JP2003147012A - Ziegler-natta catalyst for producing polyolefin having narrow mwd to broad mwd, method for producing the same, method for using the same and polyolefin produced by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a Ziegler-Natta catalyst for producing a narrow molecular weight distribution (MWD) to a broad MWD, a method for producing the same, a method for using the same and a polyolefin produced by using the same. SOLUTION: This Ziegler-Natta catalyst holds a high activity and an excellent fluff morphology in addition to polymerization using the catalyst and broadening of the MWD of the resultantly produced polyolefin. The catalyst is prepared by a method comprising (i) bringing a soluble magnesium dialkoxide compound represented by the general formula: Mg(OR")2 into contact with a halogenating agent and producing a reactional product A and (ii) bringing the reactional product A into contact with a first halogenating/titanating agent and producing a reactional product B and then (iii) bringing the resultant reactional product B into contact with a second halogenating/titanating agent and producing a catalyst component.

Description

Detailed Description of the Invention

[0001]

[See Related Application] This application is entitled “Ziegler-Natta Ca,” which was filed on Jan. 28, 1997.
talys for Orlein Polymer
US patent application serial number 08/78
No. 9,862 (incorporated herein by reference), a continuation-in-part application.

[0002]

BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION The present invention relates to a catalyst, a method for producing a catalyst, a method for using a catalyst, a polymerization method and a polymer produced by using the catalyst.
The invention relates, in another aspect, to a catalyst for polyolefins, a process for the production of said catalysts, a process for the use of said catalysts, the polymerization of polyolefins and polyolefins. The invention, in yet another aspect, relates to a Ziegler-Natta catalyst, a method of making the catalyst, a method of using the catalyst, polymerization of polyolefins and polyolefins. 2. Description of Related Technology From the early 1950s, Ziegler (Ziegle
The r) type catalysts for polyolefins, their general method of preparation and their subsequent use have become well known in the polymerization art.

However, much has come to be known about Ziegler-type catalysts, the ability to produce polyolefins with polymer yield, catalyst life, catalyst activity and specific properties when used with them. There is ongoing research into improving

Kimura dated March 10, 1981
Another issued U.S. Pat. No. 4,255,544 is
A method for polymerizing ethylene using a catalyst comprising (A) a reaction product of a magnesium compound and a titanium halide and (B) an organoaluminum compound is disclosed.
There, the component A is prepared by reacting magnesium dialkoxide, a halogen-containing silicon compound and an alcohol to produce a solid substance, and then the solid substance is treated with a titanium halide in the presence of an alkoxy-containing silicon compound. It is done by reacting with.

US Pat. No. 4,914,069 issued to Job et al. On Apr. 3, 1990 discloses the preparation of a catalyst component for olefin polymerization which exhibits improved activity and selectivity. There, the preparation of the catalyst component,
(A) halogenation of a magnesium compound containing at least one aryloxy, alkyl, carbonate or alkyloxy group using a first tetravalent titanium halide and a first electron donor, (b) resulting This is done by contacting the resulting product with a second tetravalent titanium halide and (c) washing the resulting treated halogenated product with an inert hydrocarbon liquid.
In such a method, a second electron donor is added in step (a).
Or (b) and the product of step (b) is converted to the third tetravalent titanium halide in step (b2)
After contacting at a temperature of 0 ° C. to 140 ° C., the product so treated is washed in step (c).

Shell on October 13, 1992
U.S. Pat. No. 5,155,187 issued to Y.
Generally, a polymerization method using a catalyst which is a reaction product of a silicon-containing compound, a dialkyl magnesium, an alcohol, a halide-containing metal compound, an aluminum alkoxide, and a second halide-containing metal compound is disclosed.

Buehle as of March 11, 1997
US Pat. No. 5,610,246 issued to R et al. discloses a method of polymerizing propylene using a catalyst supported on silica. The catalyst is selected from the group consisting of (1) at least one hydrocarbon-soluble magnesium-containing compound and (2) silicon halides, boron halides, aluminum halides and mixtures thereof in any order of silica. The product obtained by contacting with the first specific modifying compound and then with the second specific modifying compound.

Zandon dated May 20, 1997
U.S. Pat. No. 5,631,334 issued to
Disclosed is a method for producing a catalytic solid for the (co) polymerization of at least one olefin, the method comprising coprecipitating magnesium and at least one transition metal.

However, in spite of such advances in the prior art, none of such prior art documents mention the second titanation of the catalyst preparation step.
It is neither disclosed nor suggested that increasing the amount of titanating agent used in the cation) step will increase the MWD of the polyolefin obtained when using such a catalyst.

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

There is also a need in the art for a method of making a polyolefin catalyst.

There is also a further need in the art for methods of polymerizing olefins.

In addition to this, there is a need in the art for polyolefins that exhibit a wider MWD.

[0014] In the field of the art, furthermore, an increased M
In addition to being able to produce polyolefins exhibiting WD, there is also a need for polyolefin catalysts that exhibit high activity and have excellent fluff morphology.

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

[0016]

SUMMARY OF THE INVENTION One object of the present invention is to provide a catalyst for polyolefins.

Another object of the present invention is to provide a method of preparing a catalyst for polyolefins.

Yet another object of the present invention is to provide a method for polymerizing olefins.

Yet another object of the present invention is a broader MW.
To provide a polyolefin showing D.

Still another object of the present invention is to provide a catalyst for polyolefins which is capable of producing polyolefins having various MWDs and which is highly active and has an excellent fluff morphology.

In one aspect of the invention, a) the general formula Mg
(OR ") ₂ [wherein R" has 1 to 20 carbon atoms.
Is hydrocarbyl or substituted hydrocarbyl]
A halogenating agent capable of exchanging one halogen for one alkoxide in the soluble magnesium dialkoxide compound represented by the formula (halogenating agent)
To produce reaction product A, and b) reacting product A with the first halogenation / titanating agent (halogen).
a reaction product B by contacting with a second halogenating / titanating agent to form a catalyst component. The generated catalyst component is provided. The second halogenating / titanating agent generally comprises titanium tetrachloride, and 2
The second halogenation / titanation step comprises titanium and magnesium such that the ratio of titanium to magnesium is in the range of about 0.1 to 5. Preferably, the second halogenation / titanation step comprises titanium and magnesium in a titanium to magnesium ratio of about 2.0.

