Patent GB-1265918-A (GB)
IPC: C07C2/30
Filed: 1970-05-19
Abstract: 1,265,918. Olefin dimerization/codimerization catalysts. INSTITUT FRANCAIS DU PETROLE DES CARBURANTS ET LUBRIFIANTS. 19 May, 1970 [20 May, 1969], No. 24252/70. Heading B1E. [Also in Division C5] An olefin dimerization/codimerization catalyst is prepared by a process which comprises reacting a dihydrocarbylaluminium monohalide with water in the presence of inert solvent at a temperature below 20C, for example of from -20 to 20C, separating the resulting mixture into an insoluble solid fraction and a liquid fraction, and thereafter mixing the liquid fraction with nickel or a compound thereof. The water and dihydrocarbylaluminium monohalide may be used in amounts such that the water to dihydrocarbylaluminium monohalide molar ratio is between 0.01 to I and 2 to 1, each preferably constituting less than 30 per cent by weight of the mixture of dihydrocarbylaluminium monohalide, water and solvent; the nickel or compound thereof may be used in an amount to provide from 0.002 to 50 gram atoms of nickel per gram atom of aluminium. The dihydrocarbylaluminium monohalide is a compound having the formula R 2 A1X wherein each R is a monovalent hydrocarbon radical, for example an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, arylalkenyl, alkaryl oralkarylaryl radical, any aryl radical optionally being substituted with a monovalent heterocyclic radical which may contain from 2 to 12 carbon atoms and from 1 to 3 hetero atoms selected from nitrogen, oxygen and sulphur, and X is a halogen atom, for example a chlorine or bromine atom. The solvent may be a hydrocarbon or halohydrocarbon, for example hexane, heptane, cyclohexane, benzene, chlorobenzene or a chloronaphthalene; the solvent, which preferably contains from 3 to 20 carbon atoms and not more than three halogen atoms per molecule, may comprise at least one C 3-20  olefin which is a reactant in or a reaction product of a dimerization/codimerization process in which the catalyst is used. When nickel per se is used, it may be obtained either by partial attack on a nickel-containing alloy, for example Ni-Al, Ni-Si or Ni-Zn, to remove metal other than nickel or by reduction of a reducible nickel compound, for example nickel oxide, either as such or admixed with solid carrier material, for example alumina, silica, kieselguhr, pumice, sepiolite or carbon. Suitable nickel compounds are salts, for example the chloride, iodide, sulphate, acetate, valerate, naphthenates, sulphonates and dibutyldithiocarbamate of nickel; organic complexes, for example nickel acetylacetonate, nickel carbonyl, biscyclopentadienyl nickel and allyl nickel chloride; and complexes obtained from inorganic nickel salts and trivalent organic compounds of phosphorus, arsenic or antimony, for example triisopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, phenyldicyclopentylphosphine; dichlorophenylphosphine and di-tert-butylphosphine. Examples relate to the preparation of catalysts from diethylaluminium monochloride, water and either a nickel dichloride-triphenylphosphine complex containing two moles of triphenylphosphine per mole of nickel chloride (Example 1) or a nickeldichloride-tributylphosphine complex containing two moles of tributylphosphine per mole of nickel chloride (Examples 2, 3 and 4), the solvent used during the preparation of the catalyst being either a mixture of butene-1 and butene-2 (Example 1) or a mixture of C 6 , C 7  and C 8  olefins obtained by codimerizing propylene and butene-2 (Examples 2, 3 and 4).