KR100851032B1 - Improved hydrogen response ziegler-natta catalyst for narrowing mwd of polyolefin, method of making, method of using, and polyolefins made therewith - Google Patents

Abstract

Ziegler-Natta catalysts with improved hydrogen reactions provide polyolefins with narrow MWDs produced by polymerization using such catalysts, which generally a) form R 'to form reaction product A. A soluble magnesium dialkoxide compound of the general formula Mg (OR '') ₂ , wherein is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms, with a halogenating agent capable of exchanging one halogen with an alkoxide Contacting; b) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And c) contacting reaction product B with a second halogenated / titanate agent to form a catalyst component, wherein in at least one of steps b) and c) the first halogenated / titanate agent is Ti (OPr) ₄ And a blend of TiCl ₄ . Catalyst components, catalysts, catalyst systems, polyolefin polymers and methods of making each are described.

Description

IMPROVED HYDROGEN RESPONSE ZIEGLER-NATTA CATALYST FOR NARROWING MWD OF POLYOLEFIN, METHOD OF MAKING, METHOD OF USING, AND POLYOLEFINS MADE THEREWITH}

FIELD OF THE INVENTION

The present invention relates to a catalyst, a method for preparing the catalyst, a method for using the catalyst, a polymerizing method, and a polymer prepared from the catalyst. In another aspect, the present invention relates to a polyolefin catalyst, to a process for producing such polyolefin, to a method of using such polyolefin, to polymerization of polyolefins and to polyolefins. In another aspect, the present invention relates to a Ziegler-Natta catalyst, a process for preparing such a catalyst, a method of using such a catalyst, polyolefin polymerization and a polyolefin.

Description of the Prior Art

As known since the early 1950s, Ziegler-type polyolefin catalysts, their general methods of preparation and subsequent uses are well known in the polymerization art.

However, while much is known about Ziegler-type catalysts, there is a continuing study on the improvement of these polymer yields, catalyst cycles, catalytic activity and the ability to produce polyolefins having certain characteristics.

U.S. Patent No. 4,255,544 to Kimura et al., Filed on Oct. 1981, discloses a step for the polymerization of ethylene using a catalyst comprising (A) a reaction product of a magnesium compound and a titanium halide, and (B) an organoaluminum compound. For component A, reacting the magnesium dialkoxide with a halogen-containing silicon compound and an alcohol to provide a solid material, and then reacting the solid material with a titanium halide in the presence of an alkoxy-containing silicon compound. It is open to the public.

U.S. Pat. No. 4,914,069 to Joob et al., Filed on Apr. 1990, (a) Magnesium compounds comprising at least one aryloxy, aryl or carbonate, or akloxy group. Halogenating a tetravalent titanium with a first halide and a first electron donor; (b) contacting the resulting product with a second halide of tetravalent titanium; And (c) washing the resulting treated halogenated product with an inert hydrocarbon liquid, thereby producing an olefin polymerization catalyst component having improved activity and selectivity. In the preparation step, the second electron donor is used in step (a) or (b), and the product of step (b) is contacted in step (b2) with a third halide of tetravalent titanium at a temperature of 40-140 ° C., The post treated product is washed in step (e).

Shelly, US Patent No. 5,155,187, filed on October 13, 1992, discloses a catalyst which is a common reaction product of silicon-containing compounds, magnesiumdialkyl, alcohols, halide-containing metal compounds, aluminum alkoxides and second halide-containing metal compounds. The polymerization method to be used is disclosed.

US Pat. No. 5,610,246 to Buehler et al., Filed on March 31, 1997, discloses a propylene polymerization step using a silica-supported catalyst. The catalyst is randomly selected from (1) at least one hydrocarbon soluble magnesium-containing compound; And (2) a first modified compound of a compound selected from? U>? / U> consisting of silicon halides, broron halides, aluminum halides, and mixtures thereof, followed by a second embodiment of the modified compound and practice Product obtained by contacting.

Zandona, US Patent No. 5,631,334, filed May 20, 1997, describes the steps for preparing a catalyst solid for the (co) polymerization of at least one olefin, including magnesium coprecipitation and at least one transition metal. It is open to the public.

