )reviewed the analysis of polymers by direct
mass spectrometry. The principles and experimental aspects
for both pyrolysis and desorption methods were discussed
together with comparisons of other spectroscopic techniques.
Lattimer and Harris (E2) reviewed the use of mass spec-
trometry for the analysis of polymer additives. Derrick (E3)
discussed the use of mass spectrometry above 10000 amu.
Methods of ionization, mass separation, and detection were
reviewed and a general mechanism for the formation of gas-
eous ions from nonvolatile thermally labile compounds was
presented. Cochran (E4) critically reviewed the present and
predicted the future use of fast atom bombardment mass
spectrometry for the analysis of synthetic polymers and
polymer additives.
Ballistreri et al. (E5) used pyrolysis-mass spectrometry to
investigate the thermal fragmentation of poly(cu-amino acids).
Cyclic oligomers were formed for polyglycine, polysarcosine,
and polyproline. Polyalanine, polyphenylalanine, and poly-
tyrosine decomposed to form compounds with olefin and
nitrile end groups. The primary thermal process of poly(y-
methyl glutamate) is loss of methanol to form pyroglutamic
units, which subsequently form cyclic dimers. These authors
continued this work with a study of copolymers of the a-amino
acids, proline-sarcosine, and proline-alanine (E6).
Pidduck (E7) used controlled pyrolysis-electron impact
mass spectrometry as a general method for the identification
of halogenated polymers. Particular emphasis was placed on
the identification and rationalization of mass spectra in terms
of structure and general thermal degradation pathways for
vinyl polymers containing chlorine, polychloroprenes, chlo-
rinated hydrocarbon polymers, chlorinated polyethers, ther-
moplastic fluoropolymers, and fluoroelastomers. Inorganic
oxides, such as zinc and antimony oxides, were found to change
the polymer degradation process. Silicon and titanium oxide
fillers in fluorinated vinyl polymer materials reacted with
hydrogen fluoride to form volatile halides.
Whitehouse and co-workers (E8) presented the results of
a collaborative reproducibility study from six laboratories
using pyrolysis-mass spectrometry on a routine basis. A
variety of pyrolyzers, heating rates, mass spectrometers, and
ionizing energies were used. It appeared that the nature of
124R ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
the pyrolysis system rather than the mass spectrometer was
the major factor affecting reproducibility. For synthetic
polymers, the use of lower electron energies provided no more
information to that obtained at the more common 70 eV and
had the disadvantages of poorer sensitivity and reproducibility.
In general, synthetic polymers gave more reproducible results
than biopolymers.
Garozzo et al. (E9) studied the primary thermal decom-
position processes of aliphatic polyesters by electron impact
and chemical ionization mass spectrometry. Numerous spectra
were presented that allowed comparisonsto be made between
reduced energy (18 eV) electron impact, positive and negative
ion ammonia, and isobutane chemical ionization techniques.
Some thermally formed com ounds were found to be unstable
under electron impact congtions. Chemical ionization ex-
periments indicated that intramolecular exchange reactions
predominant in the primary thermal fragmentation processes,
causing the formation of cyclic oligomers, which were stable
under the chemical ionization conditions.
Lattimer and co-workers (EIO) used Curie-point pyroly-
sis-mass spectrometry for the quantitative analysis of com-
ponents in uncured rubber blends and compounded vulca-
nizates. The components, including styrene-butadiene rubber,
cis-polybutadiene, and polyisoprene, were analyzed from
toluene suspensions of samples obtained by extensive grinding
with li uid nitrogen. The resulting mass spectra were nor-
malizei and analyzed by target rotation factor analysis. The
average errors for the components were in the range of 2-5%,
which were comparable to infrared and nuclear magnetic
resonance spectroscopy results. Savoca et al. ( E l l )used the
same technique to study the cross-link density of natural
rubber vulcanizates.
Garozzo et al. (2312) reported on the identification of
polymers by mass spectral library searching of pyrolysis
electron impact mass spectra and pattern recognition analysis.
Montaudo and co-workers (E13)studied the thermal degra-
dation of aromatic-aliphatic polyethers with direct pyroly-
sis-mass mectrometrv. These results were comDared with
pyrolysis-g& chromat&raphy-mass spectrometry of the same
polyethers (E14).
Ohrbach and Kettrup (E15)used simultaneous thermal
analysis-mass spectrometry to follow the thermal degradation
of polyurethane foam containing the flame retardant tetra-
kis(2-chloroethyl) ethylenediphosphate.
Horna and co-workers (E16) presented electron impact and
methane and isobutane chemical ionization mass spectra of
38 acrylate and methacrylate monomers. Methane chemical
ionization was determined to be the most useful for identi-
fication of the above-mentioned compounds because the
protonated molecular ions were relatively intense and cleavage
produced abundant characteristic fragment ions.
Airaudo and co-workers (E17)used electron impact and
chemical ionization mass spectrometry to identify benzo-
thiazole derivatives leached into injections by rubber plunger
seals from disposable syringes. One of the compounds was
used as a rubber vulcanization accelerator and four others were
formed during syringe sterilization with ethylene oxide.
A method for the determination of additives in poly-
propylene by selective chemical ionization mass spectrometry
without prior separation was described by Rudewicz and
Munson (E18). These additives, including a hindered phenol,
a phosphite, and an aromatic ketone, were vaporized in a
heated glass probe under chemical ionization conditions with
a 1.1% ammonia in methane reagent gas mixture. The
principal reagent ion in this mixture, NH4+,reacted with the
additives to give very simple spectra of (M + H)+ or (M +
NHJ+ ions and little fragmentation. The selectivity of the
ammonium ion for the detection of these additives in the
hydrocarbon matrix, including the polymer pyrolysis products,
was demonstrated.
Jardine et al. (E19)used field desorption mass spectrometry
to study the thermal degradation of poly(1-butene sulfone)
and poly(propene sulfone). Ions in the spectra of these ma-
terials corresponded to ionized degradation products of the
first step in the two-stage degradation process. The observed
degradation products were the result of the rupture of the
weak links in the polymer chains and the degradation
mechanism involves @-hydrogenshifts.
Hara et al. (EN) applied field desorption mass spectrometry
to study the initiation mechanism of the thermal polymeri-

zation of a series of styrenes. Craig and Derrick (E21)
presented collision induced decomposition spectra of the
cationic radical ion of polystyrene. The peaks occurred pre-
dominantly at low masses for the decomposition of ions at the
highest masses investigated (in the range of mlz 1500 to mlz
2000). The low mass peaks were directly related to the end
group structures of polystyrene. The mechanism of decom-
position involved random initial cleavage of the polymer chain
followed by a series of consecutive depolymerizationreactions.
Lattimer and Schulten (E22) used field desorption and fast
atom bombardment (FAB) ionization to study poly(ethy1ene
imine). Both techniques gave intense protonated molecular
ions. Field desorption produced weight and number average
molecular weights that were higher than FAB. The FAB
results were attributed to fragmentation caused by the fast
atom beam. Both field desorption and FAB number average
molecular weights were higher than that obtained with elec-
trohydrodynamic ionization when compared to a previous
literature study on the same sample. This was attributed to
strong hydrogen bonding in the electrohydrodynamic exper-
iment.
Doerr et al. (E23) used field desorption and fast atom
bombardment mass spectrometry to study polyester polymers.
In the positive and negative ion modes, aliphatic polyesters,
including poly(ethy1ene adipate), poly(propy1ene adipate),
poly(buty1ene adipate), poly(penty1ene adipate), and poly-
(propylene succinate) yielded characteristic ions with a
thermally formed end group and charged ionization at one
ionic end group.
Lattimer and co-workers (E24) studied the identification
of ingredients in compounded carbon-black filled rubber
vulcanizates by electron impact, chemical ionization, field
ionization, and fast atom bombardment mass spectrometry.
The field desorption/ionization technique was found to be
the most efficient for identifying typical organic additives.
There was no clear advantage for direct analysis as compared
to extract analysis with the use of acetone, dichloromethane,
or acetonitrile. Direct analysis was faster, but solvent ex-
traction methods were more versatile.
Hummel et al. (E25) used pyrolysis-field ionization mass
spectrometry, pyrolysis-gas chromatography-mass spectrom-
etry, and pyrolysis-gas chromatography-Fourier-transform
infrared spectroscopy to study the thermal degradation of
random and block copolymers.
Mattern and Hercules (E261used laser mass spectrometry
to study polyglycol oligomers. Number average molecular
weights were found to be reproducible to *2% relative
standard deviation and consistent with field desorption and
electrohydrodynamic ionization mms spectrometry. Fletcher
and Fatiadi ( E 2 3 applied laser ionization mass spectrometry
to study pure poly(44nylpyridine) and poly(4-vinylpyridine)
cross-linked with 2% and 25% divinylbenzene. The stability
of these materials to HCl treatment was also determined.
These polymeric materials gave fragmentation patterns similar
to that of polystyrene by laser ionization. Brown and co-
workers ( E a ) used laser desorption Fourier-transform mass
spectrometry to determine the molecular weight distribution
and end group composition of poly(ppheny1ene)s synthesized
by various routes. Cotter et al. (E29) used laser desorption
time-of-flight mass spectrometryto study low molecular weight
polymers. The abundances of the fragment ions were reduced
with the use of a time-variable drawout pulse. Reliable mo-
lecular weight averages were obtained for poly(ethy1ene glycol)
and poly(propy1eneglycol) samples with oligomer molecular
weights up to 5000. Molecular weight averages for poly-
(ethylene imine) samples were low.
Kendall and co-workers (E30) studied the electrical
breakdown of thin polymer films using a specially fabricated
time-of-flight mass spectrometer that was designed to trigger
from the breakdown event. A slowly increasing potential
gradient was applied from a high impedance source through
a movable contact until breakdown occurred. Teflon FEP and
PFA films produced mainly fluorocarbon ions as high as 350
amu, while poly(ethy1eneterephthalate) and poly(ethy1ene-
tetrafluoroethylene) produced smaller species with masses at
or below 44 m u . Films exposed to oxygen ion bombardment
were also studied.
Secondary ion mass spectrometry with a time-of-flight mass
analyzer was used by Hercules and co-workers (E31)to study
a series of aliphatic polyamides (Nylons). Postacceleration
ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
ANALYSIS OF SYNTHETIC POLYMERS
voltages up to 20 kV were applied to the entrance of the
detection unit to enhance the detection efficiency, especially
for the high masses. Protonation and cationation of the repeat
unit with silver, potassium, and sodium produced high mass
ions characteristic of the polymer and repeat unit sequence
in the polymer chain. Silver and sodium cationized ions as
large as 24 monomer units for Nylon 6 and ions over mass 3500
for Nylon 66 (a6)were observed.
Briggs and Hearn (E32) presented experimental conditions
for the analysis of polymer surfaces by secondary ion mass
spectrometry. Fingerprint techniques, chemical imaging, and
the importance of the ion beam damage rate parameter were
discussed. The same authors (E33)also did a systematic study
of the effects of primary ion (He+, Ne+, Ar+, Xe+, Ga+) and
energy (1-10 keV) on the variation of secondary ion intensities
for polymer surfaces by secondary ion mass spectrometry.
Representative polymers in different physical forms included
low density polyethylene (self-supporting film), poly(tert-butyl
methacrylate) (thin film cast from solution), and poly(ethy1ene
oxide) (compressed powder). Starzyk and Barbaszewski (E34)
presented the mass spectra of secondary ions emitted from
poly(N-vinylcarbazole) thin layers under 2-keV Xe+ bom-
bardment. The temperature dependence of the secondary
emission was also studied. Fowler and Munro ( E 3 9 studied
the surface of thermal and X-ray induced degradation of
cellulose nitrate by fast atom bombardment secondary ion
mass spectrometry.
Garozzo et al. (E36) investigated the distribution of the
cyclic oligomers of poly(1actic acid), formed by both pyrolysis
of the polymer and by equilibration with magnesium chloride
catalyst, with the use of thermospray and negative ion am-
monia chemical ionization mass spectrometry. Both tech-
niques were found to be suitable for the analysis of these
oligomers.
Vargo and Olson (E37) used liquid chromatography-mass
mectrometrv to identifv antioxidant and ultraviolet light
siabilizing idditives in "polymers. Detection limits in ;he
nanogram region were reported using a moving belt interface.
Levsen and co-workers (E38) also used a moving belt interface
liquid chromatography-mass spectrometric system to study
alkylphenol ethoxylate and oxo alcohol ethoxylate surfactants.
Mass spectra were obtained in the electron impact and
chemical ionization modes with isobutane as the reagent gas.
Lai (E39) used open tubular liquid chromatography-mass
spectrometry for the characterization and molecular weight
determination of water-soluble poly(ethy1eneglycol) oligomers.
