浏览全部资源
扫码关注微信
α- 二亚胺镍催化剂与烯烃聚合—《高分子化学》教材中配位聚合部分的增补建议α- Diimine Nickel Catalyst and Olefin Polymerization—Supplementary Suggestions for the “Coordination Polymerization ” Section in the “Polymer Chemistry ” Textbook- 高分子通报 2025年38卷第1期 页码：137-145
- 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：
*傅智盛，E-mail: fuzs@zju.edu.cn
- 基金信息：山西浙大新材料与化工研究院成果转化项目(2021SZ-AT001)
DOI：10.14028/j.cnki.1003-3726.2024.24.222
中图分类号：收稿日期：2024-07-28，
录用日期：2024-09-25，
网络出版日期：2024-11-11，
纸质出版日期：2025-01-20
- 稿件说明：
移动端阅览
王程, 冯涛, 傅智盛. α-二亚胺镍催化剂与烯烃聚合：《高分子化学》教材中配位聚合部分的增补建议. 高分子通报, 2025, 38(1), 137–145.
Wang, C.; Feng, T.; Fu, Z. S. α-Diimine nickel catalyst and olefin polymerization—subpplementary subggestions for the “coordination polymerization” section in the “Polymer Chemistry” textook. Polym. Bull. (in Chinese), 2025, 38(1), 137–145.
王程, 冯涛, 傅智盛. α-二亚胺镍催化剂与烯烃聚合：《高分子化学》教材中配位聚合部分的增补建议. 高分子通报, 2025, 38(1), 137–145. DOI： 10.14028/j.cnki.1003-3726.2024.24.222.
Wang, C.; Feng, T.; Fu, Z. S. α-Diimine nickel catalyst and olefin polymerization—subpplementary subggestions for the “coordination polymerization” section in the “Polymer Chemistry” textook. Polym. Bull. (in Chinese), 2025, 38(1), 137–145. DOI： 10.14028/j.cnki.1003-3726.2024.24.222.
摘要
烯烃配位聚合是高分子化学教学中的一个重要部分。自20世纪50年代的“镍效应”发现开始，至今已七十余年。目前多数高校选用的潘祖仁教授主编的《高分子化学(第五版)》教材中，只涉及了Ziegler-Natta引发体系和茂金属引发体系，非茂后过渡金属催化剂仅在《高分子化学(增强版)》中有简短介绍，且“链行走”这一重要机理未见提及。从1995年Brookhart等报道的首个能够催化乙烯聚合制备高分子量聚乙烯的后过渡金属催化剂(即
α-
二亚胺镍催化剂)以来，近30年中，后过渡金属催化烯烃聚合，尤其是以镍金属为中心的烯烃聚合催化剂有了长足的发展。本文选取了具有链行走机理、具备催化
α-
烯烃聚合以及烯烃与极性单体共聚能力的
α-
二亚胺镍催化剂进行了详细分析，并对近年来后过渡金属烯烃聚合催化剂进行了简单介绍，提出了该部分需要增补入《高分子化学》教材的建议。
Abstract
Olefin polymerization
is a crucial part in polymer chemistry education. Since the discovery of the “nickel effect” in the 1950s
more than seventy years have passed. The textbook “
Polymer Chemistry
(
Fifth Edition
)” edited by Prof. PAN Zu-ren
widely used in many universities
primarily covers the Ziegler-Natta and metallocene initiation systems
with only a brief introduction to non-metallocene post-transition metal catalysts in the “
Polymer Chemistry
(
Enhanced Edition
)”. Moreover
the important mechanism of “chain walking” was not mentioned. Since Brookhart
et al
. reported the first post-transition metal catalyst could catalyze ethylene polymerization to produce high molecular weight polyethylene (
i
.
e
.
α
-diimine nickel catalysts) in 1995
the field of olefin polymerization catalyzed by post-transition metals
especially nickel-based catalysts
has made significant progress over the past 30 years. This paper provides a detailed analysis of
α
-diimine nickel catalysts
which exhibit the chain walking mechanism and possess the ability to catalyze
α
-olefin polymerization and the copolymerization of olefins with polar monomers. Additionally
it offers a brief overview of recent advancements in post-transition metal olefin polymerization catalysts and proposes suggestions for incorporating this content into the “
Polymer Chemistry
” textbook.