In another aspect of the invention, there is provided a polyolefin catalyst, which generally comprises a) contacting the polyolefin catalyst with a) the catalytic component of the invention together with an organoaluminum agent. Method. The catalyst component is i) the general formula Mg (OR ") ₂
[Wherein, R "is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl], and a halogenating agent capable of exchanging one halogen for one alkoxide. Contacting to form reaction product A, ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and iii) reacting product B with a second halogen. Of the second halogenation / titanation agent to the polymer to be formed with this catalyst. The second halogenation / titanating agent generally comprises titanium tetrachloride, and the second halogenation / titanation agent is determined by the desired molecular weight distribution.
In the titanation process, titanium and magnesium are included so that the ratio of titanium to magnesium is in the range of about 0.1 to 5. Preferably, the second halogenation / titanation step includes titanium and magnesium in a titanium to magnesium ratio of about 2.0. The catalyst of the present invention has a fluff morphology tailored to the polymerisation process to give polyethylene exhibiting a molecular weight distribution of at least about 5.0, and a low level of particles below about 125 microns plus a uniform particle size The distribution is shown. The activity of this catalyst depends on the polymerization conditions. The catalyst generally exhibits activity such that at least 6,000 g PE is obtained per gram of catalyst, but this activity is also 100,000 per gram of catalyst.
It is possible to exceed g PE.

In yet another embodiment of the present invention, a) contacting one or more α-olefin monomers together under polymerization conditions in the presence of the catalyst of the present invention and b) extracting the polyolefin polymer. There is provided a polyolefin polymer produced by a method comprising. Generally, the monomer is an ethylene monomer and the polymer is polyethylene.

Yet another aspect of the present invention provides a catalyst system comprising the catalyst of the present invention and an inert support. The inert support is generally a magnesium compound.

Yet another aspect of the present invention provides a method of producing a catalyst component. The catalyst component of the present invention generally comprises
i) A magnesium dialkoxide compound represented by the general formula Mg (OR ") ₂ [wherein R" is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms], and one halogen atom. Reaction product "A" is produced by contacting a halogenating agent that can be exchanged with the alkoxide of ii), and ii) reaction product "A" is contacted with the first halogenating / titanating agent to produce reaction product "B". And iii) reacting the reaction product "B" with a second halogenated
It is prepared by a method comprising contacting with a titanating agent to produce a catalyst component.

In yet another aspect of the present invention, there is provided a method of producing a catalyst suitable for use in producing a polyolefin having a desired molecular weight distribution ("MWD"). The method generally comprises the steps of a) contacting the catalyst component of the present invention with an organoaluminum agent.

In yet another aspect of the present invention, there is provided a method of polymerizing α-olefins to produce a polyolefin having the desired molecular weight distribution ("MWD"). The method generally comprises the steps of a) contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst of the invention and b) extracting the polyolefin polymer. Preferably, the monomer is ethylene and the polymer is polyethylene.

These and other objects of the invention will be apparent to those skilled in the art upon reviewing the specification and claims, including the drawings.

[0029]

DETAILED DESCRIPTION OF THE INVENTION The process of the present invention for producing a catalyst component generally produces a metal dialkoxide from a dialkyl metal and an alcohol, which is halogenated to effect halogenation / titanium conversion. The above steps include the steps of producing a catalyst and then subjecting the catalyst to a treatment with a preactivating agent, such as organoaluminum, and then heat treating the preactivated catalyst. Increasing the amount of halogenation / titanating agent used in the second halogenation / titanation step will increase the MWD of the resulting polyolefin using such a catalyst. In this way, the MWD of the resulting polyolefin can be varied.

The proposed mechanism for the method of the invention is generally as follows: MRR '+ 2R "OH → M (OR") ₂ ; 2. M (OR ") ₂ + ClAR"' _x → "A";"A" + TiCl ₄ / Ti (OR "") ₄ →
"B"; 4. “B” + TiCl ₄ → “C”; and 5. “C” + TEAl → pre-activated catalyst.

Where M is any suitable metal,
It is preferably a Group IIA metal, most preferably Mg. Wherein R, R ′, R ″, R ″ ′ and R ″ ″ are each independently a hydrocarbyl or substituted hydrocarbyl moiety, and R and R ′ are from 1 to 20 carbon atoms.
Preferably from 1 to 10 carbon atoms, more preferably from 2 to 6 carbon atoms, even more preferably from 2 to 4 carbon atoms and R ″ is generally from 3 to 20 carbon atoms. R "'generally contains 2-6 carbon atoms and R""generally contains 2-6 carbon atoms and is typically butyl. When any two or more of R, R ′, R ″, R ″ ″ and R ″ ″ are combined, they may be the same or different from each other.

In the above formula ClAR "' _x , A is a non-reducing oxyphilic non-reducing oxygen capable of exchanging one chloride for one alkoxide.
lic) compound, R ″ ′ is hydrocarbyl or substituted hydrocarbyl, and x is the valence of A minus 1. Examples of A are titanium, silicon,
Including aluminum, carbon, tin and germanium,
Among them, titanium and silicon are most preferable, and x in this case is 3. Examples of R ″ ′ include methyl, ethyl, propyl, isopropyl, etc., which have 2-6 carbon atoms.

The exact composition of the product "A" is unknown, but it is believed to contain partially chlorinated metal compounds, one example of such a compound is ClMg (O).
R ″). The reaction product “B” is probably a complex of a chlorinated metal and a partially chlorinated metal with a titanium compound, which is for example (MCl ₂ ) _y ′.
- it can be represented by _{(TiCl x (OR) 4-} x) z '. Two
The second chlorination / titanation produces a reaction product, namely catalyst component "C", which is also probably a chlorinated metal and a partially chlorinated metal-titanium compound complex. Although it seems different from the "B", which can be represented by perhaps _{(MCl 2) y · (TiCl} x '(OR) 4- x') z '. It is expected that the degree of chlorination of "C" will be greater than that of product "B". Thus, the greater degree of chlorination will produce different complexes of different compounds. While such a description of a reaction product provides the presently most valid explanation of its chemistry, such a theoretical mechanism is not meant to limit the invention as set forth in the claims.

Suitable dialkyl metals and resulting metal dialkoxides for use in the present invention include any dialkyl metal or metal dialkoxide that will produce a suitable polyolefin catalyst when used in the present invention. included. Suitable metal dialkoxides and dialkyl metals include the dialkoxides and dialkyls of the Group IIA metals. Such metal dialkoxide or dialkyl metal is most preferably magnesium dialkoxide or dialkyl magnesium.

The dialkylmagnesium [MgRR '] (R and R'as defined above) used in the practice of the present invention can be any dialkylmagnesium. Of course, R and R'may be the same or different. Non-limiting examples of suitable dialkyl magnesium include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like. Butylethyl magnesium (BEM) is the preferred dialkyl magnesium.

The metal dialkoxide used in the practice of the present invention is preferably of the general formula Mg (OR ") ₂ [wherein R"
Is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl].

