Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous <italic style="font-style: italic">α</italic>-Diimine Ni Catalysts for Modulating Ethylene Polymerization

Fan Yu; Bin Dai; Ning Liu; Bin-Yuan Liu; Chen Zou

doi:10.1007/s10118-025-3501-9

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Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization

RESEARCH ARTICLE | Updated：2026-01-30

- Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization
- Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization
- Chinese Journal of Polymer Science 2026年44卷第2期页码：331-340
- Affiliations：
  
  a.School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi 832003, China
  b.State Key Laboratory of Precision and Intelligent Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
  c.Hebei Key Laboratory of Functional Polymer, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300401, China
- Author bio：
  
  byliu@hebut.edu.cn (B.Y.L.)
  chen1215@ustc.edu.cn (C.Z.)
- Funds：
  
  This work was financially supported by the National NaturalScience Foundation of China (No. 52473338), Strategic Priority Research Program of the ChineseAcademy of Sciences (No. XDA0540000), the National NaturalScience Foundation of China (Nos. 52173004 and51873055), Advanced Materials-National Science and Technology Major Project (No.2025ZD0614000), Hebei Natural Science Foundation (No.E2022202015), and Anhui Province Science and TechnologyInnovation Tackling Key Project (No. 202423i08050025).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3501-9.
- DOI：10.1007/s10118-025-3501-9
  中图分类号：
- 收稿：2025-10-11，
  
  录用：2025-11-13，
  
  网络出版：2026-01-16，
  
  纸质出版：2026-02-05
- Accepted：
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Yu, F.; Dai, B.; Liu, N.; Liu, B. Y.; Zou, C. Alkyl alcohol chain-length mediated steric hindrance at support surface in heterogeneous α-diimine Ni catalysts for modulating ethylene polymerization. Chinese J. Polym. Sci. 2026, 44, 331–340

Fan Yu, Bin Dai, Ning Liu, et al. Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(2): 331-340.
Yu, F.; Dai, B.; Liu, N.; Liu, B. Y.; Zou, C. Alkyl alcohol chain-length mediated steric hindrance at support surface in heterogeneous α-diimine Ni catalysts for modulating ethylene polymerization. Chinese J. Polym. Sci. 2026, 44, 331–340 DOI： 10.1007/s10118-025-3501-9.

Fan Yu, Bin Dai, Ning Liu, et al. Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(2): 331-340. DOI： 10.1007/s10118-025-3501-9.

摘要

This work investigates supported

-diimine nickel catalysts for ethylene polymerization. By tuning the length of alkyl alcohol chains attached to the ligand

the distance between the nickel center and the MgCl

support surface is controlled. This modulation effectively regulates support-induced steric hindrance

influencing catalyst behavior.

Abstract

Heterogeneous polymerization represents a widely employed method in the polyolefin industry. In recent years

various heterogenization strategies for late transition metal catalysts have been developed

enabling effective control of polymer morphology and optimization of catalytic performance.

However

while most studies have focused on designing anchoring groups and advancing support approaches

systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts. In this work

we fabricated supported

-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl

supports. The ethylene polymerization behavior of these catalysts was then investigated. By precisely adjusting the alkyl alcohol chain length

the distance between the catalytically active metal center and the support surface was modulated. This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.

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references

Eagan, J. M.; Girolamo, R.; Thurber, C. M.; Macosko, C. W.; LaPointe, A. M.; Bates, F. S.; Coates, G. W. Combining polyethylene and polypropylene: enhanced performance with PE/iPP multiblock polymers. Science 2017 , 355 , 814−816..

Baur, M.; Lin, F.; Morgen, T. O.; Odenwald, L.; Mecking, S. Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization. Science 2021 , 374 , 604−607..

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..

Gao, Y. S.; Chen, J. Z.; Wang, Y.; Pickens, D. B.; Motta, A.; Wang, Q. J.; Chung, Y. W.; Lohr, T. L.; Marks, T. J. Highly branched polyethylene oligomers via group IV-catalysed polymerization in very nonpolar media. Nat. Catal. 2019 , 2 , 236−242..

[Mecking, S.; Schnitte, M. Neutral Nickel(II) Catalysts: from hyperbranched oligomers to nanocrystal-based materials. Acc. Chem. Res. 2020 , 53 , 2738–2752..

