Reverse ATRP of Methacrylonitrile with Diethyl 2,3-Dicyano-2,3-Diphenyl Succinate/SmCl3/Lactic Acid

Abstract

Diethyl 2, 3-dicyano-2, 3-diphenyl succinate (DCDPS) was applied to initiate reverse atom transfer radical polymerization of methacrylonitrile (MAN) in N,N-dimethylformamide (DMF) with SmCl3 and lactic acid (LA) as catalyst and ligand for the first time. The polymerization proceeded in a well-controlled manner as evidenced by kinetic studies. Compared with reverse atom transfer radical polymerization initiated by AIBN, the polymerization initiated by DCDPS not only showed better control of molecular weight, but also provided narrower molecular weight distribution. The slow polymerization rate and the broad polydispersity index were observed using cyclohexanone and toluene instead of DMF as reaction media. There was no apparent variation of the polymerization rate and polydispersity with initial monomer concentration. The block copolymer PMAN-b-PSt was obtained via a conventional ATRP process by using the resulting poly(methacrylonitrile) as macroinitiator.