Such metal dialkoxides are most preferably soluble and most preferably non-reducing. The non-reducing compound is MgCl ₂ rather than the insoluble Ti ⁺³ species produced by reduction of compounds such as MgRR ′, which tend to produce catalysts with a broad particle size distribution.
Has the advantage of generating. In addition, Mg (O
R ″) ₂ has a lower reactivity than MgRR ′,
Chlorination with a mild chlorinating agent followed by chlorination / titanation with a mild reaction agent and second chlorination / titanation with a more powerful reaction agent slowly followed by progressively stronger reactions. As a result, a more uniform product may be produced, ie, better control and distribution of catalyst particle size may be obtained.

Non-limiting examples of suitable species of useful metal dialkoxides include magnesium butoxide, magnesium pentoxide, magnesium hexoxide, magnesium di (2-ethylhexoxide), and the like. Any alkoxide suitable to render the system soluble is included. The most preferred metal alkoxide species is magnesium di (2-ethylhexoxide).

As a non-limiting example, an alkylmagnesium compound (MgRR '), such as butylethylmagnesium (BEM), and an alcohol (ROH), such as 2-
Magnesium dialkoxides such as magnesium di (2-
Ethylhexoxide) and the like can be produced.

MgRR '+ 2R "OH → Mg (OR")
_In the case of ₂ + RH + R′H BEM, RH and R′H are butane and ethane, respectively. This reaction occurs at room temperature and the reactants form a solution.

Any alcohol which produces the desired metal dialkoxide can be used in the practice of the present invention. It is believed that almost any alcohol that is linear or branched can be used, but it is better to use a higher branched alcohol, such as 2-ethyl-1-hexanol. It is suitable. The alcohol used is generally represented by the general formula R "OH [wherein R" has 4 carbon atoms.
-20, preferably at least 3, more preferably at least 4, even more preferably at least 5, most preferably at least 6 alkyl groups]. Good. Non-limiting examples of suitable alcohols include butanol, isobutanol, 2-
Ethyl-1-hexanol and the like are included. The preferred alcohol is 2-ethyl-1-hexanol.

The amount of alcohol added to the slurry generally ranges from about 0.5 equivalents to about 4 equivalents (equivalents based on magnesium or metal compounds throughout).
It is preferably in the range of about 1 to 3 equivalents.

Alkyl metal compounds have an electron deficient bond and are therefore very susceptible to association, resulting in the formation of high molecular weight species which exhibit a very high viscosity in solution. Such high viscosities can be reduced by adding an alkylaluminum that breaks the association between individual alkylmetal molecules, such as triethylaluminum. The preferred ratio of alkylaluminum to metal is 0.001: 1 to 1: 1, more preferably 0.01 to 0.1: 1, most preferably 0.03: 1 to 0.05: 1. . In addition, an electron donor, for example, an ether such as diisoamyl ether (DIAE) can be used for the purpose of further lowering the viscosity of the alkyl metal. The preferred ratio of electron donor to metal is 0: 1 to 10: 1, more preferably 0.1: 1 to 1: 1.

Agents useful in the step of halogenating the metal alkoxide include any halogenating agent that will produce a suitable polyolefin catalyst when used in the present invention. The halogenation step is preferably a chlorination step and the preferred halogenating agent is chloride.

Suitable chlorinating agents are of the general formula ClAR "' _x
Or ClAOR "' _x [wherein A is a non-reducing, oxygen-philic compound capable of exchanging one chloride for one alkoxide, R"' is alkyl, and x is A It is the value obtained by subtracting 1 from the valence of]. Examples of A are titanium, silicon, aluminum, carbon, tin and germanium, of which titanium and silicon are most preferred, where x is 3. R "'
Are methyl, ethyl, propyl, isopropyl and the like, and these have 2 to 6 carbon atoms. Examples of effective chlorinating agents for use in the present invention are ClTi (O ⁱ Pr) ₃ and ClSi (Me) ₃ . R "" is generally butyl.

The halogenation of the metal alkoxide compound is generally carried out in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane,
Hexane, octane, etc. are included. The preferred solvent is hexane.

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, preferably about 3: 1 to about 1: 2.
More preferably it is in the range of about 2: 1 to about 1: 2, most preferably about 1: 1.

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

After carrying out this halogenation step to halogenate the metal alkoxide, the product "A" which is a soluble halide is subjected to halogenation / titanium treatment one or more times.

The halogenating / titanating agent is preferably a tetra-substituted titanium compound, wherein the four substituents may all be the same and these substituents are halide or having from 2 to 2 carbon atoms. 10 alkoxides or phenoxides), such as TiCl ₄ or Ti (OR "") ₄ . The halogenation / titanation agent is preferably a chlorination / titanation agent.

The suitable chlorinating / titanating agent may be a single compound or a combination of compounds. The process of the present invention produces a catalyst which is still active after the first chlorination / titanation, however, preferably at least two chlorination / titanation steps are provided, each of these steps being different. A compound or combination of compounds is used, and a stronger chlorination / titanation is used in each of the sequential chlorination / titanation steps.

The first chlorinating / titanating agent is suitably a mild titanating agent, preferably a blend of a titanium halide and an organic titanate. This first chlorination /
The titanating agent is more preferably TiCl ₄ / Ti (OB
u) ₄ is a blend of TiCl ₄ and Ti (OBu) _{4 in} the range 0.5: 1 to 6: 1, most preferably 2: 1 to 3: 1. Such a blend of titanium halide and organic titanate reacts to react with an alkoxy halide of titanium, namely Ti (OR) _a X _b [where OR and X are alkoxide and halide respectively, and a + b
Is the valence of titanium, typically 4, and a
And b are both fractional, eg a = 2.5 and b = 1.5 may be generated].

Alternatively, the first chlorinating / titanating agent may be a single compound. 1 as a single compound
An example of the second chlorinating / titanating agent is Ti (OC ₂ H ₅ ) ₂
Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₂ C
l ₂ , Ti (OC ₃ H ₇ ) ₃ Cl, Ti (OC ₄ H ₉ ) C
l ₃ , Ti (OC ₆ H ₁₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ B
r ₂ and Ti (OC ₁₂ H ₂₅ ) Cl ₃ .

The first halogenation / titanation step is generally carried out by first slurrying the halogenated product "A" 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 hydrocarbon solvents.

When the halogenating / titanating agent is added to the soluble product "A", the solid product "B" precipitates at room temperature.

The amount of halogenating / titanating agent used should be sufficient to cause the solid product to precipitate out of solution. The amount of halogenating / titanating agent used is generally in the range of about 0.5 to about 5, preferably in the range of about 1 to about 4, most preferably based on the ratio of titanium to metal. It is preferably in the range of about 1.5 to about 2.5.

The solid product "B" that has precipitated in the first titanation step is then recovered using any suitable recovery technique and then 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, with the proviso that they are preferred. This second halogenating / titanating agent is a stronger halogenating / titanating agent. The more powerful second halogenating / titanating agent is
Titanium halide is preferable, and titanium tetrachloride [TiCl ₄ ] is more preferable.

