By Arthur Woodward, Frank Bovey
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Additional info for Polymer Characterization by ESR and NMR
A2, 1972, 10, 1415. RECEIVED July 7, 1980. ; ACS Symposium Series; American Chemical Society: Washington, DC, 1980. -L. YANG, J. LIUTKUS, and H. HAUBENSTOCK Chemistry Department, The City University of New York, College of Staten Island, Staten Island, NY 10301 Poly(vinyl chloride), PVC, is today one of the top three most widely used thermoplastic materials Chemically this polymer is one of the leas broad scope of its application possibl y throug the development of proper technology for the processing of the polymer and the use of suitable stabilizers.
The most important v a r i a b l e s were polymerizat i o n temperature and % conversion. Chain t r a n s f e r to monomer i s the c o n t r o l l i n g f a c t o r i n determining the molecular weight of the polymer. For PVC, a decrease i n i r r a d i a t i o n time w i l l cause a decrease i n % conversion. This w i l l minimize branching s i n c e the branching mechanism i n v o l v e s chain t r a n s f e r t o polymer (10,11). Conversions of l e s s than 10% were shown to preclude branching i n bulk polymerized v i n y l c h l o r i d e at -10° to 30°C (12) .
100,000. Aside from c r y s t a l l i n i t y and branch cont e n t , these polymers should d i f f e r only i n number of end groups per u n i t weight of sample. D i s p r o p o r t i o n a t i o n r e a c t i o n s o f t e n terminate a growing PVC chain (17), r e s u l t i n g i n unsaturated chain ends. These chain ends may be a b l e to i n i t i a t e degradation by p r o v i d i n g l a b i l e a l l y l i c atoms f o r cleavage by UV. The net e f f e c t of v a r i a b l e molecular weights i s to p r o v i d e correspondi n g l y v a r i a b l e numbers of end groups.