Preparation of Polyolefin Elastomers Using Triphenylyl-substituted <italic style="font-style: italic">α</italic>-Diimide Nickel-catalysed Ethylene Polymerization

Hu Xu; Zi-qiang Zhang; Chang-le Chen; Fu-zhou Wang

doi:10.11777/j.issn1000-3304.2025.25059

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Preparation of Polyolefin Elastomers Using Triphenylyl-substituted α-Diimide Nickel-catalysed Ethylene Polymerization

Research Article | 更新时间：2025-08-28

- Preparation of Polyolefin Elastomers Using Triphenylyl-substituted α-Diimide Nickel-catalysed Ethylene Polymerization
- Acta Polymerica Sinica Vol. 56, Issue 9, Pages: 1493-1504(2025)
- 作者机构：
  
  1.安徽大学物质科学与信息技术研究院合肥 230601
  2.中国科学技术大学高分子科学与工程系合肥 230026
- 作者简介：
  
  Chang-le Chen, E-mail: changle@ustc.edu.cn
  Fu-zhou Wang, E-mail: wangfuzhou@ahu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25059
  CLC：
- CSTR：32057.14.GFZXB.2025.7398
- Received：03 March 2025，
  
  Accepted：10 April 2025，
  
  Published Online：05 June 2025，
  
  Published：20 September 2025
- 稿件说明：
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许浒, 张自强, 陈昶乐, 王福周. 三苯甲基取代的α-二亚胺镍催化乙烯聚合制备聚烯烃弹性体. 高分子学报, 2025, 56(9), 1493-1504

Xu, H.; Zhang, Z. Q.; Chen, C. L.; Wang, F. Z. Preparation of polyolefin elastomers using triphenylyl-substituted ‍α‍-diimide nickel-catalysed ethylene polymerisation. Acta Polymerica Sinica, 2025, 56(9), 1493-1504
许浒, 张自强, 陈昶乐, 王福周. 三苯甲基取代的α-二亚胺镍催化乙烯聚合制备聚烯烃弹性体. 高分子学报, 2025, 56(9), 1493-1504 DOI： 10.11777/j.issn1000-3304.2025.25059. CSTR： 32057.14.GFZXB.2025.7398.

Xu, H.; Zhang, Z. Q.; Chen, C. L.; Wang, F. Z. Preparation of polyolefin elastomers using triphenylyl-substituted ‍α‍-diimide nickel-catalysed ethylene polymerisation. Acta Polymerica Sinica, 2025, 56(9), 1493-1504 DOI： 10.11777/j.issn1000-3304.2025.25059. CSTR： 32057.14.GFZXB.2025.7398.

摘要

在聚烯烃金属催化剂的修饰过程中，远程大位阻基团对取代位点进行修饰的策略具有潜在的能力来调节催化行为，然而这种策略在配位插入烯烃聚合反应中常常被忽略. 本研究合成并表征了一系列

-二亚胺镍催化剂

Ni1

Ni5

，这些催化剂具有不同位阻且对位被三苯甲基修饰. 在氯化二乙基铝(Et

AlCl)的活化作用下，使用这些镍催化剂进行了乙烯链行走聚合反应，同时探讨了空间位阻效应所产生的影响. 研究表明，在对位引入三苯基甲基基团能够形成远端刚性位阻，从而显著提高镍催化剂的热稳定性，并且使镍催化剂展现出更高的催化活性. 催化剂的空间位阻效应以及聚合条件的变化对乙烯聚合活性、所制备的聚乙烯分子量、支化度、热力学性能以及力学性能均具有显著影响. 尤其是异丙基取代的

Ni3

Ni5

展现出极高的催化活性，高达1.26×10

g‧mol

-1

‧h

-1

，能够生成高分子量的支链聚乙烯，并使其保持优良的力学性能和弹性性能. 值得注意的是，在120 ℃高温聚合条件下，不对称结构的

Ni5

仍然保持了较高的活性(8.10×10

g‧mol

-1

‧h

-1

Abstract

The strategy of remote bulky group substitution in modifying polyolefin catalysts has the potential to modulate catalytic behavior

a facet often overlooked in coordination insertion olefin polymerization reactions. In this study

a series of

para-

trityl substituted

α‍

-diimine nickel catalysts

Ni1

Ni5

with different steric hindrances were synthesized and characterized. Upon activation with diethylaluminum chloride (Et