Aldissi et al. (E40) studied living oligomers of ethylene
obtained by using sec-butyllithium complexed with tetra-
methylethylenediamine and deactivated by oxygen. Gas
chromatography-mass spectrometry was used to identify and
determine the molecular weight distribution of the resulting
alcohols, coupled products, and other nonoxidized compounds
in the resulting complex mixture.
Pacikovl et al. (E41) used gas chromatography-mass
spectrometry to study the oxidative degradation of polymer
materials. The behaviors of polyethylene, polypropylene,
polystyrene, poly(viny1 chloride), Nylon 6, and some co-
polymers were studied in a combustion chamber which sim-
ulated the conditions of a large scale fire.
Sanders and Morsch (E42) described the application of
mass ion profiling for studying polypropylene off-odor prob-
lems. The volatile headspace materials were cyrotrapped on
a capillary column and identified by scanning and accurate
mass profiling. The off odor was found to be ethylisopropyl
sulfide. Quantitation was then accomplished by direct in-
jection with nominal mass profiling.
NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY
A number of reviews have been published in the area of
NMR characterization of polymeric systems. Schaefer ( F I )
reviewed the characterization of polymers in the solid state
by 13C NMR spectroscopy. Axelson and Russel (F2)discussed
the characterization of polymer morphology in the solid state
and end-group analysis in solution by I3C NMR spectroscopy.
Jelinski (F3, F4) reviewed solid-state NMR characterization
of structure and dynamics in solid polymers as did Kausch
et al. (F5). Bovey and Jelinsk (F6)reviewed I3C and 2H NMR
methods for determining chain motion in macromolecules.
125R
ANALYSIS OF SYNTHETIC POLYMERS
Sillescu (F7) and Jelinski (F8) discussed 2H NMR techniques
for studying molecular dynamics in polymeric solids. Cunliffe
(F9) reviewed the topic of NMR of synthetic polymers.
Harrison et al. (FIO) and Bauer ( F I I ) reviewed techniques
for the anal sis of cross-linked polymers. Starnes (F12) de-
scribed the xC NMR characterization of poly(viny1chloride)
and related polymers. Rothwell et al. (F13) reviewed non-
medical applications of NMR imaging.
Several authors published on the subject of molecular dy-
namics studies of polymeric systems using ?HNMR as a probe.
Spiess et al. (F14, F17) studied the molecular mobility in
polymer model membranes which possessed quaternary amine
heads and aliphatic tails. Their investigation showed that the
chain flexibility near the head of the molecule was inhibited
but that mobility near the tail, which was deemed most im-
portant for membrane applications, was retained.
Spiess et al. (F15) also utilized 2H NMR to probe the glass
transition, T , in polystyrene. Spin alignment echo metho-
dology was utilized to study slow molecular processes in this
system. The authors concluded that two motional processes
were present at T , a rapid rotational diffusion process re-
stricted to an angufar range of about *lo' and a much slower
full reorientational process.
Spiess et al. (F16)described a new 2H NMR approach for
the determination of the distribution of correlation times for
local motions in glassy polymers. 'H NMR line-shape analysis
in combination with relaxation measurements was shown to
provide a much enhanced dynamic range for frequency
measurement. In this way, the correlation time distributions
were probed and heterogeneous vs. homogeneous distributions
were distinguished.
Jelinski et al. (F18) investigated the molecular basis for the
6 relaxation in poly(ary1ene sulfones) with 2H NMR spec-
troscopy. The primary mode of motion was observed to be
180° phenyl ring flips which occurred over a very broad dis-
tribution of frequencies. The effect of plasticizers was also
addressed.
Jelinski et al. (F19)also probed the interaction of water with
cross-linked epoxy resins. The study showed no free or tightly
bound water. Rather, the water was impeded in its movement
with molecules jumping from site to site with an approximate
residence time of 7 X s.
The molecular motions present in polyurethanes of
MDI/butanediol and TDI/butanediol were investigated by
Jelinski et al. (F20). Crystalline and amorphous regions were
distinguished in the MDI system whereas only amorphous
components were observed in the latter. Phase separation
in polyurethanes was also investigated by 2H NMR spec-
troscopy (F21) in order to define which fraction of the hard
segment possessed the motional characteristics of the pure
hard segment.
Fyfe et al. (F22)investigated curing in phenol/formaldehyde
resins by 2H NMR spectroscopy. The curing process was
monitored as a function of time by 2H N M R Tl measurements.
The T, values showed a rapid increase with time and then
leveled off. This behavior was consistent with the changes
in cross linking which were observed to occur in other studies.
Chain orientation in deformed polymer networks was also
studied with 2H NMR spectroscopy (F23).
Schaefer et al. (F24) investigated the molecular mechanism
for the rin flip process of polycarbonate by dipolar rotational
spin echo K3CNMR spectroscopy. Their findings indicated
that the rings of polycarbonate executed 180' ring flips su-
perimposed on wiggles. However, calculations of conforma-
tional preference maps for isolated molecules indicated that
the rings were essentially free rotors at room temperature.
Barriers which result from the close packing of adjacent chains
were discussed as the interference to free rotation.
Jones et al. (F25)also probed the phenylene ring flip process
of pol carbonate using solid-state 13CNMR line-shape analysis
with k labeled materials. This study was performed as a
function of field strength and temperature. A motional model
to determine molecular correlation times was presented (F26).
The chemical shift assignments of aromatic epoxy resins
condensed with aromatic amines was performed by solid-state
cross polarization magic angle spinning (CP-MAS) NMR
spectroscopy (3'27). Model compounds were utilized to in-
terpret the spectra of cross-linked species.
Several authors investigated the structure of polyolefins in
the solid state using 13C CP-MAS techniques. Kitamuru et
128R ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
al. (F28) probed the phase structure of semicrystalline poly-
ethylene. They observed differences in the phase structure
depending on the sample crystallization process and charac-
terized the samples in terms of crystalline, amorphous, and
amorphous interphase components.
VanderHart et al. (F29) developed a 13C CP-MAS NMR
method for determining the partitioning of end groups and
side chains between crystalline and amorphous regions in
polyethylene.
'H and 13Chigh-resolution solid-state NMR methods were
utilized to characterize the solid-state conformations and chain
packing in polypropylene by Cudby et al. (F30). This work
also discussed several parameters which were important to
the interpretation of solid-state NMR spectra of polymeric
systems.
Ganapathy et al. (F31) characterized the molecular dy-
namics of poly(viny1 acetate) in the solid state using 'H and
13C NMR methods. They characterized the motions in terms
of a distribution of correlation times and studied the effect
of water on the dynamics of this s stem.
Allen et al. (F32) used CP-MAS & NMR spectroscopy to
investigate the interaction of water with poly(methy1meth-
acrylate). They monitored the development of cross-polari-
zation of PMMA-d8 by the protons of the water as an indi-
cation of this interaction. They concluded that, in the early
stages of absorption, the water was in contact with the
backbone carbons of PMMA. The side chain came in contact
at later stages.
Thermal degradation of pol (acrylic acid) and poly(meth-
acrylic acid) was studied by 13? CP-MAS NMR spectroscopy
by Fyfe et al. (F33). The initial step in the decomposition
was identified as six-memberedring anhydride formation. A t
higher temperatures, aromatic char was observed giving rise
to phenolic resonances.
Mandelkern et al. (F34) investigated the molecular nature
of transitions in polymeric solids by high-resolution13C NMR
relaxation techniques. The collapse temperature for many
amorphous and semicrystalline polymers was determined.
Several authors have also investigated polymer morphology
using solid-state NMR tgchniques. Moeller et al. (F35) in-
vestigated polyethylene, Havens and VanderHart (F36) and
Ito et al. (F37) investigated poly(ethy1ene terephthalate),
Mackay et al. (F38) studied cellulose, and Dechter (F39)
studied poly(ethy1ene oxide). Veregen et al. (F40) used 13C
CP-MAS NMR to differentiate polypivalolactone polymorphs.
I3C CP-MAS NMR was also utilized to probe the silica surface
of fiber-reinforced composites by Koenig et al. (F41).
Belfiore (F42)determined the miscibility of polymer-diluent
blends by 13CCP-MAS techniques and studied the effect of
free volume on the molecular dynamics of polycarbonate as
observed by solid-state NMR techniques (F43).
English and Zoller (F44) developed a correlation between
the fraction of mobile component in a semicrystalline polymer
and the excess free volume in the system as calculated from
the Simha-Somcynsky equation.
Allen et al. (F45) used 13C CP-MAS NMR to study the
curing of tetra(ethy1ene glycol) dimethacrylate. T1, and TsL
were found to be dependent upon the extent of cure.
Spin diffusion techniques were utilized to study the in-
teractions in polymer blends which facilitate miscibility.
Henrichs et al. (F46) investigated poly(ethy1ene tere-
phthalate)/polycarbonate blends using a carbon spin diffusion
technique and Ernst et al. (F47) studied polystyrene/poly-
(vinyl methyl ether) blends by a proton spin diffusion tech-
nique.
The domain size in multiphase polymers was investigated
by proton spin diffusion using Goldman-Shen methodology
by Belfiore et al. (F48) and Tanaka et al. (F49).
Cross-linking in styrene-divinylbenzene systems was cor-
related to 13C NMR line width measurements by Errede et
al. (F50)and Ford et al. (F51). Schneider et al. (F52)utilized
high-resolution, broad-line and magic angle spinning 'H NMR
techniques to study cross-linking in polystyrene. NMR re-
laxation methods were utilized by Gaschke and Poschel(F53)
to study chain dynamics in cross-linked polystyrene gels and
by Charlesby (F54) to determine the effect of radiation on
polymeric systems.
Cheng et al. (F55) assigned the 13C NMR spectra of
ethylene-propylene copolymers in terms of sequence place-
ments, tacticity, and propylene inversion. Doi et al. (F56)

studied the mechanism of chain propagation in “living” po-
lypropylene synthesis by determining the structure of end
groups by NMR. Jayasuriya et al. (F57) used 13C and l9F
NMR spectroscopy to characterize the surface end groups in
polystyrene latexes. Marshall (F58) and Lander determined
the structure of alkyd paint binders using 13C NMR spec-
troscopy.
The sequence distribution of acrylamide copolymers was
studied by 13CNMR spectroscopy by Candau et al. (F59) and
Halverson et al. (F60). Polyacrylonitrile was characterized
in terms of tacticity by Kamide et al. (F61) and with regard
to the structures which cause color by Pai Verneker and Shaha
(F62).
The distribution of substituents in cellulose acetate poly-
mers was determined by Miyamoto et al. (F63)and Sei et al.
(F64) using solution-state 13CNMR spectroscopy. Solution-
and solid-state 13CNMR techniques were utilized in combi-
nation to characterize this polymer
- - by- Doyle
- et al. (F65) and
Hjertberg et al. (F66).
Cais et al. (F67) used NMR spectroscopy to characterize
the seauence distribution of vinvlidene halide and vinyl halide
copolimers. The microstructire of ethylene-vinyl chloride
copolymers was characterized by Schilling et al. (F68).
Levy and Wang (F69) studied the relationship between
poly(n-butyl methacrylate) side chain dynamics in solution
and the solvent solubility parameter. Borchardt (F70)utilized
the chemical shift values of the olefinic carbons of vinyl
monomers to calculate Alfrey-Price Q and e values. These
values were used to calculate the sequence distribution for
54 different co olymerizations. Simon et al. (F71) used
high-resolution k NMR line width measurements to follow
the extent of network formation during the polymerization
of difunctional acrylate and methacrylate monomers.
Blackband and Mansfield (F72) used NMR imaging to in-
vestigate the diffusion of water into Nylon 6.6 a t 100 “C.
The tacticity of several polymeric systems was investigated
by using 2D NMR techniques. Bruch et al. assigned the ‘H
NMR spectrum of poly(prop lene oxide) (F73) and of poly-
(vinyl butyral) (F74). Cais andYI<omentani(F75) characterized
poly(viny1idene fluoride) using two-dimensional&correlated
?FNMR spectroscopy. Chang et al. (F76)used heteronuclear
correlated 2-D NMR to assign the spectra poly(viny1amine).
The tacticity assignments of other polymers included poly-
(vinyl chloride) (F77,F78), polypropylene (F79),poly(methy1
methacrylate) (F80), and bis[N,N-di(2,3-epoxypropyl)-4-
aminophenyllmethane with its curing agent, bis(4-amino-
phenyl) sulfone (F81).Heffner et al. (F82) used nuclear
Overhauser correlated 2-D ‘H NMR to probe through-space
dipole-dipole interactions in styrene-methyl methacrylate
copolymers in order to rationalize the unusual chemical shifts
observed.
Bodenhausen (F83) discussed the use of 2-D NMR tech-
niques to assign the complex spin systems which often result
from macromolecules. Macura et al. presented modified
FOCSY (F84) and heteronuclear correlation 2-D NMR (F85)
pulse sequences which enhance the resolution and sensitivity
of these experiments when applied to macromolecules.
