RAFT Polymerization of Vinyl Acetate, Styrene and Acrylates UsingN,N-Dithiocarbamates

Homo- and block-copolymers comprised of vinyl acetate, styrene, methyl acrylate and tert -butyl acrylate monomers were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization using N,N -dithiocarbamates as transfer agents. Of the RAFT agents studied, malonate N,N -diphenyldithiocarbamate was able to produce poly(vinyl acetate) with number average molecular weights of over 50,000 and polydispersities less than 1.5. This same RAFT agent was also able to produce polystyrene and polyacrylates with reasonable control (i.e. predictable molecular weights and polydispersities less than 1.5). Thus, the one RAFT agent was used to make block copolymers of poly(methyl acrylate) and poly(vinyl acetate). The order of monomer polymerization was found to be vital in determining the success of the block copolymerization.