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Phenyl-bridged bis-salicylaldiminato binuclear titanium complexes for ethylene (co)polymerization

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Abstract

P-Phenyl-bridged bis-salicylaldiminato binuclear titanium complexes Ti2L1, Ti2L2 and the corresponding momonuclear counterpart TiL4 were synthesized and characterized by 1H NMR, 13C NMR, FT-IR, and elemental analysis. The binuclear titanium complex Ti2L1 showed good catalytic performances for ethylene polymerization and copolymerization with norbornene or 1,5-hexadiene. For ethylene polymerization, the binuclear titanium complex Ti2L1 exhibited highest activity of 8.70 × 105 g/mol(Ti).h.atm at 70 °C and retained an activity of 3.00 × 105 g/mol(Ti).h.atm at 90 °C, which showed much higher thermal stability compared with its bi- and mono-nuclear derivatives Ti2L3 and TiL4, due probably to the rigid phenyl-bridged structure offering more stable state of active metal centers. The binuclear complex Ti2L1 could catalyze ethylene copolymerization with norbornene (NB) or 1,5-hexadiene (1,5-HD) to produce copolymer bearing cyclic groups. Compared with mononuclear complex TiL4, the binuclear Ti2L1 showed higher catalytic activity and incorporation rate of comonomer for ethylene/NB copolymerization. The mononuclear complex TiL4 could barely catalyze the copolymerization of ethylene and 1,5-HD, however, the binuclear analogue Ti2L1 exhibited an activity of 1.67 × 105 g/mol(Ti)·h·atm with 4.74% of incorporation rate of 1,5-HD for ethylene/1,5-HD copolymerization, implying that the bimetallic synergistic effect could greatly improve the catalytic performance of the bis-salicylaldiminato binuclear titanium complexes.

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Acknowledgements

The authors are grateful for the financial support from the National Natural Science Foundation of China (21172269) and Major bidding projects of provincial and ministerial scientific institutions, South-Central Minzu University (PTZD22007).

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  1. Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central Minzu University, Wuhan, 430074, China

    Mengyuan Xue, Yani Luo, Senlin Ren, Tingcheng Li & Guangyong Xie

  2. Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, School of Chemical and Environmental Engineering, Jianghan University, Wuhan, 430056, China

    Qingliang You

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Xue, M., Luo, Y., Ren, S. et al. Phenyl-bridged bis-salicylaldiminato binuclear titanium complexes for ethylene (co)polymerization. J Polym Res 30, 28 (2023). https://doi.org/10.1007/s10965-022-03410-x

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