Imperial Chemical Industries Limited

Anthony D Caunt

Ian G Williams

Michael Stanley Fortuin

Paul D Gavens

John P Candlin

Alan B Newton

Peter L Law

John McMeeking

John W Kelland

Peter I Vincent

Thomas G Heggs

George David Appleyard

James Frank Jaggard

A suspension which comprises an inert liquid medium, a solid material, a transition metal compound and an agglomeration aid is dried using a spray-drying technique. The spray-drying is effected under conditions of temperature and pressure which are such as to cause evaporation of the liquid medium. The solid material is preferably in a finely-divided form and may consist essentially of a transition metal compound or may be a transition metal compound which is supported on a suitable solid inert matrix material. Alternatively, a suspension of a solid support material in a solution of a transition metal compound may be used. The agglomeration aid may be polystyrene dissolved in the inert liquid medium. The dried solid is obtained as an agglomerated solid which can be mixed with an organic compound of a non-transition metal to give an olefin polymerization catalyst system.

Process for polymerizing olefins with a spray-dried catalyst

A catalyst component is a transition metal composition which is obtained by reacting together an inert particulate material, an organic magnesium compound, a halogen-containing compound such as carbon tetrachloride or silicon tetrachloride and a specified transition metal compound. The catalyst component obtained can be used, together with an organic metal compound, to give an olefin polymerization catalyst. The catalyst can be used to effect the polymerization of olefin monomers, for example, the copolymerization of ethylene with an alpha-olefin monomer such as butene-1 in a fluidized bed reactor.

Production of catalyst component, catalyst and use thereof

Drying process and product

A solid compound of a transition metal is ground in the presence of aluminium chloride, titanium tetrachloride and at least one organo-Lewis Base compound. The transition metal compound is typically titanium trichloride. The Lewis Base compound is an organo-phosphorus compound, preferably one which also contains nitrogen, such as 2-dimethylamino-1,3-dimethyl-1,3,2-diazaphospholidine-2-oxide or an organo-sulphur compound such as diphenyl sulphone. The solid compound of the transition metal may include aluminium chloride and if the amount of this aluminium chloride is at least 50% molar, there is no need to make a separate addition of aluminium chloride to the mixture which is ground. The ground product can be used as a component of an olefine polymerization catalyst.

Transition metal compound

A catalyst component is a transition metal composition which is obtained by reacting together an inert particulate material, an organic magnesium compound, a halogen-containing compound such as carbon tetrachloride silicon tetrachloride or boron trichloride and a specified transition metal compound such as VOCl.sub.3, bis(n-butoxy) titanium dichloride or zirconium tetrabenzyl. The catalyst component obtained can be used, together with an organic metal compound, to give an olefin polymerization catalyst. The catalyst can be used to effect the polymerization of olefin monomers, for example, the copolymerization of ethylene with an alpha-olefin monomer such as butene-1 in a fluidized bed reactor.

Olefine polymerization process

A component of a polymerization catalyst is prepared by reacting an organo-magnesium compound, or a complex with an organo-aluminium compound, with a solid, inorganic oxide, then with a halogenating agent such as silicon tetrachloride or hydrogen chloride, and then reacting the product with a Lewis Base compound, particularly an ester and finally with titanium tetrachloride. The product obtained is combined with an organo-aluminium compound, preferably together with a Lewis Base, and used to polymerize an olefin monomer particularly propylene or mixtures of ethylene and a 1-olefin containing at least 4 carbon atoms. The catalyst system has a high activity, is stereospecific and has a lower proportion of halogen than some other catalyst systems.

Olefin polymerization catalyst and the production and use thereof

A component of a polymerization catalyst is prepared by reacting an organo-magnesium compound, or a complex with an organo-aluminium compound, with an halogenating agent such as silicon tetrachloride or hydrogen chloride, and then reacting the product with a Lewis Base compound, particularly an ester and finally with titanium tetrachloride. The product obtained is combined with an organo-aluminium compound preferably together with a Lewis Base and used to polymerize an olefine monomer. The catalyst has a high activity and is stereospecific.