However, despite these advances in the prior art, these prior art documents disclose polyolefins having a narrower molecular weight distribution ("MWD") of R in the mixture of TiCl ₄ / Ti (O ⁱ R) ₄ . It does not disclose or suggest that it will provide a catalyst with an enhanced hydrogen reaction that can provide.

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

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

There is another need in the art for a process for the polymerization of olfepine.                         

There is another need in the art for the narrower MWD polyolefins as well.

There is also another need in the art for catalysts with improved hydrogen reactions.

There is another need in the art for a method of preparing a polyolefin catalyst that provides a polymer with a narrow molecular weight distribution that includes the use of a TiCl ₄ / Ti (O ⁱ R) ₄ mixture.

There is another need in the art for a method of making narrower MWD polyolefins.

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

One object of the present invention is to provide a polyolefin catalyst.

Another object of the present invention is to provide a method for producing a polyolefin catalyst.

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

Yet another object of the present invention is to provide a narrower MWD polyolefin.

Still another object of the present invention is to provide a catalyst with improved hydrogen reaction.

It is a further object of the present invention to provide a process for the preparation of a polyolefin catalyst which provides a polymer having a narrow molecular weight distribution which comprises the use of a TiCl ₄ / Ti (O ⁱ R) ₄ mixture.

It is a further object of the present invention to provide a process for the preparation of narrower MWD polyolefins.

One embodiment of the present invention provides a) soluble magnesium di with a general formula Mg (OR '') ₂ where R '' is hydrocarboxyl or substituted hydrocarboxyl having 1 to 20 carbon atoms to form reaction product A. Contacting the alkoxide compound with a halogenating agent capable of exchanging one halogen with one alkoxide; 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 halogenated / titanated agent to form a catalyst component. Preferably, the first halogenated / titanated agent is a blend of Ti (OPr) ₄ / TiCl ₄ . Soluble dialkoxide compounds are alkyl magnesium compounds having the general formula MgRR 'wherein R and R' are alkyl groups of 1-10 carbon atoms, and R and R 'may be the same or different, and the alcohols are straight or branched chains, and R' Is a reaction product of a reaction involving an alcohol having the general formula R''OH, which is an alkyl group of 4-20 carbon atoms.

Yet another embodiment of the present invention provides a catalyst. Generally, the catalyst is prepared by a process comprising contacting the catalyst component of the present invention with an organoaluminum preactivator. The catalyst component is i) a magnesium dialkoxide compound having the general formula Mg (OR '') ₂ , wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1-20 carbon atoms to form reaction product A. Contacting a halogen of with a halogenating agent that can be exchanged with one alkoxide; ii) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And contacting Reaction Product B with a second halogenated / titanate agent. Preferably, the first halogenated / titanate agent is a blend of Ti (OPr) ₄ / TiCl ₄ . The catalyst of the present invention has an improved hydrogen reaction and is useful for producing polymers of desired molecular weight distribution.

Another embodiment of the present invention provides a polymer prepared by a process comprising a) contacting at least one α-olefin monomer together in the presence of a catalyst of the present invention under polymerization conditions. Preferably, the catalyst is used to polymerize polyethylene monomers to produce polyethylene polymers. The catalyst comprises i) a soluble magnesium dialkoxide compound having the general formula Mg (OR) ₂ , wherein R is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms to form reaction product A, one halogen Contacting with a halogenating agent exchangeable with an alkoxide of; ii) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And iii) contacting reaction product B with a second halogenated / titanate agent to form a catalyst product. Preferably, the halogenated / titanate 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 the organoaluminum agent.

Yet another embodiment of the present invention provides a catalyst system comprising the catalyst of the present invention and an inert support.

Yet another embodiment of the present invention provides a process for forming a catalyst component. Generally, the process comprises: a) a flexible magnesium dialkoxide compound having the general formula Mg (OR '') ₂ , wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1-20 carbon atoms to form reaction product A. Contacting one halogen with a halogenating agent that can be exchanged with one alkoxide. The process also includes: b) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And c) contacting reaction product B with a second halogenated / titanate agent to form a catalyst component or reaction product C. Preferably, the halogenated / titanate agent in at least one of steps b) and c) is Ti (OPr) ₄ / TiCl ₄ .

