MXPA97001073A - Supported catalytic for olefi polymerization - Google Patents

Abstract

The present invention relates to a supported catalyst component comprising (A) a solid particulate support having (i) a specific surface area from 100 to 1000 m2 / g, (ii) a surface hydroxyl content of not more than 5. moles of hydroxyl groups per gram of solid support, (iii) a pore volume from 0.3 to 3.0 cc / g, (iv) an average particle size of 1 to 200æm and (v) a majority of solid particulate support particles in the form of an agglomerate of subparticles, and (B) a magnesium halide, obtained by the method consisting essentially of impregnating the solid particulate support (A) with a solution of a magnesium compound (B ') which can to be transformed into magnesium halide (B) by halogenation, followed by halogenation of the magnesium compound (B ') to magnesium halide (B) with a halogenating agent (C) selected from the group consisting of hydrogen halides, and optionally recover the com Catalyst speaker supports

Description

SUPPORTED CATALYTIC FOR POLYMERIZATION OF OR EFINES This invention relates to a supported catalyst component, to a process for preparing said supported catalyst component, to a supported catalyst composition for polymerization of olefins, to an olefin polymerization process using said supported catalyst. The so-called Ziegler or Ziegler-Natta type supported catalysts can be used in the polymerization of olefins in processes of high pressure, solution, gas phase and slurry suspension. In normal grout and gas phase processes, the polymer products are obtained as solid particles. In such processes, small particles or a large particle size distribution should be avoided, since the accumulation of small particles can cause drag problems in the reactor, valves or transfer lines. In addition, the low volume densities of the polymers cause difficulties in operations where gravity feed is required, such as transfer to extruders, and increases the volume required for storage of powder or shipping containers. The Patent of E.U.A. No. 4,526,943, discloses an olefin polymerization catalyst prepared by the reaction of a soluble organomagnesium hydrocarbon compound, with a trialkylaluminum and an aliphatic alcohol to generate a precursor of soluble magnesium alkoxide to which a transition metal compound is added, usually a titanium compound. A supported catalyst is then prepared by precipitation of magnesium halide using a reducing metal halide, such as ethylaluminum dichloride. These supported catalysts can achieve high efficiencies in a transition metal base and polymer powder produced at the desired particle size and bulk density, even the high levels of alkylaluminum halide required to precipitate the catalyst, result in relatively high levels of aluminum and chloride in the final polymer. In addition, f-alcohol is generated as a byproduct of normal procedures of deactivation of catalysts, whose alcohol is difficult to remove from solvent recycling streams and requires expensive separation and purification procedures. Other efforts to control catalyst efficiencies and polymer morphology for Ziegler type catalysts focused on supporting normal Ziegler catalysts containing a transition metal compound and a magnesium halide on metal oxides such as silica and alumina supports or polymers. The Patent of E.U.A. 4,639,430 describes a support of Catalyst consisting essentially of a mixture of silica and magnesium chloride, said support having a porous texture and containing less than 100 micromoles of hydroxyl groups per gram of support, as well as olefin polymerization catalysts consisting essentially of said supports and at least one The active component of a halide of group IV, V, or Vi.

The Patent of E.U.A. 4,405,495, describes the pretreatment of a particulate silica support having a particle size distribution of 2 to 80 microns and an average particle size of 20 to 50 microns with a precursor compound containing magnesium, titanium, halo, electron donor and optionally a hydrocarbyloxy or carboxylate group. The support can be pretreated with an aluminum alkyl. The precursor dissolves the electron donor and is impregnated in the silica support. The Patent of E.U.A. 4,301,029 describes the preparation of a catalyst component by reacting a solid inorganic support with a magnesium hydrocarbyl compound, a halogenation agent, a Lewis base compound and titanium tetrachloride. Preferably after each step, the product is washed and separated. The Patent of E.U.A. 4No. 324,691 describes the preparation of a catalyst component by reacting a particulate support material, preferably first with an aluminum compound, then with an organomagnesium compound, a transition metal compound, and a pacifying agent such as hydrogen chloride. , and optionally an organometallic compound, a halogenation agent or a Lewis base. The Patent of E.U.A. 4,481,301, describes the preparation of a supported catalyst for polymerization of olefin by treating a solid porous carrier in a liquid medium with an organomagnesium compound to react it with the OH groups on the carrier, evaporating said liquid medium to precipitate the magnesium on the carrier and recovering a magnesium composition supported in the form of a free flowing powder. The powder is reacted with a tetravalent titanium compound in a liquid medium. The Patent of E.U.A. No. 3,787,384, describes the preparation of supported catalyst components by impregnating metal oxide such as silica or alumina, with an organometallic magnesium compound, selected in particular from magnesium alkyl and Grignard compounds and reacting the obtained product with a titanium halyard compound. . The Patent of E.U.A. No. 4,263,168, describes catalyst components for the polymerization of propylene and other alpha-olefins, obtained by reacting a metal oxide, such as silica or alumina, containing hydroxyls on the surface, with an organometallic magnesium compound of the formula MgR2, xX "(wherein R is a hydrocarbon radical; X is halogen, x is a number of 0.5 to 1.5), and the subsequent reaction with an electron donor compound and titanium tetrachloride. As a variant, the metal oxide either before or after the reaction with the organometallic magnesium compound can be reacted with a halogenating agent which will supply at least one halogen per hydroxy group.

The Patent of E.U.A. No. 5,139,985, discloses catalyst components obtained by the support of a magnesium dihalide or a magnesium compound which can then be converted to dihalide on a porous polymer support, and reacting this solid with a titanium halide or titanium halogenary ahoxide, optionally in the presence of an electron donor compound. The Patent of E.U.A. No. 5,064,799, discloses catalyst components obtained from the reaction of a tetravalent titanium halide and an electron donor compound with a solid obtained by reacting a metal oxide containing surface hydroxyl groups (such as silica or alumina) with a magnesium oganometallic compound of the formula MgR2 xX) < , where R is a hydrocarbon radical, X is a halogen or an OR or COX 'radical (where X' is halogen) and x is uji number from 0.5 to 1.5, used in amounts such that it does not cause titanium reduction during the subsequent reaction of the solid with the titanium halide. The Patent of E.U.A. 5,227,439, describes a solid catalyst component obtained by preparing a solution of magnesium chloride in ethanol, impregnated activated particles of silica, with this solution, adding to this suspension a compound of titanium and silica halide, eliminating ethanol to recover a solid, making reacting the solid with aluminum alkyl chloride, and recovering the solid catalyst component.