AlCl)

all Ni(II) catalysts were employed for ethylene chain-walking polymerization and the effects of spatial steric hindrance were investigated. The research indicates that the introduction of trityl groups at the

para-

position can form remote rigid steric hindrance

thereby significantly enhancing the thermal stability of the nickel catalysts and exhibiting outstanding catalytic performance. The spatial steric effects of the catalysts

as well as changes in polymerization conditions

have a significant impact on ethylene polymerization activity

the molecular weight of the resulting polyethylene

branching degree

thermodynamic properties

and mechanical properties. The isopropyl-substituted

Ni3

Ni5

exhibited extremely high catalytic activities of up to 1.26×10

g·mol

-1

·h

-1

toward ethylene polymerization producing high molecular weight branched polyethylene

while maintaining excellent mechanical and elastic properties. Notably

even at a higher polymerization temperature of 12

0 ℃

the asymmetric structure of

Ni5

still maintained high activity of up to 8.10×10

g‧mol

-1

‧h

-1

关键词

Keywords

references

Natta G. ; Pino P. ; Corradini P. ; Danusso F. ; Mantica E. ; Mazzanti G. ; Moraglio G. Crystalline high polymers of α -olefins . J. Am. Chem. Soc. , 1955 , 77 ( 6 ), 1708 - 1710 . doi: 10.1021/ja01611a109 http://dx.doi.org/10.1021/ja01611a109

Stürzel M. ; Mihan S. ; Mülhaupt R. Polymers with intrinsic self-healing ability: from mechanisms to Challenges . Chem. Rev. , 2016 , 116 , 1398 - 1433 . doi: 10.1021/acs.chemrev.5b00310 http://dx.doi.org/10.1021/acs.chemrev.5b00310

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 .

Mitchell N. E. ; Long B. K. Recent advances in thermally robust, late transition metal-catalyzed olefin polymerization . Polym. Int. , 2019 , 68 ( 1 ), 14 - 26 . doi: 10.1002/pi.5694 http://dx.doi.org/10.1002/pi.5694

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

Zheng H. D. ; Li Y. W. ; Du W. B. ; Cheung C. S. ; Li D. H. ; Gao H. ; Deng H. Y. ; Gao H. Y. Unprecedented square-planar α‍ -diimine dibromonickel complexes and their ethylene polymerizations modulated by Ni-phenyl interactions . Macromolecules , 2022 , 55 ( 9 ), 3533 - 3540 . doi: 10.1021/acs.macromol.2c00360 http://dx.doi.org/10.1021/acs.macromol.2c00360

Zhang D. F. ; Nadres E. T. ; Brookhart M. ; Daugulis O. Synthesis of highly branched polyethylene using "sandwich" (8- p -tolyl naphthyl α‍ -diimine)nickel(II) catalysts . Organometallics , 2013 , 32 ( 18 ), 5136 - 5143 . doi: 10.1021/om400704h http://dx.doi.org/10.1021/om400704h

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

Nakamura A. ; Ito S. ; Nozaki K. Coordination-insertion copolymerization of fundamental polar monomers . Chem. Rev. , 2009 , 109 ( 11 ), 5215 - 5244 . doi: 10.1021/cr900079r http://dx.doi.org/10.1021/cr900079r

Cai Z. Z. ; Xiao D. W. ; Do L. H. Fine-tuning nickel phenoxyimine olefin polymerization catalysts: performance boosting by alkali cations . J. Am. Chem. Soc. , 2015 , 137 ( 49 ), 15501 - 15510 . doi: 10.1021/jacs.5b10351 http://dx.doi.org/10.1021/jacs.5b10351

Cai Z. Z. ; Do L. H. Customizing polyolefin morphology by selective pairing of alkali ions with nickel phenoxyimine-polyethylene glycol catalysts . Organometallics , 2017 , 36 ( 24 ), 4691 - 4698 . doi: 10.1021/acs.organomet.7b00516 http://dx.doi.org/10.1021/acs.organomet.7b00516

阮晶晶 , 郑涵斗 , 蒋岩 , 王力搏 , 王斯晗 , 高海洋 . α -二亚胺镍钯配合物合成及催化混合癸烯低聚研究 . 高分子学报 , 2021 , 52 ( 12 ), 1603 - 1610 . doi: 10.11777/j.issn1000-3304.2021.21147 http://dx.doi.org/10.11777/j.issn1000-3304.2021.21147

Cherian A. E. ; Rose J. M. ; Lobkovsky E. B. ; Coates G. W. A C 2-symmetric, living α‍-diimine Ni(II) catalyst: regioblock copolymers from propylene. J. Am. Chem. Soc. , 2005 , 127 ( 40 ), 13770 - 13771 . doi: 10.1021/ja0540021 http://dx.doi.org/10.1021/ja0540021