关键词
Keywords
references
Hustad, P. D . Frontiers in olefin polymerization: reinventing the world’s most common synthetic polymers . Science , 2009 , 325 ( 5941 ), 704 – 707 .
Stürzel, M. ; Mihan, S. ; Mülhaupt, R . From multisite polymerization catalysis to sustainable materials and all-polyolefin composites . Chem. Rev. , 2016 , 116 ( 3 ), 1398 – 1433 .
焦书科 . 烯烃配位聚合理论与实践 . 2版 . 北京 : 化学工业出版社 , 2013 , 20 - 22, 35-39 .
张丹枫 . 烯烃聚合 . 上海 : 华东理工大学出版社 , 2014 , 20 – 21 .
Johnson, L. K. ; Killian, C. M. ; Brookhart, M . New Pd(II)- and Ni(II)-based catalysts for polymerization of ethylene and α- olefins . J. Am. Chem. Soc. , 1995 , 177 , 6414 – 6416 .
Mu, H. L. ; Zhou, G. L. ; Hu, X. Q. ; Jian, Z. B . Recent advances in nickel mediated copolymerization of olefin with polar monomers . Coord. Chem. Rev. , 2021 , 435 , 213802 .
Zanchin, G. ; Leone, G . Polyolefin thermoplastic elastomers from polymerization catalysis: advantages, pitfalls and future challenges . Prog. Polym. Sci. , 2021 , 113 , 101342 .
Wang, Y. ; Gao, R. ; Gou, Q. Q. ; Lai, J. J. ; Zhang, R. D. ; Li, X. Y. ; Guo, Z. F . Developments in late transition metal catalysts with high thermal stability for ethylene polymerization: α crucial aspect from laboratory to industrialization . Eur. Polym. J. , 2022 , 181 , 111693 .
潘祖仁 . 高分子化学(增强版) . 北京 : 化学工业出版社 , 2007 , 213 – 214 .
潘祖仁 . 高分子化学 . 5版 . 北京 : 化学工业出版社 , 2011 , 193 , 207 – 208 .
Wang, F. Z. ; Chen, C. L . A continuing legend: the Brookhart-type α -diimine nickel and palladium catalysts . Polym. Chem. , 2019 , 10 ( 19 ), 2354 – 2369 .
Wu, R. K. ; Wu, W. K. ; Stieglitz, L. ; Gaan, S. ; Rieger, B. ; Heuberger, M . Recent advances on α -diimine Ni and Pd complexes for catalyzed ethylene (Co) polymerization: a comprehensive review . Coord. Chem. Rev. , 2023 , 474 , 214844 .
Liu, J. Y. ; Li, Y. G. ; Li, Y. S. ; Hu, N. H . Ethylene polymerization by ( α -diimine) nickel(II)complexes bear-ing different substituents on para -position of imines activated with MMAO . J. Appl. Polym. Sci. , 2008 , 109 ( 2 ), 700 – 707 .
Zhu, L. ; Zang, D. D. ; Wang, Y. ; Guo, Y. T. ; Jiang, B. Y. ; He, F. ; Fu, Z. S. ; Fan, Z. Q. ; Hickner, M. A. ; Liu, Z. K. ; Chen, L. Q . Insight into the mechanism of thermal stability of α -diimine nickel complex in catalyzing ethylene polymerization . Organometallics , 2017 , 36 ( 6 ), 1196 – 1203 .
Wang, C. ; Wang, D. ; Xu, T. ; Zhang, Q. S. ; Fu, Z. S . Effect of N-aryl para-benzhydryl substituent on the thermal stability of α -diimine nickel catalyst . Macromol. Rapid Commun. , 2023 , 44 ( 18 ), e2300221 .
Wang, C. ; Tang, S. Z. ; He, Y. Y. ; Xu, T. ; Fu, Z. S . Preparation of polyethylene elastomers with increased high molecular weight and nearly perfect strain recovery by steric control of asymmetric α -diimine nickel catalyst . Inorg. Chim. Acta , 2024 , 569 , 122120 .
Killian, C. M. ; Tempel, D. J. ; Johnson, L. K. ; Brookhart, M . Living polymerization of α -olefins using NiII- α -diimine catalysts. Synthesis of new block polymers based on α -olefins . J. Am. Chem. Soc. , 1996 , 118 ( 46 ), 11664 – 11665 .
