Synthesis of amphiphilic triblock copolymer of polystyrene and poly(4-vinylbenzyl glucoside) via TEMPO-mediated living radical polymerization

4-Vinylbenzyl glucoside peracetate 1 was polymerized with alpha,alpha'-bis(2',2',6',6'-tetramethyl-1-piperidinyloxy)-1,4-diethylbenzene 2 in chlorobenzene using (IS)-(+)-10-camphorsulfonic acid anhydrous (CSA) as an accelerator ([1] = 0.4 M,[1]/[2]/[CSA] = 75/1/1.3) at 125 degreesC for 5 h. The polymerization afforded poly(4-vinylbenzyl glucoside peracetate) having TEMPO moieties on both sides of the chain ends, 3, with a molecular weight (M-wSLS) of 8500, a polydispersity index (M-w/M-n) of 1.09, and an average degree of polymerization of the I unit (x) of 17. Styrene (St) was polymerized with 3 in chlorobenzene at 125 degreesC (St/chlorobenzene = 1/2, w/w). The polymerization successfully afforded polystyrene - poly(4-vinyl glucoside peracetate) -polystyrene, 4, when the polymerization time was below about 2 h. Polymer 4 with the M-w,M-SLS of 12,500, 17,900, and 29,400, the compositions (y-x-y) of 20-17-20, 45-17-45, and 100-17-100, and the M-w/M-n of 1.12, 1.14 and 1.17 were modified by deacetylation using sodium methoxide in dry-THF into polystyrene - poly(4-vinyl glucoside peracetate) -polystyrene, 5. The solubility of polymer 5 was examined using a good solvent for polystyrene such as toluene and for the saccharide such as H2O. (C) 2002 Elsevier Science Ltd. All rights reserved.