Reversible Addition-Fragmentation Chain-Transfer Polymerization of Vinyl Monomers with N,N-Dimethyldiselenocarbamates

A new range of selenium-based reversible addition-fragmentation chain-transfer (RAFT) agents is described and tested in the polymerization of styrene, acrylates, vinyl esters, and N-vinylcaprolactam. The synthesized N,N-dimethyldiselenocarbamates were poor control agents for styrene polymerization, whereas polyacrylates of controlled molar masses and bearing a diselenocarbamate terminal group could be synthesized. The polymerization of vinyl acetate and vinyl pivalate proceeded in a controlled manner as confirmed by size-exclusion chromatography, matrix-assisted laser desorption ionization-time-of-flight mass spectrometry, and Se-77 NMR analyses. The capability of these RAFT agents to control the polymerization of both more-activated monomers and less-activated monomers was exemplified through the synthesis of a poly(t-butyl acrylate)-b-poly(vinyl acetate) diblock copolymer. Considering the very broad range of carbamate groups which can be envisioned, this finding opens numerous perspectives for diselenocarbamate-mediated RAFT polymerization with its specificities yet to be explored. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4361-4368