CN1856363A - Ziegler-Natta catalysts for polyolefins - Google Patents

Abstract

A Ziegler-Natta catalyst component is disclosed, which can be prepared by a method comprising the following steps: contacting a magnesium glycol compound with a halogenating agent to form a reaction product A, and contacting the reaction product A with first, second, and third halogenating/titanium esterifying agents. The catalyst component, catalyst, catalyst system, polyolefin, products prepared therefrom, and methods for forming the above substances are disclosed. The reaction products can be washed with hydrocarbon solvents to reduce the titanium [Ti] content to less than about 100 mmol/L.

Description

Ziegler-Natta catalysts for polyolefins

Cross References to Related Applications

This application is filed on October 13, 2000 and is entitled "Ziegler-Natta catalysts for polyolefins with narrow molecular weight distribution to broad molecular weight distribution, methods for their preparation and use, and polyolefins prepared therefrom (Ziegler-Natta Catalyst For Narrow to Broad MWD of Polyolefins, Method of Making, Method of Using, And Polyolefins Made Therewith)" U.S. Patent Application 09/687560, which is hereby incorporated by reference, Patent Application 09/687560 is a continuation-in-part of U.S. Patent Application 08/789,862, entitled "Ziegler-Natta Catalysts for Olefin Polymerization," filed January 28, 1997, U.S. Patent Application 08 /789862 issued January 16, 2001 as US Patent No. 6,174,971, which is also incorporated herein by reference.

Background of the Invention

technical field

The present invention generally relates to catalysts, methods of making catalysts, methods of using catalysts, methods of polymerizing and polymers made with such catalysts. More specifically, the present invention relates to polyolefin catalysts and Ziegler-Natta catalysts, methods of making such catalysts, methods of using such catalysts, polyolefin polymerization and polyolefins.

Background technique

Alkenes, also known as alkenes, are unsaturated hydrocarbons whose molecules contain one or more pairs of carbon atoms connected by double bonds. When subjected to the polymerization process, olefins can be converted into polyolefins such as polyethylene and polypropylene. One common polymerization method involves contacting olefin monomers with a Ziegler-Natta type catalyst system. A number of Ziegler-Natta type polyolefin catalysts, their general preparation and subsequent use are well known in the art of polymerization. Typically, these systems include a Ziegler-Natta type polymerization catalyst component; a cocatalyst; and an electron donating compound. One type of Ziegler-Natta type polymerization catalyst component may be a complex derived from a halide of a transition metal such as titanium, chromium or vanadium, alkane, and a metal hydride and/or a metal alkyl The base metal is usually an organoaluminum compound. The catalyst component generally comprises a titanium halide supported on a magnesium compound complexed with an aluminum alkyl. There are many published patents dealing with catalysts and catalyst systems primarily designed to polymerize propylene and ethylene, which are known to those skilled in the art. Examples of such catalyst systems are mentioned in US Patent Nos. 4,107,413, 4,294,721, 4,439,540, 4,114,319, 4,220,554, 4,460,701, 4,562,173, 5,066,738, and 6,174,971, which are incorporated herein by reference.

Conventional Ziegler-Natta catalysts comprise transition metal compounds generally represented by the general formula _MRx , where M is a transition metal compound, R is a halogen or hydrocarbyl group, and x is the valence of the transition metal. Typically, M is selected from metals of Groups IV to VII, such as titanium, chromium or vanadium, and R is chlorine, bromine or alkoxy. Commonly used transition metal compounds are TiCl ₄ , TiBr ₄ , Ti(OC ₂ H ₅ ) ₃ Cl, Ti(OC ₃ H ₇ ) ₂ Cl ₂ , Ti(OC ₆ H ₁₃ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ ) ₂ Br ₂ and Ti(OC ₁₂ H ₂₅ )Cl ₃ . Transition metal compounds are usually supported on an inert solid, for example, on magnesium chloride.

Ziegler-Natta catalysts are generally provided in supported form, ie deposited on a solid crystalline support. The support can be an inert solid that does not chemically react with any of the components of conventional Ziegler-Natta catalysts. The carrier is usually a magnesium compound. Examples of magnesium compounds that may be used to provide a source of support for the catalyst components are magnesium halides, dialkoxymagnesiums, alkoxymagnesium halides, magnesium oxyhalides, dialkylmagnesiums, magnesium oxide, magnesium hydroxide and carboxylic acids of magnesium Salt.

The nature of the polymerization catalyst affects the properties of the polymer formed with the catalyst. For example, the morphology of the polymer often depends on the morphology of the catalyst. Good polymer morphology includes uniform particle size and shape and acceptable bulk density. Furthermore, for various reasons, for example, to avoid clogging transfer or recirculation lines, it is desirable to minimize the number of very small polymer particles (ie fines). Very large particles must also be reduced as much as possible to avoid the formation of lumps and ropes in the polymerization reactor.

Another polymer property that is affected by the type of catalyst used is the molecular weight distribution (MWD), which refers to the breadth of variation in molecular length in a given polymer resin. In polyethylene, for example, narrowing the molecular weight distribution can improve toughness, ie improve puncture, tensile and impact properties. On the other hand, a broader molecular weight distribution eases processing and benefits melt strength.

Although much is known about Ziegler-Natta catalysts, continuous efforts are needed to achieve improvements in polymer yield, catalyst lifetime, catalyst activity, and the ability to produce polyolefins with specific properties.

Contents of the invention

One embodiment of the present invention provides a method for preparing a catalyst, comprising: a) contacting a magnesium glycolate compound with a halogenating agent to form a reaction product A; b) contacting the reaction product A with a first halogenated/titanate c) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; and d) contacting reaction product C with a third halogenation/titanation agent, Reaction product D is formed. The second and third halogenating/titanating agents may comprise titanium tetrachloride. The second and third halogenation/titanation steps may each include a ratio of titanium to magnesium in the range of about 0.1-5. Reaction products A, B and C may each be washed with a hydrocarbon solvent prior to the subsequent halogenation/titanation step. The reaction product D can be washed with a hydrocarbon solvent until the titanium element [Ti] content is less than about 100 mmol/L.

Another embodiment of the present invention provides a polyolefin catalyst prepared by a process generally comprising the steps of: contacting a catalyst component of the present invention with an organometallic reagent. The catalyst component is prepared by the method described above. The catalysts of the present invention can have a fluff morphology suitable for polymerization production processes, provide polyethylene with a molecular weight distribution of at least 5.0, and provide a uniform particle size distribution with fewer particles smaller than about 125 microns. The activity of the catalyst depends on the polymerization conditions. Typically the catalyst will have an activity of at least 5,000 g PE/g catalyst, but the catalyst activity may be greater than 50,000 g PE/g catalyst or greater than 100,000 g PE/g catalyst.

Another embodiment of the present invention also provides a polyolefin polymer prepared by a process comprising: a) contacting, under polymerization conditions, one or more olefin monomers in the presence of a catalyst of the present invention; b) Extraction of polyolefin polymers. Generally, the monomers are vinyl monomers and the polymers are polyolefins.

Yet another embodiment of the present invention provides a film, fiber, pipe, fabric material or article comprising a polymer prepared by the present invention. The article may be a film comprising at least one layer comprising a polymer produced by a process involving the catalyst of the invention.

Another embodiment of the present invention provides a method for preparing a catalyst, which includes: changing the precipitation of the catalyst components from the catalyst synthesis solution by adding an aluminum alkyl to control the viscosity of the catalyst synthesis solution, wherein the average of the catalyst components The particle size increases with the concentration of alkylaluminum in the synthesis solution. The method may further comprise contacting the catalyst component with an organometallic preactivator to form a catalyst, wherein the average particle size of the catalyst increases as the concentration of the alkylaluminum in the synthesis solution increases.

Another embodiment of the present invention provides a method for preparing a catalyst comprising: a) contacting a magnesium glycolate compound with a halogenating agent to form a reaction product A; b) contacting the reaction product A with a first halogenated/titanate (titanating) agent contact, form reaction product B; c) make reaction product B contact with the second halogenation/titanation agent, form reaction product C; d) make reaction product C and the 3rd halogenation/titanation agent contacting to form reaction product D; and e) contacting reaction product D with an organometallic preactivator to form a catalyst. Magnesium glycolate compounds are the reaction products of reactions involving: magnesium alkyl compounds of general formula MgRR', wherein R and R' are alkyl groups having 1 to 10 carbon atoms, and R and R' may be the same or different General formula is the alcohol of R " OH, wherein, alcohol is linear or branched, and R " is the alkyl group that has 2-20 carbon atoms; General formula is the aluminum alkyl of AlR ₃ , wherein at least one R  is an alkyl or alkoxy group or halogen having 1-8 carbon atoms, wherein each R'' may be the same or different. The average particle size of the catalyst increases with the ratio of aluminum alkyl to magnesium alkyl.

The second and third halogenating/titanating agents may include titanium tetrachloride. The second and third halogenation/titanation steps may each include a ratio of titanium to magnesium in the range of about 0.1-5. Reaction products A, B and C may be washed with a hydrocarbon solvent prior to the subsequent halogenation/titanation step. The reaction product D can be washed with a hydrocarbon solvent until the titanium element [Ti] content is less than about 100 mmol/L.

In another embodiment of the present invention there is also provided a polyolefin polymer prepared by a method comprising the steps of: a) making one or more olefin monomers in the presence of the catalyst of the present invention under polymerization conditions contacting; and b) extracting the polyolefin polymer. The average particle size of the polymer increases with the ratio of aluminum alkyl to magnesium alkyl used in the preparation of the catalyst. Generally, the monomer is ethylene monomer and the polymer is polyethylene.

Yet another embodiment of the present invention provides a film, fiber, pipe, fabric material or article comprising a polymer prepared by the present invention. The article of manufacture may be a film comprising at least one layer comprising a polymer produced by the present invention.

Other embodiments include a method of forming a catalyst for use in olefin polymerization. The method comprises reacting a chlorinating agent with a magnesium alkoxide compound to form a magnesium-titanium-alkoxide adduct, and reacting the magnesium-titanium-alkoxide adduct with an alkyl chloride compound to form a magnesium chloride carrier. The support is then reacted with titanium tetrachloride ( _TiCl4 ) to form a highly active catalyst for the production of polyolefins.

In one embodiment of the present invention, first, butyl ethyl magnesium (BEM) is reacted with an alcohol to form a magnesium alkoxide compound, wherein the alcohol is generally represented by the general formula ROH, and R is an alkyl group containing, for example, about 1-20 carbon atoms . Then the magnesium alcohol compound is combined with a chlorinating agent, wherein the chlorinating agent is generally represented by the general formula TiCl _n (OR') _4-n , wherein R' is an alkyl, cycloalkyl or aryl group, and n is 1-3 . As a result of mixing the magnesium alkoxide compound with the chlorinating agent, a magnesium-titanium-alkoxide adduct is formed.

The alkyl chloride compound is reacted with the magnesium-titanium-alkoxide adduct to form a magnesium chloride ( _MgCl2 ) support and one or more by-products such as ethers and/or alcohols. Subsequently, MgCl ₂ was treated with TiCl ₄ to form a Ziegler-Natta catalyst supported on MgCl ₂ . Polyolefins produced using this catalyst have a narrow molecular weight distribution and thus can be formed into end-use products such as barrier films, fibers and tubing.

Description of drawings

Figure 1 illustrates the settling efficiency curves for a polymer prepared with the catalyst of the present invention (Example 1) and a polymer prepared with a conventional catalyst (Comparative Example 4).

Figure 2 depicts the particle size distributions of the catalysts described in Comparative Examples 1A-2A and Examples 1A-2A.