The Patent of E.U.A. No. 5,244,854, describes a catalyst component for the polymerization of olefins obtained by reacting a tetravalent titanium halide or titanium halogen alcoholate and an electron donor compound with a solid comprising a porous metal oxide containing surface hydroxyl groups, on which it supports a magnesium dihalide or a magnesium compound that can be converted to a magnesium dihaloide. The Patent of E.U.A. 5,278,117, discloses a supported Ziegler-Natta catalyst, consisting of a cocatalyst and a solid catalyst component obtained by impregnating a granular porous solid support with a solution of magnesium chloride and a titanium tetra-alcoholate in a liquid aliphatic hydrocarbon, evaporating the solvent , impregnation with a solution of magnesium chloride in an aliphatic ester, evaporation of the solvent and activation with an aluminum alkyl chloride. It is desired to provide a supported catalyst component and a supported catalyst that can be used in olefin polymerization processes, in particular in slurry or gas phase processes, to give olefin polymers with desired morphology and bulk density at high effluent efficiencies. catalysts. In addition, it may be convenient to provide a supported catalyst component that is storage stable. SUMMARY OF THE INVENTION The present invention is based on the discernment that certain physical characteristics of the solid support, especially an agglomerated structure of the solid support particles, allows the preparation of solid polymer particles having the desired morphology and volume density. Accordingly, the present invention provides a supported catalyst component comprising (A) a solid particulate support having (i) a specific surface area of 100 to 1000 m / g as determined by nitrogen absorption using the BET technique, ( ii) a surface hydroxyl content of not more than 5 mmoles of hydroxyl groups per g of solid support as determined by adding an excess of diacylmagnesium to a slurry of the solid support and determining the amount of dialkylmagnesium remaining in solution, (iii) a pore volume of 0.3 to 3.0 cc / g as determined by nitrogen adsorption; (iv) an average particle size of 1 to 200 μm as determined via a Coulter particle size counter; and ( v) a majority of solid particulate support particles in the form of an agglomerate of subparticles containing void fractions of 5 to 30 percent as observed in micrographs electronic, and (B) a magnesium halide. According to a further aspect, the present invention provides a process for preparing a supported catalyst component comprising the steps of: impregnating a solid particulate support (A) having (i) a specific surface area of 100 to 1000 m2 / g as determined by nitrogen absorption using the BET technique, (ii) a surface hydroxyl content not greater than 5 mmoles of hydroxyl groups per g of solid support as determined by adding an excess of dialkylmagnesium remaining in solution, (iii) a pore volume of 0.3 to 3.0 cc / g as determined by nitrogen adsorption, (iv) an average particle size of 1 to 200 μ as determined via a Coulter particle size analyzer, and (v) a most particles of the solid particulate support in the form of an agglomerate of subparticles containing void fractions of 5 to 30 percent as observed in the electron micrographs, c on a solution of magnesium halide (B) or with a solution of a magnesium compound (B ') which can be converted into magnesium halide (B) by halogenation; when a magnesium compound (B) is used, the halogenation of the magnesium compound (B ') to magnesium halide with a halogenation agent (C); and optionally, recovering the supported catalyst component. In another aspect, the present invention provides a supported catalyst composition for oiefin polymerization comprising a supported catalyst component comprising (A) a solid particulate support that has (i) a specific surface area of 100 to 1000 m2 / g as determined by nitrogen uptake using the BET technique, (ii) a surface hydroxyl content of not more than 5 mmoles of hydroxyl groups per g of solid support as determined by adding an excess of dialkylmagnesium to a support slurry solid and determining the amount of dialkyl magnesium remaining in solution, (iii) a pore volume of 0.3 to 3.0 cc / g as determined by nitrogen adsorption, (iv) an average particle size of 1 to 200 μm as was determined via a Coulter particle size counter analyzer, and (v) a majority of solid particulate support particles in the form of subparticles containing fractions of vac Ios of 5 to 30 percent as observed in electron micrographs, (B) a magnesium halide, (D) a transition metal compound of Group 4 or 5, (E) an organometallic compound of Group 2 or 13, and, optionally, an electron donor (F), and a cocatalyst selected from the group consisting of alumoxanes and compounds corresponding to the formula R "2GX" 3.Z, wherein G is aluminum or boron, R "independently each time which arises, is hydrocarbyl, X "independently whenever it occurs is halide or hydrocarbyl oxide, and z is a number from 1 to 3. According to a further aspect, the present invention provides an olefin polymerization process comprising contacting one or more olefins under olefin polymerization conditions with the supported catalyst composition for olefin polymerization according to the present invention. The extraction shows electron micrographs of cross sections of two agglomerated particle carriers used in the present invention, one of average particle size of 45 μm (designated as solid support 45A) at a magnification of 100 times (Figure 1) and one of average particle size of 70 μm (designated as solid support 70A) at a 500-fold increase (Figure 2). and- These micrographs show that the solid support particles consist of subparticles that generally empty into the support particles. Detailed description of the invention. All references in the present to elements or metals that belong to a certain Group refer to the Periodic Table of the elements published and pertaining to CRC Press, Inc., 1989. Also any reference to the Group or Groups, will be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system to number groups. The term "hydrocarbyl" as used herein, means any The aliphatic, cycloaliphatic, aromatic group or any combination thereof. The term "hydrocarbyloxy" means a hydrocarbon group having an oxygen linkage between it and the element to which it is attached. Surprisingly, it has been found that the use of support in The solid particles having the characteristics (A) (i) - (v) as mentioned above, provide a supported catalyst composition which has excellent properties both in catalytic efficiency and to provide polymers of the desired morphology and volume density. As will be shown in the comparative examples, a solid support having the characteristics (A) (i) - (iv), but lacking the characteristic (A) (v) does not give a supported catalyst having the desired properties. As used in the present invention, the term "subparticle agglomerate" with reference to the texture of a support particle means that said support particle is composed of more than one subpart. This phenomenon of agglomerated particles can be observed from electron micrographs of the support particles. The normal sizes of the subparticles are less than 1 μm to about 10 μm. Alternatively, an agglomerate of subparticles can be characterized by its content of voids that exist between the subparticles. The fraction of voids as used in the present invention is determined in electron micrographs of cross sections of support particles according to the following procedure. All electron micrographs were generated in a JSM-6400 scanning electron microscope (JEOL USA, Inc.). The images used to determine the void fraction were acquired using backscattered electrons. A primary beam energy of 20 keV was used for larger support particles, however, at higher magnifications used to imagine the smaller supports, the 20ekV electron resolution was not enough. Therefore, a primary beam energy of 10 keV was used for the supports of 6 micras. The image analysis was performed on a 570 quantimeter (Leica, Inc.). The electron micrographs were imported into the image analyzer by a video camera. The particles were detected by entering the gray level to produce binary images. The operator corrected some errors of. omission of inclusion caused by the entry process. The gap percentage analysis was determined, determining the area of the images occupied by solid support and the area occupied by solid support plus voids in cross sections through support particles. The area occupied by solid support plus vacuum in cross sections through support particles. The area occupied by solid support plus vacuum, was determined from the The same binaries used to measure the area occupied by silica after these binaries were subjected to closing operations (J. Serra, Image Analysis and Mathematical Morphology, vol.1, p.50, Academic Press (1982)) suffices to cover all the internal gaps. The vacuum percentage was then determined using the following equation: vacuum fraction = 100 * (1-solid support area / closed area) To make cross sections, the support particles were vacuum-embedded in Epo-Thin (Buehler) and allowed to cure overnight at room temperature. The cross sections were created by grinding and polishing with sand silicon carbide of 120 and sand of 600, 6 μm of diamonds, and 0.3 μ of alumina. This mount was coated (approximately 4 nm) with gold alloy: palladium by electronic deposition. The normal fraction fractions of agglomerated subparticles determined according to this method vary from 5 to 30 percent, preferably from 10 to 25 percent. The agglomerates of subparticles, or in other words, the support particles, have a configuration that is substantially more spherical than the so-called granular support particles. As used in the present invention: the specific surface area means the specific surface area determined by nitrogen adsorption using the technique B.E.T. as described by S. Brunauer, P. Emmett, and E. Teller in Journal of the American Chemmical Society, 60., p. 209-319 (1939); the mean particle size and particle size distribution were determined with a Coulter particle size counter as described in Particle Characterization in Technology vol. 1, Applications and Microanalysys, pgs. 183-186, de. J.K. Beddow, CRC Press, Boca Naton, Florida, 1984; the hydroxyl content means the hydroxyl content as determined by adding an excess of dialkylmagnesium to a slurry of the solid support and determining the amount of diachiii-magnesium remaining in solution via known techniques. This method is based on the reaction of S-OH + MgR2 - > S-OMgR + RH, where S is the solid support. These hydroxyl groups (OH), wherein the support is silica, are derived from silanol groups on the silica surface; and the pore volume means the pore volume as determined by nitrogen adsorption. Preferably, in the solid particulate support (A) (v) at least 70 percent by weight, more preferably at least 90 percent of the solid particulate support is in the form of a subparticle agglomerate. The solid particulate support (hereinafter also referred to as a solid support) generally has (i) a specific surface area of 100 to 1000 m / g, (ii) a surface hydroxyl content not greater than 5 mmoles of hydroxyl groups per g of solid support, (iii) a pore volume of 0.3 to 3.0 cc / g, and (iv) an average particle size of 1 to 200 μm. When the specific surface area and pore volume are very low, this will lead to low catalyst efficiency. In addition, the amount of magnesium halide that can be supported on the support depends on the specific surface area of the support, the lower the specific surface area, the lower magnesium halide can be supported, resulting in lower catalyst efficiency. . The hydroxyl content should be as low as possible. The very high hydroxyl content decreases the catalyst efficiency. Particle size also refers to catalyst efficiency: the smaller the particle size, the greater the efficiency. The optimum particle sizes depend on the final use of the catalyst component, as discussed below. Preferably, the solid support has (i) a specific surface area of 200 to 600 m2 / g, (ii) a surface hydroxyl content of 0 to not more than 3 mmoles of hydroxyl groups per g of solid support, (iii) a pore volume from 0.5 to 2.5 cc / g, (iv) average particle size from 3 to 150 μm. Examples of suitable support materials include solid inorganic oxides, such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, and mixed oxides of silica and one or more oxides of Group 2 or 13 metals, such as oxides mixed silica-magnesia, silica-alumina. Silica, alumina and mixed oxides of silica and one or more oxides of Group 2 or 13 metals are the preferred support materials. Preferred examples of said mixed oxides are the preferred support materials. Preferred examples of said mixed oxides are silica-aluminas containing a high amount of silica, such as zeolites and zeolites subjected to a dealumination treatment to increase the silica ratio /alumina. The most preferred is silica. The solid support may contain minor amounts, up to about 5000 parts per million on a weight basis, of additional elements without detrimentally affecting the catalytic activity of the supported catalyst, usually in the oxide form. The amount of the hydroxyl groups in the support, if it exceeds the desired amount, can be reduced or eliminated by treating the support material 5 either thermally or chemically. A heat treatment involves heating the support material at temperatures from about 250 ° C to about 870 ° C., more preferably from about 600 ° C to 800 ° C for about 1 to about 24, preferably about 0 about 2 to about 20, more preferably about 3 to about 12 hours. The hydroxyl groups can also be removed chemically by treating the support material with conventional dehydroxylating agents, such as for example SiCl 4, chlorosilanes, silamines, aluminum alkyls and the like at a temperature of about -20 ° C to about 120 ° C, more preferably from about 0 ° C to 40 ° C for usually less than about 30 minutes. Any amount of water adsorbed on the solid support, or should be removed substantially, that is to say, at a level less than 0.05 g of water per g of support. This can be done by heating the support at temperatures of 150 to 250 ° C for a sufficient amount of time. The agglomerated solid silica supports, preferred for use in the present invention, are available from G RAC E Davison, a division of W.R. GRACE & CO-CONN., Baltimore, under the designations Sylopol ™ 948, Sylopol 956, Sylopol 2104, and Sylopoi 2212, Sylopol is a registered trademark of GRACE Davison. The solid support for use in the present invention is can be prepared by any methods involving an agglomeration step to produce an agglomerated support. Specific examples of an agglomeration process for preparing solid particulate supports useful in the present invention are ? ~ * described in the U.S. Patent. 2,457,970 and U.S. Patent. 10 3,607,777. The Patent of E.U.A. 2,457,970, describes a process by which a silicic acid solution is sprayed to form the silica. The Patent of E.U.A. US 2,607,777 discloses a process for forming microspherical silica gel, by spray drying a vigorously stirred slurry of a mild silica gel. 15 The supported catalyst component of the present The invention further comprises a magnesium halide (B), preferably magnesium bromide or chloride, more preferably magnesium chloride.The ratio of magnesium halide (B) to solid particulate support (A) is generally 0.5. at 5.0 mmole of (B) per gram of (A), preferably from 1.5 to 4.0 mmoles of (B) per gram of (A). Suitable magnesium halides (B) are dibromide or magnesium dichloride, more preferably magnesium dichloride.

