JP2003155305A - Hydrogen response ziegler-natta catalyst improved to narrow mwd of polyolefin, method for producing the same, use thereof and polyolefin produced by using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for forming a polyolefin having a narrower MWD. SOLUTION: This catalytic component is formed by a method comprising (a) bringing a soluble magnesium dialkoxide compound represented by the general formula: Mg(OR")2 into contact with a halogenating agent to form a reaction product A, (b) bringing the reaction product A into contact with a first halogenating/titanating agent to form a reaction product B and (c) bringing the reaction product B into contact with a second halogenating/titanating agent.

Description

Detailed Description of the Invention

RELATED TO RELATED APPLICATION This application is a continuation-in-part application of US Patent Application Serial No. 09 / 789,862 filed January 28, 1997, entitled "Ziegler-Natta Catalyst for Olefin Polymerization". is there. BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION The present invention relates to catalysts, methods of making catalysts, methods of using catalysts, methods of polymerization and polymers made using such catalysts. In another aspect, the invention provides a polyolefin catalyst, a method of making such a catalyst, a method of using such a catalyst,
It relates to polyolefin polymerization and polyolefins. In yet another aspect, the invention relates to a Ziegler-Natta catalyst, a method of making such a catalyst, a method of using such a catalyst,
It relates to polyolefin polymerization and polyolefins.

2. Description of Related Literature Ziegler-Natta polyolefin catalysts have existed since the early 1950's, and their general method of preparation and subsequent use are well known in the polymerization art.

However, much is known about Ziegler-Natta catalysts while their polymer yields,
There is constant research into improving catalyst life, catalytic activity, and the ability to produce polyolefins with certain physical properties.

US Pat. No. 4,255,544 issued to Kimura et al. On Mar. 10, 1981 contains (A) a reaction product of a magnesium compound and a titanium halide, and (B) an organoaluminum compound. Discloses a process for the polymerization of ethylene using a catalyst comprising a component A in which a magnesium dialkoxide is reacted with a halogen-containing silicon compound and an alcohol to obtain a solid material, and the solid material is then converted into titanium halide and -Prepared by reacting in the presence of the containing silicon compound.

US Pat. No. 4,914,069 issued April 3, 1990 to Job et al. Discloses the preparation of an olefin polymerization catalyst component having improved activity and selectivity, which comprises (a) at least Halogenating a magnesium compound containing one aryloxy, alkyl or carbonate or alkoxy group with a first halide of tetravalent titanium and a first electron donor; (b) converting the resulting product to a tetravalent Prepared by contacting with a second halide of titanium; and (c) washing the resulting treated halogenated product with an inert liquid hydrocarbon. In the method a second electron donor is used in step (a) or (b), and the product of step (b) is combined with a third halide of tetravalent titanium in step (b2) at 40 ° C. Contact at a temperature of 140 ° C. and then wash the treated product in step (c).

US Pat. No. 5,155,187, issued to Shelly on October 13, 1992, generally discloses silicon-containing compounds, magnesium dialkyls, alcohols, halide-containing metal compounds, aluminum alkoxides, and secondary Disclosed is a polymerization method using a catalyst which is a reaction product of a halide-containing metal compound.

Buehler et al., US Pat. No. 5,610,246, issued Mar. 11, 1997, discloses the polymerization of propylene using silica-supported catalysts. The catalyst comprises silica selected in a random order from the group consisting of (1) at least one hydrocarbon-soluble magnesium-containing compound; and (2) silicon halide, boron halide, aluminum halide and mixtures thereof. A product obtained by contacting the first modified compound with a second specific modified compound.

US Pat. No. 5,631,334 issued May 20, 1997 to Zandona discloses a (co) polymerization of at least one olefin comprising a coprecipitate of magnesium and at least one transition metal. Disclosed is a method for producing a catalyst solid for use in the method.

However, in spite of these advances in the prior art, these prior art documents show that TiCl ₄ / Ti
Due to the nature of R in a mixture of (O ⁱ R) ₄ , it is possible to provide a polyolefin having a narrow molecular weight distribution (“MWD”) with improved hydrogen response.
There is no disclosure or suggestion that a catalyst having a response) is provided.

Thus, there is a need in the art for polyolefin catalysts.

There is also another need in the art for methods of making polyolefin catalysts.

Yet another need exists in the art for olefin polymerization processes.

Yet another need exists in the art for narrower MWD polyolefins.

There is still another need in the art for catalysts with improved hydrogen response.

In the art there is a process for the preparation of a polyolefin catalyst providing a polymer with a narrow molecular weight distribution, said process comprising the use of a mixture of TiCl ₄ / Ti (O ⁱ Pr) ₄ . Yet another demand exists.

There is yet another need in the art for narrower MWD polyolefin manufacturing processes.

These and other needs in the art will be apparent to those of ordinary skill in the art upon reviewing this specification, including the drawings and claims.

SUMMARY OF THE INVENTION It is an object of the invention to provide a polyolefin catalyst.

It is another object of the present invention to provide a method of making a polyolefin catalyst.

It is a further object of the present invention to provide a process for polymerizing olefins.

It is a further object of the present invention to provide polyolefins with narrower MWD.

It is a further object of the present invention to provide a catalyst having an improved hydrogen response.

A method of making a polyolefin catalyst which provides a polymer having a narrow molecular weight distribution, the method comprising:
It is a further object of the invention to provide a process comprising using a mixture of iCl ₄ / Ti (O ⁱ Pr) ₄ .

It is yet another object of the present invention to provide a process for making narrower MWD polyolefins.

One of the embodiments of the present invention is a) the general formula Mg.
The soluble magnesium dialkoxide compound of (OR ") ₂ is contacted with a halogenating agent capable of replacing one alkoxide with one halogen to form a reaction product A, wherein R" is 1 to 20 Hydrocarbyl or substituted hydrocarbyl having carbon atoms of b); contacting reaction product A with a first halogenation / titanating agent to form reaction product B; and c) adding reaction product B to a second Providing a catalyst component prepared by a method which generally comprises contacting with a halogenating / titanating agent to produce the catalyst component. Preferably the first halogenating / titanating agent is a Ti (OPr) ₄ / TiCl ₄ mixture. Soluble magnesium dialkoxide compounds have the general formula Mg
An alkylmagnesium compound of RR ', wherein R and R'are alkyl groups having 1 to 10 carbon atoms and may be the same or different, and the general formula R "OH
Where the alcohol may be linear or branched and R ″ is an alkyl group having from 4 to 20 carbon atoms).