Another embodiment of the present invention provides a process for forming a catalyst comprising contacting the catalyst component of the present invention with an organoaluminum preactivator.

Another embodiment of the present invention provides a process for α-olefin polymerization. In general, the polymerization process comprises: a) contacting at least one α-olefin together in the presence of the catalyst of the present invention under polymerization conditions; And b) extracting the polyolefin polymer. The polymerization process is useful for preparing polymers, preferably polyethylene polymers, having a molecular weight distribution of about 7.0 or less.

These and other objects of the present invention will become apparent to those of ordinary skill in the art upon reviewing the detailed description of the invention, including the drawings and claims.

The process of the invention for preparing the catalyst component generally comprises forming a metal dialkoxide from a metal dialkyl and an alcohol, halogenating the metal dialkoxide, and at least one using a mixture of TiCl ₄ / Ti (OiPr) ₄ . Activating the catalyst in one or more steps to form a catalyst, and treating the catalyst with a preactivating agent such as organoaluminum to form a preactivated catalyst.

The mechanism proposed for the process of the invention is generally as follows:

1.MRR '+ 2R''OH-> M (OR'')₂;

2.M (OR '') ₂ + ClAR ''' _x- >"A";

3. "A" + TiCl ₄ / Ti (OPr) _4- >"B";

4. "B" + TiCl _4- >"C"; And

5. "C" + TEAl-> catalyst.                     

Wherein M can be any suitable metal, preferably a group IIA metal, most preferably Mg. Wherein R, R ', R' 'and R' '' are 1-20, preferably 1-10, more preferably 2-6 carbon atoms and most preferably 2-4 R and R Each having a hydrocarbyl or substituted hydrocarbyl moieties. Generally R '' comprises 3-20 carbon atoms, R '' 'contains 2-6 carbon atoms, and R' '' 'has 2-6 carbon atoms. The combination of two or more R, R ', R' ', and R' '' may be the same, or the R groups may be different from each other.

In the formula ClAR ''' _x , A is a non-reducing oxyphilic compound capable of exchanging one halogen with one alkoxide, R''' is hydrocarbyl or substituted hydrocarbyl, x Is A-1 valence. Examples of A include titanium, silicon, aluminum, carbon, tin and germanium, most preferred are titanium and silicon where x is three. Examples of R '''include those having methyl, ethyl, propyl, isopropyl and 2-6 carbon atoms. R '''is generally a profile.

Although the exact composition of the product "A" is not known, it is believed that it comprises a partially chlorinated metal compound, and one example may be ClMg (OR ''). The first halogenated / titanated product produces a product “B” which is a complex of chlorinated and partially chlorinated metals and titanium compounds, for example, (MCl ₂ ) _{y '} . (TiCl _x (OPr) _4-x ) _{z '} Second chlorination / titanateization results in a complex chain product “C” of chlorinated and partially chlorinated metals and titanium compounds, different from product “B”, (MCl ₂ ) _{y '} . (TiCl _x (OR ) _{4-x '} ) _z' . The degree of chlorination of product "C" is greater than the level of product "B". Larger levels of this chlorination produce different complexes of different compounds. While this description of the reaction product provides the most appropriate description of chemistry, the invention described in the claims is not limited by this theoretical mechanism.

Metal dialkyls and resulting metal dialkoxides suitable for use in the present invention include those which will produce suitable polyolefin catalysts when used in the present invention. More preferred metal dialkoxide or dialkyl is magnesium dialkoxide or dialkyl.

In an embodiment of the invention, magnesium dialkyl (MgRR ') can be any magnesium dialkyl as R and R' are as described above. R and R 'may be the same or different. Non-limiting examples of suitable magnesium dialkyl include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butylethyl magnesium and the like. Butylethylmagnesium (BEM) is the preferred magnesium dialkyl.

In an embodiment of the invention, the metal dialkoxide is preferably a magnesium compound of the general formula Mg (OR '') ₂ , wherein R '' is a hydrocarbyl or substituted hydrocarbyl of 1 to 20 carbon atoms.

