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In the presence of a small molecular protic initiator, immortal ring-opening polymerization (ROP) of lactide (LA) is a highly efficient strategy to synthesize polylactide in a controllable manner, while using polymeric alcohol as an initiator has been less investigated. A series of polymeric alcohols (PS⁻OH) composed of styrene and 4.3%⁻18% hydroxyl functional styrene (diethyl(hydroxy(4-vinylphenyl)methyl)phosphonate, St⁻OH) were synthesized through reversible addition-fragmentation transfer (RAFT) polymerization. Using PS⁻OH as an initiator, the immortal ROP of rac -LA was catalyzed by dibutylmagnesium (Mg  n  Bu₂) under various ratios of monomer to hydroxyl group within PS⁻OH to generate polystyrene- g -polylactide (PS⁻ g ⁻PLA) copolymers with different graft lengths. After thermal annealing at 115 °C, the PLA domain aggregated to nanospheres among the PS continuum. The size of the nanospheres, varying from 130.1 to 224.2 nm, was related to the graft density and length of PS⁻ g ⁻PLA. Nanoporous films were afforded through chemical etching of the PLA component.

Immortal Ring-Opening Polymerization of rac-Lactide Using Polymeric Alcohol as Initiator to Prepare Graft Copolymer