Universal (Switchable) RAFT Agents

The polymerization of most monomers that are polymerizable by radical polymerization can be controlled by the reversible addition-fragmentation chain transfer (RAFT) process. However, it is usually required that the RAFT agent be selected according to the types of monomer being polymerized. Thus, RAFT agents (dithioesters, trithiocarbonates) suitable for controlling polymerization of "more activated" monomers (MAMs; e.g., styrene, acrylates, methacrylates, etc.) tend to inhibit polymerization of "less activated" monomers (LAMs; e.g., vinyl acetate, N-vinylpyrrolidone, etc.). Similarly RAFT agents suitable for polymerizations of LAMs (xanthates, certain dithiocarbamates) tend to give little or poor control over polymerizations of MAMs. We now report a new class of "switchable" RAFT agents, N-(4-pyridinyl)-N-methyldithiocarbamates, that provide excellent control over polymerization of LAMs and, after addition of 1 equiv of a protic or Lewis acid, become effective in controlling polymerization of MAMs, allowing the synthesis of poly(MAM)-block-poly(LAM) with narrow molecular weight distributions.