Citation: Huan Qiu, Zhe-Ning Yang, Jun Ling. Facile Synthesis of Functional Poly(ε-caprolactone) via Janus Polymerization[J]. Chinese Journal of Polymer Science, ;2019, 37(9): 858-865. doi: 10.1007/s10118-019-2242-z shu

Facile Synthesis of Functional Poly(ε-caprolactone) via Janus Polymerization

Huan Qiu ^† ,
Zhe-Ning Yang ^† ,
Jun Ling ^,

Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding author: Jun Ling, lingjun@zju.edu.cn
Received Date: 29 December 2018
Revised Date: 17 February 2019
Available Online: 26 March 2019

Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable synthetic technique for functional poly(ε-caprolactone) (PCL) via Janus polymerization, which comprises cationic ring-opening copolymerization (ROP) of ε-caprolactone (CL) with 3,3-bis(chloromethyl)oxacyclobutane (CO) and (coordinated) anionic ROP of CL at a single propagating chain by rare earth metal triflates (RE(OTf)₃) and propylene oxide, thus generating block copolymers in one step. The compositions of the copolymers of poly(CL-b-(CL-r-CO)) can be modulated by various RE(OTf)₃. Scandium triflate catalyzes Janus polymerization to yield the copolymers containing the highest CO contents among all the RE(OTf)₃ catalysts used with complete conversion of CL. The chlorine in CO repeating units is ready to be transferred into azide group which affords the modification sites to react with 9-ethynyl-9-fluorenol and mPEG-alkyne, respectively, via copper(I)-catalyzed azide-alkyne cycloaddition reaction with quantitative conversions of azides, as confirmed by FTIR analyses. According to NMR and SEC analyses, copolymers (PCC-g-PEG) bearing a homo-PCL block and a PEG-grafted block of poly(CO-co-CL) demonstrate well-defined chemical structures. The investigations on thermal properties reveal the strong phase separation between PCL and PEG blocks. The amphiphilic PCC-g-PEG is able to self-assemble into micelles in aqueous solution while cylindrical and lamellar morphologies are observed in bulk. We provide an efficient protocol to synthesize functional PCL combining one-step Janus polymerization and precise post-polymerization click reaction.
- Janus polymerization,
- Functional poly(ε-caprolactone),
- Poly(3,3-bis(chloromethyl)oxacyclobutane),
- Ring-opening polymerization,
- Rare earth metal catalysts
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