Another embodiment of the invention provides a catalyst.
Generally, the catalyst comprises the catalyst components of the present invention as an organoaluminum preactivating agent.
manufactured by a method comprising contacting with t). The catalyst component is generally i) the general formula Mg (O
R ″) ₂ magnesium dialkoxide compound is contacted with a halogenating agent capable of replacing one alkoxide with one halogen to form reaction product A, where R ″ is 1 to 20 carbon atoms. Ii) contacting reaction product A with a first halogenation / titanating agent and reaction product B
And iii) contacting reaction product B with a second halogenating / titanating agent. Preferably the first halogenating / titanating agent is a Ti (OPr) ₄ / TiCl ₄ mixture. The catalysts of the present invention have improved hydrogen response and are useful for producing polymers of desired molecular weight distribution.

In yet another embodiment of the present invention there is provided a polymer prepared by a process which comprises: a) contacting together one or more α-olefin monomers under polymerization conditions in the presence of a catalyst of the present invention. To do. Preferably the catalyst is used for the polymerization of polyethylene monomers to produce polyethylene polymers. The catalyst generally comprises: i) contacting a soluble magnesium dialkoxide compound of the general formula Mg (OR) ₂ with a halogenating agent capable of replacing one alkoxide with one halogen to produce reaction product A, wherein And R is hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms; i
i) 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 a catalyst component Manufactured by a method comprising: Preferably the halogenating / titanating agent in at least one of steps b) and c) is Ti (OPr) ₄ / TiCl ₄ . The catalyst manufacturing process may further include contacting the catalyst component with an organoaluminum agent.

In yet another embodiment of the present invention, there is provided a catalyst system comprising the catalyst of the present invention and an inert support. Preferably the inert carrier is a magnesium compound.

Yet another embodiment of the present invention provides a method for forming a catalyst component. Generally, the method comprises: a) contacting a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ with a halogenating agent capable of replacing one alkoxide with one halogen to form reaction product A; Wherein R "is hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms,
Comprises. The method further comprises b) contacting reaction product A with a first halogenation / titanating agent to produce reaction product B, and c) reaction product B with a second halogenation / titanation agent.
Contacting with a titanating agent to produce a catalyst component, or reaction product C. Preferably the halogenating / titanating agent in at least one of steps b) and c) is Ti (OPr) ₄ / TiCl ₄ .

In yet another embodiment of the present invention, there is provided a method of forming a catalyst comprising contacting a catalyst component of the present invention with an organoaluminum preactivator.

In yet another embodiment of the present invention α
-Providing a method for olefin polymerization. Generally, the polymerization process comprises a) contacting one or more α-olefin monomers under polymerization conditions in the presence of a catalyst of the invention; and b) extracting the polyolefin polymer. The present polymerization process is useful for making polymers having a molecular weight distribution of less than about 7.0, preferably polyethylene polymers.

These and other objects of the invention will be apparent to those of ordinary skill in the art upon review of this specification, including the drawings and claims.

DETAILED DESCRIPTION OF THE INVENTION The process of the present invention for preparing the catalyst component generally forms a metal dialkoxide from a metal dialkyl and an alcohol, halogenates the metal dialkoxide to form TiCl ₄ /
Halogenating / titanizing in one or more steps using at least one step utilizing a mixture of Ti (O ⁱ Pr) ₄ to form a catalyst, and then the catalyst is a pre-activator,
For example, treatment with organoaluminum to form a preactivated catalyst.

The proposed mechanism for the method of the present invention is as follows: MRR '+ 2R "OH → M (OR") ₂ ; 2. M (OR ") ₂ + ClAR"'x → "A";"A" + TiCl ₄ / Ti (OPr) ₄ →
"B"; 4. “B” + TiCl ₄ → “C”; and 5. “C” + TEAl → catalyst In the above formula, M can be any suitable metal, preferably a Group IIA metal, most preferably Mg. In the above formula, R, R ', R "and R"' are each independently a hydrocarbyl or substituted hydrocarbyl moiety, and R and R'are 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. , And more preferably 2
It has from 6 to 6 carbon atoms, even more preferably from 2 to 4 carbon atoms. R "generally comprises from 3 to 20 carbon atoms and R"'generally comprises from 2 to 6 carbon atoms. Any combination of two or more of R, R ', R "and R"' may be the same or the R groups may be different from each other.

In the above formula ClAR "'x, A is a non-reducing, oxyphilic oxygen (oxyph) capable of substituting one alkoxide for chloride.
ilic) compound, R ″ ′ is hydrocarbyl or substituted hydrocarbyl, and x is A minus 1 valence. Examples of A are titanium, silicon, aluminum,
Carbon, tin and germanium are included, the most preferred of which are titanium and silicon with x = 3. R "'
Examples of include methyl, ethyl, propyl, isopropyl and equivalents having 2 to 6 carbon atoms.
R "'is generally propyl.

The exact composition of the product "A" is unknown, but it is believed to contain partially chlorinated metal compounds, an example of which would be ClMg (OR "). The first chlorination / titanation produces the product "B", which is probably a complex of chlorinated and partially chlorinated metal and titanium compounds and is, for example, (MCl ₂ ) _y '(TiCl _x (OPr ) _4-x ) _z 'could be represented by a second chlorination / titanation to produce the catalyst component "C", which is also probably a chlorinated and partially chlorinated metal and titanium compound. But different from "B" and probably represented by (MCl ₂ ) _y · (TiCl _x '(OPr) _4-x ') _z '. The level of chlorination of "C" is Will be bigger than that of "B" Due to the high level of chlorination, different complexes of different compounds will be produced.While this description of the reaction product provides the most definitive explanation of the chemistry in question at this point, it is claimed. The present invention provided is not limited to this theoretical mechanism.

