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Cation radical chain cycloaddition polymerization and cationic macrocyclopolymerization
Author(s) -
Bauld Nathan L,
Gao Daxin
Publication year - 2000
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/(sici)1097-0126(200003)49:3<253::aid-pi352>3.0.co;2-p
Subject(s) - cationic polymerization , cycloaddition , polymerization , moiety , chemistry , electrophile , living free radical polymerization , polymer chemistry , radical polymerization , cobalt mediated radical polymerization , steric effects , ionic polymerization , monomer , chain transfer , anionic addition polymerization , photochemistry , organic chemistry , polymer , catalysis
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. © 2000 Society of Chemical Industry