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Cation radical chain cycloaddition polymerization and cationic macrocyclopolymerization

✍ Scribed by Bauld, Nathan L; Gao, Daxin

Publisher: John Wiley and Sons
Year: 2000
Tongue: English
Weight: 108 KB
Volume: 49
Category: Article
ISSN: 0959-8103
DOI: 10.1002/(sici)1097-0126(200003)49:3<253::aid-pi352>3.0.co;2-p

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✦ Synopsis

Strategies for accelerating cation radical chain polymerization are proposed and implemented. In one approach, unsymmetrical monomers are prepared which have a propenyl group to provide facile ionization by the aminium salt initiator and a vinyl group to provide diminished steric effects resulting in an acceleration of the cycloaddition step in the propagation cycle. This strategy results in dramatic increases in cation radical chain polymerization rates, but cationic cyclopolymerization generating 15-membered rings (macrocyclopolymerization) is competitive because of the ease of electrophilic attack on the electron rich, unhindered, vinyl moiety. A successful strategy for accelerating cation radical cycloaddition polymerization selectively is then proposed and demonstrated.

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