Harbison and Spiess (F86) described a 2-D magic angle
spinning NMR experiment which was utilized to determine
the orientation of the chemical shielding tensor and the degree
of order in solid polymeric systems. Kentgens et al. (F87)also
used 2-D NMR in combination with MAS to investigate very
slow molecular motions in crystalline poly(oxymethy1ene).
INFRARED AND RAMAN SPECTROSCOPY
Several reviews were published on the theory and practice
used in polymer characterization utilizing infrared spectros-
,copy (IR)or Fourier transform infrared spectroscopy (FT-IR).
Koenig ( G I ) reviewed the recent developments in FT-IR
sampling techniques such as diffuse reflectance and photoa-
coustic spectroscopy which provide information on solid
polymers. Golden (G2)reviewed FT-IR reflection-absorption
spectrmopy which allows IR spectra to be recorded of as little
as a monolayer deposited on a reflective metal surface in
favorable circumstances by using simple fixed-polarizer grazing
incidence techniques. Krishnan (G3) reviewed the various
samplings accessories and sample handling techniques in
FT-IR including attenuated total reflectance (ATR), diffuse
reflectance, and photoacoustic spectroscopy. Ward (G4) re-
viewed the type of information that can be obtained con-
ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
ANALYSIS OF SYNTHETIC POLYMERS
cerning orientation in polymers by utilizing IR, Raman, and
NMR. Included were select samples which illustrated key
problems in the area of polymer physics. Graham et al. (G5)
reviewed the theory, cell design, and applications of FT-IR
photoacoustic spectroscopy.
A review of computer-assisted IR spectrometry in the
analysis of polymers and plastics was reported (G9). Tomp-
kins (G24) reviewed the techniques used to study the inter-
action of thin polymer films on metal surfaces. These tech-
niques included IR, X P S , ellipsometry, and the quartz crystal
oscillator microbalance. Quantitative analyses of polymers
using FT-IR were also reviewed (G33). Craver (G110) re-
viewed the literature on data banks and computer retrieval
in research and analysis of coatings and plastics using IR,
b a n , NMR, mass spectrometry, electronic absorption, and
emission spectroscopy. Stark et al. (G280) has reviewed the
literature on the application of near-infrared (NIR) for the
quantitative and qualitative analysis.
e
Ahlstrom (G30) reviewed the literature on yrolysis-GC,
pyrolysis-MS, and pyrolysis-FT-IR. Freed ( 31) reviewed
the references on the pyrolysis devices and on-line detectors
used in the study of polymers. Rao (G21) reviewed the
spectroscopic techniques used in studying the molecular
motion in plastic crystals as well as computer simulation used
to study the motion. These techniques included IR, Raman,
NMR, neutron scattering, and electron spin resonance (ESR).
A review of the methods used in the determination of hydroxyl
groups in polymers with special emphasis on IR and NMR
technique8 was completed (G12).
Siesler (G35) reviewed the relevant instrumental and the-
oretical background of polymer deformation and relaxation
studies by s i m u l m u s FT-IR and mechanical measurements.
Coleman and Painter (G36) reviewed the phase behavior and
thermodynamics of polymer mixtures and the application of
FT-IR for structural studies of multicomponent polymer
blends. Rabolt (G28)reviewed the far-IR studies of the crystal
structure and conformation of synthetic homopolymers, po-
lypeptides, proteins, and polynucleotides.
Sung and Hobbs (G47) reviewed the developments of ATR
dichroism/FT-IR techniques for structural characterization
of polymer surfaces. Mathias (G71) reviewed the FT-IR and
FT-NMR techniques for coatings analysis. The same author
(G123)also reviewed the literature references concerning the
analysis of polymeric coatings utilizing FT-IR and FT-NMR.
Ovaska (G158) reviewed the literature for the application of
the stretched polymer orientation method in IR spectroscopy
in the determination of the transition moment directions and
for making vibrational assignments.
Mantsch (G60) reviewed the literature covering the ap-
plication of FT-IR spectroscopy in the study of membranes
emphasizing the elucidation of the thermotropic properties
of lipids in model membranes. This technique could be used
to determine more detailed insight into phase separation and
segmental orientation and recovery mechanisms (G108).
Gilard et al. (G140) compiled a compendium of IR and I3C
NMR spectra of polymers used in the manufacturer of cos-
metics.
Resonance Raman spectroscop of conjugated macromol-
B
ecules with emphasis oh pure an doped polyacetylene was
reviewed (G29). Gerrard et al. (G205) compiled an extensive
review of Raman spectroscopy and included 397 references.
Some of these references are for polymer analysis. Maddam
(G206) reviewed the literature pertaining to polymer char-
acterization of vinyl polymers by application of Raman
spectroscopy.
Gerrard and Maddams (G255) wrote an extensive review
of polymer characterization by use of Raman spectroscopy.
This review included 251 references. Takahashi (G267) re-
viewed the literature for using IR and Raman in the study
of organic coating subjected to outdoor exposure, seawater,
and heat, and in the characterization of interfaces between
coatings and substrates, substrates or top coatings and un-
dercoatings.
Infrared measurements of the dichroic ratio of polystyrene
and poly(viny1 methyl ether) absorption bands allowed the
determination of chain orientation for each component in
blends of uniaxially stretched films (G6). Orientation studies
of uniaxially drawn olystyrene films doped with fluorescent
molecules using IR d!chroic ratios of absorption bands showed
that the fluorescent molecules oriented preferentially per-
* 127R
ANALYSIS OF SYNTHETIC POLYMERS
pendicular to the draw direction (G7). Monnerie (G42)utilized
IR dichroism, neutron scattering, and fluorescence polarization
for the determination of molecular viscoelasticity of bulk
polymers.
Krishnan (G48) demonstrated that FT-IR spectra of
polymer samples as small as 10 pm square can be obtained
by using an all-reflecting accessory. High-quality dichroic
spectra were obtained from a single polyester fiber 15 pm in
diameter. Lee and Wool (G81) utilized the IR dichroism
technique in the study of orientation relaxation of strained
monodisperse atactic polystyrene. Excellent agreement be-
tween Hermans orientation time was observed for four samples
with molecular weights ranging between 170000 and 600 000
and at band frequencies 906, 1028, and 2850 cm-'.
Endo et al. (G136)used IR dichroism studies to determine
that polyethylene dispersed in molten polycarbonate (Lexan)
exhibited phase growth that is inhibited by addition of hy-
drogenated triblock SBR due to a decrease in the interfacial
tension between the two polymers. The addition of poly-
carbonate to polyethylene decreased the orientation of poly-
ethylene developed in film extrusion when determined at
constant stress. Sartirana and co-workers (G167) obtained
the order parameters by measurin the dichroic ratio by PO-
K
larized IR spectrometry at 860 cm- . This band was assigned
to a CH out-of-plane bending vibration of the poly(p-benz-
amide) aromatic nucleus with a transition moment perpen-
dicular to the ring and forming an 85" angle with the chain
axis.
Pastor et al. (G183) measured the IR dichroic ratios of
drawn poly(truns-1-odenylene)for five absorption bands (722,
968,1070,1362,and 1468 cm-'), and these data were compared
with birefrin ence results. The value of 44" for the angle
between the &pole moment vector of the 1070-~m-~ band and
the chain axis was obtained. Tassin et al. (G211) used IR
dichroism to measure the orientation of the different se-
quences of isotopically labeled block copolymers. The ori-
entation was determined from dichroic ratios of two bands
of deuteriated polystyrene and the orientation in block co-
polymers of the central part of the chain compared to that
of the ends. The relaxation of the ends was more rapid than
that of the center, which exhibited a plateau.
Radziszewski and Michl (G214)utilized FT-IR to study the
IR linear dichroism of solid structure of several dozen sym-
metrical organic molecules of low polarity in stretched poly-
ethylene and stretched perdeuteriated polyethylene. Amram
et al. (G228)used FT-IR to study the dichroism of molecular
orientation in synthetic high cis-1,4-polyisoprene and in
natural rubber. The vibrational modes at 1663,1376,and 837
cm-' were used, and the orientation function (F)of the net-
work was determined without any a priori choice of the local
chain axis. Different F values were derived from the crys-
talline and amorphous phases of natural rubber. These results
are in agreement with conformational energy calculations
performed previously.
Ohta and Iwamoto (G70) investigated the lower limit of
coated polymer film surface thickness measurable using
ATR/IR. Subramanian and co-workers (G95)developed an
ATR IR technique for the determination of starch in poly-
i
(viny alcohol) with an error of 4~0.4%by measuring the ab-
sorbance for starch at 1095 cm-' and the absorbance for
poly(viny1 alcohol) at 1000 cm-'. Bonafini and McCarthy
(G101) utilized ATR/FT-IR, ESCA, and gravimetric analysis
to study ethylene-vinyl alcohol copolymers exposed to acid
chlorides or isocyanates. In general, the reactions were found
to be nonsurface selective. Neugebauer et al. (G114) employed
ATR/IR in the in situ analysis of poly(thiophene), poly(bi-
thiophene), and poly(3-methylthiophene).
Castillo et al. (G37) used ATR/FT-IR to study the surface
of biomedical polymers. Lapkowski (G52) showed that
ring-opening photooxidation of the cyclic acetal ring during
photopolymerization of vinyldioxanes resulted in formation
of ester groups using ATR/IR spectroscopy. Zajicek et al.
(G154) characterized the surface of kaolin-filled poly(ethy1ene
terephthalate) using the ATR/IR technique.
Gi (G248)used diffuse reflectance FT-IR to study molecular
orientation on the surface of Nylon, glass fibers, and needlelike
organic crystals. Chatzi et al. (G253) utilized diffuse reflec-
tance FT-IR to study water hydrogen bonded to Kevlar-49
fibers. IR bands at 3640 and 3560 cm-l were assigned to
absorbed water that is weakly hydrogen bonded to amide
128R ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
groups in the polymers. A broad absorption near 3450 cm-'
was attributed to liquidlike water clustered in microvoids and
other sites inside the fibers.
Yang et al. (G264) evaluated three types of diffuse reflec-
tance IR accessories. In all three accessories the specular as
well as the diffuse reflectance components had similar re-
flection and polarization characteristics. The specular com-
ponent is primarily sample-dependent rather than accesso-
ry-dependent. Diffuse reflectance IR can be used in polymer
d
analysis. Nguyen and Byrd (G274)used reflection absorption
FT-IR in the study of amine-cross-linked E P N 1001 or
polybutadiene coatings on mild steel after exposure to 80%
relative humidity environment at 40 "C. Lee and co-workers
(G275) utilized diffuse reflectance IR Fourier transform
(DRIFT) spectroscopy in the study of poly(vinylpheno1)
mixtures with poly(2-vinylpyridine).
Gurnagul et al. (G276) utilized photoacoustic/FT-IR
(PAS/FT-IR) to record spectra of bleached Kraft paper
prepared from a single sample of pulp at various degrees of
beating. Band intensity changes were observed for surface
area difference resulting from beating the pulp to different
levels and from exposing the samples to a moist atmosphere.
Landreth and Stupp (G278) employed FT-IR in a reflective
mode in an electric field to study the dynamics of molecular
structure in a liquid crystal copolymer melt. Measurements
showed that the carbonyl groups orient immediately upon
application of relatively low electric field.
Teramae and Tanaka (G40) showed that there is consid-
erable distortion of the spectrum of polymers from heat
generated at the rear surface of the film using the FT-IR
photoacoustic spectroscopy technique. Careful positioning
of a polymer film in the PA cell is required to obtain a re-
sonable spectrum. Duerst (G43) used a chamber to acous-
tically isolate the detector in IR photoacoustic spectroscopy,
and the signal-to-noise ratio is increased by a factor of 4 for
polypropylene. Davidson and Fraser (G49)demonstrated that
textile samples can be analyzed with the minimum of prep-
aration using FT-IR photoacoustic spectroscopy and that
binary and ternary mixtures can be analyzed using spectral
subtraction techniques.
Yang and co-workers (G69) utilized FT-IR photoacoustic
spectroscopy to study the distribution of polymer additives
in the surface layer of polyurethane and polyacrylate-sized
cotton yarns and finished treated glass fiber and polyester
fiber. Teramae and Tanaka (G117) utilized PAS/FT-IR to
study the subsurface layer of bilayered films such as poly-
(3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy1ate)
on polypropylene or on poly(ethy1ene terephthalate).
Yang and Fateley (G279) studied the effect of particle size
on PAS/FT-IR spectra. The peak intensities increased with
a decrease in particle size diameter, and the peak intensity
ratios were not constant for particles of different diameters.
Particle diameters smaller than the thermal diffusion length
for a specific peak showed a more dramatic increase in peak
intensity. The PAS peak shape deteriorated with an increase
in particle diameter. The effect of optical velocity of the
interferometer on PAS peak intensities is also reported.
