A novel bifunctional trithiocarbonate for styrene and methacrylate RAFT polymerization

摘要

The synthesis of butane-1,4-bis(phenylacetonitrile trithiocarbonate) and its application as a new chain transfer agent for controlled radical polymerization is reported. It is a bifunctional trithiocarbonate for the polymerization of methacrylates, and styrenic monomers and therefore a novel type of RAFT agent. Linear growth of molar masses with conversion and narrow molecular weight distributions are obtained. ABA triblock copolymers are successfully synthesized in two steps. MALDI-TOF MS and SEC prove the living character of the polymers and uniform growth of both functionalities. The pre-equilibrium kinetics are analyzed by SEC to determine transfer coefficients. The P(GMA) blocks are used as precursor for polymer-analogous reactions. The synthesis of a missing piece in the list of RAFT agents, a bifunctional trithiocarbonate that is suitable for the polymerization of methacrylates, is described. It is based on a two-step ABA triblock copolymer synthesis and a polymer-analogous reaction on P(GMA) blocks. MALDI-TOF MS analysis gives valuable results and shows the ideality of the polymerizations. Furthermore the pre-equilibrium kinetics of the new RAFT agent are analyzed.