MXPA06003170A

MXPA06003170A - Ziegler-natta catalyst for polyolefins.

Info

Publication number: MXPA06003170A
Application number: MXPA06003170A
Authority: MX
Inventors: Kayo Vizzini
Original assignee: Fina Technology
Priority date: 2003-09-22
Filing date: 2004-09-07
Publication date: 2006-06-05
Also published as: JP2007505970A; TW200528190A; EP1673166A4; KR20060126929A; CA2536804A1; EP1673166A1; JP4976129B2; BRPI0414649A; WO2005032714A1

Abstract

A Ziegler-Natta type catalyst component can be produced by a process comprising contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A, and contacting reaction product A with a first, second and third halogenating/titanating agents. Catalyst components, catalysts, catalyst systems, polyolefin, products made therewith, and methods of forming each are disclosed. The reaction products can be washed with a hydrocarbon solvent to reduce titanium species [Ti] content to less than about 100 mmol/L.

Description

ZIEGLER-NATTA CATALYST FOR POLYOLEFINS BACKGROUND OF THE INVENTION Field of the Invention The present invention relates generally to catalysts, to methods for making catalysts, to methods for using catalysts, to polymerization methods and to polymers made with such catalysts. More particularly, the present invention relates to polyolefin catalysts and to Ziegler-Natta catalysts, to methods for making such catalysts, to methods for using such catalysts, to the polymerization of polyolefin, and to polyolefins. Description of the Related Art Olefins, also called alkenes, are unsaturated hydrocarbons whose molecules contain one or more pairs of carbon atoms linked together by a double bond. When subjected to a polymerization process, the olefins can be converted to polyolefins, such as polyethylene and polypropylene. A commonly used polymerization process involves contacting an olefin monomer with a Ziegler-Natta type catalyst system. Many Zi gler-Natta type polyolefin catalysts, their general processing methods, and subsequent use are well known in the polymerization art. Typically, these systems include a Ziegler-Natta type polymerization catalyst component; a co-catalyst; and an electron donor compound. A Ziegler-Natta type polymerization catalyst component can be a complex derived from a halide of a transition metal, for example, titanium, chromium or vanadium, with a metal hydride and / or an alkyl metal that is typically an organoaluminum compound. . The catalyst component is usually comprised of a titanium halide supported on a magnesium compound complexed with an aluminum alkyl. There are many issued patents related to catalysts and catalyst systems designed primarily for the polymerization of propylene and ethylene that are known to those skilled in the art. Examples of such catalyst systems are provided in U.S. Patent Nos. 4,107,413; 4,294,721; 4,439,540; 4,114,319; 4,220,554; 4,460, 701; 4, 562.173; 5, 066, 738 and 6, 174,971 which are incorporated herein by reference. Conventional Ziegler-Natta catalysts comprise a transition metal compound generally represented by the formula: MRX wherein M is a transition metal compound, R is a halogen or a hydrocarboxyl and x is the valence of the transition metal. Typically, M is selected from a metal of group IV to VII such as titanium, chromium or vanadium, and R is chlorine, bromine or an alkoxy group. The common transition metal compounds are TiCl4, TiBr4 / Ti (OC2H5) 3 Cl, Ti (0C3H7) 2C12, Ti (OC6Hi3) 2C12, Ti (OC2H5) 2Br2 and Ti (OC12H25) C13. The transition metal compound is typically supported on an inert solid, for example, magnesium chloride. Ziegler-Níatta catalysts are generally provided on a support, ie deposited on a solid crystalline support. The support can be an inert solid, which is chemically unreactive with any of the conventional Ziegler-Natta catalyst components. The support is often a magnesium compound. Examples of the magnesium compounds that can be used to provide a support source for the catalyst component are magnesium halides, dialkoxymagnesiums, alkoxymagnesium halides, magnesium oxyhalides, dialkymagnesnes, magnesium oxide, magnesium hydroxide and magnesium carboxylates. The properties of the polymerization catalyst can affect the properties of the polymer formed using the catalyst. For example, the morphology of the polymer typically depends on the morphology of the catalyst. The good morphology of the polymer includes the uniformity of the size and shape of the particle and a density in acceptable volume. further, it is desirable to minimize the number of very small polymer particles (ie, fine products) for various reasons, such as, for example, to prevent clogging of the transfer or recirculation lines. Very large particles should also be minimized to avoid the formation of lumps and chains in the polymerization reactor. Another property of the polymer affected by the type of catalyst used is the molecular weight distribution (MWD), which refers to the width of the variation in the length of the molecules in a given polymer resin. In polyethylene, for example, the reduction of the MWD can improve the hardness, ie puncture performance, tension and impact. On the other hand, a wide MWD can favor the ease of processing and the strength of the molten material. 'While much is known about Ziegler-type catalysts, there is constant research for improvements in their polymer yield, catalyst life, catalyst activity and in their ability to produce polyolefins that have certain properties. BRIEF DESCRIPTION OF THE INVENTION One embodiment of the present invention provides a process for making a catalyst comprising: a) contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; b) contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B; c) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and d) contacting the reaction product C with a third halogenation / titanation agent to form the reaction product D. The second and third halogenation / titanation agent may comprise titanium tetrachloride. The second and third halogenation / titanation step each may comprise a titanium to magnesium ratio in the range of about 0.1 to '5. The reaction products A, B and C each can be washed with a hydrocarbon solvent before the subsequent halogenation / titanation steps. The reaction product D can be washed with a hydrocarbon solvent until the content of titanium species [Ti] is less than about 100 mmol / L. Another embodiment of the present invention provides a polyolefin catalyst produced by a process generally comprising contacting a catalyst component of the invention together with an organometallic agent. The catalyst component is produced by a process as described above. The catalysts of the invention may have a spongy morphology available for the polymerization production processes, and may provide a polyethylene having a molecular weight distribution of at least 5.0 and may provide uniform particle size distributions with. low levels of particles of less than about 125 microns. The activity of the catalyst is dependent on the polymerization conditions. Generally, the catalyst will have an activity of at least 5,000 gPE / g of catalyst, but the activity may also be greater than 50,000 gPE / g of catalyst or greater than 100,000 gPE / g of catalyst. Yet another embodiment of the present invention provides a polyolefin polymer produced by a process comprising: a) contacting one or more olefin monomers with only in the presence of a catalyst of the invention, under polymerization conditions; and b) extracting the polyolefin polymer. Generally, the monomers are ethylene monomers and the polymer is polyethylene. Still another embodiment of the present invention provides a film, fiber, tube, textile or article of manufacture comprising the polymer produced by the present invention. The article of manufacture may be a film comprising at least one layer comprising a polymer produced by a process comprising a catalyst of the invention. Another embodiment of the invention provides a process for making a catalyst comprising: altering the precipitation of a catalyst component from a catalyst synthesis solution by controlling the viscosity of a catalyst synthesis solution with the addition of aluminum alkyl, wherein the average particle size of the catalyst component is increased with an increased concentration of aluminum alkyl in the synthesis solution. The process may further comprise contacting the catalyst component with an organometallic preactivation agent to form a catalyst, wherein the average particle size of the catalyst is increased with an increased concentration of aluminum alkyl in the synthesis solution. Another embodiment of the present invention provides a process for making a catalyst comprising: a) contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; b) contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B; c) put. in contact the reaction product B with a second halogenation / titanation agent to form the reaction product C; d) contacting the reaction product C with a third halogenation / titanation agent to form the reaction product D; and e) contacting the reaction product D with an organometallic preactivation agent to form a catalyst. The magnesium dialkoxide compound is a reaction product of a reaction comprising an alkylmagnesium compound of the general formula MgRR ', wherein R and R' are alkyl groups of 1-10 carbon atoms and may be the same or different, an alcohol of the general formula R "wherein the alcohol is linear or branched and wherein R" is an alkyl group of 2-20 carbon atoms, an aluminum alkyl of the formula AIR "'3 wherein less one R "'is alkyl or alkoxide having 1-8 carbon atoms or a halide, and wherein each R"' may be the same or different.The average particle size of the catalyst is increased with an increased alkyl ratio aluminum to alkyl magnesium The second and third halogenation / titanation agent may comprise titanium tetrachloride The second and third halogenation / titanation step each may comprise a titanium to magnesium ratio in the range of about 0.1 to 5. Reaction products A, B and C can each be washed with a hydrocarbon solvent before the subsequent halogenation / titanation steps. The reaction product D can be washed with a hydrocarbon solvent until the content of the titanium species [Ti] is less than about 100 mmol / L. Yet another embodiment of the present invention provides a polyolefin polymer produced by a process comprising: a) contacting one or more olefin monomers together in the presence of a catalyst of the invention, under polymerization conditions; and b) extracting the polyolefin polymer. The average particle size of the polymer is increased with an increased ratio of alkyl aluminum to magnesium alkyl used in the preparation of the catalyst. Generally the monomers are ethylene monomers and the polymer is polyethylene. Still another embodiment of the present invention provides a film, fiber, tube, textile or article of manufacture comprising the polymer produced by the present invention. The article of manufacture may be a film comprising at least one layer comprising a polymer produced by the present invention. Other embodiments include a process for forming a catalyst for use in the polymerization of olefins. This process comprises reacting a chlorinating agent with a magnesium alkoxide compound to form an adduct of magnesium-titanium alkoxide and thus reacting the adduct of magnesium-titanium alkoxide with an alkylchloride compound to form a magnesium chloride support . The support is then reacted with titanium tetrachloride (TiCl 4) to form a highly active catalyst useful for the production of polyolefins. In one embodiment of the invention, the magnesium alkoxide compound is first formed by reacting butylethylmagnesium (BEM) with an alcohol generally represented by the formula ROH, where R is an alkyl group containing, for example, about 1 to 20. carbon atoms. The magnesium alkoxide compound is then combined with a chlorinating agent generally represented by the formula: TiCln (OR ') 4-n where R' is an alkyl, cycloalkyl or aryl group, and n is from 1 to 3. An adduct of Magnesium-titanium alkoxide is formed as a result of mixing the magnesium alkoxide compound and the chlorinating agent. An alkylchloride compound is reacted with the magnesium-titanium alkoxide adduct to form a support of magnesium chloride (MgC12) and one or more byproducts such as an ether and / or an alcohol. Subsequently, the MgCl 2 is treated with TiCl 3 to form a Ziegler-Natta catalyst supported by MgCl 2. The polyolefins produced using this catalyst have reduced molecular weight distributions and can thus be formed into end-use articles such as barrier films, fibers and tubes.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates the settlement efficiency curves for the polymer made using a catalyst of the invention (Example 1) and the polymer made a conventional catalyst (Comparative Example 4). FIG. 2 represents the particle size distributions of the catalysts described in Comparative Examples 1A-2A and Examples 1A-2A. FIG. 3 represents the particle size distributions of the catalysts described in Comparative Examples 1A-2A and in Example 4A. FIG. 4 represents the performance of the catalyst as a function of the amount of PhCOCl used for Examples 4A-10A. FIGS. 5-6 represent the particle size distributions of the catalysts formed in Examples 4A-10A. FIG. 7 represents the average catalyst particle size (D50) as a function of the amount of PhCOCl used for Examples 4A-10A. FIG. · 8 represents the particle size distributions of the catalysts described in Comparative Examples 1A-2A and Examples 4A and 11A. . FIG. 9 represents the particle size distributions of the fluff of the polymeric resins described in Comparative Examples 3A-4A and in Example 12A. FIG. 10 represents the particle size distributions of the fluff of the polymer resins described in Comparative Examples 3A-4A and in Example 13A. FIG. 11 represents the particle size distributions of the catalysts described in Example 1 A. FIG. 12 represents the particle size distributions of the catalysts described in Example 15A. DETAILED DESCRIPTION OF THE INVENTION According to one embodiment of the invention, a method for making a catalyst component generally includes the steps of forming a metal dialkoxide from a dialkyl alcohol, halogenating the metal dialkoxide to form a product of reaction, contacting the reaction product with one or more halogenation / titanation agents in three or more steps to form a catalyst component, and then treating the catalyst component with a preactivation agent such as an organoaluminum. One embodiment of the present invention may be generally as follows: 1. MRR '+ 2R "0H? (0") 2 2. M (OR ") 2 + C1AR"' X - »???" 