| 摘要 |
A catalyst for the oligomerization of 1, 3-dienes to form cyclic olefins is made by mixing in any sequence, (a) a divalent nickel compound, (b) a metal having a reducing action on the divalent nickel compound, and (c) an organic compound of an element of Group V(a) of the Periodic System which has an atomic weight of at least 30. The component (a) may be nickel chloride, sulphide, cyanide, bromide, iodide, carbonate, formate, acetate, oxalate, oxide, benzoate, hydroxide, sulphate, nitrate, acetylacetonate, acetylacetonate dialcoholate, acetylacetonate diphenolate, acetoacetic esters, benzoylacetonate, or nickel dimethyl glyoxime. Suitable metals are lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, aluminium, gallium, indium or cerium. The (c) catalyst component is preferably selected from the following groups, organic phosphines, phosphine oxides, arsines, stibines, phosphorous acid esters, thiophosphorous acid esters, or phosphorous acid tri-amides substituted by organic radicals. A long list of suitable (c) components are specified. Exemplified (c) components are triphenyl phosphine, triphenyl phosphite, triphenyl phosphine oxide, triphenyl stibine, tri- (o-tolyl) phosphine, and triphenyl arsine. Prior to, during, or after the preparation of the catalyst, a small amount, e.g. 1 to 10% by weight of the mixture, of a hydrocarbon containing ethylenic or acetylenic unsaturation, may be added to the catalyst. Specified dienes are butadiene, 2-methyl butadiene-(1, 3), 2, 3-dimethylbutadiene-(1, 3), 2-ethylbutadiene-(1, 3), pentadiene-(1, 3), hexadiene-(1, 3), hexadiene-(2, 4), cyclohexadiene-(1, 3) and cyclooctadiene-(1, 3). A halide of an element of Group II(b) or III(a) may also be included with the catalyst components. Specified halides are boron trichloride, aluminium chloride or bromide, gallium bromide, indium chloride, thallium chloride, zinc chloride, and cadmium chloride. The Periodic Table used is published in "The Handbook of Chemistry and Physics" 39th Edition, 1957/58 , on pages 400-401. Cyclic olefins prepared from butadiene are cyclooctadiene, cyclododecatriene and vinylcyclohexene. |
