III International Conference

PP-II-47ETHYLENE OLIGOMERIZATION TO LINEAR α-OLEFINS IN THE PRESENCEOF CATALYTIC SYSTEMS BASED ON THE ZIRCONYL CARBOXYLATESKhanmetov A.A., Azizov A.H., Guliyev B.V., Aliyeva R.V.Institute of Petrochemical Processes named after Yu.G.Mamedaliev of AzerbaijanNational Academy of Sciences, Baku, AzerbaijanE-mail: khanmetov@mail.ru, bilal_vahid@yahoo.comLinear α-olefins have found wide application in various areas of petrochemical synthesis.They are used for the copolymerization with ethylene, production of linear low densitypolyethylene, linear alkylbenzene, in manufacturing of surfactants, corrosion inhibitors,highly effective lubricant oils, oxoalcohols, α-olefin sulfonates, additives to oils, etc. Amongethylene oligomerization catalysts obtained on the basis of transition metals the zirconiumcontainingcatalytic systems are more perspective ones providing α-olefins synthesis withhigh selectivity. However, the known zirconium-containing catalytic systems are nottechnological, do not show high selectivity towards the most important fractions of α-olefins,such as С 4 , С 6 -С 10 , С 8 -С 18 and are sensitive to impurities and a moisture.It has been established for the first time, that the zirconyl carboxylates of structureZrO(OCOR)nCl 2 -n and Zr 2 O 3 (OCOR)nCl 2 -n, where R-alkyl С 3 -С 10 or aryl, n=1 or 2 incombination with activators – alkyl aluminium chlorides are active catalysts for ethyleneoligomerization to linear α-olefins.In the present work the investigation results of ethylene oligomerization in the presenceof above catalytic systems have been reported. It was shown that in the case of using catalyticsystems based on zirconyl carboxylates, molecular weight distribution (MWD) of ethyleneoligomers is similar with distribution observed in the presence zirconium tetracarboxylates,i.e. has character of Schulz-Flory distribution. There have been studied the influence ofvarious modifiers on catalyst activity and MWD of ethylene oligomerization products. It wasfound, that modifiers of donating type, such as ethers R 2 O, where R-alkyl С 1 -С 10 or aryl, atthe molar ratio of an ether to zirconium, equal (1-3):1 change the MWD character fromSchulz-Flory type to Puasson and the yield of С 8 -С 18 fraction reaches 75-80 % on consumedethylene. In the case of modification of indicated catalytic systems by esthers the ethyleneoligomers’ MWD has not the Schulz-Flory character and the main products of ethyleneoligomerization are С 4 -С 10 oligomers with the yield more than 90 %.It has been concluded that the deviation of oligomerization products composition from statisticaldistribution of Schulz-Flory type is caused by multi-site character of used catalytic systems.249