Synthesis of poly(4-vinylpyridine) and block copoly (4-vinylpyridine–b-styrene) by atom transfer radical polymerization using 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetradecane as ligand

Poly(4-vinylpyridine) (P4VP) and block copolymer, poly(4-vinylpyridine–b-styrene) (P4VP-b-PSt) were prepared by atom transfer radical polymerization (ATRP) using 1-phenylethyl chloride as initiator, CuCl and 5,5,7,12,12,14–hexamethyl-1,4,8,11-tetraazamacrocyclotetradecane (Me6[14]aneN4) as catalyst and ligand. The polymerization of 4VP was carried out in 2-propanol at 40 °C. GPC and NMR studies show that the plot of ln([4VP]0/[4VP]) against the reaction time is linear, and the molecular weight of the resulting P4VP increased linearly with the conversion. Within 3 h, the conversion can reach almost 90%. P4VP-b-PSt amphiphilic block copolymer with low polydispersity index (Mw/Mn ≈ 1.2) is also obtained by ATRP of St in DMF at 110 °C using P4VP–Cl as macroinitiator, CuCl/ Me6[14]aneN4 as catalyst.