电子和空间位阻协同的<italic style="font-style: italic">α</italic>-二亚胺镍催化制备聚乙烯弹性体

岳静峰; 胡小强; 齐佳俊; 王玉银; 简忠保

doi:10.11777/j.issn1000-3304.2025.25058

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电子和空间位阻协同的α-二亚胺镍催化制备聚乙烯弹性体

研究论文 | 更新时间：2025-08-28

- 电子和空间位阻协同的α-二亚胺镍催化制备聚乙烯弹性体
- Synthesis of Polyethylene Elastomers via α-Diimine Ni(II) Catalysts with Electronic and Steric Synergistic Effects
- 高分子学报 2025年56卷第9期页码：1505-1517
- 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.中国科学技术大学应用化学与工程学院合肥 230026
  3.西华师范大学化学化工学院化学合成与污染控制四川省重点实验室南充 637002
- 作者简介：
  
  E-mail: yuyinwang@cwnu.edu.cn
  zbjian@ciac.ac.cn
- 基金信息：
  
  国家自然科学基金(基金号 U23B6011);吉林省科技厅项目(20230101347JC);四川省科技厅项目(2025ZNSFSC0916)
- DOI：10.11777/j.issn1000-3304.2025.25058
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7396
- 收稿日期：2025-03-02，
  
  录用日期：2025-04-07，
  
  网络出版日期：2025-05-08，
  
  纸质出版日期：2025-09-20
- 稿件说明：
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岳静峰, 胡小强, 齐佳俊, 王玉银, 简忠保. 电子和空间位阻协同的α-二亚胺镍催化制备聚乙烯弹性体.高分子学报, 2025, 56(9), 1505-1517

Yue, J. F.; Hu, X. Q.; Qi, J. J.; Wang, Y. Y.; Jian, Z. B. Synthesis of polyethylene elastomers via α-diimine Ni(II) catalysts with electronic and steric synergistic effects. Acta Polymerica Sinica, 2025, 56(9), 1505-1517
岳静峰, 胡小强, 齐佳俊, 王玉银, 简忠保. 电子和空间位阻协同的α-二亚胺镍催化制备聚乙烯弹性体.高分子学报, 2025, 56(9), 1505-1517 DOI： 10.11777/j.issn1000-3304.2025.25058. CSTR： 32057.14.GFZXB.2025.7396.

Yue, J. F.; Hu, X. Q.; Qi, J. J.; Wang, Y. Y.; Jian, Z. B. Synthesis of polyethylene elastomers via α-diimine Ni(II) catalysts with electronic and steric synergistic effects. Acta Polymerica Sinica, 2025, 56(9), 1505-1517 DOI： 10.11777/j.issn1000-3304.2025.25058. CSTR： 32057.14.GFZXB.2025.7396.

摘要

-二亚胺镍配合物因其特有的“链行走”聚合机理对聚合物主链结构中的支化密度与支化类型进行原位调节而备受关注，目前已被广泛用于聚烯烃弹性体(POE)合成研究. 在本工作中，合成了一系列基于电子和空间位阻协同效应的对称/不对称

-二亚胺镍催化剂，并将其用于乙烯聚合反应. 通过在苯胺3

5-位点引入甲氧基，一方面使其具有给电子效应，另一方面甲氧基与2

6-位点取代基具有排斥作用，从而将轴向位阻基团推向活性中心，对中心金属进行有效屏蔽. 基于3

5-三甲氧基取代的电子和空间位阻协同策略有效促进了乙烯链增长，并抑制链转移副反应的发生，这类催化剂普遍表现出很高的催化活性(高达1.1×10

g·mol

-1

·h

-1

)，可制备出分子量可调(

= 124~2106 kDa)，支化密度可调(41/1000C~103/1000C)的聚乙烯弹性体材料. 通过高温核磁共振碳谱分析，发现聚合物微观结构以甲基支化为主，乙基、正丙基、正丁基等短支链占比约20%. 对不同分子量梯度和支化梯度的聚乙烯样品进行了力学性能测试，这些高支化聚乙烯表现出低至中等的拉伸强度(2.16~12.33 MPa)和高断裂伸长率(339%~1339%)，表明聚合物具有非常好的韧性. 这些聚乙烯材料普遍具有良好的弹性回复性能，应变回复率最高可达91%.

