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

韩迎霞; 杜莎莎; 江立航; 刘绍峰

doi:10.14028/j.cnki.1003-3726.2026.26.144

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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

综述 | 更新时间：2026-07-04

- 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
- Recent Advances in Coordination Polymerization of Nonconjugated Dienes: Insertion Pathway Competition and Polymer Microstructure Control
- 高分子通报 2026年
- 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：
  
  shaofengliu@qust.edu.cn
- 基金信息：
  
  国家自然科学基金(52573011;22371157);山东省自然科学基金(ZR2024JQ015)
- DOI：10.14028/j.cnki.1003-3726.2026.26.144
  中图分类号：
- 收稿：2026-03-19，
  
  录用：2026-04-28，
- 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, 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), doi: 10.14028/j.cnki.1003-3726.2026.26.144
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, doi: 10.14028/j.cnki.1003-3726.2026.26.144 DOI：

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), doi: 10.14028/j.cnki.1003-3726.2026.26.144 DOI：

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α-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 α-olefin polymerization systems

while simultaneously providing new molecular design strategies 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.

关键词

Keywords

references

王笃金 . 聚烯烃: 创新一直在路上 . 科学通报 , 2022 , 67 ( 17 ), 1851 – 1852 .

陈敏 , 陈昶乐 . 官能团化聚烯烃: 新催化剂、新聚合调控手段、新材料 . 高分子学报 , 2018 , ( 11 ), 1372 – 1384 .

陈敏 , 陈昶乐 . 功能化聚烯烃材料的制备与性质研究 . 高分子通报 , 2021 , ( 6 ), 26 – 34 .

董金勇 . 聚合新方法研究对我国聚烯烃高性能化技术发展的重要性和可行性 . 科学通报 , 2022 , 67 ( 17 ), 1863 – 1869 .

Zhang, M. K. ; Kränzlein, M. ; Cui, S. L. ; LaPointe, A. M. ; Coates, G. W . C－H insertion functionalization of polyolefins for versatile polyolefin-polyester compatibilization . J. Am. Chem. Soc. , 2026 , 148 ( 4 ), 4599 – 4604 .

Pérez-Ruíz, J. ; Ramírez, M. R. ; Rentero, C. ; Sessini, V. ; Mosquera, M. E. G. ; Díaz-Requejo, M. M. ; Pérez, P. J . Functionalization of polyolefins via catalytic nitrene addition . Angew. Chem. Int. Ed. , 2025 , 64 ( 51 ), e22659 .

D’Anania, O. ; De Stefano, F. ; De Rosa, C. ; Talarico, G. ; Di Girolamo, R . Closing the loop of cyclopolymerization of nonconjugated α , ω -diolefin diasteroselectivity and α -olefin polymerization enantioselectivity . ACS Catal. , 2024 , 14 ( 22 ), 16649 – 16662 .

Palucci, B. ; Zanchin, G. ; Ricci, G. ; Vendier, L. ; Lorber, C. ; Leone, G . Vanadium-catalyzed terpolymerization of α , ω -dienes with ethylene and cyclic olefins: ready access to polar-functionalized polyolefins . Macromolecules , 2021 , 54 ( 23 ), 10700 – 10711 .

Sarzotti, D. M. ; Narayan, A. ; Whitney, P. M. ; Simon, L. C. ; Soares, J. B. P . Microstructural characterization of molecular weight fractions of ethylene/1, 7-octadiene copolymers made with a constrained geometry catalyst . Macromol. Mater. Eng. , 2005 , 290 ( 6 ), 584 – 591 .

Cheng, H. N. ; Khasat, N. P . 13 C-NMR characterization of poly(1,5-hexadiene) . J. Appl. Polym. Sci. , 1988 , 35 ( 3 ), 825 – 829 .

Marvel, C. S. ; Stille, J. K . Intermolecular-intramolecular polymerization of α -diolefins by metal alkyl coördi-nation catalysts1 . J. Am. Chem. Soc. , 1958 , 80 ( 7 ), 1740 – 1744 .

Resconi, L. ; Waymouth, R. M . Diastereoselectivity in the homogeneous cyclopolymerization of 1,5-hexadiene . J. Am. Chem. Soc. , 1990 , 112 ( 12 ), 4953 – 4954 .

Sernetz, F. G. ; Mülhaupt, R. ; Waymouth, R. M . Homo-, co- and terpolymerization of 1,5-hexadiene using a methylalumoxane activated mono-Cp-amido-complex . Polym. Bull. , 1997 , 38 ( 2 ), 141 – 148 .

Doi, Y. ; Tokuhiro, N. ; Soga, K . Synthesis and structure of a “living” copolymer of propylene and 1,5-hexadiene . Die Makromol. Chem. , 1989 , 190 ( 3 ), 643 – 651 .

Naga, N. ; Imanishi, Y . Copolymerization of ethylene and 1, 5-hexadiene with zirconocene catalysts . Macromol. Chem. Phys. , 2002 , 203 ( 4 ), 771 – 777 .

