Anionic Copolymerization of <italic style="font-style: italic">α</italic>-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature

Yun-Han Wang; Rui-Xue Zhang; Hai-Tao Leng; Jia-Xing Xu; Xu-Wen Li; Yan-Shai Wang; Hong-Wei Ma; Yang Li; Li Han

doi:10.1007/s10118-025-3468-6

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Anionic Copolymerization of α-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature

RESEARCH ARTICLE | Updated：2026-01-13

- Anionic Copolymerization of α-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature
- Anionic Copolymerization of α-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature
- Chinese Journal of Polymer Science 2026年44卷第1期页码：57-67
- Affiliations：
  
  State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
- Author bio：
  
  hanli@dlut.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52373052) and Fundamental Research Funds for the Central Universities (No. DUT24MS011).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3468-6.
- DOI：10.1007/s10118-025-3468-6
  中图分类号：
- 收稿：2025-08-26，
  
  录用：2025-09-27，
  
  网络首发：2025-12-18，
  
  纸质出版：2026-01-15
- Accepted：
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Wang, Y. H.; Zhang, R. X.; Leng, H. T.; Xu, J. X.; Li, X. W.; Wang, Y. S.; Ma, H. W.; Li, Y.; Han, L. Anionic copolymerization of α-methylstyrene (AMS) and styrene (St) under the mild temperature. Chinese J. Polym. Sci. 2026, 44, 57–67

Yun-Han Wang, Rui-Xue Zhang, Hai-Tao Leng, et al. Anionic Copolymerization of α-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature[J]. Chinese Journal of Polymer Science, 2026, 44(1): 57-67. DOI: 10.1007/s10118-025-3468-6.
Wang, Y. H.; Zhang, R. X.; Leng, H. T.; Xu, J. X.; Li, X. W.; Wang, Y. S.; Ma, H. W.; Li, Y.; Han, L. Anionic copolymerization of α-methylstyrene (AMS) and styrene (St) under the mild temperature. Chinese J. Polym. Sci. 2026, 44, 57–67 DOI： 10.1007/s10118-025-3468-6.

Yun-Han Wang, Rui-Xue Zhang, Hai-Tao Leng, et al. Anionic Copolymerization of α-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature[J]. Chinese Journal of Polymer Science, 2026, 44(1): 57-67. DOI: 10.1007/s10118-025-3468-6. DOI：

摘要

The anionic copolymerization of

-methylstyrene (AMS) and styrene (St) was investigated under mild conditions (−25 °C to 25 °C). Using a stepwise feeding strategy to suppress depolymerization enabled efficient AMS incorporation

resulting in a single

composition-dependent

that enhanced the heat resistance of polystyrene (PS).

Abstract

An effective strategy for enhancing the heat resistance of polystyrene (PS) with regard to its glass transition temperature (

) involves the anionic solution copolymerization of

-methylstyrene (AMS) with styrene (St)

typically requires much lower temperature (−25  °C) and multi-step monomer feeding to achieve higher number-average molecular weight (

) block copolymers. However

the anionic copolymerization of AMS and St under the mild temperature remains largely unexplored. This study systematically investigated the anionic copolymerization of AMS and St using

-BuLi in nonpolar solvent (−25 °C to 25 °C) through both one-step and two-step approaches. We demonstrated that one-step copolymerization at 25 °C yielded only 1−3 terminal AMS units

with higher feed ratios (5 wt%−20 wt%) increasing AMS incorporation but reducing the exact molecular weight (MW) due to enhanced depolymerization

as evidenced by MALDI-TOF MS. Temperature-controlled AMS conversion at −15 °C achieved 98% AMS conversion (5 wt% feed) by suppressing side reactions and lowering the [M

]

ₑ

while 50 °C (near

) almost prevented incorporation. Despite t-BuOK regulation induced broader PDI (1.24)

via

reactive [(polymer-Li)OR

]

K intermediates

while other systems showed narrow distributions

t-BuOK outperformed THF in enhancing AMS incorporation

via

efficient ion pair dissociation. In comparison

the two-step polymerization approach demonstrated superior performance

achieving both higher AMS conversion efficiency and preferential incorporation at the initiation end. At a 20 wt% AMS feed ratio

this method yielded copolymer chains containing up to 6 AMS units on average. Thermal analysis revealed a composition-dependent single

which exhibited a systematic increase with higher AMS incorporation content. These results collectively

demonstrate the precise control over AMS incorporation and heat resistance achievable through the manipulation of polymerization conditions.

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references

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Anionic Copolymerization of α-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature

Anionic Copolymerization of α-Methylstyrene (AMS) and Styrene (St) under the Mild Temperature

DOI：10.1007/s10118-025-3468-6

摘要

Abstract

关键词

Keywords

references