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 ⁷⁷Se 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. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4361–4368