Programmed Synthesis of Copolymer with Controlled Chain Composition Distribution via Semibatch RAFT Copolymerization

It is well-known that controlled/living radical copolymerization (CLRcoP) yields gradient copolymer with the composition varying along chain length. The composition distribution of the as-synthesized product is solely determined by the comonomer reactivity ratios and is thus not well controlled. This work reports the first experimental example of the control over the copolymer composition distribution through semibatch operations. Using styrene (St)/butyl acrylate (BA) as a model system, we synthesized uniform and linear gradient copolymers via semibatch reverse addition−fragmentation chain transfer radical polymerization (RAFT) mediated by benzyl dithioisobutyrate. The comonomer feeding rate profiles for the targeted distributions were designed from a newly developed computer model that was trained from the batch RAFT copolymerizations of St and BA at different monomer compositions. The semibatch copolymerization yielded precise copolymer products having their composition distributions exactly as targeted and the polymerization rate and molecular weight profiles as predicted by the model.