Figure 3 depicts the particle size distributions of the catalysts described in Comparative Examples 1A-2A and Example 4A.

Figure 4 depicts the catalyst yield as a function of the amount of PhCOCl used in Examples 4A-10A.

Figures 5-6 depict the particle size distributions of the catalysts formed in Examples 4A-10A.

Figure 7 depicts the average catalyst particle size ( _D50 ) as a function of the amount of PhCOCl used in Examples 4A-10A.

Figure 8 depicts the particle size distribution of the catalysts described in Comparative Examples 1A-2A and Examples 4A and 11A.

Figure 9 depicts the particle size distribution of the fluffy particles of the polymeric resins described in Comparative Examples 3A-4A and Example 12A.

Figure 10 depicts the particle size distribution of the fluffy particles of the polymeric resins described in Comparative Examples 3A-4A and Example 13A.

Figure 11 depicts the particle size distribution of the catalyst described in Example 14A.

Figure 12 depicts the particle size distribution of the catalyst described in Example 15A.

Detailed ways

According to one embodiment of the present invention, the method for preparing the catalyst component generally includes the following steps: forming a metal dialkoxide from a dialkyl metal and an alcohol, forming a reaction product from a halide metal dialkoxide, and using The reaction product is contacted with one or more halogenating/titanating agents to form a catalyst component which is then treated with a preactivator such as an organoaluminum.

An embodiment of the present invention is generally as follows:

1.

2.

3.

4. ;

5.

6.

In the above general formula, M can be any suitable metal, typically a Group IIA metal, usually Mg. In the above general formula, R, R', R", R'', and R"" are each independently a hydrocarbon group or a substituted hydrocarbon group, and R and R' have 1-20 carbon atoms, generally 1-10 carbon atoms , usually 2-6 carbon atoms, can have 2-4 carbon atoms. R "generally contains 3-20 carbon atoms, R'' generally contains 2-6 carbon atoms, R"" generally contains 2-6 carbon atoms and is usually butyl. Any combination of two or more of R, R', R", R'', and R"" can also be used, and the combination of R groups can be the same or different from each other.

In the above embodiment involving the general formula _ClARx , A is a non-reducing oxophilic compound capable of exchanging a chlorine with an alkoxy group, R is a hydrocarbon group or a substituted hydrocarbon group, and x is the valence of A minus 1 . Examples of A include titanium, silicon, aluminum, carbon, tin and germanium, usually titanium or silicon, and x is 3. Examples of R'' include methyl, ethyl, propyl, isopropyl, hydrocarbon groups having 2 to 6 carbon atoms, and the like. Non-limiting examples of chlorinating agents that can be used in the present invention are ClTi( ^OiPr ) ₃ and ClSi(Me) ₃ .

The metal dialkoxides of the above embodiments are chlorinated to form the reaction product "A". Although the exact composition of product "A" is unknown, it is believed to contain partially chlorinated metal compounds, an example would be ClMg(OR").

Reaction product "A" is then contacted with one or more halogenating/titanating agents to form reaction product "B", where an example of a halogenating/titanating agent is _a combination of TiCl _and Ti(OBu) . The reaction product "B" may be chlorinated and partially chlorinated metal complexes with titanium compounds. The reaction product "B" may comprise a titanium impregnated MgCl ₂ support, for example, represented by a compound such as (MCl ₂ ) _y (TiCl _x (OR) _4-x ) _z . The reaction product "B" may precipitate out of the catalyst slurry as a solid.

The second halogenation/titanation step produces a reaction product or catalyst component, "C" may also be a halogenated or partially halogenated metal complex with a titanium compound, but unlike "B", available ( _MCl2 ) _y (TiCl _X' (OR) _4-x' ) _z' said. The degree of halogenation of "C" is expected to exceed the degree of halogenation of product "B". A greater degree of halogenation can produce complexes of different compounds.

The third halogenation/titanation step produces a reaction product or catalyst component, "D" may also be a complex of a halogenated or partially halogenated metal with a titanium compound, but unlike "B" and "C", may Denoted by (MCl ₂ ) _y (TiCl _X″ (OR) _4-x″ ) _z″ . The degree of halogenation of “D” is expected to exceed the degree of halogenation of product “C”. More halogenation will result in complexes of different compounds Although the description of the reaction products herein gives the chemically most probable explanation, the invention as claimed is not limited by this theoretical mechanism.

Metal dialkyls and resulting metal dialkoxides suitable for use in the present invention may include any material that can be used in the present invention to produce suitable polyolefin catalysts. These metal dialkoxides and metal dialkyls may include Group IIA metal dialkoxides and dialkylates. The metal dialkoxide or metal dialkyl may be a magnesium dialkoxide or dialkylmagnesium. Non-limiting examples of suitable dialkylmagnesiums include diethylmagnesium, dipropylmagnesium, dibutylmagnesium, butylethylmagnesium, and the like. Butylethylmagnesium (BEM) is a suitable dialkylmagnesium.

In the practice of the present invention, the metal dialkoxide may be a compound of magnesium having the general formula Mg(OR") ₂ , wherein R" is a hydrocarbyl or substituted hydrocarbyl group having 1-20 carbon atoms.

Metal dialkoxides may be soluble and are generally non-reducing. Non-reducing compounds have the advantage of forming _MgCl2 rather than insoluble species, which can be formed by reduction of compounds such as MgRR', resulting in the formation of catalysts with a broad particle size distribution. In addition, more uniform products can be obtained when Mg(OR"), which is _less reactive than MgRR', is used in reactions involving chlorination with mild chlorinating agents followed by a halogenation/titanation step, e.g. , better control and distribution of catalyst particle size.

Non-limiting examples of metal dialkoxides that may be used include magnesium butoxide, magnesium pentoxide, magnesium hexoxide, magnesium bis(2-ethylhexyloxy) and any alkoxide suitable for making the system soluble.

As a non-limiting example, magnesium dialkoxides, such as bis(2-ethylhexyloxy)magnesium, can be prepared by reacting an alkylmagnesium compound (MgRR') with an alcohol (ROH) as shown below.

            

The reaction can be performed at room temperature and the reactants form a solution. Each of R and R' may be any alkyl group having 1 to 10 carbon atoms, and R and R' may be the same or different. Suitable MgRR' compounds include, for example, diethylmagnesium, dipropylmagnesium, dibutylmagnesium and butylethylmagnesium. The MgRR' compound may be BEM where RH and R'H are butane and ethane, respectively.

In the practice of this invention, any alcohol which will form the desired metal dialkoxide can be used. In general, the alcohol used can be any alcohol with the general formula R"OH, wherein R" is an alkyl group having 2-20 carbon atoms, the number of carbon atoms can be at least 3, at least 4, at least 5 or at least 6. Non-limiting examples of suitable alcohols include ethanol, propanol, isopropanol, butanol, isobutanol, 2-methylpentanol, 2-ethylhexanol, and the like. Almost any alcohol is believed to work, straight or branched, higher branched chain alcohols such as 2-ethyl-1-hexanol can be used.

The amount of alcohol added can vary, for example, within a non-exclusive range of 0-10 equivalents, generally in the range of about 0.5 equivalents to about 6 equivalents (equivalents herein are relative to magnesium or metal compounds), and can be about 1 equivalent to about 3 equivalents.

Metal alkyl compounds can produce high molecular weight, very viscous species in solution. Viscosity can be reduced by adding to the reaction an aluminum alkyl such as triethylaluminum (TEAl), which blocks the association between individual metal alkyl molecules. The ratio of aluminum alkyl to metal can generally be in the range of 0.001:1 to 1:1, can be in the range of 0.01:1 to 0.5:1, and can also be in the range of 0.03:1 to 0.2:1. In addition, electron donors such as ethers (eg, diisoamyl ether (DIAE)) can be used to further reduce the viscosity of the metal alkyl. The ratio of electron donor to metal is typically in the range of 0:1 to 10:1, and may be in the range of 0.1:1 to 1:1.

The reagents used in the step of halogenating the metal alkoxides include any halogenating agent which, when used in the present invention, produces a suitable polyolefin catalyst. The halogenation step may be a chlorination step, where the halogenating agent contains chlorine (ie, is a chlorinating agent).

Halogenation of metal alkoxide compounds is usually carried out in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane, and the like. In this halogenation step, the molar ratio of metal alkoxide to halogenating agent is generally in the range of about 6:1 to about 1:3, may be in the range of about 3:1 to about 1:2, may be in the range of about 2: 1 to about 1:2, or about 1:1.

The halogenation step is generally carried out at a temperature in the range of about 0°C to about 100°C for a reaction time in the range of about 0.5 hour to 24 hours. The halogenation step can be carried out at a temperature ranging from about 20°C to about 90°C, and the reaction time can range from about 1 hour to about 4 hours.

After the halogenation step has been performed and the metal alkoxide is halogenated, the halogenated product "A" may be subjected to two or more halogenation/titanation treatments.

The halogenating/titanating agent used may be a mixture of two tetrasubstituted titanium compounds in which all four substituents are the same, the substituents being halogen or alkane having 2-10 carbon atoms Oxy or phenoxy, such as TiCl ₄ or Ti(OR"") ₄ . The halogenating/titanating agent used may be a chlorinating/titanating agent.

The halogenating/titanating agent can be a single compound or a combination of compounds. The process of the present invention provides an active catalyst after the first halogenation/titanation reaction; however, it is desirable to perform a total of at least three halogenation/titanation steps.

The first halogenating/titanating agent is usually a mild titanating agent which may be a mixture of a titanium halide and an organic titanate. The first halogenating/titanating agent can be a mixture of _TiCl4 and Ti(OBu) ₄ , wherein _TiCl4 /Ti(OBu) ₄ is in the range of 0.5:1 to 6:1, the ratio can also be 2: 1 to 3:1. It is believed that mixtures of titanium halides and organotitanates react to form alkoxy titanium halides, Ti(OR) _a X _b , where OR and X are alkoxy and halogen, respectively, and a+b is the valence of titanium, typically 4.

Alternatively, the first halogenating/titanating agent may be a single compound. Examples of first halogenating/titanating agents are Ti(OC ₂ H ₅ ) ₃ Cl, Ti(OC ₂ H ₅ ) ₂ Cl ₂ , Ti(OC ₃ H ₇ ) ₂ Cl ₂ , Ti(OC ₃ H ₇ ) ₃ Cl, Ti(OC ₄ H ₉ )Cl ₃ , Ti(OC ₆ H ₁₃ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ ) ₂ Br ₂ and Ti(OC ₁₂ H ₅ )Cl ₃ .

The first halogenation/titanation step is generally performed by first slurrying the halogenated product "A" in a hydrocarbon solvent at room/ambient temperature. Non-limiting examples of suitable hydrocarbon solvents include heptane, hexane, toluene, octane, and the like. Product "A" is at least partially soluble in hydrocarbon solvents.

After adding the halogenating/titanating agent to the soluble product "A", the solid product "B" precipitated at room temperature. The halogenating/titanating agent must be used in an amount sufficient to cause the solid product to precipitate out of solution. Generally speaking, based on the ratio of titanium to metal, the amount of halogenation/titanation agent used is generally in the range of about 0.5 to about 5, usually in the range of about 1 to about 4, and can be in the range of about 1.5 to a range of about 2.5.