Suitable metal dialkyls and resulting metal dialkoxides for use in the present invention include any that yield suitable polyolefin catalysts when used in the present invention. Suitable metal dialkoxides and dialkyls include Group IIA metal dialkoxides and dialkyls. The most preferred metal dialkoxide or dialkyl is magnesium dialkoxide or dialkyl.

In the practice of the present invention, magnesium dialkyl (MgRR ') can be any magnesium dialkyl in which R and R'are as described above.
R and R'may be the same or different. Non-limiting examples of suitable magnesium dialkyls are diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like. Butylethyl magnesium (BEM) is the preferred magnesium dialkyl.

In the practice of the present invention, a metal dialkoxide
Is preferably the general formula Mg (OR ") ₂Magnesium of
Where R ″ is 1 to 20 carbon atoms
Is hydrocarbyl or substituted hydrocarbyl.

The metal dialkoxide is most preferably soluble and most preferably non-reducing. Non-reducing compounds have the advantage that they are produced by the reduction of compounds, eg MgRR ′, to form MgCl ₂ rather than insoluble Ti ³⁺ species which tend to form catalysts with a broad particle size distribution. In addition, Mg (OR ") ₂ is MgR
Chlorination with less reactive and milder chlorinating agents than R ', followed by simultaneous chlorination with mild reagents /
Titanation and a second chlorination / titanation with a stronger reagent is a gradual and continuous stronger reaction leading to a more homogeneous product, ie better catalyst particle size control and distribution You can

Non-limiting examples of suitable species of useful metal dialkoxides include magnesium butoxide, magnesium pentoxide, magnesium hexoxide.
die), magnesium di (2-ethylhexoxide), and any alkoxide suitable for solubilizing the system. The most preferred metal alkoxide species is magnesium di (2-ethylhexoxide).

As a non-limiting example, a magnesium dialkoxide, such as magnesium di (2-ethylhexoxide), is an alkyl magnesium compound (MgRR '), such as butylethyl magnesium (BEM), and an alcohol (ROH), such as 2-. It can be produced by reacting with ethylhexanol.

MgRR '+ 2R "OH → Mg (O
In the case of R ") ₂ + RH + R'HBEM, RH and R'H are butane and ethane, respectively. The reaction occurs at room temperature and the reactants form a liquid.

Any alcohol which yields the desired metal dialkoxide in the practice of the present invention can be used. As a non-limiting example, it can be any alcohol of the general formula R ″ OH, where R ″ is an alkyl group having 4 to 20 carbon atoms. While it is believed that almost any alcohol can be used, it is preferred that higher order branched alcohols be used. The alcohol may be linear or branched. Non-limiting examples of alcohols include butanol, isobutanol, 2-ethyl-1-hexanol and the like. The preferred alcohol is 2-ethylhexanol. Generally the alcohol has at least 3, preferably at least 4, more preferably at least 5, most preferably 6 carbon atoms.

The amount of alcohol added to the slurry is generally in the range of about 0.5 equivalents to about 4 equivalents (equivalents compared to the total amount of magnesium or metal compounds), preferably about 1 to about 3 equivalents. Is.

The alkyl metal compound has an electron-deficient bond (e
electron-definition bondin
g) results in high molecular weight species that are highly associative and therefore very viscous in solution. This high viscosity can be reduced by the addition of aluminum alkyls such as triethylaluminum, which breaks the bonds between the individual alkyl metal molecules. The preferred ratio of alkylaluminum to metal is 0.001: 1.
To 1: 1, more preferably 0.01 to 0.1: 1 and most preferably 0.03: 1 to 0.05: 1. In addition, electron donors such as ethers such as diisoamyl ether (DIAE) can be used to further reduce the viscosity of the alkyl metal. The preferred ratio of electron donor to metal is 0: 1 to 10: 1 and more preferably 0.1: 1 to 1: 1.

Reagents useful in the halogenation step for halogenating metal alkoxides include any halogenating agent that yields a suitable polyolefin catalyst when used in the present invention. Preferably the halogenation step is a chlorination step and the preferred halogenating agent is chlorine.

Preferably the chloride halogenating agent (chlorinating agent) is a monochloride compound which only partially chlorinates the magnesium alkoxide. Preferred chlorinating agents are of the general formula ClAR "' _x or ClAOR"' _x , where A is a non-reducing oxygen-philic compound capable of replacing one alkoxide with one chloride,
R ″ ′ is alkyl and x is A minus 1. Examples of A are titanium, silicon, aluminum, carbon, tin and germanium, most preferably titanium and silicon and x is 3. Examples of "" are methyl, ethyl, propyl, isopropyl and equivalents having 2-6 carbon atoms. The chlorinating agent effective in the present invention is ClT
i (OiPr) ₃ and ClSi (Me) ₃ .

Halogenation of metal alkoxide compounds is generally carried out in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane and the like. The preferred solvent is hexane.

The halogenation step is generally carried out at a temperature range of about 0 ° C. to about 100 ° C. for a reaction time in the range of about 0.5 to about 24 hours. Preferably the halogenation step is at a temperature range of about 20 ° C to about 90 ° C for about 1 hour to about 4 hours.
Performed during the reaction time of time.

Once the halogenation step has been carried out and the metal alkoxide has been halogenated, the soluble product "A" undergoes one or more halogenation / titanation treatments,
At least one of them must utilize a mixture of TiCl ₄ / Ti (O ⁱ Pr) ₃ . Preferably in the first halogenation / titanation step TiCl ₄ / Ti
A mixture of (OiPr) ₃ is utilized.

Generally, the halogenating / titanating agent has all four substituents identical and the substituents are halide or divalent.
A tetrasubstituted titanium compound which is an alkoxide or phenoxide having from 10 to 10 carbon atoms, for example TiCl ₄ or Ti (OR ″ ″) x. The halogenation / titanation agent is preferably a chlorination / titanation agent.

Suitable chlorination / titanating agents may be a single compound or a combination of compounds. The process of the invention provides an active catalyst after the first chlorination / titanation step; but the chlorination / titanation is preferably carried out twice in each addition using different compounds or compound combinations. A stronger chlorinating / titanating agent is employed and used in each successive chlorinating / titanizing treatment.

