Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic <italic style="font-style: italic">α</italic>-Diimine Palladium Complexes

Feng-Bin Liu; Chun-Yu Zhang; Xue-Quan Zhang; Heng Liu; Xiao-Hua Wang

doi:10.1007/s10118-026-3594-9

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Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes

RESEARCH ARTICLE | Updated：2026-07-01

- Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes
- Chinese Journal of Polymer Science Vol. 44, Issue 7, Pages: 2177-2187(2026)
- Affiliations：
  
  State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology, Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
- Author bio：
  
  hengliu@qust.edu.cn (H.L.)
  BH146@qust.edu.cn (X.H.W.)
- Funds：
- DOI：10.1007/s10118-026-3594-9
  CLC：
- Received：19 January 2026，
  
  Accepted：27 January 2026，
  
  Online First：12 May 2026，
  
  Published：05 July 2026
- Accepted：
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Liu, F. B.; Zhang, C. Y.; Zhang, X. Q.; Liu, H.; Wang, X. H. Modulating molecular weight of polyethylenes from oligomer to polymer using highly thermal stable cationic α-diimine palladium complexes. Chinese J. Polym. Sci. 2026, 44, 2177–2187

Feng-Bin Liu, Chun-Yu Zhang, Xue-Quan Zhang, et al. Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2177-2187. DOI: 10.1007/s10118-026-3594-9.
Liu, F. B.; Zhang, C. Y.; Zhang, X. Q.; Liu, H.; Wang, X. H. Modulating molecular weight of polyethylenes from oligomer to polymer using highly thermal stable cationic α-diimine palladium complexes. Chinese J. Polym. Sci. 2026, 44, 2177–2187 DOI： 10.1007/s10118-026-3594-9.

Feng-Bin Liu, Chun-Yu Zhang, Xue-Quan Zhang, et al. Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2177-2187. DOI: 10.1007/s10118-026-3594-9. DOI：

摘要

This work reports a new family of highly thermally stable unsymmetrical cationic

-diimine palladium complexes that combine both steric blockage and intra-ligand C―H···F non-covalent linkages affording polyethylenes with tunable molecular weights and adjustable branching densities.

Abstract

Developing highly thermostable catalytic systems remains a central objective in the field of late-transition-metal olefin polymerization. In this work

we report a new series of

-diimine Pd(II) catalysts that exhibit remarkable thermal resistance in ethylene polymerization (up to 100 °C). With the aid of concerted effects of both steric blockage and intra-ligand C―H···F hydrogen bonding linkage

conformational rotation of the

-aryl groups is substantially restricted

thereby imparting exceptional thermostability to these

-diimine Pd(II) precatalysts. By tuning the chain-walking degrees through the steric influence of

ortho

-substituent of

-phenyl substituents or by adjusting the polymerization temperature

the branching density of the resulting polyethylenes can be finely m

odulated from moderately branched to hyperbranched structures (72.7–142.1/1000C). More unexpectedly

these highly thermally robust unsymmetrical

-diimine Pd(II) complexes

stabilized by intra-ligand C―H···F hydrogen bonding

are capable of producing polyethylenes with widely adjustable molecular weights

ranging from oligomers to high-molecular-weight polymers (

=0.6×10

–87.2×10

g/mol). Furthermore

ethylene/methylacrylate (E/MA) copolymers were also successfully obtained using these catalysts

achieving MA incorporation levels of up to 4.7%.

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references

Ittel, S. D.; Johnson, L. K.; Brookhart, M. Late-metal catalysts for ethylene homo- and copolymerization. Chem. Rev. 2000 , 100 , 1169−1203..

Guan, Z.; Cotts, P. M.; McCord, E. F.; McLain, S. J. Chain qalking: a new strategy to control polymer topology. Science 1999 , 283 , 2059−2062..

Guo, L.; Dai, S.; Sui, X.; Chen, C. Palladium and nickel catalyzed chain walking olefin polymerization and copolymerization. ACS Catal. 2016 , 6 , 428−441..

