A novel copper catalyst containing a hydroxyl functional group: a facile strategy to prepare block copolymers of vinyl monomer and ε-caprolactone via tandem reverse ATRP and ROP

Reverse atom transfer radical polymerization (R-ATRP) and ring-opening polymerization (ROP) are the two representative processes of the most promising living/controlled polymerization techniques. Herein, a facile and stable metal catalyst, Cu(S(SC)(N–CH3)CH2CH2OH)2, containing a hydroxyl group was first designed with an aim to prepare block copolymers of vinyl monomer and cyclic ester monomer via a combination of R-ATRP and ROP. The vinyl polymer chain end attached with a hydroxyl functionality obtained from R-ATRP was directly used as a macroinitiator to prepare the block copolymers via ROP of ε-caprolactone. 1H NMR and GPC analyses as well as ROP chain-extension reaction confirmed that the vinyl polymers possessed very high chain end functionality, and the block copolymers of the vinyl monomer and cyclic ester monomer were successfully synthesized.