The first chlorinating / titanating agent is preferably a mild titanating agent, preferably a mixture of titanium halide and an organic titanate. It is believed that the mixture of titanium halide and organic titanate reacts to form a titanium alkoxy halide, Ti (OR) aXb, where OR and X are the alkoxide and halide, respectively, and a + b is typically 4 Is the valence of titanium, and both a and b are decimals, for example a =
It may be 2.5 and b = 1.5. More preferably the first chlorination / titanation is TiCl ₄ and Ti (OiP
r) _{3 or} a mixture of TiCl ₄ and Ti (OiP
r) a mixture of ₄ . At least one of the chlorination / titanation steps must use a mixture of TiCl ₄ and Ti (OiPr) ₄ , and the first chlorination / titanation agent is a mixture of TiCl ₄ and Ti (OiPr) ₄ . Is preferred.

TiCl ₄ / Ti (OBu) ₄ or TiCl _{4
In any of 4} / Ti (OiPr) _4, the ratio of TiCl _{4 to} either Ti (OBu) ₄ or Ti (OiPr) ₄ (whichever is used) is 0.5: 1 to 6: 1, more preferably Is in the range 1: 1 to 4: 1, and most preferably 2: 1 to 3: 1. (OC
₁₂ H ₅ ) Cl ₃ The first halogenation / titanation step is generally carried out in a hydrocarbon solvent. Non-limiting examples of suitable hydrocarbon solvents include heptane, hexane, toluene, octane and the like. The product "A" is soluble in the hydrocarbon solvent.

The solid product "B" is the soluble product "A".
Is a precipitate at room temperature after addition of the first halogenation / titanating agent.

The amount of halogenating / titanating agent used must be sufficient to precipitate the solid product from solution. The amount of halogenating / titanating agent commonly used is generally about 0. 0 based on the ratio of titanium to metal.
It will be in the range of 5 to about 5, preferably in the range of about 1 to about 4, and most preferably in the range of about 1.5 to about 2.5.

The solid product "B" precipitated in the first titanation step is then recovered by any suitable recovery method and washed with a hydrocarbon solvent.

Suitable compounds for use as the second halogenation / titanation agent include those suitable for use as the first halogenation / titanation agent, but preferably the second. Reagents are more powerful reagents. The second halogenating / titanating agent is more powerful, and is preferably a titanium halide, more preferably titanium tetrachloride (TiCl ₄ ).

The second halogenation / titanation step generally involves suspending the solid product "B" in a hydrocarbon solvent (s
lurying) reaction product, or catalyst component "C". Hydrocarbon solvents listed as suitable for the first halogenation / titanation step can be used. The amount of titanium tetrachloride generally used is generally in the range of about 0.1 to about 5 equivalents, preferably about 0.15 to about 4 equivalents, most preferably about 0.175 to about 2.5 equivalents. Within the range of.

The catalyst component "C" is combined with an organometallic cocatalyst component ("pre-activator") to form a preactivated catalyst suitable for the polymerization of olefins. The cocatalyst typically used with the transition metal-containing catalyst component "C" is I
Organometallic compounds of Group a, IIa and IIIa metals such as aluminum alkyl, aluminum alkyl hydride, lithium aluminum alkyl, zinc alkyl, magnesium alkyl and the like.

The preactivator is preferably an organoaluminum compound, more preferably an aluminum alkyl of formula AlR ^ ₃ , where R ^ is an alkyl or halide having 1 to 8 carbon atoms. Suitable organoaluminum pre-activators include trialkylaluminums such as trimethylaluminum (TMA), triethylaluminum (TEAl) and triisobutylaluminum (TiBAl). The preferred pre-activating agent is T
It is EAl. The ratio of Al to titanium is 0.01:
1-2: 1 and preferably 0.25: 1-1.2: 1
Is. The catalyst is subsequently recovered and washed with a hydrocarbon solvent.

If desired, an electron donor can be added to the halogenating agent, the first mild halogenating / titanating agent, or the second, stronger halogenating / titanating agent.
Most preferably the electron donor is used in the second halogenation / titanation step. Electron donors for use in making polyolefin catalysts are well known, and any suitable electron donor that provides a suitable catalyst can be used in the present invention.

Electron donors, also known as Lewis bases, are organic compounds of oxygen, nitrogen, phosphorus, or sulfur that donate electron pairs to the catalyst.

The electron donor is an aliphatic or aromatic carboxylic acid and its alkyl ester, an aliphatic or cyclic ether,
Monofunctional or polyfunctional compounds which are advantageously selected from ketones, vinyl esters, acrylic derivatives, especially alkyl acrylates or methacrylates and silanes. A preferred example of a suitable electron donor is di-n-butyl phthalate. More preferred examples of suitable electron donors have the general formula R
Alkylsilylalkoxides of Si (OR ') ₃ , such as methylsilyltriethoxide [MeSi (OE
t ₃ )], wherein R and R ′ are alkyl having 1 to 5 carbon atoms and may be the same or different.

The support of the catalyst system of the present invention must be an inert solid that is not chemically reactive with any of the components of conventional Ziegler-Natta catalysts. The carrier is preferably a magnesium compound. Examples of magnesium compounds used to provide a support for the catalyst component are magnesium halides, dialkoxy magnesium, alkoxy magnesium halides and magnesium carboxylates. The preferred magnesium compound is magnesium chloride (MgCl ₂ ).

If desired, the Ziegler-Natta catalyst may be prepolymerized. Generally, the initial polymerization method is carried out by bringing the catalyst into contact with the cocatalyst and then bringing a small amount of the monomer into contact with the catalyst. The initial polymerization method is described in US Pat. No. 5,106,8.
04, 5, 153, 158 and 5,594, 0
71, which are incorporated herein by reference.

The catalyst can be used in any known method of homopolymerization or copolymerization of any type of α-olefin. For example, the catalyst may be ethylene, propylene, butylene, pentene, hexene, 4-methylpentene and other α having at least two carbon atoms.
-Useful for catalyzing alkenes, and mixtures thereof. Preferably the catalyst of the present invention is used in the polymerization of ethylene to produce polyethylene.