The magnesium halide is used as a solution in a polar solvent such as, for example, water alcohols, ethers, esters, aldehydes or ketones. Preferred solvents are water, alcohols such as ethanol, and ethers such as tetrahydrofuran. Normally, the solid support is suspended in the magnesium halide solution and stirred for a sufficient time, generally 2 to 12 hours. When using a polar solvent, care must be taken to remove the polar solvent substantially before adding components (D) or (E). Preferably, the supported catalyst component is obtained by impregnating the solid support with a hydrocarbon-soluble magnesium compound (B ') of the formula R2.nMgXp.xMR'y wherein R, independently whenever it occurs, is halo or hydrocarbyloxy with 1 to 20 carbon atoms in the hydrocarbyl part of same, n is 0 to 2 with the proviso that if X is halo n is almost always 1, M is aluminum, zinc or boron, R 'independently each Once it is hydrogen, hydrocarbyl or hydrocarbyloxy having 1 to 20 carbon atoms in the hydrocarbyl part of it, and has a value equal to the valence of M, and x has a value of 0 to 10, and halogenating the compound of magnesium (B ') to magnesium halide (B) with a halogenation agent (C). The use of a hydrocarbon-soluble magnesium compound allows impregnation to occur in the same hydrocarbon solvent as can be used in the subsequent steps to prepare a catalyst and catalyst component. The hydrocarbon solvents can also be easily removed from the supported catalyst component and do not leave harmful residues with the isolation of the catalyst component being convenient. Impregnation with a magnesium halide requires the use of polar solvents such as water or tetrahydrofuran which require more stringent procedures for removal before adding additional catalyst components. Also solvents such as tetrahydrofuran, form a solvate with magnesium halide that can not be easily removed by normal drying procedures and require the addition of additional amounts of a Group 13 hydrocarbyl compound to maintain high catalyst efficiency. The insoluble hydrocarbon magnesium compounds can be rendered soluble to the hydrocarbon by combining the magnesium compound with a compound MR'y in an amount sufficient to render the resulting complex hydrocarbon soluble, which usually requires no more than about 10, preferably no more of about 6, more preferably, no greater than about 3 moles of MR'y per mole of magnesium compound. More preferably, the compound (B ') is of the formula R2. nMgXn.xMR'y wherein R, independently whenever it occurs, is a hydrocarbyl group having 1 to 10 carbon atoms, X independently each time it occurs, is hydrocarbyloxy with 1 to 10 carbon atoms in ia part of hydrocarbyl thereof, n is from 0 to 2, M is aluminum or boron, R 'independently each time it occurs is hydrocarbyl with from 1 to 10 carbon atoms in the hydrocarbyl part thereof, and is 3, and x has a value from 0 to 6. The most preferred compounds MR'y are the trialkylaluminum compounds. Examples of specific magnesium compounds (B ') are -diethylmagnesium, di-n-butylmagnesium, n-butyl-s-butylmagnesium, n-butylethylmagnesium, n-butyloctylmagnesium, n-butylmagnesium butoxide, ethylmagnesium butoxide, butyl magnesium ethoxide, octylmagnesium ethoxide, butylmagnesium i-propoxide, -propoxide '* - ethylmagnesium, butylmagnesium n-propoxide, n-propoxide ethylmagnesium, s-butylmagnesium butoxide, 2,4-dimethyl-pent-3-butylmagnesium oxide, n-butylmagnesium ethoxide, s-butylmagnesium chloride, n-butylmagnesium chloride, ethylmagnesium chloride, butylmagnesium bromide, chloride of octylmagnesium, ethylmagnesium bromide, s-butylmagnesium bromide. Not all compounds Alkylmagnesium halide solvents are soluble and it may therefore be necessary to em a polar solvent, as described in connection with the above magnesium halide solvents, in order to dissolve them. However, it is not a preferred embodiment of the present invention. Even more preferably, the magnesium compound (B ') is of the formula R2Mg.xMR'y, and R independently each time it occurs is an alkyl group having from 2 to 8 carbon atoms, and M, R \ x, ey are as previously defined. The highly preferred compounds (B ') are selected from the group consisting of < < "• diethylmagnesium, n-butyl-s-butylmagnesium, n-butylethylmagnesium, and n-butyloctyl-magnesium When the solid support is impregnated with a solution of a magnesium compound (B '), which can be converted into a halide of magnesium by halogenation, should follow a halogenation step.Hiogenating agents (C) capable of halogenating magnesium compounds (B '), include hydrogen halides, silicon halides of the formula R "' bSiX'4-b wherein R '"is hydrogen or hydrocarbyl, X' is halogen and b is 0, 1, 2 or 3, carboxylic acid halides, halides of Hydrocarbyl, boron halides, phosphorus pentachloride, thionyl chloride, sulfuryl chloride, phosgene, nitrosyl chloride, a halide of a mineral acid, chlorine, bromine, a chlorinated polysiloxane, a hydrocarbyl aluminum halide, aluminum trichloride and ammonium hexafiuorosilicate. Preferably, the halogenating agent (C) is selected from the group consisting of aluminum alkyl halides, advantageously sesqui- or alkyl aluminum dihalides, hydrogen halides, silicon halides, and boron halides. Preferably the halogenating agent is a chlorinating agent. More preferably (C) is hydrogen chloride. Highly anhydrous hydrogen chloride of high purity is preferred, which contains less than 10 parts per million oxygen and less than 5 parts per million water. In the practice of the present invention, the use of a dialkylmagnesium compound (B ') in combination with a hydrogen halide is highly preferred, Especially hydrogen chloride, halogenating agent (C). This and could produce the desired form of magnesium halide, especially magnesium dichloride, on the silica surface while regenerating the solid support, especially silica, in its original form. It is thought that upon impregnating the solid support, preferably silica, the dialkylmagnesium reacts with OH groups on the support surface. It is thought that the use of hydrogen halides as the halogenating agent regenerates the OH groups on the surface of the solid support while at the same time it forms magnesium halide. The by-product of the halogenation step, When using a hydrogen halide, it is an alkane or two alkanes which can be easily separated from the supported catalyst component since they are usually gases. When magnesium compounds containing hydrocarbyloxy groups are used, alcohols are obtained as a byproduct which requires a step separate removal. Other haiogenation agents such as aluminum halides, boron or silicon, leave residues of aluminum, boron or silicon in the product. In addition, aluminum alkyl halides are strong reductive agents and their presence during the addition of component (D), as will be discussed below, can lead to the reduction of the component (D) in solution and not on the support. The reduction of the component (D) in the solution is not convenient since it can provide less desirable volume density and particle size properties to the polymer produced with said catalyst. The use of hydrogen halide reduces these and problems and does not increase the metal content of the eventual catalyst and therefore the polymer. Although lower amounts of (C) can be obtained with respect to lower chloride residues in the catalyst and therefore both possible polymer, preferably the amount of (C) is sufficient to convert substantially all (B ') to magnesium dihalide. . With substantially all of (B '), it means at least 75 mole percent of (B'), usually at least 90 mole percent of (B '), preferably by at least 95 mole percent of (B ') and more preferably at least 99 mole percent of (B'). If too much alkyl magnesium is left when the component (D) is added, it can lead to over-reduction of the components (D). The supported catalyst component described above is can be separated from the solvent or diluent and dried and stored for extended periods. At a desired time, this supported catalyst component can be combined with additional catalyst components, as described below. In accordance with a further aspect of the present invention, the supported catalyst component described above also comprises a transition metal compound of Group 4 or 5 (D), preferably of titanium, zirconium, hafnium, or vanadium. The transition metal compound of Group 4 or 5 (D), used herein The invention is preferably a halide, hydrocarbon oxide or halide / hydrocarbyl oxide mixed with titanium, zirconium, hafnium, or vanadium. Suitable Group 4 transition metal compounds are represented by the formula MX4-a (OR) a, wherein M is titanium, zirconium or hafnium, each R independently is an alkyl group having from 1 to about 20, preferably from about 1 to about 10, more preferably from 2 to about 8 carbon atoms; X is a halogen atom, preferably chlorine; and has a value of from 0 to 4. Particularly suitable titanium compounds include, for example, titanium tetrachloride, titanium tetraisopropoxide, titanium tetraethoxide, titanium tetrabutoxide, titanium tri-isopropoxide chloride, and combinations thereof. Analogs of zirconium and hafnium compounds are also suitable. Suitable Group 5 transition metal compounds are preferably vanadium compounds such as those represented by the formulas VX and V (O) X3, wherein each X is independently OR or a halide atom, preferably chloride, and each R independently it is an alkyl group having from 1 to about 20, preferably from about 2 to about 8, more preferably from about 2 to about 4, carbon atoms. Particularly suitable vanadium compounds include vanadium tetrachloride, vanadium trichloride oxide, vanadium triethoxide oxide, and combinations thereof.