The conformation, orientation, and crystallization of
spin-oriented and drawn filaments of poly(ethy1ene tere-
phthalate) were determined by using Raman spectroscopy
(G8). MacKerron (GI1) applied IR in the study of oriented
polyamide and deuteriated polyamide films. The potential
of IR for the determination of a large amount of structural
and orientation for plastic films and the limitations and
sources of error have been reported (G34).
Siesler (G44)studied the transient structural change in high
density polyethylene during uniaxial elongation by simulta-
neous mechanical and FT-IR measurements at ambient and
elevated temperatures. Changes in the microstructure were
correlated with macroscopic mechanical properties. Lasch and
co-workers (G46) showed that coupling of time-resolved and
polarization modulation IR spectroscopy provides a selective
and sensitive method for the analysis of small conformational
and orientation changes of individual components in multi-
phase polymer systems. Lee and Wool (G155) studied the
orientation relaxation of strained monodisperse attactic
polystyrene using the IR dichroism method. Wool and co-
workers (G229) simultaneously recorded the IR and Raman
spectra of stressed polyethylene film during uniaxial tension
at room temperature. The results were obtained in terms of

experimentaland theoretical calculations of the frequency shift
,and CH2 bending
coefficients for C-C stretching, CH2roc
k"ff
modes, and calculations of Young's mo ulus and fracture
stress.
Raman studies of poly(3,3-dimethyloxetane)were used to
study the effect of temperature and times of crystallization
on the structural monoclinic and orthorhombic modifications
(G16). Bulkin and co-workers (G23) studied the crystallization
kinetics of poly(ethy1ene terephthalate) using rapid scanning
Raman spectroscopy and showed that there is a four- hase
crystallization process in the solid phase. Louden (G202rused
Raman spectroscopy to study a series of poly(ary1ether ke-
tone) films of differing crystallinity. Correlations were made
between relative intensity changes in the spectra and crys-
tallinity as measured by multiple internal reflection spec-
troscopy.
Siesler (G79) simultaneouslymeasured the FT-IRspectrum
and the stress-train data to monitor the onset, progress, and
decay of strain-induced crystallization during cyclic loading-
unloading of sulfur cross-linked natural rubber. He also
studied the strain-induced crystallization of poly(chlor0prene).
IR plots showed that the average orientation angles of polymer
chains in crystalline and amorphous phases of poly(ch1o-
roprene) are 39' and 49,respectively (G80).
Point and co-workers (G220) used FT-IR to demonstrate
or confirm the existence of crystalline intercolates with
poly(oxyethy1ene)and p-dichlorobenzene,p-dibromobenzene,
p-chloroflurobenzene, or p-chloroiodobenzene, p-iodofluro-
benzene, or p-bromolotuene. The orientations of the benzene
derivative with respect to the axes of the polymer molecules
were determined from the dichroic ratio of absorption band
of both the components of the complex. Nguyen and Ishida
(G243) used FT-IR to study the crystallization behavior of
poly(ary1 ether ether ketone) (PEEK). The formation of
predominantly amorphous PEEK (quenched polymer) via
annealing followed two distinct mechanisms. One was a
low-energy relaxation process at 50-140 "C involving the
partial rotation of the ether linkage. The other process was
a crystallization above the glass transition (T,) with its onset
characterized by the rotation of the benzophenone linkages
near T,. Kishore and Pandey (G221) reviewed the literature
on characterizing the crystallinity, microstructure cycliza-
tion-isomerization, vulcanization, oxidation, and chlorination
of natural elastomers using IR and NMR.
Neag and Holsworth (G164)used IR, DSC, SEM, dynamical
analysis to determine that a cross-linking problem was due
to improper bake in production rather than a coating pre
aration and formulation problem. Gedde (GI 72) used IR, C r-
NMR, and gel-permeation chromatography to determine the
molecular structure of cross-linked polyethylene. Sanjana
(C187)employed IR, DSC, microdielectrometry,and dynamic
mechanical analysis in the study of mechanisms involved in
cross-linking of a aromatic epoxy resin by benzyldimethyl-
amine or dicyandiamide. Coates (G213) used FT-IR on-line
to monitor the state of cross-linking advancement for lami-
nates.
Pyrolysis-gas chromatography/FT-IR (PY-GC/FT-IR) has
an advantage over pyrolysis-field ionization mass spectrometry
(PY-FIMS) in the analysis of acrylic acid resins in that the
chemical natures of the pyrolysis products are determined.
However, the combination of both sets of data enables a more
thorough analysis to be performed on the pyrolysis products
(G19). Morterra and Low (G98)utilized the pyrolysis/IR
technique in the study of the thermal degradation of phe-
nol-formaldehyde resin. The pyrolysis was carried out in a
vacuum and in a nitrogen atmosphere, and no differences were
noted in the products formed during thermal decomposition
under either condition. Thermal branching and cross-linking
occurred near 350° with the formation of diphenyl ether
structures. The polymer network was found to remain es-
sentially intact until 500°, and the polymer drastically de-
composes in the 500-560O range.
Burke and co-workers (G120)compared the results obtained
from pyrolysis-MS, pyrolysis-GC, and IR for the analysis of
paint resins, and he concludes that it is advantageous to em-
ploy more than one of these techniques in the identification
of these paints in forensic problems. Gedeon and Nguyen
(GI%) utilizing pyrolysis/IR combined with a computer which
was able to calculate the heights and/or areas of the analyte
bands determined the compositions of natural rubber, buta-
ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
ANALYSIS OF SYNTHETIC POLYMERS
diene rubber, blends, and SBR blends with natural rubber,
and butadiene rubber.
IR and NMR were utilized to determine the products
formed in the thermal degradation of polyacrylonitrile (G26).
Gallaher et al. ((255) studied the IR spectrum of poly-
fumaronitrile and concludes that an IR band a t 2190 cm-' is
attributed to the presence of a p-aminonitrile functionality.
This is of interest since a similar IR band was noted in de-
graded polyacrylonitrile. Severini et al. (G227) utilized FT-IR
to study the degradation of stabilized low density polyethylene
film. This study showed that degradation started in the first
2400 h of exposure, and oxidation occurs on both sides of the
film at the same rate. Rek et al. (G241) utilized IR, NMR,
and gel permeation chromatography to study the degradation
by UV of polyurethane based on MDI and poly(ethy1ene
adipate) or poly(ethylenebuty1ene adipate).
Varlashkin and Low (G215) used FT-IR photothermal
beam-deflection spectroscopy (FT-IR/PBDS) to make spectral
depth-profiling measurements of synthetic bilayer samples
of polyethylene/nitrocellulose, a commercial plastic having
surface printing, and a single human hair. Significant sig-
h
nal noise improvements seem to be needed for utilizing this
tec nique. Fuoco and Shafer (G281) developed a capillary
GC/FT-IR microspectrometry subamibent temperature
technique where spectral identification is possible for low
nanogram to subnanogram samples for weakly to strongly
absorbing compounds. This technique could be useful in the
identification of polymer additives. Graf and co-workers
(G159) obtained polarization modulation IR ellipometeric
spectra utilizing an FT-IR spectrometer with the use of two
linear polarizen and a potoelastic modulator. Samples studied
consisted of thin films of poly(viny1 acetate) and poly(methy1
methacrylate) on Au substrates. The thickness and optical
constants of the films were calculated from the ellipsometric
measurement and compared with optical constant spectra.
Tasumi (G225) used a force field developed by Takeuchi
which was claimed to be applicable in the normal coordinate
analyses of short and long polymers in the normal coordinate
analyses of 19,19',20,20'-tetranor-@-carotene. The results
predicted v1 and us frequencies significantly lower than those
of the observed IR data. Takeuchi and Harada (G226)showed
that these calculated frequencies reported by Tasumi are no
lower than 21 cm-' from the observed frequencies. Ishino and
Ishida (G254) utilized FT-IR surface electromagnetic wave
spectroscopy in the Otto configuration to study a thin film
of poly(viny1acetate) on a copper substrate. Eng and Ishida
((399) utilized the R-A/FT-IR technique to determine the
formation of copper oxide in copper surfaces coated with
poly(vinylimidazo1es). Below 250' no major polymer degra-
dation was observed. In addition, the degraded polymer film
suppressed the oxidation of the copper surface even at 400'.
Rabek et al. (G216) developed a pressure cell for the study
of charge-transfer contact complexes between oxygen and
polymers and for high-pressure photooxidation of polymers.
This device allowed IR, UV, and visible spectra to be recorded.
Wu and co-workers ((2219) used IR spectroscopy to analyze
the microstructures of liquid-crystalline polymers in various
mesophases. Snyder and co-workers (G270) found that the
IR band intensities of crystalline n-alkanes and polyethylene
decreased nonlinearly with increasing temperature. For all
modes except the C-H stretches, the decrease was large and
far exceeds that expected from density and refractive index
effects.
The application of micro IR and micro Raman spectroscopy
for the identification of polymers was reported (GIO). Belton
and Sullivan (G169) utilized IR and reversed-phase chroma-
tography (LC) to characterize epoxy-cresol-novolac, phe-
nol-formaldehydenovalac, and tertiary amine resin systems.
Shafer and co-workers (G263) developed an accessory for
thin-layer chromatography/FT-IR that could be used in the
identification of polymer additives.
Atalla et al. (G204) performed Raman microprobe studies
of the fiber transformations during press-drying of pulp fibers
from eucalyptus and oak. Eucalyptus pulp showed areas
under the knuckles of drying screens to be approximately 10%
higher in cellulose I content than those between the knuckles,
and measurements on sheets from high yield oak showed those
press-dried at 300 O F to have higher cellulose I content than
those dried at 160 OF. Chang and Krimm (G223) utilized
Raman spectroscopy to record the longitudinal accoustic mode
129R
ANALYSIS OF SYNTHETIC POLYMERS
(LAM) in CH3-(CH2)-&H2Br and Br CH2-(CH2)18-CH2Br.
These data were compared with data for n-C20H42.These
results provide experimental support for the predictions made
from normal coordinate and intensity analyses regarding the
influence on LAM bands of mass perturbrations at the ends
of paraffinic chains and in comparable linear chain polymers.
Merino et al. (G25) described a variable temperature cell
which also allowed the polymer film to be stretched. It is used
to record in situ polarized Raman spectra of polymers. Ono
(G126) applied the method of canonical transformation in
quantizing phonons around a general static solution in a
continuum version of a model for trans-polyacetylene,
Measurement of the second-order Raman process enabled
derivation of the phonon dispersion.
Snyder and Wunder ((2132) utilized Raman spectroscopy
in the determination of long-range conformational structure
and low-frequency spectra of some highly disordered chain
molecules. The disorder-longitudinal accoustic mode (D-
LAM) band, previously observed only in the case of poly-
ethylene, was the prominent feature in the Raman spectrum
in the region below 600 cm-l of a series of six chain molecules
in the liquid or amorphous state. These included 1,4-cis-
polybutadiene, poly(ethy1ene terephthalate), poly(tetra-
methylene oxide), squalene, and poly(ethy1ene oxide). The
position and width of the D-LAM band were related to
long-range conformational disorder. The width of the band
correlated in this case with chain flexibility.
Kim et al. (G271) utilized a Raman spectroscopic-me-
chanical technique to directly assess the effects of temperature
and thermal history on the stress distribution of model com-
posites. Kobayashi et al. (G272) obtained polarized Raman
spectra of moth-shaped single crystals of orthorhombic
polyoxymethylene in order to study polymorphism and mo-
lecular aggregation states in this polymer.
Raman spectroscopy was used in the elucidation of the
molecular structure of urea-formaldehyde resins (G45). Fu-
rukawa et al. (G76) utilized Raman spectroscopy to study
poly(methylpropylsi1ane) and showed that the frequency for
the LO mode is little affected by the side chains joined to the
tetrahedrally bonded Si skeletons. However, the TO mode
frequency was greatly affected by the side chain due to the
mass effect. Allen (G97) developed a laser Raman method
for determining the homogeneity of epoxy-amine coatings.
Merino and co-workers (G103)utilized Raman spectroscopy
to study the influence of temperature and times of crystal-
lization on the structural modification of poly(3,3-dimethyl-
oxetane). Monoclinic and/or orthorhombic modifications of
this polymer could be obtained from the molten state de-
pending on the crystallization temperatures. Galiotis et al.
(G146) recorded the Raman spectra of a single fiber of Kevlar
49 subjected to uniaxial stress. The strain dependences of
six vibrational mode frequencies were determined. These
bands broaden and shift to lower frequency with increasing
stress. Pastor et al. (G200) studied the Raman spectra of
semicrystalline poly(3,3-dipropyloxetane)and determined that
the crystalline/amorphous ratio is influenced in the same
manner as other members of the branched polyoxetanes series.
Merimo (G207) studied the effect of applied stress and
stretch on thermically crystallized poly(3,3-dimethyloxetane)
using Raman. The effect of these mechanical deformations
produced a transformation from the orthorhombic to mono-
clinic structure which is the most thermodynamically stable
form. Bertoluzza and co-workers (G208) utilized IR and
Raman to study soft contact lenses. Raman spectra showed
the absence of residual monomers in the finished lenses fa-
bricated from poly(2-hydroxyethyl methacrylate). Raman
spectra of a lens recorded before implantation in a baboon
eye and the spectra recorded 36 months after implantation
did not reveal any spectral differences.
