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Synthesis of Well-defined Poly(tetrahydrofuran)-b-Poly(a-amino acid)s via Cationic Ring-opening Polymerization (ROP) of Tetrahydrofuran and Nucleophilic ROP of N-thiocarboxyanhydrides

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Abstract

The synthesis of block copolymers of poly(tetrahydrofuran)-b-poly(α-amino acid) (PTHF-b-PAA) is challenging since it is difficult to combine the two blocks produced via different/conflicting ring-opening polymerization (ROP) mechanisms. In this contribution, the cationic ROP of THF is catalyzed by rare-earth triflate [RE(OTf)3] and terminated by 2-(t-butyloxycarbonyl-amino) ethanol (BAE). After the deprotection of t-butyloxycarbonyl (Boc) group, the chain end of PTHF is quantitatively changed to amino group which thereafter initiates the nucleophilic ROP of α-amino acid N-thiocarboxyanhydrides (NTAs). Both polymerizations are well controlled, generating PTHF and PAA segments with designable molecular weights (MWs). PTHF-b-polylysine (PTHF-b-PLys) and PTHF-b-polysarcosine (PTHF-b-PSar) are obtained with MWs between 8.6 and 28.7 kg/mol. The above amphiphilic diblock copolymers form micelles in water. PTHF40-b-PSar32 acts as a surfactant to stabilize oil-in-water emulsions. Both segments of PTHF-b-PAA are biocompatible and promising in the biomedical application.

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Acknowledgments

This work was financially supported by Joint Foundation of Shaanxi Province Natural Science Basic Research Program and Shaanxi Coal Chemical Group Co., Ltd. (No. 2019JLM-46) and the National Natural Science Foundation of China (No. 21674091).

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Authors and Affiliations

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

    Peng Zhou, Xuan-Geng Dai & Jun Ling

  2. Shaanxi Key Laboratory of Macromolecular Science and Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an, 710072, China

    Jie Kong

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  1. Peng Zhou
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  4. Jun Ling
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Correspondence to Jie Kong or Jun Ling.

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Synthesis of Well-defined Poly(tetrahydrofuran)-b-Poly(a-amino acid)s via Cationic Ring-opening Polymerization (ROP) of Tetrahydrofuran and Nucleophilic ROP of N-thiocarboxyanhydrides

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Zhou, P., Dai, XG., Kong, J. et al. Synthesis of Well-defined Poly(tetrahydrofuran)-b-Poly(a-amino acid)s via Cationic Ring-opening Polymerization (ROP) of Tetrahydrofuran and Nucleophilic ROP of N-thiocarboxyanhydrides. Chin J Polym Sci 39, 702–708 (2021). https://doi.org/10.1007/s10118-021-2539-6

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