Mixtures of the transition metal compounds of the Group 4 and 5, preferably titanium and vanadium, can be used to control the molecular weight and molecular weight distribution of the polymers produced. More preferably (D) is titanium tetrachloride or zirconium tetrachloride. The molar ratio of (B) to (D) in the supported catalyst component is generally from about 1: 1 to about 40: 1 and preferably from 3: 1 to 20: 1. According to the present invention, the supported catalyst component described above, may further comprise (E) an organometallic compound of Group 2 or 13, preferably aluminum or boron, each R is independently an alkyl group having from 1 to about 20., preferably from about 1 to about 10, more preferably from about 2 to about 8 carbon atoms, X is a halogen atom, preferably chlorine, and z can independently each have a value of 1 to a value equal to valence of M and the sum of yez is equal to the valence of M. More preferably, (E) is an alkyl aluminum halide. Particularly suitable components (E) include ethyl aluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, isobutylaluminum dichloride, diisobutylaluminum chloride, octyiaiuminium dichloride, and combinations thereof.

The molar ratio of (E) to (D) is preferably from 0.1: 1 to 100: 1, more preferably from 0.5: to 20: 1, more preferably from 1: 1 to 10: 1. Preferably, the supported catalyst component of the present invention is obtained by impregnating the particulate support (A), solid, with a solution of the magnesium halide (B) or with a solution of a magnesium compound (B '), which can be converted to magnesium halide (B) by halogenation; halogenated, When a magnesium compound (B ') is used, the compound of magnesium (B ') to magnesium halide (B) with a halogenating agent (C); optionally recovering the supported catalyst component; by combining the transition metal compound (D) of Group 4 or 5, with the supported catalyst component; combining the product thus obtained with the compound (E) of organometal of Group 2 or 13; and, optionally, recovering the supported catalyst component. In a highly preferred supported catalyst component, (A) is a solid silica support, (B) is magnesium dichloride, (D) is a halide, hydrocarbyl oxide or halide mixed / hydrocarbon oxide of titanium, zirconium, hafnium or vanadium, and (E) is an alkylaluminum haiuro. Even more preferably in said component, there are 0.5 to 5.0 mmoles of (B) per gram of solid particulate support (A), (D) is titanium tetrachloride or zirconium tetrachloride or a mixture thereof, the ratio from (B) to (D) is from 1: 1 to 40: 1, (E) is an alkylaluminium haiuro, and the molar ratio of (E) to (D) is from 0.1: 1 to 100: 1 moles of (E) per mole of (D). When it is desired to use the supported catalyst component in the preparation of olefin polymers having a high degree of stereospecificity, the electron donor component can be used as the additional component (F). The electron donor can be any organic electron donor that has been proposed to be used in a Ziegler polymerization catalyst to modify either the activity or the stereospecificity of the olefin polymerization product. Any electron-donor compound capable of complexing with magnesium halides or transition metal compounds of Group 4 or 5 can be used for the preparation of the catalyst component of the present invention. Examples of such compounds include ethers, esters, ketones, alcohols, thioethers, thioesters, thioketones, thiols, sulfones, sulfonamides, lactones, amides, amides and mixtures thereof, and other compounds containing N, P and / or N atoms. S. Particularly preferred esters are aromatic carboxylic acids, such as phthalic acid, and acid esters such as ethyl benzoate. According to a further aspect, the present invention provides a process for preparing supported catalyst components described above.

Preferred embodiments for components (A), (B), (B '), (C), (E) and (F) used in the present process and their relative relationships, have been previously described herein. Although the solid component (A) can be added to the other components in an appropriate medium, it is preferred to first quench the solid support (A) in a hydrocarbon diluent. Suitable concentrations of solid support in the hydrocarbon medium vary from about 0.1 to about 15, preferably from about 0.5 to about 10, more preferably from about 1 to about 7 weight percent. The order of addition of the other components (B), (B '), (C), (D), (E), and optionally (F) in appropriate liquid medium, if desired, to the slurry of (A) ), or the slurry from (A) to the other components, is not critical, as long as a dihydrocarbyl-magnesium compound (B ') is used, the halogenating agent (C) is added to (B') before of adding the transition metal compound (D). Adding (D) to a dihydrocarbyl-magnesium compound (B) could result in the premature reduction of the component (D) which is preferably avoided. Although the slurry from (A) can be combined with a magnesium halide (B) dissolved in a polar solvent, it is preferred to combine the slurry of (A) with the hydrocarbon-soluble magnesium compound (B '), preferably dissolved in a hydrocarbon which may be the same or different from the hydrocarbon in which it is slurried (A). A contact time of usually from about 0.1 to about 10, preferably from about 0.2 to about 8, and more preferably from about 0.5 to about 4 hours, is sufficient for the purposes of the invention. In general, from 0.5 to 5.0 mmoles of (B) are employed per gram of (A), and preferably from 1.5 to 4.0 mmoles of (B) per gram of (A). The concentration of (B ') in the hydrocarbon is advantageously 0.05 to 0.30 M. In case a polar solvent is used, it is preferably removed before adding the other components. Normally, this can be done by evaporation or distillation. Preferably component (C) is added to the mixture of (A) and (B '), advantageously in a hydrocarbon medium. If the component (C) under the reaction conditions is a gas or liquid, no diluent or additional solvent is required. In case (C) is solid, it is preferably incorporated in a diluent or solvent. If (C) is gas, it is preferably bubbled through the stirred mixture of (A) and (B '). Preferably, the amount of (C) added, is sufficient to convert substantially all of (B ') to magnesium halux (B). The contact time should be sufficient to halogenate (B ') to the desired degree. Usually, the contact time is from about 0.1 to about 100, preferably from about 0.2 to about 20, more preferably from about 0.5 to about 10 hours. At this point in the process, the solvent or diluent can be removed by evaporation, filtration or decantation, and the resulting supported catalyst component consisting of solid particulate support (A) with a magnesium halide (B) deposited thereon. (also referred to as a precursor composition) can be dried and stored prior to the addition of additional optional components (D), (E), and (F). Alternatively, additional components can be added without this isolation step. The composition of the precursor is unstable in an atmosphere that contains oxygen and moisture, and before adding any additional component, oxygen and moisture should be carefully removed. Therefore, preferably the storage is under an indoor atmosphere, for example nitrogen. The transition metal component (D), if it is solid, is then advantageously dissolved in a suitable hydrocarbon medium, preferably combined with the composition of the precursor in a suitable hydrocarbon medium. Preferred hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and mixtures thereof. The contact time is usually from 0.1 to 100, preferably from .5 to 20, and more preferably from 1 to 10 hours. Two or more different transition metal compounds can be mixed before their addition to the precursor composition. Component (D) is preferably added to give a molar ratio of (B) to (D) from 1: 1 to 40: 1, and more preferably from 3: 1 to 20: 1. The concentration of (D) in the hydrocarbon is advantageously from 0.005 to 0.03 M The component (E), preferably dissolved in a hydrocarbon medium, can be combined with the composition of the precursor, but is preferably added before or after the addition of the component (D). More preferably, (E) is added after (D). The contact time is usually from 1 to 100, preferably from 2 to 50, and more preferably from 5 to 20 hours. Component (E) is preferably added to give a molar ratio of (E) to (B) from 0.1: 1 to 100: 1, more preferably from 0.5: 1 to 20: 1, more preferably from 1: 1 to 10: 1 . The concentration of (E) in the hydrocarbon is advantageously 0.005 to 0.003 M. If desired, an electron donor component (F) can be added simultaneously with or after the addition or formation of the magnesium compound (B), the transition metal compound of Group 4 or 5 (D) or organometallic compound of Group 2 or 13 (E). The suitable hydrocarbon medium which can be used to wet the solid support (A) and which can serve as a diluent or solvent for any of the other components employed, in the present invention, include aliphatic hydrocarbons, aromatic hydrocarbons, naphthine hydrocarbons , and their combinations. Particularly suitable hydrocarbons include, for example, pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane, toluene, and combinations of two or more such diurents.

The temperature employed in any step of the present process is generally from 20 ° C to 120 ° C, preferably from 0 ° C to 100 ° C, and more preferably from 20 ° C to 70 ° C. The steps of the process described above should be carried out under an inert atmosphere to exclude air (oxygen) and moisture as much as possible. Suitable inert gases include nitrogen, argon, neon, methane and the like. The supported catalyst component thus prepared can be employed, without separation or purification, in the polymerization of olefins as described below. Alternatively, the catalyst component can be stored in the hydrocarbon medium, or isolated from the hydrocarbon medium and dried and stored under inert conditions for an extended period, for example, for one or several months. In accordance with a further aspect of the present invention, a supported catalyst composition for olefin polymerization comprising the catalyst component of the present invention containing the components is provided.