The second halogenation / titanation step is generally carried out by slurrying the solid product "B" recovered in the first titanation step in a hydrocarbon solvent. . Hydrocarbon solvents mentioned as suitable for use in the first halogenation / titanation step may be used. Next, the slurry is heated to about 50 ° C. to about 90 ° C.
After slight heating to a temperature in the range of ° C, titanium tetrachloride is added.

The second halogenation / titanation agent generally comprises titanium tetrachloride, and the second halogenation / titanation step comprises titanium and magnesium in a titanium to magnesium ratio of about 0.1 to 5. Include in the range of. Preferably, this second halogenation /
In the titanation process, titanium and magnesium are included so that the ratio of titanium to magnesium is about 2.0.

The amount of titanium tetrachloride used can also be expressed in terms of equivalents, which in the present context are amounts of titanium based on magnesium or metal compounds. The amount of titanium used in the second halogenation / titanation step is generally in the range of about 0.1 to about 5.0 equivalents, preferably about 0.25 to about 4 equivalents, more preferably about 0. In the range of 0.5 to about 3 equivalents, most preferably about 0.75 to about 2.
It is in the range of 0 equivalents. In a particularly preferred embodiment, the amount of titanium tetrachloride used in the second halogenation / titanation step is about 1.0 equivalent.

Increasing the amount of halogenating / titanating agent used in this second titanation step will broaden the MWD of the resulting polyolefin. That is, the MWD of the resulting polyolefin with this catalyst will broaden as the amount of titanium tetrachloride used increases.

The combination of the catalyst component "C" produced by the method described above with the catalyst component ("pre-activator") organoaluminum produces a preactivated catalyst system suitable for the polymerization of olefins. To do. Catalysts for use with transition metal containing catalyst component "C" are typically Ia, IIa
And organometallic compounds of Group IIIa metals, such as alkyl aluminum, alkyl aluminum hydride, alkyl lithium aluminum, alkyl zinc, alkyl magnesium and the like.

Such pre-activators are preferably organoaluminum compounds. This pre-activator, organoaluminum, preferably has the formula AlR ^ ₃ [wherein R ^ is
It is an alkyl or halide having 1-8 carbon atoms]
It is an alkylaluminum represented by. The pre-activator organoaluminum is more preferably a trialkylaluminum such as trimethylaluminum (TMA), triethylaluminum (TEAl) and triisobutylaluminum (TiBAl). The most preferred pre-activating agent is TEAl. The ratio of Al to titanium is in the range of 0.1: 1 to 2: 1, preferably 0.25: 1 to 1.2: 1.

An electron donor may optionally be added with the halogenating agent, the milder first halogenating / titanating agent or the more potent second halogenating / titanating agent. Most preferably, an electron donor is optionally used in the second halogenation / titanation step.

Suitable electron donors for use in preparing the present polyolefin catalysts are well known and any suitable electron donor that provides a suitable catalyst can be used in the present invention.

Electron donors are organic compounds containing oxygen, nitrogen, phosphorus or sulfur which are capable of donating electron pairs to the catalyst, also known as Lewis bases.

Such electron donors may be monofunctional or polyfunctional compounds, preferably aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic ethers, ketones, vinyls. It is selected among esters, acrylic derivatives, especially acrylic acid or alkyl methacrylate, and silanes. A suitable example of a suitable electron donor is di-n-butyl phthalate. More suitable examples of suitable electron donors are represented by the general formula RSi (OR ') ₃ , wherein R and R'may be the same or different and are alkyl having 1-5 carbon atoms. An alkylsilyl alkoxide represented by, for example, methylsilyltriethoxide [MeSi
(OEt ₃ )] and the like.

The support of the catalyst system of the present invention must be an inert solid which is not chemically reactive with any of the components of conventional Ziegler-Natta catalysts. Such supports are preferably magnesium compounds. Examples of magnesium compounds to be used for supporting the catalyst component are magnesium halide, dialkoxy magnesium, alkoxy magnesium halide and magnesium carboxylate. The preferred magnesium compound is magnesium chloride (MgCl ₂ ).

Optionally, such Ziegler-Natta catalysts are pre-polymerized (pre-polymerize).
d) may be used. The prepolymerization step is generally carried out by contacting the catalyst with a small amount of monomer after contacting with the cocatalyst.
The prepolymerization process is described in US Pat. No. 5,106,804, 5,
153,158 and 5,594,071 (incorporated herein by reference).

The catalyst can be used in any known method of homopolymerization or copolymerization of any type of α-olefin. The catalyst is useful for catalyzing, for example, ethylene, propylene, butylene, pentene, hexene, 4-methylpentene, and other α-alkenes having at least 2 carbon atoms, and also mixtures thereof.
The catalyst of the present invention is preferably used in the polymerization of ethylene to give polyethylene.

The activity of the catalyst of the present invention depends on the polymerization method and conditions such as the apparatus used and the reaction temperature. The activity of the catalyst is generally at least 5,000 g PE / g catalyst, but it is also possible that this activity exceeds 100,000 g PE / g catalyst.

The resulting catalyst of the present invention additionally comprises
It gives a polymer with an excellent fluff morphology. in this way,
The catalyst of the present invention provides large polymer particles with a uniform size distribution, with very small fine particles (less than about 125 microns) present in only small concentrations. Since the catalyst of the present invention contains a large powder having a high powder bulk density and is easily transferred, this is suitable for the polymerization production process.

The polymerization step may be bulk, slurry or gas phase polymerization. It is preferable to use the catalyst synthesized above in slurry phase polymerization. The polymerization conditions (eg temperature and pressure) depend not only on the type of equipment used in the polymerization process, but also on the type of polymerization method used, which is known in the art. The temperature is generally about 50-10
0 ° C. range, and pressure is about 10-800 psi
Is the range.

The olefin monomer can be introduced into the polymerization reaction zone in a diluent, which is a liquid non-reactive heat transfer agent under the reaction conditions. Examples of such diluents are hexane and isobutane. When ethylene is copolymerized with another alpha-olefin, such as butene or hexene, the second alpha-olefin is present in an amount of 0.01-20 mole percent, preferably 0.02-10 mole percent. Can be made.

