Conformational structure of poly(ethylene

terephthalate). Infra-red, Raman and n.m.r.

spectra

J. ,Stokr, B. S c h n e i d e r , D. Dosko6ilovti a n d J. L o v y
Institute of Macromolecular Chemistry, CzechoslovakAcademy of Sciences, 1 62 06
Prague 6, Czechoslovakia

a n d P. S e d l t i E e k
Chemopetrol, k.p. Silon, 391 11 Plan~ had Lu~nicL Czechoslovakia
(Received 25 February 1 981; revised 21 September 1981 )

Infra-red and Raman spectra of unoriented samples of poly(ethylene terephthalate) in the crystalline
and amorphous states and in solution were measured. The dissolved polymer was also studied by n.m.r.
spectra. Digital separation of the vibrational spectra of amorphous and crystalline components made
possible the detection of some new bands, the interpretation of which is presented. By comparison with
the vibrational spectra of model compounds combined with analysis of n.m.r, spectra, the
conformational forms present in the amorphous and liquid states of poly(ethylene terephthalate) were
characterized and their populations were determined. Bands in vibrational spectra which are
characteristic of various conformational forms were defined.

Keywords Spectroscopy; infra-red; Raman; poly(ethylene terephthalate); conformational structure;

crystalline state; amorphous state

INTRODUCTION appear additional conformers generated by rotation

Vibrational spectra of poly(ethylene terephthalate) (PET) about the bonds Ca~-CO or CO-O, O-CH2 and CH2-
have been studied in a number of papers 1-19. In the CHz; for all these conformers, frequencies of characteristic
crystalline state where PET is present in an almost planar bands in vibrational spectra have been found. In this
form according to X-ray diffraction analysis2°, paper, the results of the model compound studies are used
vibrational spectra have been interpreted based on a for the characterization of the conformational forms
force-field calculation9'18'19. From infra-red spectra it existing in amorphous and liquid PET, and for the
was found that in the amorphous state PET has a yauche assignment of the corresponding vibrational spectra. As
structure of the ethyleneglycol fragment6,a'12-s4,x6, besides conformational structure, the vibrational spectra
contrary to the crystalline state where the ethyleneglycol of PET are also strongly affected by orientation, infra-red
fragment of PET has a trans structure 2°. All major and Raman spectra of completely unoriented samples
changes which are observed upon transition from the have been newly measured.
crystalline to the amorphous state, have been attributed
to this conformational change L2,5-v. Krimm 3'4 has EXPERIMENTAL
expressed the assumption that some changes in infra-red
spectra which are observed upon transition from the Sample preparation
crystalline to the amorphous state may be caused by the All samples for spectral measurements were prepared
loss of the centre of symmetry on the benzene ring which from commercially polymerized PET. The powdered
takes place in the amorphous state. Bands in amorphous sample for the measurement of infra-red spectra was
and crystalline PET have been assigned to various prepared from the dispersion which was formed by
vibrational modes 2'8'12 and bands characteristic of the cooling of the solution of PET granules in 6-caprolactam
crystalline and of the amorphous states have been defined. melt 24. The resulting sample was extracted with water
N.m.r. spectra have so far not been used in studies of the until the content of 6-caprolactam in the PET powder
conformational structure of PET. dropped below 0.1~o. The obtained PET powder con-
In our preceding studies 21-23 we have been able to sisted of particles of diameter < 6/~m; the crystallinity
characterize, by means of vibrational and n.m.r, spectra, determined by X-ray was 50-55~o and the number-
the conformational structure of methyl benzoate, average molecular weight M, was ,~ 11 x 10 3. The sample
dimethyl terephthalate, ethyl benzoate, diethyl for the measurement of Raman spectra was prepared by
terephthalate and ethyleneglycol dibenzoate in the spontaneous effusion of PET melt at 290°C from the
crystalline and liquid states of these molecules. These reactor into an ice-water bath at 0°C. The resulting
measurements have shown that in the most stable sample had the shape of a string of 3 mm diameter; its
crystalline state all these models have a completely planar crystallinity as determined from density was within 0-1~o
structure, and that in the liquid and glassy states there and the number-average molecular weight M, was
0032-3861/82/050714-08~p03.00
© 1982 Butterworth& Co (Publishers)Ltd.
714 POLYMER, 1982, Vol 23, May
 Spectroscopic study of PET conformation. J. Stokr et al.

