TW200528190A - Ziegler-natta catalyst for polyolefins - Google Patents

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

200528190 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention generally relates to a catalyst, a method for manufacturing the catalyst, a method for using the catalyst, a polymerization method, and a polymer prepared from the catalyst. The present invention is particularly related to polyolefin catalysts and Qiegler-Natta catalysts, methods of manufacturing the catalysts, methods of using the catalysts, polyolefin polymerization methods, and polyolefins. [Prior art] Olefins, also called olefins, are unsaturated hydrocarbons whose molecules contain one or more pairs of carbon atoms connected by double bonds. When a polymerization process is performed, olefins can be converted to polyolefins such as polyethylene and polypropylene. One commonly used polymerization method involves contacting an olefin monomer with a Ziegler-Natta type catalyst system. Many Ziegler-Natta type polyolefin catalysts, their general manufacturing methods and their subsequent applications are well-known as polymerization technologies. Ten thousand, these systems include Qiegler-Natta type polymer catalyst components; auxiliary catalysts; and electron donor compounds. The Ziegler-Natta type polymer catalyst component may be a combination derived from a halide of a transition metal (such as titanium, chromium, or vanadium) and a metal hydride and / or a metal alkyl (generally an organoaluminum compound). Thing. The catalyst component usually contains a titanium halide supported on a magnesium compound incompatible with an alkyl aluminum. There are many issued patents related to catalysts and catalyst systems. Those familiar with this technology are mainly designed for the polymerization of propylene and ethylene. Examples of these catalyst systems are provided in U.S. Patent Nos. 4,107,413, 4,294,72 1, 4,43 9,540, 4,114,319, 夂 220,5 54, 4,460,7 0 1 No. 4,5 62,173, 5,066,73 8 and 6;] 74,9 71, which is incorporated herein by reference to 200528190 (2). The conventional Ziegler-Natta catalyst system includes a transition metal compound generally represented by the following formula: mrx, where M is a transition metal compound, R is a halogen or a hydrocarbon group, and X is a valence of a transition metal. Generally, the 'm' is selected from the group consisting of metals from groups Iv to v11, such as titanium 'chromium or vanadium, and R is chlorine, bromine or alkoxy. General transition metal compounds are

TiCl4, TiBr4, Ti (OC2H5) 3Cl, Ti (OC3H7) 2Cl2, Ti (OC6H13) 2Cl2,

Ti (OC2H5) 2Br2, and T i (Ο C) 2 H 2 5) C 13. The transition metal compound is generally supported on an inert solid such as magnesium chloride. The Ziegler-Natta catalyst is usually arranged on a support, that is, deposited on a solid crystalline support. The carrier may be an inert solid, which is chemically non-reactive with any component of the conventional Ziegler-Natta catalyst. The carrier is often a magnesium compound. Examples of magnesium compounds that can be used to provide a carrier source for the catalyst component are magnesium halides, dialkoxy magnesium, alkoxy magnesium halides, magnesium halides, dialkyl magnesium, magnesium oxide, magnesium hydroxide And magnesium carboxylates. The nature of the polymerization can affect the properties of the polymer formed using the catalyst. For example, the polymer type generally depends on the catalyst type. Good polymer types include particle size and shape uniformity and acceptable bulk density. In addition, it is desirable to minimize the number of extremely small polymer particles (i.e., fines) due to various factors' such as, for example, avoiding blocking of conveyance or circulation lines. Very large particles must also be minimized 'to avoid the formation of lumps and threads in the polymerization reactor. Another type of polymer that is affected by the type of catalyst used is molecular weight distribution (MWD), which represents the magnitude of the change in molecular length in a particular polymer resin. For polyethylene, for example, reducing M WD can improve 200528190 (3) toughness, that is, puncture, tensile, and impact properties. On the other hand, the wide M W D contributes to ease of processing and melt strength. Although there is a lot of knowledge about Qiegler-type catalysts, it is still being studied to improve its polymer yield, catalyst life, catalyst activity, and its ability to produce polyolefins with specific properties. [Summary of the Invention] An embodiment of the present invention provides a method for manufacturing a catalyst, including: a) contacting a diol magnesium salt compound with a halogenating agent to form a reaction product A; b) subjecting the reaction product A to a first halogenation / Contacting a titanating agent to form a reaction product B; c) contacting the reaction product B with a second halogenation / titanating agent to form a reaction product C; and d) contacting the reaction product C with a third halogenating / titanating agent to form a reaction Product D. The second and third halogenating / titanating agents may include titanium tetrachloride. The second and third halogenating / titanating agents may each include a titanium to magnesium ratio ranging from about 0.1 to 5. The reaction products A, B, and C can each be washed with a hydrocarbon solvent before the subsequent halogenation / titanation step. The reaction product D can be washed with a hydrocarbon solvent until the titanium species [Ti] content is less than about 100 millimolars / liter. Another embodiment of the present invention provides a polyolefin catalyst, which is generally prepared by a method including contacting the catalyst component of the present invention with an organometallic agent. The catalyst component is prepared by the aforementioned method. The catalyst of the present invention may have a loose form that can be subjected to a polymerization manufacturing method, and may provide polyethylene having a molecular weight distribution of at least 5.0, and may provide a uniform particle size distribution containing particles having a low concentration of less than about 125 microns. The catalyst activity depends on the polymerization conditions. Generally, the 200528190 (4) catalyst has an activity of at least 5,000 gPE / g catalyst, but the activity can also be greater than 50,000 gPE / g catalyst or greater than 100,000 gPE / g catalyst. Another embodiment of the present invention provides a polyolefin polymer prepared by a method comprising the steps of: a) contacting one or more olefin monomers together in the presence of the catalyst of the present invention under polymerization conditions; and) extracting the polyolefin polymer. Usually the single system is an ethylene monomer and the polymer is polyethylene. For example, another embodiment provides a film, fiber, pipe, fabric, or article of manufacture comprising a polymer made according to the present invention. The article of manufacture may be a film comprising at least one layer, the layer comprising a polymer prepared by a method comprising the catalyst of the present invention. Another embodiment of the present invention provides a method for manufacturing a catalyst, which comprises: controlling the viscosity of the catalyst synthesis solution by adding an alkyl aluminum, and changing the precipitation of the catalyst component from the catalyst synthesis solution, wherein the catalyst The average particle size of the components increases as the concentration of alkyl aluminum in the synthesis solution increases. The method may further include contacting the catalyst component with an organometallic polyactivator to form a catalyst, wherein the average particle size of the catalyst increases as the concentration of the aluminum alkyl in the synthetic solution increases. Another embodiment of the present invention provides a method for manufacturing a catalyst, including: a) contacting a magnesium diol salt compound with a halogenating agent to form a reaction product A; b) contacting the reaction product A with a first halogenating / titanating agent Contacting to form reaction product B; o contacting reaction product B with a second halogenation / titanating agent to form reaction product C; d) contacting reaction product C with a third halogenating / titanating agent to form reaction product D; and e ) Contacting the reaction product D with an organometallic pre-activator to form a catalyst. The diol magnesium salt compound is composed of the general formula -8- 200528190 (5)

MgRR 'alkyl magnesium compounds (where R and R' are alkyl groups having 1 to 10 carbon atoms and may be the same or different), alcohols of the general formula R''OH (wherein the alcohol is a straight chain Or branched chain where R " is an alkyl group having 2 to 20 carbon atoms) and an aluminum alkyl of formula A1R "'3 (where at least one R"' is an alkyl group having 1 to 8 carbon atoms or Alkoxy or halo and wherein each R "'may be the same or different) reaction product of the reaction. The average particle size of the catalyst increases as the ratio of alkyl aluminum to alkyl magnesium increases. The second and The third halogenation / titanation agent may include titanium tetrachloride. The second and third halogenation / titanation steps may each include a titanium to magnesium ratio ranging from about 0.1 to 5. The reaction products A, B Each of C and C can be washed with a hydrocarbon solvent before the subsequent halogenation / titanation step. The reaction product D can be washed with a hydrocarbon solvent to invite titanium species [Ti] content below about 100 millimolars / liter. Another embodiment of the present invention A polyolefin polymer prepared by a process comprising the steps of: a) bringing one or more olefin monomers together in the present invention Contact under polymerization conditions in the presence of a catalyst; and b) extracting a polyolefin polymer. The average particle size of the polymer increases as the ratio of alkyl aluminum to alkyl magnesium used in the preparation of the catalyst increases. Generally The single system is an ethylene monomer and the polymer is polyethylene. Another embodiment of the present invention provides a film, fiber, pipe, fabric, or article of manufacture containing the polymer produced by the present invention. The manufacture The article may be a film comprising at least one layer comprising a polymer made by the present invention. Other embodiments include a method for forming a catalyst for the polymerization of olefins. The method includes a chlorinating agent and a magnesium alkoxide Compound reacts to form magnesium-titanium-alcohol 9-200528190 (6) Salt adduct 'reacts the magnesium-titanium-alkoxide adduct with an alkyl chloride compound to form a magnesium chloride support. The support is then reacted with tetrachloride Chin (TiC) 4) reaction to form a highly active catalyst that can be used in the manufacture of polyolefins. In one embodiment of the present invention, butyl ethyl magnesium (BEM) and Is for example containing about 1 to 20 carbons Atomic alkyl) alcohols to form a magnesium alkoxide compound. The magnesium alkoxide compound is then combined with a chlorinating agent generally represented by the formula:

TiCln (OR ') 4.η wherein R' is an alkyl group, a cycloalkyl group or an aryl group, and η is 1 to 3. The magnesium-titanium-alkoxide adduct is formed by mixing a magnesium alkoxide compound with a chlorinating agent. Alkyl chloride compounds are reacted with a magnesium-titanium-alkoxide adduct to form a magnesium chloride (MgCl2) support and one or more by-products, such as ethers and / or alcohols. After that, the MgCl2 was treated with TiCl4 to form a cigarine-nata catalyst supported by MgCl2. Polyolefins made using this catalyst have a narrow molecular weight distribution and can therefore be formed into end-use items such as barrier films, fibers and pipes. [Embodiment] According to an embodiment of the present invention, a method for manufacturing a catalyst component generally includes the following steps: forming a metal glycol salt from a metal dialkyl compound and an alcohol, and 'halogenating the metal glycol salt to form A reaction product, contacting the reaction product with one or more halogenating / titanating agents in three--10-200528190 (7) or steps to form a catalyst component and subsequently treating the catalyst with a preactivator such as organoaluminum MEDIA COMPONENTS. An embodiment of the present invention may generally be as follows: 1 · MRR 丨 + 2ROH — M (OR ”) 2 2. M (OR, 丨) 2 + C1AR” W ”An 3. 丨, A ,, + TiCl4 / Ti (OR, n,) 4 — ”B ,, 4. nB 丨 丨 + TiCl4 — " C 丨,; 5. 丨, C 丨, + TiCl4, D ,, 6.” D ”+ preactivator — In the former formula of the catalyst, M can be any suitable metal, usually a group IIA metal, and generally M g. In the foregoing formula, each of R, R ,, R "and R" "is a hydrocarbon group or a substituted hydrocarbon group moiety, and R and R 'have 1 to 20 carbon atoms, usually 1 to 10 carbon atoms, generally Is 2 to 6 carbon atoms, and may have 2 to 4 carbon atoms. R "usually contains 3 to 20 carbon atoms, R, " usually contains 2 to 6 carbon atoms' and R" "usually contains 2 to 6 carbon atoms and is generally butyl. Combinations of two or more of R, R ', R ", r", and r ", may be used, may be the same, or combinations of R groups may be different from each other. In the foregoing examples containing the formula C1AR ", a is a non-reducing oxygen-producing compound, which can be exchanged for alkoxy with chlorine, and r, '' is a hydrocarbon group or a substituted hydrocarbon group, and X is A minus 1 Examples of a include titanium, stone, aluminum, carbon, tin, and germanium, generally titanium or silicon, where χ is 3. r, and, examples include methyl, ethyl, and propyl. Base, isopropyl, and those having 2 to 6 carbon atoms. Non-limiting examples of chlorinating agents that can be used in the present invention are ClTi (OiPr) 3 and ciSi (Me) 3. 200528190 (8) The metal glycol salt is chlorinated to form the reaction "A". Although the actual composition of the product "A" is unknown, it is believed that it contains a partialized metal compound, an example of which can be ClMg (OR ";). The reaction product `` A '' is then contacted with one or more halogenating / titanating agents (such as a composition of TiCl4 and Ti (OBi04) to form a reaction product. The reaction product `` B '' may be chlorinated and partially chlorinated And titanate complexes. The reaction product "BII" may include a titanium-impregnated MgCl2 support, such as a compound such as (MCl2) y (TiClx (OR) 4_x) z. The reaction "B" may be precipitated from the catalyst slurry It is a solid. The second halogenation / titanation step produces a reaction product or catalyst component " It can also be a halogenated and partially halogenated metal and a titanic acid compound different from "B", and can be expressed as (MCl2) y (TiClx, (OR) 4_xi) z. The degree of halogenation of the pre-turbidity is higher than the product "B". This higher degree of halogenation can produce the same compound complex. The third halogenation / titanation step produces the reaction product Or catalyst component "It can also be halogenated and partially halogenated metal and titanic acid compounds, but different friends and nC", and can be expressed as (MCl2) y (TiClx " (OR) 4.x ") z ". Forecast "The degree of halogenation is higher than the product" C ". This higher degree of halogenation results in uncombination Although the description of this reaction product is the most likely chemical description in this case, the invention described in the scope of the patent application does not have this theoretical mechanism. The metal dialkyl compounds and the metal dioxides that are applicable to the present invention Alcohols include anyone that can be used in the present invention to produce a suitable polyolefin catalyst. Metal diol salts and metal alkyls can include Group 11 A metal diol salts and product chlorine such as Example B. The product C ,,,, but! [) "CM does not produce D ,,, > ,, B ,, D" and the same is provided to the salt-inclusive of these dioxane-12-200528190 (9) substrates. Metal II The alkoxide or dialkyl may be a diol magnesium salt or a dialkyl. Non-limiting examples of suitable magnesium dialkyls include diethyl magnesium, dipropyl magnesium, monobutyl magnesium, butyl Ethylmagnesium, etc. Butylethylmagnesium (BEM) is a suitable dialkylmagnesium. In carrying out the present invention, the metal diol salt may be a magnesium compound of the general formula Mg (OR) 2 where Rπ is A hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms. The metal glycol salt may be soluble and generally non-reducing. Non-reducing compounds have the advantage of forming MgCl2 instead of insoluble species, which can be formed by the reduction of compounds such as MgRR, which can lead to the formation of catalysts with a wide particle size distribution. In addition, Mg (OR), which is less reactive than M g RR ', can produce a more homogeneous product when used in a reaction involving chlorination with a mild chlorinating agent and subsequent halide / titanation steps, such as Preferred catalyst particle size control and distribution. Non-limiting examples of metal glycolate species that can be used include magnesium butoxide, magnesium pentoxide, magnesium hexanolate, magnesium di (2-ethylhexanol), and any suitable In order to make the system soluble alkoxides. For a non-limiting example, a magnesium diol salt, such as bis (2-ethylhexanol) magnesium, can be obtained by an alkyl magnesium compound (MgRR,) ROH).

MgRR, + 2 R ”OH — Mg (OR ") 2 + RH + R, H This reaction can be carried out at room temperature, and the product forms a solution. R and R 'each -13- 200528190 (10) can be any Alkyl groups of 1 to 10 carbon atoms, and may be the same or different. Suitable MgRR 'compounds include, for example, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, and butylethylmagnesium. The MgRR' The compound can be BEM, where RH and R'H are individually butane and ethane. In carrying out the present invention, any alcohol that produces the desired metal glycol salt can be used. Generally, the alcohol used can be any alcohol Alcohols of formula R "OH, where R" is an alkyl group having 2 to 20 carbon atoms, and the carbon atom may be at least 3, at least 4, at least 5 or at least 6 carbon atoms. Non-limiting of suitable alcohols Examples include ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-pentanol, 2-ethylhexanol, etc. Although almost any alcohol is believed to be usable, a linear or Branched, highly branched alcohols, such as 2-ethyl-hexanol. The amount of alcohol added can vary, such as within the non-exclusive range of 0 to 10 equivalents, usually It is in the range of about 0.5 equivalent to about 6 equivalent (equivalent is relative to the magnesium or metal compound of the whole process), and may be in the range of about 1 to about 3 equivalent. The metal alkyl compound may generate high molecular weight species, which The solution is extremely viscous. This high viscosity can be reduced by adding an aluminum alkyl such as, for example, ethyl aluminum (TEA1) to the reaction, which can destroy the association between individual alkyl metal molecules. Aluminium alkyl The general ratio to metal can be from 0.0000 to 1: 1, from 0.01 to 0.5: 1, and from 0.03: 1 to 0.2: 1. In addition, electron donors such as ether (for example, two Isoamyl ether (DIAE)) to further reduce the viscosity of the alkyl metal. The general ratio of the electron donor to the metal is 0: 1 to] 0: 1 and may be 0.1: 1 to 1::].- 14- 200528190 (11) The reagents that can be used in the step of halogenating the metal alkoxide include any halogenating agent which, when used in the present invention, produces a suitable polyolefin catalyst. The halogenation step may be a chlorination step, wherein the The halogenating agent contains a chlorine group (that is, a chlorinating agent). The halogenation of metal alkoxide compounds is usually The hydrocarbon solvent is carried out under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane and the like. In this halogenation step, the molar ratio of the metal alkoxide to the halogenating agent is usually Is in the range of about 6: 1 to about 1: 3, may be in the range of about 3: 1 to about 1 ·· 2, and may be in the range of about 2: 1 to about 1: 2, or may be About 1: 1. The halogenation step is usually performed at a temperature ranging from about 0 ° C to about 100 ° C, and the reaction time is within a range of about 0.5 to about 24 hours. The halogenation step may be performed at a temperature ranging from about 20 ° C to about 90 ° C, and the reaction time ranges from about 1 hour to about 24 hours. Once the halogenation step is performed, the metal alkoxide is halogenated, and the halide product "A" may be subjected to two or more halogenation / titanation treatments. The halogenating / titanating agent used may be a blend of two tetra-substituted titanate compounds, all four substituents are the same and the substituent is a halogen group or an alkoxy group having 2 to 10 carbon atoms or Phenoxy, such as TiCl4 or Ti (OR "") 4. The halogenating / titanating agent used may be a chlorinating / titanating agent. The halogenating / titanating agent may be a single compound or a combination of compounds. The process of the invention provides an active catalyst after the first halogenation / titanation; however, 'a total of at least three halogenation / titanation steps are desired. The first halogenating / titanating agent is generally a mild titanating agent, and its -15-200528190 (12) may be a blend of titanium halide and organic titanate. The ~ halogenated / titanium g change agent may be a TiCI4 / Ti (〇Bu) ^ @ 围 内 的 Ticl4 and T i (Ο B u) 4 blend, the ratio may be 2: 1 To 3: 1. It is believed that the blend of titanium halide and organic titanate reacts to form an alkoxy titanium halide Ti (OR) aXb, where OR and X SU are alkoxy and halo, and a + b is titanium The price is usually 4. Or the first halogenating / titanating agent may be a single compound. An example of a first halogenating / titanating agent is