Zhang, Y.; Zhang, Y.; Hu, X.; Wang, C.; Jian, Z. Advances on controlled chain walking and suppression of chain transfer in catalytic olefin polymerization. ACS Catal. 2022 , 12 , 14304−14320..

Wu, R.; Klingler Wu, W.; 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..

Zhou, A.; Yuan, R.; Mahmood, Q.; Yuan, S.; Wang, Y.; Hu, Z.; Zou, S.; Liang, T.; Sun, W. H. Benzosuberyl installed “sandwich” type unsymmetrical α-diimine nickel precatalysts for synthesizing plastomeric to elastomeric polyethylene. Polym. Chem. 2024 , 15 , 4029−4043..

Zheng, Y.; Wang, Q.; Che, Y.; Jiang, S.; Yu, Z.; Wang, Y.; Ma, Y.; Solan, G. A.; Liang, T.; Sun, W. H. High molecular weight bimodal polyethylene elastomers using N , N '-nickel catalysts appended with methoxy and trifluoromethoxy functionality. Eur. Polym. J. 2024 , 203 , 112649..

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 , 7974−7984..

Zhang, Y.; Huang, C.; Wang, X.; Mahmood, Q.; Hao, X.; Hu, X.; Guo, C.-Y.; Solan, G. A.; Sun, W. H. Highly branched unsaturated polyethylenes achievable using strained imino-cyclopenta[ b ] pyridyl-nickel precatalysts. Polym. Chem. 2017 , 8 , 995−1005..

Wang, Z.; Liu, Q.; 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..

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

Wang, Y.-B.; Nan, C.; Zhuo, W.; Zou, C.; Jiang, H.; Hao, X.-Q.; Chen, C.; Song, M.-P. Amine–imine nickel catalysts with pendant O-donor groups for ethylene (co)polymerization. Inorg. Chem. 2023 , 62 , 5105−5113..

Wang, W.; Chen, M.; Pang, W.; Li, Y.; Zou, C.; Chen, C. Palladium-catalyzed synthesis of norbornene-based polar-functionalized polyolefin elastomers. Macromolecules 2021 , 54 , 3197−3203..

Wang, F.; Chen, C. A continuing legend: the Brookhart-type α -diimine nickel and palladium catalysts. Polym. Chem. 2019 , 10 , 2354−2369..

Zou, C.; Dai, S.; Chen, C. Ethylene Polymerization and copolymerization using nickel 2-iminopyridine-N-oxide catalysts: modulation of polymer molecular weights and molecular-weight distributions. Macromolecules 2018 , 51 , 49−56..

Na, Y. N.; Dai, S. Y.; Chen, C. L. Direct synthesis of polar-functionalized linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE). Macromolecules 2018 , 51 , 4040−4048..

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 , 4143−4149..

Yang, J.; Tang, Z.; Zhang, Y.; Jian, Z. A facile and scalable α-diimine platform for nickel-catalyzed ethylene polymerization. Angew. Chem. Int. Ed. 2025 , 64 , e202512735..

Hu, X.; Kang, X.; Zhang, Y.; Jian, Z. Facile access to polar-functionalized ultrahigh molecular weight polyethylene at ambient conditions. CCS Chem. 2021 , 4 , 1680−1694..

Zhang, Y.; Kang, X.; Jian, Z. Selective branch formationin ethylene polymerization to access precise ethylene-propylene copolymers. Nat. Commun. 2022 , 13 , 725..

Yang, J.; Hu, X.; Jian, Z. Photoresponsive α-diimine nickel modulated ethylene (co)polymerization. Chin. J. Chem. 2022 , 40 , 2919−2926..

Hu, X.; Kang, X.; Jian, Z. Suppression of chain transfer at high temperature in catalytic olefin polymerization. Angew. Chem. Int. Ed. 2022 , 61 , e202207363..

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

Zheng, H.; Gao, H. Noncovalent interactions in late transition metal-catalyzed polymerization of olefins. Macromolecules 2024 , 57 , 6899−6913..

Zheng, H.; Li, Y.; Du, W.; Cheung, C. S.; Li, D.; Gao, H.; Deng, H.; Gao, H. Unprecedented square-planar α-diimine dibromonickel complexes and their ethylene polymerizations modulated by Ni–phenyl interactions. Macromolecules 2022 , 55 , 3533−3540..

