The Magic of Organocatalytic Synergism in Switchable Polymerization: One-pot Synthesis of Block Copolymers with Programmable Sequences and Compositions

Shuai-Shuai Zhu; Mao-Ji Zhao; Ying-Jie Yuan; Yong Wang

doi:10.1007/s10118-025-3476-6

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The Magic of Organocatalytic Synergism in Switchable Polymerization: One-pot Synthesis of Block Copolymers with Programmable Sequences and Compositions

RESEARCH ARTICLE | Updated：2026-01-13

- The Magic of Organocatalytic Synergism in Switchable Polymerization: One-pot Synthesis of Block Copolymers with Programmable Sequences and Compositions
- Chinese Journal of Polymer Science Vol. 44, Issue 1, Pages: 68-78(2026)
- Affiliations：
  
  Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, Hubei Engineering Research Center for Biomaterials and Medical Protective Materials, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
- Author bio：
  
  tcwy@mail.hust.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3476-6
  CLC：
- Received：13 August 2025，
  
  Accepted：08 October 2025，
  
  Online First：18 December 2025，
  
  Published：15 January 2026
- Accepted：
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Zhu, S. S.; Zhao, M. J.; Yuan, Y. J.; Wang, Y. The magic of organocatalytic synergism in switchable polymerization: one-pot synthesis of block copolymers with programmable sequences and compositions. Chinese J. Polym. Sci. 2026, 44, 68–78

Shuai-Shuai Zhu, Mao-Ji Zhao, Ying-Jie Yuan, et al. The Magic of Organocatalytic Synergism in Switchable Polymerization: One-pot Synthesis of Block Copolymers with Programmable Sequences and Compositions[J]. Chinese Journal of Polymer Science, 2026, 44(1): 68-78.
Zhu, S. S.; Zhao, M. J.; Yuan, Y. J.; Wang, Y. The magic of organocatalytic synergism in switchable polymerization: one-pot synthesis of block copolymers with programmable sequences and compositions. Chinese J. Polym. Sci. 2026, 44, 68–78 DOI： 10.1007/s10118-025-3476-6.

Shuai-Shuai Zhu, Mao-Ji Zhao, Ying-Jie Yuan, et al. The Magic of Organocatalytic Synergism in Switchable Polymerization: One-pot Synthesis of Block Copolymers with Programmable Sequences and Compositions[J]. Chinese Journal of Polymer Science, 2026, 44(1): 68-78. DOI： 10.1007/s10118-025-3476-6.

摘要

Switchable polymerization constructs block copolymers directly from monomer mixtures

yet is limited to switch between two predetermined polymerizations and deliver products with fixed sequences. Here

a programmable switchable polymerization was demonstrated by modulating the ratio of triethylborane/1

8-diazabicyclo[5.4.0

]

undec-7-ene (Et

B/DBU) to synthesize four different block copolymers from same monomer mixtures.

Abstract

Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers. However

current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions. Herein

we report the triethylborane/1

8-diazabicyclo[5.4.0

]

undec-7-ene (Et

B/DBU) pair-mediated four-component switchable polymerization of propylene oxide (PO)

phthalic anhydride (PA)

and racemic lactide (

rac

-LA)

which enables the on-demand synthesis of four different block copolymers

i.e

poly(propylene phthalate)-

polylactide (PPE-

-PLA)

PPE-

-PLA-

-poly(propylene carbonate) (PPC)

PPE-

-PPC-

-PLA

and PPE-

-PPC-

-poly(propylene oxide) (PPO)

through rationally modulating the Lewis pair (LP) ratio. Core to this protocol is that increasing the loading of Et

B accelerates the ring-opening of PO while impeding the reactivity of

rac

-LA

thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization. Therefore

the four polymerizat

ion cycles involving PO/PA ring-opening copolymerization (ROCOP)

PO/CO

ROCOP

rac

-LA ring-opening polymerization (ROP)

and PO ROP can be connected and discriminated in precisely programmed manners.

关键词

Keywords

references

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