Ti (OC2H5) 3Cl, Ti (OC2H5) 2Cl2, Ti (OC3H7) 2Cl2, Ti (〇C3H7) 3Cl, Ti (OC4H9) Cl3, Ti (OC6H) 3) 2Cl2, Ti (OC2H5) 2Br2, and Ti (OC) 2H5) Cl3. This first halogenation / titanation step is usually carried out by slurrying the halogenated product "A" in a hydrocarbon solvent at room temperature / ambient 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. The solid product "B" is precipitated at room temperature after adding the halogenation / titanating agent to the soluble product "A". The amount of halogenation / titanating agent must be sufficient to precipitate the solid product from the solution. Generally, the halogenation / titanium The amount of acidifying agent is in the range of about 0.5 to about 5 based on the ratio of titanium to metal, generally in the range of about 1 to about 4, and may be in the range of about 1.5 to about 2.5. The solid product "B " precipitated during this first halogenation / titanation step is subsequently recovered by any suitable recovery technique and then washed with a solvent such as hexane at room / ambient temperature. Generally, the solid product "B" is washed to -16-200528190 (13) [Ti] below about 100 millimolars / liter. [Ti] In the present invention, [Ti] means any titanium species that can be used as a second-generation Chigler catalyst, which may include a Chin species that is not part of the reaction product described in the present invention. The formed product "B" is then subjected to the second and third halogenation / titanation steps to obtain the product ,, c, and '' D π. After each halogenation / titanation step, the solid product can be washed to a [Ti] below the desired amount. For example, less than about 100 millimoles / liter, less than about 50 millimoles / liter, or less than 10 millimoles / liter. After the final halogenation / cinnification step, the product can be washed to a [Ti] below a desired amount, such as below about 20 millimoles / liter, below about 10 millimoles / liter, or below about 1.0 Millimoles per liter. It is believed that a lower [Ti] can produce an improved catalyst by reducing the amount of titanium that can be used as a second-generation Chigler species. It is believed that a lower [Ti] may be a factor in producing improved catalyst results such as a narrower MWD. This second halogenation / titanation step is usually performed by slurrying the solid product (solid product "B") recovered from the first titanation step in a hydrocarbon solvent. The hydrocarbon solvents listed for use in the first halogenation / titanation step can be used. The second and third halogenation / titanation steps may use different compounds or a combination of compounds from the first halogenation / titanation step. The second and third halogenation / titanation steps can use the same reagent as the first halogenation / titanation agent at a stronger concentration, but they are not necessary. The second and third halogenating / titanating agents may be titanium halides, such as titanium tetrachloride (T i c 1 4). The halogenating / titanating agent is added to the slurry. This addition can be performed at ambient / room temperature, but can also be performed at non-ambient temperature and pressure. Generally, the second and third halogenating / titanating agents include titanium tetrachloride. Generally, the second and third halogenation / titanation steps each include a titanium-to-magnesium ratio in the range of about 0 ·] -17- 200528190 (14) to 5, and a ratio of about 2 · 0 can also be used, and can be used A ratio of about 1.0. The third halogenation / titanation step is usually performed at room temperature and in a slurry, but it can also be performed at a non-ambient temperature and pressure. The amount of titanium tetrachloride or the alternate halogenation / titanating agent can also be expressed in equivalents. The equivalent in the present invention is the amount of titanium relative to magnesium or metal compounds. The amount of titanium in each of the second and third halogenation / titanation steps is generally 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, and is generally in the range of about 0.3 to about 3 equivalents. Within the range of about 0.4 to about 2.0 equivalents. In a specific embodiment, the amount of titanium tetrachloride in each of the second and third halogenation / titanation steps ranges from about 0.45 to about 1.5 equivalents. The catalyst component "D" prepared by the aforementioned method can be combined with an organometallic catalyst component ("pre-activator") to form a pre-activated catalyst system suitable for olefin polymerization. Generally, the preactivators used with the catalyst component "D" containing transition metals are organometallic compounds, such as alkyl aluminum, alkyl aluminum hydride, alkyl lithium aluminum, alkyl zinc, alkyl magnesium, and Its kind. The preactivator is usually an organoaluminum compound. The organoaluminum preactivator is generally an aluminum alkyl having the general formula A1R3, wherein at least one R is an alkyl or halo group having 1 to 8 carbon atoms, and each of R may be the same or different. The organoaluminum preactivator may be a trialkylaluminum such as, for example, trimethylaluminum (TMA), triethylaluminum (REA1), and triisopropylaluminum (TiBAl). The ratio of A1 to titanium may be in the range of 0:] to 2: 1, and is generally 0.25: 1 to] .2.: 1. -18- 200528190 (15) The Qiegler-Natta catalyst can be pre-aggregated as appropriate. Generally, the pre-polymerization method is performed by contacting a small amount of monomer with the catalyst after the catalyst is contacted with the auxiliary catalyst. The prepolymerization method is described in U.S. Patent Nos. 5,06,8 04, 5,1 5 3,1 5 8 and 5,5 94,07 1, which are incorporated herein by reference. The catalyst of the present invention can be used in any method for homopolymerization or copolymerization of any type of? -Olefin. For example, the catalyst of the present invention can be used to catalyze ethylene, propylene, butene, pentene, hexene, 4-methylpentene, and other α-flame species having at least 2 carbon atoms, and mixtures thereof. Copolymers of the foregoing can produce desired results, such as wider MWD and multimodal distributions, such as bimodal and trimodal properties. The catalyst of the present invention can be used for the polymerization of ethylene to obtain polyethylene. Various polymerization methods can be used in the present invention, such as, for example, single and / or multiple loop processes, batch processes, or continuous processes that do not involve a loop type reactor. An example where the multi-loop method of the present invention can be used is a two-loop system in which the first loop generates a polymerization reaction, wherein the polyolefin formed has a lower MW than the polyolefin obtained from the polymerization of the second loop to produce A resin with a wide molecular weight distribution and / or bimodal characteristics. In another example, another example of the multi-loop method that can be used in the present invention is a dual-loop system, in which the first loop produces a polymerization reaction, wherein the polyolefin formed has a greater polymerization than that produced by the second loop polymerization reaction. The MW of the olefin to produce a resin with a broad molecular weight distribution and / or bimodal characteristics. The polymerization method may be, for example, bulk, slurry, or gas phase. The catalyst of the present invention can be used for _ award phase polymerization. The polymerization conditions (such as temperature and pressure) depend on the type of equipment used in the polymerization method and the type of polymerization method used, and are known in the technical field. Generally, the temperature is in the range of about 50 to 100 ° C, and the pressure is in the range of about 10 to 800 psi. The catalyst-forming activity of the embodiments of the present invention depends at least in part on the polymerization method and conditions, such as, for example, the equipment and reaction temperature used. For example, in embodiments where ethylene is polymerized to produce polyethylene, the catalyst will typically have an activity of at least 5,000 g PE / g catalyst, but may have an activity of greater than 50,000 g PE / g catalyst, which activity may be greater than 1 00,000 g PE / g catalyst. In addition, the formed catalyst of the present invention can provide a polymer having an improved loose form. Thus, the catalysts of the present invention can provide large polymer particles with a uniform size distribution in which fine particles (less than about 125 microns) have only low concentrations such as, for example, less than 2% or less than 1%. The catalyst of the present invention (including large, easy-to-transport powders having a high powder bulk density) is easy to carry out a polymerization manufacturing method. Generally, the catalysts of the present invention provide polymers with less fines and higher bulk density (B.D.), where BD 値 may be greater than about 0.31 g / cc, may be greater than about 0.33 g / cc, and may even be greater than About 0.35 g / cc. The olefin monomer can be introduced into the polymerization reaction zone in a diluent (that is, a non-reactive heat transfer agent, which is a liquid under reaction conditions). Examples of the diluent are hexane and isobutane. With regard to the copolymerization of ethylene with another α-olefin, such as, for example, butene or hexene, a second olefin may be present in the range of 0.01 to 20 moles, and may be present in the range of about 0.02 to 10 moles. between. Optionally, an electron donor can be added simultaneously with the halogenating agent, the first halogenating / titanating agent, or the subsequent halogenating / titanating agent. It may be desirable to use an electron donor in the second halogenation / titanation step. The electron donor -20-200528190 (17) system for the preparation of polyolefin catalysts is well known ' and any suitable electron donor that provides a suitable catalyst can be used in the present invention. The electron donor may be a monofunctional or polyfunctional compound and may be selected from aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic ethers, ketones, vinyl esters, propenyl derivatives (especially Acrylic acid or alkyl methacrylate) and silane. An example of a suitable electron donor is di-n-butyl phthalate. A general example of a suitable electron donor is an alkylsilyl alkoxide of the general formula RS i (0 R ') 3, such as methylsilyl triethoxide [MeSi (OEt3)], where R and R 'is an alkyl group having 1 to 5 carbon atoms and may be the same or different. In terms of polymerization methods, an internal electron donor can be used in catalyst synthesis, and an external electron donor or stereoselectivity control agent (SCA) activates the catalyst during polymerization. An internal electron donor can be used for the catalyst formation reaction during the halogenation or halogenation / titanation step. Compounds suitable for use as internal electron donors for the preparation of conventionally supported Chigler-Natta catalyst components include ethers, diethers, ketones, lactones, electron donors with N, P and / or S atoms Compounds and specific types of esters. Particularly suitable esters of phthalic acid, such as diisobutyl phthalate, dioctyl, diphenyl, and benzyl butyl; esters of malonic acid, such as diethyl malonate; alkyl pivalate Esters and aryl esters; alkyl maleates, naphthenic esters and aryl esters; alkyl hydrochlorides and aryl esters such as diisobutyl carbonate, ethyl-phenyl esters and diphenyl esters; succinate esters such as amber Acid mono and diethyl esters. External supply systems that can be used to prepare the catalysts of the present invention include organic silane compounds, such as alkoxysilanes of the general formula SiRm (OR ') 4 ... where R is selected -21 · 200528190 (18) from alkyl, cycloalkyl , Aryl, and vinyl; 1 ^ is an alkyl group; and m is 0 to 3, where R may be the same as R; when m is 0, 1, or 2, the R 'groups may be the same or different And when m is 2 or 3, the R groups may be the same or different. The external donor of the present invention may be selected from a silane compound of the formula: or2

Ri--Si--R4 OR3 where R! And R4 are both alkyl or cycloalkyl groups containing a primary, secondary, or tertiary carbon atom attached to silicon; R! And R4 are the same or different; R2 and R3 is alkyl or aryl. R] may be methyl, isopropyl, cyclopentyl, cyclohexyl or third butyl; R2 and R3 may be methyl, ethyl, propyl or butyl and are not necessarily the same; and R4 may also be Methyl, isopropyl, cyclopentyl, cyclohexyl or third butyl. Specific external donor systems are cyclohexylmethyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS), cyclohexylisopropyldimethoxysilane (CIDS), dicyclopentyldi Methoxysilane (CPDS) or di-tertiary butyldimethoxysilane (DTDS). The polyethylene made using the aforementioned catalyst may have an MWD of at least 5.0 and may be greater than about 6.0. The polyolefins of the present invention are suitable for a variety of applications, such as, for example, extrusion processes to produce a wide range of products. Such extrusion methods include, for example, blown film extrusion, cast film extrusion, long-belt extrusion, blow molding, tube molding, and foamed sheet extrusion. -22- 200528190 (19) This method can include single-layer extrusion or multi-layer lamination. End-use applications that can be made using the present invention can include, for example, films, fibers, tubes, fabrics, articles of manufacture, diaper components, feminine hygiene products, automotive components, and medical materials. All references, including research documents, and all U.S. and foreign patents and patent applications, are specifically and fully incorporated herein by reference. ❿ First group of embodiments The present invention has been generally described. The following embodiments are only used to illustrate specific embodiments of the present invention, and to prove their implementation and advantages. It should be understood that the examples are provided for illustration and in no way limit the scope of the specifications or the scope and scope of patent applications. The synthetic flow chart for this type of catalyst is as follows (all ratios are relative to BEM):

(BEM + 0.03 TEA1 + 0.6 DlAE) + 2.09 2 · ethylhexanol—

Mg (OR) 2

Mg (OR) 2 + ClTi (OPr) 3—solution a solution A + (2TiC14 / Ti (OBu) 4) —catalyst b (supported mainly by MgC12) catalyst B + X TiC] 4—catalyst C Catalyst C + 0.156 TEA1—The final catalyst optimal formula is regarded as X = 0.5 to 2, before using Catalyst A to preactivate Catalyst C-23- 200528190 (20), use zero or two washes. The following modifications were made to the catalyst preparation to obtain more effective titanation: Catalyst B + X TiC14—Catalyst C Catalyst C + Y TiC14 ~ > Catalyst D Catalyst D + 0.1 56 TEA 1—Final Catalyst As mentioned above, TiC 14 is added in two steps, where X and Υ = 0.5 to 1.0. Catalyst C is usually washed by one or two persons, and the two washes are performed after the pupae to remove the soluble titanium species as the second-generation Chigler species. Example 1: In a nitrogen rinsing tank, 1412.25 grams (2.00 moles) of BEM-1, 2 7.60 grams (0.060 moles) of TEA1 (24.8% in heptane), and 1 89.70 grams (1.20 moles) ) DIAE was added to a 3 liter round bottom flask. The contents were then moved under a stream of nitrogen through a cannula to a 20 liter Buchi reactor. The flask was then rinsed with about 400 ml of hexane and it was transferred to the reactor. The stirrer was set at 350 rpm. The 2-ethylhexanol (543.60 g, 4.21 mol) was added to a 1 liter bottle and capped. It was then diluted to a total volume of 1 liter with hexane before adding to the reactor. This solution was transferred to the reactor via a conduit using a mass flow controller. The original head temperature was 25.3 ° C and reached a maximum temperature of 29.6t. After the addition (about 2 hours), the bottle was rinsed with 400 ml of hexane and it was transferred to the reactor. -24-200528190 (21) The reaction mixture was stirred overnight at 350 rpm at 0.5 bar nitrogen and the heat exchanger was switched off. Turn on the heat exchanger and set to 25 t. Adding titanium triisopropoxide to two 1-liter bottles (774.99 and 775.01 g, 2.00 mol in total) yielded two liters. The contents of each vial were transferred to the reactor via a conduit using a mass flow controller. The original headspace temperature was 2 4.6 ° C and reached a maximum of 2 5 · 9 ° C during the addition of the second bottle. The addition times of bottles 1 and 2 are respectively 1 45 and 125 minutes. After the addition, each bottle was rinsed with 200 ml of hexane and it was transferred to the reactor. The reaction mixture was stirred overnight at 350 rpm under 0.5 bar nitrogen pressure. Switch off the heat exchanger.

