The combination of bioresorbable and biodegradable hydrophilic polysaccharides with biodegradable hydrophobic polyester chains to form totally biodegradable, nonionic brushlike amphiphilic graft copolymers useful as surfactants has been investigated. In fact, a totally controlled and original three-step procedure is described which gives access to a wide range of poly(ε-caprolactone)-grafted dextran copolymer compositions. It consists of the reversible protection of the hydroxyl groups of the polysaccharide backbone by silylation, followed by the ring-opening polymerization of ε-caprolactone initiated by the free remaining hydroxyl groups of the partially silylated dextran in the presence of aluminum and tin-based catalysts. The last step relies upon the removal of silylating groups under mild acidic conditions yielding the desired amphiphilic graft copolymers.

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