Recent Advances in Catalysts for Coordination Copolymerization of Ethylene and Butadiene

LI Bo; CHEN Jian-jun; LI Shi-hui; CUI Dong-mei

doi:10.14028/j.cnki.1003-3726.2025.25.041

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Recent Advances in Catalysts for Coordination Copolymerization of Ethylene and Butadiene

更新时间：2025-07-15

- Recent Advances in Catalysts for Coordination Copolymerization of Ethylene and Butadiene
- Polymer Bulletin Vol. 38, Issue 8, Pages: 1209-1217(2025)
- 作者机构：
  
  1.中国科学院长春应用化学研究所高分子科学与技术全国重点实验室，长春 130022
  2.中石化(北京)化工研究院有限公司橡塑新型材料合成国家工程研究中心，北京 102500
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.041
  CLC：
- Received：10 March 2025，
  
  Accepted：14 April 2025，
  
  Published Online：23 June 2025，
  
  Published：20 August 2025
- 稿件说明：
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李博, 陈建军, 李世辉, 崔冬梅. 乙烯与丁二烯共聚合催化体系研究进展. 高分子通报, 2025, 38(8), 1209–1217.

Li, B.; Chen, J. J.; Li, S. H.; Cui, D. M. Recent advances in catalysts for coordination copolymerization of ethylene and butadiene. Polym. Bull. (in Chinese), 2025, 38(8), 1209–1217.
李博, 陈建军, 李世辉, 崔冬梅. 乙烯与丁二烯共聚合催化体系研究进展. 高分子通报, 2025, 38(8), 1209–1217. DOI： 10.14028/j.cnki.1003-3726.2025.25.041.

Li, B.; Chen, J. J.; Li, S. H.; Cui, D. M. Recent advances in catalysts for coordination copolymerization of ethylene and butadiene. Polym. Bull. (in Chinese), 2025, 38(8), 1209–1217. DOI： 10.14028/j.cnki.1003-3726.2025.25.041.

摘要

乙烯与丁二烯共聚物因其独特的物理力学性能和广泛的应用潜力，一直是高分子合成领域的研究热点。本文综述了乙烯与丁二烯共聚合催化体系的研究进展，重点介绍了齐格勒-纳塔催化剂、茂金属催化剂、限制几何构型催化剂、非茂金属催化剂和稀土催化剂等在共聚中的应用。研究表明，稀土催化剂在活性、丁二烯插入率及其序列分布方面表现出显著优势，活性可达1640 kg/(mol·h)，丁二烯插入率最高达89 mol%，且产物具有优异的物理力学性能。相比之下，齐格勒-纳塔催化剂活性较低，产物中常混有聚乙烯或聚丁二烯均聚物；茂金属催化剂活性和丁二烯插入率较低，且易生成环状结构；限制几何构型催化剂虽在活性和丁二烯插入率上有所提升，但对丁二烯浓度敏感；非茂金属催化剂在活性和丁二烯插入率上取得进展，但如何同时提高活性、丁二烯插入率和产物分子量仍是亟待解决的问题。展望了乙烯与丁二烯共聚合的未来发展方向，开发新型催化剂和聚合方法，实现乙烯与丁二烯的高效、可控共聚合，仍是未来研究的重点。

Abstract

Ethylene-butadiene copolymers have long been a research focus because of their unique physical and mechanical properties and broad application potential. This review provides an overview of the progress in catalytic systems for ethylene-butadiene copolymerization

with an emphasis on the applications of Ziegler-Natta

metallocene

constrained geometry

non-metallocene

and rare-earth metal catalysts in copolymerization. Rare-earth metal catalysts exhibit significant advantages in terms of activity

butadiene insertion rate

and sequence distribution

achieving an activity of 1640 kg/(mol·h) and butadiene insertion rate of 89 mol%. In contrast

Ziegler-Natta catalysts have lower activity and often produce mixtures containing polyethylene or polybutadiene; metallocene catalysts have lower activity and butadiene insertion rates and tend to form cyclic structures; constrained geometry catalysts

although improved in activity and butadiene insertion rate

are sensitive to butadiene concentration; and non-metallocene catalysts have made progress in activity and butadiene insertion rate

but the challenge of simultaneously enhancing activity

butadiene insertion rate

and copolymer molecular weight remains to be addressed. This review also discusses the future development directions of ethylene-butadiene copolymerization

highlighting that rare-earth metal catalysts are expected to play an increasingly important role in this field. The development of new catalysts and polymerization methods to achieve the efficient and controlled copolymerization of ethylene and butadiene remains a key focus for future research.

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references

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