Mechanism of Janus Polymerization: A DFT Study

Tian-Wen Bai; Xu-Feng Ni; Jun Ling; Zhi-Quan Shen

doi:10.1007/s10118-019-2318-9

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Mechanism of Janus Polymerization: A DFT Study

ARTICLE | Updated：2021-02-18

- Mechanism of Janus Polymerization: A DFT Study
- Chinese Journal of Polymer Science Vol. 37, Issue 10, Pages: 990-994(2019)
- Affiliations：
  
  Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
- Author bio：
  
  lingjun@zju.edu.cn
- Funds：
- DOI：10.1007/s10118-019-2318-9
  CLC：
- Received：26 March 2019，
  
  Revised：2019-6-12，
  
  Accepted：17 June 2019，
  
  Online First：19 August 2019，
  
  Published：2019-10
- Accepted：
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Citation: Bai, T. W.; Ni, X. F.; Ling, J.; Shen, Z. Q. Mechanism of Janus polymerization: A DFT study. Chinese J. Polym. Sci. 2019, 37, 990–994

Tian-Wen Bai, Xu-Feng Ni, Jun Ling, et al. Mechanism of Janus Polymerization: A DFT Study[J]. Chinese Journal of Polymer Science, 2019, 37(10): 990-994.
Citation: Bai, T. W.; Ni, X. F.; Ling, J.; Shen, Z. Q. Mechanism of Janus polymerization: A DFT study. Chinese J. Polym. Sci. 2019, 37, 990–994 DOI： 10.1007/s10118-019-2318-9.

Tian-Wen Bai, Xu-Feng Ni, Jun Ling, et al. 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.

摘要

Abstract

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.

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references

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