The second life of Ziegler catalyst. Ethylene polymerization reactions with TiCl4–Al[C2H5]2Cl/Mg(C4H9)2 catalyst

• Published in: Journal of applied polymer science Vol. 136; no. 16
• Main Authors: Kissin, Yury V., Rishina, Laura A., Lalayan, Svetlana S., Krasheninnikov, Vadim G.
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc 20-04-2019
• Subjects: Aliphatic compounds; Alkenes; Aluminum; Aromatic compounds; Catalysis; Catalysts; Copolymerization; DSC analysis; Ethylene; Magnesium; Materials science; NMR analysis; polyethylene; Polyethylenes; Polymers; Titanium chlorides; Ziegler catalyst; Ziegler-Natta catalysts
• ISSN: 0021-8995; 1097-4628
• DOI: 10.1002/app.47340

ABSTRACT
The Ziegler catalyst, a combination of TiCl4 and Al(C2H5)2Cl, was widely used since 1950s for the commercial manufacture of linear polyethylene. We found that addition of Mg(C4H9)2 to this catalyst at [Al]:[Mg]molar > 2 leads to the formation of a very active catalyst system for homopolymerization of ethylene and for copolymerization of ethylene and 1‐alkenes. The principal advantages of the ternary TiCl4–Al(C2H5)2Cl/Mg(C4H9)2 catalyst are very high activity (six to seven times higher than the activity of the original Ziegler catalyst), low cost, and the ease of use: the catalyst is prepared in situ from three commercially available cheap compounds soluble in aliphatic and aromatic hydrocarbons. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47340.
Addition of Mg(C4H9)2 to the Ziegler catalyst (a combination of TiCl4–Al(C2H5)2Cl) at [Al]:[Mg]molar > 2 leads to the formation of a very active catalyst system for homopolymerization of ethylene and for copolymerization of ethylene and 1‐alkenes. Gel permeation chromatography curve of ethylene/1‐hexene copolymer (CHexcopol = 6.0 mol %) produced with TiCl4–Al(C2H5)2Cl/Mg(C4H9)2 catalyst and its separation into Flory components.