18 x 103. The sample for the measurement of n.m.r. rotation about the C,~-CO or about the C O - O C H 3 bond.
spectra was prepared by melt spinning in a laboratory Analysis of infra-red, Raman and n.m.r, spectra of
apparatus; its number-average molecular weight M, was O
16.5 × 103. For the measurement of solution spectra, PET II
was dissolved in a mixture of phenol and 1,1,2,2- model compounds containing the C O - C H 2 q 2 group
tetrachloroethane in the ratio 1:3 v/w.
Infra-red spectra were measured on the infra-red
spectrometer Perkin-Elmer 580 B connected with a (ethyl benzoate 22, diethyl terephthalate 22, ethyleneglycol
multichannel analyser TN-4000 (Tracor Northern). The dibenzoate 23) has shown that in the liquid state all these
powdered sample was measured by the KBr pellet compounds contain both the form with a trans structure
technique. Infra-red spectra of amorphous PET were of this group (t) (Fiyure 1), and the two equienergetic
obtained so that the pellet with the powdered sample was mirror image forms with the CH2-C bond twisted out of
heated to ~ 290°C, quenched in liquid nitrogen, reground the plane of the ester group by rotation about the O
and pressed. The spectrum of dissolved PET was obtained CH2 bond; these forms are designated as 9auche (9)
by digital subtraction of the solvent spectrum. (Figure 1). From analysis of n.m.r, spectra the population
Raman spectra were measured on the spectrometer of the trans form (Pt) and of both 9auche forms (Po) in
Coderg LRDH-800 connected with the computer system ethyl benzoate and in diethyl terephthalate is
TN- 11 (Tracor Northern). Spectra were excited by the line p~= 0.71_+ 0.04, p0=0.29+0.04, and in ethyleneglycol
514.5 nm of the argon laser CR 3 of Coherent Co. Spectra dibenzoate p,=0.83_+0.03, p0=0.17_+0.03. In liquid
were measured in the 90 ° arrangement. The amorphous ethyleneglycol dibenzoate, the ethyleneglycol fragment
sample prepared for the measurement of Raman spectra exists predominantly in the form of the two equienergetic
in the form of a string, was quite transparent. The spectra mirror image 9auche forms designated as G (Figure 1).
of this sample measured at various orientations differed a From n.m.r, analysis the population of both G forms at
little. In order to remove this effect which indicated a room temperature is Pc = 0.915, and the population of the
partial orientation of the sample, the surface of the sample trans form (T) in the liquid state is only p r = 0.085. From
was roughened. After this treatment the spectra measured these data it follows z3 that ethyleneglycol dibenzoate in
in different orientations were identical. However, the solution at room temperature contains predominantly the
resulting spectra were very weak and for obtaining good structure tGt (~63~o), a considerable amount of the
quality spectra, about 30 accumulations were necessary. structure tG9 ( ~ 26%), a small amount of the structure tTt
Samples of medium crystallinity were obtained by heating ( ~ 6~o), and a few per cent of the structures 9G9 and tT9;
the amorphous sample to 180~C for one hour. Spectra of the content of the structure 9T9 is quite negligible.
these samples did not show any effects of orientation, and Using the above introduced symbols, PET in the
good spectra could be obtained after 3 accumulations. In crystalline state has the tTt conformational structure with
accumulating spectra of dissolved PET a programme a mutual trans orientation (TB) of ester groups.
permitting automatic subtraction of the solvent spectrum
N.m.r. spectra
after each scan was used. All Raman spectra discussed in
this paper were once smoothed by a digital three-point The determination of the conformational structure on
binomial filter. the bonds O - C H 2 and C H 2 - C H 2 of PET in solution from
13C n.m.r, spectra were measured with 10~o w/v n.m.r, spectra is more difficult than for the model
solutions of PET in the mixture of phenol with 1,1,2,2- compounds, mainly because of larger line width and
tetrachloroethane-d 2 (1:3 v/w) using the spectrometer consequently poorer resolution, even at elevated
Varian XL-200 at 50 MHz and 70°C. The carbonyl band temperature. However, for the determination of the
was measured with a digital resolution of 0.2 Hz (a) with structure of the ethyleneglycol fragment, use could be
selective decoupling of the aromatic and aliphatic protons made of band intensities in infra-red spectra (as will be
of PET (7H2 = 250 Hz), (b) with noise decoupling of the shown further in detail), from which it followed that
protons, and (c) with gated decoupling yielding the fully amorphous PET contains about 10~o and PET in solution
coupled spectrum and preserving the N O E enhancement. about 7°/o, of the tTt form.
For the determination of the conformational structure
on the O - C H 2 bond of PET we have tried to apply a
RESULTS AND DISCUSSION
Conformational forms of P E T and their symbols
The possible conformational forms of PET are 0 0
expected to be analogous to forms found in the studied H II
model compounds of PET. Measurements of infra-red C C 0 0
and Raman spectra of dimethyl terephthalate 21 and of H.~H CH2.~H
diethyl terephthalate 22 have shown that in the crystalline
state the ester groups of these molecules are always in a
mutual trans orientation T~; in the liquid state, forms with CH2 H 0 H

