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The effect of copolymerization on stereoregular polyvinyl chloride

✍ Scribed by Rosen, Irving ;Marshall, W. E.

Publisher
John Wiley and Sons
Year
1962
Weight
327 KB
Volume
56
Category
Article
ISSN
0022-3832

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✦ Synopsis

Abstract

Copolymers of vinyl chloride and vinyl acetate were prepared by tributylboroncatalyzed polymerizations at βˆ’15 and βˆ’40Β°C. The Alfrey‐Price equations were used to calculate the monomer reactivity ratios to be expected in a free‐radical propagation at βˆ’40Β°C. The experimentally determined monomer reactivity ratios were in good agreement with the theoretical values and support the concept of free‐radical initiation by the tributylboron catalyst. Vinyl acetate interrupts the regular polymer sequences in polyvinyl chloride and interferes with the crystallizability of the polymer. The infrared D~635~/D~692~ absorbance ratio of the copolymers decreased approximately linearly with vinyl acetate content. The activation energy difference between syndio‐ and isotactic placements was calculated to be about 0.3 kcal./mole.

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