3. "A" + TiCl / Ti (0R "") 4?? " 4. "B" + TiCl4? "C"; 5. "C" + TÍCI4? D. 6. "D" + preactivation agent - »catalyst In the above formulas, M can be any suitable metal, usually a Group IIA metal, typically Mg. In the above formulas, R, R ', R "and R"' are each independently hydrocarbyl or substituted hydrocarbyl moieties, with R and R 'having from 1 to 20 carbon atoms, generally from 1 to 10 carbon atoms , typically from 2 to 6 carbon atoms and may have from 2 to 4 carbon atoms. R "generally comprises from 3 to 20 carbon atoms, R" 'generally comprises from 2-6 carbon atoms and R "" generally comprises from 2-6 carbon atoms and is typically butyl. Any combination of two or more of R, R ', R ", R"' and R "" may be used, may be the same, or the combination of the R groups may be different from each other. In the above embodiment comprising the formula ClAR "'x, A is a non-reducing oxyphilic compound that is capable of exchanging a chloride for an alkoxide, R"' is a hydrocarbyl or substituted hydrocarbyl, and x is the valence of A minus 1. Examples of A include titanium, silicon, aluminum, carbon, tin and germanium, typically titanium or silicon where x is 3. Examples of R "'include methyl, ethyl, propyl, isopropyl and the like having 2-6 carbon atoms. Carbon Non-limiting examples of a chlorinating agent that can be used in the present invention are ClTi (0'Pr) 3 and ClSi (Med) 3. The metal dialkoxide of the above embodiment is chlorinated to form a reaction product. A ". While the exact composition of product" A "is unknown, it is believed that it contains a partially chlorinated metal compound, an example of which may be ClMg (OR "). The reaction product" A "is then contacted with one or more halogenation / titanation agents, such as example a combination of TiCl4 and Ti (0Bu) 4, to form the reaction product "B." The reaction product ?? " which is probably a complex of chlorinated and partially chlorinated metal and titanium compounds. The reaction product WB "may comprise a MgCl2 support impregnated with titanium and for example, may possibly be represented by a compound such as (MC12) and (TiClx (OR) 4_ x) 2. The reaction product" B "may be is precipitated as a solid from the catalyst suspension The second halogenation / titanation step produces the reaction product, or catalyst component, "C" which is also probably a complex of halogenated and partially halogenated metal and titanium compounds but different from "B" and can possibly be represented by (MCI2) and (TiClx '(OR) 4-x') z '. It is expected that the level of halogenation of "C" would be greater than that of the product "B". This larger level of halogenation can produce a different complex of compounds.The third stage of halogenation / titanation produces a reaction product, or catalyst component, "D" which is also probably a complex of metal and titanium compounds. or halogenated and partially halogenated but different from VB "and" C ", and possibly can be represented by (MC12) and (TiClx» (OR) 4-x ") z". It is expected that the level of halogenation "D" would be greater than that of product "C". This larger level of halogenation would produce a different complex of compounds. While this description of the reaction products offers the most probable explanation of the chemistry at this time, the invention as it is described in the claims is not limited by this theoretical mechanism. The metal dialkyls and resulting metal dialkoxides suitable for use in the present invention can include any that can be used in the present invention to produce a suitable polyolefin catalyst. These metal dialkoxides and dialkyls may include metal dialkoxides and dialkyls from Group IIA. The dialkoxide or dialkyl metal can be an alkyl magnesium dialkoxide. Non-limiting examples of suitable magnesium dialkyls include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butylethylmagnesium, etc. Butylethylmagnesium (BEM) is a suitable dialkyl magnesium. In the practice of the present invention, the metal dialkoxide can be a magnesium compound of the general formula Mg (OR ") 2 where R" is a hydrocarbyl or substituted hydrocarbyl of 1 to 20 carbon atoms. The metal dialkoxide can be soluble and is typically non-reducing. A non-reducing compound has the advantage of forming MgCl 2 instead of insoluble species that can be formed by the reduction of compounds such as MgRR ', which can result in the formation of catalysts having a broad particle size distribution. In addition, Mg (OR ") 2, which is less reactive than MgRR ', when used in a reaction involving chlorination with a moderate chlorinating agent, followed by the subsequent halogenation / titanation steps, can result in a uniform product for example, better control and particle size distribution of the catalyst.Non-limiting examples of metal dialkoxide species that can be used include magnesium butoxide, magnesium pentoxide, magnesium hexoxide, magnesium di (2-ethylhexoxide) and any suitable alkoxide to make the system soluble As a non-limiting example, magnesium dialkoxide, such as magnesium di (2-ethylhexoxide), can be produced by reacting an alkyl magnesium compound (MgRR ') with an alcohol ( ROH), as shown below: MgRR '+ 2 R "OH? Mg (0R ") 2 + RH + RH The reaction can take place at room temperature and the reactants form a solution R and R 'can each be any alkyl group of 1-10 carbon atoms, and they can be the same or different. Suitable MgRR 'compounds include, for example, diethyl magnesium, dipropyl magnesium, dibutyl magnesium and butyl ethyl magnesium. The compound MgRR 'can be BEM, where RH and R'H are butane and ethane, respectively. In the practice of the present invention, any alcohol can be used to produce the desired metal dialkoxide. Generally, the alcohol used can be any alcohol of the general formula R "OH where R" is an alkyl group of 2-20 carbon atoms, the carbon atoms can be at least 3, at least 4, at least 5, or at least 6 carbon atoms. Non-limiting examples of suitable alcohols include ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-pentanol, 2-ethylhexanol, etc. While it is believed that almost any alcohol can be used, linear or branched, branched alcohol of higher order, for example, 2-ethyl-1-hexanol, can be used. The amount of alcohol added may vary, such as within a non-exclusive range of from 0 to 10 equivalents, the range is generally from about 0.5 equivalent to about 6 equivalents (equivalents are relative to magnesium or metal compound throughout), and it can be in ranges of about 1 to about 3 equivalents. The metal alkyl compounds can result in high molecular weight species that are very viscous in solution. This high viscosity can be reduced by adding to the reaction an aluminum alkyl such as, for example, triethylaluminium (???), which can interrupt the association between the individual alkyl metal molecules. The typical ratio of aluminum alkyl to metal can vary from 0.001: 1 to 1: 1, can be 0.01 to 0.5: 1 and can also vary from 0.03: 1 to 0.2: 1. In addition, an electron donor such as an ether, for example, diisoamyl ether (DIAE), can be used to further reduce the viscosity of the metal alkyl. The typical electron metal donor ratio varies from 0: 1 to 10: 1 and can vary from 0.1: 1 to 1: 1. Useful agents in the halogenation step of the metal alkoxide include any halogenating agent that when used in the present invention will produce a suitable polyolefin catalyst. The halogenation step may be a chlorination step where the halogenating agent contains a chloride (ie, it is a chlorinating agent). The halogenation of the metal alkoxide compound is generally conducted in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane and the like. In this halogenation step, the mol ratio of the alkoxide to the halogenating agent is generally in the range of about 6: 1 to about 1: 3, it may be in the range of about 3: 1 to about 1: 2, it may be in the range of about 2: 1 to about 1: 2 and can also be about 1: 1. The halogenation step is generally carried out at a temperature in the range of about 0 ° C to about 100 ° C and during a reaction time in the range of about 0.5 to about 24 hours. The halogenation step can be carried out at a temperature in the range of about 20 ° to about 90 ° C and over a reaction time in the range of about 1 hour to about 4 hours. Once the halogenation step is carried out and the metal alkoxide is halogenated, the product of halu.ro "A" can be subjected to two or more halogenation / titanation treatments. The halogenation / titanation agents used can be mixtures of two titanium compounds tetra-substituted with all four substituents which are the same and substituents which are a halide or an alkoxide or phenoxide with 2 to 10 carbon atoms, such as TiCl <; Or Ti (0R "") 4. The halogenation / titanation agent used can be a chlorination / titanation agent. The halogenation / titanation agent may be an individual compound or a combination of compounds. The method of the present invention provides an active catalyst after the first halogenation / titanation; however, there is desirably a total of at least three stages of halogenation / titanation. The first halogenation / titanation agent is typically a moderate titanation agent, which may be a mixture of a titanium halide and an organic titanate. The first halogenation / titanation agent can be a mixture of TiCl4 and Ti (0Bu) in a range of 0.5: 1 to 6: 1 of TiCl4 / Ti (OBu) < i, the ratio can be 2: 1 to 3: 1. It is believed that the mixture of titanium halide and organic titanate reacts to form a titanium alkoxyhalide, Ti (OR) a¾ > where OR and X are alkoxide and halide, respectively and a + b is the valence of titanium, which is typically 4. In the alternative, the first halogenation / titanation agent may be an individual compound. Examples of a first halogenation / titanation agent are Ti (0C2H5) 3C1, Ti (OC2HS) 2Cl2, Ti (0C3¾) 2Cl2, Ti (OC3H7) 3C1, Ti (OC4H9) Cl3, Ti (0C6H13) 2C12, Ti (OC2H5) 2Br2 and Ti (0C12H5) Cl3. The first stage of halogenation / titanation is generally carried out by suspending the product from. Halogenation "A" in a hydrocarbon solvent at room temperature / room temperature. Non-limiting examples of suitable hydrocarbon solvents include heptane, hexane, toluene, octane and the like. The product "A" may be at least partially soluble in the hydrocarbon solvent. A solid product is precipitated at room temperature after the addition of the halogenation / titanation agent to the soluble product "A." The amount of halogenation / titanation agent used must be sufficient to precipitate a solid product from In general, the amount of halogenation / titanation agent used, based on the ratio of titanium to metal, will generally be in the range of about 0.5 to about 5, typically in the range of about 1 to about 4, and may to be in the range of about 1.5 to about 2.5 The solid product "B" precipitated in this first stage of halogenation / titanation is then recovered by any suitable recovery technique, and then washed at room temperature / room with a solvent, such as hexane Generally, the solid product "B" is washed until the [Ti] is less than about 100 mmol / L. The invention [Ti] represents any species of titanium capable of acting as a second generation Ziegler catalyst, which would comprise titanium species that are not part of the reaction products as described herein. The resulting product "B" is then subjected to a second and third halogenation / titanation step to produce the "C" and "D" products. After each halogenation / titanation step the solid product can be washed until the [Ti] is less than a desired amount. For example, less than about 100 mmol / L, less than about 50 mmol / L, or less than about 100 mmol / L. After the final halogenation / titanation step, the product can be washed until the [Ti] is less, than a desired amount, for example, less than about 20 mmol / L, less than about 10 mmol / L, or less. that approximately 1.0 mmol / L. It is believed that a lower [Ti] can produce improved catalyst results by reducing the amount of titanium that can act as a kind of second generation Ziegler. It is believed that a lower [Ti] can be a factor in the production of improved catalyst results such as a smaller MWD. The second stage of halogenation / titanation is generally carried out by suspending the solid product recovered from the first stage of titanation, the solid product WB ", in a hydrocarbon solvent.The hydrocarbon solvents listed as suitable for the first stage of halogenation / titanation can be used The second and the third stage of halogenation / titanation can use a different compound or combination of compounds of the first stage of halogenation / titanation The second and the third stage of halogenation / titanation can use the same agent a concentration that is stronger than that used in the first halogenation / titanation agent, but this is not a necessity The second and the third halogenation / titanation agent may be a titanium halide, such as tetrachloride titanium (TiCl 4). The halogenation / titanation agent is added to the suspension, the addition can be carried out at room temperature. environment, but it can also be carried out at different temperatures and pressures than the environment. Generally, the second and the third halogenation / titanation agent comprises titanium tetrachloride.

