Reverse ATRP of 4-vinylpyridine with Diethyl 2,3-Dicyano-2,3-Diphenylsuccinate/CuCl2/5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetradecane

Diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS) was applied to initiate reverse atom transfer radical polymerization of 4-vinylpyridine (VP) in 2-propanol with CuCl2 and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetradecane (Me6[14]aneN4) as catalyst and ligand for the first time. First-order kinetics of the polymerization rate with respect to the monomer concentration, linear increase of the molecular weight with monomer conversion and a polydispersity index in the range of 1.15–1.28 were indicatives of controlled radical polymerization. Use of Me6[14]aneN4 as the ligand had many advantages over the use of hexamethyl tris[2-(dimethylamino)ethyl]amine (Me6-TREN) and 2,2′-bipyridine (bpy). A slower polymerization rate and a broad polydispersity index were observed using CuBr2 instead of CuCl2 as catalyst. The block copolymer PVP-b-PAN was obtained via a conventional ATRP process in N, N-dimethylformamide (DMF) using the resulting poly (4-vinylpyridine) as macroinitiator.