In the present polymerization method, an internal electron donor is used during the synthesis of the present catalyst.
nor) and for the purpose of activating the catalyst during polymerization, an external electron donor or a stereoselective modifier (stere).
osselectivitycontrol agen
It may be preferred to include t) (SCA). An internal electron donor can be used during the chlorination step or the chlorination / titaniumization step during the reaction for forming the present catalyst.
Compounds suitable for use as internal electron donors to form conventional supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, electrons having N, P and / or S atoms. Included are donor compounds, and certain types of esters. In particular phthalates such as diisobutyl phthalate, dioctyl, diphenyl and benzylbutyl, malonates such as diisobutyl and diethyl malonate, alkyl and aryl pivalates, alkyl maleates, cycloalkyl and aryl, alkyl and aryl carbonates. Suitable are, for example, diisobutyl, ethylphenyl and diphenyl carbonate, succinic acid esters, such as mono and diethyl succinic acid.

An external donor that can be used in forming the catalyst according to the present invention.
rs) is an organosilane compound such as the general formula SiR _m
(OR ′) _4-m [wherein R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R ′ is an alkyl group, and m is 0-3, Here, R may be the same as R ′, and m is 0,
R'groups may be the same or different when 1 or 2, and R groups may be the same or different when m is 2 or 3.] and the like.

The external donor of the present invention preferably has the following formula:

[0079]

[Chemical 1]

[Wherein R 1 and R 4 are both alkyl or cycloalkyl groups containing silicon-bonded primary, secondary or tertiary carbon atoms, where R 1
And R4 may be the same or different, and R2 and R3 are alkyl or aryl groups]. R1 may be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl, R2 and R3 may be methyl, ethyl, propyl or butyl groups and are not necessarily identical and R4 is also It may 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 catalysts described above has at least 5.0, preferably at least 6.0,
More preferably it will exhibit a MWD of at least 6.5, even more preferably at least 7.0.

[0082]

While the invention has been generally described, the following examples are provided solely for the purpose of illustrating certain embodiments of the invention and demonstrating practice and advantages of the invention. It is understood that the examples are provided by way of illustration and are not intended to limit the scope of the specification or the claims in any way. Catalyst Preparation In this example, a controlled form polyethylene catalyst (cont)
rolled-morphology polyeth
and the use of this catalyst to fine tune the intrinsic molecular weight distribution (MWD) of the polymer obtained using this catalyst.
g) can be done. By controlling the MWD in this way, it is possible to obtain polymers of various qualities using a single catalyst system, that is, from injection molding polymer (narrow MWD) to blown film polymer (wide MWD).
Polymers of various qualities used in a range of applications can be obtained.

The catalyst preparation was carried out as follows:Process 1 BuEtMg / DIAE TEAl (1: 0.6: 0.
03) + 2-ethylhexanol (2.09)
A soluble intermediate A is produced.Process 2 Intermediate A + 1.0 ClTi (OPr)₃Soluble by
Intermediate B is formed. Process 3 Intermediate B + Ti (OBu)_Four/ TiCl_Four(2.0: 1.
0) produces a solid precatalyst.Process 4 Pre-catalyst + TiCl_Four(Which is 0.25 or 1.00
Or) TEAL to produce the final catalyst.polymerization The reactor used for the polymerization of ethylene (Engineer
The (tclave) has a capacity of 4 liters,
Propeller for mixing two opposing pitches (pitchmixin
baffle for mixing with g propellers)
4 are attached. Tele and ethylene and hydrogen
dyne-Hastings Raydist mass flow rate
Introduced into the reaction tank via the control device, during which dome filling
Back pressure regulator (dome loaded back-p
Internal reaction pressure with pressure regulator
Hold the force constant. Barber-ColemanC
Kammer Valv connected to the ontroller
e to control the temperature of the reaction with steam and cold water (reactor tank
Ket). Hexane was used as a diluent. Experimental variables: Temperature 80 ℃ Reaction time 60 minutes Pressure 125 psi 0.2 cc of catalyst slurry (10 mg of catalyst) Cocatalyst TEAl 0.25 mmol / L Flow rate H₂/ C₂To 0.25 Obtained using this catalyst under standard bench reactor conditions
Experimental data for MWD of the polymers are shown in Table 1.
As can be seen from this data, the MWD of the polymer
Is the shear response (SR5), polydispersity index (M_w/ M_n) Oh
And crossover modulus (crossover)
modulus) (G_c) It is quite narrow as measured by value.

As the data in Table 1 show, the amount of TiCl ₄ in the second titanation (step 4 above) was quadrupled (1.0 equivalent to 0.25 equivalent) to modify the catalytic synthesis. This results in a significantly wider intrinsic MWD.
This means that polymers produced under standard polymerization conditions with such modified catalysts exhibit higher shear response, higher polydispersity (M _w / M _n ), and cross. It is indicated by a lower overmodulus (Gc).

[0085]

[Table 1]

It can be seen that the above modification does not lose any of the superior fluff / catalyst morphology of the standard catalyst. As shown in Figure 1, the catalyst / fluff particle size distribution is very narrow. Additionally, the amount of particles (fines) smaller than 125 microns contained in the polymer particles produced by using the modified catalyst is small. Finally, the activity of both catalysts when analyzed by magnesium analysis is very similar (22,000 g PE / g catalyst).

While the illustrative embodiments of the invention have been described in detail, various other modifications that will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Will be understood. Therefore, it is not intended to limit the scope of the claims appended hereto to the examples and descriptions set forth herein,
Rather, the claims are to be construed as embracing all novel features which may be attributed to a patent attributed to the invention, such features being deemed by those skilled in the art to which the invention pertains. It includes all of the features that would be treated as its equivalent.