Du, W.; Zheng, H.; Li, Y.; Cheung, C. S.; Li, D.; Gao, H.; Deng, H.; Gao, H. Neutral tridentate α-sulfonato-β-diimine nickel catalyst for (co)polymerizations of ethylene and acrylates. Macromolecules 2022 , 55 , 3096−3105..

Zhong, L.; Zheng, H.; Du, C.; Du, W.; Liao, G.; Cheung, C. S.; Gao, H. Thermally robust α -diimine nickel and palladium catalysts with constrained space for ethylene (co)polymerizations. J. Catal. 2020 , 384 , 208−217..

Sun, H.; Wu, X.; Zou, W.; Dai, S. A hybrid steric ligand modification strategy promotes propylene (co)polymerization. Polymer 2024 , 302 , 127050..

Lu, Z.; Ding, B.; Dai, S. Suppression of chain walking and chain transfer in ethylene (co)polymerization with iminodibenzyl substituents containing second coordination spheres. Macromolecules 2024 , 57 , 5262−5270..

Lu, W.; Ding, B.; Dai, S. Control of chain transfer and chain walking by tailored metal–π interactions in polymerization catalysis. J. Catal. 2024 , 435 , 115550..

Fan, H.; Kang, X.; Dai, S. Stable ultrahighly branched polyethylene synthesis via externally robust chain-walking polymeriza tion. ACS Catal. 2024 , 14 , 13531−13541..

Fan, H.; Chang, G.; Wang, H.; Dai, S. The second coordination sphere effect of benzothiophene groups enhances chain transfer in ethylene (co)oligomerization. New J. Chem. 2023 , 47 , 2488−2494..

Lu, Z.; Xu, X.; Luo, Y.; He, S.; Fan, W.; Dai, S. Unexpected effect of catalyst’s structural symmetry on the branching microstructure of polyethylene in late transition metal polymerization catalysis. ACS Catal. 2023 , 13 , 725−734..

Wang, C.; Kang, X.; Dai, S.; Cui, F.; Li, Y.; Mu, H.; Mecking, S.; Jian, Z. Efficient suppression of chain transfer and branching via C s -type shielding in a neutral nickel(II) catalyst. Angew. Chem. Int. Ed. 2021 , 60 , 4018−4022..

Wang, B.; Liu, H.; Zhang, C.; Tang, T.; Zhang, X. Propylene homopolymerization and copolymerization with ethylene by acenaphthene-based α-diimine nickel complexes to access EPR-like elastomers. Polym. Chem. 2021 , 12 , 6307−6318..

Wang, X.; Ma, L.; Dong, B.; Zhang, C.; Zhang, X.; Liu, H. Axial anagostic interaction in α-diimine nickel catalysts: an ultraefficient occupation strategy in suppressing associative chain transfers to achieve UHMWPEs. Macromolecules 2025 , 58 , 1888−1897..

Qin, L.; Mahmood, Q.; Wang, Y.; Ma, Y.; Liang, T.; Sun, W.-H. Bis(tolyl)methyl- and nitro-functionalized unsymmetrical α-diimine nickel precatalysts for polyethylene elastomer: enhanced activity and thermal stability. J. Polym. Sci. 2025 , 63 , 4724−4739..

Mahmood, Q.; Hu, Z.; Ren, G.; Sun, W. H. Recent advances in nickel catalysis for thermoplastic polyethylene elastomers: synthesis strategies, properties, and future perspectives. Coord. Chem. Rev. 2025 , 541 , 216833..

Bariashir, C.; Huang, C.; Solan, G. A.; Sun, W.-H. Recent advances in homogeneous chromium catalyst design for ethylene tri-, tetra-, oligo- and polymerization. Coord. Chem. Rev. 2019 , 385 , 208−229..

Suo, H.; Solan, G. A.; Ma, Y.; Sun, W. H. Developments in compartmentalized bimetallic transition metal ethylene polymerization catalysts. Coord. Chem. Rev. 2018 , 372 , 101−116..