a mutual cis orientation of ester groups C B (Figure 1) are

t g T G

also present. The populations of the TBand Cn forms in the O O O 0

liquid state are comparable. In vibrational spectra of
liquid methyl benzoate and dimethyl benzoate zl weak
bands have been found indicating that small amounts of re ce
forms with a non-planar structure of the benzyl ester Figure I Schematicdiagram of conformational forms of poly-
group may also occur; they could be generated either by (ethylene terephthalate)

POLYMER, 1982, Vol 23, May 715

Spectroscopic study of PET conformation." J. Stokr et al.

3.0-2.6 Hz, for the considered widths of a singlet line

within 2.5-4.0 Hz (the value 2.5 Hz corresponds to the
width of the ~3CO band in a noise decoupled spectrum).
By a calculation similar to our preceding
communications22'2a, the corrected value of 3JcH yields
Pt -- 0.74 _+0.07. The accuracy of this result is lower than in
the case of ethyleneglycol dibenzoate due to the lack of
reliable information about the width of singlet lines in the
aCO multiplet of PET in solution. In spite of that it is
AJ evident that even for PET, the trans conformation on the
O--CH 2 bond strongly predominates. The value of Pt for
PET is probably slightly lower than for ethyleneglycol
dibenzoate, and nearer to the value found for ethyl
benzoate, but the differences are not beyond experimental
error.

