A Paradigm for BF<sub>3 </sub>co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

Yi-Meng Liu; Yu Zhu; Bo-Yu Xu; Zi-Lin Xu; Xing-Long Zhang; Hui Li; Qiang Liu; Shou-Ke Yan

doi:10.1007/s10118-026-3714-6

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A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

RESEARCH ARTICLE | Updated：2026-07-25

- A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature
- A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature
- Chinese Journal of Polymer Science 2026年44卷页码：1-12
- Affiliations：
  
  a.Key Laboratory of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-Plastics, Qingdao University of Science and Technology, Qingdao 266042, China
  b.State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology, Qingdao 266042, China
  c.College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
- Author bio：
  
  liuqiang@qust.edu.cn (Q.L.)
- Funds：
  
  This study was financially supported by the National Natural Science Foundation of China (No. 52373011).;The authors declare no interest conflict.Data supporting the findings of this study are available from the corresponding author upon reasonable request. Author’s contact information: liuqiang@qust.edu.cn; liuyimeng2001@163.com.
- DOI：10.1007/s10118-026-3714-6
  中图分类号：
- 收稿：2026-02-09，
  
  录用：2026-04-14，
  
  网络首发：2026-07-24，
  
  纸质出版：2026-06
- Accepted：
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Liu, Y. M.; Zhu, Y.; Xu, B. Y.; Xu, Z. L.; Zhang, X. L.; Li, H.; Liu, Q.; Yan, S. K. A paradigm for BF₃co-initiated cationic polymerization with low dispersity: introducing acetonitrile and lowering the reaction temperature. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3714-6

Yi-Meng Liu, Yu Zhu, Bo-Yu Xu, et al. A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature[J/OL]. Chinese Journal of Polymer Science, 2026, 441-12. DOI: 10.1007/s10118-026-3714-6.
Liu, Y. M.; Zhu, Y.; Xu, B. Y.; Xu, Z. L.; Zhang, X. L.; Li, H.; Liu, Q.; Yan, S. K. A paradigm for BF₃co-initiated cationic polymerization with low dispersity: introducing acetonitrile and lowering the reaction temperature. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3714-6 DOI：

Yi-Meng Liu, Yu Zhu, Bo-Yu Xu, et al. A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature[J/OL]. Chinese Journal of Polymer Science, 2026, 441-12. DOI: 10.1007/s10118-026-3714-6. DOI：

摘要

Abstract

Non-metallic cationic polymerization of low-reactivity styrene (St) derivatives remains challenging due to broad molecular weight distributions and rapid deactivation of active species. Here we show that adding only a minor amount of CH

CN (

3/97) to the conventional BF

·OEt

/COH/CH

/St system affords polystyrene with narrow dispersity (

≈ 1.3). Notably

the

increases linearly with conversion and closely matches the

n.calcd

H-nuclear magnetic resonance (

H-NMR) analysis and comparative experiments with the BF

·CH

CN co-initiation system indicate CH

CN does not coordinate strongly with BF

compared to diethyl ether (OEt

); however

it stabilizes the propagating carbocation and decreases the the propagation rate constant (

)

which leads to a narrower dispersity in the product. Lowering the temperature to −25 °C further extends the active-chain lifetime. This strategy is also effective for other low-reactivity styrene monomers

including

-chlorostyrene (

ClSt) and

-chloromethylstyrene (

CMSt)

and is even applicable to the relatively more reactive

-methylstyrene (

MeSt)

offering a versatile metal-free route to the synthesis of styrenic polymers with a narrow dispersity.

关键词

Keywords

references

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A Paradigm for BF3 co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

A Paradigm for BF3 co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

DOI：10.1007/s10118-026-3714-6

摘要

Abstract

关键词

Keywords

references

A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature