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Polypropylene
I. J. GRANT and I. M. WARD
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
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
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
(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
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
230