Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers

Hong Qiu; Peng-Fei Zhang; Jun-Peng Zhao

doi:10.1007/s10118-024-3193-6

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Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers

RESEARCH ARTICLE | Updated：2024-12-03

- Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers
- Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers
- 高分子科学（英文版） 2024年42卷第12期页码：1925-1932
- Affiliations：
  
  Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
- Author bio：
  
  msjpzhao@scut.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 52022031 and 21734004).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-024-3193-6.
- DOI：10.1007/s10118-024-3193-6
  中图分类号：
- 收稿：2024-05-05，
  
  修回：2024-06-07，
  
  录用：2024-06-10，
  
  网络首发：2024-08-30，
  
  纸质出版：2024-12-01
- Accepted：
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Qiu, H.; Zhang, P. F.; Zhao, J. P. Amine-actuated catalyst switch for one-pot synthesis of ether-ester type block copolymers. Chinese J. Polym. Sci. 2024, 42, 1925–1932

Hong Qiu, Peng-Fei Zhang, Jun-Peng Zhao. Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers[J]. Chinese Journal of Polymer Science, 2024, 42(12): 1925-1932.
Qiu, H.; Zhang, P. F.; Zhao, J. P. Amine-actuated catalyst switch for one-pot synthesis of ether-ester type block copolymers. Chinese J. Polym. Sci. 2024, 42, 1925–1932 DOI： 10.1007/s10118-024-3193-6.

Hong Qiu, Peng-Fei Zhang, Jun-Peng Zhao. Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers[J]. Chinese Journal of Polymer Science, 2024, 42(12): 1925-1932. DOI： 10.1007/s10118-024-3193-6.

摘要

Amine has been used as a selectivity-switching agent in the two-component catalytic system consisting of triethylborane and a phosphazene base. The addition of an amine promptly switches Lewis pair-catalyzed ring-opening polymerization of epoxide to organobase-catalyzed ROP of δ-valerolactone

thus facilitating one-pot block copolymerization.

Abstract

Organocatalysis has shown special potency for simplifying the construction of complex polymer structures. We are reporting here a one-pot synthetic pathway using amine as a selectivity-switching agent in the two-component catalytic system consisting of triethylborane (Et

B) and a phosphazene base. We first modelled the interactions of a variety of amines with Et

B by density functional theory calculations. The results indicate that the aliphatic diamines comprising both primary and tertiary amino groups

capable of forming stable intramolecular hydrogen bonds

undergo the strongest complexation with Et

B. Accordingly

experimental results demonstrate that the addition of such amines promptly actuates the

in situ

selectivity switch from Lewis pair-catalyzed ring-opening polymerization (ROP) of epoxide (propylene oxide

-butylglycidyl ether

or glycidyl phenyl ether) to organobase-catalyzed ROP of

-valerolactone

allowing one-pot continuous synthesis of ether-ester type block copolymers. We thus exploited the noncovalent interaction between amine and Et

B to refine the catalyst switch strategy by exempting it from loading of extra catalyst.

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references

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