聚苯乙烯-<italic style="font-style: italic">b</italic>-聚异丁烯嵌段共聚物的合成及在丁基橡胶淤浆稳定剂的应用

张星龙; 朱昱; 刘祎梦; 徐子淋; 徐博瑜; 李会; 李露; 刘强; 闫寿科

doi:10.14028/j.cnki.1003-3726.2026.26.132

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聚苯乙烯-b-聚异丁烯嵌段共聚物的合成及在丁基橡胶淤浆稳定剂的应用

研究论文 | 更新时间：2026-07-13

- 聚苯乙烯-b-聚异丁烯嵌段共聚物的合成及在丁基橡胶淤浆稳定剂的应用
- Synthesis of Polystyrene-b-Polyisobutylene Block Copolymers and Their Application in Butyl Rubber Slurry Stabilizers
- 高分子通报 2026年
- 作者机构：
  
  青岛科技大学橡塑材料与工程教育部重点实验室　青岛 266042
  青岛科技大学化工学院　青岛 266042
- 作者简介：
  
  lilu@qust.edu.cn
  liuqiang@qust.edu.cn
- 基金信息：
  
  国家自然科学基金(52373011)
- DOI：10.14028/j.cnki.1003-3726.2026.26.132
  中图分类号：
- 收稿：2026-03-09，
  
  录用：2026-04-10，
- 稿件说明：
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张星龙, 朱昱, 刘祎梦, 徐子淋, 徐博瑜, 李会, 李露, 刘强, 闫寿科. 聚苯乙烯-b-聚异丁烯嵌段共聚物的合成及在丁基橡胶淤浆稳定剂的应用. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.132

Zhang, X. L.; Zhu, Y.; Liu, Y. M.; Xu, Z. L.; XU, B. Y.; Li, H.; Li, L.; Liu, Q.; Yan, S. K. Synthesis of polystyrene-b-polyisobutylene block copolymers and their application in butyl rubber slurry stabilizers. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.132
张星龙, 朱昱, 刘祎梦, 徐子淋, 徐博瑜, 李会, 李露, 刘强, 闫寿科. 聚苯乙烯-b-聚异丁烯嵌段共聚物的合成及在丁基橡胶淤浆稳定剂的应用. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.132 DOI：

Zhang, X. L.; Zhu, Y.; Liu, Y. M.; Xu, Z. L.; XU, B. Y.; Li, H.; Li, L.; Liu, Q.; Yan, S. K. Synthesis of polystyrene-b-polyisobutylene block copolymers and their application in butyl rubber slurry stabilizers. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.132 DOI：

摘要

以枯基氯(CumCl)/四氯化钛(TiCl

)/2

6-二叔丁基吡啶(DtBP)为引发体系，在−80 ℃的二氯甲烷(CH

)中实现了苯乙烯(St)与异丁烯(IB)的顺序嵌段阳离子聚合，合成了聚苯乙烯-

-聚异丁烯两嵌段共聚物(PS-PIB)。通过调控CumCl和TiCl

的浓度，实现了St的快速引发和定量转化。核磁共振氢谱(

H-NMR)证实，当CumCl和TiCl

的浓度分别为8.7和45 mmol/L，聚合时间为3 min，聚苯乙烯(PS)的活性氯末端基相比于枯基首端基的比例约为86%；随后，加入IB单体进行嵌段聚合反应，产物经过丙酮和正己烷提纯PS和PIB均聚物后，得到了相对分子质量(

)为2.14×10

g/mol、分子量分布(

)为1.95的嵌段共聚物。使用丁酮(MEK)和PIB680模拟丁基橡胶淤浆，向其

中加入1 wt%的PS-PIB嵌段共聚物，可以使浆液稳定分散；并且实验发现，嵌段产物不经丙酮和正己烷提纯，直接使用也同样可以实现稳定乳化。

Abstract

Using a cumyl chloride (CumCl)/titanium tetrachloride (TiCl

)/2

6-di-tert-butylpyridine (DtBP) initiating system

the sequential cationic block polymerization of styrene (St) and isobutylene (IB) was successfully conducted in dichloromethane (CH

) at −80 ℃

affording polystyrene-

-polyisobutylene (PS-

-PIB). Rapid initiation and nearly quantitative conversion of styrene (St) were achieved by adjusting the concentrations of CumCl and TiCl

in the system. Proton nuclear magnetic resonance (

H-NMR) spectroscopy revealed that when the concentrations of CumCl and TiCl

were 8.7 and 45 mmol/L

respectively

and the polymerization time was 3 min

the proportion of active chlorine end groups relative to cumyl initiating end groups in the resulting polystyrene (PS) reached approximately 86%. Upon the subsequent addition of the IB monomer

block copolymerization proceeded successfully. After purification with acetone and n-hexane to remove residual PS and PIB homopolymers

a PS-

-PIB diblock copolymer with a number-average molecular weight (

) of 2.14×10

g/mol and a molecular weight dispersity (

) of 1.95 was obtained. A simulated butyl rubber slurry was prepared using methyl ethyl ketone (MEK) and PIB680

and the addition of 1 wt% PS-

-PIB afforded a stable dispersion. Notably

the experimental results further demonstrated that the crude block copolymer product could be directly used without acetone and n-hexane purification

while still achieving stable emulsification.

关键词

Keywords

references

Powers, W. K. ; Wang, C. H . Stabilized slurries of isoolefin polymers . USA patent , US4474924 . 1984-10-02 .

程斌 , 马育红 , 张婷 , 武冠英 . 丁基橡胶淤浆稳定剂的合成与测评 . 合成橡胶工业 , 2002 , 25 ( 2 ), 72 – 74 .