Abstract

Nickel(II)

-diimine complexes have attracted significant attention due to their unique "chain-walking" polymerization mechanism

which enables

in situ

regulation of branching density and branching type in polymer backbone

and have been widely investigated for polyolefin elastomer (POE) synthesis. In this work

a series of symmetric/asymmetric

α‍

-diimi

ne nickel catalysts based on electronic and steric synergistic effects were synthesized and applied in ethylene polymerization. By introducing methoxy groups at the 3

5-positions of the aniline moiety

these substituents not only exhibit electron-donating effects

but also generate steric repulsion with 2

6-position substituents

thereby pushing axial steric groups close to the active center for effectively shielding the central metal. The 3

‍4

‍5-trimethoxy substitution strategy combining electronic and steric effects significantly promotes chain propagation while suppressing chain transfer reactions. These catalysts generally demonstrate high catalytic activities (up to 1.1×10

g·mol

-1

·h

-1

)

producing polyethylene elastomers with tunable molecular weights (

=124-2106 kDa) and tunable branching densities (41-103 branches/1000C). High-temperature

C-NMR analysis reveals that the polymer microstructure is dominated by methyl branches

with around 20% of short-chain branches (ethyl

-propyl

-butyl

etc.

) in total branches. Tensile testing of polyethylene samples with different molecular weights and branching densities show that these highly branched polyethylenes exhibit low-to-moderate tensile strength (2.16-12.33 MPa) and high elongation at break (339%-1339%)

indicating excellent toughness. These polyethylene materials generally demonstrate favorable elastic recovery properties

achieving a maximum strain recovery of 91%.

关键词

Keywords

references

Patel R. M. ; Jain P. ; Story B. ; Chum S. Polyethylene: an account of scientific discovery and industrial innovations . Innovations in Industrial and Engineering Chemistry . Washington, DC: American Chemical Society, 2008 , 71 - 102 . doi: 10.1021/bk-2009-1000.ch004 http://dx.doi.org/10.1021/bk-2009-1000.ch004

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 , 117 ( 23 ), 6414 - 6415 . doi: 10.1021/ja00128a054 http://dx.doi.org/10.1021/ja00128a054

Johnson L. K. ; Mecking S. ; Brookhart M. Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(II) catalysts . J. Am. Chem. Soc. , 1996 , 118 ( 1 ), 267 - 268 . doi: 10.1021/ja953247i http://dx.doi.org/10.1021/ja953247i

Mecking S. ; Johnson L. K. ; Wang L. ; Brookhart M. Mechanistic studies of the palladium-catalyzed copolymerization of ethylene and α -olefins with methyl acrylate . J. Am. Chem. Soc. , 1998 , 120 ( 5 ), 888 - 899 . doi: 10.1021/ja964144i http://dx.doi.org/10.1021/ja964144i

Zanchin G. ; Leone G. Polyolefin thermoplastic elastomers from polymerization catalysis: advantages, pitfalls and future challenges . Prog. Polym. Sci. , 2021 , 113 , 101342 . doi: 10.1016/j.progpolymsci.2020.101342 http://dx.doi.org/10.1016/j.progpolymsci.2020.101342

Camacho D. H. ; Salo E. V. ; Ziller J. W. ; Guan Z. B. Cyclophane-based highly active late-transition-metal catalysts for ethylene polymerization . Angew. Chem. Int. Ed , 2004 , 43 ( 14 ), 1821 - 1825 . doi: 10.1002/anie.200353226 http://dx.doi.org/10.1002/anie.200353226

Ding B. H. ; Jiang L. H. ; Kang X. H. ; Dai S. Y. Enhancing suppression of chain transfer via catalyst structural evolution in ethylene (co)polymerization . Chin. J. Chem. , 2023 , 41 ( 12 ), 1509 - 1516 . doi: 10.1002/cjoc.202200842 http://dx.doi.org/10.1002/cjoc.202200842