The features and aspects of the present invention are as follows. 1. a) a soluble magnesium dialkoxide compound represented by the general formula Mg (OR ") ₂ [wherein R" is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] Contacting a halogenating agent that can be exchanged with one alkoxide to form reaction product A, b) contacting reaction product A with a first halogenating / titanating agent to form reaction product B And c) contacting reaction product B with a second halogenation / titanating agent to produce a catalyst component,
The second halogenating / titanating agent comprises titanium tetrachloride and step c) results in titanium tetrachloride and magnesium compound having a ratio of titanium tetrachloride to magnesium compound in the range of about 0.1 to about 5. A catalyst component prepared by a method comprising. 2. Alkyl magnesium whose soluble magnesium dialkoxide compound is represented by the general formula MgRR '[wherein R and R'may be the same or different and is an alkyl group having 1 to 10 carbon atoms]. The compound and the general formula R ″ OH [wherein R ”has 4 to 20 carbon atoms.
Which is an alkyl group of the above]. The catalyst component according to claim 1, which is a reaction product of a reaction comprising a linear or branched alcohol. 3. The catalyst component according to claim 2, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide). 4. The catalyst component according to claim 2, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium. 5. The alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2
-The catalyst component according to claim 2, which is ethylhexanol. 6. A catalyst component according to claim 2 wherein said reaction further comprises an alkylaluminum. 7. The catalyst component according to claim 6, wherein the alkylaluminum is triethylaluminum. 8. The first chlorinating / titanating agent is a blend of two tetra-substituted titanium compounds, wherein all four substituents are the same and these substituents are halides or have from 2 carbon atoms. 10. The catalyst component according to item 1, which is 10 alkoxides or phenoxides. 9. 9. The catalyst component according to claim 8, wherein the first chlorinating / titanating agent is a blend of titanium halide and organic titanate. 10. The first chlorinating / titanating agent is TiCl ₄
/ Ti (OBu) ₄ T in the range of 0.5: 1 to 6: 1
The catalyst component according to claim 9, which is a blend of iCl ₄ and Ti (OBu) ₄ . 11. The catalyst component of claim 1, wherein the reaction further comprises an electron donor. 12. The electron donor to magnesium ratio is about 0:
The catalyst component of claim 9, which ranges from 1 to about 10: 1. 13. The catalyst component according to claim 10, wherein the electron donor is an ether. 14. The halogenating agent is represented by the general formula ClAR ″ ′ _x [wherein A is a non-reducing, oxygen-philic compound and R ″ ′ is
_x is a hydrocarbyl moiety having about 2 to 6 carbon atoms, and x is the valence of A minus 1]. 15. a) i) a soluble magnesium dialkoxide compound represented by the general formula Mg (OR ″) ₂ [wherein R ″ is hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms]; Contacting the halogen with a halogenating agent capable of exchanging one alkoxide to form reaction product A, ii) contacting reaction product A with the first halogenating / titanating agent to form reaction product B And iii) contacting reaction product B with a second halogenation / titanation agent to form a catalyst component, said second halogenation / titanation agent being titanium tetrachloride. And step iii) comprises titanium tetrachloride and a magnesium compound such that the ratio of titanium tetrachloride to magnesium compound ranges from about 0.1 to about 5. A catalyst produced by a method comprising contacting a catalyst component produced by the method with an organoaluminum as a preactivating agent. 16. Alkyl magnesium whose soluble magnesium dialkoxide compound is represented by the general formula MgRR '[wherein R and R'may be the same or different and is an alkyl group having 1 to 10 carbon atoms]. The compound and the general formula R "OH [wherein R" has a carbon number of 4-2.
16. The catalyst according to claim 15, which is the reaction product of a reaction comprising a linear or branched alcohol represented by the formula: 0 alkyl group]. 17. 17. The catalyst according to item 16, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide). 18. 17. The catalyst according to claim 16, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium. 19. The alcohol is ethanol, propanol,
17. The catalyst according to claim 16, which is isopropanol, butanol, isobutanol or 2-ethylhexanol. 20. 17. The catalyst according to claim 16, wherein the reaction further comprises an alkylaluminum. 21. 21. The catalyst according to claim 20, wherein the alkylaluminum is triethylaluminum. 22. The first chlorinating / titanating agent is a blend of two tetra-substituted titanium compounds, wherein all four substituents are the same and these substituents are halides or have from 2 carbon atoms. Item 16. The catalyst according to Item 15, which is 10 alkoxides or phenoxides. 23. 23. The catalyst according to claim 22, wherein the first chlorination / titanation agent is a blend of titanium halide and organic titanate. 24. The first chlorinating / titanating agent is TiCl ₄
/ Ti (OBu) ₄ T in the range of 0.5: 1 to 6: 1
24. The catalyst according to paragraph 23, which is a blend of iCl ₄ and Ti (OBu) ₄ . 25. Sixteenth, wherein the reaction further comprises an electron donor.
The catalyst according to the item. 26. The electron donor to magnesium ratio is about 0:
The catalyst of claim 25, which is in the range of 1 to about 10: 1. 27. 27. The catalyst according to claim 26, wherein the electron donor is an ether. 28. The halogenating agent is represented by the general formula ClAR ″ ′ _x [wherein A is a non-reducing, oxygen-philic compound and R ″ ′ is
_x is a hydrocarbyl moiety of from about 2 to 6 carbon atoms, and x is paragraph 15, wherein the catalyst represented by the valence of A which is a value obtained by subtracting 1]. 29. The pre-activator organoaluminum has the formula AlR ^ ₃ , where R ^ is the same or different and is an alkyl or halide having 1-8 carbon atoms and at least one R ^ is alkyl. [15] The catalyst according to [15], which is an alkylaluminum represented by: 30. 30. The catalyst according to claim 29, wherein the organoaluminum that is the preactivating agent is a trialkylaluminum. 31. The catalyst of claim 15 wherein the ratio of aluminum to titanium is in the range 0.1: 1 to 2: 1. 32. The catalyst has a fluff morphology suitable for the polymerisation process and gives polyethylene with a molecular weight distribution of at least about 5.0, and at least 6,000 g of P per g of catalyst.
Fifteenth, which exhibits E activity and a uniform particle size distribution in addition to a low amount of particles less than about 125 microns
The catalyst according to the item. 33. a) i) a soluble magnesium dialkoxide compound represented by the general formula Mg (OR ″) ₂ [wherein R ″ is hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms]; Contacting the halogen with a halogenating agent capable of exchanging one alkoxide to form reaction product A, ii) contacting reaction product A with the first halogenating / titanating agent to form reaction product B And iii) contacting reaction product B with a second halogenation / titanation agent to form a catalyst component, said second halogenation / titanation agent being titanium tetrachloride. And step iii) comprises titanium tetrachloride and a magnesium compound such that the ratio of titanium tetrachloride to magnesium compound ranges from about 0.1 to about 5. In the presence of a catalyst that generated by law contacting one or more α- olefin monomers together under polymerization conditions it was prepared by the method comprising the polymer. 34. 34. The polymer of claim 33, wherein the catalyst is iv) a catalyst prepared by a method further comprising contacting the catalyst component with an agent, an organoaluminum. 35. 34. The polymer according to item 33, wherein the monomer is an ethylene monomer. 36. 34. The polymer according to claim 33, wherein the polymer is polyethylene. 37. Alkyl magnesium whose soluble magnesium dialkoxide compound is represented by the general formula MgRR '[wherein R and R'may be the same or different and is an alkyl group having 1 to 10 carbon atoms]. The compound and the general formula R "OH [wherein R" has a carbon number of 4-2.
34. The polymer according to claim 33, which is a reaction product of a reaction comprising a linear or branched alcohol represented by the formula: 0 is an alkyl group]. 38. 38. The polymer according to item 37, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide). 39. 38. The polymer according to claim 37, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium. 40. The alcohol is ethanol, propanol,
38. The polymer according to item 37, which is isopropanol, butanol, isobutanol or 2-ethylhexanol. 41. 38. The polymer according to claim 37, wherein the reaction further comprises an alkylaluminum. 42. 42. The polymer according to item 41, wherein the alkylaluminum is triethylaluminum. 43. The first chlorinating / titanating agent is a blend of two tetra-substituted titanium compounds, wherein all four substituents are the same and these substituents are halides or have from 2 carbon atoms. 38. The polymer according to item 37, which is alkoxide or phenoxide of 10. 44. The polymer of claim 43, wherein the first chlorinating / titanating agent is a blend of a titanium halide and an organic titanate. 45. The first chlorinating / titanating agent is TiCl ₄