Metal dialkoxides are most preferred soluble and most preferred non-reducing. Non-reducing compounds have the advantage of forming MgCl ₂ in place of the insoluble Ti ^{+ 3} species formed by reduction of compounds such as MgRR ′ which tend to form catalysts having a wide particle size distribution. In addition, Mg (OR '') ₂ is less reactive than MgRR 'and is chlorinated with chlorinated agents, followed by chlorinated / titanated with mild reagents and second chlorinated / titanated with stronger reagents. Are progressive, successful and stronger reactions that can produce a more uniform product, ie better catalytic particle size and distribution.

Non-limiting examples of preferred species of useful metal dialkoxides include magnesium butoxide, magnesium pentoxide, magnesium hexoxide, magnesium hexide, magnesium di (2-ethylhexoxide), and system solubility. Any suitable alkoxide is included. Most preferred metal alkoxide species is magnesium di (2-ethylhexoxide).

As a non-limiting example, magnesium dialkoxides such as magnesium di (2-ethylhexoxide) may be substituted with alkyl magnesium compounds (MgRR ') such as butyl ethyl magnesium (BEM) and alcohols (ROH) such as 2-ethylhexanol. Can be prepared by reaction.

MgRR '+ 2R''OH-> Mg (OR'') ₂ + RH + R'H

In the case of BEM, RH and R'H are butane and ethane, respectively. The reaction takes place at room temperature and the reactants form a solution.

In the practice of the present invention, any alcohol that produces the desired metal dialkoxide may be used. As a non-limiting example, the alcohol can be any alcohol of the general formula R''OH, wherein R '' is an alkyl group of 4 to 20 carbon atoms. Although it is believed that most alcohols can be used, higher order branched alcohols are preferred. The alcohol can be linear or branched. Non-limiting examples of alcohols include butanol, isobutanol, 2-ethyl-1-hexanol and the like. Preferred alcohols are 2-ethylhexanol. In general, the alcohol used will have at least 3, preferably at least 4, more preferably at least 5, most preferably at least 6 carbon atoms.

The amount of alcohol added to the slurry is generally in the range of 0.5-4 equivalents (equivalent is relative throughout the magnesium or metal compound), preferably in the range of about 1-3 equivalents.

Alkyl metal compounds have high association due to electron-deficient binding which results in viscous high molecular weight species in solution. This high viscosity can be reduced by the addition of aluminum alkyl, such as triethylaluminum, which breaks the association between each alkyl metal molecule. The preferred ratio of alkyl aluminum to metal is from 0.001: 1 to 1: 1, preferably from 0.01: 1 to 0.1: 1 and most preferably from 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 metals. Preferred ratios of the electron donor to the metal range from about 0: 1 to 10: 1 and more preferably from about 0.1: 1 to 1: 1.

Agents useful in the halogenation step for halogenating metal alkoxides include any halogenating agent that produces a suitable polyolefin catalyst for use in the present invention. Preferably the halogenation step is a chlorination step and the preferred halogenation agent is chloride.                     

Preferably, the chloride halogenating agent (“chlorinating agent”) is a monochloride compound that only partially chlorides magnesium alkoxide. Preferred chlorinating agents are those of the general formula ClAR ''' _x or ClAOR''' wherein A is an alkoxide non-reducing oxyphylic compound capable of exchanging one chloride with an alkoxide, R '''is alkyl and x is A-1. has _x Examples of A are titanium, silicon, aluminum, carbon, tin and germanium, most preferred are tin and silicon where x is 3. Examples of R '''are those having methyl, ethyl, propyl, isopropyl and 2-6 carbon atoms. Examples of effective chlorinating agents of the present invention are ClTi (O ⁱ Pr) ₃ and ClSi (Me) ₃ .

In general, halogenation of the metal alkoxide compound is carried out in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane and the like. Preferred solvent is hexane.

Generally, the halogenation step is carried out at a temperature of about 0-100 ° C., for a reaction time of 0.5-24 hours. Preferably, the halogenation step is carried out for a reaction time of about 1 to 4 hours at a temperature of about 20 ~ 90 ℃.