Infra-red and Raman spectra

Infra-red and Raman spectra of crystalline,
semicrystalline and amorphous PET, and of PET
dissolved in the mixture of phenol and 1,1,2,2-
tetrachloroethane are shown in Figure 2. The spectra of
semicrystalline and amorphous PET and of PET in
solution are directly measured spectra. The spectrum of
E I crystalline PET was obtained by digital subtraction of the
spectrum of amorphous PET from the spectrum of
semicrystalline PET. In infra-red and Raman spectra
obtained in this way we have detected some bands which
have not been described previously for unoriented PET in
the crystalline or amorphous states. This concerns the
band at 1086 cm - ~in infra-red spectra of crystalline PET,
and the bands at 1582, 975, 683 and 415 cm -~ in Raman
spectra of crystalline PET. We have compared the
I I I I I I I I I I I I I I character and the experimental wavenumber values of the
1800 1600 1400 1200 I000 8 0 0 600 400 200
vibrational bands of PET with wavenumber values and
Cm-I
assignment to vibrational modes as calculated for the
Figure 2 Vibrational spectra of polylethylene terephthalate). planar form of PET by Boerio et al. 19. Based on this
Infra-red spectra: (A) crystalline, (B) semicrystalline, (C) amorphous, comparison we have refined the interpretation of some
(D) solution. Raman spectra: (E) crystalline, (F) semicrystalline,
(G) amorphous, (H) solution. Dotted parts of the spectra indicate vibrational bands of the tTt form of PET as shown in
solvent bands Table 1.
From Table 1 it is seen that the bands in vibrational
spectra of PET can be divided into four groups: I-bands
similar procedure as that used in our previous the intensity of which practically does not change upon
communications22'2a for ethyl benzoate and transition from crystalline to amorphous state or
ethyleneglycol dibenzoate, using the 3JcH coupling solution; II-bands appearing only in infra-red and Raman
constant obtained by analysis of the carbonyl band in ~aC spectra of crystalline PET, and bands the intensity of
n.m.r, spectra measured with selective heteronuclear which is significantly higher in spectra of crystalline
decoupling of the aromatic protons. Contrary to the samples than in the spectra of amorphous or liquid
model compounds, the ~aCO band of PET did not exhibit samples (Table 2); III-bands appearing only in infra-red
any fine structure in the present case. The value of 3JcH and Raman spectra of amorphous and liquid PET, and
was determined by comparison of the experimentally bands the intensity of which is significantly higher in
measured width of the 13CO band with the width of the spectra of amorphous or liquid samples than in the
simulated band of the AA'A"A"'X system (where X spectra of crystalline samples (Table 3); IV-bands which
corresponds to ~aco and AA'A"A'" to protons of the appear both in the infra-red and Raman spectra of
ethylene fragment). As mentioned above, the content of amorphous or liquid PET, but which appear either only in
tTt forms in liquid PET is practically equal as in the infra-red, or only in the Raman spectra of crystalline
ethyleneglycol dibenzoate. As the shape of the ~aCO PET (Table 4).
bands depends very little on the population of the T and G The same classification can also be applied to
forms, in the present band-shape simulation the same vibrational bands of model compounds of PET, in which
values of interproton coupling constants within the conformationally sensitive bands have been assigned to
ethylene fragment were used as those found and applied in various types of conformational structures based on the
the analysis of the ethyleneglycol dibenzoate spectra 23. comparison of vibrational spectra of various crystalline
The found value of the aJcHconstant was corrected for the forms and of amorphous and liquid samples, and on
effect of the irradiating field similarly as in our preceding analysis of n.m.r, spectra of liquid samples.
communications22'2a. The corrected value of aJcH was Bands of type I evidently correspond to vibrations

716 POLYMER, 1982, Vol 23, May

 v
Spectroscopic study of PET conformation."J, Stokr et al.

Table I Interpretation of infra-red and Raman spectra of poly(ethylene terephthalate). The symbol PED stands for 'potential energy
distribution'

v (cm -1) This work v (cm - t ) Taken from ref. 19

I .r. Raman I ;r. Raman Catc.