Experimental proof was presented for the relationship
between film thickness of the probed surface layer and ab-
sorbance using the FT-IR/ATR technique (G13). The mo-
lecular weight of poly(buty1ene terephthalate) in the solid state
was determined by FT-IR using the extinction coefficients
for the absorption bands arisen from the OH and COzH end
groups (G18). Curry et al. (G32) identified polymers where
the amount available for identification was as little as 2 mg
using FT-IR.
Hindle (G118) and Mercer (G119) discussed the utilization
of IR for measuring film and coating thickness. Bartick (G125)
130R ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
demonstrated the usefulness of combining microscopy with
FT-IR in the analysis of conventionally sized polymer and
paper samples. The method required little or no sample
preparation and was particularly suitable for recording IR
spectra of razor-sliced polymer samples or clumps of fiber.
Coleman et al. (G245) used FT-IR to study the effect of
temperature on hydrogen bonding on poly(1,4-butylene-
hexamethylene carbamate). The spectral changes associated
with hydrogen bonding are discussed and compared with
previous studies on semicrystalline polyamides.
Davidson et al. (G148) characterized polymeric materials
by identifying gases evolved from heated samples by appli-
cation of dispersive IR. Skrovanek and co-workers (G149)
studied the effect of temperature upon hydrogen bonding for
Nylon 11 using IR. Kardan et al. (G151) obtained IR and
Raman spectra of hexahydroxybenzene hexahexanoate and
used the diskotic hexaheptanoate and hexaoctanoate as model
compounds for polymers. Harthcock and co-worker (G152)
demonstrated the application of transmittance and reflectance
micro/FT-IR in the analysis of polymeric materials. White
(G153) described a computer-controlled stage which can be
used to position transmittance samples for IR microanalysis.
Examples of automated operation using macro programming
are described.
Teng and Shumaker (G156)developed a new technique for
eliminating interference fringes from infrared spectra of thin
polymer films. Lalov et al. (G157) developed theory for the
IR absorption and vibrational CD (VCD) spectra of helical
polymers in the frequency range of the frequency sum for two
vibrational excitations. Kwei and co-workers (G250)extended
the enthalpy-IR frequency shift correlation for simple acids
and bases to study hydrogen bonding in polymer systems.
Arnaudov et al. (G251) utilized IR to study the polyconden-
sation of diphenyl oxide with formaldehyde and determined
that the structure of the oligomeric product and the densified
prepolymer was mainly linear.
IR was used to determine that there is an intermolecular
association between poly(viny1 chloride) and di-n-butyl
phthalate (G15). Compton (G145) used FT-IR and Fourier
self-deconvolvedIR spectra as an aid to conformational studies
of syndiotactic poly(viny1chloride). Fourier self-deconvolution
was utilized to enhance the detail present in the carbon-
chlorine stretching region of the IR spectrum for samples
covering a range of syndiotacticities. Burley and Dworkin
(G186) utilized IR and NMR in the study of ligand exchange
reactions in alkyl and estertin poly(viny1chloride) stabilizers.
Bowley et al. (G199) studied the low frequency region
Raman spectra of ten poly(viny1 chloride) gels prepared from
two polymers of different syndiotacticticy and five solvents.
The study showed that a single line occurs between 93 and
106 cm-I. The peak occurring at 83 cm-' in solid poly(viny1
chloride) is assigned to a torsional mode. With dioctyl
phthalate gels, the frequency increased with increasing sol-
vent/solute ratio and temperature. Herres (G231) utilized
ATR/FT-IR, PAS/FT-IR, and minispec NMR to determine
the plasticizer content in TiOz filled poly(viny1 chloride).
Bowmer et al. (G252)used IR to study ethylene-vinyl chloride
copolymers (obtained from partial reduction of poly(viny1
chloride)). IR bands at 665 and 610 cm-I are assigned to
isolated CHCl units.
IR was used both qualitatively and quantitatively in the
characterization of thermally polymerized bis[4-(3-ethynyl-
phenoxy)phenyl] sulfone. The polymer had predominantly
trans conjugated polyene structure (G20). Miya and co-
workers (G51) demonstrated that intermolecular hydrogen
bonding occurs between chitosan and poly(viny1alcohol) using
FT-IR. Lippert et al. (G38) reported on the studies of poly-
(N-vinylimidazole) complexes using both Raman and IR
spectroscopy. Skrovanek et al. (G56) studied the IR spectrum
of amorphous benzenedicarboxylic acid-hexamethylenedi-
amine polymer using FT-IR and found tht the strength of the
hydrogen bond decreased with an increase in temperature.
Reflection/absorptionFT-IRstudies of polybutadiene coatings
and an amine-cured epoxy coating on cold-rolled steel which
were exposed to 40 "C and 80% relative humidity for 7 months
showed that these materials decomposed under these con-
ditions (G72). Sbampato and Kawano (G73) utilized IR and
UV/Vis spectroscopy to study the affect of X-ray radiation
upon poly(viny1chloride) films. The study indicated that the
film was dehydrochlorinated forming polyenyl radicals which

subsequently reacted with oxygen to form carbonyl groups.
Nichols et al. (G100) utilized FT-IR to study bacteria,
bacteria-polymer mixtures, and microbial biofilms. Nguyen
and Ishida (G14) studied the IR spectra of poly(ary1-ether-
ether-ketone) at elevated temperatures and various times.
The polymer was shown to retain some degree of local order
at 380O. Schultz et al. (G121) developed a method to estimate
cellulose crystallinity using FT-IR and dynamic thermogra-
vimetry. Hon and Gui (G238) showed that carbonyl and
aldehyde groups were formed in photoirradiated cellulose
nitrate by application of FT-IR. Kulczycki (G137) calculated
the vibrational frequencies of crystalline bis-phenol-a poly-
carbonate. The 13 force constants for the carbonate group
were determined from normal coordinate calculations.
Chang and Hsu (G139) used IR to determine the relative
amount, location, and orientation of residual water and PO-
lyphosphoric acid molecules in poly(ppheny1enebenzobis-
thiazole) films. Walters et al. (G142) used FT-IR to study
B u O ~ C C H ~ N H CCH~)~C:CC:C(CH~)~O&NHCH~CO~BU
O~(
homopolymer as a function of temperature. Two endotherms
were observed in the thermograms which correlate with
spectroscopic changes. Weber et al. (G147) utilized IR, XPS,
and electrochemistry to study Nafion films prepared from
hexamethylphosphortriamide solutions. Bolton and Scherer
(G150) used Raman to study the types of ethanol hydrogen
bonding in cellulose acetate films.
Lang and co-workers (G198) used IR and a micro diamond
cell for the rapid identification of single fibers of cotton, wool, (G130)utilized IR to study the intermolecular interactons of
and acrylic fibers and to interpret the effeds of dying of three
Orlon acrylic fiber samples. Gordon et al. (G212) utilized
diffuse reflectance IR to follow the reaction sequences block
copolymers containing rigid-rod segments of (poly[benzo-
[ 1,2-d;4,5-d1bisimidazole-2,6-diyl)-1,4-phenylene and ran-
dom-coil segments of (poly [2,2'-(rn-phenylene-5,5'-bibenz-
imidazole)]). Lang and Katon (G249) have utilized IR and
Raman microspectroscopy in the analysis of failed circuit
boards. Ruan and Litt (G259) characterized the ladder
polymer, poly(4-(3-pyridyl)-8-methyl-2,3,6,7-quinolino) using even at 140 "C. Domke and Steinke (G282) used FT-IR in
IR and NMR. Shih et al. (G262) used both FT-IRand Raman
to study hydrolyzed maleic anhydride-1-octadecene co-
polymer. The copolymer assumed different conformations
at different degrees of ionization in aqueous solution.
The same authors (G268) also utilized IR and DSC to study
the melting behavior of poly(ary1 ether ether ketone). Ste-
venson et al. (G269)used both IR and 13C NMR to study the
carbonization of poly(acrylonitri1e) and acrylonitrile-acrylic
acid copolymer. Braise (G273) utilized IR to study the
cross-linking of oxydianiline-pyromellitic dianhydride co-
polymer. The study showed that 5-hm films were cross-linked
by heating at 230-250 "C for 5 min, while samples corss-linked
initially at 150 "C did not cure completely when heated at 150
"C.
IR was used to determine the amount of natural rubber,
butadiene rubber, and styrene-butadiene rubber in ternary
rubber blends (G17). Stadler et al. (GI75)utilized IR to study
hydrogen bonding vs. temperature for polymers formed by
reacting polybutadiene with 4-phenyl-1,2,4-triazolene-3,5-
dione. The carbonyl stretching vibrations at 1700 and 1723
cm-' could be attributed to hydrogen bonded and free urazole
groups, respectively, and with increasing temperature the
fraction of bonded groups decreases. Lu ahd Hs (G176) de-
termined the molecular compositions of various extracted
fractions from raw natural rubber such as pure rubber, soluble
rubber and protein, and gel rubber and protein by application
of IR.
Mandelkern and co-workers (G257) utilized Raman spec-
troscopy to study the low-frequency spectra of a series of
hydrogenated polybutadienes. A broad band in the vicinity
of 200 cm-' was designated as the D-LAM band. This band
reflected the region of configurational disorder. The band
intensity was a linear function of the degree of crystallinity
when account is taken of the interfacial region. Thus, only
the disordered, or liquidlike, regions contributed to the band
intensity. The frequency of D-LAM increased with an increase
in branching, indicating a decrease in the number of trans
bonds in the chain backbone.
Mirabella (G22) demonstrated the use of band-ratioing
techniques in the quantitative analysis of ethylene-vinyl
acetate copolymer and ethylene-propylene copolymer using
internal reflection spectroscopy IRS/IR. Graf (G124) et al.
ANALYTICAL CHEMISTRY, VOL. 59. NO. 12, JUNE 15, 1987
ANALYSIS OF SYNTHETIC POLYMERS
recorded reflection spectra of poly(viny1acetate) on a copper
substsrate using FT-IR equipped with two linear polarizers.
Data collected included both phase and intensity information.
By use of the principles of ellipsometry, the differential phase
retardation and differential amplitude were calculated from
these measurements. The optical constants of poly(viny1
acetate) determined by IR ellipsometry compared favorably
with reference spectra. Wintersgill et al. (G165) utilized
FT-IR, conductivity, and/or NMR to study poly(viny1acetate)
complex with alkali metal salts.
IR and melting point determinations were used to distin-
guish between polyolefins based on ethylene, propylene, or
their mixture (G39). Maddams and Woolmington (G54) re-
ported on the IR studies of linear low density polyethylenes
containing methyl, ethyl, butyl, isobutyl, and hexyl branches.
Maroncelli and co-workers (G66) studied the IR spectra of
CD2 substituted n-alkanes, and the results of this study enable
new details of the chains conformation in polymethylene
systems to be determined. Beckett et al. (G109) recorded the
IR spectra of crystalline isotactic polypropylene in its various
polymorphic forms in the region 100-500 cm-l. Labrie et al.
(G131) showed that polypropylene can be used as IR windows
below 800 cm-l under cryogenic conditions.
Spells (G127) studied the influence of matrix isotopic CH2
in CD2upon the chain conformation of solution crystallized
deuteriated polyethylene. The results implied that isotopic
fractionation is unimportant. Benedetti and eo-workers
the carboxyl groups of the side chains of diethyl maleate
functionalized high density polyethylene and C-H of poly-
(vinyl chloride). As the poly(viny1chloride) concentration
increased in these mixtures, the carbonyl stretching band of
functionalized HDPE shifted to lower frequencies and the
band becomes broader. The different frequency positions of
the carbonyl band with respect to its concentration in this
blend was attributed to interactions between the C=O group
and poly(viny1chloride) giving no complete phase separation
the quantitative determination of oxidative structures in low
density polyethylene. The amount of carboxyl,ester, ketone,
aldehyde, lactone, and a and 0unsaturated ketone structures
present were calculated from the deconvoluted carbonyl peak
area.
Snyder and eo-workers (G141) used Raman to show a D-
LAM band characteristic of long range conformational dis-
order in semicrystalline polyethylene. The frequency and
shape of this band when compared with molten polyethylene
indicated that the noncrystalline component in bulk crystalline
polyethylene was conformationally liquidlike for crystallinities
up to at least 90%. Wunder and Merajver (G143) utilized
Raman spectroscopy to study the melt anisotropy of ultra-
high-molecular-weight polyethylene. On the basis of the
spectrscopic evidence ordered regions persisted in the melt
above the calorimetrically determined melting point and that
part of the polyethylene chain was in an environment which
is similar to the orthorhombic crystal.
