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The Infra-red Spectrum of Syndiotactic

Polypropylene
I. J. GRANT and I. M. WARD

The infra-red spectrum of syndiotactic polypropylene is reported, and com-


parison made with that of the isotactic polymer. It is concluded that several
o f the absorption bands in the range 1 500 c m - ~ to 200 c m - 1 are characteristic
of the portions o f chains in the syndiotactic helical configuration, and therefore
give an empirical measure of the stereoregularity.

IN A previous publication 1 the infra-red (i.r.) spectra of isotactic and atactic


polypropylene were described. Assignments for the principal vibrations
were attempted following the preliminary analysis of the isotactic poly-
propylene spectrum proposed by PeraldoL Similar attempts have also been
made by Krimm ~, Tobin 4, and Liang, Lytton and Boone 5. With the
exception of Tobin it is assumed that the multiplicity of absorptions arises
from the interactions between modes of vibration of different units within
a chain molecule rather than between units belonging to different chain
molecules.
The present communication describes the measurement of the i.r. spectrum
of syndiotactic polypropylene and considers the general assignment of
absorptions in both the isotactic and syndiotactic polymers.

EXPERIMENTAL
Preparation of samples
The spectrum of isotactic polypropylene was obtained' from a standard
commercial grade moulding powder and the atactic polymer spectrum was
obtained from a polymer prepared with a non-stereospecific catalyst. The
syndiotactic spectrum was obtained from an experimental sample of polymer
prepared by a method similar to that described by Natta et al?. To confirm
that this polymer was primarily syndiotactic high resolution proton magnetic
resonance (p.m.r,) spectra and X-ray diffraction spectra were obtained.
Figure 1 is a high resolution p.m.r, spectrum of the syndiotactic poly-
propylene used for the i.r. spectra. This p.m.r, spectrum was obtained from
a 15% w / v solution of the polymer in orthodichlorobenzene at 140°C using
a Varian Associates A60 spectrometer. This spectrum shows the presence
of equivalent methylene protons only, as would be expected for syndiotactic
polymer 7, the more complicated ABC2 type spectrum for isotactic polymer
being absent within the sensitivity of the spectrometer. In a similar manner
the X-ray diffraction photographs showed reflections identical to those
described by Natta et al. 8 for syndiotactic polymer and complete absence
of reflections expected for isotactic polymer.
Measurement of i.r. spectra
The i.r. spectrum of isotactic polypropylene was recorded using films of
thickness 0.15mm to 1.0mm. The i.r. spectra of the syndiotactic and
223
I. J. G R A N T and I. M. WARD

Figure 1---60 Mc/s proton


magnetic resonance spectrum
of a 15 per cent w/v solution
of syndiotactic polypropylene
in or tho-dichlorobenzene at
140"C
%

I I I I I I
125 100 75 50 25 0
Frequency, c / s

100
(a) (b)
80

60

40

20
I I ¢~ I

80

60
0

~- ~o
0
ul
~ 20
I I I T I I I I
3100 3000 2900 2800 2700
Wavenumber, cm -1
80

60
Figure 2--Infra-red spectra of the
40 3 I00 cm - t to 2700 cm -1 region
of: (a) Syndiotactic polypropy-
20 lene, 25"C; (b) Isotactic poly-
propylene, 25"C; (c) Molten syn-
0 r i diotaetic polyproylene; (d) Molten
3100 30100 29100 2800 2700 isotactic polypropylene; (e) Atactic
Wavenumber, cm -1 polypropylene, 25" C
224
THE INFRA-RED SPECTRUM OF SYNDIOTACTIC POLYPROPYLENE