Naga, N. ; Imanishi, Y . Copolymerization of ethylene and 1,7-octadiene, 1,9-decadiene with zirconocene catalysts . Macromol. Chem. Phys. , 2002 , 203 ( 15 ), 2155 – 2162 .

Naga, N. ; Toyota, A . Unique insertion mode of 1,7-octadiene in copolymerization with ethylene by a constrained-geometry catalyst . Macromol. Rapid Commun. , 2004 , 25 ( 18 ), 1623 – 1627 .

Shi, X. C. ; Wang, Y. X. ; Liu, J. Y. ; Cui, D. M. ; Men, Y. F. ; Li, Y. S . Stereospecific cyclopolymerization of α , ω -diolefins by pyridylamidohafnium catalyst with the highest activity . Macromolecules , 2011 , 44 ( 4 ), 1062 – 1065 .

Shi, X. C. ; Tang, X. Y. ; Li, Y. S . Random copolymers of propylene with 1,5-hexadiene containing only cyclopentane units in main chain and tailoring structure and mechanical properties of the copolymers . Polymer , 2011 , 52 ( 14 ), 3053 – 3058 .

De Stefano, F. ; Villaccio, R. ; D’Anania, O. ; Talarico, G. ; De Rosa, C. ; Scoti, M . Combining cyclic units and unsaturated pendant groups by propene/1,5-hexadiene copolymerization toward functional isotactic polypropylene . ACS Macro Lett. , 2024 , 13 ( 4 ), 407 – 414 .

He, L. L. ; Wang, B. ; Yang, F. ; Li, Y. S. ; Ma, Z . Featured crystallization polymorphism and memory effect in novel butene-1/1,5-hexadiene copolymers synthesized by post-metallocene hafnium catalyst . Macromolecules , 2016 , 49 ( 17 ), 6578 – 6589 .

Wang, B. ; Wang, Y. X. ; Cui, J. ; Long, Y. Y. ; Li, Y. G. ; Yuan, X. Y. ; Li, Y. S . Cyclopolymerization of Si-containing α , ω -diolefins by a pyridylamidohafnium catalyst with high cyclization selectivity and stereoselectivity . Macromolecules , 2014 , 47 ( 19 ), 6627 – 6634 .

Wang, Y. F. ; Huang, D. ; Gao, X. H. ; Wang, F. ; Cai, H. ; Pan, L. ; Li, Y. S . Low reflective index, highly transparent, and ultra-low dielectric constant materials prepared via effective copolymerization of 4-methyl-1-pentene and a Si-containing α , ω -diolefin . Polym. Chem. , 2024 , 15 ( 25 ), 2573 – 2582 .

Wallace, M. A. ; Wentz, C. M. ; Sita, L. R . Optical purity as a programmable variable for controlling polyolefin tacticity in living coordinative chain transfer polymerization: application to the stereomodulated LCCTP of α , ω -nonconjugated dienes . ACS Catal. , 2021 , 11 ( 8 ), 4583 – 4592 .

Wang, H. B. ; Zhao, Y. N. ; Nishiura, M. ; Yang, Y. ; Luo, G. ; Luo, Y. ; Hou, Z. M . Scandium-catalyzed regio- and stereoselective cyclopolymerization of functionalized α , ω -dienes and copolymerization with ethylene . J. Am. Chem. Soc. , 2019 , 141 ( 32 ), 12624 – 12633 .

Guo, F. ; Nishiura, M. ; Koshino, H. ; Hou, Z. M . Scandium-catalyzed cyclocopolymerization of 1,5-hexadiene with styrene and ethylene: Efficient synthesis of cyclopolyolefins containing syndiotactic styrene-styrene sequences and methylene-1,3-cyclopentane units . Macromolecules , 2011 , 44 ( 16 ), 6335 – 6344 .

Coates, G. W. ; Waymouth, R. M . Enantioselective cyclopolymerization of 1,5-hexadiene catalyzed by chiral zirconocenes: a novel strategy for the synthesis of optically active polymers with chirality in the main chain . J. Am. Chem. Soc. , 1993 , 115 ( 1 ), 91 – 98 .

Hustad, P. D. ; Coates, G. W . Insertion/isomerization polymerization of 1,5-hexadiene: synthesis of functional propylene copolymers and block copolymers . J. Am. Chem. Soc. , 2002 , 124 ( 39 ), 11578 – 11579 .

Naga, N. ; Shiono, T. ; Ikeda, T . Cyclopolymerization of 1,7-octadiene with metallocene/methylaluminoxane . Macromol. Chem. Phys. , 1999 , 200 ( 6 ), 1466 – 1472 .

Nomura, K. ; Liu, J. Y. ; Fujiki, M. ; Takemoto, A . Facile, efficient functionalization of polyolefins via controlled incorporation of terminal olefins by repeated 1,7-octadiene insertion . J. Am. Chem. Soc. , 2007 , 129 ( 46 ), 14170 – 14171 .