Afifi and Hafez (G163) assigned the IR bands at 700,
800-1000, 1370, and 1600-1700 em-' for 18 commercial
polyethylene films. Moehring and co-workers (GI 79) devel-
oped an quantitative FT-IR method of analysis for the dif-
ferent double bonds present in polyolefins. The method was
optimized by measuring the melted substances by the integral
absorbances of the olefinic bands using computer-generated
band profiles. The integral extinction coefficients of the vinyl,
trans-vinylene, and vinylidene double bonds were determined
by the analysis of model compounds. Jona et al. (G184)
calculated the IR intensities for some polymethylene chain
molecules containing conformational defects or polar heads.
Takeuchi and co-workers (G209)performed normal coordinate
calculations for the in-plane vibrations of several trans-polyene
chains from butadiene to polyacetylene to obtain a set of force
constants commonly applicable to short and long polyenes.
Hagemann and Snyder (G224) showed that the 690-cm-I IR
band observed in the solution and bulk crystallized poly-
ethylene and for similar bands observed for crystalline n-
alkanes consists of an overlapping complex of binary com-
bination bands associated with u5 and ug branches of a planar
polymethylene chain.
Heuvel and Hisman (G84) evaluated a quantitative model
for fitting an IR spectrum of poly(ethy1ene terephthalate) over
131 R
ANALYSIS OF SYNTHETIC POLYMERS
the region 720-1100 cm-'. This model fitted the experimental
IR transmission spectra of yarns measured with the electrical
vector parallel and perpendicular to the fiber axis. Each of
the trans bands near 972 and 845 cm-' resulted from two
components, a broad and a narrow one. These components
resulted from the presence of amorphous and crystalline
phases of PET. Xue (G116) employed diffuse reflectance
FT-IR to record external reflection spectra of stretched and
unstretched samples of poly(ethy1eneterephthalate) films and
fibers. Information about the molecular orientation of the
film and fiber surfaces was obtained. Yazdanian et al. (G134)
developed a quantitative IR method for poly(ethy1ene tere-
phthalate) fibers in conventional yarns. Hu and co-workers
(G133) recorded polarized IR spectra of oriented films of
polyesters prepared from bromohydroquinone and 4,4'-di-
carboxy-lJ0-diphenoxydecane in order to determine the
alignment of the polymer chains induced by shearing.
Yang and Fateley (G189)utilized PAS/FT-IR to study the
uniformity and depth of penetration of cotton yarns, poly-
(ethylene terephthalate) fibers, and poly(viny1 chloride)
composite films. Huang et al. (G236) studied the IR spectra
of poly(ethy1ene terephthalate)/polycarbonate dry mixed
blends which had been heated to 260-290 OC. Block co-
polymer formation a t the interface was found.
Adar and Noether (G144) used a Raman microprobe to
record polarized spectra of spin-oriented and drawn filaments
of poly(ethy1ene terephthalate). Various bands and their
intensities correlated with conformation of the glycol linkage,
orientation of the chains, and crystallinity. It was determined
that bands previously assigned to crystallinity actually result
from the trans conformation of the glycol group. DeBlase and
co-workers (G82) presented Raman data for poly(ethy1ene
terephthalate) and the low frequency region clearly showing
that annealing above T, increased PET crystallinity. In ad-
dition, evidence was presented that a broad Raman band
results from an oriented amorphous phase. Bulkin et al. (G83)
using Raman spectroscopy studied poly(ethy1ene tere-
phthalate) yarns, annealed a t different temperatures, and
found that three distinct events take place in the fibers:
conformational change, chain orientation, and recrystallinity.
Bower et al. (G235) utilized Raman spectroscopy to study
the molecular orientation in biaxially oriented sheets of
poly(ethy1ene terephthalate). The orientation of the chain
axis was closer to that predicted by the rubber network model.
The benzene ring planes were preferentially oriented toward
the planes of the sheets. The chain axis orientation was nearly
uniaxial and similar to that observed for uniaxially drawn
samples indicating that there is no direct connection between
the processes of chain axis orientation and preferential ori-
entation of the benzene-ring planes. Kim et al. (G256) used
Raman spectroscopy to study the conformational reorgani-
zation of poly(ethy1ene terephthalate) and poly(propy1ene
terephthalate). The asymmetry of the C=O stretching vi-
bration as a function of annealing from amorphous to crys-
talline polymer was analyzed. An apparently anomalous
behavior of C=O stretch band half width as a function of
density for poly(ethy1ene terephthalate) is due to the C=O
asymmetry. Bulkin et al. (GI74) employed Raman spec-
troscopy in the analysis of bulk and fibers of poly(ethy1ene
terephthalate), and the data provided information about
conformation, orientation, and crystallinity.
Nyquist and Schuetz (G53) attributed the increase in the
tensile strength of cured butyl acrylate/methyl meth-
acrylate/acrylic acid/2-isopropenyl-2-oxazolinecopolymer
latex to the formation of an amide-ester linkage between latex
particles. The same co-workers also reported an IR method
for the determination of 2-isopropenyl-2-oxazoline-styrene
copolymers. Christenson and co-workers (G239) utilized IR,
NMR, dynamic mechanical, and DSC to study the mor-
phology, physical, and mechanical properties of polyurethanes
based on MDI-butanediol. The phase mixing in these rubbers
decreased with increasing hard-segment (HS)length while HS
stability increased with increasing HS length. The importance
of hydrogen bonding to the stability of the HS was supported
by variable-temperature IR experiments. Usmani (G260)
utilized IR to show that unreacted isocyanate groups in po-
lyurethane coating were depleted in several hours a t 60 "C
and 95% relative humidity.
Provder et al. (G50) studied the cure reaction kinetics of
some model organic coatings based polyurethanes using FT-IR
132R ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
and thermal mechanical analysis. Carlson et al. ((287) used
both FT-IR and thermal-mechanical analysis to study the
kinetic parameters in curing of isophorone diisocyanate trimer
and polyester gel coat systems. Painter and Thomson (GI 73)
utilized IR to study urethanes containing polydiacetylenes,
and the study showed that there is a range of hydrogen bonded
states that varied systematically with temperature. Raman
and FT-IR were used in the study of the chemical composition,
structure, and state of the cure of epoxy resin systems (G27).
Thuillier et al. (G242) used IR and NMR to study the mi-
crowave curing effects on poly(bispheno1 A diglycidyl ether).
Starkweather et al. (G57) treated the IR spectral data for
crystalline and amorphous poly(tetrafluoroethy1ene) by two-
component factor analysis, and found that bands in the region
700-800 cm-' and 1400-1800 cm-l were peculiar to the
amorphous spectrum. The vibrational assignment for poly-
(vinylidene fluoride) was revised based upon polarized Raman
data and normal coordinate analyses (G74),and IR was used
to study the degree of phase transformation of poly(viny1idene
fluoride) in the presence of electric fields and a t various
temperatures (G75).
Lu and Hsu (G128) utilized FT-IR to study the crystalli-
zation of poly(viny1idene fluoride) from the melt in the
presence of a weak electric field. The electric field caused
chain conformations which exists mainly in trans sequences
associated with either the p or y phases. With no electric field,
the a phase was obtained. Siesler ((2129) measured simul-
taneously FT-IR spectra of poly(viny1idene fluoride) and
tensile stress a t variable temperatures. It was shown that in
the temperature range 348-423 K the drawing process is in-
homogeneous and occurs via formation of a neck. The I1 (a)-I
((3) phase transformation was restricted to temperatures below
423 K, and its onset is generally related to the formation of
the neck.
Hussla and Philpott (GI 77) studied the vibrational prop-
erties of liquid perfluorinated polyethers on Au surfaces by
polarization modulated FT-IR reflection-absorption spec-
troscopy under ultrahigh vacuum down to the glass transition
at approximately 180 K. Gerbier and co-workers (G185)
utilized ATR/IR to study sputter cleaning of bulk poly(tet-
rafluoroethylene). The sputtering produced a fine powder by
breaking long chains of PTFE which gave roughly the same
spectra as the bulk sample. Lauchlan and Rabol (G197) used
oriented polarized Raman scattering measurements to in-
vestigate the anisotropic scattering properties of a uniaxically
stretched filament of planar zigzag poly(viny1idene fluoride).
Comparison of these new vibrational assignments with those
calculated from existing valence force fields gave reasonable
agreement but suggests that the force field could be improved
by refinement incorporating these latest frequency assign-
ments.
Pacansky and co-workers (C230) utilized IR to study the
effect of electron beam irradiation upon poly(perfluoro-
propylene oxide)9. The study showed that acid fluoride groups
are formed which hdyrolyze to form carboxylic acid and HF.
Latour and Moreira (G232) studied the IR spectra of poly-
(vinylidene fluoride) and copolymers of vinylidene fluoride-
trifluoroethylene in the region 10-55 cm-l. The effect of the
crystalline phase was found to be small. Muralidhar and Pillai
(6233) studied the IR spectra of poly(viny1idene fluoride)
barium titanate composites. The concentration of the a form
was reduced and the concentration of the y form was increased
for poly(viny1idene fluoride) with addition of barium titanate.
Afanas'eva et al. (G234) utilized transmission and reflection
IR to determine refractive indexes in the films of poly(tet-
rafluoroethylene) and hexafluoropropylene-tetralfuoroe-
thylene copolymer over the range 800-2200 cm-'.
Latour (G41) characterized a chlorotrifluoroethylene-vi-
nylidene fluoride copolymer using IR and X-ray. Ahmed et
al. ((2247) confirmed the structures of bis(4-fluorophenyl)
sulfone-4,4-dimercaptodiphenylsulfide copolymer and bis-
(4-fluorophenyl) sulfone-4,4-dibenzenethiol copolymer by
application of IR. Urban and Koenig (G277) employed
i
PAS FT-IR to study films of poly(viny1idene fluoride) and
poly ethylene terephthalate). Poly(viny1idene fluoride) films
over poly(ethy1ene terephthalate) changed the thermal dif-
fusion length such that the sample of PVF2 on PET becomes
optically transparent and thermally thick. By changing the
mirror velocity of the Michelson interferometer, it is possible
to obtain spectra at various sample depths. The intensity of

the carbonyl band of the lower PET film decreased by a factor
of 1y2,which agreed with theoretical predictions for thermdy
thic and optically transparent samples.
Kostov and co-workers (G58)used IR to study the effect
of oxidation on high-impact polystyrene and develop a method
to determine the efficiency of the added antioxidants. Tan-
nenbaum et al. (G161) utilized FT-IRto show that sulfonated
polystyrene in blends with polyurethane forms salts with the
tertiary nitrogen in the hard segment of the polyurethane
component. Fitzgerald and Weiss (G188) utilized IR to study
the effect of water and organic solvents on the metal salts of
sulfonated polystyrene. The SO3 anion frequencies were
lowered by the addition of solvents. Hamaide et al. (G222)
utilized FT-IR to characterize neutral phosphonato-, phos-
phinato-, and carboxybetaine moieties linked to styrene-vi-
nylpyridine copolymer and 4-dimethylaminomethylstyrene-
styrene copolymers.
Rao and co-workers (G59) studied blends of poly(ethy1ene
oxide) and poly(methy1methacrylate) using IR spectroscopic
techniques and showed that poly(ethy1ene oxide) had a
preferentially planar zigzag structure in the blends and that
blending is preferred with isotactic poly(methy1 methacrylate)
compared to the syndiotactic form. Grainger et al. (G67) used
IR to confirm the structures of polyethylene oxide-polystyrene
multiblock copolymers. Dwivedi and Jayasuriya (G181)
utilized FT-IR and a cylindrical internal reflection cell to study
poly(ethy1ene oxide) and determined that three complexes
1!
41, 2:1, and 1:l water ethylene oxide exist in aqueous solution.
Matsuura and Fuku ara (G240) performed detailed normal
coordinate analyses on a large number of models of poly(ox-
yethylene). The systematic treatment provided well-defined
correlations between conformation and vibrational spectra.
The modes in the region 800-1050 cm-' associated with C-0
and C-C stretching and CH2 rocking modes are highly de-
pendent on the conformation of the polymer chain.
Philippova et al. (G102) studied the dilute CCl, solution-
phase IR spectra of poly(ethy1ene glycol) with molecular
weights ranging from 300 to 6000. The dependence of the
equilibrium constants of the polymer molecular weight was
determined for different forms of intramolecular and inter-
molecular hydrogen bonds. Teeters and Frech (G193) used
Raman to study the temperature dependence of the spectra
of poly(propy1ene oxide) and poly(propy1ene oxide) salt com-
plexes. The 239-cm-I band assigned to a torsional or bending
mode of the polymer backbone is the most sensitivie to the
presence of NaSCN. Frequency shifts in the anion stretching
vibrations suggested the presence of ion pairs. Bartlett and
Cooney (G244) utilized Raman to tudy poly(oxyethy1ene)
chain confirmations in nonionic surfactants. The study of
palkylphenoylpoly(oxyethy1ene) provides evidence for two
dominant confirmations: a helical or coil conformation,
common to all poly(oxyethene) materials, and a zigzag con-
formation associated with the presence of the aromatic ring.