/ Ti (OBu) ₄ T in the range of 0.5: 1 to 6: 1
The polymer according to item 44, which is a blend of iCl ₄ and Ti (OBu) ₄ . 46. The thirty-seventh aspect wherein the reaction further comprises an electron donor.
The polymer according to the item. 47. The electron donor to magnesium ratio is about 0:
47. The polymer according to clause 46, which is in the range of 1 to about 10: 1. 48. 48. The polymer according to item 47, wherein the electron donor is an ether. 49. The halogenating agent is represented by the general formula ClAR ″ ′ _x [wherein A is a non-reducing, oxygen-philic compound and R ″ ′ is
_x is a hydrocarbyl moiety of from about 2 to 6 carbon atoms, and x is a polymer of paragraph 37, wherein represented by a value obtained by subtracting 1 from the valence of A]. 50. The pre-activator organoaluminum has the formula AlR ^ ₃ , where R ^ is the same or different and is an alkyl or halide having 1-8 carbon atoms and at least one R ^ is alkyl. The polymer according to Item 37, which is an alkylaluminum represented by the formula: 51. 51. The polymer according to claim 50, wherein the organoaluminum that is the preactivating agent is a trialkylaluminum. 52. The polymer according to clause 51, wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1. 53. a) a soluble magnesium dialkoxide compound represented by the general formula Mg (OR ") ₂ [wherein R" is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] Contacting a halogenating agent that can be exchanged with one alkoxide to form reaction product A, b) contacting reaction product A with a first halogenating / titanating agent to form reaction product B And c) contacting reaction product B with a second halogenation / titanating agent to produce a catalyst component,
The second halogenating / titanating agent comprises titanium tetrachloride and step c) results in titanium tetrachloride and magnesium compound having a ratio of titanium tetrachloride to magnesium compound in the range of about 0.1 to about 5. A method of making a catalyst component comprising. 54. Alkyl magnesium whose soluble magnesium dialkoxide compound is represented by the general formula MgRR '[wherein R and R'may be the same or different and is an alkyl group having 1 to 10 carbon atoms]. The compound and the general formula R "OH [wherein R" has a carbon number of 4-2.
54. The method according to claim 53, which is the reaction product of a reaction comprising a linear or branched alcohol represented by the formula: 55. 55. The method of claim 54, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide). 56. 55. The method of claim 54, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium. 57. The alcohol is ethanol, propanol,
55. The method according to item 54, which is isopropanol, butanol, isobutanol or 2-ethylhexanol. 58. 55. The method of claim 54, wherein the reaction further comprises an aluminum alkyl. 59. 55. The method of claim 54, wherein the alkyl aluminum is triethyl aluminum. 60. The first chlorinating / titanating agent is a blend of two tetra-substituted titanium compounds, wherein all four substituents are the same and these substituents are halides or have from 2 carbon atoms. 54. The method according to claim 53, which is 10 alkoxides or phenoxides. 61. 61. The method of claim 60, wherein the first chlorinating / titanating agent is a blend of titanium halide and organic titanate. 62. The first chlorinating / titanating agent is 0.5: 1
The method of claim 61 which is a blend of TiCl ₄ and Ti (OBu) _{4 in} the range from 1 to 6: 1. 63. a) i) a soluble magnesium dialkoxide compound represented by the general formula Mg (OR ″) ₂ [wherein R ″ is hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms]; Contacting the halogen with a halogenating agent capable of exchanging one alkoxide to form reaction product A, ii) contacting reaction product A with the first halogenating / titanating agent to form reaction product B And iii) contacting reaction product B with a second halogenation / titanation agent, said second halogenation / titanation agent comprising titanium tetrachloride and the steps of: iii) titanium tetrachloride and magnesium compound, wherein the ratio of titanium tetrachloride to magnesium compound is about 0.
A process for the preparation of a catalyst comprising contacting a catalyst component produced by a process comprising in the range of 1 to about 5 with a preactivating agent organoaluminum. 64. The first chlorinating / titanating agent is a blend of two tetra-substituted titanium compounds, wherein all four substituents are the same and these substituents are halides or have from 2 carbon atoms. 64. The method according to paragraph 63, which is alkoxide or phenoxide of 10. 65. 65. The method of claim 64, wherein the first chlorinating / titanating agent is a blend of titanium halide and an organic titanate. 66. The first chlorinating / titanating agent is TiCl ₄
/ Ti (OBu) ₄ T in the range of 0.5: 1 to 6: 1
The method of claim 65 which is a blend of iCl ₄ and Ti (OBu) ₄ . 67. Alkyl magnesium whose soluble magnesium dialkoxide compound is represented by the general formula MgRR '[wherein R and R'may be the same or different and is an alkyl group having 1 to 10 carbon atoms]. The compound and the general formula R "OH [wherein R" has a carbon number of 4-2.
65. The method according to claim 64, which is the reaction product of a reaction comprising a linear or branched alcohol represented by the formula: 68. 68. The method of claim 67, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide). 69. 68. The method of claim 67, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethyl magnesium. 70. The alcohol is ethanol, propanol,
68. The method according to claim 67, which is isopropanol, butanol, isobutanol or 2-ethylhexanol. 71. 68. The method of claim 67, wherein the reaction further comprises an aluminum alkyl. 72. 72. The method of claim 71, wherein the alkylaluminum is triethylaluminum. 73. 73. The method of claim 72, wherein the reaction further comprises an electron donor. 74. The ratio of the electron donor and magnesium is about 0:
74. The method according to clause 73, which ranges from 1 to about 10: 1. 75. 75. The method according to clause 74, wherein the electron donor is an ether. 76. The halogenating agent has the general formula ClAR ″ ′ _x , where A is a non-reducing, oxygen-philic compound, and R ″ ″ _x is a hydrocarbyl moiety having about 2 to 6 carbon atoms. ] The method of Claim 63 represented by these. 77. The halogenating agent is TiCl / Ti (O ⁱ P
The method of claim 76 which is a blend of r) ₃ . 78. 64. The method of claim 63, wherein the pre-activator organoaluminum is an alkylaluminum. 79. The electron donor is added in step a) i), ii) or i.
ii) present in any one of the steps and wherein the electron donor to metal ratio is in the range of about 0: 1 to about 10: 1.
The method according to item 3. 80. a) i) a soluble magnesium dialkoxide compound represented by the general formula Mg (OR ″) ₂ [wherein R ″ is hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms]; Contacting the halogen with a halogenating agent capable of exchanging one alkoxide to form reaction product A, ii) contacting reaction product A with the first halogenating / titanating agent to form reaction product B And iii) contacting reaction product B with a second halogenation / titanation agent to form catalyst product C, wherein said second halogenation / titanation agent is Comprising titanium chloride and step iii) comprising titanium tetrachloride and magnesium compound such that the ratio of titanium tetrachloride to magnesium compound ranges from about 0.1 to about 5. A method of polymerizing an α-olefin, comprising contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst produced by the method. 81. The method of claim 80, further comprising b) extracting the polyolefin polymer. 82. 82. The method according to clause 81, wherein the polymer exhibits a molecular weight distribution of at least 5.0. 83. 83. The method according to clause 82, wherein the polymer is polyethylene. 84. 81. The method of claim 80, wherein said catalyst is a catalyst formed by the method further comprising iv) contacting reaction product C with an agent, organoaluminum. 85. The first chlorinating / titanating agent is a blend of two tetra-substituted titanium compounds, wherein all four substituents are the same and these substituents are halides or have from 2 carbon atoms. 81. The method according to item 80, which is alkoxide or phenoxide of 10. 86. 85. The method of claim 84, wherein the first chlorinating / titanating agent is a blend of titanium halide and an organic titanate. 87. The first chlorinating / titanating agent is TiCl ₄
/ Ti (OBu) ₄ T in the range of 0.5: 1 to 6: 1
87. The method of claim 86, which is a blend of iCl ₄ and Ti (OBu) ₄ . 88. The halogenating agent in step i) is of the general formula ClA
Item 80. R "' _x , wherein A is a non-reducing, oxygen-philic compound and R"' _x is a hydrocarbyl moiety having about 2 to 6 carbon atoms. The method described. 89. 89. The method according to claim 88, wherein the halogenating agent is ClTi (O ⁱ Pr) ₃ . 90. 85. The method according to claim 84, wherein the agent, organoaluminum, is triethylaluminum. 91. The electron donor is present in any one of steps i) -iv) and the electron donor to metal ratio is about 0: 1.
85. The method of paragraph 84, which ranges from about 10: 1.