Sym-
Cryst. Amorph. Solution Cryst. Amorph. Solution Semicryst. tTt metry PED

1724
1729 1728 1714 1730 1733 Ag S(90)
1721
1718 1725 1711 1727 1721 Bu S(93)
1684" 1690"
1647"
1616 1616 16081" 1616 1616 1616 1615 1606 Ag T(74),~(25)
1560* 1560 1581 1582 1580 1580 -- 1576 Ag T(82),~(13)
1554 * 1556*
1526 1531" 1530 *
1507 1506 15O4 1504 1504 8u ~(54), T(39)
1473 1479" 14751, 1475 1465 Bu ~'(62), ~'(35)
1463 1469" 1462 1452 Ag 4'(58), ~'(44)
1458" 1456 1456 1455 1449
1442" 1443 1443 1445
1419 1418 1395 Ag fl(62), ~'(28)
1412 1412 1412 1412 1414 1410 1407 8u T(46), $(39)
1407"
1387
1370" 1374 1374 t 1374 1375
13631,
1343 1342 1341 * 1337 1334 Bu /~(55), e'(41 )
1309" 1308 1308 13121, 1310 1316 Ag 4(71)
1293 Bu T(138)
1287 1286* 1288 1288 1288* 1295 1273 Ag T(37), t I (32), ~(18), ~(18)
1281 - 1285 Bg e'(62),/~(48)
1265 1266 1266 1270 1273 1263 1254 Bu q (50), T'(38), 8(23)
1248 1248 1250 1250" ~1, 1271 Au ~'(94)
1187
1178" 1176 11771, 1178 1180 1192 t178 Ag ~(72), T(15)
-- 1174 8g ~(43), ~'(39)
1139 1138"
t126 1122 1125 1126 1126 Bu ~(26), q (26), 4(19), T(12)
1120 1119 1124 1119 1118 Ag tl (38), r(35), 3/(15)
1112"
1102 1101" 1102 1109 8u #~(56), T(33)
1097 1103" 1105" 1096 1100 Ag T(31), r(28), t 1(10)
1086 *
1043" 1043 1043
1031 1030"1,
1023
1019 1018 1019 t 1018" 1018 1019 Bu ~Z(37), T(28), ~(27)
998 997* 1000 1002 Ag t2 (80), r (20)
988 991 Au #2(126)
975* - 972 Bg #2(136)
971 975 977 973 971 8u t2(89)
935* 935*
901" 898 900 * t
885* 886 887
875 871 Au ~2(81), M(24),Z(15)
873 875 875 - 868 Bu tz (29), u(23), 8 (14)
- 859 Bg ta2(114)
857* 858 859 861 857 844 Ag T(27),q (15),e(12),T(t l),r(10)
849 842 847* 837 837 Au /3(97)
840"1,
828 830 8271,
811" -t 810
793 794 ~T 795 795 797 ~ 800 799 Bg Z(48), #3 (48), M(40)
775* 780* 776 * t
727 728 731 t 732 734* 727 723 Au #3 (60), #2 (43)
705* 705 709* 703 703 704 701 693 Ag £(36), 8(22), T'(14)
680 682"1, 683 683 ~1, -- 673 8g Z(86), ~3 (39)
667
632* 633 636"1, 632 633 633 626 628 Ag (60), ¢(15)
619 617"
- 559 Ag 3`(37), ~(22)
524* 532 530 * t 530*
507 500 510 498* Bu T'(37), e(19)
461" -- 470 Au Z(89), M(79)
437 429* 424* 430* 438 459 Bu u(31), 3`(27), 8(16)
430 411 Au Z(135)
415" 408* -- 373 Ag 3`'(23), ~(21), ~(10)
378 388* 385* 382 384 Bu 3,(29), 3`'(18), 8 (17)
340
30O
270* 280 270 265 278 282 Ag e(33), ~(28),u(21)
235*
215"
121 119 Bg T3

