Citation: Jingfeng Yue, Zhenxin Tang, Yuxing Zhang, Zhongbao Jian. Oligomeric α-diimine nickel catalysts for enhanced ethylene polymerization[J]. Chinese Chemical Letters, ;2026, 37(1): 111930. doi: 10.1016/j.cclet.2025.111930 shu

Oligomeric α-diimine nickel catalysts for enhanced ethylene polymerization

Jingfeng Yue ^{a, b} ,
Zhenxin Tang ^a ,
Yuxing Zhang ^{a, *,} ,
Zhongbao Jian ^{a, b, *,}

a.
State Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China

yxzhang7@ciac.ac.cn

zbjian@ciac.ac.cn

Received Date: 10 July 2025
Revised Date: 23 September 2025
Accepted Date: 29 September 2025
Available Online: 30 September 2025

Figures(5)

Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni₁ and its corresponding oligomeric nickel catalysts (Ni₃ and Ni₅) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni₅ was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni₁. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni₅ in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 10¹⁶ Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m²/day), suggesting potentially practical applications.
- Polyolefin,
- Oligomeric catalyst,
- Polyethylene elastomer,
- Ethylene polymerization,
- Nickel catalyst
1. [1]
  V.K. Soni, R. Rani, G. Singh, Eur. Polym. J. 226 (2025) 113741. doi: 10.1016/j.eurpolymj.2025.113741
2. [2]
  M. Stürzel, S. Mihan, R. Mülhaupt, Chem. Rev. 116 (2016) 1398–1433. doi: 10.1021/acs.chemrev.5b00310
3. [3]
  M.P. McDaniel, Adv. Catal. 53 (2010) 123–606. doi: 10.1002/9780470504437.ch10
4. [4]
  M.M. Stalzer, M. Delferro, T.J. Marks, Catal. Lett. 145 (2015) 3–14. doi: 10.1007/s10562-014-1427-x
5. [5]
  C. Copéret, F. Allouche, K.W. Chan, Angew. Chem. Int. Ed. 57 (2018) 6398–6440. doi: 10.1002/anie.201702387
6. [6]
  H. Makio, T. Fujita, Acc. Chem. Res. 42 (2009) 1532–1544. doi: 10.1021/ar900030a
7. [7]
  G. Zanchin, G. Leone, Prog. Polym. Sci. 113 (2021) 101342. doi: 10.1016/j.progpolymsci.2020.101342
8. [8]
  R.M. Patel, P. Jain, B. Story, S. Chum, Polyethylene: an account of scientific discovery and industrial innovations, in: W.H. Flank, M.A. Abraham, M.A. Matthews (Eds.), Innovations in Industrial and Engineering Chemistry, American Chemical Society, 2008, pp. 71–102.
9. [9]
  P.S. Chum, K.W. Swogger, Prog. Polym. Sci. 33 (2008) 797–819. doi: 10.1016/j.progpolymsci.2008.05.003
10. [10]
  C. Wang, X. Li, S. Chen, T.Y. Shan, Materials 18 (2025) 1334. doi: 10.3390/ma18061334
11. [11]
  L.L. Böhm, Angew. Chem. Int. Ed. 42 (2003) 5010–5030. doi: 10.1002/anie.200300580
12. [12]
  R.J. Witzke, A. Chapovetsky, M.P. Conley, D.M. Kaphan, M. Delferro, ACS Catal. 10 (2020) 11822–11840. doi: 10.1021/acscatal.0c03350
13. [13]
  J.R. Severn, J.C. Chadwick, R. Duchateau, N. Friederichs, Chem. Rev. 105 (2005) 4073–4147. doi: 10.1021/cr040670d
14. [14]
  Z.S. Ma, M.L. Xu, N.N. Zhu, C. Tan, C.L. Chen, Chin. J. Chem. 41 (2023) 1155–1162. doi: 10.1002/cjoc.202200785
15. [15]
  H.S. Schrekker, V. Kotov, P. Preishuber-Pflugl, P. White, M. Brookhart, Macromolecules 39 (2006) 6341–6354. doi: 10.1021/ma061032v
16. [16]
  C.W. Hong, Z.H. Wang, H. Jiang, et al., Chin. Chem. Lett. 34 (2023) 107918. doi: 10.1016/j.cclet.2022.107918
17. [17]
  L.C. Simon, H. Patel, J.B.P. Soares, R.F. de Souza, Macromol. Chem. Phys. 202 (2001) 3237–3247. doi: 10.1002/1521-3935(20011101)202:17<3237::AID-MACP3237>3.0.CO;2-T
18. [18]
  Q. Wang, Z. Zhang, C. Zou, C.L. Chen, Chin. Chem. Lett. 33 (2022) 4363–4366. doi: 10.1016/j.cclet.2021.12.036
19. [19]
  M.R. Ribeiro, A. Deffieux, M.F. Portela, Ind. Eng. Chem. Res. 36 (1997) 1224–1237. doi: 10.1021/ie960475s
20. [20]
  Y. Choi, J.B.P. Soares, Macromol. Chem. Phys. 210 (2009) 1979–1988. doi: 10.1002/macp.200900294
21. [21]
  H. Zhang, C. Zou, H.P. Zhao, Z.G. Cai, C.L. Chen, Angew. Chem. Int. Ed. 60 (2021) 17446–17451. doi: 10.1002/anie.202106682