The solid product "B" precipitated in the first halogenation/titanation step is then recovered using a suitable recovery technique and then washed with a solvent such as hexane at room/ambient temperature. Generally, the solid product "B" is washed until [Ti] is less than about 100 mmol/L. In the present invention, [Ti] represents any titanium species capable of acting as a second generation Ziegler-Natta catalyst, and may include titanium species that are not part of the reaction products described herein. The resulting product "B" is then subjected to a second and third halogenation/titanation step to produce products "C" and "D". After each halogenation/titanation step, the solid product can be washed until [Ti] is less than the required amount. For example, less than about 100 mmol/L, less than about 50 mmol/L, or less than about 10 mmol/L. After the last halogenation/titanation step, the product can be washed until [Ti] is less than the required amount. For example, less than about 20 mmol/L, less than about 10 mmol/L, or less than about 1.0 mmol/L. It is believed that the lower [Ti] yields an improved catalyst due to the reduced amount of titanium, making it useful as a second generation Ziegler catalyst species. It is believed that the lower [Ti] is a factor leading to improved catalysts, such as catalysts having narrow molecular weight distributions.

The second halogenation/titanation step is generally carried out by slurrying the solid product recovered from the first titanation step, solid product "B", in a hydrocarbon solvent. Hydrocarbon solvents suitable for use in the first halogenation/titanation step can be used. The second and third halogenation/titanation steps may use different compounds or combinations of compounds than in the first halogenation/titanation step. The second and third halogenation/titanation steps may use the same but higher concentrations of reagents as in the first halogenation/titanation step, but this is not required. The second and third halogenating/titanating agents may be titanium halides, such as titanium tetrachloride ( _TiCl4 ). A halogenating/titanating agent is added to the slurry. The addition can be performed at ambient/room temperature, but also at temperatures and pressures different from ambient conditions.

Typically, the second and third halogenating/titanating agents comprise titanium tetrachloride. Typically the second and third halogenation/titanation steps each include a ratio of titanium to magnesium in the range of about 0.1 to 5, the ratio can also be about 2.0, and the ratio can be about 1.0. The third halogenation/titanation step is typically performed in the slurry at room temperature, but may also be performed at temperatures and pressures different from ambient conditions.

The amount of titanium tetrachloride or other halogenating/titanating agent used may also be expressed in equivalents, where equivalents are the amount of titanium relative to the magnesium or metal compound. The amount of titanium in the second and third halogenation/titanation steps, respectively, generally ranges from about 0.1 to about 5.0 equivalents, can range from about 0.25 to about 4 equivalents, and usually is from about 0.3 to about 3 equivalents , desirably in the range of about 0.4 to about 2.0 equivalents. In a particular embodiment, the amount of titanium tetrachloride used in the second and third halogenation/titanation steps ranges from about 0.45 to about 1.5 equivalents, respectively.

Catalyst component "D" prepared by the method described above can be combined with an organometallic catalyst component (a "preactivator") to form a preactivated catalyst system suitable for olefin polymerization. Typically, preactivators used with transition metal-containing catalyst component "D" are organometallic compounds such as aluminum alkyls, alkylaluminum hydrides, lithium aluminum alkyls, zinc alkyls, magnesium alkyls, and the like.

Preactivators are usually organoaluminum compounds. The organoaluminum preactivator is generally an aluminum alkyl having the general formula AlR ₃ , wherein at least one R is an alkyl group or halogen having 1-8 carbon atoms, and each R may be the same or different. The organoaluminum preactivator may be a trialkylaluminum such as trimethylaluminum (TMA), triethylaluminum (TEAl) and triisobutylaluminum (TiBAl). The ratio of aluminum to titanium is in the range of about 0.1:1 to 2:1, typically 0.25:1 to 1.2:1.

Optionally, the Ziegler-Natta catalyst can be prepolymerized. Generally, the prepolymerization process works by contacting a small amount of monomer with the catalyst after the catalyst has been contacted with the cocatalyst. The prepolymerization process is described in US Patent Nos. 5,106,804, 5,153,158, and 5,594,071, which are hereby incorporated by reference.

The catalysts of the present invention can be used in any process for the homopolymerization or copolymerization of alpha-olefins of any type. For example, the catalyst of the present invention can be used to catalyze ethylene, propylene, butene, pentene, hexene, 4-methylpentene and other alpha-olefins having at least two carbon atoms, and mixtures thereof. The copolymers described above can produce desirable results, eg, broader MWD and multimodal distributions, such as bimodal and trimodal properties. The catalysts of the present invention can be used to polymerize ethylene to produce polyethylene.

Various polymerization processes can be used in the present invention, for example, single and/or multiple loop processes, batch processes not involving loop-type reactors, or continuous processes. An example of a multi-loop process that can be used to carry out the invention is a two-loop system, wherein a first loop carries out a polymerization reaction in which the resulting polyolefin has a lower MW than the polyolefin produced by the second loop polymerization, The resulting resin thus has a broad molecular weight distribution and/or has bimodal properties. Alternatively, another example of a multi-loop process that can be used to carry out the present invention is a dual-loop system in which a first loop undergoes a polymerization reaction in which the resulting polyolefin has a higher MW, so that the resulting resin has a broad molecular weight distribution and/or bimodal properties.

The polymerization process can be, for example, a bulk, slurry or gas phase polymerization. The catalysts of the present invention can be used in slurry phase polymerizations. Polymerization conditions (eg, temperature and pressure) depend on the type of equipment used in the polymerization process and the type of polymerization process employed, and such conditions are known in the art. Generally, the temperature is in the range of about 50-110°C and the pressure is in the range of about 10-800 psi.

The activity of catalysts obtained according to embodiments of the present invention depends at least in part on the polymerization method and conditions, eg, the equipment used and the temperature of the reaction. For example, in the embodiment of polymerizing ethylene to produce polyethylene, the typical catalyst activity is at least 5,000 g PE/g catalyst, but the activity can also exceed 50,000 g PE/g catalyst, and the activity can exceed 100,000 g PE/g catalyst.

In addition, the catalyst obtained in the present invention can improve the fluff morphology of the polymer. Thus, the catalysts of the present invention yield large polymer particles with a uniform size distribution, while fine particles (less than about 125 microns) are present in low concentrations, eg, less than 2% or less than 1%. The catalysts of the present invention comprise large, easily transferable powders with high powder bulk densities, which are compatible with polymerization processes. Generally, the catalysts of the present invention result in a reduction of small particles and an increase in bulk density (B.D.) in the polymer, wherein the B.D. grams per cubic centimeter.

The olefin monomer can be fed to the polymerization reaction zone in a diluent which is an inactive heat exchanger which is liquid under the reaction conditions. Examples of such diluents are hexane and isobutane. For copolymerization of ethylene with another alpha-olefin such as butene or hexene, the second alpha-olefin may be present in an amount of 0.01-20 mole percent, and may be between about 0.02-10 mole percent.

Optionally, an electron donor may be added with the halogenating agent, the first halogenating/titanating agent or the subsequent halogenating/titanating agent. In the second halogenation/titanation step, it is desirable to use an electron donor. Electron donors for use in the preparation of polyolefin catalysts are well known and any suitable electron donor which produces a suitable catalyst may be used in the present invention. Electron donors, also known as Lewis bases, are organic compounds of oxygen, nitrogen, phosphorus, or sulfur that are capable of donating electron pairs to a catalyst.

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 ethers or cyclic ethers, ketones, vinyl esters, acryloyl derivatives (especially acrylic Alkyl esters or alkyl methacrylates) and silanes. An example of a suitable electron donor is di-n-butyl phthalate. An example of a class of suitable electron donors are alkylsilyl alkoxides of the _general formula RSi(OR') , for example, methylsilyl triethanolate [MeSi( _OEt )], where R and R' is an alkyl group having 1 to 5 carbon atoms, and R and R' may be the same or different.

For polymerization processes, internal electron donors can be used for catalyst synthesis, while external electron donors or stereoselectivity control agents (SCAs) can be used to activate catalysts during polymerization. An internal electron donor may be used in the catalyst formation reaction during the halogenation or halogenation/titanation step. Compounds suitable as internal electron donors for the preparation of conventional supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, electron donor compounds having N, P and/or S atoms and A special class of esters. Particularly suitable are: esters of phthalic acid such as diisobutyl phthalate, dioctyl phthalate, diphenyl phthalate and benzyl butyl phthalate; malonic acid esters such as diisobutyl malonate and diethyl malonate; alkyl pivalate and aryl pivalate; alkyl maleate, cycloalkyl maleate and maleate aryl carbonates; alkyl and aryl carbonates such as diisobutyl carbonate, ethylphenyl carbonate and diphenyl carbonate; succinates such as monoethyl succinate and succinic acid diethyl ester.

External electron donors useful in the preparation of the catalysts of the present invention include organosilicon compounds such as alkoxysilanes of the general formula SiR _m (OR') _4-m , wherein R is selected from the group consisting of alkyl, cycloalkyl, aryl and Vinyl; R' is an alkyl group; m is 0-3, R and R' can be the same; when m is 0, 1 or 2, the R' group can be the same or different; when m is 2 or 3, R The groups can be the same or different.

The external electron donor of the present invention can be selected from the general formula as:

A silane compound, wherein, R ₁ and R ₄ are alkyl or cycloalkyl groups containing primary, secondary or tertiary carbon atoms connected to silicon, R ₁ and R ₄ are the same or different; R ₂ and R ₃ are alkyl or aryl. _R1 can be methyl, isopropyl, cyclopentyl, cyclohexyl or tert-butyl; _R2 and _R3 can be methyl, ethyl, propyl or butyl and need not be the same; _R4 can also is methyl, isopropyl, cyclopentyl, cyclohexyl or tert-butyl. Specific external electron donors are cyclohexylmethyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS), cyclohexylisopropyldimethoxysilane (CIDS), dicyclopentanyl Dimethoxysilane (CPDS) or Di-tert-butyldimethoxysilane (DTDS).

The MWD of polyethylene produced using the catalysts described above is at least 5.0 and may be greater than about 6.0.

The polyolefins of the present invention are suitable for use in various applications, for example, in extrusion processes, resulting in a wide range of products. These extrusion processes include, for example, blown film extrusion, cast film extrusion, slot tape extrusion, blow molding, pipe extrusion, and foamed sheet extrusion. These processes can include monolayer extrusion or multilayer coextrusion.

End products that can be made using the present invention include, for example, films, fibers, tubing, textile materials, manufactured goods, diaper components, feminine hygiene products, automotive parts, and medical materials.

All references cited herein, including research papers, all US and foreign patents and patent applications, are hereby expressly and completely incorporated by reference.

The first set of embodiments

Having generally described the invention, the following examples are only intended to illustrate certain embodiments of the invention, demonstrating its practice and advantages. It should be understood that the examples are given by way of illustration and are not intended to limit the scope of the invention described or claimed in any way.

The synthetic scheme used to synthesize such catalysts is as follows (all ratios are relative to BEM):

The optimal formulation is considered to be X = 0.5 to 2, with 0-2 washes with TEA1 before preactivating Catalyst C. In order to make the titanation more effective, the catalyst preparation was improved as follows:

As indicated above, the addition of _TiCl4 was done in two steps, where X and Y = 0.5-1.0. Catalyst C typically undergoes one or two washes, with the two washes being done after Y to remove soluble titanium species which are second generation Ziegler catalyst species.

Example 1:

In a nitrogen-purged box, 1412.25 g (2.00 mol) of BEM-1, 27.60 g (0.060 mol) of TEAl (24.8% in heptane) and 189.70 g (1.20 mol) of DIAE were added to 3 Liter round bottom flask. The vial contents were then transferred by cannula under nitrogen flow into a 20 liter Buchi reactor. The flask was then washed with about 400 ml of hexane and the wash was transferred to the reactor. The rotational speed of the stirrer was set at 350 rpm.