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

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 , 9182−9191..

[Zhai, F.; Jordan, R. F. (α-Diimine)nickel complexes that contain menthyl substituents: synthesis, conformational behavior, and olefin polymerization catalysis. Organometallics 2017 , 36 , 2784-2799..

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 , 16316−16319..

Rhinehart, J. L.; Mitchell, N. E.; Long, B. K. Enhancing α -diimine catalysts for high-temperature ethylene polymerization. ACS Catal. 2014 , 4 , 2501−2504..

Wang, F.; Yuan, J.; Li, Q.; Tanaka, R.; Nakayama, Y.; Shiono, T. New nickel(Ⅱ) diimine complexes bearing phenyl and sec -phenethyl groups: synthesis, characterization and ethylene polymerization behavior. Appl. Organomet. Chem. 2014 , 28 , 477−483..

Du, S.; Kong, S.; Shi, Q.; Mao, J.; Guo, C.; Yi, J.; Liang, T.; Sun, W.-H. Enhancing the activity and thermal stability of nickel complex precatalysts using 1-[2,6-Bis(bis(4-fluorophenyl)methyl)-4-methyl phenylimino ] -2-aryliminoacenaphthylene derivatives. Organometallics 2015 , 34 , 582−590..

Sui, X.; Hong, C.; Pang, W.; Chen, C. Unsymmetrical α -diimine palladium catalysts and their properties in olefin (co)polymerization. Mater. Chem. Front. 2017 , 1 , 967−972..

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 , 2675−2682..

Zhu, L.; Zang, D.; Wang, Y.; Guo, Y.; Jiang, B.; He, F.; Fu, Z.; Fan, Z.; 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 , 1196−1203..

Camacho, D. H.; Salo, E. V.; Ziller, J. W.; Guan, Z. Cyclophane-based highly active late-transition-metal catalysts for ethylene polymerization. Angew. Chem. Int. Ed. 2004 , 43 , 1821−1825..

Dai, S.; Li, S.; Xu, G.; Wu, C.; Liao, Y.; Guo, L. Flexible cycloalkyl substituents in insertion polymerization with α -diimine nickel and palladium species. Polym. Chem. 2020 , 11 , 1393−1400..

Wang, C.; Wang, D.; Fu, Z.; Qin, Y.; Zhang, Q.; Fan, Z. Combining 1,2-diketopyracene with bulky benzhydryl-substituted anilines to obtain highly active α -diimine nickel catalysts at elevated temperature. J. Catal. 2022 , 413 , 311−320..

[Wang, X.; Dong, B.; Yang, Q.; Liu, H.; Zhang, C.; Zhang, X. α -Diimine nickel complexes bearing axially bulky terphenyl and equatorially bulky dibenzobarrelene groups: synthesis, characterization and olefin polymerizati on studies. Polym. Chem . 2020 , 11 , 6783−6793..

Qin, Y.; Wang, F.; Wang, X.; Zhang, C.; Liu, H.; Wu, G.; Zhang, X. Thermally robust α -diimine nickel complexes for 1,3-butadiene polymerization enhanced by intra-ligand H…F interaction. Mol. Catal. 2022 , 524 , 112286..

Xia, J.; Kou, S.; Zhang, Y.; Jian, Z. Strategies cooperation on designing nickel catalysts to access ultrahigh molecular weight polyethylenes. Polymer 2022 , 240 , 124478..

Rose, J. M.; Cherian, A. E.; Coates, G. W. Living polymerization of α-olefins with an α-diimine Ni(II) catalyst: formation of well-defined ethylene-propylene copolymers through controlled chain-walking. J. Am. Chem. Soc. 2006 , 128 , 4186−4187..

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 , 13770−13771..

Zhang, D.; 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 , 5136−5143..

Pan, H.; Zhu, L.; Li, J.; Zang, D.; Fu, Z.; Fan, Z. A thermal Stable α -diimine palladium catalyst for copolymerization of ethylene with functionalized olefins. J. Mol. Catal. A-Chem. 2014 , 390 , 76−82..

