Copolymerization of ethylene with norbornene by using metallocene/TIBA/B(C6F5)3 system

Document Type : Original research


SINOPEC (Beijing) Research Institute of Chemical Industry Co., Ltd., No. 14 Beisanhuan Donglu, Chao Yang District, Beijing (100013), China


Cyclic olefin copolymer is a type of high-performance polyolefin material, which is prepared by using a single-site catalyst in solution polymerization. The common activator of this system is alkyl aluminoxane or organic  boron/aluminum system. Among them, organic boron is mostly triphenylcarbenium tetrakis(pentafluorophenyl)borate or dimethylanilinium tetrakis(pentafluorophenyl)borate. In this study, ethylene and norbornene were copolymerized with metallocene catalyst activated with the combination of tris(pentafluorophenyl)boron and triisobutylaluminium. Compared with homopolymerization of ethylene, copolymerization shows high activity. The molecular weight of the polymer increased significantly with the increase of the insertion rate of norbornene. Fineman-Ross method was used to calculate the reactivity ratio, which showed that the reactivity ratio of norbornene was much lower than that of ethylene. The high copolymerization activity may indicate that, although norbornene has a lower coordination probability, its insertion rate is higher than ethylene. The copolymer with higher norbornene incorporation has a higher glass transition temperature, and the relationship between them is linear.