(A), (B), (D), (E) and, optionally (F), as described herein in combination with a cocatalyst. The catalyst components and compositions of the present invention can be used advantageously in high pressure, solution, slurry and gas phase polymerization processes.

Suitable cocatalysts include, for example, alumoxanes and compounds corresponding to the formula R "ZGX" 3.2, wherein G is aluminum or boron, R "independently each time it is hydrocarbyl, X" independently each time it is presented is halide or hydrocarbyl oxide, and z is a number from 1 to 3. Preferred compounds of this formula are those wherein z is 2 or 3, more preferably 3. Particularly suitable compounds include triethylaluminum, trimethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum , diethylaluminum chloride, diethylaluminum ethoxide, and combinations of two or more of said compounds. Suitable alumoxanes include those represented by the formula (-AI (E) -O-) x for cyclic alumoxanes and R (-AI (R) O-) xAIR2 for linear alumoxanes wherein R is an alkyl group having from 1 to about 8 carbon atoms and x has a value of 1 to 50, preferably greater than about 5. Alumoxanes are usually prepared by reacting water with a trialkylaluminum compound under conditions to control the highly exothermic reaction, such as in dilute concentrations or using water in solid form, for example as crystalline water of salts or as water absorbed from inorganic oxide compounds. Particularly suitable alumoxanes include, for example, methylaiumoxane, hexaisobutyltetraalumoxane, methylalumoxane wherein a number of methyl groups have been replaced by other alkyl groups such as isobutyl, and combinations thereof. Also, mixtures of alumoxanes with alkylaluminum compounds such as, for example, triethylaluminum or tributylaluminum can be employed. The cocatalyst can be used in a suspension or in a suspension polymerization process in amounts that provide a ratio of aluminum or boron atoms in the cocatalyst per transition metal atom (D) in the supported catalyst component of about 1. 1 to about 100: 1, preferably from about 5: 1 to about 500: 1, more preferably from about 5: 1 to about 200: 1. The cocatalyst can be used in a high polymerization solution or process pressure in amounts that provide a ratio of aluminum or boron atoms per transition metal atom of from about 0.1: 1 to about 50: 1, preferably from about 1: 1 to about 20: 1, more preferably about 2: 1 to around 15: 1. In a slurry olefin polymerization process, the solid support (A) generally has a mean particle diameter of about 1 μm to about 200 μm, more preferably from about 5 μm to about 100 μm, and more preferably from about 20 μm to about 80 μm. In a gaseous phase oieffine polymerization process, the solid support (A), preferably, has a mean particle diameter of about 20 μm to about 200 μm, more preferably about 30 μm to about 150 μm, and yet more preferably from about 50 μm to about 100 μm. In a high pressure olefin polymerization solution and process, the solid support (A) preferably has a mean particle diameter of from about μm to about 40 μm, more preferably from about 2 μm to about 30 μm, and further preferably from about 3 μm to about 20 μm. Suitable olefins that can be polymerized in contact with the catalyst composition present, include, for example, alpha olefins having from 2 to about 20, preferably from about 2 to about 12, more preferably from about 2 to about 8 carbon atoms. carbon and combinations of two more of said alpha-olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof. Preferably, the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-hexene, 1-octene, and combinations of ethylene and / or propene with one or more of said other alpha-olefins. A slurry process typically utilizes an inert hydrocarbon diluent and temperatures of about 0 ° C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. Preferred temperatures are from about 60 ° C to about 95 ° C. The pressures generally vary from 1 to 100 bar. The solution process is carried out at temperatures of the temperature at which the resulting polymer is soluble in an inert solvent or the particular monomer up to about 275 ° C, preferably at temperatures of about 130 ° C to about 260 ° C, more preferably from about 150 ° C to about 240 ° C. As inert solvents, hydrocarbons and preferably aliphatic hydrocarbons are normally used. In solution processes, the pressure is usually from 1 to 100 bar. Normal operating conditions for gas phase polymerizations are from 20 to 100 ° C, more preferably from 40 to 80 ° C. In gaseous phase processes, the pressure is normally subatmospheric at 100 bar. The high pressure processes are carried out at temperatures of approximately 100 to around 400 ° C and at pressures in the range of 500 to 3000 bar. Having described the invention, the following examples are provided as an additional illustration thereof, and should not be construed as limiting. Unless stated otherwise, all parts and percentages are expressed on a weight basis. Examples The solid supports (A) used in the following examples include a series of agglomerated silica gels available from Grace Davison under the trade name SYLOPOL with average particle sizes of 6, 12, 20, 45 and 70 μm as specified by the provider (given the nomenclature 6A, 12A, 20A, 45A, and 70A, respectively). In the Comparative Examples, a series of granulated silica gels available from Grace Davison, also under the trade name SYLOPOL of 13, 26, and 41 μm mean particle sizes, were used as well as two other granulated silicas Davison 952 and Davison Syloid 245 , having respective particle sizes of 6 and 90 μm. The granulated silicas were given the nomenclature 13G, 26G, 41G, 6G, and 90G, respectively. The properties of these solid supports are summarized in Table 1. Table 1 Size Area Content Volume of surface hydroxyl pore Particle texture (u) mmol / y m2 / q cc / q 6A 5.8 2.2 315 1.56 agglomerate 12A 13.2 2.1 268 1.67 agglomerated 20A 19.6 2.0 305 1.66 agglomerate A5A A5.0 2.0 255 1.50 chipboard 70A 70.0 2.0 259 1.50 agglomerated 6G 6.0 2.3 A00 1.50 granulate 13G 12.6 2.0 268 1.67 granulate 26G 26.0 2.0 271 1.70 granulate A1G A1.0 2.0 273 1.80 granulate 90G 90.0 1.1 350 1.50 granulate All the silicas used in the Examples and Comparative Examples present were dried at 750 ° C under nitrogen in a fluidized bed, to obtain the surface hydroxyl content as specified in Table 1. The butyl compound -ethyl-magnesium (B ") used was obtained from AKZO under the trade name Magala BEM, as a 15% by weight solution in heptane. In the following examples, the flow regime for the melt index value, 12, and for the value, 10, are determined by E and N conditions of ASTM D 1238, respectively. The melt flow ratio, MFR, ol? 0 / l2, is a number without dimension derived by dividing the flow regime to Condition N by the flow regime in Condition E and was discussed in section 7.3 of ASTM D 1238 The apparent bulk density was determined as a volume density not established according to the ASTM 1895 procedure using a paint volume meter from Sargent-Welch Scientific Company (Catalog No. S-64985) as the cylinder in place of one specified by the ASTM procedure. The polymer particle size was determined by sieving the powder through two groups of Normal Test Sieve of E.U.A. that meet the criteria of ASTME-11. To approximately 100 grams of polymer, 0.1 grams of finely divided carbon smoke was added and the mixture was then sieved through a number of 20, 30, 35, 40 and 60 sieves corresponding to openings of 850, 600, 500, 425, and 250 microns, respectively. The weight of the material remaining on the sieves, is then measured by difference and the material is then passed through the sieve number 60 is then sieved through sieves of the number 80, 100, 140, and 200, which corresponds to openings of 180, 150, 106 and 75 microns, respectively. The percentage of the material passing through each screen is calculated and then plotted on logarithmic probability paper with the sieve size on the Y axis. The average powder size as measured by weight is determined by the intersection of the best adjustment curve through the points with the 50% probability line. A normal reference for measuring particle size is Particle Size: Measurement, Interpretation and Application by Riyad R. Irani and Clayton F. Callis, John Wiley & Sons, I nc. , New York, 1963. In each of the following examples and comparative experiments, unless stated otherwise, the catalyst components are mixed at room temperature in a dry, oxygen-free atmosphere. In slurry polymerization experiments, unless otherwise stated, a stirred 5 I autoclave reactor is charged with approximately 1850 g of anhydrous hexane and the vapor space is swept with hydrogen before being heated to 85 ° C. Hydrogen is added to a pressure of 585 kPa followed by sufficient ethylene to carry a total pressure of 1205 kPa. The ethylene is continuously supplied to the reactor by a feed demand regulator. The required amount of supported catalyst component is premixed with cocatalyst to give the desired molar ratio of cocatalyst to supported catalyst component. The resulting catalyst mixture is added to the reactor to initiate the polymerization. After 45 minutes, the ethylene feed is stopped and the reactor is vented and cooled and the polymer is filtered and dried at 80 ° C overnight in a vacuum oven. After drying, the polymer is weighed to calculate the efficiency of the catalyst. The polymer samples are stabilized, and subsequently the melt flow is determined, the melt flow ratio, particle size and volume density were determined where applicable. Examples 1-4 15 g of solid support 12A are slurried in 250 ml of hexane. Butylethyl magnesium (BEM) (30 mmol) is added to the stirred suspension and the mixture is stirred for two hours. Anhydride HCl (60 mmol) is bubbled through the suspension for 15 minutes followed by nitrogen to remove any excess HCl. The suspension is slowly evaporated under vacuum at room temperature for twelve hours to leave a free dry flow powder. 1.31 g of this solid is resuspended under nitrogen in 74 ml of hexane to which 0.38 g of a 10% solution of titanium tetrachloride (TTC) in hexane is added. The slurry is stirred for twelve hours followed by the addition of 0.66 ml of 1.50 M diethylammonium chloride (DEAC) in heptane followed by further stirring for 24 hours. Before the polymerization, a hexane solution of triisobutylaluminum cocatalyst (TiBAl) (0.15 M in hexane) was added to give a molar ratio of TiBAI / Ti of 150: 1. In Example 2, Example 1 was repeated but now 1.33 ml of 1.50 M DEAC in heptane was added. In Example 3, Example 1 was repeated but now 2.00 ml of 1.50 M DEAC in heptane was added. In Example 4, Example 1 was repeated but now a drying step after the addition of HCl was not used, all reagents being added sequentially to the vessel. The results are given in Table 2. The symbols Etl, EAL, and Eci are the efficiencies of the catalyst expressed as polymer of 106g per g of Ti, Al, and Cl, respectively.