Mu, H. L.; Pan, L.; Song, D. P.; Li, Y. S. Neutral nickel catalysts for olefin homo- and copolymerization: relationships between catalyst structures and ca talytic properties. Chem. Rev. 2015 , 115 , 12091−12137..

[Chen, J. W.; Wang, W. B.; Zou, C.; Chen, C. L. Mechanical recycling of mixed plastics by supramolecular dynamic cross-linking strategy. J. Am. Chem. Soc. 2025 , 147 , 24747–24758..

Cai, H.; Gao, H.; Li, B.; Liu, X. Y.; Ma, Z.; Pan, L.; Li, Y. S. Ethylene-propylene block copolymers featuring dual crystalline networks: high-performance elastomers and sustainable high-density polyethylene/isotactic polypropylene blends upcycling. Chem. Eng. J. 2025 , 520 , 165651..

[Cai, H.; Li, B.; Liu, X. Y.; Ma, Z.; Pan, L.; Li, Y. S. Intelligent self-healing design of conventional polyolefin materials. Macromolecules 2025 , 58 , 7895−7906..

Stürzel, M.; Mihan, S.; Mülhaupt, R. From multisite polymerization catalysis to sustainable materials and all-polyolefin composites. Chem. Rev. 2016 , 116 , 1398−1433..

Zou, C.; Chen, J. W.; Khan, M. A.; Si, G. F. C hen, C. L., Stapler strategies for upcycling mixed plastics. J. Am. Chem. Soc. 2024 , 146 , 19449−19459..

Han, X. W.; Zhang, X.; Zhou, Y. Y.; Maimaitiming, A.; Sun, X. L.; Gao, Y. S.; Li, P. Z.; Zhu, B. Y.; Chen, E. Y. X.; Kuang, X. K.; Tang, Y. Circular olefin copolymers made de novo from ethylene and α-olefins. Nat. Commun. 2024 , 15 , 1462..

Chen, J. Z.; Gao, Y. S.; Marks, T. J. Early transition metal catalysis for olefin-polar monomer copolymerization. Angew. Chem. Int. Ed. 2020 , 59 , 14726−14735..

Huang, L.; Yang, Y.; Shao, J. J.; Xiong, G.; Wang, H. B.; Nishiura, M.; Hou, Z. M. Synthesis of tough and fluorescent self-healing elastomers by scandium-catalyzed terpolymerization of pyrenylethenylstyrene, ethylene, and anisylpropylene. J. Am. Chem. Soc. 2024 , 146 , 2718−2727..

Zhang, Z.; Kang, X.; Jiang, Y.; Cai, Z.; Li, S.; Cui, D. Access to disentangled ultrahigh molecular weight polyethylene via a binuclear synergic effect. Angew. Chem. Int. Ed. 2023 , 62 , e202215582..

Wa ng, Q.; Chen,M.; Zou, C.; Chen, C. L. Direct synthesis of polar-functionalized polyolefin elastomers. Angew. Chem. Int. Ed. 2025 , 64 , e202423814..

Qu, W. C.; Bi, Z. X.; Zou, C.; Chen, C. L. Light, Heat, and force-responsive polyolefins. Adv. Sci. 2024 , 11 , 2307568..

[Li, J.; Shao, L,. 2024 , CN117362828A.

[Murray, R. E.; Mawson, S.; Williams, C. C.; Schreck, D. J., 2000 , PCT Int. Appl . WO 037511A2..

[Canich, J. M.; Hlatky, G. G.; Turner, H. W., 1992 , PCT Appl. WO92-00333.

[Johnson, L. K.; Killian, C. M.; Brookhart, M. New Pd(II)-based and Ni(II)-based catalysts for polymerization of ethylene and alpha-olefins. J. Am. Chem. Soc. 1995 , 117 , 6414–6415..

Zheng, H . D.; Qiu, Z. L.; Gao, H.; Li, D. H.; Cheng, Z. C.; Tu, G. S.; Gao, H. Y. Noncovalent ni-phenyl interactions promoted α-diimine nickel-catalyzed copolymerization of ethylene and methyl acrylate. Macromolecules 2024 , 57 , 5279−5288..

Tang, S.; Zhao, Y. J.; Nozaki, K. Accessing divergent main-chain-functionalized polyethylenes via copolymerization of ethylene with a CO 2 /butadiene-derived lactone. J. Am. Chem. Soc. 2021 , 143 , 17953−17957..

