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1H NMR Characterization of rac-Et(2-MeInd)2ZrMe2 Activation by Diisobutylaluminum Aryloxide (2,6-tBu2PhO-)AliBu2статья
- Авторы: Faingol’d E.E., Zharkov I.V., Saratovskikh S.L., Panin A.N., Lashmanov N.N., Vinnikov D.S., Chernyak A.V., Bravaya N.M.
- Журнал: Petroleum Chemistry
- Том: 65
- Номер: 7
- Год издания: 2025
- Издательство: Pleiades Publishing, Ltd
- Местоположение издательства: Road Town, United Kingdom
- Первая страница: 810
- Последняя страница: 817
- DOI: 10.1134/s096554412560078x
- Аннотация: The paper reports the 1H NMR characterization results for the products of rac-Et(2-MeInd)2ZrMe2 activation by diisobutylaluminum aryloxide 2,6-tBu2PhO-)AliBu2 (hereinafter referred to as AliBu2(OAr)), with and without olefins (1-hexene/ethylene/propylene). The olefin-free reaction between the catalyst and AliBu2(OAr) caused the decomposition of dimethylated zirconocene with liberation of methane and isobutene, likely due to the formation of a cationic complex [rac-Et(2-MeInd)2ZrMe]+[MeAliBu2(OAr)]–, unstable at room temperature. In the presence of 1-hexene, rac-Et(2-MeInd)2ZrMe2 was effectively activated by diisobutylaluminum aryloxide to generate a catalytically active intermediate with a growing polymer chain—[rac-Et(2-MeInd)2ZrCH2CH(iBu)Pol]+· [MeAliBu2(OAr)]–—and to form polyhexene. After complete depletion of hexene-1, the working catalyst was deactivated with the formation of rac-Et(2-MeInd)2Zr(H)CH2CH(iBu)Pol, MeAliBu(OAr), and isobutene. In the presence of ethylene and propylene, the 1H NMR signals of the olefins weakened over time, and insoluble polymer particles accumulated on the tube walls. A reaction mechanism was proposed for the rac-Et(2-MeInd)2ZrMe2/ AliBu2(OAr) system, accounting for pathways both with and without olefins.
- Добавил в систему: Файнгольд Евгений Ефимович