Rose J. M. ; Deplace F. ; Lynd N. A. ; Wang Z. G. ; Hotta A. ; Lobkovsky E. B. ; Kramer E. J. ; Coates G. W. C 2 -symmetric Ni(II) α‍ -diimines featuring cumyl-derived ligands: synthesis of improved elastomeric regioblock polypropylenes . Macromolecules , 2008 , 41 ( 24 ), 9548 - 9555 . doi: 10.1021/ma8019943 http://dx.doi.org/10.1021/ma8019943

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

Ma Z. S. ; Xu M. L. ; Zhu N. N. ; Tan C. ; Chen C. L. Heterogeneous α‍ -diimine nickel catalysts with improved catalytic performance in ethylene polymerization . Chinese J. Chem. , 2023 , 41 ( 10 ), 1155 - 1162 . doi: 10.1002/cjoc.202200785 http://dx.doi.org/10.1002/cjoc.202200785

Zhong S. H. ; Tan Y. X. ; Zhong L. ; Gao J. ; Liao H. ; Jiang L. ; Gao H. Y. ; Wu Q. Precision synthesis of ethylene and polar monomer copolymers by palladium-catalyzed living coordination copolymerization . Macromolecules , 2017 , 50 ( 15 ), 5661 - 5669 . doi: 10.1021/acs.macromol.7b01132 http://dx.doi.org/10.1021/acs.macromol.7b01132

Dong Z. M. ; Ye Z. B. Hyperbranched polyethylenes by chain walking polymerization: synthesis, properties, functionalization, and applications . Polym. Chem. , 2012 , 3 ( 2 ), 286 - 301 . doi: 10.1039/c1py00368b http://dx.doi.org/10.1039/c1py00368b

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 ( 45 ), 10634 - 10635 . doi: 10.1021/ja991931h http://dx.doi.org/10.1021/ja991931h

Leatherman M. D. ; Svejda S. A. ; Johnson L. K. ; Brookhart M. Mechanistic studies of nickel(II) alkylagostic cations and alkyl ethylene complexe . J. Am. Chem. Soc. , 2003 , 125 , 3068 - 3081 . doi: 10.1021/ja021071w http://dx.doi.org/10.1021/ja021071w

Guo L. H. ; Sun W. T. ; Li S. K. ; Xu G. Y. ; Dai S. Y. Bulky yet flexible substituents in insertion polymerization with α‍ -diimine nickel and palladium systems . Polym. Chem. , 2019 , 10 ( 35 ), 4866 - 4871 . doi: 10.1039/c9py00857h http://dx.doi.org/10.1039/c9py00857h

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 ( 4 ), 300 - 307 . doi: 10.1016/j.scib.2019.11.019 http://dx.doi.org/10.1016/j.scib.2019.11.019

王文兵 , 邹陈 , 陈昶乐 . 芘环基二亚胺镍催化剂的合成及其乙烯聚合/共聚的性能研究 . 高分子学报 , 2023 , 54 ( 11 ), 1697 - 1707 .

Li J. ; Wang Y. ; Cai W. ; Yang G. ; Tian Q. H. ; Huang Y. S. ; Peng D. ; Zou C. ; Tan C. Dual-site polymeric heterogeneous α‍ -diimine Ni catalysts with tailored spatial distribution for ethylene polymerization . Macromolecules , 2023 , 56 ( 8 ), 3015 - 3023 . doi: 10.1021/acs.macromol.2c02344 http://dx.doi.org/10.1021/acs.macromol.2c02344

Soshnikov I. E. ; Bryliakov K. P. ; Antonov A. A. ; Sun W. H. ; Talsi E. P. Ethylene polymerization of nickel catalysts with α‍ -diimine ligands: factors controlling the structure of active species and polymer properties . Dalton Trans. , 2019 , 48 ( 23 ), 7974 - 7984 . doi: 10.1039/c9dt01297d http://dx.doi.org/10.1039/c9dt01297d

Tran T. V. ; Do L. H. Tunable modalities in polyolefin synthesis via coordination insertion catalysis . Eur. Polym. J. , 2021 , 142 , 110100 . doi: 10.1016/j.eurpolymj.2020.110100 http://dx.doi.org/10.1016/j.eurpolymj.2020.110100

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 Q. Y. ; Zhang R. D. ; Ma Y. P. ; Solan G. A. ; Liang T. L. ; Sun W. H. Branched polyethylenes attainable using thermally enhanced bis(imino)acenaphthene-nickel catalysts: exploring the effects of temperature and pressure . Appl. Catal. A Gen. , 2019 , 573 , 73 - 86 . doi: 10.1016/j.apcata.2019.01.016 http://dx.doi.org/10.1016/j.apcata.2019.01.016