I00

60
40
20
l I r "i I ~ l i I I

8040
GO (b)

20
I I I ~ I I I I T I I

.-~ (c)
c" 8 0
._o 60
n
i/i~) 40
20 j J
r [

8040_60(d) l ~

20~ - ~
I r i I J f i I I r

80- (e)
GoL-
40
20 ~
I 1 I I I r I I I r
5.0 G-O 7.0 8-0 9"0 10"0 11.0 12'0 13"0 14'0 15-0
WaveLength, p
Figure 3--Infra-red spectra of the 2000 crn-1 to 666 cm-1 region of: (a)
Syndiotactic polypropylene, 25°C; (b) Isotactic polypropylene, 25°C; (c) Molten
syndiotactic polypropylene; (d) Molten isotactic polypropylene; (e) Atactic
polypropylene, 25"C

atactic polymer samples were recorded using films of thickness 0.15 mm


to 0-3 mm supported between rocksalt plates of 4 m m thickness in the
4 000 cm -1 to 666 cm -t spectral region, In the 666 cm -1 to 222 cm -1 region
the syndiotactic spectrum was recorded using unsupported films of 0"5 mm
to 1-0 mm thickness. The molten spectra of syndiotactic and isotactic poly-
propylene were obtained from films supported between rocksalt plates
225
I. J, G R A N T and I. M. W A R D

100
(a)
80

to ¢,~
to a-)
40-

C 2O
~. 0 J ~ a t J I I l I I I I I I I I

60

40

20' ~
~ L I t i I [ I [ I J I I I I ]
0 1 19 23 27 31 35 39 43
WaveLength, ~,

Figure 4--Infra-red spectra of the 666 cm -~ to 222 crn -z region of: (a) Syndiotactic
polypropylene, 25°C; (b) Isotactic polypropylene, 25°C

placed in a thermostatically controlled oven maintained at a temperature


20 ° above the melting point of the polymer.
The i.r. spectra were measured using a Grubb Parsons single beam
spectrometer Type $3 equipped with a rocksalt prism for the region
1 500cm -1 to 6 6 6 c m -1 and a lithium fluoride prism for the region
4 000 cm -1 to 1 500 cm-L In addition spectra were obtained for the range
666 cm -1 to 222 cm -1 using a Grubb Parsons DM4 Spectrometer (with the
cooperation of Dr A. E. Martin). In the region 4 000 cm -x to 666 cm -~ the
spectrometer was calibrated against gas samples contained in a 10 cm gas
cell and in the region 666 cm -1 to 222 cm -1 atmospheric water vapour was
used to calibrate the instrument.
RESULTS
The i.r, spectra of syndiotactic, isotactic and atactic polypropylene along
with the spectra of molten syndiotactic and molten isotactic polypropylene
are shown in Figure 2 for the 3 100 cm -1 to 2 700 cm -1 region and in
Figure 3 for the 2 000 cm -1 to .666 cm -1 region. Figure 4 shows the spectra
of syndiotactic and isotactic polypropylene for the 666 cm -1 to 222 cm -1
spectral region.
The frequencies of the absorption bands together with indications of
their intensity and tentative assignment are listed in Tables 1 and 2 for
syndiotactic and isotactic polypropylene respectively. Table 1 also records
the frequencies observed in the molten spectrum together with indications
of their intensities.
DISCUSSION
(i) Comparison of solid phase spectra
It can be seen that although the principal internal carbon-hydrogen
stretching and bending vibration absorptions of the isotaetic and syndiotactic
226
THE INFRA-RED SPECTRUM OF SYNDIOTACTIC POLYPROPYLENE

T a b l e 1. Characteristics of syndiotactic polypropylene absorption bands

Frequency Relative Frequency Relative


cm - ~ strength above m.pt strength Tentative assignment

2955 S 2955 S Asymm.--CH 3 stretching


2923 S 2920 S Asymm. ---CH 2 stretching
2882 Sh. 2X---CH2 bending
2869 Sh. 2869 Sh. Symm. ----CHa stretching
2841 S 2839 S Symm. - - C H 2 stretching
2809 W 2809 W - 4 2 H stretching
1461 S 1457 S Asymm. ---CH3 bending
1437 Sh. 1437 Sh. ---CH2 bending
1376 S 1378 S Symm. - - C H 3 bending
1369 Sh. 1369 Sh.
1347 Sh.
1332 W
1311 W
1290 W
1262 W
1242 W
1229 W 1229 W
1200 W 1205 W
1162 M
1154 M 1155 M - - C H 3 wagging (amorphous)
1128 W
1083 W
1061 W
1034 W
1002 M
976 S 972 M
963 M 961 M
935 W
905 W 899 W
868 M 868 vW
839 W 835 W
811 M 816 W
775 W
750 W
567 W Water vapour absorption
537 W
484 M
469 M
431 W
344 W
(S--strong, M--medium, W--weak, Sh.--shoulder, *--not determined in this work.)

