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Supported Catalyst for Ethylene Polymerization and the Copolymerization of Ethylene with Alpha-Olefins, Its Preparation and Use

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Supported Catalyst for Ethylene Polymerization and the Copolymerization of Ethylene with Alpha-Olefins, Its Preparation and Use Europaisches Patentamt J European Patent Office 00 Publication number: 0 446 989 A2 Office europeen des brevets EUROPEAN PATENT APPLICATION © Application number: 91200481.9 © int. CIA C08F 4/655, C08F 10/02 © Date of filing: 06.03.91 Priority: 16.03.90 IT 1969890 Inventor: Masi, Francesco 18.09.90 IT 2150390 Via Kennedy 36 I-20097 San Donato Milanese, Milan(IT) Date of publication of application: Inventor: Pondrelli, Maddalena 18.09.91 Bulletin 91/38 Via Gramsci 54 I-40054 Budrio, Bologna(IT) States: Designated Contracting Inventor: Polesello, Mario AT BE CH DE DK ES FR GB GR LI LU NL SE Viale Frassinetti 29 1-31046 Oderzo, Treviso(IT) Applicant: MONTEDIPE S.r.l. Inventor: Borghi, Italo 16, Piazza della Repubblica Via 49 1-20124 Milan(IT) Aldighieri 1-44100 Ferrara(IT) Inventor: Luciani, Luciano Via Mac Alister 37 1-44100 Ferrara(IT) Representative: Roggero, Sergio et al Inventor: Invemizzi, Renzo Ing. Barzano & Zanardo Milano S.p.A. Via Via Primaticcio 98 Borgonuovo 10 1-20157 Milan(IT) 1-20121 Milano(IT) Supported catalyst for ethylene polymerization and the copolymerization of ethylene with alpha-oiefins, its preparation and use. © A supported Ziegler-Natta catalyst active in ethylene polymerization and in the copolymerization of ethylene with alpha-olefins consists of: (A) a cocatalyst in the form of an organometallic compound of aluminium, and (B) a solid catalyst component obtained by: - (i) impregnating a granular solid support with a solution of a titanium alcoholate and magnesium chloride in a liquid aliphatic hydrocarbon, followed by evaporation of the hydrocarbon solvent; - (ii) impregnating the support treated in (i) with a solution of magnesium chloride in a liquid aliphatic ester, followed by evaporation of the ester solvent; and CM - (iii) activating the support treated in (ii) by contact with an alkyl aluminium halide. < In a preferred embodiment, measured quantities of a silicon halide are introduced in stage (i) and/or (ii), this considerably improving catalytic activity. 00 In a particular embodiment, zirconium or hafnium are introduced into the solid catalyst component (B) in O) addition to titanium, to obtain catalysts able to produce polyethylenes with a widened molecular weight CO distribution. <* Q_ LU Rank Xerox (UK) Business Services EP 0 446 989 A2 This invention relates to a supported catalyst for ethylene polymerization and the copolymerization of ethylene with alpha-olefins, its preparation and use. It is known that ethylene or general alpha-olefins can be polymerized by the low pressure process using Ziegler-Natta catalysts. These catalysts are generally formed from a compound of group IV to group VI 5 elements of the periodic table (transition metal compounds) mixed with an organometallic compound or hydride of group I to group III elements of the periodic table. The known art comprises Ziegler-Natta catalysts in which the transition metal compound is fixed to a solid support, such as a magnesium halide. For example, US patent 4,296,223 describes a solid catalyst component obtained by interacting magnesium dichloride, a titanium alcoholate and an aluminium chloride, w and US patent 4,192,772 describes a solid catalyst component obtained by interacting a magnesium compound, a titanium compound, a zirconium compound and an aluminium halide. These catalysts normally allow olefinic polymers to be obtained with a narrow and wide molecular weight distribution respectively, but do not enable the polymer to be obtained directly in the form of flowable granules. Solid catalyst components are also known in the art obtained by activating with an aluminium halide a complex 15 containing magnesium, titanium, halogen, alkoxy groups and an electron donor. Such a complex can be deposited on a support, particularly a porous support, and then activated to provide solid catalyst components particularly suitable for the polymerization or copolymerization of ethylene in the gaseous phase. For this known art reference should be made to the descriptive part of US patents 4,354,009, 4,359,561, 4,370,456, 4,379,758 and 4,383,095. These supported catalysts enable polyethylenes to be 20 obtained in flowable granular form, however problems often arise deriving from the poor rheology of the polymer because of the presence of fines, and the friability of the granules. A further problem is the unsatisfactory productivity in terms of the quantity of polymer obtained per unit weight of catalyst. This probably derives from the difficulty of depositing the catalyst components on the support in highly active form. Finally, known catalysts are generally insufficiently flexible for use in the production of olefinic 25 polymers with differing characteristics .according to requirements. According to the present invention it has now been found possible to obtain a solid catalyst