The activity of the catalyst of the present invention depends at least in part on the polymerization method and conditions. Generally, the catalyst has an activity of at least 6000 gPE / g catalyst, but the activity can also be greater than 100000 gPE / g catalyst.

In addition, the catalysts obtained according to the invention have an excellent fluff morphology.
to give a polymer having y). Thus, the catalysts of the present invention provide large polymer particles with a uniform size distribution and small and extremely fine particles (less than about 125 microns).
Is only present in low concentrations. The catalysts of the present invention which contain large, easily transported particles having a high powder bulk density are suitable for polymerisation processes.

The polymerization method can be a bulk, slurry or gas phase method. The catalyst synthesized as described above is preferably used in slurry phase polymerization. Polymerization conditions (eg, temperature and pressure) depend on the type of equipment used and the type of polymerization process performed and are known in the art. Generally the temperature is about 50-2
In the range of 00 ° C and the pressure will be in the range of about 10-800 psi.

The olefin monomer can be introduced into the polymerization reaction zone in a diluent which is a non-reactive heat transfer agent which is liquid under the reaction conditions. Examples of such diluents are hexane and isobutane. For copolymerization of ethylene with other α-olefins such as butene or hexene, the second α-olefin is 0.01 to 20 mole percent,
It can preferably be present in 0.02 to 10 mole percent.

In order to activate the catalyst in the polymerization due to the polymerization method, an internal electron donor (i
external electron donor and external electron donor (external electron donor)
n donor) or a stereoselective modifier (stereo)
selectivity control agen
t) It would be preferable to include (SCA). Internal electron donors can be used in the catalyst formation reaction during the chlorination or chlorination / titanation steps. Compounds suitable as internal electron donors for the preparation of conventional supported Ziegler-Natta catalyst components include ether, diether, ketone, lactone, electron donor compounds containing N, P and / or S atoms and certain groups of esters. Is included. Particularly suitable are esters of phthalic acid, such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate; esters of malonic acid, such as diisobutyl and diethyl malonate; alkyl and aryl pivalates; alkyl, cycloalkyl and aryl maleates; alkyl and Aryl carbonates such as diisobutyl, ethylphenyl and diphenyl carbonate; esters of succinic acid such as monoethyl and diethyl succinate.

External donors that can be used to prepare the catalysts of the present invention include organosilane compounds, such as alkoxysilane compounds of the general formula SiRm (OR ') _4-m , where R is an alkyl group, Selected from the group consisting of a cycloalkyl group, an aryl group and a vinyl group, R'is an alkyl group, and m is 0-3, wherein R is
May be the same as R ', the R'groups may be the same or different when m is 0, 1 or 2, and when m is 2 or 3, the R group is It may be the same or different.

Preferably the external donor of the present invention is of the formula

[0076]

[Chemical 1]

Wherein R ₁ and R ₄ are both alkyl or cycloalkyl groups containing a primary, secondary or tertiary carbon atom bonded to silicon, and R ₁ and R ₄ are R ₂ and R ₃ , which may be the same or different, are selected from silane compounds in which alkyl or aryl groups are present.

R ₁ can be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl, R ₂ and R ₃ can be methyl, ethyl, propyl, or butyl groups, and need not necessarily be the same. And R ₄ can also be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl. Specific external donors are cyclohexylmethyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS), cyclohexylisopropyldimethoxysilane (CIDS), dicyclopentyldimethoxysilane (CPDS) or di-t-butyldimethoxysilane (DTDS).

Polyethylene produced using the above catalysts has a MWD of less than about 7.0, preferably less than 6.0, more preferably less than about 5.5, and even more preferably less than about 5.0. Will.

While the present invention has been generally described above, the following examples are provided as specific embodiments of the invention and to demonstrate its practice and features. The examples are given by way of illustration and are not intended to limit the specification or claims to comply with any aspect.

[0081]

The following examples are merely illustrative of certain specific embodiments of the invention and are not intended to limit the scope of the claims.

Catalyst Manufacture This example allows for the production of narrower molecular weight distribution (MWD) polymers controlled contr.
An example of a polyethylene catalyst of the rolled morphology is provided. The narrow MWD of the catalyst can be utilized to provide a suitable resin for injection molding applications.

The following is a synthetic strategy for controlled geometry catalysts. Standard tabletop reactor conditions (stan
dard bench reactor condition
Table 1 lists important data relating to the MWD of the polymers obtained with the catalyst of the present invention.

As can be seen from this data, the MWD of the polymer is shear response (SR5) and polydispersity (poly).
Very narrow as assessed by the dispersity (Mw / Mn) value.

The catalyst was prepared as follows: Step 1 BuEtMg / DIAE / TEAI (1: 0.6: 0.
03) + 2-ethylhexanol (2.09) gives the soluble intermediate A.

Step 2 Intermediate + 1.0 ClTi (OPr) ₃ gives soluble intermediate B.

Step 3 Intermediate B + Ti (OPr) ₄ / TiCl ₄ (2.0:
1.0) gives a solid precatalyst.

Step 4 Pre-catalyst + TiCl ₄ (0.25) + TEAL
Gives the final catalyst.

Polymerization Reactor used for the polymerization of ethylene (Autoclave Engineer
r) has a capacity of 4 liters and has four mixing dividers (b) with two opposing pitch mixing propellers.
Affles) are equipped. Teledyne-Hastain Gray Dust (Tel
edyne-Hastings Raydist) Introduced through mass flow controller while dome loaded back pressure regulator (dome loaded back-pr).
The internal reactor maintained a constant reaction pressure. The reaction temperature (in the reactor jacket) is Barber-Coleman.
Kammer valve (Kammer connected to the controller
Maintained with steam and cold water using Valve). Hexane was used as the diluent.

Experimental condition values Temperature 80 ° C. Reaction time 60 minutes Pressure 125 psi Catalyst 0.2 cc Slurry (about 10 mg catalyst) Cocatalyst TEAL 0.25 mmol / liter Flow rate H ₂ / C ₂ 0.25

[0091]

[Table 1]

Although certain specific illustrative embodiments of the present invention have been described, it will be appreciated by those skilled in the art that various other modifications will be apparent and can be readily carried out without departing from the scope of the invention. Ah Accordingly, the scope of the claims set forth herein is not limited to the examples and specifications set forth herein, but rather to all equivalents of the invention to one of ordinary skill in the art to which this invention belongs. It should be construed to include all the patentable novel features of the present invention including the features.