Doskocilova and co-workers (G78) utilized vibrational and
NMR techniques to study dimethyl 2,2,4-trimethylglutarate
and dimethyl 2-methoxymethyl-2,4-dimethylglutarateas
model compounds for spectra-structure analysis of poly-
(methyl methacrylate). Joss and Wool (G85) used IR to study
the vitrification and physical aging in poly(methy1 meth-
acrylate) as a function of annealing and thermal cycling at
temperatures between ambient and 150". Koennecke (G86)
utilized FT-IR to determine that there is intermolecular in-
teraction between carbonyl groups in poly(methy1 meth-
acrylate) and the oxygen atoms in polyoxymethylenes.
Schlotter and Rabolt (G122) employed a thermostated
grazing incidence reflection (GIR) IR cell to record spectra
of thin monolayer films of poly(methy1 methacrylate) as a
function of temperature. The study revealed the onset of
molecular motion known to occur at the glass temperature
(approximately100 "C for poly(methy1methacrylate)). Grieve
and Cabines (G135) recommended that IR and other instru-
mental techniques be utilized in forensic investigation of fibers
fabricated from modified acrylic polymers. Jin and Meyer
(G160) employed FT-IR to follow the kinetics of formation
of cross-linked poly(methy1methacrylate)-polyurethane in-
terpenetrating polymer networks. Mumby et al. (G166)
studied the molecular orientation of Langmuir-Blodgett (L-B)
monolayers of poly(octadecy1methacrylate) and poly(octadecy1
acrylate) by application of IR. The carbonyl groups were
oriented approximately perpendicular to the substrate surface
ANALYTICAL CHEMISTRY, VOL. 59,NO. 12,JUNE 15, 1987
ANALYSIS OF SYNTHETIC POLYMERS
independently of polymer type and of disposition surface
pressure within the range investigated. Pennacchis et al.
(G168) studied the compatibility of four para-substituted
phenol-formaldehyde resin blends with poly(methy1 meth-
acrylate) (PMMA). The hydrogen bonding between the
phenolic resins and PMMA was manifested by a shift of the
carbonyl stretching frequency by -25 cm-'.
Dybal et al. (G180) used IR and Raman to measure the
carbonyl stretching vibrations of poly(methy1methacrylate)
of various stereoregularity in solution and in the solid state.
For ordered structures of syndiotactic PMMA, the transition
dipole coupling of ester groups in ordered sequences leads to
a splitting of the C=O stretching vibration into three com-
ponents with frequencies equal in the solid state and in so-
lution and of different activity in Raman and IR spectra.,
Mariam et al. (G192) used FT-IR to study the compatibility
in comblike azo liquid-crystal polyacrylates. Luoma and
Rowland (G237) utilized GC/IR and LC/IR to determine
compositional changes associated with aging in acrylic
structural adhesives.
Masetti et al. (G266) obtained polarized Raman spectra of
highly oriented trans-polyacetylene. Novel data on the po-
larization properties of the two resonantly enhanced Raman
bands of trans-(CH) were obtained by using the 609.6-nm line
of a dye laser. Changes of the observed band shapes and of
the corrected intensities with the scattering configuration are
consistent with conjugation lengths. For short conjugated
polymer segments, the electronic transition moment was not
apparently strictly aligned along the chain direction.
Polyacetylenewas studied by several scientists using either
IR or Raman spectroscopy. Mulazzi (G61) proposed a theo-
retical model as an aid in interpreting the properties of the
polarized resonant Raman spectra recorded for stretched
samples of trans-polyacetylene. Dorsinville et al. (G62)studied
the infrared photoinduced absorption in trans-polyacetylene
in the liquid phase in the region 2000-6000 cm-I and dem-
onstrated that it is capable of supporting charged solutions
even in solution. Eckhardt et al. (G63) recorded the anti-
Stokes Raman scattering of trans-polyacetylene and reported
that the line shapes are quite consistent with a disorder model
in which the variation is attributed to a disorder-induced
distribution of conjugation lengths. Bozovic and co-workers
(G64) showed by application of IR that Bates-Baker type
copolymers contain predominantly planar cis-polyacetylene
rather than 3i helical structure. Terlemezyan et al. (G6.5)used
IR to determine that the BF, anion in aqueous solution did
not prevent the irreverislbe oxidative attack of dissolved ox-
ygen on trans-polyacetylene.
Lefrant and co-workers ((288) reviewed the vibrational
studies of doped polyacetylene conductors. Resonant Raman
was used to study disorder in polyacetylene and in studying
the effect of hydrostatic pressure on polyacetylene (G89492).
Zerbi et al. (G104) reviewed the structural analysis of doped
and undoped trans-polyacetylene based upon vibrational
transitions with the assumption of mechanical and dynamic
harmonicity. Masetti et al. (G105) recorded the resonance
Raman spectrum of highly oriented trans-polyacetylene, and
the polarization properties of the Raman active phonons were
determined for the first time. Changes in the Raman band
shapes observed upon changing the scattering configuration
implied that the dispersion of the Raman bands originated
from conjugation length distribution. Bloor (G106) reviewed
the Raman data of conjugated polymers including polydi-
acetylenes and disordered polyacetylenes. Iwahana and
K m a n y (G107)studied the effect of bond-length distribution
on Raman scattering of trans-polyacetylene.
Kuzmany and Knoll (G194)measured the resonance Raman
cross section and polarization of light scattered from trans-
polyacetylene. For the main vibrational line at 1460 cm-', a
resonance enchantment of 2 orders of magnitude was observed
for excitation with 1.7 eV. Yacoby and Roth (G195) studied
the resonance Raman scattering of polyacetylene doped with
Br2,12,and AsF6 and compensated by NH,. Burzynski et al.
(G196) used lasar Raman optical-wave-guidestudy of mono-
and multilayer Lagmuir-Blodgett films of poly(diacety1ene)
containing carboxylic acid groups. The study of the Raman
spectral change as a function of the blue-to-red polymer-form
conversion revealed that the phase transformation involves
a two-phase heterogeneous process. Lyall and co-workers
((2201)measure the resonance Raman excitation profile of two
133R
ANALYSIS OF SYNTHETIC POLYMERS
vibrational modes of Langmuir-Blodgett films of a polydi-
acetylene. The excitation profiles were used to determine both
the strength of the vibronic coupling and the differences in
ground and excited states. Hicks and Gammel (G258) ex-
tended the Su (1982) model for the coupled electron-phonon
system in polyacetylene to include phonons. Two localized
IR-active vibrational states were found. Significant mixing
was found between the Gladstone mode of the solution and
the lower-frequency modes in the acoustic phonon branch,
creating for a charged solition, an IR-active acoustic phonon
branch.
The vibrational spectrum of poly@-phenylene) was calcu-
lated by using the force constants and the electrooptical fields
from toluene (G68). Kim et al. (G93) assigned the vibrational
spectrum of benzanilide and performed a normal coordinate
analysis, and the data are useful as a model for interpreting
the vibrational data for poly@-phenylene terephthalamide).
Some of the same co-workers performed a normal vibrational
analysis of poly(p-phenyl terephthalamide), a rigid-rod
polymer (G210). Murali et al. (G171) utilized IR to show that
there is a proton transfer of acidic proton in sulfonated
polyphenylene to the nitrogen atoms in ethyl acrylate-4-
vinylpyridine copolymer.
Brisson and Brisse (G94) characterized a series of dibenz-
amides using IR, Raman,and X-ray diffraction data. The IR
and Raman data showed that the position of the amide V band
depended on the r angle and could be used to infer whether
the T angle was near 180’. These data were useful in the
interpretation of the vibrational data for poly(methy1ene
terephthalamides). Gopal and Srinivasan (G115) utilized IR
and NMR to characterize six polyamide-polyureas prepared
by the copolymerization of 3,3’-diaminobenzanilide or 44’-
diaminobenzanilidewith TDI, HMDI, or MDI in DMF at 30’
for 2 h.
Ishida and Scott (G191) used FT-IR interfaced with a
computerized microreaction injection molding machine to
study the Nylon 6 molding process. The molecular data
obtained for Nylon 6 helped in understanding its transient
crystalline behavior prior to the completion of the polymer-
ization reaction, crystalline kinetics, and structural changes
of the polymer chain. Zelmanovic et al. (G218) simultaneously
determined the gauge and orientation of polymer film of Nylon
66 using IR spectroscopy.
Trefonas and West (G77) utilized IR, NMR, and UV
spectroscopy to study the reaction of polycyclohexyl-
methylsilylene with m-chloroperbenzoicacid and found that
a block copolymer was produced containing cyclohexyl-
methylsilylene units and cyclohexylmethylsiloxane units.
Fuhrmann and Glaenzer (GI11)developed a computer-aided
IR method for the analysis of poly(dimethylsi1oxane) in
emulsions, pastes, and pharmaceutical preparations, and on
the surfaces of materials such as rubber stoppers. Murthy
et a1 (G112) developed a method for determining poly(di-
methylsiloxane) on cotton fabrics using ATR/FT-IR and
methanol. The methanol was needed to swell the cotton
fabrics in order to release poly(dimethylsi1oxane) onto the
ATR late. West and Zhang (G113) utilized IR, UV, proton,
and PC NMR data to characterize copolymers containing
diphenylsilylene units. Copolymers were formed by the re-
action of Ph2SiC12and R,R’SiC12 (where R = methyl or hexyl
and R’ = phenethyl, cyclohexyl, or hexyl) in the presence of
sodium in toluene.
Culler and co-workers (G138) used FT-IR to characterize
the nature of the chemical reactions at the silane matrix resin
interphase of a composite material. The system studied was
(y-aminopropyl)triethoxysilane,a difunctional epoxy resin
with and without E glass fiber composite. Kohn (G170)
utilized IR and UV-size exclusion chromatography methods
to determine the placement and to quantify the Si-H, Si-OH,
and Si-Ph groups in poly(dimethylsi1oxanes). Jenden (G203)
utilized laser Raman spectroscopy to monitor artificial
weathering of alkyd and silicone-modified alkyd varnishes.
The data showed the improved weather resistance of sili-
cone-modified coatings compared to alkyds. Klimisch and
Chandra (G246) used ATR/FT-IR to quantitatively determine
the amount of poly(dimethy1siloxanes) on human skin. Lipp
(G265) utilized Fourier self-deconvolutionto the FT-IRspectra
of poly(dimethylsi1oxane) oligomers for determining chain
length information from IR spectra and was applicable to
oligomers having molecular weights as high as 15 000.
134R ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
Sergides and co-workers (G96) determined the optical
constants n and k of polyacrylonitrile in the IR region
700-3100 cm-l by using theoretical calculations and experi-
mental IR reflectance spectra. Excellent agreement between
theory and experiment was obtained for the k values. Bauer
and co-workers (G162) used IR s ectroscopy in the evaluation
of the cyanate conversion in soliC Yand gelled aromatic cyanate
oligomers. Shimada and co-workers (G261) used FT-IR to
study the stabilization reaction of polyacrylonitrite in the
production of carbon fibers. Three types of reactions, cy-
clization, dehydrogenation, and oxygen uptake, were shown
to occur almost simultaneously in the stabilization process in
air.
Shaaban et al. (G178) determined the structure of poly-
(ethylene cinnamylsuccinate)by application of IR and NMR.
The peroxide-initiated cross-linking of poly(ethy1ene cinna-
mylsuccinate) with styrene in dioxane yielded an insoluble
compound, and the hydrolyzed product was analyzed utilizing
IR. Cousin and Prud’homme (G182) used FT-IR and 13C
NMR to study specific interactions in polyester-poly(viny1-
halide) blends. Miscible blends exhibited a frequency shift
of the carbonyl stretching vibration and an increase of its
width at half-height. In contrast the carbonyl stretching
vibration is not perturbed in immiscible blends. Xue et al.
(G217) studied the surface orientation of polyester fibers by
using a modified sampling technique. The fiber axis was
arranged parallel to incident radiation first, and then per-
pendicular to it. The differences in total absorbances and
relative intensity changes in the spectra showed the features
of specular reflection. The technique has the adGantage over
ATR in that there is no optical contact problem.
THERMAL ANALYSIS
Several review articles covering the thermal analysis of
polymers were published in the last two years. The use of
thermal analysis for both qualitative and quantitative analysis
of polymer systems has been explored by Maurer (HI).
Elastomers, cross-linked polymers, and partially hydrolyzed
polymers were discussed in this review. The determination
of the heat capacity for completely glassy or fully cyrstallized
polymers with the subsequent use of these data to quantitate
intermediate states was discussed by Wunderlich (H2). The
application of thermomechanical analysis for the character-
ization of multiphase copolymer systems was reviewed by
Yilgor and co-workers (H3). Harrison et al. (H4) presented
an extensive review of various thermal techniques for studying
cross-linking in polymers. The theory of polymer-polymer
miscibility, with emphasis on the thermodynamic require-
ments for miscibility, as well various methods for quantifying
the interaction between components in blends was reviewed
by Paul (H5). DeFrancis and Sichina (H6) reviewed the use
of thermal techniques for quality assurance applications for
composites.