Shim, J. S. ; Asthana, S. ; Omura, N. ; Kennedy, J. P . Novel thermoplastic elastomers. I. Synthesis and characterization of star-block copolymers of PSt- b -PIB arms emanating from cyclosiloxane cores . J. Polym. Sci. A Polym. Chem. , 1998 , 36 ( 17 ), 2997 – 3012 .

Storey, R. F. ; Shoemake, K. A . Poly(styrene- b -isobutylene) multiarm star-block copolymers . J. Polym. Sci. A Polym. Chem. , 1999 , 37 ( 11 ), 1629 – 1641 .

Kaszas, G. ; Puskas, J. E. ; Kennedy, J. P. ; Hager, W. G . Polyisobutylene-containing block polymers by sequential monomer addition. Ⅱ. Polystyrene-polyisobutylene-polystyrene triblock polymers: synthesis, characterization, and physical properties . J. Polym. Sci. Part A Polym. Chem. , 1991 , 29 ( 3 ), 427 – 435 .

Storey, R. F. ; Chisholm, B. J . Aspects of the synthesis of poly(styrene-b-isobutylene- b -styrene) block copolymers using living carbocationic polymerization . Macromolecules , 1993 , 26 ( 25 ), 6727 – 6733 .

Everland, H. ; Kops, J. ; Nielsen, A. ; Iván, B . Living carbocationic polymerization of isobutylene and synthesis of ABA block copolymers by conventional laboratory techniques . Polym. Bull. , 1993 , 31 ( 2 ), 159 – 166 .

Gyor, M. ; Fodor, Z. ; Wang, H. C. ; Faust, R . Polyisobutylene-based thermoplastic elastomers. I. Synthesis and characterization of polystyrene-polyisobutylene-polystyrene triblock copolymers . J. Macromol. Sci. Part A , 1994 , 31 ( 12 ), 2055 – 2065 .

Taylor, S. J. ; Storey, R. F. ; Kopchick, J. G. ; Mauritz, K. A . Poly[(styrene- co - p -methylstyrene)-b-isobutylene-b-(styrene-co-p-methylstyrene) ] triblock copolymers. 1. Synthesis and characterization . Polymer , 2004 , 45 ( 14 ), 4719 – 4730 .

Xu, S. C. ; Yang, K. ; Liu, Q. ; Li, H. ; Zhang, H. ; Zhuang, T. ; Yan, S. K. ; Ding, J. W . A cost-effective strategy for the synthesis of polystyrene-polyisobutylene-polystyrene triblock copolymer (SIBS) based on dicumyl chloride/TiCl 4 /Ti(O i Pr) 4 initiating system . J. Polym. Sci. , 2023 , 61 ( 8 ), 700 – 708 .

Hasebe, T. ; Kamigaito, M. ; Sawamoto, M . Living cationic polymerization of styrene with TiCl 3 (O i Pr) as a Lewis acid activator . Macromolecules , 1996 , 29 ( 19 ), 6100 – 6103 .

Puskas, J. E. ; Kaszas, G . Living carbocationic polymerization of resonance-stabilized monomers . Prog. Polym. Sci. , 2000 , 25 ( 3 ), 403 – 452 .

Aoshima, S. ; Kanaoka, S . A renaissance in living cationic polymerization . Chem. Rev. , 2009 , 109 ( 11 ), 5245 – 5287 .

Ishihama, Y. ; Sawamoto, M. ; Higashimura, T . Living cationic polymerization of styrene by the 1-phenylethyl chloride/tin tetrachloride initiating system in the presence of tetra-n-butylammonium chloride . Polym. Bull. , 1990 , 24 ( 2 ), 201 – 206 .

Higashimura, T. ; Ishihama, Y. ; Sawamoto, M . Living cationic polymerization of styrene: new initiating systems based on added halide salts and the nature of the growing species . Macromolecules , 1993 , 26 ( 4 ), 744 – 751 .

Kwon, O. S. ; Gho, C. G. ; Choi, B. S. ; Choi, S. K . Living cationic polymerization of styrene by the bifunctional initiating system 1, 4-bis(1-chloroethyl)benzene/SnCl 4 in the presence of 2, 6-di-tert-butylpyridine . Macromol. Chem. Phys. , 1994 , 195 ( 6 ), 2187 – 2194 .

Puskas, J. E. ; Chan, S. W. P. ; McAuley, K. B. ; Kaszas, G. ; Shaikh, S . Living carbocationic copolymerization of isobutylene with styrene . J. Polym. Sci. A Polym. Chem. , 2007 , 45 ( 9 ), 1778 – 1787 .

Cao, X. Y. ; Faust, R . Polyisobutylene-based thermo-plastic elastomers. 5. Poly(styrene-b-isobutylene-b-styrene) triblock copolymers by coupling of living poly(styrene- b -isobutylene) diblock copolymers . Macromolecules , 1999 , 32 ( 17 ), 5487 – 5494 .

Kwon, Y. ; Cao, X. Y. ; Faust, R . Synthesis of poly( α -methylstyrene-b-isobutylene) copolymers by living cationic sequential block copolymerization: investigation on the crossover from livi ng poly( α -methylstyrene) chain end to isobutylene . Macromolecules , 1999 , 32 ( 21 ), 6963 – 6968 .

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聚苯乙烯-b-聚异丁烯嵌段共聚物的合成及在丁基橡胶淤浆稳定剂的应用

Synthesis of Polystyrene-b-Polyisobutylene Block Copolymers and Their Application in Butyl Rubber Slurry Stabilizers

DOI：10.14028/j.cnki.1003-3726.2026.26.132

摘要

Abstract

关键词

Keywords

references