Synthesis of block copolymers through umpolung or treatment of propagating end of living cationic polytetrahydrofuran

Block copolymers containing polytetrahydrofuran segments were synthesized by umpolung or propagating end of the cationic living polymer and successive anionic polymerization of methacrylates (RMAs) or radical polymerization of RMAs, acrylonitrile (AN), and styrene (St). Living polytetrahydrofuran (poly-THF) was prepared by cationic polymerization of tetrahydrofuran (THF), whose propagation end was reduced by samarium(II) iodide (SmI2). Anionic polymerizations of RMAs were conducted by addition of the monomers to the reduced poly-THF to obtain poly(THF-b-RMAs). On the other hand, the 2-bromoisobutyrate group, which can act as an initiator of radical polymerization, was introduced to the cationic propagating end of poly-THF by adding sodium 2-bromoisobutyrate. Block copolymers were synthesized by living radical polymerization of RMAs, St, or AN using the 2-bromoisobutyrate-capped poly-THF as a macroinitiator and copper(I) bromide (CuBr) as a catalyst.