Patent GB-876638-A (GB)
Title: Improvements in and relating to polymerisation of monoolefines
IPC: B01J21/06
Filed: 1958-05-21
Abstract: Mono-olefines are polymerized, e.g. in bulk or in an organic solvent or diluent, in the presence of a catalyst comprising a Group IV(a) metal oxide supported on alumina which has been heat-treated at a temperature of at least 400 DEG C. in a non-reducing atmosphere under conditions which provide for the removal of any decomposition products.  The Periodic Table used is the Mendeleeff Table.  The preferred oxides are of titanium, zirconium, thorium, or hafnium. Specified mono-olefines are ethylene, propylene, butylenes, and hexenes.  In the polymerization, the catalyst may be in the form of fluidized particles, as a fixed bed, or as a counter-current or cocurrent moving bed of particles.  The organic solvent or diluent present during polymerization may be benzene, toluene, xylene, xylene-p-cymene mixtures, cyclohexane, t-butylbenzene, ethylxylenes, or tetrahydro- or decahydro-naphthalene.  The catalyst support may be made of gamma-alumina or an amorphous alumina admixed if desired with silica.  The catalyst is made by depositing on the support either an oxygen-containing Group IV(a) compound which is converted to the oxide by heating, or a salt of a Group IV(a) metal with an inorganic or organic acid which can be converted by aqueous, acidic, or alkaline hydrolysis to the hydrous oxide.  The deposition of the catalyst may be effected from aqueous or organic solvent solution. Suitable compounds from which the catalyst can be formed are tetraethyl zirconate, tetrabutyl titanate, tetramyl hafnate, tetraoctyl thorate, tetraoctylphenyl titanate, titanyl acetate, zirconium tetrapropionate, zirconyl stearate, hafnium tetravalerate, thorium tetra-acetate, isopropoxyzirconyl laurate, ethoxytitanyl acetate, butoxytitanyl butyrate, decyloxythoryl decanoate, or chlorides or nitrates of titanium, zirconium, hafnium, or thorium. The polymer may be separated from the polymerizate by extraction with an organic solvent.  The polymerization may be effected batchwise or continuously.ALSO:A polymerization catalyst for monoolefines comprises a Group IV(a) metal oxide of the Table according to Mendeleeff, supported on alumina, which has been heat-treated at a temperature of at least 400 DEG C. in a non-reducing atmosphere and under conditions which provide for the removal of any decomposition products.  The catalyst support may be made of gamma-alumina or an amorphus alumina admixed, if desired, with silica.  The catalyst is generally made by depositing on the support either an oxygen-containing Group IV(a) compound which is converted to the oxide by heating, or a salt of a Group IV(a) metal with an inorganic or organic acid which can be converted by aqueous, acidic, or alkaline hydrolysers to the hydrous oxide.  The deposition may be effected from an aqueous or organic solvent solution.  Suitable compounds from which the catalyst can be formed are tetraethyl zirconate, tetrabutyl titanate, tetramyl hafnate, tetraoctyl thorate, tetraoctylphenyl titanate, titanyl acetate, zirconium tetrapropionate, zirconyl stearate, hafnium tetravalerate, thorium tetraacetate, isopropoxyzirconyl laurate, ethoxytitanyl acetate, butoxytitanyl, butyrate, decyloxythoryl decanoate, or chlorides or nitrates of titanium, zirconium, hafnium, or thorium.  Exemplified catalysts are (1) gamma-alumina pellets impregnated with tetraisopropyl titanate, soaked in distilled water for 24 hours and heat-treated in an atmosphere of argon, (2) alumina pellets treated with a solution of titanium tetrachloride and the latter hydrolysed with an aqueous solution of ammonium hydroxide, and the impregnated pellets subsequently heat-treated at 700 DEG C. in an inert atmosphere, (3) alumina pellets impregnated with isopropoxytitanium oxatate which is formed in situ from tetraiospropyl titanate treated with anhydrous oxalic acid, and the pellets pyrolyzed in argon for 41 hours at 700 DEG C., (4) alumina pellets impregnated with isopropoxyzirconium oxalate which was formed in situ and heat-treated at 700 DEG C., (5) alumina pellets impregnated with a solution of polymeric hydroxytitanyl stearate and pyrolyzed in argon for 44.5 hours at 700 DEG C., (6) alumina pellets impregnated with polymeric isopropoxytitanium malonate and activated by pyrolyses at 500 or 700 DEG C., and (7) alumina pellets impregnated with polymeric isopropoxytitanium maleate and activated by pyrolyses at 700 DEG C. in an argon atmosphere.