Mahmood, Q.; Zeng, Y.; Yue, E.; Solan, G. A.; Liang, T.; Sun, W.-H. Ultra-high molecular weight elastomeric polyethylene using an electronically and sterically enhanced nickel catalyst. Polym. Chem. 2017 , 8 , 6416−6430..

Wang, J.; Zhang, K.; Ye, Z. One-pot synthesis of hyperbranched polyethylenes tethered with polymerizable methacryloyl groups via selective ethylene copolymerization with heterobifunctional comonomers by chain walking Pd-diimine catalysis. Macromol. Chem. Phys. 2008 , 41 , 2290−2293..

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 , 456−464..

Liu, B.; Fang, M.; Jie, S; Bu, Z.; Li, B. Nickel(II) α-diimine catalysts with carboxyl groups for ethylene oligomerization and polymerization. Chinese J. Polym. Sci. 2016 , 34 , 221−228..

Wang, F.; Tanaka, R.; Nakayama, Y.; Shiono, T.; Cai, Z. Precision chain-walking polymerization of trans -4-octene catalyzed by α-diimine nickel(II) catalysts bearing ortho - sec -phenethyl groups. Macromol. Rapid Commun. 2016 , 37 , 1375−1381..

Mundil, R.; Sokolohorskyj, A.; Hosek, J.; Cvacka, J.; Cisarova, I.; Kvicala, J.; Merna, J. Nickel and palladium complexes with fluorinated alkyl substituted α -diimine ligands for living/controlled olefin polymerization. Polym. Chem. 2018 , 9 , 1234−1248..

Pierro, I.; Zanchin, G.; Parisini, E.; Marti-Rujas, J.; Canetti, M.; Ricci, G.; Bertini, F.; Leone, G. Chain-walking polymerization of α-olefins by α-diimine Ni(II) complexes: effect of reducing the steric hindrance of ortho- and para-aryl substituents on the catalytic behavior, monomer enchainment, and polymer properties. Macromolecules 2018 , 51 , 801−814..

Ye, Z.; Zhu, S. Newtonian flow behavior of hyperbranched high-molecular-weight polyethylenes produced with a Pd-diimine catalyst and its dependence on chain topology. Macromolecules 2003 , 36 , 2194−2197..

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 , 7106−7110..

Dai, S.; Chen, C. Palladium-catalyzed direct synthesis of various branched, carboxylic acid-functionalized polyolefins: characterization, derivatization, and properties. Macromolecules 2018 , 51 , 6818−6824..

Xia, J.; Zhang, Y.; Kou, S.; Jian, Z. A concerted double-layer steric strategy enables an ultra-highly active nickel catalyst to access ultrahigh molecular weight polyethylenes. J. Catal. 2020 , 390 , 30−36..

Wang, Y.; Gao, R.; Gou, Q.; Lai, J.; Zhang, R.; Li, X.; Guo, Z. Developments in late transition metal catalysts with high thermal stability for ethylene polymerization: a crucial aspect from laboratory to industrialization. Eur. Polym. J. 2022 , 181 , 111693..

Dai, S.; Chen, C. Direct synthesis of functionalized high-molecular-weight polyethylene by copolymerization of ethylene with polar monomers. Angew. Chem. Int. Ed. 2016 , 55 , 13281−13285..

Dai, S.; Sui, X.; Chen, C. 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 , 9948−9953..

Tempel, D. J.; Johnson, L. K.; Huff, R. L.; White, P. S.; Brookhart, M. Mechanistic studies of Pd(Ⅱ)- α -diimine-catalyzed olefin polymerizations. J. Am. Chem. Soc. 2000 , 122 , 6686−6700..

Zhong, S.; Tan, Y.; Zhong, L.; Gao, J.; Liao, H.; Jiang, L.; Gao, H.; Wu, Q. Precision synthesis of ethylene and polar monomer copolymers by palladium-catalyzed living coordination copolymerization. Macromolecules 2017 , 50 , 5661−5669..

Zhang, Y.; Wang, C.; Mecking, S.; Jian, Z. Ultrahigh branching of main-chain-functionalized polyethylenes by inverted insertion selectivity. Angew. Chem. Int. Ed. 2020 , 59 , 14296−14302..

