配位聚合二烯烃橡胶的官能化

刘金良; 王凤; 刘恒; 张学全

doi:10.11777/j.issn1000-3304.2026.26075

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配位聚合二烯烃橡胶的官能化

综述 | 更新时间：2026-06-17

- 配位聚合二烯烃橡胶的官能化
- Functionalization of Polydienes by Coordination Polymerization
- 高分子学报 2026年页码：1-25
- 作者机构：
  
  青岛科技大学高分子科学与工程学院橡塑材料与工程教育部重点实验室青岛 266000
- 作者简介：
  
  王凤，女，1985年生，青岛科技大学高分子科学与工程学院副教授，博士生导师. 2014年博士毕业于中国科学院长春应用化学研究所，2015~2017以色列理工学院化学系博士后. 主要研究方向为二烯烃的配位可控聚合、合成橡胶的官能化与高性能化、二烯烃橡胶的可控降解与回收利用. 作为负责人主持国家自然科学基金青年项目1项、重点研发项目子课题1项，山东省面上基金1项，吉林省自然科学基金1项，吉林省教育厅基金1项，国家重点实验室开放基金2项. 在高分子领域知名期刊ACS Macro Lett.，Chem. Commu.，Polym. Chem.等上发表SCI论文40余篇，授权中国发明专利4项，授权美国发明专利1项.
  张学全，男，1962年生，青岛科技大学高分子科学与工程学院教授，博士生导师. 1993~1994年英国里丁大学高级访问学者；1996~2000年韩国三星集团三星综合技术院、三星综合化学公司高级研究员；2000~2020年中国科学院长春应化所研究员；2020年至今青岛科技大学教授. 致力于以烯烃、双烯烃为单体的新型聚烯烃和合成橡胶催化剂、聚合方法学和产业化研究. 迄今在在Adv. Opt. Mater.、Macromolecules等国内外杂志公开发表论文360余篇，撰写《稀土顺丁橡胶》等著作两部，申请和获授权国际国内发明专利150余项.
- 基金信息：
  
  国家重点研发计划(2022YFC2104702);山东省自然科学基金(基金号 ZR2024MB025)
- DOI：10.11777/j.issn1000-3304.2026.26075
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7614
- 收稿：2026-03-13，
  
  录用：2026-04-29，
  
  网络首发：2026-06-17，
- 稿件说明：
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刘金良, 王凤, 刘恒, 张学全. 配位聚合二烯烃橡胶的官能化. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26075.

Liu, J. L.; Wang, F.; Liu, H.; Zhang, X Q. Functionalization of polydienes by coordination polymerization. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26075.
刘金良, 王凤, 刘恒, 张学全. 配位聚合二烯烃橡胶的官能化. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26075. DOI： CSTR： 32057.14.GFZXB.2026.7614.

Liu, J. L.; Wang, F.; Liu, H.; Zhang, X Q. Functionalization of polydienes by coordination polymerization. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26075. DOI： CSTR： 32057.14.GFZXB.2026.7614.

摘要

聚二烯烃橡胶多应用于复杂多组分体系，其分子骨架主要由碳、氢元素组成，整体极性较低. 这一结构特征使其与各类极性填料、助剂等组分的相容性较差，进而限制了材料综合性能的提升与应用范围的拓展. 在聚二烯烃橡胶分子链中引入含杂原子的官能团，可在保留其优异弹性的基础上，显著改善与极性组分间的界面相互作用及相容性，是当前提升聚二烯烃橡胶综合性能、拓宽其应用场景的重要技术途径. 配位聚合能够精准调控聚二烯烃橡胶的链结构与立体构型，是制备高结构规整性橡胶材料的关键方法，已在多种工业橡胶的生产中得到应用. 然而，受杂原子对催化活性中心的毒化作用影响，采用配位聚合法制备官能化聚二烯烃橡胶仍面临较大挑战. 本文系统综述了基于配位聚合路线构筑官能化聚二烯烃橡胶的研究进展，重点归纳出两类主要策略：一是通过共轭二烯烃与含极性官能团的单体直接共聚，在聚合过程中实现官能化；二是基于反应性基团官能化法，利用聚合形成的活性链端与特定小分子试剂反应，实现链端功能化. 同时，总结了不同金属催化体系在调控聚合行为与官能团引入方面的特点，以期为该领域的后续发展提供清晰思路与理论参考.

Abstract

Polydiene rubbers are widely used in complex multicomponent systems. The backbone of polydienes is mainly composed of carbon and hydrogen atoms

resulting in their inherently low polarity

leading to their poor compatibility with various polar fillers

additives

and other components

which consequently limits their overall performance and broader applications. Introducing heteroatom-containing functional groups into the polymer chains can significantly enhance the interfacial interactions and compatibility with polar components

while preserving their excellent elasticity. Therefore

functionalization has recently emerged as an important strategy for improving the comprehensive performance of polydiene rubbers and expanding their potential applications. Coordination polymerization enables p

recise control over the chain microstructure and stereoregularity of polydiene rubbers and has become a key strategy for preparing highly regular rubber materials. This method has also been widely applied in the industrial production of synthetic rubbers. However

the preparation of functionalized polydiene rubbers

via

coordination polymerization remains highly challenging because the heteroatoms in polar functional groups often poison the catalytically active centers. To address these challenges

this review systematically summarizes recent advances in the synthesis of functionalized polydiene rubbers

via

coordination-polymerization strategies. Two main approaches are highlighted: (1) direct copolymerization of conjugated dienes with polar functional comonomers to achieve in-chain functionalization during polymerization

and (2) chain-end functionalization

in which the active chain ends generated during polymerization react with specific small-molecule reagents to introduce functional groups at the chain termini. For the latter

four different methods

including nucleophilic addition

nucleophilic substitution

metal methathesis

and functionalized co-catalyst activation

were employed to incorporate functional groups into the

-end

and both

- and

-ends. In addition

the characteristics of different catalytic systems in regulating polymerization behavior and facilitating functional group incorporation are discussed

with the aim of providing useful insights and theoretical guidance for future developments in this field.

关键词

Keywords

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