Preparation of TiCl4 / Ti (OBu) 4 A titanium tetrachloride / titanium tetrabutoxide mixture was prepared in a 5-liter round bottom flask using standard Schlenk line technology. In a 1 liter pressurized bottle, 6 8 0.0 0 g (1.99 mol) T i (Ο B u) 4 was diluted with hexane to a total volume of 1 liter. This solution was then moved to the reactor by a catheter. The bottle was rinsed with 200 ml of hexane and transferred to the reactor. In a 1-liter graduated cylinder, 440 milliliters (~ 760 g, 4.0 旲 ears) of TiCl4 was diluted in the hospital to a total volume of 1 liter. The solution in the 5 liter flask was stirred, and the TiC 14 solution was added dropwise to the reactor through a conduit under N 2 pressure. After the addition was complete, the 1-liter graduated cylinder was rinsed with 200 ml of hexane 'and the system was transferred to the reactor. After 1 hour, the reaction mixture was diluted to a total volume of 4 liters' with hexane and stored in a flask before use. Turn on the heat exchanger and set to 25 ° C. The TiCl4 / Ti (OBu) 4 mixture was transferred to a 20 liter reactor via a conduit and a mass flow controller. The original head space temperature was 2 4 · 7 ° C, and reached -25- 200528190 (22) 2 6 during the 25 minute addition. (TC maximum temperature. After the addition, the container was rinsed with one liter of hexane and Let it stir for 小时 hours. Turn off the stirrer and allow the solution to settle for 30 minutes. The solution is decanted by pressurizing the reactor to 1 bar, lowering the dipping tube, making sure that no solid catalyst passes through the connected to transparent Plastic hose. The catalyst was then washed three times using the following method. Using a pressurized container on a balance, 2.7 kg of hexane was weighed into the container, and then moved to the reactor. Turn on the stirrer and stir the catalyst mixture 1 5 minutes. Then turn off the stirrer and allow the mixture to settle for 30 minutes. Repeat the process. After the third addition of hexane, allow the slurry to settle overnight and turn off the heat exchanger. Decant the supernatant and place 2.0 kg Hexane was added to the reactor. Restart the stirring at 350 rpm, open the heat exchanger and set to 25 ° C. In a 2 liter graduated cylinder, add 440 ml (760 g, 4.00 mol) of titanium tetrachloride. The TiCl4 diluted to one liter with hexane, half dissolved Moved to the reactor via the duct and mass flow controller. The original head temperature was 2 4.7 ° C, and the booster port was 0.5 ° C during the addition. The total addition time was 45 minutes. After one hour, the stirrer was turned off The solid settles for 30 minutes. The supernatant liquid is decanted, and the catalyst is washed once with hexane according to the method described above. After the washing is completed, 2.0 kg of hexane is transferred to the reactor and re-stirred. Use 500 ml of solution to complete. After the addition, the graduated cylinder was rinsed with 400 ml of hexane, which was added to Buchi. After one hour of reaction, the stirrer was turned off and the solid was allowed to settle for 30 minutes. The medium was washed three times with hexane. Then 2.0 kg of hexane was transferred to the reactor. Added to a one-liter pressurized bottle] 44.8 g (312 mmol) TEA1 -26- 200528190 (23) (25.2% in hexane ). Cap the bottle and dilute to one liter with hexane. This solution is then transferred to the reaction mixture via a tube using a mass flow controller. During the 1 20 minute addition, the color of the slurry turns dark brown. Original head temperature Is 24.5 t and reaches a maximum temperature of 25.3 ° C. Add After that, the bottle was rinsed with 400 ml of hexane, and it was transferred to the reactor. After 1 hour of reaction, the stirrer was turned off and the catalyst was allowed to settle for 30 minutes. The supernatant liquid was decanted and the catalyst was washed according to the method described above. Once. After washing, 2.7 kg of hexane was added to the reactor. The contents were then moved to a three-gallon pressurized container. The Buchi was rinsed with 1.0 kg and 5.0 kg of hexane and added to the pressurized container. The media yield is 32.2 grams. In one embodiment, the composition expressed by weight percentage is: C1 5 3.4%; A1 2.3%; Mg 1 1.8% and Ti 7.9%. The observation range of each element is: C 1 4 8.6-5 5.1%; A1 2.3-2.5%; Mg 11.8-14.1% and Ti 6.9-8.7%. The range of each element can be: Cl 40.0-65.0 ° /. ; A1 0.0-6.0%; M g 6 · 0 -1 5 · 0%; and T i 2 · 0-1 4.0%. Table 1 shows the [Ti] measured from the samples after TiCl4 / Ti (OBi〇4), three washes, the first TiCI4 addition, one wash and the second TiCl4 addition, and three subsequent washes. Analysis 1-4 was after the addition of TiCl4 / Ti (OBi〇4. Decantation 5 and 6 were after the first addition of TiCl4. Decantation 7 ·] 〇 was after the second addition of TiCl4. 200528190 (24) Table 1 Decanted sample (ppm) mm ο 1 / L 1 —— 2 1000 3 06.9 2 .... 8 000 116.9 3 ... 2000 29.2 4 __〇 ^ 1 1000 14.6 5 ——2 20000 292.3 6 ..-_ 〇 ^ 4 4000 5 8.5 7 1 9000 277.7 8 __0.4 4000 5 8.5 9 _0 ^ 09 ^ 2 5 925 13.5 10 Λ ^ 〇6 4 64 0.9

Comparative Example 1: Comparative Example 1 was prepared in the same manner as in Example 1, except that the third titanation was omitted, and the second titanation was performed using a quarter of TiCI4. Comparative Example 2: Comparative Example 2 was prepared in the same manner as in Example 1, except that the second and third titanation steps were performed using 0.5 equivalent of TiCl4 during each titanation step. Comparative Example 3: -28- 200528190 (25) Comparative Example 3 was performed in the same manner as Comparative Example 1, except that the amount of TiC14 during the second titanation was about four times that of Comparative Example 1. A hexane wash was performed after the second titanation. In one embodiment, the composition expressed by weight percentage is: C 1 57.0%; A 1 2.0%; Mg 9.5% and Ti 10.0%. The range of each element can be: Cl 55.0-57.0; A1 2.0-2.6%; M g 8 · 9-9 · 5%; and T i 1 0.0 -1 1 · 0%.

Comparative Example 4: Comparative Example 4 was prepared in the same manner as Comparative Example 3, except that it was washed twice with hexane after the second titanation. In one embodiment, the composition in terms of weight percentage is: C1 5 3.0%; A1 2.3%; Mg 9.7% and Ti 9.5%. The range of each element can be: Cl 52.6-53.0; A1 2.0-2.3%; M g 9.7-10 · 6%; and T i 8.7-9 · 5%. Table 2 lists the catalysts prepared. Table 2 ___ ·

Catalyst X Washing times Y Washing times Comparative Example 1 0.5 0 0 NA For Example 2 0.5 1 0.5 2 Example 1 1 .0 1 1 .0 2 Comparative Example 3 2.0 1 0 NA Comparative Example 4 2.0 2 0 NA -29 -200528190 (26) Table 3 shows the M WD data of the polymers prepared in Example 1 and Comparative Examples 1 to 4. For specific catalyst / co-catalyst systems, this data shows that a narrower M W D can be achieved by increasing the number of washings or adding a third titanation step using T i C 14. Generally, the polymer resin characteristic W WD increases in the following order: Comparative Example 1 <Comparative Example 2 <Comparative Example 4 <Example 1 <Comparative Example 3]. SR5 D (Mw / Mn) after X, followed by washing catalyst, washing times (HLMI / MI5) Comparative Example 1 TEA1 0 0 10.9 6.2 Comparative Example 2 TEA1 1 2 10.9 ΝΑ Example 1 TEA1 1 2 12.6 6.8 Comparative Example 3 TEA1 1 ΝΑ 11.8-12.8 5.9-6.8 Comparative Example 4 TEA1 2 ΝΑ 10.8-12.0 6.0-6.3 Example 1 ΤΒΑ1 1 2 11.9 7.0 Comparative Example 3 ΤΒΑ1 1 ΝΑ 12.2-13.6 6.9-7.3 Comparative Example 4 ΤΙΒΑ1 2 ΝΑ 11.4-11.8 6.6-7.5

As shown in Table 4, each catalyst provides a powder with low fines (particles smaller than 125 micrometers); however, the catalyst prepared using the two titanation step in the present invention is fixed to provide a fluff with a higher bulk density. . -30- 200528190 (27) Table 4 Catalyst D50 (micron) Fluff D50 (micron) Fine% BD (g / cc) 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 a substantial effect on the sedimentation efficiency of the polymer, as shown in the laboratory-derived sedimentation efficiency curve shown in Figure 1. The rapid disappearance of the original 10 ml of fluff from the solution exhibited by the polymer of the present invention prepared using the catalyst of Example 1 of the present invention indicates a higher settling rate and better than the conventional catalyst of Comparative Example 1: Polymer Type. Control of viscosity of synthetic solution It has been found that by changing the viscosity of the solution during the synthesis of the catalyst, it is possible to change the precipitation of the catalyst components from the solution. It has been found that changes in the precipitation of such catalyst components affect the catalyst formed and the particle size of polymers made using the catalyst. The viscosity of the catalyst synthesis solution may vary depending on the relative amount of alkyl aluminum present. The particle size of the catalyst and the polymer produced from the catalyst may vary depending on the relative amount of alkyl aluminum. ® 5 can be prepared with varying amounts of aluminum alkyl in the synthetic solution and tested with polymer fluff made from the catalyst. Example 2 describes the synthesis used in the catalyst preparation. Table 5 shows the catalyst and polymer sizes formed. -31-200528190 (28) Example 2: The synthesis used is as follows, all ratios are relative to BEM: 1 · (BEM + X TEA1 + 0.6 DIAE) + (2 + 3X) 2 · ethylhexanol — Mg ( 0-2-ethhex) 2 * [Al (0-2-ethhex) 3] 2 · Mg (0-2-ethhex) 2 · [AUOd-ethhexhJ + ClTiCOPr)> — ·, Α ', 3 · ”A” + 2TiCl4 / Ti (Obu) 4— ”B” (supported mainly by MgCl2) 4 · ,, B ”+ Y TiCl4— 丨, C ,, 5 ·“ C ”, + Z TiCl4- &gt;” D, 7 · ”D” + 0.156TEA1—catalyst Four catalysts were prepared in a one-liter Buchi reactor according to this general synthesis method, Y = Z = 1. Change the amount of TEA1 in the first reaction to investigate Effect on catalyst particle size. The relative amount of 2-ethylhexanol is adjusted during the synthesis of each catalyst to prevent reduction of the titanium complex due to any unreacted aluminum or alkylmagnesium species. The table below The synthesized catalysts, the relative amounts of BEM, TEA1, and 2-ethylhexanol, the average particle size of the catalysts, and the average particle size of the polyethylene resin prepared using each catalyst are shown in the table below. Particle size distribution data. As shown in the table, The average particle size distribution increases with increasing TEA1 concentration. -32- 200528190 (29) Table 5 Catalyst BEM TEA1 2-ethylhexanol BEM: TEA1 Catalyst polymer fluff equivalent equivalent equivalent ratio D50 (micron) D50 (micron) 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, catalysts and formation The average particle size of both fluffs increased with the increase of TEA1 concentration used in the original catalyst synthesis solution. The viscosity of the catalyst synthesis solution can be changed by changing the relative amount of alkyl aluminum y. Solution viscosity The change can therefore change the nature of the precipitation of the catalyst component from the solution, which can affect the average particle size of the catalyst component formed and the polymer made from the catalyst. The average particle size of the catalyst component has been found It increases with the increase of the concentration of alkyl aluminum in the synthetic solution. It has been found that the average particle size of the polymer resin prepared by the catalyst increases with the increase of the concentration of alkyl aluminum in the synthetic solution. Plus. The amount of alkylaluminum can be measured as the ratio of alkylaluminum to alkylmagnesium, which can range from about 0.01: 1 to about 10: 1. Polyethylene produced using the aforementioned catalyst may have a MWD of at least 4.0 and may be greater than about 6.0. The catalysts 101 in Table 5 are the same as in the first embodiment. In one embodiment, the composition expressed by weight percentage is: C1 53.4%; A1 2.J%, Mg 1] · 8% and Ti 7.9%. The range of each element can be: C1 -33- 200528190 (30) 4 0.0-6 5.0; A1 0.0-6.0%; Mg 6.0-15.0%; and Ding 2.0-1 4 · 0% 〇 In the examples The catalysts in Table 5 are 102: C1 47. 0%; A1 3.4%; Mg〗 3.1% and T i 4 · 0%. The range of each element can be: C 1 40.0- 65.0; A1 0.0-6.0%; Mg 6.0-15.0%; and Ding 2.0-14.0 //. In one embodiment, the catalysts in Table 5 are 103: C 1 50 · 0%; A1 2.4%; Mg 1 2.1% and T i 3.9%. The range of each element can be: C1 40.0- 65.0; A1 0.0-6.0%; Mg 6.0-15.0%; and Ding 2.0- 1 4 · 0%. In one embodiment, the catalysts 104 in Table 5 are: C 1 5 3 · 0 ° / 〇; A1 3.1%; Mg 1 2.8% and Ti 4.2%. The range of each element can be: Cl 4 0.0-65.0; A1 0.0-6.0%; Mg 6.0-15.0%; and Ding 2.0- 14.0%. The polyolefin of the present invention is suitable for various applications such as, for example, an extrusion method to produce a wide variety of products. Such extrusion methods include, for example, blown film extrusion, cast film extrusion, long-belt extrusion, blow molding, tube molding, and foamed sheet extrusion. This method may include single-layer extrusion or multilayer co-extrusion. End-use applications that can be manufactured with the present invention can include, for example, films, fibers, tubing, fabrics, articles of manufacture, diaper components, feminine hygiene products, automotive components, and medical materials. According to an alternative embodiment of the present invention, the polyolefin polymerization catalyst is formed using a method including several reactions. First, an alkyl magnesium compound (ie, Mg (R *) 2, where R * can be the same or different and have about 1 to 20 carbon-34-200528190 (31) atoms), such as BEM, is Reaction with an alcohol to form a soluble magnesium alkoxide compound according to the following reaction: BEM + 2 ROH Mg (OR) 2 where R is an alkyl group containing, for example, about 1 to 20 carbon atoms. The alcohol represented by the formula ROH may be branched or unbranched. An example of a suitable alcohol is 2-ethylhexanol. Any reaction conditions and order of adding BEM and alcohol reactants to magnesium alkoxide compounds can be used. In one embodiment, the alcohol is added to the BEM solution to form a reaction mixture, which is maintained at ambient temperature and pressure. The reaction mixture is generally stirred for a time sufficient to form a soluble magnesium alkoxide compound. ′ The formed magnesium alkoxide compound is mixed with a mild chlorinating agent to form a magnesium-titanium-alkoxy adduct according to the following formula:

Mg (OR) 2 + TiCln (〇R〇4-n [Ti (OR〇4-nCln * Mg (OR) 2] m

Wherein R 'is an alkyl group, a cycloalkyl group or an aryl group, n is [] to 3, and m is at least 1 and may be greater than 1. The η system is expected to be 1. The reagents include butyl iCln (〇R,) 4-n, where R, = alkyl or aryl, and η is 丨, and T i (〇 1 p r) 3, where 1 p r is isopropyl. Any conditions suitable for the formation of a magnesium · chin-alkoxide adduct can be used in this method. In one embodiment, the method is performed at ambient temperature and pressure. The reactants are mixed for a time sufficient to form a magnesium-titanium-oxyl adduct. It is believed that the adduct is formed due to the steric hindrance of the epi-p-35-200528190 (32) salt compound, which makes it difficult to replace the chlorine atom of the titanate with a magnesium alkoxide ligand. In fact, the adduct is almost (but not completely) converted to MgCl2. Thereafter, the magnesium-titanium alkoxide adduct is mixed with an alkyl chloride compound to be converted into a MgCl2 support. The reaction proceeds as follows:

[Ti (OR ') 4_nClnMg (OR) 2] m + R &quot; C1 "TiMgCl2" + R &quot; OR where R &quot; is an alkyl group containing, for example, about 2 to 18 carbon atoms, where "TiMgCl2" means impregnation MgCl2 support of titanium. Although R "may be a branched or unbranched chain, in certain embodiments it is desirable that R" is not branched. Possible alkyl chloride compounds include benzamidine chloride, chloromethyl ethyl ether, and tertiary butyl chloride, with benzamidine chloride as the preferred embodiment. The amount of alkyl chloride added to the magnesium alkoxide adduct can exceed the amount required for the reaction. The ratio of the amount of benzamidine chloride to the amount of Mg (for example, BEM) in the reaction mixture can be in the range of about 1 to 20 (ie, about 1: 1 to about 20: 1), or about 1 to 10, A range of about 4 to 8 can be expected. The reaction can be carried out under any conditions suitable for precipitating a magnesium chloride support. In one embodiment, the reactants are refluxed for a time sufficient to precipitate the MgCl2 support. In embodiments using third butyl chloride, the reactants may be heated during reflux. In embodiments using benzamidine chloride or chloromethyl ethyl ether, the reactants may be at room temperature during reflux. The reaction also produces one or more by-products such as ethers (shown in the previous reaction). It is believed that the presence of Ti during the precipitation of MgCl2 plays a major role in manufacturing highly active catalysts. -36- 200528190 (33) After separating the MgCl2 support from the reaction mixture, the support can be washed with, for example, hexane to remove any contaminants therefrom. The MgCl2 support is then treated with TiC 14 to form a catalyst slurry according to the following formula: “TiMgCl2” + 2 TiCl4—catalyst. This treatment can be performed under any conditions (such as ambient temperature and pressure) suitable for forming a catalyst slurry. . The catalyst slurry is washed with, for example, hexane and then dried. The formed catalyst may be preactivated with an aluminum alkyl compound such as triethylaluminum (TEAL) to prevent the catalyst from corroding the polymerization reactant. Specifically, the titanium chloride in the catalyst is converted into titanium alkyl when reacted with the aluminum alkyl compound. Or titanium chloride can be converted to HC1 when exposed to moisture, resulting in corrosion of the polymerization reactor. The second group of embodiments has generally described the present invention, and the following examples serve as specific embodiments of the present invention and illustrate their implementation and advantages. It should be understood that these examples are provided for illustration without limiting the details or the scope of patent application below. Unless otherwise stated, all experimental examples were performed in an inert atmosphere using standard S c h 1 e nk techniques. Several catalysts (Sample C-M) were prepared according to the method of the present invention. In addition, two conventional catalysts called sample a and sample b were prepared. Sample B was prepared according to US Patent No. 5,5 63,22 5 for comparison with other catalyst samples. Many compounds required in the examples, namely 2-ethylhexanol, benzamidine chloride, n-butyl chloride, third butyl chloride, chloromethyl ethyl-37- 200528190 (34) ether, ClTKO ^ rh and TiCh It was purchased from Aldrich Chemical Copany and used as received. A heptane solution containing 15.6% by weight of BEM and 0.04% by weight of A1 was purchased from Ak ζ ο Ν ο b e 1. The catalyst particle size distribution, including the average particle size of all catalyst samples, was determined using M a 1 v e r η M a s t e r s i z e r. All particle size distributions listed herein were calculated on a volume average basis. The department was purchased from P hi 11 ips and passed through a 3 A molecular sieve column, F 2 0 0 alumina column and a purification column filled with BASF R3-11 copper catalyst at a rate of 12 ml / min. . An Autoclave Engineer reactor was used to perform ethylene polymerization in the presence of each catalyst sample. This reactor has a capacity of four liters and the unit has four mixing baffles with two opposing pitch propellers. Using a back pressure regulator installed on the dome to maintain the reaction pressure and using steam and cold water to maintain the reaction temperature, ethylene and hydrogen were caused to the reactor. Hexane was introduced into the reactor as a diluent. Unless stated otherwise, polymerization was performed under the conditions listed in Table 3A. The particle size distribution of the fluff particles of polyethylene formed was obtained by sieving analysis using a CSC Scientific Sieve Shaker. The percentage of fines is defined as the weight percentage of fluffy particles smaller than 125 microns.

Comparative Example 1 A Comparative Catalyst Sample A was prepared by placing a heptane solution containing 15.6% by weight of BEM (7 0.83 g, 100 mmol) into a one-liter reactor. Secondly, 26.45 g (203 mmol) of 2-ethylhexanol was slowly added to the solution containing β EM. The reaction mixture was stirred at ambient temperature for one hour. Its -38- 200528190 (35) times ’will be 7 7.50 grams (100 millimoles)! 0 M clTi (0iPr) 3 hexane solution was slowly added to the mixture. The reaction mixture was stirred at ambient temperature for one hour to form a [] \ ^ (0-2-ethylhexyl) 2 (: 1-but 丨 (〇 丨? 1 *) 3] adduct. After that, 'ΓΝΒΤ (34.04 A solution of gram (100 mol) and Tici4 (37.84 g '200 mol) in hexane (250 ml) was added to the resulting solution. The reaction mixture was stirred at ambient temperature for one hour to A white precipitate was formed. The precipitate was allowed to settle and the supernatant liquid was decanted. The precipitate was washed three times with about 2000 liters. The solid was recrystallized in about 500 ml of hexane. Add 50 ml containing TiC14 (18.97 g, 100 mmol) in hexane. The slurry was stirred at ambient temperature for one hour. The solid was allowed to settle and the supernatant was decanted. The solid was washed once with 200 ml of hexane. After that Approximately 150 ml of hexane was added to the precipitate. The catalyst was treated again with 50 ml of a hexane solution containing TiCU (18.97 g, 100 mmol). The slurry was stirred at ambient temperature for one hour. The solids were allowed to settle The decanter was decanted. The catalyst was washed twice with 200 ml of hexane. The precipitate was then precipitated. Approximately 150 ml of hexane was added to the material. The final catalyst was prepared by reacting with 7.16 g (15.6 mmol) of a 25% by weight TEAL heptane solution at ambient temperature for one hour.

Comparative Example 2A Comparative Catalyst Sample B was prepared by adding 330 ml of a 15% by weight dibutylmagnesium heptane solution, 13.3 ml of a tetraisobutylalumoxane pentane solution, and 3 ml of diisocyanate. Pentyl ether and 153 ml of hexane were prepared by introducing them into a one-liter flask. The mixture was stirred at 50 ° C for 10 hours. Next, 0.2 ml of Ti C 14 and a mixture of third butyl chloride (96.4 ml) and D1AE (27.7 ml) were added. -39- 200528190 (36) The mixture was stirred at 5 for 3 hours. The precipitate was allowed to settle and the supernatant liquid was decanted. The solid was washed three times with hexane (100 ml) at room temperature. The solid was reslurried in 100 ml of hexane. Anhydrous HC1 was introduced into the reaction mixture over 20 minutes. The solid was filtered off and washed twice with 100 ml of hexane. The solid was suspended in hexane again. 50 ml of pure TiC 14 was added to the slurry, and the mixture was stirred at 80 ° C for two hours. The supernatant liquid was decanted and the catalyst was washed four times with 100 ml of hexane. The catalyst was dried at 50 ° C under a stream of N2.

Example 1 A Catalyst sample C was prepared according to the present invention as follows: a three-necked, 250 ml round-bottomed flask equipped with a dropping funnel, a separator, and a condenser was placed in a 15.5 wt% BEM (17.71 g, 25 MM) in heptane. Next '6.61 g (51 mmol) of 2-ethylhexanol was slowly added to the BEM-containing solution, and the reaction mixture was stirred at ambient temperature for one hour. Subsequently, 19.38 g (25 mmol) of this solution was added to this solution: (1 butyl) (0 &gt; 1 *) 3 (1 M in hexane). The reaction mixture was stirred at ambient temperature for one hour to form [Mg (0- 2-ethylhexyl hCITiCOiprh] adduct. Second, 18.51 g (200 mmol) of third butyl chloride was added to the resulting solution so that the molar ratio of the third butyl chloride to B EM was about 8 : 1. The reaction mixture is heated at a reflux temperature of 80 ° C for 24 hours to form a MgCl2 precipitate (that is, the subsequent catalyst carrier). The white precipitate is allowed to settle and the yellowish yellow liquid is decanted. 100 ml of hexane was washed three times, and then about 100 ml of hexane was added to the precipitate, and then TiC1 4 (9.485 g, 50 mmol) was slowly added to the resulting solution. The slurry was stirred for one hour at ambient temperature. The solid was allowed to settle down to 40-200528190 (37) and the supernatant liquid was decanted. The catalyst was washed four times with 50 ml of hexane.

Example 2 A The method of Example 1 A was followed to form a catalyst sample 0. The reaction rate was accelerated by adding a larger amount of third butyl chloride to the flask. In particular, 'a solution in which 37.02 g (400 mmol) of third butyl chloride was added to a flask' was heated at 55 ° C for twenty-four hours. This solution therefore contains tertiary butyl chloride / B] EM (16 equivalents relative to BEM) with a molar ratio of about 16: 1. As expected ', the yield of Example 2 A was found to be increased compared to Example 1a. The following Table 1 A provides the composition of the catalysts formed in Comparative Examples a and 2 a and Examples 1 a and 2 A. .

Table 1A Catalyst sample Mg Ti Α1 C1 (wt.%) (Wt.%) (Wt.%) (Wt.%) A 11.92 6.8 2.7 51.71 B 22.8 2 · 3 66.7 C] 3.] 7 0.8 48.05 D 11.01 4.9 47.77 Specifications The amounts of M g and c 1 in C and D are similar to those in sample a. The amounts of Ti in samples C and D are between the amounts of Ti in samples a and b. Example] In A and 2A, the by-products of the reaction with tert-butyl-41-200528190 (38) chloride were detected by proton nuclear magnetic resonance spectroscopy (1H NMR) and gas chromatography mass spectrometry (GCMS) analysis. It was found that the main by-product was 2-ethylhexanol 'instead of the predicted third butyl 2-ethylhexyl ether or third butyl-2-isopropyl ether. Based on this result, it was deduced that some reduction reactions may occur in the mixture, and isobutene may be formed, which is removed from the reaction. Figure 1 A illustrates the particle size distribution of samples A-D. Both the catalysts a and B had a narrow particle distribution. The average particle size of the catalyst of Sample B was slightly larger than that of Sample A. The catalyst samples c and D prepared using the third butyl chloride have a broader bimodal distribution.

Example 3 A Following the method of Example 1 A, the difference is that the main chloride (n-butyl chloride) is added to the flask to replace the third butyl chloride to form a molar ratio of about 16: 1. A solution of n-butyl chloride / BEM (16 equivalents relative to BEM). Unfortunately, n-butyl chloride cannot be precipitated after heating in 501 for 24 hours. [Τί ((νΡΓ) 3 (: 1M§ (〇κ) 2] η). It is inferred that this observation shows that the mechanism of chlorination involves carbonized species that require stability Step of dissociation and elimination (E1). Example 4A A catalyst sample K was prepared as follows: the device was equipped with a dropping funnel, a separator and a two-necked device, and a 500-ml round-bottomed flask was placed in a 15.6% by weight BENE ( 8.85 g, 12.5 mmol) and 100 ml of hexane in heptane solution. Secondly, '3.31 g (25 mmol) of 2-ethylhexanol was slowly added to the solution containing BEM, and the reaction mixture was exposed to the environment. Stir for one hour at the temperature. -42- 200528190 (39) Then add 9.69 g (1 2.5 mmol) of ClTi (CV P ··) 3 'to the aforementioned mixture. The reaction mixture is stirred at ambient temperature for one hour. Next, 17.6 grams (125 millimoles) of benzamidine chloride (PhCOCl) was added to the solution, so that the molar ratio of Ph C 0 C 1 to BE Μ was approximately 〇: 1 (1 eq based on be μ) The reaction mixture was stirred at ambient temperature for rainy hours to form a MgCl2 precipitate. The white precipitate was allowed to settle and decanted. The precipitate was washed three times with 100 ml of hexane. After that, 100 ml of hexane was added to the precipitate, and then TiCl4 (4.25 g, 25 mmol) was slowly added to the solution. The resulting slurry Stir at ambient temperature for one hour. Allow the yellowish solids to settle and remove the yellow liquid. The catalyst was washed three times with 50 ml of hexane. Obviously, the reaction to form the MgCl2 support from PhCOCl does not need to be the same as the third one. Heating during the butyl chloride reaction. As shown in FIG. 3, the particle size distribution of the catalyst sample K formed using PhCOCl can be equal to the particle size distribution of the catalyst samples A and B.

Examples 5A-10A Follow the method of Example 4A to prepare another six samples (samples E-J). The difference is that the amount of PhCOCl is changed each time, so that the molar equivalent to BEM is 1.2 to 7.2. Figure 4 shows the catalyst production as a function of the amount of PhCOCl used in Examples 4A-10A. The catalyst output first increased with the increase in the concentration of PhCOCl, and then became fixed at about 7.0 eq, reaching a maximum output of about 1.7 g. The following Table 2 A provides the catalyst group formed in Example 4 A-] 0 A.

Table 2A

As shown in Table 2A, the titanium content decreases as the degree of PhCOCl increases to 60 equivalents, and remains constant at higher equivalents. The Ti content of the catalyst sample Η_κ is the same as that of the catalyst sample B, but lower than that of the catalyst sample a. This reduction in titanium may explain the possible involvement of the butanate product or unreacted PhCOCl. NMR and GCMS analysis confirmed that the main by-products of the chlorination reaction were 2-ethylhexyl benzate and isopropyl butyrate. These esters and unreacted Ph C 0 C1 (both are Lewis bases) can be combined with electron-deficient titanium or magnesium. It is believed that the formation of this complex makes the titanium more detached from the support. It is believed that the complex with MgC] 2 carrier will hinder the Tic] 4 epitaxy -44- 200528190 (41) configuration in the subsequent titanation. It is interesting to note that the titanium concentration becomes fixed at above seven equivalents of PhCOCl. This actinide corresponds to the chlorination of all ClTUCVPrh and Mg (OR) 2. Above this P h C 0 C 1 amount, the amount of ester is also fixed, indicating that the ester plays an important role in determining the final amount of titanium in the catalyst. The particle size distributions of the catalyst samples E-Η and I-K (formed with different concentrations of PhCOCl) are shown individually in Figures 5 and 6. Sample E formed from the lowest concentration of PhCOCl (1.2 equivalents relative to BEM) has a broad bimodal distribution. Increasing the concentration of PhCOCl produces a catalyst with a narrower unimodal distribution, thus improving the catalyst type. In addition, as shown in Fig. 7, the average particle size (D 5 0) decreased slightly as the concentration of P h C 0 C1 increased. It is inferred that both PhCOCl and ester products can be mismatched with unsaturated magnesium sites on a developing MgCl2 support. As mentioned earlier, 'these Lewis bases help the extraction of titanium from the developing steps. As such, it is believed that the kinetics of carrier formation will change due to the absence of titanium complexes.

Example 1 1 A catalyst sample L was prepared as follows: A two-necked 250 ml round bottom flask equipped with a dropping funnel, a separator, and a condenser was placed in a 15.6 wt. BEM (4.43 g, 6.25 mmol) in heptane solution and 30 ml of hexane (30 liters) ° After that, 1.6 66 g (12. 5 mmol) of 2 ethylhexanol Add slowly to a solution containing BEM, and stir the reaction mixture at ambient temperature for one hour. Thereafter, a solution of ClTKCVPrh (iM in hexane, 4.85 g '6 · 25 pen ears) was slowly added to the mixture, and the reaction mixture was stirred at ambient temperature for one hour. Then, a hexane solution (25 ml) containing chloromethylethyl ether-45- 200528190 (42) (CM EE) (9.4 5 g, 100 mmol) was added to the solution, so that CMEE had no effect on BEM. The ear ratio is approximately 8: 1 (8 equivalents relative to BEM). The reaction mixture was stirred at ambient temperature for one hour, and a MgC] 2 precipitate was formed. The white precipitate was allowed to settle and the supernatant liquid was decanted. The η Shen Yuan was washed three times with 50 ml of the hospital. Then, 30 ml of Jiyuan was added to Shenyuan, and then TiCl4 (2.13 g, 125 mmol) was slowly added to the solution (30 mL). The resulting slurry was stirred at ambient temperature for one hour. The yellowish solid was allowed to settle and the yellow supernatant liquid was decanted. Catalyst · Followed by washing with 500 ml three times in the hospital. FIG. 9 shows the particle size distributions of the catalyst samples [, mainly catalyst K, and catalyst samples a and B. The catalyst sample mainly composed of c Μ Ε Ε has a particle size distribution slightly wider than that of sample A, sample B, and catalyst δ pattern K mainly composed of p h C Ο C 1. The particle size distribution of the cM E E-based catalyst has a shoulder of about 7 microns. Comparative Example 3 A ^ ^ was suspected to be polymerized under the conditions listed in Table 3 A in the presence of catalyst samples A and TE A L auxiliary catalysts.

Comparative Example 4A Ethylene was polymerized under the conditions shown in Table 3A in the presence of catalyst sample B and TEAL auxiliary catalyst. ¥

Example] 2A -46- 200528190 (43) Ethylene was polymerized using catalyst samples c and D prepared with third butyl chloride under the conditions listed in Table 3A. FIG. 9 shows the loose particle size distributions of the polymers prepared in Examples 12 A and Comparative Examples 3 A and 4A. The particle size distributions obtained using catalyst samples C and D were extremely wide. In contrast, the distributions obtained from catalyst samples A and B are extremely narrow. The fluff produced from samples C and D contained more fines than the fluff produced from samples A and B. The fluffs made from samples C and D also had relatively low bulk density.

Table 3 A Thinner—Jane temperature (° c) ___J0 H2 / C2 -__ 2/8 Pressure (psig) -2 5 Auxiliary catalyst TEAL (0.75 T = r -S // Λ ^ Provided in Table 4A below Properties of polymer resins using catalyst samples A, B, c and D

200528190 (44)

Table 4A Density (g / cc) of Mg-based active resin, melt index, 2.1kg (dg / min) melt index, 5.0kg (dg / min) sr2 (hlmi / mi2) sr5 (HLMI / MI5) Wax (%) A 20,694 0.9647 3.75 12.06 35.6 11.1 1.4 B 10,000 0.9584 0.47 1.4 29.5 10.2 1.3 C 18.766 0.9674 0.59 1.6 28.1 10.3 0.7 D 41.390 0.9578 1.06 3.2 30.0 9.8 0.6 Each catalyst sample is mainly magnesium-based It is determined by first dissolving the catalyst and the polymer formed by them in an acid to extract the residual Mg. The catalytic activity was determined based on the residual Mg content. As shown in Table 4A, the activity of catalyst sample C, mainly Mg, was slightly lower than that of sample A and higher than that of catalyst sample B. The activity of catalyst sample D was higher than that of catalyst samples A and B. The shear response of polymers prepared using catalyst samples was calculated by finding the ratio of the high load melt index (HLMI) to the melt index. The shear response of the polymers prepared from catalyst samples C and D is similar to that of the polymer of sample B, but slightly lower than that of the polymer of sample A. All polymers produced similar amounts of wax.

Comparative Example 1 3 A Ethylene was polymerized under the conditions listed in Table 3 A using a catalyst sample E-K prepared with benzamidine chloride. Figure 10A shows the loose particle size distribution of the polymer (Sample G-K) prepared in this example. The average particle size of PhPOCl-based resin is -48- 200528190 (45) The particle size (D 5G) is larger than that of Sample A and Sample B resins. Table 5A below compares the type of the PhPOCl catalyst sample with the type of polymer formed using the PhPOCl catalyst sample.

Table 5 A Catalyst type Polymer type Catalyst sample D10 (micron) D50 (micron) D90 (micron) D90-D10 D50 (micron) Fine (%) F 10.08 19.12 30.94 20.86 6 17.9 4.6 G 9.87 16.76 24.89 15.02 65 8.0 1.8 Η 10.37 19.77 30.42 20.05 5 3 2.1 4.4 I 9.58 15.89 23.39 13.81 5 3 3.4 1. .7 J 9.32 14.38 2 0.35 11.03 3 7 8.3 8.1 KK 5.74 12.56 2 1.74 16.00 404 2.2 A 5.29 10.85 18.32 13.03 292 1 .0 B 7.26 14.24 22.67 15.14 286 0.2 Based on replication theory, the polymer type can be related to the catalyst type. However, the polymer type of sample F-K obviously does not correspond to (ie, disproportionate) the catalyst type, while samples A and B obviously correspond. Table 6A below provides the properties of polymers prepared using PhPOCl catalyst samples (Sample E-K) and catalyst samples A and B. -49- 200528190 (46)

Table 6A Density (g / cc) of Mg-based active resin Melt index, 2.16 kg (dg / min) Melt index, 5.0 kg (dg / min) sr2 (HLMI / MI2) sr5 (HLMI / MI5 ) 鱲 (%) E 39000 0.9669 8.97 29.25 32.0 9.8 0.8 F 40000 0.9633 3.42 10.39 30.1 9.9 0.2 G 37000 0.9633 4.32 13.05 30.4 10.1 0.3 Η 25000 0.9636 2.33 6.60 27.8 9.8 0.3 I 26000 0.9626 2.90 10.89 37.7 10.0 0.2 J 25000 0.9636 4.90 14.48 28.5 9.6 0.3 Κ 38000 0.9601 1.51 4.16 29.2 10.6 0,5 A 20694 0.9647 3.75 12.06 35.6 11.1 1.4 B 10000 0.9584 0.47 1.4 29.5 10.2 1.3

The activity of SiUi E · K, mainly Mg, was higher than that of samples A and B. The activity usually decreases with the increase of Phcocl equivalent. Except for sample κ, it has an equivalent of 10. Sample E-K polymer has the same density as Sample A and B polymers. The melt flow rate (ie, the melt index) of the polymer of sample E-K and the polymer of sample a is higher than that of sample B polymer. The shear reaction of the sample E-K polymer was the same as that of the sample B polymer, but slightly lower than that of the sample A polymer. All polymers produced similar amounts of wax.

Comparative Example 1 4 A As described above, a catalyst sample mainly composed of PhCOCl (hereinafter referred to as "-50-50200528190 (47) S style Iι") was prepared by washing MgCL with hexane. This example is compared Catalyst sample: h and another catalyst sample h (which is prepared in the same way as sample n, but the washing step is omitted). It is believed that the elimination of the washing step can greatly reduce the time and cost of catalyst manufacturing. The following table 7 A shows the sample composition and the catalyst composition of h. Table 7A The equivalent weight (% by weight) (light%) (weight 0 / 〇) (% by weight) of the catalyst washing PhCOCl Ti A1 Mg C1 Ιι Yes 6 2.6 &lt; 0.2 12.39 43.02 12 None 6 1.8 &lt; 0.2 11.78 38.21

Skipping the washing step reduces the titanium concentration by about 30%. The washed catalyst sample Iι showed a pale yellow color. The unwashed catalyst sample also appeared yellow during the TiCl4 addition. However, when this TiCI4 came into contact with the mother liquor, it immediately became colorless. It is inferred that the complex of ester and TiCl4 can produce yellow, and PhCOCl can react with Tic 14 to form a colorless compound. This observation supports previous discussions of the dependence of titanium concentration on the amount of PhCOCl. It is believed that excessive amounts of PhCOCl and ester (if not removed) will coincide with both TiCl2 and the surface of the support, preventing the deposition of titanium on the surface of the support. As shown in Figure 11, the particle size distributions of samples I] and 12 are almost the same. Therefore, the catalyst particle size distribution is not affected by the washing step. This observation is not surprising since the washing step is performed after the MgC] 2 carrier is formed. Samples I] and] 2 were both used to polymerize ethylene. The catalyst and polymer types of Sample I] and -51-200528190 (48) are provided in Table 8A below.

Table 8 A Catalyst type polymer type, washing step D] 〇 〇 5 0 D 9 0 D 9 〇 D 5 0 Details? (Micron) (micron) (micron) D 1 〇 (micron) (%) Yes 9.58 15.89 23.39 13.81 5 3 3.4 1.7 M 9.21 15.48 23.02 13.81 23 9.2 23.7

Table 8A further supports the conclusion that the particle size distribution is not affected by the washing step. The amount of fines formed in the polymer is greatly increased when the washing step is omitted. The increase in detail may lead to low production capacity. The series of properties of the polymers formed using catalyst samples h and 12 are shown in Table 9A below.

Table 9A Active bulk density (g / cc) based on Mg Resin density (g / cc) Melt index 2.16 kg (dg / min) Melt index 5.0 kg (dg / min) sr2 (HLMI / mi2) sr5 (HLMI / mi5) Wax (%) Yes 26000 0.23 0.9626 2.90 10.89 37.7 10.0 ----- 0.2 Μ y \\\ 14800 0.29 0.9557 0.48 1.36 24.8 8.8 0.1

As shown in Table 9A, the polymerization activity of the unwashed catalyst was almost half that of the washed catalyst. The density of the two polymers is almost the same. However, the shear-52-200528190 (49) reaction data show that the unwashed catalyst has a narrower molecular weight distribution than the washed 'strip catalyst. It is believed that the presence of phcoci and ester in the catalyst affects the distribution of active sites in the catalyst.

In Example 15A, the effect of BEM concentration on catalyst properties was also investigated. The first catalyst sample (Phase L) based on PhCOCl was prepared using a BEM solution diluted with 100 ml of hexane. For comparison, a second sample (Phase M) with PhCOCl as the main catalyst was prepared using a BEM solution diluted in 20 ml of hexane. FIG. 12 shows the catalyst particle size distribution of the catalyst samples L and M. FIG. The distribution of the two catalysts is very similar. The composition and properties of the catalyst patterns L and M and the polymers prepared therefrom are shown individually in Tables 10A and IIA below.

Table 1 0 A Catalyst Sample Yield Ti A1 Mg C1 (g) (wt%) (wt%) (wt%) (wt%) L 0.86 3.5 &lt; 0.2 12.34 43.23 M 0.8 1 3.8 &lt; 0.2 12.55 47.55

Table 1 A Density (g / cc) of active resin based on Mg catalyst sample Melt index 2.] 6 kg (dg / min) Melt index 5 kg (dg / min) sr2 (HLMI / MI2) sr5 fHLMl / Ml5) Wax (%) L 40000 0.9609 2.07 6.19 28.0 9.4 0.3 M 40000 0.9633 3.42 10.39 30.1 9.9 0.2 -53- 200528190 (50) Table 10A and Π A show that the BEM concentration is basically the catalyst composition and polymer properties no effect. The conclusion is that novel catalysts are synthesized using alkyl chlorides such as n-butyl chloride, tertiary butyl chloride, and chloromethyl ethyl ether. The benzamidine chloride and chloromethyl ethyl ether form a catalyst with a satisfactory particle size distribution, while the third butyl chloride produces a bimodal distribution, and the n-butyl chloride cannot form MgCl2. This catalyst preparation was optimized by changing the amount of benzamidine chloride added to the magnesium alkoxide adduct. As predicted, the catalyst production increased with the amount of benzamidine chloride and became saturated at about seven equivalents of benzamidine chloride relative to BEM. The catalyst particle size distribution becomes narrower as the amount of benzamidine chloride increases. Experiments were also performed to observe the effect of omitting the washing step after carrier formation. Compared with the washed catalyst, the unwashed catalyst sample has lower activity and lower shear response. The effect of BEM concentration on catalyst properties was also examined. Particle size distribution, catalyst composition, and polymer properties are not affected by BEM concentration. Although the embodiments of the present invention have been shown and described, those skilled in the art can make modifications without departing from the spirit and teachings of the present invention. The embodiments described in the present invention are for illustration only and not for limitation. When revealing a chemical mechanism or theory, it is provided on the basis of information and credibility, and not necessarily bound by that person. The invention disclosed in the present invention can have many changes and modifications and is included in the scope of the present invention. Therefore, the scope of protection is not limited to the foregoing description, but is limited only by the scope of the following patent applications. All equivalents. -54- 200528190 (51) [Brief description of the diagram] Figure 1 illustrates the settlement efficiency curve of a polymer prepared using the catalyst of the present invention (Example) and a polymer prepared using a conventional catalyst (Comparative Example 4). . Fig. 2 shows the particle size distributions of the catalysts described in Comparative Examples 1 A-2 A and Examples 1 A-2 A. Figure 3 shows the particle size distributions of the catalysts described in Comparative Examples 1 A-2A and 4A. Fig. 4 shows the catalyst yield expressed as a function of the amount of PhCOCl used in Examples 4A-10A. 5 to 6 show particle size distributions of the catalysts formed in Examples 4A-10A. Figure 7 shows the average catalyst particle size (D50) as a function of the amount of PhCOCl used in Examples 4A-10A. Fig. 8 shows the particle size distributions of the catalysts described in Comparative Examples 1 A-2A and Examples 4A and 1 1 A. Fig. 9 shows the loose particle size distributions of the polymer resins described in Comparative Examples 3A-4A and Example 12A. Fig. 10 shows the loose particle size distributions of the polymer resins described in Comparative Examples 3A-4A and 13A. FIG. 11 shows the particle size distribution of the catalyst described in Example 14A. FIG. 12 shows the particle size distribution of the catalyst described in Example 15A. -55-

Claims (1)

200528190 (1) X. Application for patent scope 1. A method for manufacturing a catalyst component, comprising: a) forming a reaction product A by contacting a magnesium diol salt compound with a halogenating agent; b) making the reaction product A Contacting the first halogenation / titanating agent to form a reaction product B; 0 contacting the reaction product B with a second halogenation / titanating agent to form a reaction product C; and d) contacting the reaction product C with a third halogenation / titanium The acidifying agent is contacted to form catalyst component D. 2. The method according to item 1 of the scope of patent application, wherein the halogenating agent has the general formula C1AR "'X, where A is a non-reducing oxygenophilic compound and R"' is a hydrocarbon group having about 2 to 6 carbon atoms , And X is the valence of A minus 1 ° 3 · As the method of the scope of patent application, the halogenating agent is ClTUC ^ Pr) "4 _As the method of scope of patent application, the first Halogenating / titanating agents are blends of two tetra-substituted titanium compounds, all four substituents being the same, and these substituents are halogen or alkoxy or benzene having 2 to 10 carbon atoms 5. The method according to item 4 of the patent application, wherein the first halogenating / titanating agent is a blend of titanium halide and organic titanate. 6 · The method according to item 5 of the patent application, The first halogenating / titanating agent is a blend of TiCI4 and Ti (0Bu) 4, and 200528190 (2) TiCl4 / Ti (OBu) 4 is in the range of 0.5: 1 to 6]. 7 · If applied The method of item 1 of the patent scope, wherein the second and third halogenating / titanating agents comprise titanium tetrachloride. The method according to item 7, wherein steps (c) and (d) comprise a ratio of titanium tetrachloride to magnesium ranging from about 0.1 to about 5. 9 · The method according to item 1 of the patent application range, wherein Products A, B, and C are washed with a hydrocarbon solvent before the subsequent halogenation / titanation step. '10. The method according to item 9 of the patent application, wherein the reaction products A, B, and C are washed with a hydrocarbon solvent until subsequent Prior to the halogenation / titanation step, the [Ti] content of the titanium species is less than about 100 millimolars per liter. 1 1. The method according to item 1 of the patent application, wherein the reaction product D is washed with a hydrocarbon solvent until the titanium species [Ti ] The content is less than about 20 millimoles per liter. 1 2 · The method according to item 1 of the patent application scope, wherein the electron donor is present in any one or more of steps a), b), c) or d) In which, the ratio of the electron donor to the metal is in the range of about 0: 1 to about 10: 1. 1 · If the method according to item 1 of the patent application scope further includes placing the catalyst of the present invention in 1 4 · The method according to item 13 of the patent application scope, wherein the inert carrier is magnesium 15. The method of claim 1 further comprising: e) contacting D with an organometallic pre-activator to form a pre-activated catalyst system. 1 6. A method comprising the following Step method to obtain: catalyst: -57- 200528190 (3) a) contact the catalyst component with an organometallic pre-activator, wherein the catalyst component is prepared by a method including the following steps: i) Contacting the magnesium diol salt compound with a halogenating agent to form a reaction product A; ii) contacting the reaction product A with a first halogenation / titanating agent to form a reaction product B; iii) contacting the reaction product B with a second halogenation / Contacting a titanating agent to form a reaction product C; and iv) contacting the reaction product C with a third halogenating / titanating agent to form a catalyst component. 17. The catalyst according to item 16 of the scope of patent application, wherein the organometallic preactivator is an aluminum alkyl having the general formula A1R3, wherein at least one R is an alkyl having 1 to 8 carbon atoms or Halo, and wherein each R may be the same or different. 18 · The catalyst according to item 17 in the scope of patent application, wherein the organic metal preactivator is trialkylaluminum. 19. The catalyst according to item 18 of the scope of patent application, wherein the second and third halogenating / titanating agents comprise titanium tetrachloride. 2 0. If the catalyst for item 19 of the scope of patent application, the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1. 2 1 · The method according to item 16 of the application, wherein the reaction products A, B and C are washed with a hydrocarbon solvent before the subsequent halogenation / titanation step. 22. The method according to item 6 of the patent application scope, wherein the catalyst component is washed with a hydrocarbon solvent until the titanium species [T i] content is less than about 20 mmol / 200528190 (4) liters. 23 · —A polymer prepared by a method including the following steps: a) One or more olefin monomers are brought together in the presence of a catalyst under polymerization conditions, wherein the catalyst is prepared by a method including the following steps: 1) contacting a magnesium diol salt compound with a halogenating agent to form a reaction product A; ii) contacting the reaction product A with a first halogenating / titanating agent to form a reaction product B; iii) contacting the reaction product B with a second Contacting a halogenation / titanating agent to form a reaction product C; and iv) contacting the reaction product C with a third halogenating / titanating agent to form a catalyst component; and b) extracting a polyolefin polymer. 24. The polymer according to item 23 of the patent application range, wherein the catalyst is prepared by a method further comprising the following steps: v) The catalyst component is brought into contact with an organoaluminum reagent. 25. The polymer according to item 23 of the application, wherein the second and third halogenating / titanating agents comprise titanium tetrachloride. 26. The polymer according to item 23 of the application, wherein the reaction products A, B and C are washed with a hydrocarbon solvent before the subsequent halogenation / titanation step. 2 7 · A thin film, fiber, pipe, fabric or article of manufacture containing a polymer such as the one covered by the patent application No. 23. -59- 200528190 (5) 2 8 · —A method for olefin polymerization, comprising: a) contacting one or more olefin monomers together in the presence of a catalyst under polymerization conditions, wherein the catalyst includes Prepared by the following steps: i) contacting a magnesium diol salt compound with a halogenating agent to form a reaction product A; ii) contacting the reaction product A with a first halogenating / titanating agent to form a reaction product B; iii) making Contacting the reaction product B with a second halogenated / titanating agent to form a reaction product C; and iv) contacting the reaction product C with a third halogenating / titanating agent to form a catalyst component to form a reaction product D; and b ) Extracting a polyolefin polymer; wherein at least one reaction product A, B and C is washed with a hydrocarbon solvent before the subsequent halogenation / titanation step; and wherein the reaction product D is washed with a hydrocarbon solvent until the [Ti] content of the titanium species is lower than About 100 millimoles / liter. 29. The method of claim 28, wherein the polymer has a molecular weight distribution of at least 4.0. 30. The method of claim 28, wherein the polymer has a bulk density of at least 0.31 g / cc. 3 1-An article containing a polymer prepared by the method of claim 28 of the patent application. 3 2 —A method for manufacturing a catalyst, comprising: controlling the viscosity of the catalyst synthesis solution by adding an alkyl aluminum to change the catalyst-60- 200528190 (6) precipitation of the component from the catalyst synthesis solution, wherein the The average particle size of the catalyst component increases as the concentration of the alkyl aluminum in the synthetic solution increases. 33. The method of claim 32, further comprising contacting the contacting component with an organometallic pre-activator to form a catalyst, wherein the average particle size of the catalyst is as a result of the alkyl aluminum being synthesized. The increase in the concentration of the solution increases. 34. The method of claim 32, wherein the catalyst synthesis solution comprises: contacting a magnesium diol salt compound with a halogenating agent to form a reaction product A; and reacting the reaction product A with a series of halogenated / titanium Contacting an acidifying agent to form a catalyst component; and contacting the catalyst component with an organometallic pre-activator to form a catalyst; wherein the average particle size of the catalyst is a function of the concentration of the alkyl aluminum in the synthetic solution. Increase and increase. 35. The method of claim 34, wherein at least one of the reaction product A and the produced reaction product is washed with a solvent after each halogenation / titanation step to remove contaminants. 3 6 · A method for manufacturing a catalyst, comprising: a) contacting a diol magnesium salt compound with a halogenating agent to form a reaction product A; b) contacting the reaction product A with a first halogenating / titanating agent to form a reaction Product B; -61-200528190 (7) c) contacting reaction product B with a second halogenating / titanating agent to form reaction product C; and d) contacting reaction product C with a third halogenating / titanating agent to form a reaction Product D; and e) contacting reaction product D with an organometallic preactivator to form a catalyst; wherein the magnesium diol salt compound is a reaction product including a reaction of the following compound: an alkyl magnesium compound of the general formula MgRR ', Wherein R and R 'are radicals with 1 to 10 carbon atoms and may be the same or different; alcohols of the general formula R''OH, where the alcohol is straight or branched, and where R' 'is Is an alkyl group having 2 to 20 carbon atoms; and an aluminum alkyl having the general formula A1R ", 3, wherein at least one R" 'is an alkyl or alkoxy or halo group having 1 to 8 carbon atoms , And each R "'can be the same or different, and the average particle size of the catalyst varies with Increasing the proportion of the alkyl aluminum to magnesium alkyl group increases. 37. The method according to item 36 of the scope of patent application, wherein the ratio of the aluminum alkyl to the magnesium alloy is in the range of about 0.01: 1 to about 10: 1. 38. The method according to item 36 of the scope of patent application, wherein steps c) and d) each include titanium tetrachloride as a halogenating / titanating agent, and the ratio of titanium tetrachloride to magnesium is between about 0 · In the range of 1 to about 5. 39. The method according to item 36 of the application, wherein the magnesium diol salt compound is bis (2-ethylhexanol) magnesium. 40. The method according to item 36 of the patent application, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium, or butylethyl-62-200528190 (8) magnesium. 4 1 · The method according to item 36 of the application, wherein the alcohol is selected from the group consisting of ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-pentanol and 2-ethylhexanol . 42. The method of claim 36, wherein the organic metal preactivator comprises an aluminum alkyl. 43. The method of claim 36, wherein the first halogenating / titanating agent is a blend of two tetra-substituted titanium compounds, all four substituents are the same, and the substituents are Is a halo group or an alkoxy or phenoxy group having 2 to 20 carbon atoms. 44. The method of claim 43 in the patent application, wherein the first halogenating / titanating agent is a blend of titanium halide and organic titanate. 4 5 · The method according to item 44 of the patent application, wherein the first halogenating / titanating agent is a blend of TiCl4 and Ti (OBu) 4, and TiCl4 / Ti (OBu) 4 is between 0.5: 1 to 6: 1 range. 46. The method of claim 36, wherein the reaction further includes an electron donor. 47. The method of claim 46, wherein the ratio of the electron donor to magnesium is in the range of about 0: 1 to about 10: 1. 48. The method according to item 46 of the patent application scope, wherein the electron donor system is an ether. 4 9 · The method according to item 36 of the scope of patent application, wherein the halogenating agent is of the general formula C1AR ", where A is a non-reducing oxygen-promoting compound, and R" 'is a compound having about 2 to 6 carbons. A hydrocarbon group of an atom, and χ is the valence of a -63-200528190 Ο) minus 1. 50. The method of item 49 in the scope of patent application, wherein the halogenating agent is CITKCVPrh. The method of item 36, wherein at least one of the reaction products A, B, C, and D is washed with a hydrocarbon solvent until the content of the titanium species [τ i] is less than about 100 millimolars / liter. 5 2 · 如The method of claim 36, wherein the electron donor system exists in any one or more of steps a), b), c) or d), and the ratio of the electron donor to the metal system is Within the range of about 0: 1 to about 10: 1. 5 3 · The method according to item 36 of the patent application scope, further comprising placing the catalyst of the present invention on an inert carrier. 5 4 · If applying for a patent The method according to item 53, wherein the inert carrier is a magnesium compound. 5 5-A method including the following steps The prepared catalyst: a) The catalyst component is contacted with an organometallic pre-activator, wherein the catalyst component is prepared by a method including the following steps: i) the general formula Mg (0R ”) 2 The magnesium diol salt compound is contacted with a halogenating agent that can exchange one halogen with one alkoxy group to form a reaction product A, wherein R "is a hydrocarbon group or substituted hydrocarbon group having 1 to 20 carbon atoms; ii) making the reaction product A is in contact with a first halogenation / titanating agent to form a reaction product B; Hi) contacting the reaction product B with a second halogenation / titanating agent to form a reaction product C; -64- 200528190 (10) iv) reacting Product C is contacted with a third halogenating / titanating agent to form a catalyst component; wherein the magnesium diol salt compound is a reaction product including a reaction of the following compound: an alkyl magnesium compound of the general formula MgRR1, where R and R 'Is an alkyl group having 1 to 10 carbon atoms and may be the same or different; an alcohol of the general formula R "OH, wherein the alcohol is a straight or branched chain, and wherein R, is a group having 2 to An alkyl group of 20 carbon atoms; and an aluminum alkyl of the general formula A1R · '' 3, wherein at least one R '&quot; is an alkyl or alkoxy or halo group with] to 8 carbon atoms, and each R "'may be the same or different; and wherein the average particle size of the catalyst is The proportion of alkyl magnesium increases with the increase. 56. If the catalyst in the scope of patent application No. 55, the organometallic pre-activator is an aluminum alkyl of the general formula A1R3, at least one of which R is 1 to 8 An alkyl or halo group of 6 carbon atoms, wherein each R may be the same or different. 57. The catalyst according to item 56 of the patent application scope, wherein the organic metal preactivator is trialkylaluminum. 58. The catalyst as claimed in claim 55, wherein the second and third halogenating / titanating agents comprise titanium tetrachloride. 5 9 · If the catalyst in the scope of patent application No. 55, the ratio of aluminum to titanium is in the range of 0 · 1: 1 to 2: 1. 6 0 — A polymer prepared by a method including the following steps: a) One or more olefin monomers are contacted together in the presence of a catalyst under polymerization conditions, wherein the catalyst includes the following steps: Method -65- 200528190 (11) i) The following compounds are contacted: an alkyl magnesium compound of the general formula MgRIT, where R and R 'are radicals having 1 to 10 carbon atoms t and may be the same or Are different; alcohols of the general formula R Η ，, where the alcohol is a straight or branched chain, and wherein R "is a radical having 2 to 20 carbon atoms; and an aluminum alkyl of the general formula AIR" '3 Wherein at least one R is an alkyl or alkoxy or halo group having 1 to 8 carbon atoms, and each of the R "'may be the same or different; to form a diol of the general formula Mg (OR") 2 A magnesium salt; ii) contacting the diol magnesium salt compound with a halogenating agent to form a reaction product A, wherein R "is a hydrocarbon group or a substituted hydrocarbon group having 1 to 20 carbon atoms; iii) the reaction product A and the first Contacting the halogenating / titanating agent to form a reaction product B; and iv) contacting the reaction product B with a second halogenating / titanating agent to form Reaction product C; and v) contacting reaction product C with a third halogenating / titanating agent to form a catalyst component; and vi) contacting the catalyst component with an organoaluminum reagent; and b) extracting polyolefin to polymerize Wherein the average particle size of the polymer increases as the ratio of the academic foundation to the academic table used in step i} increases. 61. The polymer of item 60 of the patent application, wherein the reaction product At least one of A, B, and C is washed with a hydrocarbon solvent before the subsequent halogenation / titanation step. 62 · The polymer according to item 60 of the patent application range, wherein the monomer -66- 200528190 (12) is ethylene Monomer. 6 3 · The polymer according to item 60 of the patent application, wherein the polymer is polyethylene. 6 4 · The polymer according to item 60 of the patent application, wherein the polymer has at least 4 · Molecular weight distribution of 0. 6 5 · The polymer according to item 60 of the patent application range, wherein the polymer has a bulk density of at least 0 · 3 1 g / cc. 6 6 ·-A kind containing as described in the patent application range 60 Polymer film, fiber, pipe, weaving 67. A method of controlling the particle size of a polyolefin polymer comprising: a) contacting one or more olefin monomers together in the presence of a catalyst under polymerization conditions, wherein the catalyst is obtained by including It is prepared by the following steps: i) contacting the following compound: a compound of the general formula M g RR ', wherein R and R' are alkyl groups having 1 to 10 carbon atoms and may be the same or different; An alcohol of the general formula R "OH, wherein the alcohol is a straight or branched chain, and wherein R" is an alkyl group having 2 to 20 carbon atoms; and an alkyl group of the general formula A1R "'3 Aluminum, wherein at least one R '' 'is a radical or alkoxy or halo having 1 to 8 carbon atoms, and each of the R' 'can be the same or different; to form the general formula Mg (OR ”) 2 of the soluble magnesium diol salt; ii) contacting the soluble magnesium diol salt salt compound with a halogenating agent that can exchange a halogen with an alkoxy group to form a reaction product A, wherein R "is 1 to 20 carbons Atomic hydrocarbon group or substituted hydrocarbon group; -67- 200528190 (13) iii) reacting product A with the first halogenating / titanating agent Contacting to form reaction product B; and iv) contacting reaction product B with a second halogenated / titanating agent to form reaction product C; and v) contacting reaction product C with a third halogenating / titanating agent to form A catalyst component; and vi) contacting the catalyst component with an organoaluminum reagent; and b) extracting a polyolefin polymer; wherein the average particle size of the polymer is in accordance with the aluminum alkyl used in step i) The increase in the proportion of alkyl magnesium increases. -68-