Investigation of the free radical polymerization of styrene in the presence of several 1,1‐disubstituted ethylenes

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Department of Chemistry


A variety of 1,1‐disubstituted ethylenes, having an electron‐withdrawing (capto) and an electron‐donor (dative) substituent on the same carbon, were synthesized and added to styrene polymerizations. The dative substituents investigated were alkoxy or alkylcarbonate. After the addition of a polystyryl radical to a disubstituted ethylene, the resulting alkoxy or carbonate radicals could potentially fragment, resulting in chain termination and the formation of alkyl radicals. This process is called addition‐fragmentation chain transfer (AFCT). The polymers produced during this study were examined for evidence of copolymerization and AFCT. The relative stability of the radicals generated by the fragmentation process appears to be the predominant factor controlling the ratio of copolymerization versus AFCT.

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Copyright © 1993 John Wiley & Sons, Inc. Publisher’s version of record:

Publication Title

Journal of Polymer Science Part A: Polymer Chemistry