Citation: Tian-Wen Bai, Xu-Feng Ni, Jun Ling, Zhi-Quan Shen. Mechanism of Janus Polymerization: A DFT Study[J]. Chinese Journal of Polymer Science, ;2019, 37(10): 990-994. doi: 10.1007/s10118-019-2318-9 shu

Mechanism of Janus Polymerization: A DFT Study

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: 26 March 2019
Revised Date: 12 June 2019
Available Online: 19 August 2019

Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxide, three stages are identified by kinetic study including (1) fast cationic polymerization with slow anionic one, (2) fast anionic polymerization with dormant cationic one, and (3) reactivation of cationic polymerization with coupling of anionic and cationic chain ends. In this work, density functional theory (DFT) calculation is employed to investigate the reaction details of ionic polymerization and dormancy. A " tripedal crow” configuration is proposed to illustrate the unique high-coordinated ligand exchange configuration in anionic polymerization in different stages. The trigger of dormancy is determined as chain structures rather than concentration of triflate anion according to both calculation and experimental results.
- Rare earth metal catalysts,
- Ring-opening polymerization,
- Ionic polymerization,
- Reaction mechanism,
- Quantum chemical computation
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