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Isobutylalumoxanes as high-performance activators of rac-Et(2-MeInd)2ZrMe2 in copolymerization of ethylene with propylene and ternary copolymerization of ethylene, propylene, and 5-ethylidene-2-norbornene

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Abstract

Isobutylalumoxanes have been obtained by hydrolysis of triisobutylaluminium (TIBA) with water in the form of vapour (1) or ice particles (2) at AlTIBA/H2O = 2 mol/mol. 1H NMR spectra of hydrolyzates showed the presence of unreacted TIBA indicating the formation of alumoxanes larger than iBu2Al-O-AliBu2 which one can expect based on the molar ratio of reagents. Alumoxanes 1 and 2 demonstrate high activating ability for rac-Et(2-MeInd)2ZrMe2 in copolymerization reactions of ethylene with propylene and terpolymerization of ethylene with propylene and 5-ethylidene-2-norbornene. Alumoxane 1 demonstrates high structural and chemical stability during long-term storage (for 1 year) that results in consistent activating ability and similarity of molecular weight characteristics of polymer formed. Alumoxane 2 is much less structurally stable which is manifested in considerable changes of 1H NMR spectra of the product even after several days of storage. It essentially loses activating ability after 3 months’ storage. The alumoxanes with high activating ability have been also obtained by in situ TIBA hydrolysis with water intentionally incorporated into toluene (~1 × 10−2 mol/l) prior to polymerization also at AlTIBA/H2O = 2 mol/mol. The differences of catalytic systems with different activators are also reflected in differences in microstructure, molecular-weight, thermal-physical characteristics and physical-mechanical properties of copolymers formed.

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Acknowledgments

The financial support from Russian Sciences Foundation (Grant 13-03-01011 a and 13-03-12181 ofi_m) is acknowledged.

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Authors and Affiliations

  1. The Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Academician Semenov Avenue 1, Chernogolovka, Moscow Region, 142432, Russian Federation

    Natalia M. Bravaya, Andrei N. Panin, Eugeny E. Faingol’d, Stanislav L. Saratovskikh, Olga N. Babkina, Igor’ V. Zharkov & Eugenia O. Perepelitsina

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  1. Natalia M. Bravaya
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Correspondence to Natalia M. Bravaya.

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Bravaya, N.M., Panin, A.N., Faingol’d, E.E. et al. Isobutylalumoxanes as high-performance activators of rac-Et(2-MeInd)2ZrMe2 in copolymerization of ethylene with propylene and ternary copolymerization of ethylene, propylene, and 5-ethylidene-2-norbornene. Polym. Bull. 73, 473–491 (2016). https://doi.org/10.1007/s00289-015-1505-2

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