Lin, F.; Morgen, T. O.; Mecking, S. Living aqueous microemulsion polymerization of ethylene with robust Ni(II) phosphinophenolato catalysts. J. Am. Chem. Soc. 2021 , 143 , 20605−20608..

Chen, J. W.; Chen, A.; Zou, C.; Chen, C. L. Synthesis of photoresponsive fast self-healing polyolefin composites by nickel-catalyzed copolymerization of ethylene and lignin cluster monomers. Angew. Chem. Int. Ed. 2024 , 63 , e202404603..

Yang, Q. K.; Kang, X. H.; Liu, Y.; Mu, H. L.; Jian, Z. B. Ultrahigh molecular weight ethylene-acrylate copolymers synthesized with highly active neutral nickel catalysts. Angew. Chem. Int. Ed. 2025 , 64 , e202421904..

Chen, Y. S.; Wang, L.; Yu, H. J.; Zhao, Y. L.; Sun, R. L.; Jing, G. H.; Huang, J.; Khalid, H.; Abbasi, N. M.; Akram, M. Synthesis and application of polyethylene-based functionalized hyperbranched polymers. Prog. Polym. Sci. 2015 , 45 , 23−43..

Zou, C.; Chen, C. L. Polar-functionalized, crosslinkable, self-healing, and photoresponsive polyolefins. Angew. Chem. Int. Ed. 2020 , 59 , 395−402..

Zou, C.; Pang, W. M.; Chen, C. L. Influence of chelate ring size on the properties of phosphine-sulfonate palladium catalysts. Sci. China Chem. 2018 , 61 , 1175−1178..

Wang, W. B.; Wang, Q.; Zou, C.; Chen, C. L. Synthesis of ultra-high-molecular-weight polyethylene by transition-metal-catalyzed precipitation polymerization. Precis. Chem. 2024 , 2 , 63−69..

Tan, C.; Si, G. F.; Zou, C.; Chen, C. L. Recent advances in nickel mediated copolymerization of olefin with polar monomers. Angew. Chem. Int. Ed. 2025 , 64 , e202424529..

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..

Wang, Q.; Zhang, Z.; Zou, C.; Chen, C. L. A general cocatalyst strategy for performance enhancement in nickel catalyzed ethylene (co)polymerization. Chinese Chem. Lett. 2022 , 33 , 4363−4366..

Bi, Z. X.; Zhang, Z.; Bahri-Laleh, N.; Wang, Q.; Zou, C. B(C 6 F 5 ) 3 grafted inorganic fillers for supported titanium-catalyzed synthesis of UHMWPE composites. Polym. Chem. 2024 , 15 , 1393−1398..

[Rice, C. G. C.; Evans, A.; Turner, Z. R.; Wattoom, J.; O'Hare, D. Strategies for enhancing the processability of UHMWPE. Ind. Chem. Mater. 2025 , 3 , 178–190..

[Chang, H.F.; Li, H.M.; Li, C.G.; Huo, X.J.; Ding, C. The effects of a new aminosilane external donor on propylene polymerization with MgCl 2 -supported Ziegler-Natta catalyst. J. Polym. Res. 2024 , 31 , 35..

[Zou, C.; Tan, C.; Chen, C. L. Heterogenization strategies for nickel catalyzed synthesis of polyolefins and composites. Acc. Mater. Res. 2023 , 4 , 496–506..

McDaniel, M. P. A review of the phillips supported chromium catalyst and its commercial use for ethylene polymerization. Adv. Catal. 2010 , 53 , 123−606..

Choi, Y.; Soares, J. B. P. Synthesis of supported nickel diimine catalysts for ethylene slurry polymerization. Macromol. Chem. Phys. 2009 , 210 , 1979−1988..

Xu, R.W.; Liu, D.B.; Wang, S.B.; Mao, B.Q. Preparation of spherical MgCl 2 -supported late-transition metal catalysts for ethylene polymerization. Macromol.Chem. Phys. 2006 , 207 , 779−786..

[Tafazolian, H.; Culver, D. B.; Conley, M. P. a well-defined Ni(II) α-diimine catalyst supported on sulfated zirconia for polymerization catalysis. Organometallics 2017 , 36 , 2385−2388..