2-Ethylhexanol (543.60 g, 4.21 moles) was added to the 1 liter bottle and capped. It was then diluted with hexane to a total volume of 1 liter before being added to the reactor. This solution was transferred to the reactor via cannula using a mass flow controller. The initial top temperature was 25.3°C and the maximum temperature reached was 29.6°C. After the addition (approximately 2 hours), the bottle was washed with 400 mL of hexane and the wash was transferred to the reactor. The reaction mixture was stirred overnight at 350 rpm under a nitrogen pressure of 0.5 bar and the heat exchanger was closed.

Start the heat exchanger and set to 25 °C. Titanium triisopropoxide chloride (774.99 and 775.01 grams, 2.00 moles total) was added to two 1 liter bottles to give a total of two liters of material. Transfer the contents of each vial to the reactor via a cannula using a mass flow controller. The initial head space temperature was 24.6°C and reached a maximum of 25.9°C during the addition of the second bottle. The addition times were 145 minutes and 125 minutes for bottle 1 and bottle 2, respectively. After the addition was complete, each bottle was washed with 200 ml of hexane and the wash was transferred to the reactor. The reaction mixture was stirred overnight at 350 rpm and 0.5 bar nitrogen pressure. Turn off the heat exchanger.

Preparation of TiCl ₄ /Ti(OBu) ₄

A mixture of titanium tetrachloride/titanium tetrabutoxide was prepared in a 5 liter round bottom flask using standard schlenk system techniques. In a 1 L pressure bottle, dilute 680.00 g (1.99 mol) of Ti(OBu) ₄ with hexane to a total volume of 1 L. The solution was then transferred to the reactor via cannula. The bottle was washed with 200 ml of hexane and the wash was transferred to the reactor. In a 1 L graduated cylinder, 440 mL (~760 g, 4.00 mol) of _TiCl4 was diluted with hexane to a total volume of 1 L. The solution in the 5-L flask was stirred, and the _TiCl solution was added dropwise to the reactor through _a cannula under N pressure. After the addition was complete, the 1 L graduated cylinder was washed with 200 mL of hexane and the wash was transferred to the reactor. After 1 h, the reaction mixture was diluted with hexane to a total volume of 4 L and stored in a flask until use.

Start the heat exchanger and set to 25 °C. The TiCl ₄ /Ti(OBu) ₄ mixture was transferred to a 20 L reactor via cannula and mass flow controller. The initial headspace temperature was 24.7°C and reached a maximum of 26.0°C during the 225 minute feed. After the addition, the vessel was washed with 1 liter of hexane and allowed to stir for 1 hour.

The stirrer was turned off and the solution was allowed to settle for 30 minutes. The solution was decanted by pressurizing the reactor to 1 bar, lowering the dip tube, and ensuring that no solid catalyst passed through the attached clear plastic tubing. The catalyst was then washed 3 times according to the following steps. Using a pressure vessel at equilibrium, weigh 2.7 kg of hexane into the vessel and transfer to the reactor. The stirrer was started and the catalyst mixture was stirred for 15 minutes. The stirrer was then turned off and the mixture was allowed to settle for 30 minutes. Repeat this step. After the third addition of hexane, the slurry was allowed to settle overnight and the heat exchanger was turned off.

The supernatant was decanted, and 2.0 kg of hexane was added to the reactor. Stirring was resumed at 350 rpm, the heat exchanger was started and set to 25°C. In a 1 liter graduated cylinder, add 440 ml (760 g, 4.00 moles) of titanium tetrachloride. Dilute the _TiCl4 to 1 L with hexane and transfer half of the solution to the reactor via cannula and mass flow controller. During the addition, the initial top temperature of 24.7°C increased by 0.5°C. The total addition time was 45 minutes. After 1 hour, the stirrer was turned off and the solids were allowed to settle for 30 minutes. The supernatant was decanted, and the catalyst was washed once with hexane according to the above procedure. After the wash was complete, 2.0 kg of hexane was transferred to the reactor and stirring was resumed. The remaining 500 mL of solution was used to complete the second addition of _TiCl4 in a similar manner as above. After the addition, the graduated cylinder was rinsed with 400 ml of hexane and the rinse was added to the Buchi reactor. After 1 hour of reaction, the stirrer was turned off and the solids were allowed to settle for 30 minutes. The supernatant was then decanted, and the catalyst was washed three times with hexane. Then 2.0 kg of hexane was transferred to the reactor.

In a 1-liter pressure bottle, 144.8 g (312 mmol) of TEA1 (25.2% in hexane) were charged. The bottle was capped and diluted to 1 L with hexane. This solution was then cannula transferred into the reaction mixture using a mass flow controller. During the 120 minute addition, the color of the slurry turned to dark brown. The initial top temperature was 24.5°C and the maximum temperature reached 25.3°C. After the addition, the bottle was rinsed with 400 ml of hexane and the wash 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 was decanted, and then the catalyst was washed once according to the above steps. After washing, 2.7 kg of hexane was added to the reactor. The contents of the reactor were then transferred to a three gallon pressure bottle. The Buchi reactor was washed with 1.0 kg and 0.5 kg of hexane, and the washings were added to the pressure bottle. The estimated catalyst yield was 322 grams.

In one embodiment, the weight percentages of the composition are: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti 7.9%. The ranges observed for the individual elements were: Cl 48.6-55.1%; Al 2.3-2.5%; Mg 11.8-14.1%; Ti 6.9-8.7%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti 2.0-14.0%.

Table 1 lists [Ti] measured on samples after addition of _TiCl4 /Ti(OBu) ₄ , three washes, first addition of _TiCl4 , one wash and second addition of _TiCl4 , followed by three washes. Decant samples 1-4 correspond to after addition of _TiCl4 /Ti(OBu) ₄ , and decant samples 5 and 6 correspond to after the first addition of _TiCl4 . Decant samples 7-10 correspond to after the second addition of _TiCl4 .

Table 1 Decanted sample Ti (ppm) mmol/L 1 2.1 21000 306.9 2 0.8 8000 116.9 3 0.2 2000 29.2 4 0.1 1000 14.6 5 2 20000 292.3 6 0.4 4000 58.5 7 1.9 19000 277.7 8 0.4 4000 58.5 9 0.0925 925 13.5 10 0.0064 64 0.9

Comparative example 1:

Comparative Example 1 was prepared in a similar manner as in Example 1, except that the third titanation step was omitted, and the second titanation step was performed using a quarter of the amount of TiCl ₄ .

Comparative example 2:

Comparative Example 2 was prepared in a similar manner as in Example 1, except that the second and third titanation steps were performed using 0.5 equivalents of _TiCl4 in each titanation step.

Comparative example 3:

Comparative Example 3 was prepared in a similar manner to Comparative Example 1, except that the amount of TiCl ₄ used in the second titanation step was about 4 times that used in Comparative Example 1. After the second titanation, a hexane wash was performed. In one embodiment, the weight percentages of the composition are: Cl 57.0%; Al 2.0%; Mg 9.5% and Ti 10.0%. The range of each element can be: Cl 55.0-57.0%; Al 2.0-2.6%; Mg 8.9-9.5%; Ti 10.0-11.0%.

Comparative example 4:

Comparative Example 4 was prepared in a similar manner to Comparative Example 3, except that after the second titanation step, two hexane washes were performed. In one embodiment, the weight percentages of the composition are: Cl 53.0%; Al 2.3%; Mg 9.7% and Ti 9.5%. The range of each element can be: Cl 52.6-53.0%; Al 2.0-2.3%; Mg 9.7-10.6%; Ti 8.7-9.5%.

Table 2 lists the prepared catalysts.

Table 2 catalyst x Cleaning times Y Cleaning times Comparative example 1 0.5 0 0 NA Comparative 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

Table 3 presents the MWD data for the polymers prepared using Example 1 and Comparative Examples 1-4. For a given catalyst/cocatalyst system, this data suggests that narrower MWDs can be obtained by increasing the number of washes or by adding a third titanation step with _TiCl4 . Generally, the intrinsic MWD of the polymer resin increases in the following order, that is, Comparative Example 1<Comparative Example 2<Comparative Example 4<Example 1<Comparative Example 3.

table 3 catalyst Co-catalyst number of washes after X Number of washes after Y SR5 (HLMI/ _MI5 ) D(Mw/Mn) Comparative example 1 TEAl 0 0 10.9 6.2 Comparative example 2 TEAl 1 2 10.9 NA Example 1 TEAl 1 2 12.6 6.8 Comparative example 3 TEAl 1 NA 11.8-12.8 5.9-6.8 Comparative example 4 TEAl 2 NA 10.8-12.0 6.0-6.3 Example 1 TIBAl 1 2 11.9 7.0 Comparative example 3 TIBAl 1 NA 12.2-13.6 6.9-7.3 Comparative example 4 TIBAl 2 NA 11.4-11.8 6.6-7.5

As shown in Table 4, each catalyst provided a powder with fewer small particles (particles smaller than 125 microns); however, the catalysts of the present invention prepared by the two titanation steps generally provided fluff with high bulk density.

Table 4 catalyst D ₅₀ (microns) Fluff D ₅₀ (microns) % fines BD (g/cubic centimeter) 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 an important influence on the settling efficiency of the polymer, as confirmed in the laboratory by the settling efficiency curve shown in Figure 1 . The inventive polymer prepared with the inventive catalyst of Example 1 exhibited a rapid disappearance of the initial 10 ml of fluff from solution, meaning that the polymer had a faster faster sedimentation rate and better polymer morphology.

Viscosity Control of Synthetic Solutions

It has been found that by varying the viscosity of the solution during catalyst synthesis, the precipitation of catalyst components from solution can be altered. It has been found that altering the precipitation of the catalyst components affects the particle size of the resulting catalyst and polymers prepared with the catalyst. The viscosity of the catalyst synthesis solution can be varied depending on the relative amount of aluminum alkyl present. Thus, the particle size of the catalyst and the polymer produced with the catalyst can be varied depending on the relative amounts of aluminum alkyl used.

Catalysts were prepared in synthetic solutions with varying amounts of aluminum alkyls and tested together with polymer fluff prepared with this catalyst. Example 2 describes the synthetic scheme used in the preparation of the catalyst and Table 5 shows the dimensions of the resulting catalyst and polymer.

Example 2:

The synthetic scheme used was as follows (all ratios are relative to BEM):

1.

2.

3.

4. ;

5.

7.

Four catalysts were prepared in a 1 liter Buchi reactor according to this general synthetic scheme where Y=Z=1. Change the amount of TEAl in the first step reaction to study the effect on the particle size of the catalyst. The relative amount of 2-ethylhexanol was adjusted in each catalyst synthesis to prevent reduction of the titanium complex by any unreacted aluminum or magnesium alkyls. The following table lists the synthesized catalysts, the relative amounts of BEM, TEAl and 2-ethylhexanol used, the average particle size of the catalyst and the average particle size of the polyethylene resin prepared with each catalyst.

The table below provides the particle size distribution data obtained for each catalyst. As shown in the table, the average particle size distribution increases with increasing amount of TEAl.

table 5 catalyst BEM TEAl 2-Ethylhexanol BEM:TEAl catalyst polymer fluff equivalent equivalent equivalent Proportion D ₅₀ (microns) D ₅₀ (microns) 101 1.0 0.03 2.09 1.0:0.03 13.0 399 102 1.0 0.3 2.9 1.0∶0.3 16.1 420 103 1.0 0.5 3.5 1.0:0.5 18.3 418 104 1.0 1.0 5.0 1.0:1.0 21.7 504

As shown in Table 5, the average particle size of both the catalyst and the resulting fluffy particles increased with the increase of the amount of TEAl in the catalyst synthesis initial solution. By varying the relative amounts of aluminum alkyls, the viscosity of the catalyst synthesis solution can be varied. Thus, a change in solution viscosity can alter the precipitation properties of the catalyst component precipitated from solution, which can affect the average particle size of the catalyst component and the polymer produced with the catalyst. It can be seen from the table that the average particle size of the catalyst components increases with the increase of the alkylaluminum concentration in the synthesis solution. It can also be seen that the average particle size of the polymer resin produced with this catalyst increases with the concentration of the alkylaluminum in the synthesis solution.

