Design and Synthesis of a Cyclic Double-Grafted Polymer Using Active Ester Chemistry and Click Chemistry via A "Grafting onto" Method

Meng Liu; Lu Yin; Shuangshuang Zhang; Zhengbiao Zhang; Wei Zhang; Xiulin Zhu

doi:10.3390/polym11020240

Design and Synthesis of a Cyclic Double-Grafted Polymer Using Active Ester Chemistry and Click Chemistry via A "Grafting onto" Method

Polymers (Basel). 2019 Feb 1;11(2):240. doi: 10.3390/polym11020240.

Authors

Meng Liu¹, Lu Yin², Shuangshuang Zhang³, Zhengbiao Zhang⁴, Wei Zhang⁵, Xiulin Zhu^{6

7}

Affiliations

¹ Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China. 20164209036@stu.suda.edu.cn.
² Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China. yinlu0701@163.com.
³ Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China. sgny19910327@163.com.
⁴ Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China. zhengbiaozhang@suda.edu.cn.
⁵ Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China. weizhang@suda.edu.cn.
⁶ Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China. xlzhu@suda.edu.cn.
⁷ Global Institute of Software Technology, No 5. Qingshan Road, Suzhou National Hi-Tech District, Suzhou 215163, China. xlzhu@suda.edu.cn.

Abstract

Combing active ester chemistry and click chemistry, a cyclic double-grafted polymer was successfully demonstrated via a "grafting onto" method. Using active ester chemistry as post-functionalized modification approach, cyclic backbone (c-P2) was synthesized by reacting propargyl amine with cyclic precursor (poly(pentafluorophenyl 4-vinylbenzoate), c-PPF4VB_6.5k). Hydroxyl-containing polymer double-chain (l-PS-PhOH) was prepared by reacting azide-functionalized polystyrene (l-PSN₃) with 3,5-bis(propynyloxy)phenyl methanol, and further modified by azide group to generate azide-containing polymer double-chain (l-PS-PhN₃). The cyclic backbone (c-P2) was then coupled with azide-containing polymer double-chain (l-PS-PhN₃) via CuAAC reaction to construct a novel cyclic double-grafted polymer (c-P2-g-Ph-PS). This research realized diversity and complexity of side chains on cyclic-grafted polymers, and this cyclic double-grafted polymer (c-P2-g-Ph-PS) still exhibited narrow molecular weight distribution (M_w/M_n < 1.10).

Keywords: active ester chemistry; cyclic double-grafted polymer; topological architecture; “grafting onto” approach.