Popeney, C. S.; Camacho, D. H.; Guan, Z. Efficient incorporation of polar comonomers in copolymerizations with ethylene using a cyclophane-based Pd(II) α -diimine catalyst. J. Am. Chem. Soc. 2007 , 129 , 10062−10063..

Popeney, C. S.; Guan, Z. A mechanistic investigation on copolymerization of ethylene with polar monomers using a cyclophane-based Pd(Ⅱ) α -diimine catalyst. J. Am. Chem. Soc. 2009 , 131 , 12384−12393..

Zheng, H.; Zhong, L.; Du, C.; Du, W.; Cheung, C. S.; Ruan, J.; Gao, H. Combining hydrogen bonding interactions with steric and electronic modifications for thermally robust α -diimine palladium catalysts toward ethylene (co)polymerization. Catal. Sci. Technol. 2021 , 11 , 124−135..

[Gong, Y.; Li, S.; Tan, C.; Kong, W.; Xu, G.; Zhang, S.; Liu, B.; Dai, S. π-π Interaction effect in insertion polymerization with α -diimine palladium systems. J. Catal . 2019 , 378 , 184-191..

Wang, X.; Dong, B.; Yang, Q.; Liu, H.; Hu, Y.; Zhang, X. Boosting the thermal stability of α -diimine palladium complexes in norbornene polymerization from construction of intraligand hydrogen bonding and simultaneous increasing axial/equatorial bulkiness. Inorg. Chem. 2021 , 60 , 2347−2361..

Goettker-Schnetmann, I.; Wehrmann, P.; Roehr, C.; Mecking, S. Substituent effects in ( κ 2 - N,O )-salicylaldiminato nickel(Ⅱ)-methyl pyridine polymerization catalysts: terphenyls controlling polyethylene microstructures. Organometallics 2007 , 26 , 2348−2362..

Hu, X.; Zhang, Y.; Zhang, Y.; Jian, Z. Unsymmetrical strategy makes significant differences in α-diimine nickel and palladium catalyzed ethylene (co)polymerizations. ChemCatChem 2020 , 12 , 2497−2505..

Wu, J.-J.; Deng, B.; Hou, J.-H.; Huang, X.-Y.; Tang, H.-Y.; Wang, K.-T. Thermal-stable asymmetric α-diimine nickel(II) catalysts: synthesis, characterization, and its norbornene (co)polymerization behavior. Appl. Organomet. Chem. 2022 , 36 , e6712..

Wang, F.; Tanaka, R.; Li, Q.; Nakayama, Y.; Yuan, J.; Shion o, T. Synthesis and application of α-diimine Ni(II) and Pd(II) complexes with bulky steric groups to polymerization of ethylene and methyl methacrylate. J. Mol. Catal. A: Chem. 2015 , 398 , 231−240..

Falivene, L.; Cao, Z.; Petta, A.; Serra, L.; Poater, A.; Oliva, R.; Scarano, V.; Cavallo, L. Towards the online computer-aided design of catalytic pockets. Nat. Chem. 2019 , 11 , 872−879..

Falivene, L.; Credendino, R.; Poater, A.; Petta, A.; Serra, L.; Oliva, R.; Scarano, V.; Cavallo, L. SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps. Organometallics 2016 , 35 , 2286−2293..

Wang, Y.; Dai, S. Exploring the o -aryl halogen effects of α-diimine Pd(Ⅱ) catalysts on ethylene (co)polymerization. Catal. Sci. Technol. 2025 , 15 , 2822−2828..

Yuan, W.; Dai, S. Synthesis of functionalized hyperbranched polyethylene with high density polar groups using triarylnaphthyl iminopyridyl palladium catalysts. Eur. Polym. J. 2024 , 216 , 113294..

Ding, B.; Dai, S. Palladium-catalyzed synthesis of hyperbranched polar functionalized polyethylene with high density hydrophilic groups. ACS Appl. Polym. Mater. 2023 , 5 , 9536−9542..

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Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes

DOI：10.1007/s10118-026-3594-9

摘要

Abstract

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Keywords

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