  1. Gibson VC, Spitzmesser SK (2003) Advances in non-metallocene olefin polymerization catalysis. Chem Rev 103: 283-315
  2. Kaminsky W (2001) Olefin polymerization catalyzed by metallocenes. Adv Catal 46: 89-159
  3. Hamielec AE, Soares JBP (1996) Polymeriza­tion reaction engineering - metallocene catalysts. Prog Polym Sci 21: 651-706
  4. Wang W, Hou L, Zhang T (2020) Integrated effect of comonomer and catalyst on copoly­merization of ethylene with allylcyclopentane or allylcyclohexane by using metallocene catalysts. Chemistry Select 5: 7581-7585
  5. Brauer E, Wiegleb H, Helmstedt M (1986) Char­acterization of ethylene homo- and copolymers. V. Molecular characterization of (norbornene-ethylene) copolymers by size-exclusion chroma­tography, viscosimetry and osmometry. Polym Bull 15: 551-557
  6. Ruchatz D, Fink G (1998) Ethene-norbornene copolymerization using homogenous metallo­cene and half-sandwich catalysts: Kinetics and relationships between catalyst structure and polymer structure. 2. Comparative study of different metallocene- and half-sandwich/methyl-aluminoxane catalysts and analysis of the copo­lymers by 13C nuclear magnetic resonance spec­troscopy. Macromolecules 31: 4674-4680
  7. Tritto I, Boggioni L, Sacchi MC, Locatelli P, Ferro DR, Provasoli A (1999) Ethylene-norbornene copolymers prepared with metallo­cene-based catalysts. New sequence assignments by 13C NMR. Macromol Rapid Commun 20: 279-283
  8. Boggioni L, Losio S, Tritto I (2018) Microstructure of copolymers of norbornene based on assign­ments of 13C NMR spectra: evolution of a metho-dology. Polymers 10: 647/1-647/24
  9. Boggioni L, Tritto I (2013) Polyolefins with cyclic comonomers. Adv Polym Sci 258: 117-142
  10. Lago WSR, Aymes-Chodur C, Ahoussou AP, Yagoubi N (2017) Physico-chemical ageing of ethylene-norbornene copolymers: A review. J Mater Sci 52: 6879-6904
  11. Soleimannezhad A, Mortazavi SMM, Ahmadjo S, Mansouri S, Rashedi R (2022) Study on polymerization conditions in homo- and copolymer syntheses of norbornene/1-hexene with nickel-based late-transition metal catalyst. Iran Polym J 31: 237-245
  12. Shakeri SE, Mortazavi SMM, Ahmadjo S, Zohuri GH (2022) Synthesis and gas permeation of polynorbornene by dinuclear a-diimine Ni-based catalysts: Experimental and quantum chemistry modeling. J Polym Res 29: 201
  13. Samira M, Omidvar M, Soleimannezhad A, Shakeri SE, Mortazavi SMM, Ahmadjo S (2022) Copolymerization of cyclic monomers by nickel a-diimine catalysts: Catalyst structure, polymer characterization. J Polym Res 29: 409
  14. Mansouri S, Omidvar M, Mortazavi SMM, Ahmadjo S (2022) 5-Ethylidene-2-norbornene Polymerization by a-diimine nickel catalyst: A revealing insight into the pivotal function of binuclear and mononuclear catalyst structure in tailoring polymer architecture. Macromol React Eng 16: 2100052
  15. Shakeri SE, Mortazavi SMM, Ahmadjo S, Zohuri GH(2020) Comparison of mono and dinuclear a-diimine Ni-based catalysts for synthesis of polynorbornene and its micro-structure study. J Macromol Sci A 57: 837-843
  16. Land HT, Osan F, Wehrmeister T (1997) TOPAS - new cycloolefin copolymers applying metallo­cene technology. Polym Mater Sci Eng 76: 22-23
  17. Kaminsky W, Arndt M, Beulich I (1997) New materials and kinetic aspects by copolymeriza­tion of cyclic olefins with metallocene catalysts. Polym Mater Sci Eng 76: 18-19
  18. Zeng Y, Mahmood Q, Zhang Q, Liang T, Sun W (2018) Highly thermo-stable and electroni­cally controlled palladium precatalysts for vinyl homo/co-polymerization of norbornene-ethyl­ene. Eur Polym J 103: 342-350
  19. Nomura K, Oshima M, Mitsudome T, Hara­kawa H, Hao P, Tsutsumi K, Nagai G, Ina To, Takaya H, Sun, W, Yamazoe S (2017) Synthe­sis and structural analysis of (imido)vanadium dichloride complexes containing 2-(2'-Benz-im­idazolyl)pyridine ligands: Effect of Al cocatalyst for efficient ethylene (co) polymerization. ACS Omega 2: 8660-8673
  20. Pei L, He S, Gao J, Liao H, Gao H (2017) Homo-and copolymerizations of ethylene and norborn­ene using bis(β-ketoamino) titanium catalysts containing pyrazolone rings. Polymers 9: 262/1- 262/12
  21. Nomura K, Izawa I, Kuboki M, Inoue K, Aoki H, Tsutsumi K (2022) Solution XAS analysis for reactions of phenoxide-modified (arylimido) vanadium(V) dichloride and (oxo)vanadium(V) complexes with Al alkyls: Effect of Al cocatalyst in ethylene (co)polymerization. Catalysts 12: 198
  22. Wang W, Nomura K (2005) Remarkable effects of aluminum cocatalyst and comonomer in ethyl­ene copolymerizations catalyzed by (arylimido) (aryloxo)vanadium complexes: Efficient synthe­sis of high molecular weight ethylene/norborn­ene copolymer. Macromolecules 38: 5905-5913
  23. Marconi R, Ravasio A, Boggioni L, Tritto I (2009) Silyl-terminated ethylene-co-norbornene copolymers by organotitanium-based catalysts. Macromol Rapid Commun 30: 39-44
  24. Boggioni L, Sidari D, Losio S, Stehling UM, Auriemma F, Di Girolamo R, De Rosa C, Tritto I (2018) Ethylene-co-norbornene copolymeriza­tion in the presence of a chain transfer agent. Eur Polym J 107: 54-66
  25. Chien JCW, Tsai WM, Rausch MD (1991) Iso­specific polymerization of propylene catalyzed by rac-ethylenebis(indenyl)methylzirconium cation. J Am Chem Soc 113: 8570-8571
  26. Pellecchia C, Proto A, Longo P, Zambelli A (1991) Group 4 transition metal complex cations for olefin polymerization. Makromol Chem Rap­id Commun 12: 663-667
  27. Massey AG, Park AJ (1964) Perfluoro­phenyl derivatives of the elements. I. Tris(pentafluorophenyl)boron. J Organomet Chem 2: 245-250
  28. Yang X, Stern CL, Marks TJ (1992) Cationic metallocene polymerization catalyst: the first base free zirconocene hydride. Angew Chem 104: 1406-1408
  29. Grassi A, Maffei G, Milione S, Jordan R F (2001) Synthesis of ethylene-co-norbornene polymers promoted by MAO free catalysts based on group 4 dicarbollide complexes. Macromol Chem Phys 202: 1239-1245
  30. Lee H, Hong SD, Park YW, Jeong BG, Nam DW, Jung HY, Jung MW, Song KH (2004) Control of symmetry in active cationic ansa-zirconocene species: catalyst preparation, characterization and ethylene-norbornene copolymerization. J Organomet Chem 689: 3402-3411
  31. Jang Y, Sung HK, Kwag H (2006) Effects of tris(pentafluorophenyl)borane on the activa­tion of the Ni(II)-based catalyst in the addition polymerization of norbornene. Eur Polym J 42: 1250-1258
  32. Lee L, Shih R, Ou H, Lee T (2003) Solubility of ethylene in mixtures of toluene, norbornene, and cyclic olefin copolymer at various temperatures and pressures. Ind Eng Chem Res 42: 6977-6985
  33. Lee L, Ou H, Hsu H (2005) The experiments and correlations of the solubility of ethylene in tolu­ene solvent. Fluid Phase Equilibr 231: 221-230
  34. Lee LS, Shih RF, Ou HJ, Lee TS (2005) Solubili­ty of ethylene in toluene and norbornene mixture at various temperatures and pressures. J Chin Inst Eng 28: 1127-1138
  35. Yano A, Hasegawa S, Yamada S, Akimoto A (1999) Influence of activators on ethylene polymerization with diphenylmethylidene- (cyclopentadienyl)(fluorenyl)zirconium dichlo­ride catalysts at high temperature. J Mol Catal A 148: 77-86
  36. Park SY, Choi KY, Song KH, Jeong BG (2003) Kinetic modeling of ethylene-norbornene copo­lymerization using homogeneous metallocene catalysts. Macromolecules 36: 4216-4225
  37. Tritto I, Boggioni L, Zampa C, Sacchi MC, Fer­ro DR (2006) Ethylene-norbornene copolymers by ansa fluorenyl metallocenes: Mechanistic considerations on the basis of tetrad and pentad analysis. Top Catal 40: 151-161
  38. Arndt-Rosenau M, Beulich I (1999) Microstruc­ture of ethene/norbornene copolymers. Macro­molecules, 32: 7335-7645
  39. Tritto I, Marestin C, Boggioni L, Zetta L, Provasoli A, Ferro D. (2000) ethylene-norbornene copolymer microstructure. Assessment and advances based on assignments of 13C NMR spectra. Macromolecules 33: 8931-8944
  40. Forsyth J, Perena JM, Benavente R, Perez E, Tritto I, Boggioni L, Brintzinger HH (2001) Influence of the polymer microstructure on the thermal properties of cycloolefin copolymers with high norbornene contents. Macromol Chem Phys 202: 614-620
  • Receive Date: 09 December 2022
  • Revise Date: 24 December 2022
  • Accept Date: 27 December 2022
  • First Publish Date: 27 December 2022