The amount of aluminum alkyl can be measured in terms of the ratio of aluminum alkyl to magnesium alkyl, which can vary from about 0.01:1 to about 10:1. Polyethylene produced with the catalysts described above has a MWD of at least 4.0 and may be greater than about 6.0.

Catalyst 101 in Table 5 is the same as in Example 1 above. In one embodiment, the weight percentages of the composition are: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti 7.9%. The range of each element can be: Cl40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti 2.0-14.0%.

Catalyst 102 in Table 5 has, in one embodiment: Cl 47.0%; Al 3.4%; Mg 13.1% and Ti 4.0%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti2.0-14.0%.

Catalyst 103 in Table 5 has, in one embodiment: Cl 50.0%; Al 2.4%; Mg 12.1% and Ti 3.9%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti2.0-14.0%.

Catalyst 104 in Table 5 has, in one embodiment: Cl 53.0%; Al 3.1%; Mg 12.8% and Ti 4.2%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti 2.0-14.0%.

The polyolefins of the present invention are suitable for use in various applications, for example, in extrusion processes, resulting in a wide range of products. These extrusion processes include, for example, blown film extrusion, cast film extrusion, silt tape extrusion, blow molding, pipe extrusion, and foamed sheet extrusion. These processes can include monolayer extrusion or multilayer coextrusion. End products that can be made using the present invention include, for example, films, fibers, tubing, textile materials, manufactured goods, diaper components, feminine hygiene products, automotive parts, and medical materials.

According to an alternative embodiment of the present invention, a process comprising several reactions is used to form the polyolefin polymerization catalyst. First, alkylmagnesium compounds (ie, Mg(R ^* ) ₂ , where R ^* can be the same or different alkyl groups having about 1-20 carbon atoms), such as BEM, react with alcohols to form Soluble magnesium alcohols:

                  

wherein R is an alkyl group containing, for example, about 1 to 20 carbon atoms. Alcohols represented by the general formula ROH may be branched or unbranched. An example of a suitable alcohol is 2-ethylhexanol. Any suitable reaction conditions and order of addition for converting the BEM and alcohol reactants to the magnesium alkoxide compound 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 stirred for sufficient time to form a soluble magnesium alkoxide compound.

The resulting magnesium alkoxide compound is mixed with a mild chlorinating agent to form a magnesium-titanium-alkoxide adduct, which proceeds according to the following equation:

       

Wherein R' is an alkyl group, a cycloalkyl group or an aryl group, n is 1-3, m is at least 1, and can also be greater than 1. Hope n is 1. Reagents include TiCl _n (OR') _4-n , where R' = alkyl or aryl, and n is 1, or Ti(O ⁱ Pr) ₃ Cl, where ⁱ Pr represents isopropyl. Any suitable conditions for forming magnesium-titanium-alkoxide adducts may be employed to carry out the process. In one embodiment, the process is performed at ambient temperature and pressure. The reactants are mixed long enough to form a magnesium-titanium-alkoxide adduct. It is believed that the adducts form because the magnesium-titanium-alkoxide compound is sterically hindered, making it difficult for the chlorine atoms in the titanium compound to exchange places with the magnesium alkoxide ligand. Essentially, the adduct is substantially but not completely converted to _MgCl2 .

Subsequently, the magnesium-titanium-alkoxide adduct was mixed with an alkyl chloride compound to transform the adduct into a _MgCl2 support. The reaction steps are as follows:

     

where R" is an alkyl group containing, for example, about 2-18 carbon atoms, and "TiMgCl ₂ " denotes a titanium-impregnated MgCl ₂ support. Although R" may be branched or unbranched, in certain embodiments R" is desirably unbranched. Possible alkyl chloride compounds include benzoyl chloride, chloromethyl ethyl ether, and tert-butyl chloride, with benzoyl chloride being desirable in certain specific embodiments. Added to The amount of alkyl chloride in the magnesium alkoxide adduct can exceed the required amount of reaction.The ratio of the amount of benzoyl chloride to the amount of Mg (for example, BEM) in the reaction mixture can vary in the scope of about 1-20 ( That is, a ratio of about 1:1 to a ratio of about 20:1), or about 1-10, desirably in the range of about 4-8. The reaction can be carried out under any conditions suitable for precipitating a magnesium chloride support. In one implementation In this way, the reaction mixture is refluxed for a time long enough to precipitate the MgCl carrier. In embodiments using _tert -butyl chloride, the reactants may be heated during reflux. When using benzoyl chloride or chloromethyl ethyl chloride In the embodiment of base ether, reactant can be maintained at room temperature in the process of reflux. Also can produce one or more by-products such as ether (as shown in above-mentioned reaction) by this reaction.It is believed that, in The presence of Ti in the process of precipitating _MgCl plays a major role in producing highly active catalysts.

After the _MgCl2 support is separated from the reaction mixture, the support can be washed with, for example, hexane to remove any remaining contaminants on the support. The MgCl _{carrier is} then treated with TiCl to form a catalyst slurry according to the following equation:

                

The treatment process can be carried out under any suitable conditions for forming a catalyst slurry, for example, at ambient temperature and pressure. The catalyst slurry is washed with eg hexane and then dried. The resulting catalyst can be preactivated with an alkylaluminum compound such as triethylaluminum (TEAL) to prevent the catalyst from corroding the polymerization reactor. More specifically, when the titanium chloride in the catalyst reacts with the alkylaluminum compound, the titanium chloride is converted into an alkyltitanium. In addition, when titanium chloride is exposed to moisture, it may be converted to HCl, resulting in corrosion of the polymerization reactor.

The second group of embodiments

Having generally described the invention, the following examples are given as specific embodiments of the invention and serve to demonstrate its practice and advantages. It should be understood that the examples are given by way of illustration and are not intended to limit the scope of the invention described or claimed in any way.

All experimental examples were performed under an inert atmosphere using standard Schlenk system techniques unless otherwise indicated. Several catalysts (sample CM) were prepared according to the method of the present invention. In addition, two types of conventional catalysts were prepared, called Sample A and Sample B, where Sample B was prepared according to US Patent No. 5,563,225, and they were used for comparison with other catalyst samples. Many of the compounds required in the examples, namely 2-ethylhexanol, benzoyl chloride, n-butyl chloride, tert-butyl chloride, chloromethyl ethyl ether, ClTi(O ⁱ Pr) ₃ and TiCl ₄ , were purchased from From Aldrich Chemical Company and used as received. A heptane solution containing 15.6 wt% BEM and 0.04 wt% Al was purchased from Akzo Nobel. Catalyst particle size distributions were measured using a Malvem Mastersizer, including the mean particle size _D50 , and all particle size distributions given here are calculated on a volume average basis.

Hexane was purchased from Phillips and, for purification, passed through a 3A molecular sieve column, a F200 alumina column, a column packed with BASF R3-11 copper catalyst at a rate of 12 ml/min. Ethylene polymerization was carried out in the presence of each catalyst sample using an autoclave. The reactor has a capacity of 4 liters and is equipped with four mixing partitions with two opposing screw propellers. Ethylene and hydrogen were fed to the reactor while maintaining the reaction pressure with a dome loaded back pressure fitted in the dome and the reaction temperature with steam and cooling water. Hexane was added to the reactor as diluent. Polymerizations were performed under the conditions described in Table 3A unless otherwise indicated. The particle size distribution of the resulting polyethylene fluffy particles on a mass basis was obtained by screening analysis using a CSC Scientific sieve shaker. The percentage of small particles is defined as the weight percent of fluffy particles smaller than 125 microns.

Comparative Example 1A

Comparative Catalyst Sample A was prepared by adding a solution of 15.6 wt% BEM (70.83 g, 100 mmol) in heptane to a 1 liter reactor. Then, 26.45 g (203 mmol) of 2-ethylhexanol was slowly added to the solution containing BEM. The reaction mixture was stirred at ambient temperature for 1 hour. Then, 77.50 g (100 mmol) of 1.0 M ClTi(OiPr) ₃ in hexane was slowly added to the above mixture. The reaction mixture was stirred at ambient temperature for 1 hour, forming a [Mg(O-2-ethylhexyl)2ClTi(OiPr)3] adduct. Then, a hexane solution (250 mL) of a mixture of TNBT (34.04 g, 100 mol) and TiCl ₄ (37.84 g, 200 mmol) was added to the resulting solution. The reaction mixture was stirred at ambient temperature for 1 hour and a white precipitate formed. The precipitate was allowed to settle and the supernatant was decanted. The pellet was washed three times with approximately 200 mL of hexane. The precipitate was reslurried in about 150 mL of hexane and 50 mL of _TiCl4 (18.97 g, 100 mmol) in hexane was added. The slurry was stirred at ambient temperature for 1 hour. The solid was allowed to settle and the supernatant was decanted. The solid was washed once with 200 mL of hexane. About 150 ml of hexane was then added to the precipitate. The catalyst was treated again with 50 mL of _TiCl4 (18.97 g, 100 mmol) in hexane. The slurry was stirred at ambient temperature for 1 hour. The solid was allowed to settle and the supernatant was decanted. The catalyst was washed twice with 200 ml of hexane. About 150 ml of hexane was added to the precipitate. The final catalyst was obtained by reacting with 7.16 g (15.6 mmol) of 25% by weight TEAL in heptane at ambient temperature for 1 hour.

Comparative Example 2A

By adding 330 ml concentration of 15 wt % dibutylmagnesium in heptane, 13.3 molar concentration of 20 wt % tetraisobutylaluminoxane in pentane, 3 ml diisobutylaluminoxane into a 1 liter flask Amyl ether and 153 ml of hexane were used to prepare Comparative Catalyst Sample B. The mixture was stirred at 50°C for 10 hours. Then, 0.2 mL of TiCl ₄ and a mixture of tert-butyl chloride (96.4 mL) and DIAE (27.7 mL) were added. The mixture was stirred at 50°C for 3 hours. The precipitate was allowed to settle and the supernatant 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 HCl was added to the reaction mixture over 20 minutes. The solid was filtered and washed twice with 100 mL of hexane. The solid was then resuspended in hexanes. 50 mL of pure _TiCl4 was added to the slurry, and the mixture was stirred at 80 °C for 2 h. The supernatant was decanted, and the catalyst was washed ten times with 100 ml of hexane. Dry the catalyst under _N flow at 50 °C.

