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

Polv(4-vinylpyridine) (P4VP) and block copolymer, poly(4-vinylpyridine-b-styrene) (P4VP-b-PSt) were prepared by atom transfer radical polymerization (ATRP) using I-phenylethyl chloride as initiator, CuCl and 5,5,7,12,12,14-hexamethyl- 1,4,8,11 -tetraazamacrocyclotetradecane (Me-6[14]aneN(4)) as catalyst and ligand. The polymerization of 4VP was carried out in 2-propanol at 40 degreesC. 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 (M-w/M-n approximate to 1.2) is also obtained by ATRP of St in DMF at 110 degreesC using P4VP-Cl as macroinitiator, CuCl/ Me-6[14]aneN(4) as catalyst. (C) 2003 Elsevier Ltd. All rights reserved.