22. [22]
  R.B. Huang, R. Duchateau, C.E. Koning, J.C. Chadwick, Macromolecules 41 (2008) 579–590. doi: 10.1021/ma7024557
23. [23]
  R. Guimarães, F.C. Stedile, J.H.Z. dos Santos, J. Mol. Catal. A Chem. 206 (2003) 353–362. doi: 10.1016/S1381-1169(03)00411-4
24. [24]
  L.K. Johnson, C.M. Killian, M. Brookhart, J. Am. Chem. Soc. 117 (1995) 6414–6415. doi: 10.1021/ja00128a054
25. [25]
  L.K. Johnson, S. Mecking, M. Brookhart, J. Am. Chem. Soc. 118 (1996) 267–268. doi: 10.1021/ja953247i
26. [26]
  S. Mecking, L.K. Johnson, L. Wang, M. Brookhart, J. Am. Chem. Soc. 120 (1998) 888–899. doi: 10.1021/ja964144i
27. [27]
  X.Q. Hu, Y.X. Zhang, B. Li, Z.B. Jian, Chin. J. Chem. 39 (2021) 2829–2836. doi: 10.1002/cjoc.202100312
28. [28]
  J.S. Yang, X.Q. Hu, Z.B. Jian, Chin. J. Chem. 40 (2022) 2919–2926. doi: 10.1002/cjoc.202200480
29. [29]
  J.S. Yang, Y.X. Zhang, Z.B. Jian, Chem. Res. Chinese Univ. 39 (2023) 797–802. doi: 10.1007/s40242-023-3149-3
30. [30]
  Y.X. Zhang, Y.X. Zhang, X.Q. Hu, Z.B. Jian, ACS Catal. 12 (2022) 14304–14320. doi: 10.1021/acscatal.2c04272
31. [31]
  R.Y. Yuan, Y.Z. Wang, Q. Mahmood, et al., Polymer 293 (2024) 126690. doi: 10.1016/j.polymer.2024.126690
32. [32]
  Y.T. Zheng, Q.C. Wang, Y.P. Che, et al., Eur. Polym. J. 203 (2024) 112649. doi: 10.1016/j.eurpolymj.2023.112649
33. [33]
  Z. Lu, B.H. Ding, S.Y. Dai, Macromolecules 57 (2024) 5262–5270. doi: 10.1021/acs.macromol.4c00493
34. [34]
  Z. Lu, X.W. Xu, Y. Luo, et al., ACS Catal. 13 (2023) 725–734. doi: 10.1021/acscatal.2c04525
35. [35]
  H.D. Zheng, Y.W. Li, W.B. Du, et al., Macromolecules 55 (2022) 3533–3540. doi: 10.1021/acs.macromol.2c00360
36. [36]
  H.D. Zheng, Z.L. Qiu, H. Gao, et al. Macromolecules 57 (2024) 5279–5288. doi: 10.1021/acs.macromol.4c00766
37. [37]
  W.C. Anderson Jr., J.L. Rhinehart, A.G. Tennyson, B.K. Long, J. Am. Chem. Soc. 138 (2016) 774–777. doi: 10.1021/jacs.5b12322
38. [38]
  P. Preishuber-Pflugl, M. Brookhart, Macromolecules 35 (2002) 6074–6076. doi: 10.1021/ma020230t
39. [39]
  R.K. Wu, T.M. Lenz, L. Stieglitz, et al., J. Catal. 426 (2023) 270–282. doi: 10.1016/j.jcat.2023.07.019
40. [40]
  M. Delferro, T.J. Marks, Chem. Rev. 111 (2011) 2450–2485. doi: 10.1021/cr1003634
41. [41]
  B. Heurtefeu, C. Bouilhac, É. Cloutet, D. Taton, A. Deffieux, H. Cramail, Prog. Polym. Sci. 36 (2011) 89–126. doi: 10.1016/j.progpolymsci.2010.09.002
42. [42]
  D. Peng, M.H. Xu, C. Tan, C.L. Chen, Macromolecules 56 (2023) 2388–2396. doi: 10.1021/acs.macromol.3c00261
43. [43]
  R.Y. Zhang, S.J. Liu, C.W. Zhuo, H. Cao, X.H. Wang, Macromolecules 57 (2023) 132–141.
44. [44]
  Z.Z. Zhou, S.J. Liu, L.H. Yang, et al., ACS Catal. 13 (2023) 15116–15125. doi: 10.1021/acscatal.3c04274
45. [45]
  L.H. Yang, S.J. Liu, Z.Z. Zhou, et al., Macromolecules 57 (2023) 150–161.
46. [46]
  M.H. Ji, G.F. Si, Y. Pan, C. Tan, M. Chen, J. Catal. 415 (2022) 51–57. doi: 10.1016/j.jcat.2022.09.029
47. [47]
  Z. Dong, W.J. Huang, X.Q. Liu, et al., Macromolecules 54 (2021) 9385–9392. doi: 10.1021/acs.macromol.1c01000
48. [48]
  J.A. Molina de la Torre, A.C. Albéniz, Eur. J. Inorg. Chem. 22 (2017) 2911–2919. doi: 10.1002/ejic.201700323
49. [49]
  C. Sondermann, M. Pižl, A. Paretzki, C. Feil, et al., Eur. J. Inorg. Chem. 31 (2020) 3010–3015. doi: 10.1002/ejic.202000455
50. [50]
  S.A. Svejda, L.K. Johnson, M. Brookhart, J. Am. Chem. Soc. 121 (1999) 10634–10635. doi: 10.1021/ja991931h
51. [51]
  Y.X. Zhang, X.H. Kang, Z.B. Jian, Nat. Commun. 13 (2022) 725. doi: 10.1038/s41467-022-28282-z
52. [52]
  J. Xia, Y.X. Zhang, S.Q. Kou, Z.B. Jian, J. Catal. 390 (2020) 30–36. doi: 10.1016/j.jcat.2020.07.017
53. [53]
  H.Y. Ji, Y.X. Zhang, Y. Chi, Z.B. Jian, Polymer 290 (2024) 126591. doi: 10.1016/j.polymer.2023.126591
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