Once the halogenation step is performed and the metal alkoxide is halogenated, the soluble product "A" undergoes at least one halogenation / titanate treatment in which at least one must use a mixture of TiCl ₄ / Ti (O ⁱ Pr) ₃ . Preferably, the halogenation / titanate step uses a mixture of TiCl ₄ / Ti (O ⁱ Pr) ₃ .

In general, the halogenated / titanate agent is a tetrasubstituted with all four identical substituents and substituents with halides or alkoxides or phenoxides with 2 to 10 carbon atoms such as TiCl ₄ or Ti (OR '''') _x. Titanium compound. Preferably, the halogenated / titanate agent is a chlorinated / titanate agent.

Preferred halogenated / titanate agents can be a single compound or a combination of compounds. The process of the present invention provides an active catalyst after the first chlorination / titanate step; Preferably, however, the chlorination / titanate is carried out twice using different compounds or combinations of compounds in each addition, each using a stronger chlorination / titanate agent with successive chlorination / titanate treatments. .

Preferably, the first chlorinated / titanate agent is a mild titanate agent such as, for example, a blend of titanium halides and organic titanates. Blends of titanium halides and organic titanates are OR and X, respectively, alkoxides and halides, a + b is the equivalent of titanium generally 4 and a and b are fractional, titanium alkoxy halides having a = 2.5 and b = 1.5 Is considered to react to form Ti (OR) _a X _b .

More preferably, the first chlorinated / titanate agent is a blend of TiCl ₄ and Ti (OiPr) ₃ or a blend of TiCl ₄ and Ti (OiPr) ₄ . At least one chlorinated / titanate step should use a blend of TiCl ₄ and Ti (OiPr) ₄ , with the first chlorinated / titanate agent preferably being a blend of TiCl ₄ and Ti (OiPr) ₄ .

In the case of TiCl ₄ / Ti (OBu) ₄ or TiCl ₄ / Ti (OiPr) ₄ , the ratio of TiCl ₄ to Ti (OBu) ₄ or Ti (OiPr) ₄ (whichever is used) is 0.5: 1 to 6 : 1, more preferably 1: 1 to 4: 1, most preferably 2: 1 to 3: 1 (OC ₁₂ H ₅ ) Cl ₃ ).

In general, the first halogenation / titanate step is carried out in a hydrocarbon solvent. Non-limiting examples of suitable hydrocarbon solvents include heptane, hexane, toluene, octane and the like. Product "A" is soluble in hydrocarbon solvents.

After adding the first halogenated / titanate agent to the soluble product "A", the solid product "B" precipitates at room temperature.

The amount of halogenated / titanate agent used should be sufficient to precipitate the solid product from the solution. In general, based on the ratio of titanium to metal, the amount of halogenated / titanate agent used is in the range of about 0.5 to 5, preferably about 1 to 4, most preferably about 1.5 to 2.5.

The solid product “B” precipitated in the first titanation step is recovered by any suitable recovery technique and washed with a hydrocarbon solvent.

Compounds suitable for use as the second halogenated / titanate agent preferably include those suitable for use as the first halogenated / titanate agent except when the second agent is a stronger agent. The second halogenated / titanate agent is more potent, preferably titanium halide, more preferably titanium tetrachloride [TiCl ₄ ].

Generally, the second halogenation / titanate step is performed by slurrying the solid product “B” in a hydrocarbon solvent to produce a reaction product, or catalyst component “C”. Hydrocarbon solvents listed as suitable for the first halogenation / titanate step may be used. Generally, the amount of titanium tetrachloride used is about 0.1-5 equivalents, preferably about 0.15-4 equivalents, most preferably about 0.175-2.5 equivalents.

Catalyst component "C" may be combined with an organoaluminum cocatalyst component (preactivator) to form a suitable preactivated catalyst for the polymerization of the olefins. Typically, cocatalysts used with transition metals containing catalyst component "C" are organometals of Groups Ia, IIa, and IIIa metals such as aluminum alkyl, aluminum alkyl hydride, lithium aluminum alkyl, zinc alkyl, magnesium alkyl, and the like. Compound.