p o l y m e r s are v e r y similar, there are considerable differences in the range


1 500 c m -x to 220 c m -1. It is p a r t i c u l a r l y noticeable that the ab so r p t i o n s
at 1 1 6 7 c m -1, 9 9 7 c m -x and 841 c m -1 w h i c h are considered b y some
w o r k e r s ~,9 to be associated with the threefold helix of isotactic poly-
p r o p y l e n e are absent f r o m the spectrum of the syndiotactic polymer. T h e
spectrum of t h e syndiotactic p o l y m e r does, however, contain a considerable
227
I. J. GRANT and I. M. WARD

Table 2. Characteristics of isotactic polypropylene absorption bands


Frequency Relative Frequency
cm-1 strength above m.pt Assignment (Re[. 1)
2958 S 2956 Asymm. - - C H a stretching
(A and E modes)
2923 S 2915 Symm. - - ~ H 3 stretching
2881 S 2X--CHz bending
2869 S 2871 Symm. - - ~ H a stretching
2839 S 2844 Symm. ---CH 2 stretching
2810 W 2810 ---CH stretching
1458 1451 Asymm. - - C H 3 bending
(A and E modes)
1440 Sho - - C H 2 bending (E)
1377 S 1373 Symm. ----CH3 bending (E)
1360 M 1353 ---CH bending (E)
1329 W 1317 ----CH~ wagging (E)
1303 W ---CH bending (A)
1297 W ----CH2 twisting (E)
1255 W 1248 ---CH wagging (A)
1219 W - - C H wagging (E)
1168 S
1153 Sh. 1150 - - C H 3 wagging (amorphous)
1103 W 1100
1045 W
997 S 996
972 S 971
940 W
899 W 897
841 S 830
809 M 810
567 W Water vapour absorption
528 M
458 S Assignments of these bands
398 M not attempted by McDonald
322 W and Ward 1
247 W
(S---strons, M - - m e d i u m . W - - w e a k , Sh.----shouldcr. *--not determined in this work.)

n u m b e r of a b s o r p t i o n s which are n o t present in the m o l t e n spectrum.


T h e s e occur at 1 332, 1 311, 1 290, 1 262, 1 242, 1 162, 1 128, 1 083, 1 034,
1 002, 935, 867"5 a n d 811 c m -1 a n d we consider that they are characteristic
of the syndiotactic helix.
T h e n u m b e r of f u n d a m e n t a l v i b r a t i o n s for a r e p e a t unit of a p o l y p r o p y l e n e
helix is ( 3 N - 4 ) where N is the n u m b e r of a t o m s in one c o m p l e t e t u r n
of the helix. F o r isotactic p o l y p r o p y l e n e , with three m o n o m e r units in
o n e c o m p l e t e t u r n of t h e helix ~°, ( 3 N - 4 ) = ( 3 x 2 7 - 4 ) = 7 7 modes of
v i b r a t i o n a n d for syndiotactic p o l y p r o p y l e n e with a b i n a r y helix 7 consisting
of four m o n o m e r units in a c o m p l e t e turn this analysis yields
(3 x 36 - 4) = 104 m o d e s of vibration. C o m p a r i s o n of the u n p o l a r i z e d spectra
of isotactic a n d syndiotactic p o l y p r o p y l e n e , shown in Figures 2 a n d 3,
clearly shows that there are m a n y m o r e e x t e r n a l v i b r a t i o n s in the syndio-
228
THE INFRA-RED SPECTRUM OF SYNDIOTACTIC POLYPROPYLENE

tactic spectrum compared with the isotactic spectrum. The ( 3 N - 4 ) analysis


for the number of fundamental modes of vibration indicates that the ratio
of the number of isotactic modes to syndiotactic modes is 77/104=0"74.
In the spectral range 4 0 0 0 c m -~ to 220cm -1, for unpolarized spectra,
there are 30 isotactic absorption bands and 39 syndiotactic absorption bands
which yield an isotactic to syndiotactic ratio of 0.77. The close agreement
of calculated and observed ratios suggests that this approach to assigning
the modes of vibration in a syndiotactic polypropylene helix is substantially
correct.