Table 2 Support BEM / HCUBE Mq / Ti DEAC / Ti n EAI J? Ci Relationship Dens. Size silica Mmol / moll marble / moll (g / 10m) I? O / b yoK. particle [mmol / qlmol / moll kg / m3 polymer Example 1 12A 2.0 2.7 10.0 5 1.27 0.014 0.048 1.21 9.63 22.0 (352) 159 Ex. 2 12A 2.0 2.7 10.0 10 0.93 0.010 0.031 1.66 9.42 21.0 (336) 172 Ex. 3 12A 2.0 2.7 10.0 15 1.06 0.011 0.033 1.51 9.53 22.0 (352) 175 Ex. 4 12A 2.0 2.7 10.0 5 1.12 0.012 0.042 1.47 8.86 18.3 (293) 173 6 Examples 5-9 Example 1 was repeated, using the TiBAI / titanium cocatalyst ratios specified in Table 3. The results are given in the same box. Table 3 Ej TiBal / Ti ETl EAI = ct k Relation Dens. Size fmol / moll (q / 10m) '1,002 vol. particle ib / foot * - polymer (ka / nr5) ÍUl 25 0.62 0.037 0.023 0.84 9.86 23.1 163 (370) 6 50 0.67 0.022 0.025 1.09 9.83 22.7 177 (363) 7 75 0.70 0.015 0.026 1.14 9.83 22.7 171 (363) 8 100 0.94 0.016 0.034 1.30 g.sg 22.4 174 (358) 9 150 0.89 0.010 0.033 1.66 9.38 21.3 179 (341) Examples 10-12 In Example 10, 18 g of the 6A solid support was lettered in 500 ml of Isopar ™ E (available from Exxon Chemical). BEM (36 mmol) was added to the stirred suspension and the reaction mixture was stirred for two hours. Then the anhydride HCl was bubbled through the suspension until an aliquot of the hydrolyzed slurry in water gave a neutral pH. The slurry was purged with nitrogen for 10 min to remove any excess HCi. To 178 ml of this solution, 2.30 g of a 10% by weight solution of titanium tetrachloride in Isopar E were added. The resulting mixture was stirred for twelve hours followed by the addition of 8 ml of a 1.50 M DEAC in heptane. . The additional agitation takes place for 24 hr. Before polymerization, cocatalyst of TiBAl (0.15 M in hexane) was added to give a molar ratio of TiBal / Ti of 100: 1 In Example 11, 15 g of solid support 12A was let down in 333 ml of Isopar E. BEM (30 mmol) was added to the stirred suspension and the suspension was stirred for two hours. Anhydride HCl was then bubbled through the suspension until an aliquot of the hydrolyzed slurry in water gave a neutral pH. The slurry was subsequently purged with nitrogen for 10 min. to remove any excess HCl. To 132 ml of this solution, 1.15 g of a 10% by weight solution of titanium tetrachloride in isopar E was added. The slurry was then stirred for another 24 hours. Prior to polymerization, TiBal co-catalyst (0.15 M in hexane) was added, to give a TiBAI / Ti molar ratio of 100.

In Example 12, 18 g of 20A solid support was let down in 500 ml of isopar E. BEM (36 mmole) was added to the stirred suspension and the mixture was stirred for two hours. Then it bubbled HCl anhydride through the suspension until an aliquot of the slurry hydrolyzed in water gave a neutral pH. The slurry was then purged with nitrogen for 10 min to remove any excess HCl. To 178 ml of this solution, 2.30 g of a 10 wt% solution of titanium tetrachloride in Isopar E was added. The slurry was then stirred for twelve hours followed by the addition of 8 ml of 1.50 M DEAC in heptane. followed by additional stirring further stirring for 24 hr. Prior to polymerization, the TiBal co-catalyst (0.15 M in hexane) was added to give a TiBal / Ti molar ratio of 100.

. * Cu ad ro 4 Ej \ Support BEM / HCL / BEM Ma / T¡ DEAC / Ti Et, EAI = c? Faith Relationship Dens. Silica size Imol / mop mol / moll f mol / molí (a / 10m) íio h vol. particle [mmol / lb / polymer / ka] 6A 2.0 2.0 10.0 10.0 1.69 0.018 0.056 1.83 8.86 20.7 109 (331) 1 1 12A 2.0 2.0 10.0 10.0 0.98 0.010 0.033 1.72 8.95 19.7 1 56 (315) 4- * O) 12 20A 2.0 2.0 10.0 10.0 0.60 0.006 0.020 2.08 9.33 23.8 251 (381) Examples 13-18 In Example 13, Example 1 was repeated, except that 0.66 ml of 1.50 M dichloride (EADC) in heptane was now used., instead of DEAD. In Example 14, Example 1 was repeated, except that 1.33 ml of EADC 1.50 M in heptane was now used instead of DEAD. In Example 15, Example 1 was repeated, except that 1.98 ml of 1.50 M EADC in heptane was now used instead of DEAD. In Example 16, 15 g of solid support 45A was dissolved in 250 ml of hexane. BEM (30 mmol) was added to the stirred suspension followed by stirring for two hours. Anhydride HCl was then bubbled through the suspension for 30 min. followed by nitrogen to remove any excess HCl. The suspension was slowly evaporated subsequently, under vacuum at room temperature for twelve hours to leave a free-flowing dry powder. A 1.30 g sample of this solid was resuspended under nitrogen in 74 ml of hexane to which 0.38 g of a 10% by weight solution of titanium tetrachloride in hexane was added. The slurry was stirred for twelve hours followed by the addition of 0.66 ml of 1.50 M EADC in heptane. This mixture was stirred for 24 hours. Before the polymerization, TiBAi co-catalyst (0.15 M in hexane) was added to give a molar TiA / Ti ratio of 150: 1. In Example 17, Example 16 was repeated except that 1.33 ml of 1.50 M EADC in heptane was added. In Example 18, Example 16 was repeated except that 1.98 ml of 1.50 M EADC in heptane was added.

C u ad ro 5 EL Support BEM / HCIJBEM Mq / Ti EADC / Ti ETl fe Relation Dens. Silica size fmol / molemol / mollmol / moll (a / 10nru1io fe particle vol [mmol / qj Ib / pie3 polymer kq / m3ul 13 12A 2.0 2.7 10.0 5.0 0.67 0.87 8.67 22.7 155 (363) 14 12A 2.0 2.7 10.0 10.0 0.57 0.51 9.72 19.4 156 (310) 15 12A 2.0 2.7 10.0 15.0 0.58 0.47 10.04 18: 1 156 (290) 16 45A 2.0 2.7 10.0 5.0 0.44 1.70 9.88 21.1 266 (338) -fc- 17 45A 2.0 2.7 10.0 10.0 0.58 0.71 '- 10.34 20.5 280 (328) 18 45A 2.0 2.7 10.0 15.0 0.36 0.48 10.64 17.7 290 (283) Examples 19-22 In Examples 19-22, four suspensions were prepared, each containing 18 g of the solid support 12A leached in 500 ml of Isopar E. BEM (36 mmol) was added to the stirred suspension and the mixture was stirred for two hours. Anhydride HCl was then bubbled through the suspension for 30, 35, 40 and 45 minutes, respectively, followed by nitrogen purging for 10 minutes. The analysis of the slurry at this point for chloride and magnesium concentrations gave a molar ratio of CI: Mg of 1.66, 1.97, 2.00 and 2.26. To a 400 ml sample of the slurry, 0.46 g of titanium tetrachloride in 10 ml of Isopar E was then added. The slurry was stirred for 24 hours followed by the addition of 16.3 ml of 1.50 M DEAC in heptane, followed by additional agitation for 24 hours. Prior to the polymerization, the TiBal co-catalyst (0.15 M in hexane) was added to give a TiBal / Ti ratio of 100.

