Synthesis of α,ω-isocyanate telechelic polymethacrylate soft segments with activated ester side functionalities and their use for polyurethane synthesis

The synthetic route for the preparation of ,-isocyanate-telechelic poly(methyl methacrylate-co-acryloxysuccinimide) and ,- isocyanate-telechelic poly(methyl methacrylate-co-acrylamidohexanoic succinimide) soft segments is presented. The strategy includes reversible addition fragmentation chain transfer (RAFT) copolymerization and two post polymerization modification steps. The RAFT polymerizations result in copolymers with an activated ester proportion within the polymer chains of 8% N-acryloxysuccinimide and 5% 6-acrylamidohexanoic succinimide. The reactivity ratios of the monomer pairs were determined. In a first post polymerization reaction carboxylic acid homo telechelic polymers were prepared by reacting the -dithiobenzoate end-group with an excess of azobis(cyanovaleric acid). In a second modification step the - and -carboxylic acid end-groups were reacted with hexamethylene diisocyanate and 100% isocyanate telechelic copolymers were obtained. Finally segmented polyurethanes were prepared by coupling hexamethylene diisocyanate (HDI) end capped soft segments with hard segments composed of 1,4-butanediol and HDI. (c) 2013 Society of Chemical Industry