Prospects for the Use of Al/Mg Cocatalysts (Alk<sub><i>n</i></sub>AlCl<sub>3</sub>–<i><sub>n</sub></i> + Alk<sub>2</sub>Mg) in the Polymerization of Olefins. Studies of the Interactions between the Activator Components

Based on previously accumulated experimental material on the use of {nEt2AlCl + Bu2Mg} mixtures for the activation of Ti postmetallocene precatalysts for ethylene polymerization, an attempt is made to find the reason for the universal activating ability of such cocatalysts by analyzing the chemical processes occurring during the interaction of alkylaluminum chlorides and dibutylmagnesium. 1H and 27Al NMR spectroscopy data indicate that in nonsolvating media the formation of ionic products (with which earlier the unique activating ability of Al/Mg activators was associated) does not occur. The “true” Al/Mg cocatalysts are uncharged adducts of MgCl2 with alkylaluminum chlorides and/or trialkylaluminum. It was shown that all used Al/Mg cocatalyst compositions are capable of activating a model titanium dichloride complex with a saligenin ligand with varying efficiencies. The product of the ethylene polymerization is an ultrahigh molecular weight polymer (Mv from 1.1 to 5.1 × 106 Da); the latter is evidenced by the possibility of solid-phase processing of nascent polymer powders into high-strength, high-modulus tapes (breaking strength up to 2.4 GPa and elastic modulus up to 112 GPa).

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Publication Details

Journal
Organometallics
Published
2024-11-21
DOI
https://doi.org/10.1021/acs.organomet.4c00361
Citations
5
Primary Topic
biodegradable polymer synthesis and properties
Type
article
Field-Weighted Citation Impact
0.87

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article

Prospects for the Use of Al/Mg Cocatalysts (AlknAlCl3–n + Alk2Mg) in the Polymerization of Olefins. Studies of the Interactions between the Activator Components

Evgenii K. Golubev, Boris M. Bulychev, Svetlana Gagieva, Dmitrii A. Kurmaev et al.
5 citations
Organometallics
biodegradable polymer synthesis and properties
0.87
article

Prospects for the Use of Al/Mg Cocatalysts (AlknAlCl3–n + Alk2Mg) in the Polymerization of Olefins. Studies of the Interactions between the Activator Components

Evgenii K. Golubev, Boris M. Bulychev, Svetlana Gagieva, Dmitrii A. Kurmaev, Maria D. Evseeva, Vladislav А. Тuskaev, Т. В. Стрелкова
article en
5 citations

Abstract

Based on previously accumulated experimental material on the use of {nEt2AlCl + Bu2Mg} mixtures for the activation of Ti postmetallocene precatalysts for ethylene polymerization, an attempt is made to find the reason for the universal activating ability of such cocatalysts by analyzing the chemical processes occurring during the interaction of alkylaluminum chlorides and dibutylmagnesium. 1H and 27Al NMR spectroscopy data indicate that in nonsolvating media the formation of ionic products (with which earlier the unique activating ability of Al/Mg activators was associated) does not occur. The “true” Al/Mg cocatalysts are uncharged adducts of MgCl2 with alkylaluminum chlorides and/or trialkylaluminum. It was shown that all used Al/Mg cocatalyst compositions are capable of activating a model titanium dichloride complex with a saligenin ligand with varying efficiencies. The product of the ethylene polymerization is an ultrahigh molecular weight polymer (Mv from 1.1 to 5.1 × 106 Da); the latter is evidenced by the possibility of solid-phase processing of nascent polymer powders into high-strength, high-modulus tapes (breaking strength up to 2.4 GPa and elastic modulus up to 112 GPa).

OrganometallicsVol. 43(23)
Lomonosov Moscow State University (RU), A. N. Nesmeyanov Institute of Organoelement Compounds (RU), Institute of Synthetic Polymeric Materials (RU)
Russian Science Foundation
Openalex Percentile: Top 29%
biodegradable polymer synthesis and properties
0.87
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