McCord, E. F. ; McLain, S. J. ; Nelson, L. T. J. ; Ittel, S. D. ; Tempel, D. ; Killian, C. M. ; Johnson, L. K. ; Brookhart, M . 13 C NMR analysis of α -olefin enchainment in poly-( α -olefins) produced with nickel and palladium α -diimine catalysts . Macromolecules , 2007 , 40 ( 3 ), 410 – 420 .
邢震艳 . 不同骨架的不对称( α- 二亚胺)镍催化剂的催化聚合研究 . 硕士学位论文 , 杭州 : 浙江大学 , 2020 .
张昊 . α -二亚胺镍催化剂催化乙烯/甲基丁香酚共聚及其机理研究 . 硕士学位论文 , 杭州 : 浙江大学 , 2020 .
Johnson, L. K. ; Mecking, S. ; Brookhart, M . Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(II) cata-lysts . J. Am. Chem. Soc. , 1996 , 118 ( 1 ), 267 – 268 .
Small, B. L. ; Brookhart, M. ; Bennett, A. M. A . Highly active iron and cobalt catalysts for the polymerization of ethylene . J. Am. Chem. Soc. , 1998 , 120 ( 16 ), 4049 – 4050 .
Britovsek, G. J. P. ; Gibson, V. C. ; McTavish, S. J. ; Solan, G. A. ; White, A. J. P. ; Williams, D. J. ; Kimberley, B. S. ; Maddox, P. J . Novel olefin polymerization catalysts based on iron and cobalt . Chem. Commun. , 1998 , ( 7 ), 849 – 850 .
Wang, C. M. ; Friedrich, S. ; Younkin, T. R. ; Li, R. T. ; Grubbs, R. H. ; Bansleben, D. A. ; Day, M. W . Neutral nickel(II)-based catalysts for ethylene polymerization . Organometallics , 1998 , 17 ( 15 ), 3149 – 3151 .
Younkin, T. R. ; Connor, E. F. ; Henderson, J. I. ; Friedrich, S. K. ; Grubbs, R. H. ; Bansleben, D. A . Neutral, single-component nickel(II)polyolefin catalysts that tolerate heteroatoms . Science , 2000 , 287 ( 5452 ), 460 – 462 .
Baur, M. ; Lin, F. ; Morgen, T. O. ; Odenwald, L. ; Mecking, S . Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization . Science , 2021 , 374 ( 6567 ), 604 – 607 .
傅智盛 , 臧丹丹 , 范志强 , 李杰威 . 一种聚乙烯橡胶及其加工方法 . 中国专利 , CN201410200113.6 , 2016-05–11 .
徐涛 , 傅智盛 , 李寒莹 . 常温下非晶态聚乙烯内聚能密度的测定及其应用 . 高分子通报 , 2024 , 37 ( 2 ), 263 – 269 .
傅智盛 , 朱良 , 范志强 . 亚乙基苊( α- 二亚胺)镍烯烃催化剂及其制备方法与应用 . 中国专利 , CN2012-10276331.9 , 2014-04–09 .
傅智盛 , 何峰 , 范志强 . 亚乙烯基苊( α- 二亚胺)镍烯烃催化剂、制备方法及应用 . 中国专利 , CN2017-10996283.3 , 2018-05–08 .
傅智盛 , 何峰 , 邢震艳 , 朱越洲 , 范志强 . 5,6-二甲基苊( α- 二亚胺)镍烯烃催化剂及其制备与应用 . 中国专利 , CN201710326135.0 , 2018-11–23 .
0
浏览量
93
下载量
0
CSCD
- 网络PDF下载
- Meta-XML下载
- BibTeX下载
- Endnote下载
- RefMan 下载
- NoteExpress下载
- NoteFirst下载
关联资源
相关文章
相关作者
相关机构
- 技术支持由北京北大方正电子有限公司提供 京ICP备09064830号-19
京公网安备11010802024621 - 本系统建议在Chrome、 IE9+ 以上版本浏览器阅读本站内容，360浏览器请切换至极速模式
- Cookies帮助我们提供服务并提供个性化体验。使用本网站，即表示您同意我们使用Cookies