Example 1A

Catalyst sample C was prepared according to the invention as follows: Into a 250 ml three-necked round bottom flask equipped with dropping funnel, septum and condenser was added a solution of 15.6 wt% BEM (17.71 g, 25 mmol) in heptane . Then, 6.61 g (51 mmol) of 2-ethylhexanol was slowly added to the solution containing BEM. The reaction mixture was stirred at ambient temperature for 1 hour. Then, 19.38 g (25 mmol) of ClTi( ^OiPr ) ₃ (1M in hexane) was added to this solution. The reaction mixture was stirred at ambient temperature for 1 hour, forming a [Mg(O-2-ethylhexyl) _2ClTi ( ^OiPr ) ₃ ] adduct. Then, 18.51 g (200 mmol) of tert-butyl chloride was added to the resulting solution to give a molar ratio of tert-butyl chloride to BEM of about 8:1. The reaction mixture was heated at reflux temperature (ie, about 80° C.) for 24 hours, forming a precipitate of MgCl ₂ (ie, resulting in a catalyst support). The white precipitate was allowed to settle and the pale yellow supernatant was decanted. The precipitate was washed three times with about 100 mL of hexane. About 100 mL of hexane was then added to the precipitate, and then _TiCl4 (9.485 g, 50 mmol) was slowly added to the resulting solution. The slurry was stirred at ambient temperature for 1 hour. The solid was allowed to settle and the supernatant was decanted. The catalyst was washed 4 times with 50 mL of hexane.

Example 2A

The procedure of Example 1A was followed to form Catalyst Sample D, except that the reaction rate was accelerated by adding a larger amount of tert-butyl chloride to the flask. Specifically, 37.02 g (400 mmol) of tert-butyl chloride was added to the solution in the flask, and the solution was heated at 55°C for 24 hours. The solution thus contained a tert-butyl chloride/BEM molar ratio of about 16:1 (16 equivalents relative to BEM). As expected, Example 2A gave a higher yield than Example 1A.

Table 1A below lists the compositions of the catalysts formed in Comparative Examples 1A and 2A and Examples 1A and 2A.

Table 1A Catalyst sample Mg(wt%) Ti(wt%) Al(wt%) Cl (weight%) A 11.92 6.8 2.7 51.71 B 22.8 2.3 - 66.7 C 13.17 3.6 0.8 48.05 D. 11.01 4.9 - 47.77

The amounts of Mg and Cl in samples C and D are similar to the corresponding amounts in sample A. The amount of Ti in samples C and D is between the amount of Ti in samples A and B.

For Examples 1A and 2A, proton nuclear magnetic resonance ( ¹ H NMR) and gas chromatography-mass spectrometry (GCMS) analysis were used to detect the by-product of the reaction of Ti(O ⁱ Pr) ₃ ClMg(OR) ₂ ] _n with tert-butyl chloride. product. The major by-product was found to be 2-ethylhexanol, rather than the expected tert-butyl 2-ethylhexyl ether or tert-butyl-2-isopropyl ether. Based on this result, it was assumed that some kind of reduction reaction occurred in the mixture, possibly forming isobutene, which was removed from the reaction. Figure 1A illustrates the particle size distribution of samples AD. Both Sample A and B catalysts had narrow particle size distributions. The average particle size of the sample B catalyst is slightly larger than the average particle size of the sample A catalyst. Catalyst samples C and D prepared with tert-butyl chloride had a broad bimodal distribution.

Example 3A

The procedure of Example 1A was followed, except that primary chlorine, n-butyl chloride was added instead of tert-butyl chloride to the flask, resulting in a n-butyl chloride/BEM molar ratio of about 16:1 (16 equivalents relative to BEM) )The solution. Unfortunately, n-butyl chloride was unable to precipitate [Ti(O ⁱ Pr) ₃ ClMg(OR) ₂ ] _n after heating at 50 °C for 24 h. It is hypothesized that this observation indicates that the chlorination mechanism involves a dissociative elimination (E1) step that requires the presence of a stable carbocation.

Example 4A

Catalyst sample K was prepared as follows: Into a 500 mL three-neck round bottom flask equipped with a dropping funnel, septum and condenser was added a solution of 15.6 wt% BEM (8.85 g, 12.5 mmol) in heptane and 100 mL hexane. Then, 3.31 g (25 mmol) of 2-ethylhexanol was slowly added to the solution containing BEM, and the reaction mixture was stirred at ambient temperature for 1 hour. Then, 9.69 g (12.5 mmol) of ClTi(OiPr) ₃ was slowly added to the above mixture, and the reaction mixture was stirred at ambient temperature for 1 hour. Then, 17.6 g (125 mmol) of benzoyl chloride (PhCOCl) was added to the solution so that the molar ratio of PhCOCl to BEM was about 10:1 (10 equivalents to BEM). The reaction mixture was stirred at ambient temperature for 2 h, a precipitate of _MgCl2 formed. The white precipitate was allowed to settle and the supernatant was decanted. The precipitate was washed three times with 100 mL of hexane. About 100 mL of hexane was then added to the precipitate, and then _TiCl4 (4.25 g, 25 mmol) was slowly added to the solution. The resulting slurry was stirred at ambient temperature for 1 hour. The pale yellow solid was allowed to settle, and the supernatant yellow liquid was decanted. The catalyst was washed 3 times with 50 mL of hexane.

Apparently, the reaction to form the _MgCl2 support from PhCOCl does not require heating as is done with tert-butyl chloride. Also, as shown in FIG. 3 , the particle size distribution of catalyst sample K formed using PhCOCl was comparable to that of catalyst samples A and B.

Examples 5A-10A

Six more samples (samples E-J) were prepared according to the procedure of Example 4A, except that the amount of PhCOCl used each time was different, so that the molar equivalent relative to BEM varied in the range of 1.2-7.2.

Figure 4 shows the catalyst yield as a function of the amount of PhCOCl used in Example 4A-410. Catalyst yield first increased with increasing PhCOCl concentration and then remained constant at about 7.0 equivalents, giving a maximum yield of about 1.7 grams. Table 2A below lists the compositions of the catalysts formed in Examples 4A-10A.

Table 2A Catalyst sample Equivalent of PhCOCl Ti(wt%) Al(wt%) Mg(wt%) Cl (weight%) E. 1.2 5.0 <0.2 13.02 51.34 f 2.4 3.8 <0.2 12.55 47.55 G 3.6 3.1 <0.2 12.47 40.24 h 4.8 2.7 <0.2 12.48 41.07 I 6.0 2.6 <0.2 12.39 43.02 J 7.2 2.6 <0.2 10.87 43.03 K 10 2.6 <0.2 11.30 42.35 A - 6.8 2.7 11.92 51.71 B - 2.3 - 22.8 66.7

As shown in Table 2A, the titanium content decreased as the PhCOCl concentration increased to 6.0 equivalents, while it remained constant at higher equivalents. The Ti content of catalyst sample HK is similar to that of catalyst sample B and lower than that of catalyst sample A. Possible explanations for the decrease in titanium content may involve benzoate product or unreacted PhCOCl. NMR and GCMS analysis confirmed that the main by-products of the chlorination reaction were 2-ethylhexyl benzoate and isopropyl benzoate. These esters and unreacted PhCOCl, both Lewis bases, can complex with electron-deficient titanium or magnesium. It is believed that the formation of such complexes will allow more titanium to be extracted from the support. It is also believed that complexation with the _MgCl2 support prevents _TiCl4 from epitaxial bonding in subsequent titanation. Interestingly, when the content of PhCOCl is greater than 7 equivalents, the content of titanium remains constant. This value corresponds to all ClTi(O ⁱ Pr) ₃ and Mg(OR) ₂ being chlorinated. Above this amount of PhCOCl, the amount of ester also remains constant, indicating that ester plays an important role in determining the amount of titanium in the final catalyst.

The particle size distributions of catalyst samples EH and IK formed using different concentrations of PhCOCl are shown in Fig. 5 and Fig. 6, respectively. Catalyst sample E formed with the lowest concentration of PhCOCl (1.2 equivalents relative to BEM) exhibited a broad bimodal distribution. Increasing the content of PhCOCl produces a catalyst with a narrower unimodal distribution and thus improves the morphology of the catalyst. In addition, as shown in Figure 7, the average particle size (D ₅₀ ) decreased slightly with the increase of PhCOCl concentration. It is hypothesized that both PhCOCl and the ester product can complex with unsaturated magnesium sites on the growing _MgCl2 support. As mentioned above, these Lewis bases facilitate the extraction of titanium from the growing support. Also, it is believed that the kinetics of support formation are altered by the lack of titanium complexation.

Example 11A

Catalyst sample L was prepared as follows: To a 250 mL three-necked round bottom flask equipped with a dropping funnel, septum and condenser was added a solution of 15.6 wt% BEM (4.43 g, 6.25 mmol) in heptane and 30 mL Hexane (30 mL). Then, 1.66 g (12.5 mmol) 2-ethylhexanol was slowly added to the solution containing BEM, and the reaction mixture was stirred at ambient temperature for 1 hour. Then, a solution of ClTi(OiPr) ₃ (1 M in hexane, 4.85 g, 6.25 mmol) was slowly added to the above mixture, and the reaction mixture was stirred at ambient temperature for 1 hour. Then, to this solution was added a hexane solution (25 mL) containing chloromethyl ethyl ether (CMEE) (9.45 g, 100 mmol) so that the molar ratio of CMEE to BEM was about 8:1 (relative to BEM is 8 equivalents). The reaction mixture was stirred at ambient temperature for 1 h, a precipitate of _MgCl2 formed. The white precipitate was allowed to settle and the supernatant was decanted. The precipitate was washed three times with 50 mL of hexane. Then 30 mL of hexane was added to the precipitate, and a solution of _TiCl4 (2.13 g, 125 mmol) in hexane (30 mL) was added slowly to the solution. The resulting slurry was stirred at ambient temperature for 1 hour. The pale yellow solid was allowed to settle and the yellow supernatant was decanted. The catalyst was then washed 3 times with 50 ml of hexane.

Figure 9 depicts the particle size distributions of CMEE-based catalyst sample L, PhCOCl-based catalyst sample K, and catalyst samples A and B. The CMEE-based catalyst sample has a slightly wider particle size distribution than Sample A, Sample B, and PhCOCl-based catalyst sample K. The shoulder width of the particle size distribution peak of the CMEE-based catalyst is about 7 microns.

Comparative Example 3A

Ethylene polymerization was carried out in the presence of Catalyst Sample A and the TEAl cocatalyst under the conditions listed in Table 3A.

Comparative Example 4A

Ethylene polymerization was carried out in the presence of Catalyst Sample B and the TEAl cocatalyst under the conditions listed in Table 3A.

Example 12A

Ethylene polymerization was carried out under the conditions listed in Table 3A using catalyst samples C and D prepared from tert-butyl chloride. Figure 9 illustrates the particle size distribution of the fluffy particles of the polymers prepared in Example 12A and Comparative Examples 3A and 4A. The particle size distributions obtained with catalyst samples C and D were broad. In contrast, the distributions obtained for catalyst samples A and B are relatively narrow. The fluff prepared from samples C and D contained more small particles than the fluff prepared from samples A and B. The fluff prepared from samples C and D had a relatively low bulk density.

Table 3A Thinner Hexane temperature(℃) 80 H ₂ /C ₂ 2/8 pressure (psig) 125 Co-catalyst TEAL (0.75 mmol/L)

Table 4A below lists the properties of the polymer resins prepared using catalyst samples A, B, C and D.

Table 4A Catalyst sample Mg-based activity Resin Density (g/cm3) Melt index, 2.1 kg (10 g/min) Melt index, 5.0 kg (10 g/min) SR ₂ (HLMI/MI ₂ ) SR ₅ (HLMI/MI ₅ ) 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 0.9574 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

The magnesium-based activity of each catalyst sample was determined by first dissolving the catalyst and the polymer formed from the catalyst in acid to extract the remaining Mg. Catalyst activity was determined from the remaining Mg content. As shown in Table 4A, the magnesium-based activity of Catalyst Sample C was slightly lower than that of Catalyst Sample A and higher than that of Catalyst Sample B. The activity of catalyst sample D is higher than the corresponding activities of catalyst samples A and B. The shear response of the polymers prepared with the catalyst samples was calculated by determining the ratio of High Load Melt Index (HLMI) to Melt Index. The shear response of the polymers prepared from catalyst samples C and D was similar to that of the sample B polymer, but slightly lower than that of the sample A polymer. The amount of wax produced was comparable for all polymers.