C u a d ro 6 HCl support BEM / silica HCL / B Mq / Ti DEAC / Ti ET, | 9 Dens. Tama time [mmol / ql EM fmol / moll fmol / moll (q / 1 Om) I vol. partic (min) fmol / Ib / ft * 3 molm kl / m3 polymer 12A 30 2.0 1.66 10.0 10.0 0.885 1.54 9 10 19.3 171 (309) 12A 35 2.0 1.97 10.0 10.0 0.935 1.95 9.18 19.3 166 (309) 12A 40 2.0 2.00 10.0 10.0 0.850 1.60 9.13 19.2 172 (307) 12A 45 2.0 2.26 10.0 10.0 0.609 0.79 9.93 21.7 157 (347) Comparative Examples 1-15 In Comparative Examples 1-4, 5 g of the 6G solid support in 250 ml of hexane was let. BEM (10 mmol) was added to the stirred suspension and the suspension was stirred for two hours. Anhydride HCl was then bubbled through the suspension for 30 min. followed by nitrogen to remove any excess HCl. The suspension was slowly evaporated subsequently, under vacuum at room temperature for twelve hours to leave a free-flowing dry powder. The solid was resuspended under nitrogen in 250 ml of hexane and 1.7 g of a 10% by weight solution of titanium tetrachloride in hexane was added, followed by further stirring for 24 hours. A 50 ml aliquot of this coat was collected and 2, 3, 4 and 5 ml, respectively, of EADC 1.0 M in hexane, respectively, were added to the sample which was stirred for 24 hours. Prior to polymerization, TiBAl co-catalyst (0.15 M in hexane) was added to give a TiBal / Ti molar ratio of 150. In Comparative Examples 5-8, Comparative Examples 1-4 were repeated except that after the addition of HCl, no drying step was carried out. In Comparative Example 9, 5 g of 13G solid support in 500 ml of isopar E was lettered. BEM (10 mmoies) was added to the stirred suspension and the reaction mixture was stirred for two hours. Then, the anhydride HCl was bubbled through the suspension until an aliquot of the hydrolyzed slurry in water gave a neutral pH. The coat was purged with nitrogen for 10 minutes to remove any excess HCl. To this slurry, 1 10 μl of titanium tetrachloride was added. The resulting mixture was stirred for twelve hours followed by the addition * of 6.7 ml of a 1.50 M solution of DEAC in heptane. The additional agitation takes place for 24 hr. Prior to polymerization, the TiBal co-catalyst (0.15 M in hexane) was added to give a Ti: Cal / Ti molar ratio of 100: 1. In Comparative Example 10, Example was repeated Comparative 9 except that now 5 g of the 30G solid support was used instead of 5 g of 13G. In Comparative Example 1 1, Comparative Example 9 was repeated, except that 5 g of the 45G solid support was now used instead of 5 g of 13G. In Comparative Examples 12-15, Comparative Examples 5-8 were repeated, except that instead of 6G solid support, 90G solid support was now used. The results of Comparative Examples 1-15 are summarized in Table 7.

C uadro 7 EL Support BEM / HCL / BEM Mq / Ti DEAC / Ti IT, fe Ratio Dens. Size silica fmol / moll marble / moll fmol / moll (q / 10m) íiofe vol. particle fmmol / al Ib / oie3 polymer kq / m3? 1 1 6G 2.0 2.7 10.0 10 0.831 0.21 14.67 16.3 (261) 107 2 6G 2.0 2.7 10.0 15 0.737 0.12 16.70 15.8 (253) 102 3 6G 2.0 2.7 10.0 20 0.727 0.12 16.62 15.1 (242) 96 4 6G 2.0 2.7 10.0 25 0.483 0.11 15.62 12.5 (200) 122 5 6G 2.0 2.7 10.0 10 0.524 0.22 13.41 13.7 (219) 112 tn 6 6G 2.0 2.7 10.0 15 0.781 0.10 19.43 15.3 (215) 103 7 6G 2.0 2.7 10.0 20 0.662 0.05 25.3? 15.5 (248) 109 8 6G 2.0 2.7 10.0 25 0.463 0.07 24.6 14.4 (230) 108 9 13G 2.0 2.0 10.0 10 0.27 5.77 8.45 14.6 (234) 91 10 30G 2.0 2.0 10.0 10 0.19 4.04 8.51 15.3 (245) 114 11 45G 2.0 2.0 10.0 10 0.19 5.83 8.89 14.8 (237) 111 12 90G 2.0 2.7 10.0 10 0.208 0.08 18.18 13.6 (218) 304 13 90G 2.0 2.7 10.0 15 0.241 0.09 17.83. 14.6 (234) 275 ; uadro 7 EL Support BEM / HCL / BEM Mq / Ti DEAC / Ti ET, fe ratio Dens. Size silica fmol / moll fmol / moll fmol / moll (0/1 Om) í? O_fe vol. particle fmmol / ql Ib / pie3 polymer kq / m3 ÍUl 14 90G 2.0 2.7 10.0 20 0.197 0.10 18.71 13.8 (221) 216 15 90G 2.0 2.7 10.0 25 0.246 0.16 16.62 14.5 (232) 115 Ül ül Example 23 To 153.4 kg of anhydrous heptane stirred under ambient pressure and a nitrogen atmosphere was added 28.1 kg of a solid support 12A. 42.0 kg of a 1.47% by weight solution of BEM in heptane was then added to the beam. The slurry was stirred for three hours followed by the addition of 3.96 kg of anhydrous hydrogen ride. The heptane was then stirred to leave a free flowing powder with a magnesium concentration of 1.64 mmole / g of support and a molar ratio of CI: Mg of 1.96. 64.5 kg of this support was added to 726 kg of stirred isopentane under ambient pressure and a nitrogen atmosphere. This mixture was stirred for 30 min followed by the addition of 2.58 kg of pure titanium tetraride via pressurized stainless steel addition cylinder. The resulting slurry was stirred for an additional seven hours followed by the addition of 136 kg of 12.2% by weight solution of DEAC in hexane to produce a catalyst with a molar ratio of Mg.Ti.AI of 2.0: 0.25: 2.5. After stirring for an additional nine hours, the slurry was mixed with 8 molar equivalents of TiBAl co-catalyst with respect to the titanium component. The resulting coat was pumped directly into a continuous process reactor in which the polymerization of ethylene takes place at a temperature of 85 ° C and a pressure of 1205 kPa. The titanium efficiency is 0.6 x 106 g polymer / g Ti. Examples 24-27 In Examples 24-27, 11 g of 6A solid supports were letred in 531 ml of Isopar E. BEM (22.3 ml of 0.982 M in heptane, 21.92 mmol) was added to the stirred suspension and the slurry was stirred during two hours. Anhydride HCl was then bubbled through the suspension until an aliquot of the hydrolyzed slurry in water gives a neutral pH. The slurry was subsequently purged with nitrogen for 10 min. to remove any excess HCl. To 50.5 ml of this slurry, 6.6 ml of a solution made by mixing 5.5 ml of an equimolar mixture of titanium tetraride and vanadium oxytriride and 94.5 ml of Isopar E were added. The slurry was then stirred for twelve hours followed by the addition 2.0, 3.3, 4.7 and 6.0 ml, respectively, of 1.50 M DEAC solution in heptane followed by additional stirring for 96 hr. The molar ratio of Mg / Ti / V / AI is 2 / 1.8 / 1.8 / 3 (Ex. 24); 2 / 1.8 / 1.8 / 5 (Ex 25); 2 / 1.8 / 1.8 / 7 (Ex. 27), and the DEAC content is 3, 5, 7, and 9 mmol / g SiO2 respectively. Before the polymerization, triethylaluminum cocatalyst (TEA) (0.15 M is Isopar E) was added to give a molar ratio of TEA / Ti of 9: 1. A 3.79 I autoclave reactor was charged with two liters of Isopar E and an amount of 1-octene so that its molar concentration in the reactor is 0.99 M. The reactor was heated to 185 ° C and 14 kPa of hydrogen was added. They added to the reactor followed by enough ethylene to reach the total pressure of 3100 kPa. After, 6 μmol of Ti equivalents of the catalyst prepared as described above, was injected into the reactor. The temperature and pressure of the reactor / / were kept constant by continuously feeding ethylene during the polymerization and cooling the reactor as required. After 10 minutes, the ethylene was removed and the hot solution transferred in a nitrogen-purged resin kettle. After drying the samples were weighed to determine catalyst efficiencies followed by melt flow measurements. The results are given in Table 8. Table 8 Relationship 10 DEAC / Ti §n I, (a / 10m) Reí. I10l, 24 3.0 0.24 7.59 7.01 25 5.0. 0.53 6.13 6.82 26 7.0 0.47 5.66 6.73 15 27 9.0 0.47 Example 29-32 Example 26 was repeated, but now the molar ratio of TEA / Ti varied. The results are given in Table 9. Table 9 20 Relationship TEA / Ti n (Q / 10m) Rei. LOL, 28 2.5 0.40 4.32 6.73 29 5.0 0.59 6.59 6.70 25 30 9.2 0.47 5.66 6.73 31 12.9 0.51 6.33 6.74 Example 33 The void fraction of three different granular solid supports and three different agglomerated solid supports was determined according to the procedure described above. The results are summarized in Table 10. Table 10 Support Fraction of voids f% 1 6G without gaps 45G without gaps 70G without gaps 6A 13.48 45A 15.51 70A 20.32 Example 34 15 g of the solid support 70A was letred in 333 ml of anhydrous hexane. BEM (30 mmol) was added to the stirred suspension which was further stirred for two hours. Anhydride HCl was then bubbled through the suspension until an aliquot of slurry hydrolyzed in water gave a neutral pH. The slurry was then purged with nitrogen for 10 min. to remove any excess HCi. To 132 ml of this slurry was added 1.15 g of a 10% by weight solution of titanium tetrachloride in hexane. The slurry was then stirred for twelve hours followed by the addition of 4 ml of 1.50 M DEAC in heptane. The mixture was then stirred for 24 hours before the removal of hexane in vacuo for 12 hr at 30 ° C. In a gas phase polymerization experiment, a stirred 5 L autoclave reactor was charged with 1450 g of anhydrous sodium chloride (A.C.S., Grade, Fisher Scientific) which was previously dried under nitrogen at 250 ° C for 4 hr. The vapor space was then flushed with nitrogen before the addition of 3 ml of a 1.0 M solution of triethylaluminum in hexane. The reactor was then heated to 80 ° C and maintained for 1 hr. The reactor was then vented and 0.25 g of the solid catalyst followed by 4 ml of a 1.0 M solution of triethylaluminum in hexane was added under a pad of nitrogen. At this point, the reactor was re-vented and sufficient propylene was added to bring the total pressure to 620 kPa. Propylene was continuously supplied to the reactor by a demand power regulator in the line. After an operation time of 1 hr and 40 min., The propylene was blocked and the reactor was cooled and vented. The contents of the reactor were then washed with enough water to dissolve all the salt. This gave the polymer product which was dried under vacuum at room temperature to give 44.7 g of polypropylene.