Olefine polymerization catalyst

A titanium trihalide component of an olefine polymerization catalyst is prepared by reacting together a titanium tetrahalide and an organo-aluminium compound, and treating the solid reaction product with a hydrocarbon solution of an alkyl aluminium dihalide. It is preferred that the solid reaction product is treated with a complexing agent, particularly an ether such as di-isoamyl ether before contacting with the alkyl aluminium dihalide. The titanium trihalide can then be used together with an organo-metallic compound to polymerize an olefine monomer, particularly propylene. The catalyst system may include further components in addition to the titanium trihalide and organo-metallic compound.

Titanium trihalide composition

A solid compound of a transition metal is ground in the presence of aluminum chloride; titanium tetrachloride and at least one specified organic sulphur-containing compound are added, the whole mixture is ground and the ground product is then washed with an aromatic liquid. The transition metal compound is typically titanium trichloride. The organic sulphur-containing compound can be a sulphone, a sulphonamide or a condensed ring system containing at least one heterocyclic sulphur atom. The organic sulphur-containing compound can be diphenylsulphone. The solid compound of the transition metal may be one which also includes aluminum chloride. The quantities of materials added to the transition metal compound are, for each mole of the transition metal compound, 0.10 up to 2.50 moles of the organic sulphur-containing compound, 0.01 up to 0.50 mole of titanium tetrachloride and 0.01 up to 2.50 moles of aluminum chloride. The ground and washed product can be used as a component of an olefine polymerization catalyst.

Process for the production of polymer or copolymer of an olefin monomer

A transition metal product, for example a titanium trichloride material, is obtained by milling a solid transition metal compound with a carboxylic acid or an ester thereof, for example methylmethacrylate and contacting with an organo-Lewis Base such as an amine, an organo-phosphorus compound or a sulphone derivative. The organo-Lewis Base may be milled with the transition metal compound or may be added to the transition metal compound as a solution in an inert liquid. The product can be used as a component of an olefine polymerization catalyst.

Transition metal catalyst

A titanium trihalide is ground with an organic Lewis Base compound which contains at least one phosphorus atom, and optionally at least one nitrogen atom, and a titanium tetrahalide, the Lewis Base and the titanium tetrahalide being used in amounts of 5 to 75, preferably 5 to 50%, molar and 1 to 50, preferably 5 to 30% molar respectively relative to the titanium trihalide. The materials are conveniently milled together and the milled product can be used as a component of an olefine polymerization catalyst and when such catalysts are used to polymerize propylene a high activity is achieved together with satisfactory stereospecificity.

A solid compound of a transition metal is ground in the presence of aluminium chloride; titanium tetrachloride and at least one specified organic sulphur-containing compound are added, the whole mixture is ground and the ground product is then washed with an aromatic liquid. The transition metal compound is typically titanium trichloride. The organic sulphur-containing compound can be a sulphone, a sulphonamide or a condensed ring system containing at least one heterocyclic sulphur atom. The organic sulphur-containing compound can be diphenylsulphone. The solid compound of the transition metal may be one which also includes aluminium chloride. The quantities of materials added to the transition metal compound are, for each mole of the transition metal compound, 0.10 up to 2.50 moles of the organic sulphur-containing compound, 0.01 up to 0.50 mole of titanium tetrachloride and 0.01 up to 2.50 moles of aluminium chloride. The ground and washed product can be used as a component of an olefine polymerization catalyst.

Treatment of transition metal compound

An olefine polymerisation catalyst comprises a titanium trichloride component of high surface area, an organo-metallic component, a Lewis Base component and optionally a polyene. The TiCl.sub.3 component which may have a high porosity is conveniently obtained by the reaction of TiCl.sub.4 and an organo-aluminium compound, treating the reaction product with a complexing agent and then contacting this product with TiCl.sub.4. The organo-metallic component is preferably aluminium triethyl, the Lewis Base component hexamethylphosphoric triamide and the polyene is cycloheptatriene. This system has high polymerisation activity combined with good stereospecificity. Polypropylene can be obtained in high yield thereby giving low catalyst residues and the polymer has a high stiffness modulus.

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Anthony D Caunt