Typically the second and the third stage of halogenation / titanation each one comprises a titanium to magnesium ratio in a range of about 0.1 to 5., a ratio of approximately 2.0 can also be used, and a ratio of approximately 1.0 can be used. The third stage of halogenation / titanation is generally carried out at room temperature and in a suspension, but it can also be carried out at temperatures and pressures different from the ambient ones. The amount of tetrachloride titanium used, or the alternative halogenation / titanation agent, can also be expressed in terms of equivalents, an equivalent herein is the amount of titanium relative to the magnesium or metal compound. The amount of titanium from each of the second and the third halogenation / titanation step will generally be in the range of about 0.1 to about 5.0 equivalents, may be in the range of about 0.25 to about 4 equivalents, typically is in the range of about 0.3 to about 3 equivalents, and it may be desirable to be in the range of about 0.4 to about 2.0 equivalents. In a particular embodiment, the amount of tetrachloride titanium used in each of the second and the third stage of halogenation / titanation is in the range of about 0.45 to about 1.5 equivalents. The catalyst component WD "made by the process described above can be combined with an organometallic catalyst component (a" preactivation agent ") to form a preactivated catalyst system activated for the polymerization of olefins. preactivation which are used together with the catalyst component containing transition metal of WD "are organometallic compounds such as alkyl aluminum, aluminum alkyl hydrides, lithium alkyl aluminum, zinc alkyls, magnesium alkyls and the like. The preactivating agent is generally an organoaluminum compound. The organoaluminum preactivating agent is typically an aluminum alkyl of the formula AIR3 wherein at least one R is an alkyl having 1-8 carbon atoms or a halide, and wherein each of the Rs may be the same or different . The organoaluminum preactivating agent may be a trialkyl aluminum such as, for example, trimethyl aluminum (TMA), triethyl aluminum (TEA1) and triisobutyl aluminum. (TiBAl). The ratio of Al to titanium may be in the range of 0.1: 1 to 2: 1 and typically is 0.25: 1 to 1.2: 1. Optionally, the Ziegler-Natta catalyst can be pre-polymerized. Generally, a prepolymerization process is affected by contacting a small amount of monomer with the catalyst after the catalyst has contacted the co-catalyst. A pre-polymerization process is described in U.S. Patent Nos. 5,106,804; 5,153,158; and 5,594,071, incorporated herein by reference. The catalyst of the present invention can be used in any process for the homopolymerization or copolymerization of any type of o-olefins. For example, the present catalyst may be useful for catalyzing ethylene, propylene, butylene, pentene, hexene, 4-methylpentene and other α-alkenes having at least 2 carbon atoms, and also for mixtures thereof. The copolymers of the above can produce desirable results such as broader MWD and multi-modal distributions such as bimodal and t imodal properties. The catalysts of the present invention can be used for the polymerization of ethylene to produce polyethylene. Various polymerization processes can be employed with the present invention, such as, for example, single and / or multiple spiral processes, batch processes or continuous processes that do not involve a spiral type reactor. An example of a multiple spiral process which the present invention can employ is a double spiral system in which the first spiral produces a polymerization reaction in which the resulting polyolefin has a MW lower than the polyolefin produced from the reaction of polymerizing the second loop, thereby producing a resulting resin having the broad molecular weight distribution and / or bimodal properties. In the alternative, another example of a multiple spiral process which may employ the present invention is a double spiral system in which the first spiral produces a polymerization reaction in which the resultant polyolefin MW larger than the polyolefin produced from the polymerization reaction of the second spiral, in order to thereby produce a resulting resin having broad molecular weight distribution and / or bimodal characteristics. The polymerization process can be, for example, in volume, in suspension phase or gas. A catalyst of the invention can be used in the suspension phase polymerization. The polymerization conditions (e.g., temperature and pressure) are dependent on the type of equipment used in the polymerization process, as well as the type of polymerization process used, and are known in the art. Generally, the temperature will be in a range of approximately 50-110 ° C, and the pressure in a range of approximately 10-800 psi. The activity of the catalyst resulting from the embodiments of the present invention is by. at least partially dependent on the process and the polymerization conditions, such as, for example, the equipment used and the reaction temperature. For example in the ethylene polymerization mode to produce polyethylene, generally the catalyst will have an activity of at least 5,000 g PE / g catalyst but may have an activity higher than 50,000 g PE / g catalyst, and the activity may be greater than 100,000 g PE / g of catalyst. Additionally, the catalyst resulting from the present invention can provide a polymer with improved sponge morphology. Thus, the catalyst of the present invention can provide large polymer particles with a uniform size distribution, wherein the fine particles (less than about 125 microns) are only present in low concentrations, such as for example, less than 2% or less than 1% The catalysts of the present invention, which include easily transferred, large powders with high powder volume densities, are available for polymerization production processes. Generally, the catalysts of the invention provide polymer with smaller fine products and higher bulk densities (B.D.) where the value of B.D. it can be larger than about 0.31 g / cc, can be larger than about 0.33 g / cc, and can even be larger than about 0.35 g / cc. The olefin monomer can be introduced into the polymerization reaction zone in a diluent, which is a non-reactive heat transfer agent which is a liquid under the reaction conditions. Examples of such a diluent are hexane and isobutane. For the copolymerization of ethylene with another alpha-olefin, such as, for example, butene or hexene, the second alpha-olefin may be present at 0.01-20 mole percent and may be present between about 0.02-10 mole percent. Optionally, an electron donor can be added with the halogenation agent, the first halogenation / titanation agent and / or the subsequent halogenation / titanation agent or agents. It may be desirable to have an electron donor used in the second stage of halogenation / titanation. Electron donors for use in the preparation of polyolefin catalysts are well known, and any suitable electron donor can be used in the present invention which will provide a suitable catalyst. Electron donors, also known as Lewis bases, are organic compounds of oxygen, nitrogen, phosphorus or sulfur that can donate a pair of electrons to the catalyst. The electron donor can be a monofunctional or polyfunctional, it can be selected from among the aliphatic or aromatic carboxylic acids and their alkyl esters, the aliphatic or cyclic ethers / ketones, vinyl esters, acrylic derivatives, particularly alkyl acrylates or methacrylates. and silanes. An example of a suitable electron donor is di-n-butyl phthalate. A generic example of a suitable electron donor is an alkylsilylalkoxide of the general formula RSi (OR ') 3, for example, methylsilyltriethoxide [MeSi (OEt3)], where R and R are alkyls with 1-5 carbon atoms and can be the same or different. For the polymerization process, an internal electron donor can be used in the synthesis of the catalyst and an external electron donor or stereoselectivity control agent (SCA) to activate the catalyst in the polymerization. An internal electron donor can be used in the catalyst formation reaction during the stages of halogenation or halogenation / titanation. Compounds suitable as an internal electron donor for preparing conventional, supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, electron donors with N, P and / or S atoms and specific classes of esters. Particularly suitable are esters of phthalic acid, such as diisobutyl, dioctyl, diphenyl and benzylbutylphthalate; esters of malonic acid, such as diisobutyl and diethylmalonate; alkyl and arylpivalates; alkyl, cycloalkyl and arylmaleates; alkyl and aryl carbonates such as diisobutyl, ethylphenyl and diphenylcarbonate; esters of succinic acid, such as mono and diethyl succinate. External donors which can be used in the preparation of a catalyst according to the present invention include organosilane compounds such as alkoxysilanes of the general formula SiRm (OR ') 4_m where R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group; R 'is an alkyl group; and m is 0-3, wherein R can be identical with R '; when m is 0, 1 or 2, the R 'groups may be identical or different; and when m is 2 or 3, the R groups may be identical or different. The external donor of the present invention can be selected from a silane compound of the following formula: OR2. OR3 wherein Ri and R4 are both an alkyl or cycloalkyl group containing a primary, secondary or tertiary carbon atom bonded to silicon, Ri and R4 which are the same or different; R2 and R3 are alkyl or aryl groups. i can be methyl, isopropyl, cyclopentyl, cycloalkyl or t-butyl; R2 and R3 may be methyl, ethyl, propyl or butyl groups and not necessarily the same; and R 4 may also be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl. Specific external donors are cyclohexylmetidimethoxy silane (CMDS), diisopropyldimethoxysilane (DIDS) cyclohexylisopropyl dimethoxysilane (CIDS), dicyclopentyl dimethoxysilane (CPDS) or di-t-butyl dimethoxysilane (DTDS). The polyethylene produced using the catalyst described above may have a MWD of at least 5.0, and may be greater than about 6.0. The polyolefins of the present invention are suitable for use in a variety of applications such as, for example, an extrusion process, to produce a wide range of products. These extrusion processes include, for example, extrusion of film by blowing, extrusion of film by casting, extrusion of divided tape, blow molding, extrusion of tubes and extrusion of foam sheet. These processes may comprise mono-layer extrusion or multi-layer co-extrusion. End-use applications that can be made using the present invention can include, for example, films, fibers, tubes, textile, manufacturing articles, diaper components, feminine hygiene products, automobile components and medical materials.

All references cited herein, including research articles, all US and foreign patents and patent applications, are specifically and completely incorporated by reference. 1PRIMER SET OF EXAMPLES The invention having been generally described, the following examples are provided merely to illustrate certain embodiments of the invention, and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the scope of the specification or claims in any way. The synthetic scheme used for this family of catalysts is as follows (all ratios are related to BEM): (BEM + 0.03 TEAI + 0.6 DIAE) + 2.09 2-Ethylhexanol? Mg (OR) 2 Mg (OR) 2 + ClTi (OPr) 3? Solution A Solution A + (2TiCl4 / Ti (OBu) 4)? Catalyst B (support based on gCl2) Catalyst B + X TiCl ~ > Catalyst C Catalyst C + 0.156 TEAI? Final Catalyst The optimal formulation was considered as X = 0.5 to 2, with zero to two washes before the preactivation of catalyst C with TEAI. The following modifications were made to the preparation of the catalyst for a more effective titanation: Catalyst B + X TiCl4? Catalyst C Catalyst C + Y TiCl, - »Catalyst D Catalyst D + 0.156 ??? 1? Final Catalyst As shown, the TiCl4 addition is completed in two stages where X and Y = 0.5 to 1.0. Catalyst C is usually washed one to two times, while two washes are completed after Y to remove the soluble titanium species that act as second-generation Ziegler species. In the 'nitrogen purge box, 1412.25 g (2.00 mol) of BE -1, 27.60 g (0.060 mol) of TEA1 (24.8% in heptane) and 189.70 g (1.20 mol) of DIAE were added a 3 L round bottom flask. The contents were transferred to the 20 L Buchi reactor via the cannula via a flow of nitrogen. The flask was then rinsed with approximately 400 ml of hexane which was transferred to the reactor. The agitator was adjusted to 350 rpm. The 2-ethylhexanol (543.60 g, 4.21 mol) was added to a 1 L bottle and capped. It was then diluted to a total volume of 1 L with hexane before addition to the reactor. This solution was transferred to the reactor via the cannula using the mass flow cohtroller. The temperature of the initial head was 25.3 ° C and reached a maximum temperature of 29.6 °. After the addition (approximately 2 hours), the bottle was rinsed with 400 ml of hexane that was transferred to the reactor. The reaction mixture was allowed to stir at 350 rpm overnight under a nitrogen pressure of 0.5 bar and the heat exchanger was turned off. The heat exchanger was switched on and adjusted to 25 ° C. The chlorotitanium triisopropoxide was added to two bottles of 1 L (774.99 and 775.01 g, 2.00 moles total) to give a total of two liters. The contents of each bottle were transferred to a reactor via the cannula using the mass flow controller. The temperature of the initial head space was 24.6 ° C and reached a maximum temperature of 25.9 ° C during the addition of the second bottle. The addition times were 145 and 125 minutes for bottles 1 and 2, respectively. After the addition, each bottle was rinsed with 200 ml of hexane which was transferred to the reactor. The reaction mixture was allowed to stir at 350 rpm overnight under a nitrogen pressure 0.5 bar. The heat exchanger went out. Preparation of TiCl / Ti (OBu) 4. Mixtures of titanium tetrachloride / titanium tetrabutoxide were prepared in a 5 liter round bottom flask using standard Schlenk line techniques. In a 1 L pressure bottle, 680.00 g (1.99 moles) of Ti (OBu) was diluted to a total volume of 1 L with hexane. This solution was then transferred with cannula to the reactor. The bottle was rinsed with 200 ml of hexane and transferred to the reactor. In a cylinder measuring 1 L, 440 ml (~ 760 g, 4.00 moles) of TÍCI4 was diluted to a total volume of 1 L with hexane. The solution in the 5-liter flask was stirred and the T1C4 solution was added to the reactor dropwise under N2 pressure via the cannula. After the addition was completed, the 1 L cylinder was rinsed with 200 ml of hexane which was transferred to the reactor. After 1 hour, the reaction mixture was diluted to a total volume of 4 L with hexane and stored in the flask before use. The entire heat exchanger was switched on and adjusted to 25 ° C. The mixture of TIC4 / T1 (OBu) 4 was transferred to the 20 liter reactor via the cannula and the mass flow controller. The initial head space temperature was 24.7 ° C and reached a maximum temperature of 26.0 ° C during the addition of 225 minutes. After the additions, the vessel was rinsed with one liter of hexane and allowed to stir for 1 hour. The agitator was turned off and the 'solution allowed to settle' for 30 minutes. The solution was decanted by pressurizing the reactor at 1 bar, by lowering the dip tube and by making sure that no solid catalyst came through the attached clear plastic hose. The catalyst was then washed three times using the following procedure. Using a pressure vessel on a scale, 2.7 kg of hexane were weighed into the vessel and then transferred to the reactor. The agitator was turned on and the catalyst mixture was stirred for 15 minutes. The agitator was then turned off and the mixture allowed to settle for 30 minutes. This procedure was repeated. After the third addition of hexane, the suspension was allowed to settle overnight and the heat exchanger was turned off. The supernatant was decanted and 2.0 kg of hexane were added to the reactor. The stirring was done at 350 rpm and the heat exchanger was turned on and adjusted to 25 ° C. In a one-liter graduated cylinder, 440 milliliters (760 g, 4.00 moles) of tetrachloride titanium were added. The TiCl4 was diluted to one liter with hexane, and half of the solution was transferred to the reactor via the cannula and the mass flow controller. The initial head temperature at 24.7 ° C increased 0.5 ° C during the addition. The total addition time was 45 minutes. After one hour, the agitator was turned off and the solids were left sitting for 30 minutes. The supernatant was decanted, and the catalyst was washed once with hexane following the procedures described in the above. After he completed the wash2.0 kg of hexane were transferred to the reactor and the stirring was put back on. The second addition of TiCl4 was completed in a manner similar to that described above using the remaining 500 milliliters of solution. After the addition, the cylinder was rinsed with 400 milliliters of hexane, which was added to Buchi. After one hour of reaction, the stirrer was turned off and the solids allowed to settle for 30 minutes. The supernatant was then decanted, and the catalyst was washed three times with hexane. 2.0 kg of hexane was then transferred to the reactor. In a one liter pressure bottle, 144.8 g (312 mmol) of TEA1 (25.2% in hexane) were added. The bottle was capped and diluted to one liter with hexane. This solution was then transferred to the reaction mixture via the cannula using the mass flow controller. During the 120 minute addition, the color of the suspension turned dark brown. The temperature of the initial head was 24.5 ° C and reached a maximum temperature of 25.3 ° C. After the addition, the bottle was rinsed with 400 milliliters of hexane, which was transferred to the reactor. After 1 hour of reaction, the stirrer was switched off and the catalyst was left sitting for 30 minutes. The supernatant was decanted and the catalyst was washed once following the previously described procedures. After washing, 2.7 kg of hexane was added to the reactor. The contents were then transferred to a three-gallon pressure vessel. The Buchi was rinsed with 1.0 kg and 0.5 kg of hexane, which were added to the pressure vessel. The estimated catalyst yield was 322 g. In one embodiment, the composition in percent by weight was: Cl 53.4%; At 2.3%; Mg 11.8% and Ti at 7.9%. The intervals observed for each element were; Cl at 48.6-55.1%; At 2.3-2.5%; Mg at 11.8-14.1%; and Ti of 6: 9-8.7%. The intervals for each element can be; Cl at 40.0-65.0%; At 0.0-6.0%; Mg at 6.0-15.0%; and Ti of 2.0-14.0%. Table 1 lists the [Ti] measured from the samples after the addition of TiCl4 / Ti (OBu), three washes, a first addition of TiCl4, one wash and second addition of TiCl4 and three subsequent washes. The decantations 1-4 are after the addition of TiCl4 / Ti (OBu) 4. The decantations 5 and 6 are after the addition of TiCl4. Decanting 7-10 'after the second addition of TiCl4. Table 1 Sample Decanted Ti (ppm) mmol / L .1 2.1 21000 306.9 2 0.8 8000 116.9 3 0.2 2000 29.2 0.1 1000 14.6 5 2 2000 292.3 6 '0.4 4000 58.5 n 1.9 19000 277.7 8 0.4 4000 58.5 9 0.0925 925 13.5 10 0.0064 64 0.9 Comparative Example 1: Comparative Example 1 was prepared in a manner similar to that of Example 1 except that the third titanation was omitted and the second titanation was carried out using a quarter of the amount of TÍCI4. Comparative Example 2: Comparative Example 2 was prepared in a manner similar to Example 1 except that a second and a third titanation step was performed using 0.5 equivalents of TÍCI4 during each titanation step. Comparative Example 3: Comparative Example 3 was prepared in a manner similar to Comparative Example 1 except that the amount of TÍCI4 used during the second titanation was approximately four times that used during Comparative Example 1. A hexane wash was performed after the second titanation. In one embodiment, the composition in percent weight was: Cl at 57.0%; At 2.0%; Mg at 9.5% and Ti at 10.0%. The intervals for each element can be; Cl at 55.0-57.0%; At 2.0-2.6%; Mg at 8.9-9.5%; and You from 10.0-11.0%. Comparative Example 4: Comparative Example 4 was prepared in a manner similar to Comparative Example 3 except that two hexane washings were performed after the second titanation. In one embodiment, the composition in percent by weight was: CI 53.0%; At 2.3%; Mg 9.7% and Ti at 9.5%. The intervals for each element can be; Cl at 52.6-53.0%; At 2.0-2.3%; Mg at 9.7-10.6%; and Ti of 8.7-9.5%. Table 2 lists the prepared catalysts. Table 2 Table 3 provides the MWD data provided for polymers made with Example 1 and Comparative Examples 4. For a given catalyst / cocatalyst system, the data shows that a smaller MWD can be achieved by increasing the number of washes or the addition of a third titration step with TiCl4. In general, intrinsic MWD of the polymer resin is increased in the following order. Comparative Example 1 < Comparative Example 2 < Comparative Example 4 < Example 1 < Comparative Example 3. Table 3 Catalyst Cocatalyst Number Number SR5 D of (HLMI / MI5) (/ Mn) Washes Afterwards after X of Y Example TEA1 0 0 10.9 6.2 Comparative 1 Example TEAl 1 2 10.9 NA Comparative 2 Example TEAl 1 2 12.6 6.8 Example TEAl 1 NA 11.8-12.8 5.9-6.8 Comparative 3 Example TEAl 2 NA 10.8-12.0 6.0-6.3 Comparative 4 Example 1 TIBA1 1 2 11.9 7.0 Example TIBA1 1 NA 12.2-13.6 6.9-7.3 Comparative 3 Example TIBA1 2 NA 11.4-11.8 6.6-7.5 Comparative 4 As shown in Table 4, each of the catalysts provides powder with low levels of fine products (particularly lower than 125 microns); however, catalysts of the invention prepared with two titanation steps consistently provide fluffiness with higher bulk densities. Table 4 Catalyst D50 Sponge% of Fines B.D. (micras) Dso (g / cc) (micras) Comparative Example 1 9.4 260 0.0 0.38 Comparative Example 2 7.8 237 0.6 0.40 Comparative Example 4 10.1 287 1.6 0.34 Example 1 9.2 264 0.6 0.38 These properties have substantial effects on the settling efficiency of the polymer as evidenced by the laboratory derived settlement efficiency curves given in Figure 1. The rapid disappearance of the initial 10 ml of fluffiness from the solution exhibiting by the inventive polymer made with the inventive catalyst of Example 1 involves a larger settlement ratio and better polymer morphology than that made with the conventional catalyst of Comparative Example 4. Viscosity Control of the Synthesis Solution It has been found that varying the viscosity of a solution during the synthesis of the catalyst, the precipitation of the catalyst component of the solution can be altered. This alteration of the precipitation of the catalyst component has been found to affect the resulting particle size of the catalyst and the polymer produced using the catalyst. The solution viscosity of the catalyst synthesis can be altered depending on the relative amount of aluminum alkyl present. Therefore, the particle size of the catalyst and the polymer produced from the catalyst can be altered depending on the relative amount of aluminum alkyl used. The catalysts were prepared with varying amounts of aluminum alkyl in the synthesis solution and tested together with the resulting sponge polymer produced from the catalysts. Example 2 describes the synthesis used in the preparation of the catalyst and Table 5 shows the resulting catalyst and polymer sizes. Example 2: The synthesis used is as follows with all the relations in relation to BEM: 1. (BEM + X TEAI + 0.6 DIAE) + (2 + 3X) 2-ethylhexanol? Mg (? -2-ethex) 2 · [Al (? -2-ethex) 3J 2. Mg (0-2-ethex) 2 »[Al (? -2-ethex) 3] + ClTi (OPr) x? "A" 3. "A" + 2TiCl4 / Ti (Obu) 4? ?? "(support based on MgCl2) 4. ???" + And TiCl? "C"; 5. "C" + Z TiCl4? "D" 7. "D" + 0.156 TEAI? Catalyst Four catalysts were prepared in a one liter Buchi reactor according to this general synthesis with = = = = 1. The amounts of tEAl were changed in the first reaction to study the resulting effect on the particle size of the catalyst. The relative amount of 2-ethylhexanol was adjusted during each catalyst synthesis to prevent reduction of the titanium complexes by any of the unreacted aluminum or magnesium alkyl species. The following table lists the synthesized catalysts, the relative amounts of BEM, TEAl and 2-ethylhexanol employed, the average particle size for the catalysts and the average particle size of the polyethylene resin produced using each catalyst. The following table provides the · particle size distribution data that was obtained for each catalyst. As shown, the average particle size distribution increases with increased TEAl levels. Table 5 CataliTEAl 2- BEM: TEAl Catalyst Polymeric zador ethylhexanol spongy polymer EquivaEquivaEquivarelación Dso D50 lenses lens lenses (micras) (micras) 101 1.0 0.03 2.09 1.0: 0.03 13.0 399 102 1.0 0.3 2.9 1.0: 0.3 16.1 420 103 1.0 0.5 3.5 1.0: 0.5 18.3 418 104 1.0 1.0 5.0 1.0: 1.0 21.7 504 As shown in Table 5, the average particle size of both the catalyst and the resulting fluffiness increase with increased TEA1 levels used in the initial solutions of catalyst synthesis. By varying the relative amount of aluminum alkyl, the viscosity of the catalyst synthesis solution can be altered. The variation of the solution viscosity can thus alter the precipitation properties of the catalyst component from the solution, which can affect the average particle size resulting from the catalyst component and the resulting polymer produced from this catalyst. It is observed that the average particle size of the catalyst component increases with an increased concentration of aluminum alkyl in the synthesis solution. It is also noted that the average particle size of the resulting polymer resin produced by the catalyst is increased with an increased concentration of aluminum alkyl in the synthesis solution. The amount of aluminum alkyl can be measured in terms of the ratio of alkyl aluminum to alkyl magnesium, which can vary from about 0.01: 1 to about 10: 1. The polyethylene produced using the catalyst described above may have a MWD of at least 4.0, and may be greater than about 6.0. The 'catalyst 101 in Table 5 is the same as in Example 1 as described in the above. In one embodiment, the composition in percent by weight was: CI 53.4%; At 2.3%; Mg 11.8% and - Ti at 7.9%. The intervals for each element can be: Cl at 40.0-65.0%; At 0.0-6.0%; Mg at 6.0-15.0%; and Ti of 2.0-14.0%. Catalyst 102 in Table 5 had, in one embodiment: Cl 47.0%; At 3.4%; Mg 13.1% and Ti at 4.0%. The intervals for each element can be: Cl at 40.0-65.0%; At 0.0-6.0%; Mg at 6.0-15.0%; and Ti of 2.0-14.0%. Catalyst 103 in Table 5 had, in one embodiment: Cl 50.0%; At 2.4%; Mg 12.1% and Ti at 3.9%. The intervals for each element can be: Cl at 40.0-65.0%; At 0.0-6.0%; Mg at 6.0-15.0%; and Ti of 2.0-14.0%. Catalyst 104 in Table 5 had, in one embodiment: Cl 53.0%; At 3.1%; Mg 12.8% y. Ti at 4.2%. The intervals for each element can be: Cl at 40.0-65.0%; At 0.0-6.0%; Mg at 6.0-15.0%; and Ti of 2.0-14.0%. The polyolefins of the present invention are suitable for use in a variety of applications such as, for example, an extrusion process, to produce a wide range of products. These extrusion processes include, for example, extrusion of film by blowing, extrusion of film by casting, extrusion of divided tape, blow molding, extrusion of tubes and extrusion of foam sheet. These processes may comprise mono-layer extrusion or multi-layer co-extrusion. End-use applications that can be made using the present invention can include, for example, films, fibers, tubes, textile, manufacturing articles, diaper components, feminine hygiene products, automotive components and medical materials. According to an alternative embodiment of the invention, a polyolefin polymerization catalyst is formed using a process comprising several reactions. First, an alkyl magnesium compound (ie, Mg (R *) 2 / where R * can be the same or different alkyl group having about 1 to 20 carbon atoms), such as BEM, is reacted with an alcohol to form a magnesium alkoxide compound according to the following reaction: BEM + 2 ROH - > Mg (0R) 2 where R is an alkyl group containing, for example, about 1 to 20 carbon atoms. The alcohol represented by the formula ROH can be branched or unbranched. An example of a suitable alcohol 2-ethylhexanol. Any of the suitable reaction conditions and the addition sequence for converting the BEM and the alcohol reagents to a magnesium alkoxide compound can be used. In a modality, the alcohol is added to a BEM solution to form a reaction mixture, which is maintained at ambient temperature and pressure. The reaction mixture is stirred for a sufficient period of time to form the soluble magnesium alkoxide compound. The resulting magnesium alkoxide compound is mixed with a moderate chlorinating agent to form a magnesium-titanium alkoxide adduct according to the following equation: Mg (0R) 2 + TiCln (OR ') 4-n? [Ti (OR ') 4-nCln »Mg (OR) 2] m where R' is an alkyl, cycloalkyl or aryl group, n is from 1 to 3, and m is at least 1, and may be greater than 1. Desirably, n is 1. Reagents include TiCln (OR ') 4-n where R' = alkyl or aryl and n is 1, and alternatively Ti (01Pr) 3Cl, where i ~ Pr represents isopropyl. Any of the suitable conditions for forming the magnesium-titanium alkoxide adduct can be employed for this process. In one embodiment, the process is carried out at ambient temperature and pressure. The reagents are mixed for a sufficient period of time to form the magnesium-titanium alkoxide adduct. It is believed that the adduct is formed because the magnesium-titanium alkoxide compound is spherically hindered, making it difficult for the chloride atoms of the titanium compound to metastasize with the magnesium alkoxide ligands. In essence, the adduct is almost but not completely converted to MgCl2. Accordingly, the magnesium-titanium alkoxide adduct is mixed with an alkylchloride compound such that it is converted to a MgCl 2 support. The reaction proceeds as follows: [Ti (OR ') 4-nCl "Mg (OR) 2] m + R" C1? TiMgCl2"+ R" OR where R "is an alkyl group containing, for example, about 2 to 18 carbon atoms and where "TiMgCla" represents the MgCl2 support impregnated with titanium. While R "may be branched or unbranched, it may be desirable in some embodiments to have" unbranched "R. Possible alkylchloride compounds include benzoyl chloride, chloromethyl ethyl ether and t-butyl chloride, with benzoyl chloride which is desirable in particular embodiments. The amount of alkylchloride added to the magnesium alkoxide adduct may be in excess of that required for the reaction. The ratio of the amount of benzoyl chloride to the amount of Mg (e.g., BEM) in the reaction mixture can vary from about 1 to 20 (i.e., from a ratio of about 1: 1 to the ratio of about 20). 1) or from about 1 to 10, and it may be desirable to vary from about 4 to 8. The reaction can be carried out in any of the conditions suitable for precipitating the magnesium chloride support. In one embodiment, the reagents are heated to reflux for a sufficient period of time to precipitate the MgCl2 support. In embodiments employing t-butylchloride, the reagents can be heated during reflux. In embodiments employing benzoyl chloride or chloromethyl ethyl ether, the reagents may be at room temperature during reflux. One or more byproducts such as an ether (shown in the above reaction) are also produced by the reaction. It is believed that the presence of Ti during the precipitation of MgCl2 plays a major role in producing a highly active catalyst. After separation of the MgCl 2 support from the reaction mixture, the support can be washed with, for example, hexane, to remove any of the contaminants therefrom. The MgCl2 support is then treated with TiCl4 to form a catalyst suspension according to the following equation: "TiMgCl2" + 2 TÍCI4 - »catalyst This treatment can be carried out in any of the suitable conditions, for example at ambient temperature and pressure, to form a · catalyst suspension. The catalyst suspension is washed with, for example, hexane, and then dried. The resulting catalyst can be pre-activated using an aluminum alkyl compound, such as triethylaluminum (TEAL), to prevent the catalyst from corrosion of the polymerization reactor. More specifically, the titanium chlorides in the catalyst are converted to titanium alkyls when reacted with an alkyl aluminum compound. Otherwise, the titanium chlorides could be converted to HCl when exposed to moisture, resulting in corrosion of the polymerization reactor. SECOND SET OF EXAMPLES The invention having been described in general, the following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims that follow in any way. Unless otherwise mentioned, all experimental examples were conducted under an inert atmosphere using standard Schlenk techniques. Various catalysts (C-M samples) were prepared according to the process of the present invention. In addition, two types of conventional catalysts referred to as sample? and sample B were prepared, where sample B was prepared according to US Patent No. 5,563,225, for comparison with the other catalyst samples. Many of the compounds required for the examples, ie, 2-ethylhexanol, benzoyl chloride, n-butyl chloride, t-butyl chloride, chloromethyl ethyl ether, ClTi (OiPr) 3 and TiCl 4 / were purchased from Aldrich Chemical Company and They were used as received. A heptane solution containing 15.6% by weight of BEM and 0.04% by weight of Al was purchased from Akzo Nobel. The particle size distribution of the catalyst, including the average particle size D5o, for all catalyst samples was determined using a Malvern Mastersizer, and all particle size distribution values given herein were calculated on a basis of average in volume. Hexane was purchased from Phillips and passed through a 3A molecular sieve column, an F200 alumina column and a column filled with BASF copper catalyst R3-11 at a rate of 12 mL / min. for purification. An Autoclave Engineer reactor was used for the polymerization of ethylene in the presence of each of the catalyst samples. This reactor has a capacity of four liters and was adjusted with four mixing diverters having two opposing spacing thrusters. Ethylene and hydrogen were introduced into the reactor while maintaining the reaction pressure using a counter-pressure regulator charged in the dome, and the reaction temperature using steam and cold water. Hexane was introduced to the reactor as a diluent. Unless indicated otherwise, the polymerization was carried out under the conditions set forth in Table 3A. The mass-based spongy particle size distribution for the resulting polyethylene was obtained by screened analysis using a CSC Scientific Sieve Shaker. The percentage of fine products is defined as the percentage of the weight of spongy particles smaller than 125 microns. COMPARATIVE EXAMPLE 1A Sample A of comparative catalyst was prepared by charging a one liter reactor with the heptane solution containing 15.6% by weight of BEM (70.83 g, 100 mmol). Then, 26.45 g (203 mmol) of 2-ethylhexanol was added slowly to the solution containing BEM. The reaction mixture was stirred for one hour at room temperature. Then, 77.50 g (100 mmol) of 1.0 M hexane solution of ClTi (0iPr) 3 were slowly added to the above mixture. The reaction mixture was stirred for one hour at room temperature to form an adduct [Mg (0-2-ethylhexyl) 2C1TÍ (OiPr) 3] · Then, the hexane solution (250 ml) of a mixture of TNBT (34.04 g , 100 mol) and TiCl 4 (37.84 g, 200 mmol) was added to the resulting solution. The reaction mixture was stirred for one hour at room temperature to form a white precipitate. The precipitate was allowed to settle, and the supernatant was decanted. The precipitate was washed three times with approximately 200 ml of hexane. The solid was re-suspended in approximately 150 ml of hexane and 50 ml of a hexane solution containing TiCl 4 (18.97 g, 100 mmol) was added. The suspension was allowed to stir for one hour at room temperature. The solid was allowed to settle, and the supernatant was decanted. The solid was washed once with 200 ml of hexane. Approximately 150 ml of hexane were then added to the precipitate. The catalyst was treated again with 50 ml of a hexane solution containing TÍCI4 (18.97 g, 100 mmol). The suspension was stirred for one hour at room temperature. The solid was allowed to settle, the supernatant was decanted. The catalyst was washed twice with 200 ml of hexane. Approximately 150 ml of hexane was then added to the precipitate. The final catalyst was obtained by reaction with 7.16 g (15.6 mmol) of 25% by weight heptane solution of TEAL for one hour at room temperature. COMPARATIVE EXAMPLE 2? Sample B of comparative catalyst was prepared by introducing 330 ml of 15% by weight dibutylmagnesium heptane solution, 13.3 ml of 20% by weight tetraisobutylaluminoxane pentane solution, 3 ml of diisoamyl ether and 153 ml of hexane to a one liter flask. The mixture was stirred for 10 hours at 50 ° C. Then, 0.2 ml of TiCl4 and the mixture of t-butylchloride (96.4 ml) and DIAE (27.7 ml) were added. The mixture was stirred at 50 ° C for 3 hours. The precipitate settled and the supernatant was decanted. The solid was washed three times with hexane (100 ml) at room temperature. The solid was resuspended in 100 ml of hexane. Anhydrous HC1 was introduced into the reaction mixture for 20 minutes. The solid was filtered and washed with 100 ml of hexane twice. The solid was suspended again in hexane. 50 ml of TÍCI4 was added to the suspension and the mixture was stirred for two hours at 80 ° C. The supernatant was decanted and the catalyst was washed with 100 ml of hexane ten times. The catalyst was dried at 50 ° C under N2 flow. EXAMPLE 1A Sample C of catalyst was prepared according to the present invention as follows: a 250 ml round bottom flask, three neck equipped with an addition funnel, a septum and a condenser was charged with. the heptane solution containing 15.6% by weight of BEM (17.71 g, 25 mmol). Then, 6.61 g (51 mmol) of 2-ethyl hexanol was added slowly to the solution containing BEM, and the reaction mixture was stirred for one hour at room temperature. To this solution, 19.38 g (25 mmol) of 01 (¾) 3 (1 M in hexanes) were added. The reaction mixture was stirred for one hour at room temperature to form an adduct [Mg (? -2-ethylhexyl) 2CITi (01Pr) 3]. Then, 18.51 g (200 mmol) of t-butyl chloride were added to the resulting solution such that the molar ratio of t-butyl chloride to BEM was about 8: 1.

The reaction mixture was heated for 24 hours at reflux temperature, i.e., about 80 ° C, to form a MgCl 2 precipitate (i.e., securing the catalyst support). The white precipitate was allowed to settle and the yellowish supernatant was decanted. The precipitate was washed three times with approximately 100 ml of hexane. Approximately 100 ml of hexane were then added to the precipitate, followed by the slow addition of TiCl 4 (9485 g, 50 mmol) to the resulting solution. The suspension was stirred for one hour at room temperature. The solid was allowed to settle, and the supernatant was decanted. The catalyst was washed four times with 50 ml of hexane. EXAMPLE 2A The procedure of Example 1A was followed to form catalyst sample D, except that the reaction ratio was accelerated by adding a higher amount of t-butyl chloride to the flask. In particular, 37.02 g (400 mmol) of t-butyl chloride were added to the solution in the flask, and the solution was heated at 55 ° C for twenty-four hours. The solution therefore contained a molar ratio of t-butyl chloride / BEM of about 16: 1 (16 equivalents to BEM). As expected, an increase in the yield was observed for Example 2A as compared to Example 1A. Table 1A below provides the compositions of the catalysts formed in Comparative Examples 1A and 2A and Examples and 1A and 2A. TABLE 1A The amounts of Mg and Cl in samples C and D were similar to those in sample A. The amounts of Ti in samples C and D were between the amount of Ti in samples A and B. For Examples 1A and 2A, the byproduct of the reaction of Ti (01Pr) 3ClMg (OR) 2] n with. T-butyl chloride was examined by proton nuclear magnetic resonance (1H NMR) and gas chromatography mass spectrometry analysis (GCMS). The main by-product was found to be 2-ethyl hexanol before the expected t-butyl 2-ethylhexyl ether or t-butyl-2-isopropyl ether. Based on this result, it is postulated that some reduction reaction could occur in the mixture, possibly forming isobutene that is removed from the reaction. FIG. 1A illustrates the particle size distributions of samples A-D. Both of the catalysts of sample A and B have reduced particle distributions. The average particle size of the catalyst in sample B is slightly larger than that in sample A. Catalyst samples C and D prepared with t-butyl chloride have a broader bimodal distribution. EXAMPLE 3A The procedure of Example 1A was followed except that a primary chloride, n-butyl chloride, was added to the flask in place of t-butyl chloride to form a solution having a mole ratio of n-butyl chloride / BEM of approximately 16: 1 (16 equivalents to BEM). Unfortunately, n-butyl chloride was not able to precipitate [Ti (01Pr) 3 ClMg (0) 2] n after heating for 24 hours at 50 ° C. It is postulated that this observation suggests that the mechanism of chlorination involves a stage of dissociative elimination (El) that requires a stable carbocation species. EXAMPLE 4A Sample K of catalyst was prepared as follows: A 500 ml, three-necked round bottom flask equipped with an addition funnel, septum and condenser was charged with a heptane solution containing 15.6% by weight of BEM (8.85 g, 12.5 mmol) and 100 mL of hexane. Then, 3.31 g (25 mmol) of 2-ethylhexanol were added slowly to the solution containing BEM, and the reaction mixture was stirred for one hour at room temperature. Then 9.69 g (12.5 mmol) of CITi (0iPr) 3 se. slowly added to the above mixture, and the reaction mixture was stirred for one hour at room temperature. Then, 17. G g (125 mmol) of benzoyl chloride (PhCOCl) was added to the solution such that the molar ratio of PhCOCl to BEM was about 10: 1 (10 equivalents to BEM). The reaction mixture was stirred for two hours at room temperature to form a precipitate of MgCl2. The white precipitate was allowed to settle, and the supernatant was decanted. The precipitate was washed with 100 ml of hexane for three times. Then, 100 ml of hexane was added to the precipitate, and TiCl 4 (4.25 g, 25 mmol) was then slowly added to the solution. The resulting suspension was stirred for one hour at room temperature. The yellowish solid was allowed to settle, and the yellow supernatant was decanted. The catalyst was washed three times with 50 ml of hexane. Notably, the reaction to form the MgCl 2 support from PhCOCl did not require heating as did the reaction with t-butyl chloride. Also, as shown in FIG. 3, the particle size distribution of catalyst sample K formed using PhCOCl was compared to the particle size distributions of catalyst samples A and B. EXAMPLES 5A-10A The procedure of Example 4A was followed to prepare six more samples (samples E-J), except that the amount of PhCOCl was varied each time such that the molar equivalence to BEM varied to 1.2 to 7.2. FIG. 4 shows the performance of the catalyst as an amount of PhCOCl used in Examples 4A-10A. The catalyst performance first increased as the PhCOCl concentration increased and then became constant at an equivalent of about 7.0, achieving a maximum yield of 1.7 g. Table 2A below provides the compositions of the catalysts formed in Examples 4A-10A. TABLE 2A Sample of Equiv. of Ti Al Mg Cl Catalyst PhCOCl (% in (en {% In (% by weight) weight) weight) weight E 1.2 5.0. < 0.2 13.02 51.34 F 2.4 3.8 < 0.2 12.55 47.55 G 3.6 3.1 < 0.2 12.47 40.24 'H 4.8 2.7 < 0.2 12.48 41.07 I 6.0 2.6 < 0.2 • 12.39 - 43.02 J 7.2 2.6 < 0.2 10.87 43.03 K 10 2.6 < 0.2 11.30 42.35 A - 6.8 2.7 11.92 51.71 . B - 2.3 - 22.8 66.7 As shown in TABLE 2, the titanium content decreased with the PhCOCl concentration increased to 6.0 equivalents and remained constant at higher equivalents. The Ti content of the H-K samples of the catalyst was similar to that of the catalyst sample B and less than that of the catalyst sample A. A possible explanation for this decrease in the amount of titanium may involve the unreacted benzoyl ñata product or PhCOCl. The analyzes of MR- and GCMS confirmed that the byproducts greater than the | clpration ratio are benzoate 2-ethylhexyl and isopropyl benzoate. These esters and unreacted PhCOCl, all Lewis bases, are capable of forming complexes with electron deficient titanium or magnesium. It is believed that the formation of such a complex would allow more extraction of titanium from the support. It is also believed that a complex of MgCl2 support would prevent the epitaxial placement of TiCl4 in the subsequent titanation. It is interesting that the level of titanium becomes constant above seven equivalents of PhCOCl. This value corresponds to the chlorination of all ClTi (01Pr) 3 and Mg (OR) 2-Above this amount of PhCOCl, the amount of esters is also constant, suggesting that the esters play an important role in determining the amount of titanium in the final catalyst. The particle size distribution of sample E-H and catalyst I-K, which formed using different concentrations of PhCOClm is illustrated in Figs. 5 and 6 respectively. Sample E, which was formed from the lowest concentration of PhCOCl (1.2 equivalents to BEM), exhibited a broad bimodal distribution. The increase in PhCOCl levels produced a catalyst with smaller unimodal distributions and thus improved the morphology of the catalyst. In addition, as shown in FIG. 7, the average particle size (D50) decreases slightly with the increased PhCOCl concentration. It is postulated that both the PhCOCl and the ester products are capable of complexing with the unsaturated magnesium sites in the development of MgCl2 support. As described above, these Lewis bases could help in the extraction of titanium from of the support in development. As such, it is believed that the dynamics of support formation would be altered by the absence of the titanium complex. EXAMPLE HA Sample L of the catalyst was prepared as follows: A three-neck 250 mL round bottom flask equipped with an addition funnel, a septum and a condenser was charged with a heptane solution containing 15.6% by weight of BEM (4.43 g, 6.25 mmol) and with 30 mL of hexane. (30 mL). Then, 1.66 g (12.5 mmol) of 2-ethyl hexanol were added slowly to the solution containing BEM, and the reaction mixture was stirred for one hour at room temperature. Then, a solution of CITi) (01Pr) 3 (1M hexanes, 4.85 g, 6.25 mmol) was added slowly to the above mixture, and the reaction mixture was stirred for one hour at room temperature. A solution of hexane (25 mL) containing chloromethyl ethyl ester (CMEE) (9.45 g, 100 mmol) was then added to the solution such that the molar ratio of CMEE to BEM was approximately 8: 1 (8 equivalents to BEM) ). The reaction mixture was stirred for one hour at room temperature, resulting in the formation of a MgCl 2 precipitate. The white precipitate was allowed to settle and the supernatant was decanted. The precipitate was washed three times with 50 mL of hexane. Then 30 mL of hexane were added to the precipitate, followed by the slow addition of a solution of hexane (30 mL) of TiCl 4 (2.13 g, 125 mmol) to the sol. The resulting suspension was stirred for one hour at room temperature. The yellowish solid was allowed to settle, and the yellow supernatant was decanted. The catalyst was subsequently washed with 50 mL of <; hexane for three times. FIG. 9 represents the particle size distributions of sample L of catalyst based on CMEE, sample K of catalyst based on PhCOCl and samples A and B of catalyst. The CMEE-based catalyst sample has a slightly larger particle size distribution than sample A, sample B and catalyst sample K based on PhCOCl. The particle size distribution of the CMEE-based catalyst has a bump of about 7 microns. COMPARATIVE EXAMPLE 3A Ethylene was polymerized in the presence of sample A of catalyst and a co-catalyst of TEAL under the conditions set forth in Table 3A. COMPARATIVE EXAMPLE 4A Ethylene was polymerized in the presence of sample B of catalyst and a co-catalyst of TEAL under the conditions set forth in Table 3A. COMPARATIVE EXAMPLE 12A Ethylene was polymerized using sample C and D of catalyst prepared with t-butyl chloride under the conditions set forth in Table 3A. FIG. 9 illustrates the flux particle size distributions of the polymers prepared in Example 12A and Comparative Examples 3A and 4A. The particle size distributions obtained using catalyst samples C and D are very broad. In contrast, the distributions obtained from catalyst samples A and B are relatively small. The spongy material made from samples C and D contained more fine products than the spongy material made from samples A and B. The spongy material made from samples C and D also had a relatively low volume density. TABLE 3A Table 4A below provides the properties of the polymer resins produced using catalyst samples A, B, C, and D. TABLE 4A The magnesium-based activity of each catalyst sample was determined by first dissolving the catalyst and the polymer formed therefrom in acid to extract the remaining Mg. The activity of the catalyst was determined based on the residual Mg content. As shown in Table 4A, the Mg-based activity of sample C of catalyst was slightly lower than that of sample A of catalyst and higher than that of sample B of catalyst. The activity of sample D of catalyst was higher than the activities of samples A and B of catalyst. The shear responses of the polymers produced using the catalyst samples were calculated by finding the ratio of the high load melt index (HLMI) to the melt index. The shear responses of the polymers produced from catalyst samples C and D were similar to the shear response of the sample B polymer but slightly less than the shear responses of the sample A polymer. The wax produced was comparable for all polymers. EXAMPLE 13A Ethylene was polymerized using catalyst E-K samples prepared using benzoyl chloride under the conditions set forth in Table 3A. FIG. 10A illustrates the fluffy particle size distributions of the polymers prepared in this example (G-K samples). The average particle sizes (D50) of the PhPOCl-based resins were large compared to those of the resins of sample A and sample B.

Table 5A immediately compares the morphologies of the PhPOCl catalyst samples with the morphologies of the polymers formed using the PhPOCl catalyst samples. TABLE 5A Based on the theory of replication, the morphology of the polymer can be related to the morphology of the catalyst. However, the morphology of the polymer does not appear to correspond (ie, are not proportional) to the morphology of the catalyst for F-K samples, considering that such are presented to correspond to samples A and B.

Table 6A below provides the properties of the polymers produced using the PhPOCl catalyst samples (E-K samples) and catalyst samples A and B. TABLE 6A The Mg-based activities of the EK samples are higher than the activities of samples A and B. The activity generally decreased as the PhCOCl equivalents increased with the exception of the K sample, which had an equivalence of 10. The densities of the polymers of the EK sample were similar to those of the polymers of samples A and B. The rates of melt flow (ie, melt indexes) of the polymers of the EK samples and the polymer of the sample? were higher than those of the polymer of sample B. The shear responses of the polymers of the EK samples were similar to those of the polymer of sample B but slightly less than those of the polymer of sample A. The amount of The wax produced was comparable for all polymers. EXAMPLE 14A As previously described, catalyst sample I based on PhCOCl (later referred to herein as "sample?") Was prepared by washing the precipitate of MgCl 2 with hexane. This example compares the catalyst sample Ii with another catalyst sample I2 which was prepared in the same manner as the sample Ii minus the washing step. It is believed that the elimination of the washing step could provide significant reduction of time and cost in the production of the catalyst. Table 7A below shows the catalyst compositions of samples Ii and I2. TABLE 7A Washer Catalyst Equiv. of Ti To MG Cl PhCOCl (% in (% in (in (¾ weight) weight) weight) weight) Ii Si 6 2.6 <; 0.2 12.39 43.02 I2 No 6 1.8 < 0.2 11.78 38.21 The elimination of the washing step gave approximately a 30% reduction in the titanium level. The sample ?? of washed catalyst appeared light yellow. A yellow color was also evident in the sample I2 of unwashed catalyst during the addition of TÍCI4. However, as the TiCl4 made contact with the mother liquor, it immediately became colorless. It is postulated that the ester complex with TiCl can produce the yellow color while PhCOCl can react with the TÍCI4 to form a colorless compound. This observation supports the previous discussion of the dependence of the titanium level on the amount of PhCOCl. It is believed that the excess PhCOCl and ester, if not removed, will form a complex with both TiCl2 and the support surface, preventing the deposition of titanium on the support surface. As shown in FIG. 11, the particle size distributions of samples II and 12 were almost identical. Therefore, the particle size distribution of the catalyst was not affected by the washing step. This observation is not surprising, since the washing step was carried out after the formation of the MgCl2 support. Both samples Ii and I2 were used to polymerize ethylene. Table 8A below provides the catalyst and polymer morphologies for samples Ii and I2. TABLE 8A Table 8A further supports the conclusion that particle size distribution is not affected by the washing step. The number of fine products formed in the polymer increased significantly when the washing step was eliminated. This increase in fine products could be due to lower productivity. The properties of the polymers formed using catalyst samples Ii and I2 are shown in Table 9A below. TABLE 9A Activity Stage Density Density Index IND SR2 SR5 Wash Wax Based on de of (HLMI / (HLMI / (%) Mg Volume Resin Fusion Fusion MI2) MI5) (g / cc) (g / cc) 2.16 kg 5.0 kg (dg / min) (dg / min) Yes 26000 0.23 0.9626 2.90 10.89 37.7 10.0 0.2 No. 14800 0.29 0.9557 0.48 1.36 24.8 8.8 0.1 As depicted in Table 9A, the polymerization activity of the unwashed catalyst was almost half that of the washed catalyst. The densities of the two polymers were almost the same. The shear response data, however, indicates that the unwashed catalyst had a lower molecular weight distribution than the washed catalyst. It is believed that the presence of the PhCOCl and ester in the catalyst affects the distribution of the active site in the catalyst. EXAMPLE 15A The effect of the concentration of BEM on the properties of the catalyst was also studied. A first catalyst sample based on PhCOCl (sample L) was prepared using a BEM solution diluted with 100 ml of hexane. For comparison purposes, a second catalyst sample based on PhCOCl (sample M) was prepared using a solution of BEM diluted with 20 ml of hexane. FIG. 12 shows the particle size distributions of the catalyst from samples L and M of catalyst. The distributions of both catalysts are very similar. The compositions and properties of the samples L and M of the catalyst and the polymers made therefrom are presented in Table 10A and 11A, respectively. TABLE 10A Ti Performance Sample At Mg Cl Catalyst (g) (% by weight) (% by weight) (% by weight) (% by weight) L 0.86 3.5 < 0.2 12.34 43.23 M 0.81 3.8 < 0.2 12.55 47.55. TABLE HA Tables 10A and 11A show that there is no essential effect of the concentration of BEM on the catalyst composition and the properties of the polymer. In conclusion, new catalysts were synthesized using alkylchlorides such as n-butyl chloride, t-butyl chloride and chloromethyl ethyl ether. Benzoyl chloride and chloromethyl ethyl ether formed catalysts with satisfactory particle size distributions while t-butyl chloride resulted in a bimodal distribution and n-butyl chloride failed to form MgCl 2. The catalyst preparation was optimized to vary the amount of benzoyl chloride added to the magnesium alkoxide adduct. As expected, the yield of the catalyst was increased with increased amounts of benzoyl chloride and came to be saturated in about seven equivalents of benzoyl chloride relative to BEM. The particle size distribution of the catalyst became smaller as the amount of benzoyl chloride increased. An experiment was also carried out to observe the effect of eliminating the washing step after the formation of the support. The unwashed catalyst sample exhibited a lower activity and a lower shear response than the washed catalyst. The effect of the concentration of BEM on the properties of the catalyst was also examined. The particle size distribution, catalyst composition and polymer properties were not affected by the BEM concentration. While embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the art. invention. The modalities described herein are exemplary only, and are not proposed to be limiting. Where mechanism and chemical theory are disclosed, such is provided based on information and belief without necessarily proposing that it be related by it. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the description set forth in the foregoing, but is only limited by the claims that follow, that scope including all equivalents of subject matter of the claims.

Claims

CLAIMS 1. A process for making a catalyst component, characterized in that it comprises: a) generating a reaction product A by contacting a magnesium dialkoxide compound with a halogenating agent; b) contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B; c) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and d) contacting the reaction product C with a third halogenation / titanation agent to form the catalyst component D.
2. The process according to claim 1, characterized in that the halogenating agent is of the general formula C1AR ". 'X, wherein A is a non-reducing oxyphilic compound, R "f is a hydrocarbyl portion having from about 2 to 6 carbon atoms, and x is the valence of A minus 1.
3. The process according to the claim 1, characterized in that the halogenating agent is CITi. { OiFr) 3.
4. The process according to claim 1, characterized in that the first halogenation / titanation agent is a mixture of two titanium compounds tetra-substituted with all four substituents which are the same and substituents which are a halide or an alkoxide or phenoxide with 2 to 10 carbon atoms.
5. The process in accordance with the claim 4, characterized in that the first halogenation / titanation agent is a mixture of a titanium halide and an organic titanate.
6. The process in accordance with the claim 5, characterized in that the first halogenation / titanation agent is a mixture of TiCl and Ti (OBu) 4 in a range of 0.5: 1 to 6: 1 of TiCl / Ti (OBu) 4.
7. The process according to claim 1, characterized in that the second and the third halogenation / titanation agent comprise titanium tetrachloride.
The process according to claim 7, characterized in that steps c) and d) each comprise a ratio of titanium to magnesium tetrachloride in the range of about 0.1 to about 5.
9. The process according to claim 1 , characterized in that the reaction products A, B and C are washed with a hydrocarbon solvent before the subsequent halogenation / titanation steps.
The process according to claim 9, characterized in that the reaction products A, B and C are washed with a hydrocarbon solvent until the content of titanium species [Ti] is less than about 100 mmol / L before the subsequent halogenation / titanation steps.
The process according to claim 1, characterized in that the reaction product D is washed with a hydrocarbon solvent until the content of titanium species [Ti] is less than about 20 mmol / L.
The process according to claim 1, characterized in that an electron donor is present in any of one or more of steps a), b), c) or d), and wherein the ratio of the electron donor to metal it is in the range of about 0: 1 to about 10: 1.
13. The process according to claim 1, characterized in that it further comprises placing the catalyst of the invention on an inert support.
14. The process according to claim 13, characterized in that the inert support is a magnesium compound.
15. The process according to claim 1, characterized in that it further comprises: e) contacting D with an organometallic preactivation agent to form a preactivated catalyst system.
16. A catalyst, characterized in that it is produced by a process comprising: a) contacting a catalyst component with an organometallic preactivation agent, wherein the catalyst component is produced by a process comprising, i) contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; ii) contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B; iii) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and iv) contacting the reaction product C with a third halogenation / titanation agent to form a catalyst component.
The catalyst according to claim 16, characterized in that the organometallic preactivation agent is an aluminum alkyl of the formula A1R3 wherein at least one R is an alkyl having 1-8 carbon atoms or a halide, and in 'where each R can be the same or different.
18. The catalyst according to claim 17, characterized in that the organometallic preactivation agent is a trialkyl aluminum.
The catalyst according to claim 18, characterized in that the second and the third halogenation / titanation agent comprise titanium tetrachloride.
20. The catalyst according to claim 19, characterized in that the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.
21. The process according to claim 16, characterized in that the reaction products A, B and C are washed with a hydrocarbon solvent before the subsequent halogenation / titanation steps.
22. The process according to claim 16, characterized in that the catalyst component is washed with a hydrocarbon solvent until the content of the titanium species [Ti] is less than about 20 mmol / L.
23. A polymer, characterized in that it is produced by a process comprising: a) contacting one or more olefin monomers together in the presence of a catalyst under polymerization conditions, wherein the catalyst is produced by a process comprising ) contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; ii) contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B iii) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and iv) contacting the reaction product C with a third halogenation / titanation agent to form a catalyst component; and b) extracting the polyolefin polymer 24.
The polymer according to claim 23, characterized in that the catalyst is produced by a process further comprising: v) contacting the catalyst component with an organoaluminum agent.
The polymer according to claim 23, characterized in that the second and third halogenation / titanation agent comprise titanium tetrachloride.
26. The polymer according to claim 23, characterized in that the reaction products A, B and C are washed with a hydrocarbon solvent before the subsequent halogenation / titanation steps.
27. A film, fiber, tube, textile or article of manufacture, characterized in that they comprise the polymer of claim 23.
28. A process for polymerization of define, characterized in that it comprises: a) contacting one or more monomers of define together in the presence of a catalyst under polymerization conditions, wherein the catalyst was produced by a process comprising: i) contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; ii) contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B; iii) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; iv) contacting the reaction product C with a third halogenation / titanation agent to form a catalyst component; b) extracting the polyolefin polymer; wherein at least one reaction product A, B and C are washed with a hydrocarbon solvent prior to the subsequent halogenation / titanation steps; and wherein the reaction product D is washed with a hydrocarbon solvent until the content of titanium species [Ti] is less than about 100 mmol / L.
29. The process according to claim 28, characterized in that the polymer has a molecular weight distribution of at least 4.0.
30. The process according to claim 28, characterized in that the polymer has a bulk density of at least 0.31 g / cc.
31. An article, characterized in that it comprises the polymer produced by the process of claim 28.
32. A process for making a catalyst, characterized in that it comprises: altering the precipitation of a catalyst component from a catalyst synthesis solution by controlling the viscosity of the catalyst. a catalyst synthesis solution with the addition of aluminum alkyl, wherein the average particle size of the catalyst component is increased with an increased concentration of aluminum alkyl in the synthesis solution.
33. The process according to claim 33, characterized in that it further comprises contacting the catalyst component with an organometallic preactivation agent to form a catalyst, wherein the average particle size of the catalyst is increased with an increased concentration of alkyl. aluminum in the synthesis solution.
34. The process in accordance with the claim 33, characterized in that the catalyst synthesis solution comprises: contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; and contacting the reaction product A with a series of halogenation / titanation agents to form a catalyst component; and contacting the catalyst component with an organometallic preactivation agent to form a catalyst; where the average particle size of the catalyst is. increases with an increased concentration of aluminum alkyl in the synthesis solution.
35. The process according to claim 34, characterized in that at least one of the reaction product A and the resulting reaction products after each halogenation / titanation step is washed with a solvent to remove the contaminants.
36. A process for making a catalyst, characterized in that it comprises: a) contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; b) contact the reaction product? with a first halogenation / titanation agent to form the reaction product B c) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and d) contacting the reaction product C with a third halogenation / titanation agent to form the reaction product D; and e) contacting the reaction product D with an organometallic preactivation agent to form a catalyst; wherein the magnesium dialkoxide compound is a reaction product of a reaction comprising an alkylmagnesium compound of the general formula MgRR ', wherein R and R' are alkyl groups of 1-10 carbon atoms and can be the same or different, an alcohol of the general formula R "OH wherein the alcohol is linear or branched and wherein R" is an alkyl group of 2-20 carbon atoms, and an aluminum alkyl of the formula A1R '"3 wherein at least one R "'is an alkyl or alkoxide having 1-8 carbon atoms or a halide, and wherein each R"' may be the same or different, and wherein the average particle size of the catalyst it increases with an increased ratio of alkyl aluminum to alkyl magnesium 37.
The process according to claim 36, characterized in that the ratio of alkyl aluminum to alkyl magnesium is in the range of about 0.01: 1 to about 10: 1.
The process of compliance with the indication 36, characterized in that steps c), and d) each comprise titanium tetrachloride as the halogenation / titanation agent and the ratio of titanium to magnesium tetrachloride in the range of about 0.1 to about 5.
39. The compliance process with claim 36, characterized in that the magnesium dialkoxide compound is a magnesium di (2-ethylhexoxide).
40. The process according to claim 36, characterized in that the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethylmagnesium.
41. The process according to claim 36, characterized in that the alcohol is selected from the group consisting of ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-pentanol and 2-ethylhexanol.
42. The process according to claim 36, characterized in that the organometallic preactivation agent comprises an aluminum alkyl.
43. The process according to claim 36, characterized in that the first halogenation / titanation agent is a mixture of two titanium compounds tetra-substituted with all four substituents which are the same and substituents which are a halide or an alkoxide or phenoxide with 2 to 10 carbon atoms.
44. The process in accordance with the claim 43, characterized in that the first halogenation / titanation agent is a mixture of a titanium halide and an organic titanate.
45. The process in accordance with the claim 44, characterized in that the first halogenation / titanation agent is a mixture of TiCl4 and Ti (OBu) 4 in a range of 0.5: 1 to 6: 1 of TiCl / Ti (OBu) 4.
46. The process according to claim 36, characterized in that the reaction further comprises an electron donor.
47. The process according to claim 46, characterized in that the ratio of electron donor to magnesium is in the range of from about 0: 1 to about 10: 1. •
48. The process according to claim 46, characterized in that the electron donor is an ether.
49. The process according to claim 36, characterized in that the halogenating agent is of the general formula C1AR "'X, wherein A is a non-reducing oxyphilic compound, R"' is a hydrocarbyl portion having about 2 to 6 carbon atoms, and x is the valence of A minus 1.
50. The process according to claim 49, characterized in that the halogenating agent is CITi (C ^ Pr) 3.
51. The process according to claim 36, characterized in that at least one of the reaction products A, B, C and D are washed with a hydrocarbon solvent until the content of species of titanium [Ti] is less than about 100 mmol / L.
52. The process according to claim 36, characterized in that an electron donor · is present in any of one or more of steps a), b), c) or d) and wherein the ratio of electron donor to metal it is in the range of about 0: 1 to about 10: 1.
53. The process according to claim 36, characterized in that it further comprises placing the catalyst of the invention on an inert support.
54. The process according to claim 53, characterized in that the inert support is a magnesium compound.
55. A catalyst, characterized in that it is produced by a process comprising: a) contacting a catalyst component with an organometallic preactivation agent, wherein the catalyst component is produced by a process comprising, i) contacting a magnesium dialkoxide compound of the general formula Mg (0R ") 2 with a halogenating agent capable of exchanging a halogen for an alkoxide to form a reaction product A, where R" is a hydrocarbyl or substituted hydrocarbyl having 1 at 20 carbon atoms; ii) contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B; iii) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and iv) contacting the reaction product C with a third halogenation / titanation agent to form a catalyst component; wherein the magnesium dialkoxide compound is a reaction product of a reaction comprising an alkylmagnesium compound of the general formula MgRR, wherein R and R 'are alkyl groups of 1-10 carbon atoms and may be the same or different, an alcohol of the general formula R "0H wherein the alcohol is linear or branched and wherein R" is an alkyl group of 2-20 carbon atoms and an aluminum alkyl of the formula AIR "'3 whereby less one R "'is an alkyl or alkoxide having 1-8 carbon atoms or a halide, and wherein each R"' may be the same or different, and wherein the average particle size of the catalyst is increased with a increased ratio of alkyl aluminum to alkyl magnesium
56. The catalyst according to claim 55, characterized in that the organometallic preactivation agent is an aluminum alkyl of the formula A1R3, wherein at least one R is an alkyl having 1- 8 carbon atoms or a halide, and where each R can be the same or different.
57. The catalyst according to claim 56, characterized in that the organometallic preactivation agent is a trialkyl aluminum.
58. The catalyst according to claim 55, characterized in that the second and the third halogenation / titanation agent comprise titanium tetrachloride.
59. The catalyst according to claim 55, characterized in that the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.
60. A polymer, characterized in that it is produced by a process comprising: a) contacting one or more olefin monomers together in the presence of a catalyst under polymerization conditions, wherein the catalyst is produced by a process comprising: i) contacting an alkyl magnesium compound of the general formula MgRR ', wherein R and R' are alkyl groups of 1-10 carbon atoms and can be the same or different, with an alcohol of the general formula R " OH wherein the alcohol is linear or branched and wherein R "is an alkyl group of 2-20 carbon atoms, and an aluminum alkyl of the formula A1R '" 3, wherein at least one R' "is an alkyl or an alkoxide having 1-8 carbon atoms or a halide, and wherein each R "'may be the same or different, to form a magnesium dialkoxide of the general formula Mg (0R") 2; ii) contacting the magnesium dialkoxide compound with a halogenating agent to form a reaction product A, where R "is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms; reaction product A with a first halogenation / titanation agent to form the reaction product B, iv) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and v) putting in contacting the reaction product C with a third halogenation / titanation agent to form a catalyst component, and vi) contacting the catalyst component with an organoaluminum agent, and b) extracting the polyolefin polymer; The average polymer particle increases with an increased ratio of alkyl aluminum to alkyl magnesium used in step i)
61. The polymer according to the claim 60, characterized in that at least one of the reaction products A, B and C is washed with a hydrocarbon solvent before the subsequent halogenation / titanation steps.
62. The polymer according to claim 60, characterized in that the monomers are ethylene monomers.
63. The polymer according to claim 60, characterized in that the polymer is polyethylene.
64. The polymer according to claim 60, characterized in that the polymer has a molecular weight distribution of at least 4.0.
65. The polymer according to claim 60, characterized in that the polymer has a bulk density of at least 0.31 g / cc.
66. A film, fiber, tube, textile or article of manufacture, characterized in that they comprise the polymer of claim 60.
67. A process for controlling the particle size of the polyolefin polymer, characterized in that it comprises: a) putting in contact one or more olefin monomers with only in the presence of a catalyst under polymerization conditions, wherein the catalyst is produced by a process comprising: i) contacting an alkyl magnesium compound of the general formula MgRR ', in where R and R 'are alkyl groups of 1-10 carbon atoms and may be the same or different, with an alcohol of the general formula R "OH wherein the alcohol is straight or branched and wherein R" is an alkyl group of 2-20 carbon atoms and an aluminum alkyl of the formula A1R '"3, wherein at least one R"' is an alkyl or an alkoxide. having 1-8 carbon atoms or a halide, and wherein each R '"may be the same or different, to form a magnesium dialkoxide of the general formula Mg (0R") 2 /' ii) to contact the compound of soluble magnesium dialkoxide with a halogenation agent capable of exchanging a halogen for an alkoxide to form a reaction product A, where R "is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms; contacting the reaction product A with a first halogenation / titanation agent to form the reaction product B, iv) contacting the reaction product B with a second halogenation / titanation agent to form the reaction product C; and v) contacting the reaction product C with a third halogenation / titanation agent to form a catalyst component, and vi) contacting the catalyst component with an organoaluminum agent, and b) extracting the polymer of polyolefin, wherein the average particle size of the polymer is increased with an increased ratio of alkyl aluminum to alkyl magnesium used in step i).