(ii) Comparison of molten and atactic spectra


Comparison of molten isotactic, molten syndiotactic and atactic spectra
shows that, in the first place, the three are approximately similar. Several
absorption bands which are characteristic either of the isotactic or syndio-
tactic polymer disappear or are reduced in intensity on melting but return
to their original intensity upon cooling. One common feature of these
spectra is the bands at 1 155 cm -1 and 973 cm -~ which retain their original
intensity on melting. These two bands are found in the i.r. spectra of all
steric forms of polypropylene whether in a solid or in a molten state sug-
gesting that these bands derive from the chemical rather than the structural
nature of polypropylene.
Subsidiary differences are observed between the molten spectra and
that of the atactic polymer. It is interesting to note that the molten syndio-
tactic and atactic spectra are very closely similar and differ significantly
from the molten isotactic spectrum. For example in both the molten
syndiotactic and atactic spectra the absorption ca. 973 cm -~ appears as a
doublet s with peaks at 976 and 963 cm -1 and bands in the 1 200cm -~
region appear to be very similar. This suggests first that the pattern of
stereoregularity in the atactic polymer, although not sufficiently regular to
allow .crystallization is nearer to that in a syndiotactic rather than an
isotactic polymer; and secondly that certain absorptions are observed in
the molten state which are characteristic of the chain configurations of
syndiotactic and isotactic polymers, even though the absorptions character-
istic of the different types of helix are no longer present. This interpretation
was confirmed by the similarity of the p.m.r, spectra of syndiotactic and
atactic polymers.

(iii) Conclusion
In the previous publication from this laboratory 1 McDonald and Ward
following Perald& and Krimm 3 assumed that both the internal and external
modes of vibration would be affected by the intramolecular interactions.
On the other hand, Liang, Lytton and Boone 5 assumed that only the
external modes of vibration would be affected.
These unpolarized spectra of syndiotactic polypropylene do not throw
any further light on this particular controversy. The present investigation
does, however, suggest that the approach of considering several of the
absorptions in the 1 500 to 220 cm -1 region as arising from interactions
within the helix to be a correct one. Furthermore, in syndiotactic polymer, as
229
I. J. GRANT and I. M. WARD

in isotactic polymer, certain absorptions characterize the portions of chains


existing in the helical configuration and therefore give an empirical measure
of the stereoregularity. This measure will depend on the presence of at least
four m o n o m e r units being alternately d and 1 substituted, as against
three being identically substituted in the isotactic case.
(Received A u g u s t 1964)
Research Department,
I C I Fibres Ltd,
H o o k s t o n e R o a d , Harrogate

REFERENCES
1 McDON^LO, M. P. and WARD,I. M. Polymer, Lond. 1961, 2, 341
2 PERALDO, M. Gazz. chim. ital. 1959, 89, 798
3 KmMM, S. Advanc. Polym. Sci. 1960, 2, 51
4 TOBIN,M. C. J. phys. Chem. 1960, 64, 216
LI.~O, C. Y., LYTTON,M. R. and BOONE,C. J. 1. Polym. Sci. 1961, 54, 523
N^TrA, G., PASQUON,I. and ZAMBF-LLI,A. J. Polym. Sci., Part C, Polymer Symposia
No. 4, p 411
r TINCnER, W. C., American Chemical Society Division of Polymer Chemistry, Papers
presented at Atlantic City Meeting Vol. III, p 142, 1962
s NArr^, G., PASQUtm, I., C o ~ I ~ , P., PERJa_DO,M., I~OORARO,M. and Z~B~LLI,
A. Atti. Accad. Lincei, 1960, 28, 539
9 BRADER, J. J. J. appl. Polym. Sci. 1960, 3, 370
lo Nm'rA, G., CORRADINI,P. and CESAm, M. Atti Accad. Lincei, 1'956,21, 365

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