| 摘要 |
Alkyl aluminium compounds are prepared by treating a non-a -olefin (as defined) with a low molecular weight alkyl aluminium compound (as defined) using as catalyst a compound of Groups IV(a), V(a), VI(a) (i.e. Ti, V and Cr groups). The non-a -olefin is defined as an olefinic hydrocarbon or mixtures thereof wherein at least 40% of the molecules have a non-terminal olefinic double bond. The mixture may contain up to 50 mol. per cent of olefins of chain length equal to or less than that of one or more of the alkyl groups of the aluminium compound. The alkyl aluminium compound is defined as having alkyl groups with fewer carbon atoms than the non-a -olefin employed in the process and may have one or two H atoms attached directly to aluminium. The catalyst may be a halide preferably the chloride and/or a compound having an oxygen atom linking the metal with a carbon atom. More particularly the catalyst may be an alcoholate, a chelate, or a phenolate e.g. methylates, ethylates, propylates, isopropylates, phenolates, cresolates, acetylacetonates, salicylates, benzoylacetonates, 2-furoylacetonates; of Ti, Zr, V, U, Cr, Th, W, Ta, or Nb. The low molecular weight alkyl aluminium compound is preferably tri-isobutyl aluminium but may also be tri-ethyl, propyl or n-butyl aluminium, di-isobutyl aluminium chloride or diethyl aluminium hydride, the preferred compounds having alkyl groups containing at the most 4 C atoms. The non-a -olefins suitable for the process are but-2-ene, pent-2-ene, hex-3-ene, oct - 2,3 or 4 - ene, dec - 5 - ene, tridec-6-ene but preferably having at least 6 C atoms. The non-a -olefin may be obtained (a) by dehydration of an alcohol or mixture of alcohols; (b) by thermal or catalytic cracking of hydrocarbon feedstocks (c) from the residue left after removal of a -olefins by polymerizing with a Ziegler catalyst. The non-a -olefin and the low molecular weight alkyl aluminium compound may be used in molar ratio 1.5: 1 to 10: 1 and the catalyst in amount 0.05 to 10% but preferably 0.5 to 5% mol. The reaction temperature may be 50-250 DEG C. but preferably 100-150 DEG C. whilst preferred reaction conditions are 0.1 to 2% mol. of catalyst at a temperature of 150-200 DEG C. In examples 1-3, 1-octanol is dehydrated with 100% phosphoric acid and the octenes mixed with tri-isobutyl aluminium. TiCl4 was added to the mixture, which was then heated and the isobutene produced collected in a cold tap. In other examples various octenes are used whilst examples 15-53 relate to various catalysts used in processes involving octenes. Primary alcohols are made by the oxidation of the alkyl aluminium compound prepared as above, to form an aluminium alcoholate followed by hydrolysis of the alcoholate. In an example the reaction product from a mixture of non-a -octenes is oxidized by bubbling in air and then hydrolyzing with 10% hydrochloric acid, to give 1-octanol after separation and purification. The preparation of 1-octanol is exemplified using various catalysts and starting materials. Specifications 827,901, 941,016 and 993,666 are referred to. |