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

Dai S. Y. ; Sui X. L. ; Chen C. L. Highly robust palladium(II) α‍ -diimine catalysts for slow-chain-walking polymerization of ethylene and copolymerization with methyl acrylate . Angew. Chem. Int. Ed. , 2015 , 54 ( 34 ), 9948 - 9953 . doi: 10.1002/anie.201503708 http://dx.doi.org/10.1002/anie.201503708

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

Bi Z. X. ; Zhou J. J. ; Zhu N. N. ; Peng D. ; Chen C. L. Heterogeneous nickel catalysts for the synthesis of ethylene-based polyolefin elastomers . Macromolecules , 2024 , 57 ( 3 ), 1080 - 1086 . doi: 10.1021/acs.macromol.3c02378 http://dx.doi.org/10.1021/acs.macromol.3c02378

Wang L. Y. ; Liu M. ; Mahmood Q. ; Yuan S. F. ; Li X. X. ; Qin L. D. ; Zou S. ; Liang T. L. ; Sun W. H. Enhancing the thermal stability of α‍ -Diimine Ni(II) catalysts for ethylene polymerization via symmetrical axial shielding strategy . Eur. Polym. J. , 2023 , 194 , 112112 . doi: 10.1016/j.eurpolymj.2023.112112 http://dx.doi.org/10.1016/j.eurpolymj.2023.112112

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 . doi: 10.11777/j.issn1000-3304.2018.18146 http://dx.doi.org/10.11777/j.issn1000-3304.2018.18146

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

Chen E. Y. Coordination polymerization of polar vinyl monomers by single-site metal catalysts . Chem. Rev. , 2009 , 109 ( 11 ), 5157 - 5214 . doi: 10.1021/cr9000258 http://dx.doi.org/10.1021/cr9000258

Zou C. ; Chen C. L. Polar-functionalized, crosslinkable, self-healing, and photoresponsive polyolefins . Angew. Chem. Int. Ed. , 2020 , 59 ( 1 ), 395 - 402 . doi: 10.1002/anie.201910002 http://dx.doi.org/10.1002/anie.201910002

Xu M. H. ; Chen A. ; Li W. ; Li Y. G. ; Zou C. ; Chen C. L. Efficient synthesis of polar functionalized polyolefins with high biomass content . Macromolecules , 2023 , 56 ( 4 ), 1372 - 1378 . doi: 10.1021/acs.macromol.3c00086 http://dx.doi.org/10.1021/acs.macromol.3c00086

Zhao M. H. ; Chen C. L. Accessing multiple catalytically active states in redox-controlled olefin polymerization . ACS Catal. , 2017 , 7 ( 11 ), 7490 - 7494 . doi: 10.1021/acscatal.7b02564 http://dx.doi.org/10.1021/acscatal.7b02564

Rhinehart J. L. ; Mitchell N. E. ; Long B. K. Enhancing α‍ -diimine catalysts for high-temperature ethylene polymerization . ACS Catal. , 2014 , 4 ( 8 ), 2501 - 2504 . doi: 10.1021/cs500694m http://dx.doi.org/10.1021/cs500694m

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

Gao M. L. ; Du S. Z. ; Ban Q. ; Xing Q. F. ; Sun W. H. Ethylene polymerization by 2,3-diiminobutylnickel bromide pre-catalysts bearing remote benzhydryl substituents . J. Organomet. Chem. , 2015 , 798 , 401 - 407 . doi: 10.1016/j.jorganchem.2015.04.024 http://dx.doi.org/10.1016/j.jorganchem.2015.04.024

Li Y. F. ; Chen Y. ; Li P. ; Hu P. P. ; Xu G. Y. ; Li C. ; Zhang S. J. ; Wang F. Z. Regulation of α‍ -diimine nickel catalyzed olefin polymerization by remote site modifications . Polymer , 2024 , 302 , 127074 . doi: 10.1016/j.polymer.2024.127074 http://dx.doi.org/10.1016/j.polymer.2024.127074

Urzúa J. I. ; Torneiro M. Divergent synthesis of porous tetraphenylmethane dendrimers . J. Org. Chem. , 2017 , 82 ( 24 ), 13231 - 13238 . doi: 10.1021/acs.joc.7b02302 http://dx.doi.org/10.1021/acs.joc.7b02302

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⁰

Preparation of Polyolefin Elastomers Using Triphenylyl-substituted α-Diimide Nickel-catalysed Ethylene Polymerization

DOI：10.11777/j.issn1000-3304.2025.25059

摘要

Abstract

关键词

Keywords

references