The preactivator is preferably an organoaluminum compound, more preferably aluminum alkyl of the general formula AlR ^ ₃ , wherein R ^ is alkyl or halide having 1 to 8 carbon atoms. Preferred organoaluminum preactivators include, for example, trialkyl aluminums such as trimethyl aluminum (TMA), triethyl aluminum (TEAl) and triisobutyl aluminum (TiBAl). Preferred preactive agent is TEAl. The ratio of Al to titanium ranges from 0.01: 1 to 2: 1, preferably from 0.25: 1 to 1.2: 1. Subsequently, the catalyst is recovered and washed with a hydrocarbon solvent.

Optionally, the electron donor can be added with a halogenating agent, a first mild halogenated / titanate agent, or a second stronger halogenated / titanate agent. Most preferably, the electron donor is used in the second halogenation / titanate step. Electron donors for use in the preparation of polyolefin catalysts are well known and any suitable electron donor can be used in the present invention to provide a suitable catalyst.

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

Electron donors are monofunctional or multifunctional, advantageously selected from aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic esters, ketones, vinyl esters, acrylic derivatives, especially alkyl acrylates or methacrylates and silanes This can be Preferred examples of suitable electron donors are di-n-butyl phthalate. More preferred examples of suitable electron donors are alkylsilylalkoxides of the general formula RSi (OR ') ₃ , for example methylsilylethoxy, wherein R and R' are alkyl having from 1 to 5 carbon atoms and may be the same or different. Side [MeSi (OEt ₃ )].

The support of the catalyst system of the present invention should be a chemically non-reactive inert solid with any component of a conventional Ziegler-Natta catalyst. Adjuvants are preferably magnesium compounds. Examples of magnesium compounds used to provide an adjuvant for the catalyst component are magnesium halides, dialkoxymagnesium, alkoxymagnesium halides and carboxylates of magnesium. Preferred magnesium compound is magnesium chloride (MgCl ₂ ).

Optionally, the Ziegler-Natta catalyst may be pre-polymerized. In general, the prepolymerization process is accomplished by contacting a small amount of monomer with the catalyst after the catalyst is contacted with the co-catalyst. Pre-polymerization processes are described in US Pat. No. 5,106,804; 5,153,158; 5,153,158; And 5,584,071.

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

The activity of the catalyst of the present invention depends at least in part on the polymerization process and conditions. In general, the activity of the catalyst is at least 6,000 gPE / g catalyst, but may also be greater than 100,000 gPE / g catalyst.

In addition, the resulting catalysts provide polymers with good fluff morphology. Thus, the catalyst of the present invention provides large polymer particles with a uniform size distribution, where small, extremely fine particles (up to about 125 microns) are present only at low concentrations. The catalyst of the present invention, including large, high powder bulk concentrations and easily transported powders, can be modified to suit the polymerization production process.

The polymerization process can be in bulk, slurry or gas phase. Preference is given to using catalysts synthesized in the slurry phase polymerization. Polymerization conditions (eg temperature and pressure) depend not only on the type of polymerization process used, but also on the type of apparatus used and are well known in the art. In general, the temperature may be in the range of about 50-200 ° C., and the pressure in the range of 10-800 psi.

The olefin monomer can be introduced into the polymerization reaction zone of the diluent, which is a liquid non-reactive transfer agnet, under the reaction conditions. Examples of such diluents are hexane and isobutane. For example, in the case of copolymerization of ethylene with another alpha-olefin such as butene or hexene, the second alpha-olefin may be present at 0.01-20 mole percent, preferably 0.02-10 mole percent.

For the polymerization process, it is preferred to include an internal electron donor in the synthesis of the catalyst and an external electron donor or stereoselectivity control agent (SCA) for activating the catalyst in the polymerization. Internal electron donors can be used in the formation of catalysts during the chlorination or chlorination / titanate steps. Compounds suitable as internal electron-donors for preparing conventional supported Ziegler-Natta catalyst components include those of ethers, diethers, ketones, lactones, electron donor compounds and esters having N, P and / or S atoms. Contains classes In particular, esters of phthalic acid such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate; Esters of malonic acid such as diisobutyl and diethylmalonate; Alkyl and arylpivalates; Alkyl, cycloalkyl and arylmaleates; Alkyl and aryl carbonates such as diisobutyl, ethyl-phenyl and diphenylcarbonate; Succinic esters such as mono and diethyl succinate are suitable.

