Recent Advances in Coordination Polymerization of Nonconjugated Dienes: Insertion Pathway Competition and Polymer Microstructure Control

HAN Ying-xia; DU Sha-sha; JIANG Li-hang; LIU Shao-feng

doi:10.14028/j.cnki.1003-3726.2026.26.144

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Recent Advances in Coordination Polymerization of Nonconjugated Dienes: Insertion Pathway Competition and Polymer Microstructure Control

更新时间：2026-07-27

- Recent Advances in Coordination Polymerization of Nonconjugated Dienes: Insertion Pathway Competition and Polymer Microstructure Control
- Polymer Bulletin Vol. 39, Issue 8, Pages: 1373-1389(2026)
- 作者机构：
  
  青岛科技大学高分子科学与工程学院　青岛 266042
  青岛科技大学高性能有机光学聚合物与先进制造技术全国重点实验室　青岛 266042
  青岛科技大学山东省聚烯烃材料与循环利用重点实验室　青岛 266042
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2026.26.144
  CLC：
- Received：19 March 2026，
  
  Accepted：28 April 2026，
  
  Online First：03 July 2026，
  
  Published：20 August 2026
- 稿件说明：
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韩迎霞, 杜莎莎, 江立航, 刘绍峰. 非共轭二烯烃配位聚合研究进展：插入路径竞争与聚合物结构调控. 高分子通报, 2026, 39(8), 1373–1389.

Han, Y. X.; Du, S. S.; Jiang, L. H.; Liu, S. F. Recent advances in coordination polymerization of nonconjugated dienes: insertion pathway competition and polymer microstructure control. Polym. Bull. (in Chinese), 2026, 39(8), 1373–1389.
韩迎霞, 杜莎莎, 江立航, 刘绍峰. 非共轭二烯烃配位聚合研究进展：插入路径竞争与聚合物结构调控. 高分子通报, 2026, 39(8), 1373–1389. DOI： 10.14028/j.cnki.1003-3726.2026.26.144.

Han, Y. X.; Du, S. S.; Jiang, L. H.; Liu, S. F. Recent advances in coordination polymerization of nonconjugated dienes: insertion pathway competition and polymer microstructure control. Polym. Bull. (in Chinese), 2026, 39(8), 1373–1389. DOI： 10.14028/j.cnki.1003-3726.2026.26.144.

摘要

非共轭二烯烃是在配位聚合体系中表现出特殊反应行为的一类单体，分子中含有2个彼此不共轭的碳碳双键，在过渡金属催化剂作用下可产生多种插入路径并形成不同结构类型的聚合物，包括分子内环化形成环状结构、悬挂双键的保留、主链内部双键的生成以及长链支化结构的构筑。非共轭二烯烃参与聚合使反应过程较传统

-烯烃体系更加复杂，同时为聚烯烃结构调控与功能化提供了新的分子设计途径。随着茂金属、后茂金属及限定几何构型催化剂等配位聚合体系的发展，研究逐步深化了对非共轭二烯烃插入方式及聚合物微观结构调控规律的认识，并获得了一系列具有环状结构、悬挂双键及长链支化等特征的聚烯烃材料。本文综述了非共轭二烯烃配位聚合的研究进展，归纳了不同插入路径的形成机理与结构特征，总结了催化剂结构、单体结构及反应条件对聚合行为和聚合物结构的影响，并讨论了该类单体在聚烯烃结构设计与功能化材料构筑中的应用前景。

Abstract

Nonconjugated dienes are a class of monomers that exhibit unique reactivity in coordination polymerization systems. These monomers contain two electronically isolated carbon-carbon double bonds

which can undergo multiple insertion pathways in the presence of transition metal catalysts

leading to diverse polymer microstructures. Typical structural motifs generated from these reactions include intramolecular cyclization to form cyclic units

retention of pendant double bonds

formation of internal double bonds in the polymer backbone

and the construction of long-chain branched architectures. The incorporation of nonconjugated dienes significantly increases the complexity of polymerization processes compared to conventional

-olefin polymerization systems

while simultaneously providing new molecular design stra

tegies for polyolefin structure regulation and functionalization. With the development of coordination polymerization systems such as metallocene

post-metallocene

and constrained geometry catalysts

research has gradually deepened the understanding of the insertion modes of nonconjugated dienes and the regulation rules of polymer microstructures

and a series of polyolefin materials with characteristics such as cyclic structures

pendant double bonds

and long-chain branching have been obtained. This review summarizes the recent advances in the coordination polymerization of nonconjugated dienes. The mechanisms and structural characteristics of different insertion pathways are discussed

and the effects of the catalyst structure

monomer structure

and reaction conditions on the polymerization behavior and polymer microstructure are summarized. In addition

the potential applications of these monomers in polyolefin structure design and the development of functionalized polymeric materials are discussed.

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references

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