Journal
ORGANOMETALLICS
Volume 26, Issue 9, Pages 2252-2257Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om060893p
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Methylaluminum sesquichloride (Al2Cl3Me3, MAS), in the presence of ethyl trichloroacetate (ETAC), is found to be an effective catalyst for the production of polyethylene. Optimal catalyst productivities are obtained for a MAS:ETAC ratio of 1:1 at a reaction temperature of 75 degrees C. The polymerization is first order in both ethylene and MAS/ETAC concentration. NMR studies indicate that a 1:1 adduct is formed between binuclear MAS and ETAC, which is postulated to be a direct precursor to the active species. The productivity at elevated temperatures is limited by a radical decomposition process. Screening of various additives revealed that many halogenated organic reagents can act as activators, including carbon tetrachloride and p-toluene sulfonyl chloride. Improved productivities are obtained using sulfonyl chloride activators due to circumvention of radical decomposition pathways.
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