The main features and aspects of the present invention are as follows.

1. a) contacting a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ with a halogenating agent capable of substituting one alkoxide for one halogen to form reaction product A, where R" Is 1
Hydrocarbyl or substituted hydrocarbyl having from 20 to 20 carbon atoms, b) contacting reaction product A with a first halogenation / titanating agent to produce reaction product B, and c) reacting product B with Contacting with a second halogenation / titanating agent to produce a catalyst component, wherein the first halogenation /
A catalyst component produced by a method comprising the titanating agent being a mixture of Ti (OPr) ₄ / TiCl ₄ .

2. Soluble magnesium dialkoxide compounds have the general formula MgRR ′ (wherein R and R ′ are from 1 to 10).
Alkylmagnesium compounds of an alkyl group having 1 carbon atom and which may be the same or different and the general formula R "OH, in which the alcohol may be linear or branched and R" is 4 Catalyst component according to claim 1, which is the reaction product of a reaction comprising: an alkyl group having -20 carbon atoms.

3. 3. The catalyst component according to the above 2, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide).

4. The above-mentioned 2 in which the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium.
The catalyst component described.

5. 3. The catalyst component according to 2 above, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.

6. The catalyst component of claim 2 wherein the reaction further comprises an aluminum alkyl.

7. 7. The catalyst component according to 6 above, wherein the aluminum alkyl is triethylaluminum.

8. The first halogenation / titanating agent is Ti
The catalyst component of claim 1 which is a Ti (OPr) ₄ / TiCl ₄ mixture having a ratio of Cl ₄ to Ti (OPr) _{4 in} the range of about 0.5: 1 to about 6: 1.

9. The catalyst component of claim 1 wherein the reaction further comprises an electron donor.

10. The catalyst component of claim 9 wherein the ratio of electron donor to magnesium is in the range of about 0: 1 to about 10: 1.

11. The above 1 in which the electron donor is an ether
0 catalyst component.

12. The halogenating agent has the general formula ClAR "'
_x , where A is a non-reducing lipophilic compound,
The catalyst component according to claim 1, wherein R ″ ′ _x is a hydrocarbyl moiety having about 2 to 6 carbon atoms, and x is A minus 1.

13. a) contacting the catalyst component with an organoaluminum pre-activator, wherein the catalyst component is i) replacing a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ with one alkoxide for one halogen. To produce a reaction product A, wherein R ″ is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms; ii) reaction product A is first halogenated. / Contacting with a titanating agent to produce reaction product B, and iii) contacting reaction product B with a second halogenated / titanating agent to produce a catalyst component. , Where the first halogenating / titanating agent is T
A catalyst produced by a process comprising a mixture of i (OPr) ₄ / TiCl ₄ .

14. The soluble magnesium dialkoxide compound is an alkylmagnesium compound of the general formula MgRR ', where R and R'are alkyl groups having 1 to 10 carbon atoms and may be the same or different; The reaction product of a reaction comprising an alcohol of "OH, where the alcohol may be linear or branched and R" is an alkyl group having from 4 to 20 carbon atoms. 13. The catalyst according to 13.

15. 15. The catalyst according to the above 14, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide).

16. 15. The catalyst according to 14 above, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium.

17. 15. The catalyst according to the above 14, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.

18. 15. The catalyst according to 14 above, wherein the reaction further comprises an aluminum alkyl.

19. 19. The catalyst according to the above 18, wherein the aluminum alkyl is triethylaluminum.

20. The first halogenation / titanating agent is T
The ratio of iCl ₄ to Ti (OPr) ₄ is about 0.5: 1.
The catalyst of claim 13 which is a mixture of Ti (OPr) ₄ / TiCl _{4 in} the range of about 6: 1 to about 6: 1.

21. 15. The catalyst according to 14 above, wherein the reaction further comprises an electron donor.

22. The catalyst of claim 21, wherein the ratio of electron donor to magnesium is in the range of about 0: 1 to about 10: 1.

23. The above 2 in which the electron donor is an ether
2. The catalyst according to 2.

24. The halogenating agent has the general formula ClAR "'
_x , where A is a non-reducing lipophilic compound,
The catalyst according to claim 13, wherein R ″ ′ _x is a hydrocarbyl moiety having about 2 to 6 carbon atoms, and x is A minus 1.

25. 14. The catalyst according to 13 above, wherein the second chlorination / titanation agent is titanium halide.

26. The catalyst of claim 25, wherein the second chlorinating / titanating agent is titanium tetrachloride and the titanium to magnesium range is 0: 1 to 2: 1.

27. The organoaluminum preactivating agent is an aluminum alkyl of the formula AlR ^ ₃ (wherein R ^ is 1
The catalyst according to 13 above, which is an alkyl or halide having 8 carbon atoms, R ^ may be the same or different and at least one R ^ is alkyl.

28. 26. The catalyst according to the above item 25, wherein the organoaluminum preactivating agent is a trialkylaluminum.

29. 14. The catalyst according to 13 above, wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.

30. The catalyst has a feathery shape suitable for the polymerisation process and provides polyethylene with a molecular weight distribution greater than about 7.0, at least 6000 gPE / g
13. Having the activity of a catalyst and particles below about 125 microns give a low level of uniform particle size distribution.
The described catalyst.

31. a) contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst, wherein the catalyst is i) a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ and one alkoxide; Contact with a halogenating agent capable of substituting one halogen to produce reaction product A, where R ″ is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms; ii) reaction product A Contacting a first halogenation / titanating agent to form reaction product B, and iii) contacting reaction product B with a second halogenating / titanating agent to form a catalyst component. Of the first halogenating / titanating agent is T
A polymer produced by a method comprising a mixture of i (OPr) ₄ / TiCl ₄ .

32. The polymer of claim 31, wherein the catalyst further comprises iv) contacting the catalyst component with an organoaluminum agent.