Example 13A

Ethylene polymerization was carried out under the conditions listed in Table 3A using catalyst sample EK prepared from benzoyl chloride. Figure 10A illustrates the particle size distribution of the fluffy particles of the polymer prepared in this example (Sample GK). The average particle size (D ₅₀ ) of the PhCOCl-based resin is larger compared to the average particle size of the sample A and sample B resins.

The morphology of the PhPOCl catalyst sample is compared to that of the polymer formed with the PhCOCl catalyst sample in Table 5A below.

Table 5A Catalyst form polymer form Catalyst sample D10 (micron) D50(micron) D90(micron) D90-D10 D ₅₀ (microns) Small particles (%) f 10.08 19.12 30.94 20.86 617.9 4.6 G 9.87 16.76 24.89 15.02 658.0 1.8 h 10.37 19.77 30.42 20.05 532.1 4.4 I 9.58 15.89 23.39 13.81 533.4 1.7 J 9.32 14.38 20.35 11.03 378.3 8.1 K 5.74 12.56 21.74 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 the principle of replication, the morphology of the polymer is related to that of the catalyst. However, for Examples F-K, the morphology of the polymer does not appear to correspond to that of the catalyst (ie, not proportional), whereas for Samples A and B, the two morphologies appear to correspond.

Table 6A below lists the properties of the polymers prepared with the PhCOCl catalyst samples (Samples E-K) and Catalyst Samples A and B.

Table 6A catalyst Mg-based activity Resin Density (g/cm3) Melt index, 2.16 kg (10 g/min) Melt index, 5.0 kg (10 g/min) SR ₂ (HLMI/MI ₂ ) SR ₅ (HLMI/MI ₅ ) wax(%) 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 h 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 K 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 magnesium-based activities of samples E-K are greater than the corresponding activities of samples A and B. The activity generally decreased with increasing PhCOCl equivalent weight, with the exception of sample K, which had an equivalent weight of 10. The densities of the Samples E-K polymers are similar to the densities of the Samples A and B polymers. The melt flow rates (ie, melt indices) of the Samples E-K polymers and the Sample A polymer were greater than the corresponding values for the Sample B polymer. The shear response of the Samples E-K polymers was similar to that of the Sample B polymer, but slightly lower than that of the Sample A polymer. The amount of wax prepared was comparable for all polymers.

Example 14A

PhCOCl-based catalyst sample I (hereinafter referred to as "sample I ₁ ") was prepared by washing the MgCl ₂ precipitate with hexane as described above. This example compares catalyst sample I ₁ with another catalyst sample I ₂ prepared in the same manner but omitting the washing step. It is believed that omitting the cleaning step significantly reduces the time and cost required to produce the catalyst. Table 7A below shows the catalyst composition of samples I ₁ and I ₂ .

Table 7A catalyst Whether to clean Equivalent of PhCOCl Ti(wt%) Al(wt%) Mg(wt%) Cl (weight%) I ₁ yes 6 2.6 <0.2 12.39 43.02 I ₂ no 6 1.8 <0.2 11.78 38.21

Omitting the cleaning step reduces the titanium content by about 30%. The washed catalyst sample I ₁ was light yellow. Unwashed catalyst sample _I2 was also very distinctly yellow during the addition of _TiCl4 . However, catalyst sample _I2 immediately turned colorless when _TiCl4 was exposed to the mother liquor. It was hypothesized that complexes of esters with _TiCl4 would give a yellow color, while PhCOCl reacted with _TiCl4 to form a colorless compound. This observation supports the previous discussion on the dependence of titanium content on the amount of PhCOCl. It is believed that excess PhCOCl and esters, if not removed, complexed with _TiCl2 and the support surface, preventing the deposition of titanium on the support surface.

As shown in Fig. 11, the particle size distributions of samples _I1 and _I2 are basically the same. Therefore, the catalyst particle size distribution is not affected by the washing step. This observation is not surprising since the washing step was performed after the formation of the _MgCl2 support. Samples I ₁ and I ₂ were used to polymerize ethylene. Table 8A below lists the catalyst and polymer morphologies for Samples ₁₁ and ₁₂ .

Table 8A Catalyst form polymer form Whether to clean D ₁₀ (microns) D ₅₀ (microns) D ₉₀ (microns) D ₉₀ -D ₁₀ D ₅₀ (microns) Small particles (%) yes 9.58 15.89 23.39 13.81 533.4 1.7 no 9.21 15.48 23.02 13.81 239.2 23.7

Table 8A further confirms the conclusion that the particle size distribution is not affected by the washing step. When the washing step was omitted, the number of small particles formed in the polymer increased significantly. The increased number of small particles may be due to the lower yield. The properties of the polymers formed using catalyst samples I ₁ and I ₂ are shown in Table 9A below.

Table 9A Whether to clean Mg-based activity Bulk density (g/cubic centimeter) Resin Density (g/cm3) Melt index 2.16 kg (10 g/min) Melt index 5.0 kg (10 g/min) SR ₂ (HLMI/MI ₂ ) SR ₅ (HLMI/MI ₅ ) wax(%) yes 26000 0.23 0.9626 2.90 10.89 37.7 10.0 0.2 no 14800 0.29 0.9557 0.48 1.36 24.8 8.8 0.1

As shown in Table 9A, the polymerization activity of the unwashed catalyst was almost half that of the washed catalyst. The densities of the two polymers are almost the same. However, the shear response data indicated that the unwashed catalyst had a narrower molecular weight distribution than the washed catalyst. It is believed that the presence of PhCOCl and esters in the catalyst affects the distribution of active sites in the catalyst.

Example 15A

The effect of BEM concentration on catalyst properties was also investigated. A first PhCOCl-based catalyst sample (Sample L) was prepared using the BEM solution diluted with 100 mL of hexane. For comparison purposes, a second PhCOCl-based catalyst sample (Sample M) was prepared using the BEM solution diluted with 20 mL of hexane. Figure 12 shows the catalyst particle size distribution for catalyst samples L and M. The distribution of the two catalysts is very similar. The compositions and properties of catalyst samples L and M and the polymers prepared from them are listed in Tables 10A and 11A below, respectively.

Table 10A Catalyst sample Yield (g) Ti(wt%) Al(wt%) Mg(wt%) Cl (weight%) L 0.86 3.5 <0.2 12.34 43.23 m 0.81 3.8 <0.2 12.55 47.55

Table 11A Catalyst sample Mg-based activity Resin Density (g/cm3) Melt index, 2.16 kg (10 g/min) Melt index, 5 kg (10 g/min) SR ₂ (HLMI/MI ₂ ) SR ₅ (HLMI/MI ₅ ) 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

Tables 10A and 11A show that BEM concentration has essentially no effect on catalytic composition and polymer properties.

In summary, new catalysts were synthesized using alkyl chlorides such as n-butyl chloride, tert-butyl chloride, and chloromethyl ethyl ether. The catalyst formed from benzoyl chloride and chloromethyl ethyl ether had a satisfactory particle size distribution, while t-butyl chloride gave a bimodal distribution and n-butyl chloride did not form _MgCl2 . Catalyst preparation was optimized by varying the amount of benzoyl chloride added to the magnesium alkoxide adduct. As expected, the catalyst yield increased with increasing amount of benzoyl chloride and reached saturation at about 7 equivalents of benzoyl chloride to BEM. The particle size distribution of the catalyst becomes narrower with the increase of the amount of benzoyl chloride.

An experiment was also performed to observe the effect of omitting the wash step after carrier formation. Unwashed catalyst samples showed lower activity and lower shear response than washed samples. The effect of BEM concentration on catalyst properties was also examined. Particle size distribution, catalyst composition, and polymer properties were not affected by BEM concentration.

While embodiments of the present invention have been shown and described, modifications to the foregoing embodiments can be made by those skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to limit the invention. The chemical mechanisms or theories disclosed herein are given based on information and opinions, without being bound by them. Many variations and modifications may be made to the invention disclosed herein and remain within the scope of the invention. Accordingly, the scope of the invention is not limited by the foregoing description, but is only limited by the claims which follow, that scope including equivalents of the subject matter of all claims.

Claims (67)

