Determination of the Coordination Polymerization Kinetic Parameters—The Modification of Coordination Polymerization in <italic style="font-style: italic">Polymer Chemistry</italic>

FU Zhi-sheng

doi:10.14028/j.cnki.1003-3726.2025.24.387

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Determination of the Coordination Polymerization Kinetic Parameters—The Modification of Coordination Polymerization in Polymer Chemistry

更新时间：2025-05-23

- Determination of the Coordination Polymerization Kinetic Parameters—The Modification of Coordination Polymerization in Polymer Chemistry
- Polymer Bulletin Vol. 38, Issue 6, Pages: 942-949(2025)
- 作者机构：
  
  浙江大学，高分子合成与功能构造教育部重点实验室，高分子科学与工程学系，山西浙大新材料与化工研究院，浙江大学-星庐科技高端聚烯烃联合研发中心，杭州 310058
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.24.387
  CLC：
- Received：21 December 2024，
  
  Accepted：26 January 2025，
  
  Published Online：25 March 2025，
  
  Published：20 June 2025
- 稿件说明：
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傅智盛. 配位聚合动力学参数的测定：《高分子化学》教材中配位聚合部分的修改建议. 高分子通报, 2025, 38(6), 942-949.

Fu, Z. S. Determination of the coordination polymerization kinetic parameters—the modification of coordination polymerization in Polymer Chemistry. Polym. Bull. (in Chinese), 2025, 38(6), 942-949.
傅智盛. 配位聚合动力学参数的测定：《高分子化学》教材中配位聚合部分的修改建议. 高分子通报, 2025, 38(6), 942-949. DOI： 10.14028/j.cnki.1003-3726.2025.24.387.

Fu, Z. S. Determination of the coordination polymerization kinetic parameters—the modification of coordination polymerization in Polymer Chemistry. Polym. Bull. (in Chinese), 2025, 38(6), 942-949. DOI： 10.14028/j.cnki.1003-3726.2025.24.387.

摘要

烯烃配位聚合是高分子化学教学中的一个重要模块。自20世纪50年代Ziegler和Natta用TiCl

-Al（C

）

催化乙烯聚合，或Natta用TiCl

-Al（C

）

Cl催化丙烯聚合开始，至今已七十余年。目前大多高校选用的潘祖仁先生主编的《高分子化学（第五版）》和增强版教材中，涉及的乙烯或丙烯配位聚合的动力学参数都是早期测得的活性中心数和增长速率常数。由于早期实验条件有限，对聚合机理的认识也有一定的局限性，而且仅限于TiCl

-Al（C

）

或TiCl

-Al（C

）

Cl催化体系，导致测得的活性中心数[C

]

很低（约0.1%~1% Ti），增长速率常数也很低（如80 L·mol

−1

·s

−1

）。实际上，随着人们对配位聚合的认识不断深入，新型的烯烃配位聚合催化体系不断涌现，如负载型的Ziegler-Natta催化体系、茂金属催化体系、FI催化体系和非茂后过渡金属催化体系。同时，随着实验条件的不断改善，实验手段和技术的不断进步，人们能够更加准确地测量乙烯或丙烯配位聚合的动力学参数，逐渐认识到在烯烃配位聚合过程中，活性中心数和增长速率常数实际上可以很高。本文就近年来对负载型Ziegler-Natta催化体系、茂金属催化体系和非茂后过渡金属催化体系进行的聚合动力学参数测试的方法和结果进行了详细分析，提出了该部分内容需要在《高分子化学》教材中进行修改和完善的建议。

Abstract

Olefin coordination polymerization is an important module in polymer chemistry education. Since Ziegler and Natta used TiCl

-Al(C

)

to catalyze ethylene polymerization or Natta used TiCl

-Al(C

)

Cl to catalyze propylene polymerization in the 1950s

more than seventy years have passed. Currently

the textbook “

Polymer Chemistry

edition)” and its enhanced version edited by Prof. PAN Zu-ren

widely used in most universities

where the kinetic parameters for ethylene or propylene coordination polymerization are based on the activity center numbers and chain propagation rate constants measured early on. Owing to the limited experimental conditions in the early days

there were certain limitations in understanding the polymerization mechanism; it was confined to TiCl

-Al(C

)

or TiCl

-Al(C

)

Cl catalytic systems

leading to very low activity center numbers [C

]

(approximately 0.1%–1% Ti) and chain propagation rate constants (such as 80 L·mol

−1

·s

−1

). As our understanding of coordination polymerization has deepened

new olefin coordination polymerization catalytic systems have emerged

such as supported Ziegler-Natta catalytic systems

metallocene catalytic systems

FI catalytic systems

and non-metallocene post-transition metal catalytic systems. At the same time

with continuous improvements in the experimental conditions and techniques

the kinetic parameters of ethylene or propylene coordination polymerization can now be measured more accurately. Researchers have gradually realized that the activity center numbers and chain propagation rate constants in olefin coordination polymerization can actually be quite high. This article provides a detailed analysis of the methods and results of recent investigations on polymerization kinetic parameters using supported Ziegler-Natta catalytic systems

metallocene catalytic systems

and non-metallocene post-transition metal catalytic systems

and offers suggestions for revising and improving this section in the

Polymer Chemistry

textbook.

关键词

Keywords

references

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⁰

Determination of the Coordination Polymerization Kinetic Parameters—The Modification of Coordination Polymerization in Polymer Chemistry

DOI：10.14028/j.cnki.1003-3726.2025.24.387

摘要

Abstract

关键词

Keywords

references