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Cation radical chain cycloaddition polymerization: a fundamentally new polymerization mechanism
Author(s) -
Bauld Nathan L.,
Gao Daxin,
Aplin J. Todd
Publication year - 1999
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199911)12:11<808::aid-poc207>3.0.co;2-m
Subject(s) - chemistry , cycloaddition , polymerization , moiety , intramolecular force , chain transfer , cobalt mediated radical polymerization , intermolecular force , alkene , polymer chemistry , radical polymerization , photochemistry , kinetic chain length , living free radical polymerization , monomer , polymer , molecule , organic chemistry , catalysis
Cation radical chain cycloaddition polymerization, a fundamentally new addition polymerization method involving cation radical intermediates in each propagation step, is described and demonstrated. The cycloaddition reactions of appropriately constituted difunctional monomers, catalyzed by tris(4‐bromophenyl)aminium hexachloroantimonate in dichloromethane solvent at 0 °C, is shown to afford polymers having average molecular weights of up to 150 000. Both cyclobutanation and Diels–Alder polymers were obtained in this way. The surprising efficiency of these polymerization reactions is believed to be the result of rapid intramolecular hole transfer from the site at which the hole is originally generated in the cycloaddition step to a reactive, terminal alkene moiety. Consequently, chain propagation is much more efficient than in the cycloadditions of corresponding monofunctional compounds, which necessarily involve intermolecular hole transfer. Copyright © 1999 John Wiley & Sons, Ltd.