Controlled Cationic Polymerization of Styrene and Its Derivatives Initiated by Polymethyl-substituted Dibenzyl Chloride

Zi-lin Xu; Yu Zhu; Yi-meng Liu; Xing-long Zhang; Bo-yu Xu; Hui Li; Lu Li; Qiang Liu; Shou-ke Yan

doi:10.11777/j.issn1000-3304.2026.26061

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Controlled Cationic Polymerization of Styrene and Its Derivatives Initiated by Polymethyl-substituted Dibenzyl Chloride

更新时间：2026-07-27

- Controlled Cationic Polymerization of Styrene and Its Derivatives Initiated by Polymethyl-substituted Dibenzyl Chloride
- Acta Polymerica Sinica Pages: 1-12(2026)
- 作者机构：
  
  1.青岛科技大学，橡塑材料与工程教育部重点实验室，青岛 266042
  2.青岛科技大学，化工学院，青岛 266042
- 作者简介：
  
  Lu Li, E-mail: lilu@qust.edu.cn
  Qiang Liu, E-mail: liuqiang@qust.edu.cn
  Shou-ke Yan, E-mail: skyan@qust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26061
  CLC：
- CSTR：32057.14.GFZXB.2026.7616
- Accepted：19 May 2026，
  
  Online First：27 July 2026，
- 稿件说明：
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徐子淋, 朱昱, 刘祎梦, 张星龙, 徐博瑜, 李会, 李露, 刘强, 闫寿科. 多甲基取代双苄基氯引发苯乙烯及其衍生物可控阳离子聚合. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26061.

Xu, Z. L.; Zhu, Y.; Liu, Y. M.; Zhang, X. L.; Xu, B. Y.; Li, H.; Li, L.; Liu, Q.; Yan, S. K. Controlled cationic polymerization of styrene and its derivatives initiated by polymethyl-substituted dibenzyl chloride. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26061.
徐子淋, 朱昱, 刘祎梦, 张星龙, 徐博瑜, 李会, 李露, 刘强, 闫寿科. 多甲基取代双苄基氯引发苯乙烯及其衍生物可控阳离子聚合. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26061. DOI： CSTR： 32057.14.GFZXB.2026.7616.

Xu, Z. L.; Zhu, Y.; Liu, Y. M.; Zhang, X. L.; Xu, B. Y.; Li, H.; Li, L.; Liu, Q.; Yan, S. K. Controlled cationic polymerization of styrene and its derivatives initiated by polymethyl-substituted dibenzyl chloride. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26061. DOI： CSTR： 32057.14.GFZXB.2026.7616.

摘要

通过可控阳离子聚合合成双端官能化聚合物，一般需使用对二枯基氯(DCC)双端引发剂，其价格昂贵，化学性质不稳定，需低温储存. 苄基氯可以引发阳离子聚合，但其引发效率一般较低. 本工作在SnCl

共引发的4-乙酰氧基苯乙烯(STO)聚合体系内，系统考察了苄基氯的取代基结构对其表观引发效率(

app

)的影响. 实验结果表明，苄基氯的取代基决定其引发效率，苯环上的甲基取代基数量越多，其引发效率越高. 当选用多甲基取代基的双苄基氯引发剂，如2

4-双(氯甲基)-1

5-三甲基苯(Ⅶ)和3

6-二(氯甲基)杜烯(Ⅷ)时，可以实现可控引发(

app

≈1)，所得的聚4-乙酰氧基苯乙烯(PSTO)的分子量分布也较窄(MWD，

=1.14~1.25)；通过调整双苄基氯引发剂的用量，能有效调控PSTO的分子量(

). 进一步研究发现，Ⅶ和Ⅷ同样可以实现对低活性单体苯乙烯(St)的可控引发，合成窄分子量分布的聚苯乙烯(

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113974873&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113974827&type=

0.67733335

0.84666669

=1.22~1.24)；但是对于单体聚合活性较高的对甲基苯乙烯(pMSt)，其

app

仅能达到0.5左右. 通过Gaussian 16软件进行Mulliken电荷计算，进一步证实苄基氯类引发剂的苄基碳原子的负电荷值和其引发能力密切关联，甲基取代基越多的苄基氯引发剂，其苄基碳原子的负电荷值越大，引发能力越强. 本工作所开发的新型双端苄基氯引发剂化学性质稳定，可有效替代DCC用于STO、St等低活性苯乙烯衍生物单体的可控阳离子聚合，以制备双端官能化聚合物，具有广泛的应用价值.

Abstract

The synthesis of bimodal functionalized polymers

via

cationic polymerization typically requires bimodal initiators such as

-dichlorobenzyl chloride (DCC)

which are expensive

chemically unstable

and require low-temperature storage. Benzyl chloride can initiate cationic polymerization

but its initiation efficiency is generally low. In this study

the effect of the substituent structure of benzyl chloride on its apparent initiation efficiency (

app

) was systematically investigated within the SnCl

co-initiated 4-acetoxybenzene (STO) polymerization system. Experimental results demonstrated that the substituent of benzyl chloride determined its initiation efficiency

with higher methylation on the benzene ring leading to greater efficiency. When using bimethylbenzyl chloride initiators with multiple methyl substituents

such as 2

4-bis(methyl)chloro-1

5-trimethylbenzene (Ⅶ) and 3

6-bis(methyl)chlorodiene (Ⅷ)

controllable initiation (

app

≈1) was achieved

resulting in a narrow molecular weight distribution (MWD

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113974839&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113974874&type=

3.30200005

2.62466669

=1.14-1.25). By adjusting the dosage of the bimethylbenzyl chloride initiator

the molecular weight (

) of the polymer could be effectively controlled. Further studies revealed that Ⅶ and Ⅷ could also achieve controllable initiation of the low-reactivity monomer styrene (St)

synthesizing polystyrene with a narrow molecular weight distribution (

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113974852&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113974860&type=

2.62466669

2.53999996

=1.22-1.24). However

-methylstyrene (pMSt)

which exhibited high monomer polymerization activity

demonstrated relatively low initiation efficiency. Mulliken charge calculations performed with Gaussian 16 software further confirmed that the negative charge value of benzyl carbon atoms in benzyl chloride initiators was closely correlated with their initiation capability. The novel bifunctional benzyl chloride initiator developed in this study exhibited stable chemical properties and could effectively replace DCC for the active cationic polymerization of low-reactivity styrene derivatives

such as STO and St

enabling the preparation of bifunctional polymers with broad application potential.

关键词

Keywords

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