* Poorly defined bands

t Wavenumbers may be affected by solvent bands

POLYMER, 1982, Vol 23, May 717

Spectroscopic study of PET conformation." J. Stokr et al.
Table 2 Bands of type II of poly(ethylene terephthalate) (PET), bands can correspond either to harmonic or combination
and analogous bands of ethyleneglycol dibenzoate (EDB) vibrations, or they may be connected with the ordering of
PET u (cm - 1 ) EDB u (cm - 1 )
PET molecules in crystalline domains. In this category
I.r. Raman I.r. Raman has been included also the band at 988 cm- l which, due to
its behaviour, is thought to be in connection with regular
1684"t 1690"t folding of the polymer chain 1°, even though aromatic
1473 1482 hydrogen coordinates predominate in its vibrational
1463 1473
1419 1418 interpretation as seen from Table 1.
1387 t Table 3 summarizes bands of group III which appear in
1343 1341 spectra of amorphous and liquid samples of PET and
1281 which are absent from vibrational spectra of crystalline
1248
1184
PET, and also analogous bands of liquid ethyleneglycol
1187
1126 dibenzoate which are absent from vibrational spectra of
1112"t the crystalline form with the planar structure of this model
1097 1099 compound. From this Table and from Figure 2 it can be
1086"t seen that many bands characteristic of the amorphous
1023 t
998
and liquid state of PET agree by wavenumbers, intensity
988 and activity in infra-red and Raman spectra with the
975* bands of liquid ethyleneglycol dibenzoate. All bands of
971 981 ethyleneglycol dibenzoate appearing upon dissolution of
849 859
667 t
crystals with the tTt structure, correspond to the G form
507 of the ethyleneglycol fragment, and in some cases it was
461 * possible to differentiate bands of the Gg and Gt
437 conformational forms.
415* 408 From the analogy between the vibrational spectra of
405
378
ethyleneglycol dibenzoate and PET, all bands of PET
280 291 shown in Table 3 (with the exception of the band at 530
121 cm -1) can be assigned to the G conformational form of
the ethyleneglycol fragment, and it can also be assumed
All bands of PET shown in this Table are characteristic of the tTt
forms in the crystalline state
that the bands of PET which appear at equal
* Poorly defined bands wavenumbers as the bands of the Gg and Gt forms of
t Bands which have not been assigned to calculated vibrational ethyleneglycol dibenzoate, are also in vibrational spectra
modes of PET characteristic of these forms. This classification of
bands is given in Table 3.
The band appearing in infra-red and Raman spectra of
which are not appreciably affected by conformational amorphous and liquid PET at 530 cm -1 might, in
structure or crystallinity of PET.
Bands of type II may be either characteristic of the tTt
conformational structure of PET, or they may be Tab/e 3 Bands of type III of poly(ethylene terephthalate) (PET)
connected with the ordering of PET molecules in and analogous bands of ethyleneglycol dibenzoate (EDB)
crystalline domains. In Table 2 the infra-red and Raman PET p (cm - 1 ) EDB u (cm - 1 )
lines of PET can be divided into two groups. The first of I.r. Raman I.r. Raman
these contains bands and lines which correspond to those
calculated by Boerio et al. is for the planar structure of 1554 a
PET. When bands of this type can be observed in 1456 c 1455 c 1461 1463
1443 d 1443 d 1438 1440
vibrational spectra of liquid and amorphous samples, 1412 c 1416
they are shifted by 1-7 cm -1 with respect to their 1407 asd 1404
positions in the crystalline state. As all these lines are 1374 1374 1370 1370
sensitive to conformational and therefore also to 1139
1043 c 1046 1040
geometrical structure of the monomeric unit, these shifts
1031
indicate that the geometrical structure of the t Tt form of 935 a 935as
PET in the amorphous state differs somewhat from the 898 899
structure in the crystadline state. 886 882 884
From infra-red spectra of amorphous and crystalline 830
811 ad 810 d 816 813
PET which were normalized to equal intensities of 619 a 617 a
conformationally insensitive bands, the content of the t Tt 532 530 a 522 522
form was estimated from the factor necessary for digital 408 a
subtraction of the crystalline from the amorphous 340 d 335 335
300
component of the spectrum, yielding 10___3% of tTt. An 235
analogous procedure yielded 7 + 3% of t T t form in the 215
solution of PET.
The other group of vibrational bands of type II, marked All bands of PET shown in this Table are characteristic of G
conformational structures
in Table 2 by the index t, contains those bands which
a Poorly defined bands
cannot be assigned to any calculated mode of the tTt s Bands appearing only in solution
structure, and which can be observed only in the spectra c Bands corresponding probably to Gt forms
of crystalline samples as weak or very weak bands. These d Bands corresponding probably to Gg forms

718 POLYMER, 1982, Vol 23, May

 Spectroscopic study of PET conformation." J. ~tokr et al.

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POLYMER, 1982, Vol 23, May 719

Spectroscopic study of PET conformation." J. Stokr et al.