Zhong L. ; Li G. L. ; Liang G. D. ; Gao H. Y. ; Wu Q. Enhancing thermal stability and living fashion in α -diimine-nickel-catalyzed (co)polymerization of ethylene and polar monomer by increasing the steric bulk of ligand backbone . Macromolecules , 2017 , 50 ( 7 ), 2675 - 2682 . doi: 10.1021/acs.macromol.7b00121 http://dx.doi.org/10.1021/acs.macromol.7b00121

Popeney C. S. ; Camacho D. H. ; Guan Z. B. Efficient incorporation of polar comonomers in copolymerizations with ethylene using a cyclophane-based Pd(II) α -diimine catalyst . J. Am. Chem. Soc. , 2007 , 129 ( 33 ), 10062 - 10063 . doi: 10.1021/ja072502j http://dx.doi.org/10.1021/ja072502j

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 . doi: 10.1039/c9py00226j http://dx.doi.org/10.1039/c9py00226j

Zhang Y. X. ; Zhang Y. X. ; Hu X. Q. ; Wang C. Q. ; Jian Z. B. Advances on controlled chain walking and suppression of chain transfer in catalytic olefin polymerization . ACS Catal. , 2022 , 12 ( 22 ), 14304 - 14320 . doi: 10.1021/acscatal.2c04272 http://dx.doi.org/10.1021/acscatal.2c04272

Guan Z. ; Cotts P. M. ; McCord E. F. ; McLain S. J. Chain walking: a new strategy to control polymer topology . Science , 1999 , 283 ( 5410 ), 2059 - 2062 . doi: 10.1126/science.283.5410.2059 http://dx.doi.org/10.1126/science.283.5410.2059

Hu X. Q. ; Kang X. H. ; Jian Z. B. Suppression of chain transfer at high temperature in catalytic olefin polymerization . Angew. Chem. Int. Ed. , 2022 , 61 ( 33 ), e 202207363 . doi: 10.1002/anie.202207363 http://dx.doi.org/10.1002/anie.202207363

Chen C. L. Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning . Nat. Rev. Chem. , 2018 , 2 ( 5 ), 6 - 14 . doi: 10.1038/s41570-018-0003-0 http://dx.doi.org/10.1038/s41570-018-0003-0

Chen Z. ; Brookhart M. Exploring ethylene/polar vinyl monomer copolymerizations using Ni and Pd α ‍-diimine catalysts . Acc. Chem. Res. , 2018 , 51 ( 8 ), 1831 - 1839 . doi: 10.1021/acs.accounts.8b00225 http://dx.doi.org/10.1021/acs.accounts.8b00225

Yang J. S. ; Zhang Y. X. ; Jian Z. B. Macrocyclic binuclear α‍ -diimine nickel catalysts for ethylene polymerization . Chem. Res. Chin. Univ. , 2023 , 39 ( 5 ), 797 - 802 . doi: 10.1007/s40242-023-3149-3 http://dx.doi.org/10.1007/s40242-023-3149-3

Guo L. H. ; Dai S. Y. ; Sui X. L. ; Chen C. L. Palladium and nickel catalyzed chain walking olefin polymerization and copolymerization . ACS Catal. , 2016 , 6 ( 1 ), 428 - 441 . doi: 10.1021/acscatal.5b02426 http://dx.doi.org/10.1021/acscatal.5b02426

郭春文 , 范宏 , 王文俊 , 李伯耿 . 配体骨架烷基取代基对 α -二亚胺镍催化乙烯聚合的影响 . 高分子学报 , 2009 , ( 8 ), 823 - 827 . doi: 10.3321/j.issn:1000-3304.2009.08.018 http://dx.doi.org/10.3321/j.issn:1000-3304.2009.08.018

王玉银 , 胡小强 , 穆红亮 , 夏艳 , 迟悦 , 简忠保 . 空间位阻与氟效应协同增强镍系乙烯聚合 . 化学学报 , 2022 , 80 ( 6 ), 741 - 747 . doi: 10.6023/A22020066 http://dx.doi.org/10.6023/A22020066