External donors that can be used in the preparation of the catalysts according to the invention include organosilanes such as alkoxysilanes of the general formula SiR _m (OR ') _4-m , wherein R is an alkyl group, a cycloalkyl group, an aryl group and a vinyl group Is selected from the group consisting of; R 'is an alkyl group; And when m is 0-3, R may be the same as R ', and when m is 0, 1 or 2, the R' groups may be the same or different; When m is 2 or 3, the R groups can be the same or different.

Preferably, the external donor of the present invention is selected from silane compounds of the formula:

Wherein R ₁ and R ₄ are alkyl or cycloalkyl groups containing primary, secondary, tertiary carbon atoms attached to the silane, and R ₁ and R ₄ are the same or different; R ₂ and R ₃ are alkyl or aryl groups. R ₁ may be methyl, isobutyl, cyclopentyl, cyclohexyl or t-butyl; R ₂ and R ₃ may be methyl, ethyl, propyl or butyl groups but need not be identical; In addition, R ₄ may be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl. Specific external donors include cyclohexylmethyldimethoxy silane (CMDS), diisopropyldimethoxysilane (DIDS), cyclohexylisopropyl dimethoxy silane (CIDS), dicyclopentyldimethoxysilane (CPDS) or di-t-butyl Dimethoxysilane (DTDS).

Polyethylenes made using the catalysts described above have MWDs less than about 7.0, preferably less than 6.0, more preferably less than 5.5, most preferably less than 5.0.

Generally described invention, the following examples are provided as specific embodiments of the present invention, and to illustrate the practice and advantages of the present invention. It is understood that these embodiments are given by way of example and are not intended to limit the description or claims of the invention in any way.

Example

The following examples are provided merely to illustrate certain embodiments of the present invention and are not meant to limit the claims.

Catalyst manufacturing

This example provides an illustration of a controlled-type polyethylene catalyst that allows for the preparation of narrower molecular weight distribution (MED) polymers. The inherent molecular weight distribution (MWD) of the catalyst can be utilized to provide a resin suitable for injection molding applications.

Below is a synthesis strategy for controlled-form catalysts. Prominent data on the polymer MWD given by this catalyst under standard bench reactor conditions are shown in Table 1. As can be seen from this data, the MWD of the polymer is apparently as narrow as the value measured by the shear response (SR5) and polydispersity (M _w / M _n ) values.

The catalyst is prepared as follows:

Step 1

BuEtMg / DIAE / TEAl (1: 0.6: 0.03) + 2-ethylhexanol (2/09) to prepare soluble intermediate A.

Step 2

Intermediate A + 1.0 ClTi (OPr) ₃ to give soluble intermediate B. ₃ .

Step 3

Intermediate B + Ti (OPr) ₄ / TiCl ₄ (2.0: 1.0) to give a solid precatalyst.

Step 4

Precatalyst to provide the final catalyst + TiCl ₄ (0.25) + TEAl.

polymerization

The reactor used for the polymerization of ethylene (autoclave engineer) is equipped with four mixing baffles with a four liter capacity and two different angle mixing propellers. Ethylene and hydrogen are introduced into the reaction tube through the Teledyne-Hastings Raydist mass flow controller while the dome mounted back-pressure regulator maintains the internal reactor pressure constant. The reaction temperature is maintained with steam and coolant (in a reactor jacket) using a Kammer Valve connected to a Barber-Coleman controller. Hexane was used as diluent.                     