Schrekker, H. S.; Kotov, V.; Preishuber-Pflugl, P.; White, P.; Brookhart, M. Efficient slurry-phase homopolymerization of ethylene to branched polyethylenes using α-diimine nickel(II) catalysts covalently linked to silica supports. Macromolecules 2006 , 39 , 6341−6354..

Preishuber-Pflugl, P.; Brookhart, M. Highly active supported nickel diimine catalysts for polymerization of ethylene. Macromolecules 2002 , 35 , 6074−6076..

Hu, T.; Li, Y. G.; Liu, J. Y.;Li, Y. S. Syntheses and ethylene polymerization behavior of supported salicylaldimine-based neutral nickel(II) catalysts. Organometallics 2007 , 26 , 2609−2615..

Zhang, H.; Zou, C.; Zhao, H. P.; Cai, Z. G.; Chen, C. L. Hydrogen-bonding-induced heterogenization of nickel and palladium catalysts for copolymerization of ethylene with polar monomers. Angew. Chem. Int. Ed. 2021 , 60 , 17446−17451..

Fu, X.; Zhang, L. J.; Tanaka, R.; Shiono, T.; Cai, Z. G. Highly robust nickel catalysts containing anilinonaphthoquinone ligand for copolymerization of ethylene and polar monomers. Macromolecules 2017 , 50 , 9216−9221..

[Okada, M.; Nakayama, Y.; Shiono, T. Heterogenization of an anilinonaphthoquinone-chelated nickel complex for ethylene polymerization using silica-supported modified methylaluminoxane. Macromol. Chem. Phys. 2014 , 215 , 1792–1796..

Correa, S. A.; Daniliuc, C. G.; Stark, H. S.; Rojas, R. S. Nickel catalysts activated by rGO modified with a boron lewis acid to produce rGO-hyperbranched PE nanocomposites. Organometallics 2019 , 38 , 3327−3337..

Zou, C.; Wang, Q.; Si, G. F.; Chen, C. L. A co-anchoring strategy for the synthesis of polar bimodal polyethylene. Nat. Commun. 2023 , 14 , 1442..

[Liang, T.; Goudari, S.B.; Chen, C.L. A simple and versatile nickel platform for the generation of branched high molecular weight polyolefins. Nat. Commun. 2020 , 11 , 372..

[Wucher, P.; Schwaderer, J. B.; Mecking, S. Solid-supported single-component Pd(II) catalysts for polar monomer insertion copolymerization. ACS Catal. 2014 , 4 , 2672–2679..

Peng, D.; Xu, M. H.; Tan, C.; Chen, C. L. Emulsion polymerization strategy for heterogenization of olefin polymerization catalysts. Macromolecules 2023 , 56 , 2388−2396..

[Ma, Z. S.; Wang, W. B.; Pang, W. M.; Liao, D. H. Zou, C., Preparation of toughened bimodal ultrahigh-molecular-weight polyethylene by a coanchoring strategy. ACS Appl. Polym. Mater. 2024 , 6 , 13210–13216..

[Zou, C.; Si, G. F.; Chen, C.L. A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites. Nat. Commun. 2022 , 13 , 1954..

[Sun, Y.; Wang, Q.; Pan, Y.; Pang, W. M.; Zou, C. Chen, M., SiO 2 -supported Ni(II) and Fe(II) catalysts bearing sodium-sulfonate group for olefin polymerization. Chin. J. Chem. 2022 , 40 , 2773–2779..

[Nie, N.; Yu, F.; Liu, B. Y.; Peng, D. Homo- and hetero-polymerization of ethylene catalyzed by α-diimine nickel complexes with hydroxyl groups. Eur. Polym . J. 2024 , 210 , 112962..

Liu, D.; Zhu, F.M.; Lin, S. A. Ethylene polymerization over MgCl 2 /AlEt n (OEt) 3-n supported half-titanocene catalysts. Acta Polymerica Sinica (in Chinese) 2008 , 12 , 1129−1134..

Severn, J. R.; Chadwick, J. C. MAO-Free Activation of Metallocenes and other Single-Site Catalysts for Ethylene Polymerization using Spherical Supports based on MgCl 2 . Macromol. Rapid Commun. 2004 , 25 , 1024−1028..

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Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization

Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization

DOI：10.1007/s10118-025-3501-9

摘要

Abstract

关键词

Keywords

references