33. 32. The polymer according to the above 31, wherein the monomer is an ethylene monomer.

34. 31. The polymer according to the above 31, wherein the polymer is polyethylene.

35. The soluble magnesium dialkoxide compound is an alkylmagnesium compound of the general formula MgRR ', where R and R'are alkyl groups having 1 to 10 carbon atoms and may be the same or different; The reaction product of a reaction comprising an alcohol of "OH, where the alcohol may be linear or branched and R" is an alkyl group having from 4 to 20 carbon atoms. 31. The polymer according to 31.

36. 36. The polymer according to 35 above, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide).

37. The polymer according to the above 35, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium.

38. The polymer according to the above 35, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.

39. The polymer of claim 35, wherein the reaction further comprises an aluminum alkyl.

40. 40. The polymer according to 39 above, wherein the aluminum alkyl is triethylaluminum.

41. The first halogenation / titanating agent is T
The ratio of iCl ₄ to Ti (OPr) ₄ is about 0.5: 1.
The polymer of claim 31 which is a mixture of Ti (OPr) ₄ / TiCl _{4 in} the range of to about 6: 1.

42. The polymer of claim 35, wherein the reaction further comprises an electron donor.

43. The polymer of claim 42, wherein the ratio of electron donor to magnesium is in the range of about 0: 1 to about 10: 1.

44. The above 4 in which the electron donor is an ether
3. The polymer described in 3.

45. The halogenating agent has the general formula ClAR "'
_x , where A is a non-reducing lipophilic compound,
The polymer according to claim 31, wherein R ″ ′ _x is a hydrocarbyl moiety having about 2 to 6 carbon atoms, and x is A minus 1.

46. 32. The polymer according to above 31, wherein the second chlorinating / titanating agent is titanium halide.

47. The polymer of claim 48, wherein the second chlorinating / titanating agent is titanium tetrachloride and the titanium to magnesium ratio is 0: 1 to 2: 1.

48. The organoaluminum preactivating agent is an aluminum alkyl of the formula AlR ^ ₃ (wherein R ^ is 1
33. The polymer according to claim 32, which is an alkyl or halide having 8 carbon atoms, R ^ may be the same or different and at least one R ^ is alkyl).

49. 47. The polymer according to the above 46, wherein the organoaluminum preactivating agent is a trialkylaluminum.

50. 48. The polymer according to 47 above, wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.

51. a) contacting a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ with a halogenating agent capable of substituting one alkoxide for one halogen to form reaction product A, where R" Is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms; b) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and c) reaction product. Contacting B with a second halogenating / titanating agent to form a catalyst component, wherein the first halogenating / titanating agent is Ti (OPr) ₄ / Ti.
A method for producing a catalyst component comprising a mixture of Cl ₄ .

52. The soluble magnesium dialkoxide compound is an alkylmagnesium compound of the general formula MgRR ', where R and R'are alkyl groups having 1 to 10 carbon atoms and may be the same or different; The reaction product of a reaction comprising an alcohol of "OH, where the alcohol may be linear or branched and R" is an alkyl group having from 4 to 20 carbon atoms. 51. The method described in 51.

53. 53. The method according to 52 above, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide).

54. 53. The method according to 52 above, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium.

55. 53. The method according to 52 above, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.

56. 53. The method according to 52 above, wherein the reaction further comprises an aluminum alkyl.

57. 57. The method according to 56 above, wherein the aluminum alkyl is triethylaluminum.

58. The first halogenation / titanating agent is T
The ratio of iCl ₄ to Ti (OPr) ₄ is about 0.5: 1.
52. The method according to 51 above, wherein the mixture is a Ti (OPr) ₄ / TiCl ₄ mixture in the range of from about 6: 1.

59. 52. The method according to 51 above, wherein the second chlorinating / titanating agent is titanium halide.

60. 59. The method according to 59, wherein the second chlorinating / titanating agent is titanium tetrachloride and the range of titanium to magnesium is 0: 1 to 2: 1.

61. A method of making a catalyst comprising: a) contacting a catalyst component with an organoaluminum pre-activator, wherein the catalyst component is i) a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ in one alkoxide. Is contacted with a halogenating agent capable of substituting one halogen to produce reaction product A, wherein R ″ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms; ii) reaction formation Contacting product A with a first halogenation / titanating agent to form reaction product B, and iii) contacting reaction product B with a second halogenation / titanating agent. Manufactured by, wherein the first halogenating / titanating agent is Ti (OPr) ₄
A process that comprises a / a mixture of TiCl _4.

62. The first halogenation / titanating agent is T
The ratio of iCl ₄ to Ti (OPr) ₄ is about 0.5: 1.
A method according to claim 61, wherein the mixture is a Ti (OPr) ₄ / TiCl ₄ mixture ranging from about 6: 1.

63. 63. The method according to claim 62, wherein the ratio of TiCl ₄ to Ti (OPr) ₄ is about 2: 1.

64. The soluble magnesium dialkoxide compound is an alkylmagnesium compound of the general formula MgRR ', where R and R'are alkyl groups having 1 to 10 carbon atoms and may be the same or different; The reaction product of a reaction comprising an alcohol of "OH, where the alcohol may be linear or branched and R" is an alkyl group having from 4 to 20 carbon atoms. 61. The method according to 61.

65. 62. The method according to 61 above, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide).

66. 62. The method according to 61 above, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium.

67. The method according to 61 above, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.

68. The method of claim 61, wherein the reaction further comprises an aluminum alkyl.

69. 69. The method according to 68 above, wherein the aluminum alkyl is triethylaluminum.

70. The method of claim 61, wherein the reaction further comprises an electron donor.

71. 71. The method of claim 70, wherein the electron donor to magnesium ratio is in the range of about 0: 1 to about 10: 1.

72. The above 7 in which the electron donor is an ether
The method described in 1.

73. The halogenating agent has the general formula ClAR "'
_x , where A is a non-reducing lipophilic compound,
The method of claim 61, wherein R ″ ′ _x is a hydrocarbyl moiety having about 2 to 6 carbon atoms.

74. The halogenating agent is TiCl / Ti (O
61. The method according to 61 above, which is a mixture of iPr) ₃ .

75. 62. The method according to 61 above, wherein the second chlorinating / titanating agent is titanium halide.