[Brief description of drawings]

FIG. 1 is a graph showing catalyst / fluff particle size distribution.

Continued front page    (72) Inventor Tame Jei Kofu             United States Texas 77062             Ton Grand Najette Court 14803 F-term (reference) 4J028 AA02A AB02A AC05A AC06A                       AC07A BA00A BA01A BB00A                       BB01A BC15B BC18B CB36A                       EB02 EB04 EB05 EB08 EB10                       GA06

Claims (6)

[Claims] 1. a) General formula Mg (OR ") ₂ [wherein R"
Is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl] and is reacted with a halogenating agent capable of exchanging one halogen for one alkoxide with a soluble magnesium dialkoxide compound represented by Produce product A, b) contact reaction product A with a first halogenation / titanating agent to produce reaction product B, and c) react reaction product B with a second halogenation / titanium agent. Contacting an agent to produce a catalyst component,
The second halogenating / titanating agent comprises titanium tetrachloride and step c) results in titanium tetrachloride and magnesium compound having a ratio of titanium tetrachloride to magnesium compound in the range of about 0.1 to about 5. A catalyst component produced by a method comprising. 2. a) i) the general formula Mg (OR ") ₂ [wherein
R "is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] and the soluble magnesium dialkoxide compound is contacted with a halogenating agent capable of exchanging one halogen for one alkoxide. To form reaction product A, ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and iii) reaction product B with a second halogenation. / Contacting a titanating agent to produce a catalyst component, wherein the second halogenating / titanating agent comprises titanium tetrachloride and step iii) comprises titanium tetrachloride and a magnesium compound. The catalyst component produced by the process comprising a pre-activator, wherein the ratio of titanium tetrachloride to magnesium compound is in the range of about 0.1 to about 5. A catalyst prepared by a method comprising contacting with an organoaluminum. 3. a) i) the general formula Mg (OR ") ₂ [wherein
R "is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] and the soluble magnesium dialkoxide compound is contacted with a halogenating agent capable of exchanging one halogen for one alkoxide. To form reaction product A, ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and iii) reaction product B with a second halogenation. / Contacting a titanating agent to produce a catalyst component, said second halogenating / titanating agent comprising titanium tetrachloride and step iii) comprising titanium tetrachloride and a magnesium compound. One or more in the presence of a catalyst formed by a method comprising a titanium tetrachloride to magnesium compound ratio in the range of about 0.1 to about 5. α
A polymer prepared by a method comprising contacting olefin monomers together under polymerization conditions. 4. A) General formula Mg (OR ") ₂ [wherein R"
Is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl] and is reacted with a halogenating agent capable of exchanging one halogen for one alkoxide with a soluble magnesium dialkoxide compound represented by Produce product A, b) contact reaction product A with a first halogenation / titanating agent to produce reaction product B, and c) react reaction product B with a second halogenation / titanium agent. Contacting an agent to produce a catalyst component,
The second halogenating / titanating agent comprises titanium tetrachloride and step c) results in titanium tetrachloride and magnesium compound having a ratio of titanium tetrachloride to magnesium compound in the range of about 0.1 to about 5. A method of making a catalyst component comprising. 5. a) i) general formula Mg (OR ") ₂ [wherein
R "is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] and the soluble magnesium dialkoxide compound is contacted with a halogenating agent capable of exchanging one halogen for one alkoxide. To form reaction product A, ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and iii) reaction product B with a second halogenation. / Contacting with a titanating agent, wherein the second halogenation / titanating agent comprises titanium tetrachloride and step iii) comprises titanium tetrachloride and magnesium compound to magnesium compound to titanium tetrachloride. Ratio of about 0.
A process for the preparation of a catalyst comprising contacting a catalyst component produced by a process comprising in the range of 1 to about 5 with a preactivating agent organoaluminum. 6. a) i) the general formula Mg (OR ") ₂ [wherein
R "is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] and the soluble magnesium dialkoxide compound is contacted with a halogenating agent capable of exchanging one halogen for one alkoxide. To form reaction product A, ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B, and iii) reaction product B with a second halogenation. / Contacting a titanating agent to produce catalyst product C, said second halogenating / titanating agent comprising titanium tetrachloride and step iii) comprising titanium tetrachloride and magnesium One or more compounds in the presence of a catalyst formed by a process comprising a compound such that the ratio of titanium tetrachloride to magnesium compound ranges from about 0.1 to about 5. A method of polymerizing an α-olefin, comprising contacting the above α-olefin monomer together under polymerization conditions.