Han, Y. X. ; Li, M. N. ; Liu, S. F. ; Li, Z. B . Hafnium-catalyzed controlled polymerization of 1,5-hexadiene toward polyolefin-based graft copolymers for poly(lactic acid) toughening with high transparency . Organometallics , 2025 , 44 ( 17 ), 1926 – 1936 .

Bonnet, F. ; Visseaux, M. ; Barbier-Baudry, D. ; Dormond, A . Copolymerization of isoprene with nonconjugated α , ω -dienes using a single component samarocene catalyst . Macromolecules , 2002 , 35 ( 4 ), 1143 – 1145 .

Hou, W. J. ; Zhang, D. ; Camacho-Fernandez, M. A. ; Zhang, Y. L. ; Liu, G. X. ; Tang, Y. ; Guan, Z. B. ; Huang, Z . Double-linear insertion mode of α , ω -dienes enabled by thio-imino-quinoline iron catalyst . ACS Catal. , 2020 , 10 ( 24 ), 15092 – 15103 .

Yang, T. T. ; Qin, Y. W. ; Dong, J. Y . Nonconjugated α , ω -diolefin/propylene copolymerization to long chain-branched polypropylene by Ziegler-Natta catalyst: overcoming steric hindrance by introducing an extra electronic pulling effect . Macromolecules , 2018 , 51 ( 22 ), 9234 – 9249 .

董金勇 . Ziegler-Natta催化剂的功能化及聚烯烃高性能化 . 高分子通报 , 2021 , ( 6 ), 15 – 25 .

Liu, Y. ; Qin, Y. W. ; Dong, J. Y . Assessing 1,9-decadiene/ethylene copolymerization with Ziegler-Natta catalyst to access long chain-branched polyethylene . ACS Omega , 2021 , 6 ( 1 ), 675 – 679 .

Santoro, O. ; Piola, L. ; Mc Cabe, K. ; Lhost, O. ; Den Dauw, K. ; Fernandez, A. ; Welle, A. ; Maron, L. ; Carpentier, J. F. ; Kirillov, E . Comonomer-controlled synthesis of long-chain branched (LCB)-polyethylene . Eur. Polym. J. , 2022 , 177 , 111477 .

Froese, R. D. ; Arriola, D. J. ; den Doelder, J. ; Hou, J. B. ; Kashyap, T. ; Lu, K. R. ; Martinetti, L. ; Stubbert, B. D . A commercially viable solution process to control long-chain branching in polyethylene . Science , 2024 , 383 ( 6688 ), 1223 – 1228 .

Zhu, B. B. ; Wang, H. T. ; Liu, K. ; Sun, M. H. ; Shi, Z. J. ; Wang, S. ; Huang, X. F. ; Shi, S. B. ; Zheng, J. Y. ; Yang, X. ; Liu, P. W. ; Wang, W. J . Development of polyolefin elastomers with distinct dual long-chain branch structures . Macromolecules , 2025 , 58 ( 19 ), 10336 – 10347 .

De Stefano, F. ; Scoti, M. ; De Rosa, C. ; Di Girolamo, R . Synthesis and characterization of 4-methyl-1-pentene/1,5-hexadiene isotactic copolymers with enhanced low-temperature mechanical performance . Macromolecules , 2024 , 57 ( 7 ), 3160 – 3172 .

Leone, G. ; Palucci, B. ; Zanchin, G. ; Vignali, A. ; Ricci, G. ; Bertini, F . Dynamically cross-linked polyolefins via hydrogen bonds: tough yet soft thermoplastic elastomers with high elastic recovery . ACS Appl. Polym. Mater. , 2022 , 4 ( 5 ), 3770 – 3778 .

简忠保 . 功能化聚烯烃合成: 从催化剂到极性单体设计 . 高分子学报 , 2018 , ( 11 ), 1359 – 1371 .

陈敏 , 陈昶乐 . 镍催化剂用于功能化聚烯烃材料的制备 . 科学通报 , 2022 , 67 ( 17 ), 1881 – 1894 .

Wang, Q. ; Sun, H. X. ; Zou, C. ; Chen, C. L . Photo-, thermal-, and electro-responsive polyolefin-based actuators . Angew. Chem. Int. Ed. , 2026 , 65 ( 8 ), e23449 .

Huang, X. F. ; Zheng, J. Y. ; Zhou, J. Y. ; Wu, Y. F. ; Wang, J. W. ; Raza, S. ; Liu, P. W. ; Wang, W. J. ; Shi, S. B . Recent advances in transition metal-catalyzed ethylene/polar olefin copolymerization . Coord. Chem. Rev. , 2026 , 548 , 217147 .

Xiao, Y. K. ; Liu, P. W. ; Wang, W. J. ; Li, B. G . Dynamically cross-linked polyolefin elastomers with highly improved mechanical and thermal performance . Macromolecules , 2021 , 54 ( 22 ), 10381 – 10387 .

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