component and a catalyst which are highly active in suspension or gaseous-phase polymerization, and are able to produce ethylene polymers and copolymers of ethylene with alpha-olefins in the form of flowable granules having excellent morphology. Specifically, the present invention is based on the discovery that magnesium 30 chloride can be deposited in highly active amorphous form on a porous support by two separate partial impregnations, from a solution of magnesium chloride in aliphatic hydrocarbon and in aliphatic ester respectively. It has also been found that such a catalyst can produce ethylene polymers with a molecular weight distribution varying from narrow to wide by simple modifications introduced into the catalyst. In accordance therewith the present invention provides a supported Ziegler-Natta catalyst active in 35 ethylene polymerization and in the copolymerization of ethylene with alpha-olefins, consisting of: (A) a cocatalyst in the form of an organometallic compound of aluminium, and (B) a solid catalyst component containing titanium, magnesium, chlorine and alkoxy groups on a support, with a molar ratio of titanium to magnesium of between 1 :1 and 1 :6 and a titanium content of between 1 and 9% by weight (expressed as metal), obtained by: 40 - (i) impregnating a granular porous solid support with a solution of magnesium chloride MgCb and a titanium tetraalcoholate Ti(OR)4. (where Ft is a linear or branched C1-C5 alkyl radical) in a molar ratio of between 0.1:1 and 0.5:1, in a liquid aliphatic hydrocarbon, followed by evaporation of the hydrocarbon solvent, in order to deposit on the support a complex of formula Ti(OR)4..(0.1-0.5)MgCl2; - (ii) impregnating the support treated in (i) with a solution of magnesium chloride in a liquid aliphatic 45 ester, followed by evaporation of the solvent, to obtain on completion of the operation the deposition on the support of a complex of formula Ti(OR)4.(1-6)MgCl2; and - (iii) activating the support treated in (ii) by contact with an alkylaluminium chloride, operating at a temperature of between 10 and 100° C for a time of between 10 minutes and 24 hours. According to a preferred embodiment, in stage (i) and/or (ii) a silicon halide is additionally added in a 50 quantity to obtain an atomic ratio of the silicon in said silicon halide to the titanium in the titanium tetraalcoholate of between 0.5:1 and 8:1 . In the best embodiment the silicon halide is added in stage (ii) in a quantity to obtain a silicon:titanium atomic ratio of between 2.0:1 and 6.0:1 . The use of the silicon halide unexpectedly improves the catalyst activity, even in polymerizations conducted with very large hydrogen quantities, in the production of polyethylenes with a high melt flow index. 55 The organometallic aluminium compound forming the cocatalyst (A) is conveniently chosen from trialkylaluminiums, alkylaluminium hydrides and alkylaluminium halides (especially chlorides) containing from 1 to 5 carbon atoms in the alkyl portion. Trialkylaluminiums with from 2 to 4 carbon atoms in the alkyl portion are preferred, such as triethylaluminium, tributylaluminium and triisobutylaluminium. EP 0 446 989 A2 The support for the solid catalyst component (B) is chosen from granular, preferably spherical, porous solids with a mean particle size of the order of microns and a narrow particle size distribution. The supports can be organic, such as olefinic or styrene polymers, or inorganic such as silica or aluminium. Microspheroidal silica (size 20-100 p.) is preferred with a BET surface area of between 150 and 400 5 m2/g, a total porosity > 80% and a mean pore radius of between 50 and 200 A. Such a silica can be either used as such or be previously activated. The activation can be effected by heating the silica in an inert atmosphere to a temperature of between about 100°C and about 650 °C for a time of between 1 and 20 hours, or by bringing the silica into contact with an organometallic compound such as an alkylmagnesium or an alkylaluminium, such as butylmagnesium, butyl octylmagnesium or triethylaluminium, operating at w ambient or higher than ambient temperature, for example 60° C. According to a preferred embodiment the silica is activated by treatment with butyl octylmagnesium in a quantity of the order of 10-20% of the silica by weight. According to the present invention such a support is impregnated [stage (i)] with a solution of titanium tetraalcoholate Ti(OR)4. and magnesium chloride dissolved in a liquid aliphatic hydrocarbon solvent. 75 Preferred examples of of titanium tetraalcoholates Ti(OR)4 are tetra n-propoxytitanium, tetra n-butox- ytitanium, tetra i-propoxytitanium and tetra i-butoxytitanium. The magnesium chloride used for the purpose is an anhydrous or substantially anhydrous magnesium chloride (water content less than 1% by weight). Solvents suitable for the purpose are aliphatic hydrocarbons liquid under normal temperature conditions, such as pentane, hexane, heptane, octane, nonane and decane. The lower-boiling solvents such as pentane, 20 hexane and heptane are preferred, as they can be removed by evaporation at relatively low temperature.
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