76. 62. The method according to claim 61, wherein the second chlorinating / titanating agent is titanium tetrachloride and the titanium to magnesium ratio is 0: 1 to 2: 1.

77. 62. The method according to 61 above, wherein the organoaluminum preactivating agent is an aluminum alkyl.

78. The method of claim 61, wherein the electron donor is present in any one of steps a), i), ii), or iii) and the ratio of electron donor to metal is in the range of about 0: 1 to about 10: 1. .

79. A method of polymerizing an α-olefin, comprising the steps of: a) contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst, wherein the catalyst is i) soluble in the general formula Mg (OR ″) ₂ . A magnesium dialkoxide compound of claim 1 is contacted with a halogenating agent capable of replacing one alkoxide with one halogen to form reaction product A, wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or A 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 produced by a process that comprises the cause to produce a reaction product C, for the first halogenation / titanation agent comprises that the mixture of Ti (OPr) ₄ / TiCl ₄ Law.

80. 80. The method of 79 above, further comprising b) extracting the polyolefin polymer.

81. 81. The method according to 80 above, wherein the polymer has a molecular weight distribution of less than about 7.0.

82. 81. The method according to 80 above, wherein the polymer is polyethylene.

83. iv) The method described in 79 above, wherein the catalyst is produced by a method further comprising contacting the reaction product C with an organoaluminum agent.

84. The first halogenation / titanating agent is T
The ratio of iCl ₄ to Ti (OPr) ₄ is about 0.5: 1.
The process of claim 79 wherein the mixture is a Ti (OPr) ₄ / TiCl ₄ mixture in the range of to about 6: 1.

85. 85. The method according to claim 84, wherein the ratio of TiCl ₄ to Ti (OPr) ₄ is about 2: 1.

86. The halogenating agent in step i) is of the general formula ClAR "' _x , where A is a non-reducing oxyphile and R"' _x is a hydrocarbyl moiety having about 2 to 6 carbon atoms. The method according to 79 above.

87. The halogenating agent is ClTi (OiP
The method according to 86 above, wherein r) ₃ .

88. 87. The method according to 86 above, wherein the second chlorinating / titanating agent is titanium halide.

89. 89. The method according to claim 88, wherein the second chlorinating / titanating agent is titanium tetrachloride and the titanium to magnesium ratio is in the range of 0: 1 to 2: 1.

90. 80. The method according to 79 above, wherein the organoaluminum agent is triethylaluminum.

91. 79. An electron donor is present in any one of steps I) to iv) and the electron donor to metal ratio is in the range of about 0: 1 to about 10: 1.
The method described.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tame Jei Kofu             United States Texas 77062             Ton Grand Najette Court 14803 F-term (reference) 4J028 AA02 AB02 AC04 AC07 BA02                       BB02 BC15 EB01 EB02 EC01                       GA06

Claims (6)

[Claims] 1. A) a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ is contacted with a halogenating agent capable of replacing one alkoxide with one halogen to form a reaction product A. Wherein R ″ is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms, b) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and c) contacting reaction product B with a second halogenating / titanating agent to form a catalyst component, wherein the first halogenating / titanating agent is Ti (OPr).
A catalyst component produced by a process comprising a mixture of ₄ / TiCl ₄ . 2. A) contacting a catalyst component with an organoaluminum pre-activator, wherein the catalyst component comprises i) a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ and one alkoxide. Contact with a halogenating agent capable of substituting with halogen to produce reaction product A, wherein R ″ is hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms; ii) reaction product A Contacting a first halogenation / titanating agent to form reaction product B, and iii) contacting reaction product B with a second halogenating / titanating agent to form a catalyst component. According to the method, wherein the first halogenation / titanating agent is Ti (OPr)
₄ / TiCl ₄ mixture, wherein the catalyst is prepared by a method comprising: 3. A) contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst, wherein the catalyst is i) a soluble magnesium dialkoxide compound of the general formula Mg (OR ″) _2. Contacting one alkoxide with a halogenating agent capable of substituting one halogen to produce reaction product A, wherein R ″ is hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms; ii. ) Contacting reaction product A with a first halogenation / titanation agent to form reaction product B, and iii) contacting reaction product B with a second halogenation / titanation agent to form a catalyst component Produced by a method comprising producing a first halogenating / titanating agent of Ti (OPr)
A polymer made by a process comprising a mixture of ₄ / TiCl ₄ . 4. A) a soluble magnesium dialkoxide compound of the general formula Mg (OR ") ₂ is contacted with a halogenating agent capable of replacing one alkoxide with one halogen to form reaction product A. Wherein R ″ is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms; b) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and C) comprising contacting reaction product B with a second halogenation / titanation agent to form a catalyst component, wherein the first halogenation / titanation agent is Ti (OPr) ₄ / Ti
A method for producing a catalyst component comprising a mixture of Cl ₄ . 5. A method of making a catalyst, comprising: a) contacting a catalyst component with an organoaluminum preactivator, wherein the catalyst component is i) a soluble magnesium dialkoxide of the general formula Mg (OR ") _2. The compound is contacted with a halogenating agent capable of replacing one alkoxide with one halogen to form reaction product A, wherein R "is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms. Ii) contacting reaction product A with a first halogenation / titanation agent to form reaction product B, and iii) contacting reaction product B with a second halogenation / titanation agent. Wherein the first halogenating / titanating agent is Ti (OPr)
₄ / TiCl ₄ mixture. 6. A method of polymerizing an α-olefin, comprising: a) contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst, wherein the catalyst is i) the general formula Mg (OR). ") ₂ of the soluble magnesium dialkoxide compound is contacted with a halogenating agent capable of replacing one alkoxide with one halogen to form reaction product A, wherein R" is 1 to 20 carbons. Atom-bearing hydrocarbyl or substituted hydrocarbyl; ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and iii) reaction product B with a second halogen. of / brought into contact with the titanium agent is prepared by a process comprising generating a reaction product C, for the first halogenation / titanation agent is a mixture of Ti (OPr) ₄ / TiCl ₄ The method comprising the Rukoto.