王子豪 , 陈敏 , 陈昶乐 . 不对称 α -二亚胺镍催化制备聚烯烃弹性体 . 化学学报 , 2023 , 81 ( 6 ), 559 - 564 . doi: 10.6023/A23040162 http://dx.doi.org/10.6023/A23040162

Allen K. E. ; Campos J. ; Daugulis O. ; Brookhart M. Living polymerization of ethylene and copolymerization of ethylene/methyl acrylate using "sandwich" diimine palladium catalysts . ACS Catal. , 2015 , 5 ( 1 ), 456 - 464 . doi: 10.1021/cs5016029 http://dx.doi.org/10.1021/cs5016029

Dai S. Y. ; Chen C. L. Direct synthesis of functionalized high-molecular-weight polyethylene by copolymerization of ethylene with polar monomers . Angew. Chem. Int. Ed , 2016 , 55 ( 42 ), 13281 - 13285 . doi: 10.1002/anie.201607152 http://dx.doi.org/10.1002/anie.201607152

Peng D. ; Chen C. L. Photoresponsive palladium and nickel catalysts for ethylene polymerization and copolymerization . Angew. Chem. Int. Ed , 2021 , 60 ( 41 ), 22195 - 22200 . doi: 10.1002/anie.202107883 http://dx.doi.org/10.1002/anie.202107883

Lu Z. ; Xu X. W. ; Luo Y. ; He S. B. ; Fan W. G. ; Dai S. Y. Unexpected effect of catalyst's structural symmetry on the branching microstructure of polyethylene in late transition metal polymerization catalysis . ACS Catal. , 2023 , 13 ( 1 ), 725 - 734 . doi: 10.1021/acscatal.2c04525 http://dx.doi.org/10.1021/acscatal.2c04525

Dai S. Y. ; Zhou S. X. ; Zhang W. ; Chen C. L. Systematic investigations of ligand steric effects on α -diimine palladium catalyzed olefin polymerization and copolymerization . Macromolecules , 2016 , 49 ( 23 ), 8855 - 8862 . doi: 10.1021/acs.macromol.6b02104 http://dx.doi.org/10.1021/acs.macromol.6b02104

Li M. ; Wang X. B. ; Luo Y. ; Chen C. L. A second-coordination-sphere strategy to modulate nickel- and palladium-catalyzed olefin polymerization and copolymerization . Angew. Chem. Int. Ed. , 2017 , 56 ( 38 ), 11604 - 11609 . doi: 10.1002/anie.201706249 http://dx.doi.org/10.1002/anie.201706249

Vaccarello D. N. ; O'Connor K. S. ; Iacono P. ; Rose J. M. ; Cherian A. E. ; Coates G. W. Synthesis of semicrystalline polyolefin materials: precision methyl branching via stereoretentive chain walking . J. Am. Chem. Soc. , 2018 , 140 ( 20 ), 6208 - 6211 . doi: 10.1021/jacs.8b02963 http://dx.doi.org/10.1021/jacs.8b02963

Long B. K. ; Eagan J. M. ; Mulzer M. ; Coates G. W. Semi-crystalline polar polyethylene: ester-functionalized linear polyolefins enabled by a functional-group-tolerant, cationic nickel catalyst . Angew. Chem. Int. Ed. , 2016 , 55 ( 25 ), 7106 - 7110 . doi: 10.1002/anie.201601703 http://dx.doi.org/10.1002/anie.201601703

Meinhard D. ; Wegner M. ; Kipiani G. ; Hearley A. ; Reuter P. ; Fischer S. ; Marti O. ; Rieger B. New nickel(II) diimine complexes and the control of polyethylene microstructure by catalyst design . J. Am. Chem. Soc. , 2007 , 129 ( 29 ), 9182 - 9191 . doi: 10.1021/ja070224i http://dx.doi.org/10.1021/ja070224i