analogy with the vibrational spectra of model amorphous states indicates that, similarly as in
compounds, indicate a small amount of the ethyleneglycol dibenzoate, the bands appearing in infra-
conformational form with the plane of the ester group red and Raman spectra of liquid and amorphous samples
twisted out of the plane of the benzene ring. in consequence of the loss of the centre of symmetry on the
Bands of type IV are summarized in Table 4. These ethyleneglycol fragment, are bands characteristic of the
bands have the property that at the wavenumber of a occurrence of G forms. This interpretation is indicated in
conformationally sensitive band in infra-red spectra, a Table 4.
conformationally insensitive band is found in Raman In Table 4 are also included Raman bands at 1018 and
spectra, and vice versa. This indicates that the 1103 cm- 1 which are interpreted as characteristic of the
conformational isomers corresponding to these occurrence of CBisomers, and bands at 385,430, 498, 1250
wavenumbers in the spectra of liquid and amorphous and 1270 cm- 1, which are interpreted as characteristic of
PET differ from the tTt conformational form present in the occurrence of G isomers, even though these bands
the crystalline state by the activity of bands in infra-red have no analogy in vibrational spectra of model
and Raman spectra, while the vibrational interactions, compounds. This classification has been adopted only on
and therefore also the position of the bands, remains the the basis of the vibrational interpretation of these bands
same as in the tTt conformation. (Table 1) and is not unequivocal.
Bands of this type are also observed in vibrational In addition, Table 4 also contains bands for which, even
spectra of model compounds 21-23. In dimethyl on the basis of vibrational interpretation, a decision about
terephthalate and diethyl terephthalate, these bands are their connection with TB-CB isomerism, or occurrence of
sensitive to the mutual cis-trans isomerism of ester groups G forms cannot be made.
(Cs-Ts), due to the presence of the centre of symmetry in
the centre of the benzene ring in TB isomers, and to its CONCLUSIONS
absence in Ca isomers. Type IV bands of PET, with
wavenumbers coinciding with those CB isomers of Bands of infra-red and Raman spectra characteristic of
dimethyl terephthalate and diethyl terephthalate, can also the various conformational forms appearing in
in PET be assigned to CB isomers, and this assignment is amorphous and liquid poly(ethylene terephthalate) (PET)
shown in Table 4. This structural interpretation is in are summarized in Tables 2-4. It was found that most of
agreement with the assignment of these bands to these bands also appear in vibrational spectra of liquid
vibrational modes (Table 1) in which coordinates of C and samples of model compounds (methyl benzoate, dimethyl
H atoms of the benzene ring predominate. All bands of the terephthalate, ethyl benzoate, diethyl terephthalate and
C a isomer are very weak and therefore it is difficult to ethyleneglycol dibenzoate).
make an estimate of the population of this conformer in The relative intensities of conformationally sensitive
amorphous and liquid PET. As the ratio of the intensities and conformationally insensitive bands in vibrational
of bands characteristic of the form Ca to the intensities of spectra of PET indicate that the contents of the tTt form
conformationally insensitive bands in amorphous and in the solution of PET (7~o) is equal within experimental
liquid PET is approximately equal as in DMT and DET, error to the contents of this form in liquid ethyleneglycol
it may be assumed that similarly as in the model dibenzoate; evidently also for the TB-CB conformers
compounds, the population of the T8and CBconformers is differing by mutual orientation of the carbonyl groups on
approximately equal both in liquid and in amorphous the benzene ring, the population of these conformers in
PET. amorphous and liquid PET is similar as in the model
Bands of type IV are also observed in ethyleneglycol compounds (DMT, DET) where the population of these
dibenzoate. In crystalline ethyleneglycol dibenzoate these conformers in the liquid state is comparable. In
bands occur at 1120, 481 and 353 cm -1 in infra-red vibrational spectra of PET in solution, bands of gG and tG
spectra, and at 1099 and 391 cm-1 in Raman spectra. In forms can be identified, similarly as in vibrational spectra
this case the described behaviour of these bands is due to of liquid ethyleneglycol dibenzoate.
the presence of the centre of symmetry in the Analysis of 13C n.m.r, spectra of PET in solution has
ethyleneglycol fragment in the planar structure of the shown that the population of the t conformational forms
crystalline state, and by the loss of this centre of symmetry (Pt =0.74___0.07~o) and g conformational forms is equal,
in the liquid state where practically only nonplanar within experimental error, as in ethyl benzoate. Based on
conformers are present. As the loss of the centre of these results it may be assumed that the population of the
symmetry manifested in infra-red spectra of liquid basic conformational forms of PET in the liquid state is
samples of ethyleneglycoldibenzoate is almost exclusively approximately equal as in the model compounds, with
connected with the occurrence of G conformational forms approximately 63~o of form tGt, 26~o of form tGg, and 7~
(the content of tTg and gTg forms is very small), the of form t Tt. The populations of the other conformational
Raman bands at 1114, 487 and 353 cm- ~and the infra-red forms (gGg, tGg, gTg) are very low.
bands at 1097 and 280 cm -1 in liquid ethyleneglycol The vibrational spectra of amorphous PET indicate
dibenzoate may be described as bands characteristic of that the conformational structure of the amorphous state
the G conformational forms. does not significantly differ from the conformational
In vibrational spectra of PET, those bands of group IV structure of PET in solution.
which are assigned to vibrational modes in which
coordinates of the ethyleneglycol fragment predominate,
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conformational forms of PET in the liquid and 4 Krimm, S. Adv. Polym. Sci. 1960, 2, 51

720 POLYMER, 1982, Vol 23, May

 v

Spectroscopic study of PET conformation." J. Stokr et al.

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