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Computer-aided design of a destabilized RAFT adduct radical: Toward improved RAFT agents for styrene-block-vinyl acetate copolymers

Coote, M.L. and Henry, D.J. (2005) Computer-aided design of a destabilized RAFT adduct radical: Toward improved RAFT agents for styrene-block-vinyl acetate copolymers. Macromolecules, 38 (13). pp. 5774-5779.

Link to Published Version: http://dx.doi.org/10.1021/ma050415a
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Abstract

High-level ab initio molecular orbital calculations indicate that a fluorine Z substituent significantly destabilizes the RAFT adduct radical, R'SO•(Z)SR, relative to known Z substituents. This destabilization of the RAFT adduct radical lowers the fragmentation enthalpy relative to normal dithioesters, but without stabilizing the C=S bond of the product RAFT agent, as in xanthate- or dithiocarbamate-mediated polymerization. On the basis of these calculations, it is predicted that, provided appropriate R groups are chosen, RAFT agents containing fluorine Z substituents (i.e., S=C(F)SR, fluorodithioformates, or "F-RAFT" agents) should provide a basis for improved control of monomers with reactive propagating radicals (such as vinyl acetate) and should have the advantage that their C=S bonds remain reactive enough for control of monomers with more stable propagating radicals (such as styrene) and hence the production of styrene-vinyl acetate copolymers.

Publication Type: Journal Article
Publisher: American Chemical Society
Copyright: © 2005 American Chemical Society
URI: http://researchrepository.murdoch.edu.au/id/eprint/4981
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