Abstract
The codimerization of vinylaromatic compounds with ethylene in the presence of nickel-containing catalysts modified with electron-acceptors was studied. NiX2–P(OC6H5)3–Al(C2H5)3–BF3(C2H5)2O systems have found to be highly effective catalysts for the codimerizations of vinylaromatic compounds with ethylene. A new method for selective synthesis of phenylbutenes has been developed. The reactivities of vinylaromatic compounds were studied in the codimerization reaction with ethylene. The monomer reactivities in the codimerization were found to be in the following order: p-chlorostyrene>p-methylstyrene>α-methylstyrene>>α-phenylstyrene. The effect of different factors (nature and composition of catalyst component, method for preparing catalyst, monomer concentrations, reaction temperature) on the codimerization rate and selectivity was studied. The effect of solvent on the rate of styrene codimerization with ethylene was studied. The solvent with strong codimerization ability decreased catalytic activity. Detailed kinetic studies on the selective codimerization of styrene or α-methylstyrene with ethylene were carried out. The results obtained were considered as proof for the “process of hydride mechanism” proceeding via the formation of nickel intermediate π-benzyl complexes. On the basis of proposed reaction mechanism, a kinetic equation has been derived; the rate constant and activation energy of ethylene insertion into Ni–C bond in the intermediate π-benzyl complex were determined.
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Mamedaliev, G., Azizov, A. Study on the Codimerization of Vinylaromatic Compounds with Ethylene in the Presence of Modified Nickel-Containing Catalysts. Polym J 17, 1075–1084 (1985). https://doi.org/10.1295/polymj.17.1075
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DOI: https://doi.org/10.1295/polymj.17.1075