Dai J. J. ; Dai S. Y. Flexible α -diimine Ni(II) and P d(II) catalysts featuring backbone and axial cycloalkyl substituents in ethylene (co)polymerization . J. Polym. Sci. , 2025 , 63 ( 7 ), 1527 - 1535 . doi: 10.1002/pol.20241186 http://dx.doi.org/10.1002/pol.20241186

Dai S. Y. ; Li S. K. ; Xu G. Y. ; Wu C. ; Liao Y. D. ; Guo L. H. Flexible cycloalkyl substituents in insertion polymerization with α -diimine nickel and palladium species . Polym. Chem. , 2020 , 11 ( 7 ), 1393 - 1400 . doi: 10.1039/c9py01901d http://dx.doi.org/10.1039/c9py01901d

Rhinehart J. L. ; Brown L. A. ; Long B. K. A robust Ni(II) α‍ -diimine catalyst for high temperature ethylene pol ymerization . J. Am. Chem. Soc. , 2013 , 135 ( 44 ), 16316 - 16319 . doi: 10.1021/ja408905t http://dx.doi.org/10.1021/ja408905t

Li S. K. ; Dai S. Y. 8-Arylnaphthyl substituent retarding chain transfer in insertion polymerization with unsymmetrical α -diimine systems . Polym. Chem. , 2020 , 11 ( 45 ), 7199 - 7206 . doi: 10.1039/d0py01231a http://dx.doi.org/10.1039/d0py01231a

Li S. K. ; Xu G. Y. ; Dai S. Y. A remote nonconjugated electron effect in insertion polymerization with α ‍-diimine nickel and palladium species . Polym. Chem. , 2020 , 11 ( 15 ), 2692 - 2699 . doi: 10.1039/d0py00218f http://dx.doi.org/10.1039/d0py00218f

Gong Y. F. ; Li S. K. ; Tan C. ; Kong W. Y. ; Xu G. Y. ; Zhang S. J. ; Liu B. Y. ; Dai S. Y. π‍ -‍ π interaction effect in insertion polymerization with α -diimine palladium systems . J. Catal. , 2019 , 378 , 184 - 191 . doi: 10.1016/j.jcat.2019.08.034 http://dx.doi.org/10.1016/j.jcat.2019.08.034

Dai J. J. ; Dai S. Y. Impact of o -aryl halogen effects on ethylene polymerization: steric vs . electronic effects . Dalton Trans. , 2024 , 53 ( 22 ), 9286 - 9293 . doi: 10.1039/d4dt00850b http://dx.doi.org/10.1039/d4dt00850b

Wang Z. ; Liu Q. B. ; Solan G. A. ; Sun W. H. Recent advances in Ni-mediated ethylene chain growth: nimine-donor ligand effects on catalytic activity, thermal stability and oligo-/polymer structure . Coord. Chem. Rev. , 2017 , 350 , 68 - 83 . doi: 10.1016/j.ccr.2017.06.003 http://dx.doi.org/10.1016/j.ccr.2017.06.003

Ma X. ; Hu X. Q. ; Zhang Y. X. ; Mu H. L. ; Cui L. ; Jian Z. B. Preparation and in situ chain-end-functionalization of branched ethylene oligomers by monosubstituted α -diimine nickel catalysts . Polym. Chem. , 2019 , 10 ( 20 ), 2596 - 2607 . doi: 10.1039/c9py00433e http://dx.doi.org/10.1039/c9py00433e

Fang J. ; Sui X. L. ; Li Y. G. ; Chen C. L. Synthesis of polyolefin elastomers from unsymmetrical α ‍-diimine nickel catalyzed olefin polymerization . Polym. Chem. , 2018 , 9 ( 30 ), 4143 - 4149 . doi: 10.1039/c8py00725j http://dx.doi.org/10.1039/c8py00725j

Yan Z. P. ; Chang G. R. ; Zou W. P. ; Luo G. ; Dai S. Y. Synthesis of lightly branched ultrahigh-molecular-weight polyethylene using cationic benzocyclohexyl nickel catalysts . Polym. Chem. , 2023 , 14 ( 2 ), 183 - 190 . doi: 10.1039/d2py01087a http://dx.doi.org/10.1039/d2py01087a

