Quantum chemical calculation driven insights into deep eutectic solvent‐accelerated photoinduced reversible complexation‐mediated polymerization

Author:

Li Shen1,Fu Xin2,Zhou Yin‐Ning3ORCID,Liu Zhong‐Xin1,Hou Lin‐Xi2ORCID,Luo Zheng‐Hong3ORCID

Affiliation:

1. School of Chemical Engineering and Technology Hainan University Haikou China

2. Department of Materials‐Oriented Chemical Engineering, School of Chemical Engineering Fuzhou University Fuzhou China

3. Department of Chemical Engineering, School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites Shanghai Jiao Tong University Shanghai China

Abstract

AbstractDeep eutectic solvent (DES) is used as both photocatalyst and solvent for photoinduced reversible complexation‐mediated polymerization (photo‐RCMP), which enables a rapid polymerization to produce polymers with predictable molar mass and low molar mass dispersity (Đ). This work illustrates a comprehensive understanding of DES‐accelerated RCMP's mechanism and kinetic features through quantum chemical calculations and kinetic modeling. According to the results, electrons transferring from hydrogen bond in DES to iodine atom in alkyl iodide (RI) initiator under light irradiation lowers the decomposition free energy of complex RI‐DES. This procedure facilitates the generation of primary radicals, thus contributing to the DES‐accelerated phenomenon. In the meantime, the reaction paths are identified by computation as (i) decomposition of RI‐DES under light irradiation generates active radicals and ·I‐DES complex and (ii) combination of two ·I‐DES releases iodine (I2) and regenerates DES. In addition, kinetic modeling based on the method of moments successfully identifies kinetic features of polymerization in the presence and absence of DES, respectively. Kinetic modeling shows a fast increase in primary radicals concentration and rapid build‐up of the photo‐RCMP activation‐deactivation equilibrium, demonstrating that DES is a beneficial photocatalyst and solvent to enable the rapid generation of primary radicals and accelerate the completion of catalytic cycle. This research provides an in‐depth understanding of DES‐involved photo‐RCMP and lays a theoretical foundation for expanding the application of DES to other polymerization systems.

Funder

National Natural Science Foundation of China

Publisher

Wiley

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