1. A preparation method of catalyst component, comprising: a) generating reaction product A by contacting a magnesium glycolate compound with a halogenating agent; b) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; c) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; and d) Contacting reaction product C with a third halogenation/titanation agent to form catalyst component D. 2. The method of claim 1, wherein the halogenating agent has the general formula _ClAR'x where A is a non-reducing oxophile and R' is a hydrocarbyl moiety having about 2-6 carbon atoms , x is the compound price of A minus 1. 3. The method of claim 1, wherein the halogenating agent is ClTi( ^OiPr ) ₃ . 4. The method of claim 1, wherein the first halogenation/titanation agent is a mixture of two tetrasubstituted titanium compounds having the same four substituents, the substituents being halogen Or an alkoxy or phenoxy group having 2 to 10 carbon atoms. 5. The method of claim 4, wherein the first halogenating/titanating agent is a mixture of a titanium halide and an organic titanate. 6. The method of claim 5, wherein the first halogenation/titanation agent is TiCl4 with a _TiCl4 /Ti ₍ OBu) ₄ ratio in the range of 0.5:1 to 6:1 and Ti(OBu) ₄ mixture. 7. The method of claim 1, wherein the second and third halogenating/titanating agents comprise titanium tetrachloride. 8. The method of claim 7, wherein step c) and step d) each comprise a ratio of titanium tetrachloride to magnesium in the range of about 0.1 to about 5. 9. The method of claim 1, wherein the reaction products A, B and C are washed with a hydrocarbon solvent before the subsequent halogenation/titanation step. 10. The method according to claim 9, characterized in that, the reaction products A, B and C are cleaned with a hydrocarbon solvent before the subsequent halogenation/titanate step until the titanium element [Ti] content less than about 100 mmol/L. 11. The method of claim 1, wherein the product D is washed with a hydrocarbon solvent until the titanium element [Ti] content is less than about 20 mmol/L. 12. The method of claim 1, wherein an electron donor is present in any one or more of steps a), b), c) or d), wherein the ratio of electron donor to metal is between about In the range of 0:1 to about 10:1. 13. The method of claim 1, further comprising placing the catalyst of the present invention on an inert support. 14. The method of claim 13, wherein the inert support is a magnesium compound. 15. The method of claim 1, further comprising: e) contacting D with an organometallic preactivator to form a preactivated catalyst system. 16. A catalyst prepared by a method comprising the steps of: a) contacting a catalyst component with an organometallic preactivator, wherein said catalyst component is prepared by a process comprising i), ii), iii) and iv), i) contacting the magnesium glycolate compound with a halogenating agent to form reaction product A; ii) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; iii) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; and iv) contacting the reaction product C with a third halogenating/titanating agent to form a catalyst component. 17. The catalyst of claim 16, wherein the organometallic preactivator is an aluminum alkyl of the general formula _AlR , wherein at least one R is an alkyl or halogen having 1 to 8 carbon atoms , each R may be the same or different. 18. The catalyst of claim 17, wherein the organometallic preactivator is an aluminum trialkyl. 19. The catalyst of claim 18, wherein the second and third halogenating/titanating agents comprise titanium tetrachloride. 20. The catalyst of claim 19, wherein the ratio of aluminum to titanium is in the range of 0.1:1 to 2:1. 21. The method of claim 16, wherein the reaction products A, B and C are washed with a hydrocarbon solvent prior to the subsequent halogenation/titanation step. 22. The method of claim 16, wherein the catalyst component is washed with a hydrocarbon solvent until the titanium element [Ti] content is less than about 20 mmol/L. 23. A polymer produced by a method comprising the steps of: a) contacting one or more olefin monomers in the presence of a catalyst under polymerization conditions, Wherein, the catalyst is prepared by a method comprising i), ii), iii) and iv), i) contacting the magnesium glycolate compound with a halogenating agent to form reaction product A; ii) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; iii) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; iv) contacting the reaction product C with a third halogenation/titanation agent to form a catalyst component; and b) Extraction of polyolefin polymers. 24. The polymer of claim 23, wherein the catalyst is prepared by a process further comprising v) wherein v) is contacting the catalyst components with an organoaluminum reagent. 25. The polymer of claim 23, wherein the second and third halogenating/titanating agents comprise titanium tetrachloride. 26. The polymer of claim 23, wherein the reaction products A, B and C are washed with a hydrocarbon solvent prior to the subsequent halogenation/titanation step. 27. A film, fiber, pipe, fabric material, or manufactured article comprising the polymer of claim 23. 28. A method of polymerizing olefins, comprising: a) contacting one or more olefin monomers in the presence of a catalyst under polymerization conditions, wherein the catalyst is prepared by a process comprising i), ii), iii) and iv), i) contacting the magnesium glycolate compound with a halogenating agent to form reaction product A; ii) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; iii) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; iv) contacting reaction product C with a third halogenating/titanating agent to form reaction product D; b) extracting polyolefin polymers; wherein at least one of the reaction products A, B and C is washed with a hydrocarbon solvent prior to the subsequent halogenation/titanation step; and The reaction product D is washed with a hydrocarbon solvent until the titanium element [Ti] content is less than about 100 mmol/L. 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 grams per cubic centimeter. 31. An article comprising a polymer prepared by the method of claim 28. 32. A method of preparing a catalyst comprising: The precipitation of the catalyst component from the catalyst synthesis solution is changed by controlling the viscosity of the catalyst synthesis solution by adding aluminum alkyl, wherein the average particle size of the catalyst component increases with the increase of the concentration of alkyl aluminum in the synthesis solution. 33. The method of claim 32, further comprising contacting the catalyst component with an organometallic preactivator to form a catalyst, wherein the average particle size of the catalyst increases with increasing aluminum alkyl concentration in the synthesis solution. Increase. 34. The method of claim 32, wherein the catalyst synthesis solution comprises: contacting the magnesium glycolate compound with a halogenating agent to form reaction product A; contacting reaction product A with a series of halogenating/titanating agents to form a catalyst component; and contacting the catalyst component with an organometallic preactivator to form the catalyst; Wherein, the average particle diameter of the catalyst increases with the increase of the alkylaluminum concentration in the synthesis solution. 35. The method of claim 34, wherein at least one of the reaction product A and the reaction product obtained after each halogenation/titanation step is washed with a solvent to remove contaminants. 36. A method for preparing a catalyst, comprising: a) contacting the magnesium glycolate compound with a halogenating agent to form a reaction product A; b) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; c) contacting reaction product B with a second halogenation/titanation 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 preactivator to form a catalyst; Wherein, the magnesium glycolate compound is the reaction product of the reaction comprising the following substances: an alkylmagnesium compound having the general formula MgRR', wherein R and R' are alkyl groups having 1-10 carbon atoms, and R and R' can be the same Or different; general formula is the alcohol of R " OH, wherein, alcohol is linear or branched, and R " is the alkyl group that has 2-20 carbon atoms; General formula is the alkyl aluminum of AlR ₃ , wherein at least one R'' is alkyl or alkoxy or halogen having 1 to 8 carbon atoms, wherein each R'' can be the same or different; and The average particle size of the catalyst increases with increasing ratio of aluminum alkyl to magnesium alkyl. 37. The method of claim 36, wherein the ratio of aluminum alkyl to magnesium alkyl is in the range of about 0.01:1 to about 10:1. 38. The method of claim 36, wherein steps c) and d) each comprise titanium tetrachloride as the halogenation/titanation agent, the ratio of titanium tetrachloride to magnesium being between in the range of about 0.1 to about 5. 39. The method of claim 36, wherein the magnesium glycolate compound is bis(2-ethylhexyloxy)magnesium. 40. The method of claim 36, wherein the alkylmagnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium, or butylethylmagnesium. 41. The method of claim 36, wherein the alcohol is selected from the group consisting of ethanol, propanol, isopropanol, butanol, isobutanol, 2-methylpentanol, and 2-ethylhexanol. 42. The method of claim 36, wherein the organometallic preactivator comprises an aluminum alkyl. 43. The method of claim 36, wherein the first halogenating/titanating agent is a mixture of two tetrasubstituted titanium compounds having the same four substituents, wherein the substituents are halogen or Alkoxy or phenoxy having 2 to 10 carbon atoms. 44. The method of claim 43, wherein the first halogenating/titanating agent is a mixture of a titanium halide and an organic titanate. 45. The method of claim 44, wherein the first halogenation/titanation agent is TiCl4 with a _TiCl4 /Ti ₍ OBu) ₄ ratio in the range of 0.5:1 to 6:1 and Ti(OBu) ₄ mixture. 46. The method of claim 36, wherein the reaction further comprises an electron donor. 47. The method of claim 46, wherein the ratio of electron donor to magnesium is in the range of about 0:1 to about 10:1. 48. The method of claim 46, wherein the electron donor is an ether. 49. The method of claim 36, wherein the halogenating agent has the general formula _ClAR'x where A is a non-reducing oxophile and R' is a hydrocarbyl moiety having about 2-6 carbon atoms , x is the compound price of A minus 1. 50. The method of claim 49, wherein the halogenating agent is ClTi(OiPr) ₃ . 51. The method of claim 36, wherein at least one of the reaction products A, B, C and D is washed with a hydrocarbon solvent until the titanium element [Ti] content is less than about 100 mg mol/liter. 52. The method of claim 36, wherein an electron donor is present in any one or more of steps a), b), c) or d), the ratio of the electron donor to metal In the range of about 0:1 to about 10:1. 53. The method of claim 36, further comprising placing the catalyst of the invention on an inert support. 54. The method of claim 53, wherein the inert support is a magnesium compound. 55. A catalyst prepared by a method comprising the steps of: a) contacting a catalyst component with an organometallic preactivator, wherein said catalyst component is prepared by a process comprising i), ii), iii) and iv), i) contacting a magnesium glycolate compound of the _general formula Mg(OR″) with a halogenating agent capable of exchanging an alkoxy group with a halogen, wherein R″ is a hydrocarbyl group having 1 to 20 carbon atoms, to form the reaction product A or substituted hydrocarbyl; ii) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; iii) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; and iv) contacting the reaction product C with a third halogenation/titanation agent to form a catalyst component; Wherein, the magnesium glycolate compound is the reaction product of the reaction comprising the following substances: an alkylmagnesium compound having the general formula MgRR', wherein R and R' are alkyl groups having 1-10 carbon atoms, and R and R' can be the same Or different; general formula is the alcohol of R " OH, wherein, alcohol is linear or branched, and R " is the alkyl group that has 2-20 carbon atoms; General formula is the alkyl aluminum of AlR ₃ , wherein at least One R'' is an alkyl or alkoxy group or halogen having 1 to 8 carbon atoms, wherein each R'' can be the same or different; and The average particle size of the catalyst increases with increasing ratio of aluminum alkyl to magnesium alkyl. 56. The catalyst of claim 55, wherein the organomagnesium preactivator is an aluminum alkyl of the general formula _AlR , wherein at least one R is an alkyl or halogen having 1 to 8 carbon atoms , each R may be the same or different. 57. The catalyst of claim 56, wherein the organic preactivator is an aluminum trialkyl. 58. The catalyst of claim 55, wherein the second and third halogenating/titanating agents comprise titanium tetrachloride. 59. The catalyst of claim 55, wherein the ratio of aluminum to titanium is in the range of 0.1:1 to 2:1. 60. A polymer produced by a method comprising the steps of: a) contacting one or more olefin monomers in the presence of a catalyst under polymerization conditions, wherein the catalyst is formed by a process comprising i), ii), iii), iv), v) and vi) be made of, i) contacting an alkylmagnesium compound of the general formula MgRR' with an alcohol of the general formula R"OH and an aluminum alkyl of the general formula _AlR'3 to form _a magnesium glycolate of the general formula Mg(OR"), wherein R and R' in the general formula MgRR' are alkyl groups with 1-10 carbon atoms and R and R' can be the same or different, the alcohols of the general formula R"OH can be linear or branched, and R" is An alkyl group with 2-20 carbon atoms, at least one R' in the general formula _AlR'3 is an alkyl or alkoxy group or a halogen with 1-8 carbon atoms, and each R'' can be the same or different; ii) contacting the magnesium glycolate compound with a halogenating agent to form a reaction product A, wherein R" is a hydrocarbyl or substituted hydrocarbyl having 1-20 carbon atoms; iii) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; iv) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; v) contacting reaction product C with a third halogenation/titanation agent to form a catalyst component; and vi) contacting the catalyst component with an organoaluminum reagent; and b) extracting polyolefin polymers; Therein, the average particle size of the polymer increases with increasing ratio of aluminum alkyl to magnesium alkyl used in step i). 61. The polymer of claim 60, wherein at least one of the reaction products A, B, and C is washed with a hydrocarbon solvent prior to the subsequent halogenation/titanation step. 62. The polymer of claim 60, wherein the monomer is an ethylene monomer. 63. The polymer of claim 60, wherein the polymer is polyethylene. 64. The polymer of claim 60, wherein the polymer has a molecular weight distribution of at least 4.0. 65. The polymer of claim 60, wherein the polymer has a bulk density of at least 0.31 grams per cubic centimeter. 66. A film, fibre, pipe, fabric material or manufactured article comprising the polymer of claim 60. 67. A method of controlling particle size of a polyolefin polymer comprising: a) contacting, under polymerization conditions, one or more olefin monomers in the presence of a catalyst, wherein the catalyst is prepared by a process comprising i), ii), iii), iv), v) and vi) have to, i) contacting an alkylmagnesium compound of the general formula MgRR' with an alcohol of the general formula R"OH and an aluminum alkyl of the general formula _AlR'3 to form _a soluble magnesium glycolate of the general formula Mg(OR"), Wherein R and R' in the general formula MgRR' are alkyl groups with 1-10 carbon atoms and R and R' can be the same or different, the alcohol of the general formula R"OH can be linear or branched, and R" is an alkyl group with 2-20 carbon atoms, at least one R in the general formula _AlR'3 is an alkyl or alkoxy group or a halogen with 1-8 carbon atoms, and each R' can be the same or different; ii) contacting said soluble magnesium glycolate compound with a halogenating agent capable of exchanging a halogen for an alkoxy group to form a reaction product A, wherein R" is a hydrocarbyl or substituted hydrocarbyl group having 1-20 carbon atoms; iii) contacting reaction product A with a first halogenation/titanation agent to form reaction product B; iv) contacting reaction product B with a second halogenation/titanation agent to form reaction product C; v) contacting reaction product C with a third halogenation/titanation agent to form a catalyst component; and vi) contacting the catalyst component with an organoaluminum reagent; and b) extracting polyolefin polymers; Therein, the average particle size of the polymer increases with increasing ratio of aluminum alkyl to magnesium alkyl used in step i).

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