Svejda S. A. ; Johnson L. K. ; Brookhart M. ; Low-temperature spectroscopic observation of chain growth and migratory insertion barriers in (α-diimine) Ni(II) olefin polymerization catalysts . J. Am. Chem. Soc. , 1999 , 121, 106344110635 . doi: 10.1021/ja991931h http://dx.doi.org/10.1021/ja991931h

He F. ; Wang D. ; Wu A. Y. ; Jiang B. Y. ; Zhang Z. ; Cheng Z. M. ; Fu Z. S. ; Zhang Q. S. ; Fan Z. Q. Highly resilient polyethylene elastomers prepared using α‍ -diimine nickel catalyst with highly conjugated backbone . Appl. Organomet. Chem. , 2018 , 32 ( 12 ), e 4566 . doi: 10.1002/aoc.4566 http://dx.doi.org/10.1002/aoc.4566

Hu X. Q. ; Wang C. Q. ; Jian Z. B. Comprehensive studies of the ligand electronic effect on unsymmetrical α‍ -diimine nickel(II) promoted ethylene (co)polymerizations . Polym. Chem. , 2020 , 11 ( 24 ), 4005414012 . doi: 10.1039/d0py00536c http://dx.doi.org/10.1039/d0py00536c

Wang Y. Y. ; Wang C. Q. ; Hu X. Q. ; Xia Y. ; Chi Y. ; Zhang Y. X. ; Jian Z. B. Benzosuberyl substituents as a "sandwich-like" function in olefin polymerization catalysis . Chinese J. Polym. Sci. , 2021 , 39 ( 8 ), 98441993 . doi: 10.1007/s10118-021-2562-7 http://dx.doi.org/10.1007/s10118-021-2562-7

Lu W. Q. ; Fan W. G. ; Dai S. Y. A rigid-flexible double-layer steric strategy promoting ethylene polymerization and copolymerization in alkane solvents . Inorg. Chem. Front. , 2023 , 10 ( 1 ), 10841117 . doi: 10.1039/d2qi01895k http://dx.doi.org/10.1039/d2qi01895k

Ji H. Y. ; Zhang Y. X. ; Chi Y. ; Jian Z. B. Concerted flexible and steric strategy in α‍ -diimine nickel and palladium mediated insertion (Co-)Polymerization . Polymer , 2024 , 290 , 126591 . doi: 10.1016/j.polymer.2023.126591 http://dx.doi.org/10.1016/j.polymer.2023.126591

Muhammad Q. ; Tan C. ; Chen C. L. Concerted steric and electronic effects on α ‍-diimine nickel- and palladium-catalyzed ethylene polymerization and copolymerization . Sci. Bull . 2020 , 65 , 300 - 307 . doi: 10.1016/j.scib.2019.11.019 http://dx.doi.org/10.1016/j.scib.2019.11.019

Zhong L. ; Zheng H. D. ; Du C. ; Du W. B. ; Liao G. F. ; Cheung C. S. ; Gao H. Y. Thermally robust α‍ -diimine nickel and palladium catalysts with constrained space for ethylene (co)polymerizations . J. Catal. , 2020 , 384 , 20841217 . doi: 10.1016/j.jcat.2020.02.022 http://dx.doi.org/10.1016/j.jcat.2020.02.022

Xia J. ; Zhang Y. X. ; Kou S. Q. ; Jian Z. B. A concerted double-layer steric strategy enables an ultra-highly active nickel catalyst to access ultrahigh molecular weight polyethylenes . J. Catal. , 2020 , 390 , 304136 . doi: 10.1016/j.jcat.2020.07.017 http://dx.doi.org/10.1016/j.jcat.2020.07.017

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Synthesis of Polyethylene Elastomers via α-Diimine Ni(II) Catalysts with Electronic and Steric Synergistic Effects

DOI：10.11777/j.issn1000-3304.2025.25058

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Abstract

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Keywords

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