Claims (30)

1. CLAIMS 1.
2. A supported catalyst component comprising (A) a solid particulate support having (i) a specific surface area of 100 to 1000 m2 / g as determined by nitrogen absorption using the BET technique, (ii) a surface hydroxyl content of not more than 5 mmoles of hydroxyl groups per g of solid support as determined by adding an excess of dialkylmagnesium to a slurry of the solid support and determining the amount of dialkylmagnesium remaining in solution, (iii) a pore volume of 0.3 to 3.0 cc / g as determined by nitrogen adsorption, (iv) an average particle size of 1 to 200 μm as determined via a Coulter particle size analyzer, and (v) a majority of solid particulate support particles in the form of an agglomerate of subparticles containing void fractions of 5 to 30 percent as observed in electron micrographs, and (B) a macular halide. gnesio The supported catalyst component of claim 1, wherein at least 70 weight percent of the solid particulate support (A) (v) is in the form of a subparticle agglomerate.
3. 3. The supported catalyst component according to claim 1 or 2, wherein the solid particulate support (A) is silica.
4. 4. The supported catalyst component according to any of claims 1-3, wherein the magnesium halide (B) is magnesium chloride. The supported catalyst component according to any of claims 1-4, wherein the ratio of magnesium halide (B) to solid particulate support (A) is 0.
5. 5 to 5.0 mmole of (B) per gram of (TO).
6. 6. The supported catalyst component according to any of claims 1-5, obtained by impregnating the solid particulate support (A) with a solution of a magnesium compound (B ') soluble in hydrocarbon of the formula R2-nMgXn. xMR'y wherein R, independently whenever it occurs, an alkyl group having from 2 to 8 carbon atoms, M is aluminum, zinc or boron, R 'independently each time it occurs is hydrocarbyl with from 1 to 10 carbon atoms in the hydrocarbyl part thereof x has a value from 0 to 6, and y is 3, which can be transformed into magnesium halide (B) by halogenation, followed by halogenation of the magnesium compound (B ') to magnesium halide with a halogenation agent (C) selected from the group consisting of hydrogen haiides, and optionally recovering the supported catalyst component.
7. The supported catalyst component according to claim 6, wherein a sufficient amount of halogenating agent (C) is used to convert at least 75 mole percent of (B ') to magnesium dihalide.
8. 8. The supported catalyst component according to any of claims 1-7 further comprising (D) a transition metal compound of Group 4 or 5 selected from the group consisting of a halide, hydrocarbyl oxide or mixed halide / oxide of titanium, zirconium, hafnium or vanadium hydrocarbyl.
9. 9. The supported catalyst component according to claim 8, wherein (D) is titanium tetrachloride and zirconium tetrachloride.
10. The supported catalyst component according to claim 8 or 9, wherein from 1 to about 40 moles of magnesium halide (B) is employed per mole of transition metal compound of Group 4 or 5 (D).
11. 11. The supported catalyst component according to any of claims 1-10 further comprising (E) an organometallic compound of Group 2 or 13.
12. 12. The supported catalyst component according to claim 11, wherein (E) is an alkylaluminum halide.
13. The supported catalyst component according to claim 11 or 12, wherein 0.1 to 100 moles of (E) is employed per moi of (D).
14. 14. A catalyst component according to any of claims 1-12, further comprising an electron donor (F).
15. 15. A process for preparing a supported catalyst component comprising the steps of: impregnating a solid particulate support (A) having (i) a specific surface area of 100 to 1000 m2 / g as determined by nitrogen absorption using the BET technique, (ii) a surface hydroxyl content not greater than 5 mmoles of hydroxyl groups per g of solid support as determined by adding an excess of dialkylmagnesium remaining in solution, (iii) a pore volume of 0.3 to 3.0 cc / g as determined by nitrogen adsorption, (iv) an average particle size of 1 to 200 μ as determined via a Coulter particle size counter analyzer, and (v) a majority of solid particulate support particles in the shape of an agglomerate of subparticles containing fractions of voids of 5 to 30 percent as observed in electron micrographs, with a solution of magnesium halide (B) or with a solution n of a magnesium compound (B ') which can be transformed into magnesium haiuro (B) by halogenation; when a magnesium compound (B) is used, the halogenation of the magnesium compound (B ') to magnesium halide with a haiogenation agent (C); and optionally, recovering the supported catalyst component.
16. The process according to claim 15, wherein at least 70 weight percent of the solid (a) (v) solid support is in the form of a subparticle agglomerate.
17. 17. The process according to claim 15 or 16, wherein the solid particulate support (A) is silica.
18. 18. The process according to any of claims 15-17 wherein the magnesium compound (B ') is a magnesium compound soluble in hydrocarbons of the formula R2Mg.xMR'y, wherein R independently each time it is presented is an alkyl group having from 2 to 8 carbon atoms, M is aluminum, zinc or boron, R 'independently each time it occurs is hydrocarbyl with 1 to 10 carbon atoms in the hydrocarbyl part thereof, x has a value of 0 to 6, and y is 3, and the halogenating agent (C) is selected from the group consisting of hydrogen halides.
19. 19. The process according to claim 18, wherein (C) is hydrogen chloride.
20. 20. The process according to any of claims 15-19 wherein 0.5 to 5.0 moles of magnesium halide (B) or the magnesium compound that can be transformed into magnesium halide by halogenation (B ') is used by gram of solid particulate support (A).
21. 21. The process according to any of claims 15-19, wherein a sufficient amount of halogenating agent (C) is used to convert substantially all (B) to magnesium dihalide.
22. 22. The process according to any of claims 15-21, wherein the magnesium compound (B ') is dissolved in a hydrocarbon medium selected from the group of aliphatic and cycloaliphatic hydrocarbons.
23. 23. The process according to any of claims 15-22, comprising the additional step of: combining the supported catalyst component with a transition metal compound of Group 4 or 5 (D9 selected from the group consisting of a halide, hydrocarbyl oxide or halide / mixed hydrocarbyl oxide of titanium, zirconium, hafnium or vanadium
24. 24. The process according to claim 23, wherein from 1 to about 40 moles of magnesium halide (B) or the compound of magnesium (B ') is used per mole of the transition metal compound of Group 4 or 5 (D)
25. 25. The process according to any of claims 15-24 comprising the additional step of: combining the supported catalyst component with an organometallic compound of Group 2 or 3 (E).
26. 26. The process according to claim 25, wherein (E) is an alkyl aluminum halide.
27. 27. The process according to any of claims 25-26, wherein 0.1 to 100 moles of (E) are used per mole of (B).
28. The process according to any of claims 15-27, comprising the step of: combining the supported catalyst component with an electron donor (F).
29. 29. A supported catalyst composition for olefin polymerization, comprising (A) a solid particulate support having (i) a specific surface area of 100 to 1000 m2 / g as determined by nitrogen uptake using the BET technique, ( ii) a surface hydroxyl content not greater than 5 mmoles of hydroxyl groups per g of solid support as determined by adding an excess of dialkylmagnesium to a slurry of the solid support and determining the amount of dialkylmagnesium remaining in solution, ( iii) a pore volume of 0.3 to 3.0 cc / g as determined by nitrogen adsorption; (iv) an average particle size of 1 to 200 μm as determined via a Coulter particle size counter; and (v) ) a majority of solid particulate support particles in the form of subparticles containing fractions of voids of 5 to 30 percent as observed in electron micrographs, (B) a halide of m agnesium, (D) a transition metal compound of Group 4 or 5, (E) an organometallic compound of Group 2 or 13, and, optionally, an electron donor (F), and a cocatalyst selected from the group consisting of aiumoxanes and compounds corresponding to the formula R "ZGX" 3-Z, wherein G is aluminum or boron, R "independently each time it occurs, is hydrocarbyl, X" independently each time it occurs is halide or hydrocarbyl oxide , and z is a number from 1 to 3.
30. 30. An olefin polymerization process comprising contacting one or more olefins under olefin polymerization conditions with a supported catalyst composition for olefin polymerization according to claim 29.