Following the trends of recent years, there was significant
work in the area of combined techniques. Combined ther-
mogravimetric analysis/mass spectroscopy (TGA/MS) has
been used by Prime (H7) to study the curing and decompo-
sition reaction of phenolic resins. Stark and Seferis (H8)
showed that while different thermal techniques examine
different phenomena regarding the curin reaction, data from
the different methods can be correlatecf to give insight into
the overall curing process. Combined TGA/GC has been used
by Costa and co-workers (239) to study the thermal degra-
dation of polystyrene in the presence of chloroalkanes and
found this combined method most useful for examining the
products of the early stages of decomposition. Russel and
Koberstein (HIO) described a method for performing simul-
taneous small-angle X-ray scattering and differential scanning
calorimetry (DSC). This method was used to study the
melting and crystallization of polyethylene fractions. McEwen
et al. (H11)described a method for combining TGA and
Fourier transform infrared (FT-IR) spectroscopy which allows
for both the identification and quantitation of the various
components present in polymer systems.
Thermally stimulated discharge current (TSDC) was used
by Chowdhury (H12) to examine charge transfer efficiencies
and conductivities of various epoxy/silicone composites. Gotro
et al. (H13)has used DSC, FT-IR, and dynamic mechanical
analysis (DMA) to characterize the usefulness of a bis(ma1e-
imide)/bis(cyanate) epoxy thermosetting resin for use in

composites for fabricated circuit boards. The effect of COz,
at pressures up to 25 atm, on the glass transition temperature
of several polymers was studied and a reduction in the glass
transition temperature of up to 50 OC has been observed (H14).
Stenberg and Bjork (H16) used DSC to study the efficiency
of various antioxidants in natural rubber a a function of
sample e and thickness. Staub (HI7) applied DSC, TGA,
and TM? to the study of elastomers and has been able to
quantitate levels of EPDM and natural rubber in mixtures
of the two. Zoller (H18) applied high-pressure volume dila-
tometry to the characterization of polymer blends in the melt.
Eckhoff and Bagley (H15) examined the effect of rapid
exothermic processes on the accuracy of data generated from
a power-compensating DSC. Experiments with distilled water
show as much as a 44% difference between the peak area for
the exothermic and endothermic transitions.
Several authors used DSC to examine the curing process
of epoxy resins. Temple and Coulson (H19) discussed the use
of DSC for determining the cure of an epoxy from both the
shift in T after the curing process and percent conversion
methods. %he merits and applicability to plant quality control
applications of both techniques are discussed. Shah et al.
(H20) studied the curing of phenolphthalein-basedepoxy resin
with phthalic anhydride by DSC and found that the kinetics
were independent of the concentration of phthalic anhydride
and scan rate. Barton (H21) reviewed the use of DSC as a
method for monitering the kinetics of epoxy curing reactions.
Karasz (H22) used temperature-copolymer composition
diagrams for determining the compatibility of a copolymer
blend. Limitations of the use of T for determining com-
patibility in blends are discussed. D%C was used by Natan-
sohn (H23) to study the exotherm associated with the phase
separation in miscible polymer blends. Brekner and co-
workers (H24)used dynamic mechanical measurements to
study the effect of molecular weight on the compatibility of
blends of polystyrene (PS) and poly(viny1 methyl ether)
(PVME). It is reported that low molecular weight PS has a
greater com atability with PVME than high molecular weight
PS. Greenierg et al. (H25)studied the change in T for
composites of poly(acry1ic acid) and ceramic fillers. $hey
found that different fillers gave the maximum change in T,
a t different volume fractions of filler.
Galliglia et al. (H26)studied the thermal properties of
poly(t-caprolactam) blended with other crystallizable poly-
mers. They found that the polymers crystallized separately,
but the presence of one crystalline phase greatly increased
the crystallization rate of the second phase.
Calaharra et al. (H27) studied the thermal decomposition
of poly(ethy1ene oxide), poly(methy1 methacrylate),and blends
of the two polymers. They found maximum stability for a
blend containing 80 % poly(ethy1ene oxide), indicating that
these two polymers had a stabilizing effect on each other.
Martuscelli and co-workers (H28) studied blends of poly-
(ethylene oxide) (PEO) and poly(viny1 acetate) (PVA) and
found significant changes in the crystallization kinetics rate
constant and spherulite growth rate as PVA is added to PEO.
Barnum et al. (H29) examined the excess heat capacity found
for two miscible blends. The deviation in heat capacity was
always found to be positive and the results are discussed in
terms of the free energy, enthalpy, and entropy of mixing.
Hagstroem (H30) developed phase diagrams for blends of
high density polyethylene with some low molecular weight
compounds. Mechanical properties (stress-strain curves) were
related to phase compositions from the phase diagram. Kerch
and Irgens (H31) used DTA to study the effect of composition
on the melting and crystallization of polypropylene and
polyethylene blends. Allen et al. (H32) used DMS and DSC
to study blends of isotactic PMMA with atactic and syndio-
tactic rich PMMA. They found that some blends showed two
melting points, one for isotactic PMMA and a second for the
blend. A study of the thermal and thermomechanicalbehavior
of blends of Nylon 6 and ethylene based multifunctional
polymer indicated a reaction of the amino end groups of Nylon
6 with functional groups of the ethylene copolymer to form
a graft polymer which acted as an interfacial agent (H33).
Copolymers of ethylene with other common monomers (e.g.,
acrylonitrile, styrene, etc.) were examined by Krul (H34) and
found to be more thermally stable than polyethylene. Burfield
and Kashiwa (H35)also studied the disruptive effects of
various comonomers on the crystallization of linear low density
ANALYTICAL CHEMISTRY, VOL. 59, NO. 12, JUNE 15, 1987
ANALYSIS OF SYNTHETIC POLYMERS
polyethylene. Rim (H36) did an extensive examination of the
effects of side chain crystallizability on the glass transition
temperature and melting temperature of poly(a-olefin-co-
maleic anhydride). Meister et al. (H37) found that the sym-
metry of side groups (methyl to ethylphenyl) can reduce or
eliminate the crystallinity and increase the glass transition
temperature of phosphazenes.
The effect of varying the side chain length on the properties
of polymers made from vinyl esters of fatty acids having
various chain lengths was related to the relative packing mode
by $hibasaki and Fukuda (H38).The process for thermal
degradation of copolymers of styrene with some metal acry-
lates was studied using TGA by Gronowski and Wojtczak
(H39). They reported that while zinc increases stability, other
metals (Co, Cu, and Ni) decrease thermal stability. Bataille
and Granger (H40) have examined the thermal stability of
methyl methacrylate-styrene copolymers as a function of
polymerization conditions and found that increasing reaction
time gave a more thermally stable polymer.
Utracki (H41) extended the Couchman equation for the
change in T, with composition by addition of a proportionality
factor. This proportionality fador can be used as an indication
of the degree of miscibility of the blend. Kihira and Yama-
mura (H42) examined the effect of various levels of meth-
yacrylic acid in a copolymer with methyl methacrylate. Shifts
in the glass transition temperature and dynamic loss curves
suggest that hydrogen bonding effects are restricting segmental
movement. DSC was used to examine the change in mi-
crostructure for ethylene-vinyl chloride copolymers (H43).
Zhouy et al. (H44) found that melting points and glass tran-
sition temperatures for liquid crystal polyesters prepared using
2-substituted hydroquinones are independent of the polarity
of the substitution group but steric effects due to the sub-
stitution group are the main causes for changes. Pasztor (H45)
used DSC to determine the relative levels of EPDM rubber
in blends of EPDM and SAN based on the magnitude of the
change in specific heat at the glass transition. Chartoff and
Butler (H46) used dynamic mechanical analysis to study the
miscibility of polymer blends.
An increasingly important area of polymer analysis is the
use of dynamic mechanical techniques, referred to as DMA
or DMS. Dynamic mechanical measurements can be made
as a function of frequency and/or temperature and there is
some discussion as to if this is a thermal technique. Since
dynamic mechanical studies can be studied as a function of
temperature, they are covered in this review article for the
first time under thermal properties.
Bucknall (H47)has recently reviewed the mechanical
properties of high impact polymers. Bazuin and co-workers
recently used dynamic methods to explore both the glass
transition (H48) and the melt (H49)regions of plasticized
polystyrene based ionomers.
Kontou et al. (H50) used DSC and DMS to study the
heterogeneity of epoxy networks and has reported that cured
epoxies consist of two phases having high and low cross-link
densities. Sideridis and co-workers (H51) used DMS to study
iron filled epoxies and found the modulus to be dependent
on the dynamic stress strain fields around the filler. Wan-
tanabe et al. (H52) explored the relation between the ionic
conductivity and the dynamic mechanical properties of
polymer complexes formed by a segmented polyether-poly-
(urethane urea) and lithium perchlorate. They reported that
a two-phase system is formed with the lithium perchlorate
primarily residing in the polyether phase. Mitchell and Porter
(H53) studied the effects of uniaxial draw on the morphology
of poly(ethy1ene oxide) using X-ray diffraction, DMS, and
DSC. They concluded that a system of extended chain
molecules was formed. Qian (H54) studied the thermome-
chanical behavior of acrylic fibers.
Turi and Khanna (H55) used DSC and thermomechanical
analysis to study the heat setting history of Nylon 6. The heat
setting history was found to be related to the dimensional
stability and dyeability of the system. Chen et al. (H56)
studied the melting and crystallization of Nylon 11 at high
pressures and found two crystalline forms at low pressures
but only one form at high pressures. Chen and co-workers
(H57) studied the crystallization rate of poly(ethy1ene tere-
phthalate) in the presence of sodium benzoate and adipic
acid-bis(hydroxyethy1)terephthalate copolymer. Aleman
(H58) characterized poly(buty1ene terephthalate) by DSC
135R
 ANALYSIS OF SYNTHETIC POLYMERS
determinin T,and examining the melting behavior. Wun-
derlich a n f Grebowciz (H59)reviewed the heat capacity
measurements of liquid crystal polymers and polymeric
crystals with conformational disorders.
Turner and Schwartz (H60) studied the glass transition
temperature of poly(N4nylpryolidone) using DSC and found
that both water and residual monomer can cause significant
variation in the measured glass transition temperature of the
polymer. DSC was also used to examine the state of water
in poly(viny1 alcohol) membranes (H61).
Gaurari et al. (H62)used thermally stimulated current to
study the effect of tacticity on various thermal transitions,
including T , for poly(methy1 methacrylate).
The specific heat capacity and thermal conductivity were
measured for polyethylene a t temperatures below 2 K by
Finlayson and Mason (H63). Gan et al. (H64) used DSC to
examine ethylene-propylene copolymers. In addition to a
decrease in T, for the system it was found that a minimum
of 9-10 ethylene triads in sequence are needed for crystalli-
zation to occur. Karmazsin and co-workers (H65) examined
the thermal degradation in air of fresh and aged polyethylene
using TGA and thermodilatometry. It was found that the
onset of decomposition occurred a t lower temperatures for
aged polymer. However, addition of stabilizers had a greater
effect on aged polyethylene than on virgin polyethylene.
Yadav et al. (H66)studied isothermal lamellar thickening of
polyethylene by DSC. Two melting peaks were observed. A
high-temperature peak was attributed to the isothermally
annealed phase, and the low-temperature peak was attributed
to the fraction which crystallized on cooling to room tem-
Derature. Fractionation based on molecular weight was also I (69) Leljenaar. S. R.; van den Heuvel, C. J. M.; Huysmans, W. G. 8 . Makro-
observed (H66).
Castles and co-workers ( H W )examined the effects of chain
structure and processing variables on the microstructure and
linear viscoelastic behavior of a series of copolyether-ester
block copolymers. DSC and TGA were used to determine the
curing temperature, the extent of cross-linking, and other
properties of some polyester resins (H68).
Wunderlich and Cheng (H69) characterized poly(ether ether
ketone) by thermal techniques. Prime and Seferis (H70)used
TGA/MS to examine the catalyzed thermal oxidative de-
composition of poly(ether ether ketone). Studies by Inoue
and Hosina (H71) found that having a high cis or trans com-
ponent affected the thermal properties of polyamides by
changing the crystalline content of the polymer. Hirata et
al. (H72) studied the thermal and oxidative degradation of
poly(methy1 methacrylate). Thermal degradation was found
to be a two-step process, independent of impurities such as
oligomers,while oxidation appeared to be a four-stage process,
having a significant dependence on impurities. Balog et al.
(H73) found poor correlation for the oxidative stability of
polymers between DTA and flammability tests.
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1 4 1R