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

Na Liu; Bo Liu; Changguang Yao; Dongmei Cui

doi:10.3390/polym8010017

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

Polymers (Basel). 2016 Jan 15;8(1):17. doi: 10.3390/polym8010017.

Authors

Na Liu^{1

2}, Bo Liu³, Changguang Yao^{4

5}, Dongmei Cui⁶

Affiliations

¹ State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China. liunn@ciac.ac.cn.
² University of the Chinese Academy of Sciences, Changchun Branch, Changchun 130022, China. liunn@ciac.ac.cn.
³ State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China. liubo@ciac.ac.cn.
⁴ State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China. chgyao@ciac.ac.cn.
⁵ University of the Chinese Academy of Sciences, Changchun Branch, Changchun 130022, China. chgyao@ciac.ac.cn.
⁶ State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China. dmcui@ciac.ac.cn.

Abstract

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 (MgⁿBu₂) 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.

Keywords: RAFT polymerization; grafting-from; immortal ring-opening polymerization; nanoporous film; polymeric alcohol.

Abstract

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