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Blending the Effectiveness of Anionic Polymerization with the Versatility of RAFT by Use of the Atom Transfer Radical Addition–Fragmentation Technique
Author(s) -
Forrester Michael J.,
Bradley William,
Lin FangYi,
Hernández Nacú B.,
Williams R. Chris,
Kraus George,
Cochran Eric W.
Publication year - 2019
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201900065
Subject(s) - chain transfer , reversible addition−fragmentation chain transfer polymerization , raft , chemistry , living free radical polymerization , polymerization , living polymerization , radical polymerization , polymer chemistry , atom transfer radical polymerization , anionic addition polymerization , copolymer , fragmentation (computing) , ionic polymerization , photochemistry , polymer , organic chemistry , computer science , operating system
The efficient conversion of a living anionic polymer chain end to a macrochain transfer agent suitable for reversible addition–fragmentation chain transfer (RAFT) polymerization is reported. Conversion to the macrochain transfer agent efficiency reached as high as 97% by capping the polyanion with alcohol, coupling with α‐bromoisobutryl bromide, followed by atom‐transfer radical addition–fragmentation with bis(thiobenzyl)disulfide to add the chain transfer agent functionality. To our knowledge, this is the most efficient marriage of anionic and reversible addition–fragmentation transfer polymerization reported to date, and can be carried out under common industrial processing conditions. The combination of these polymerization methods broadens the scope of commercially accessible block copolymers by exploiting the advantages of both RAFT and anionic polymerization chemistries.