Abstract
AbstractA polysaccharide macroinitiator (M̄n = 5000 to 28000) (1), having a reactive chlorine atom at the reducing end, was prepared by ring‐opening polymerization of 1,6‐anhydro‐2,3,4‐tri‐O‐benzyl‐β‐D‐glucose (TBLG) with antimony pentachloride as initiator in presence of acetyl chloride in dichloromethane at −60°C. Macroinitiator 1 in combination with silver hexafluoroantimonate was found to induce the polymerization of 6,8‐dioxabicyclo[3.2.1]octane (DBO) in tetrahydrofuran, 2‐methyltetrahydrofuran, or tetrahydropyran at −78 to 0°C. Fractionation of the reaction products gave a block copolymer (2) composed of poly(TBLG) and poly(DBO) segments. Debenzylation of 2 provided an amphiphilic block copolymer (3) consisting of hydrophilic (1→6)‐α‐D‐glucopyranan (dextran) and hydrophobic poly(DBO) [(1→6)‐linked polysaccharide skeleton] segments. Block copolymer 3 is soluble in dimethyl sulfoxide and swells in water and chloroform.
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