Experimental Variables:

Temperature 80 ℃

60 minutes reaction time

Pressure 125psi

0.2 cc slurry of catalyst (ca. 10 mg catalyst)

Cocatalyst TEAl@0.25mmole/L

Flow Rate H ₂ / C ₂ @ 0.25

MWD data for controlled form catalysts catalyst ppt. reagent M15 (dg / min) HLMI (dg / min) SR5 M _w / M / _n Standard TiCl ₄ (OBU) ₄ 1.86 19.5 10.4 5.4 Variant 9 TiCl ₄ (OPr) ₄ 9.07 85.2 9.4 4.9

While exemplary embodiments of the present invention have been described in detail, various other modifications will be apparent to those skilled in the art, and those skilled in the art without departing from the spirit and scope of the present invention. It is understood that it can be easily prepared by those with. Therefore, it is not intended that the scope of the claims appended hereto be limited to the embodiments and descriptions described herein, but rather that the claims are treated equally by one of ordinary skill in the art to which this invention belongs. It is intended to include all the features, including all the properties of the patentable novelty present in the present invention.

Claims (91)

a) a soluble magnesium dialkoxide compound of the general formula Mg (OR '') ₂ , wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms, Contacting with a halogenating agent exchangeable with one alkoxide; b) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And c) contacting reaction product B with a second halogenated / titanate agent to form a catalyst component, The catalyst component prepared by the process, characterized in that the first halogenated / titanating agent is Ti (OPr) ₄ / TiCl ₄ . The method of claim 1, Soluble magnesium dialkoxide compound R and R 'are alkyl groups of 1 to 10 carbon atoms and alkyl magnesium compounds of the general formula MgRR' which may be the same or different, and the alcohol is linear or branched and R '' is 4 to 20 carbon atoms A catalyst component, characterized in that the reaction product of the reaction containing an alcohol of the general formula R''OH which is an alkyl group. The method of claim 2, A soluble magnesium dialkoxide compound is a catalyst component, characterized in that magnesium di (2-ethylhexoxide). The method of claim 2, A catalyst component characterized in that the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethyl magnesium. The method of claim 2, Catalyst component, characterized in that the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol. The method of claim 2, Catalyst component, characterized in that the reaction further comprises aluminum alkyl. delete The method of claim 1, The first halogenation / I chloride titanate Ti (OPr) _4, a 0.5 ratio of TiCl ₄ for: 1-6: 1 within the range of Ti (OPr) ₄ / TiCl catalyst component, characterized in that the blend of the _four. The method of claim 1, A catalyst component, characterized in that an electron donor is added to said halogenating agent, said first halogenated / titanate, or said second halogenated / titanate. delete delete The method of claim 1, Halogenating agent A is a non-reducing oxyphilic compound selected from the group consisting of titanium, silicon, aluminum, carbon, tin and germanium, R ''' _x is a hydrocarbyl moiety having 2 to 6 carbon atoms, x is A- Catalyst component, characterized in that the general formula ClAR ''' _x monovalent. A catalyst prepared by a process comprising contacting a catalyst component with an organoaluminum preactivator, The catalyst component i) a soluble magnesium dialkoxide compound of the general formula Mg (OR '') ₂ , wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms, to form a reaction product A, Contacting with a halogenating agent exchangeable with one alkoxide; ii) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And iii) contacting reaction product B with a second halogenated / titanate agent to form a catalyst component; And said first halogenated / titanate is Ti (OPr) ₄ / TiCl ₄ . The method of claim 13, Soluble magnesium dialkoxide compound R and R 'are alkyl groups of 1 to 10 carbon atoms and alkyl magnesium compounds of the general formula MgRR' which may be the same or different, and the alcohol is linear or branched and R '' is 4 to 20 carbon atoms A catalyst, characterized in that the reaction product of a reaction comprising an alcohol of the general formula R''OH which is an alkyl group. delete delete delete delete delete The method of claim 13, The first halogenation / I chloride titanate Ti (OPr) _4, the ratio of TiCl ₄ to 0.5: 1-6: 1 within the range of Ti (OPr) ₄ / TiCl ₄ catalyst, characterized in that a blend of a. The method of claim 14, The catalyst characterized in that the reaction further comprises an electron donor. delete delete The method of claim 13, Halogenation agent A is a non-reducing oxyphilic compound selected from the group consisting of titanium, silicon, aluminum, carbon, tin and germanium, R ''' _x is a hydrocarbyl moiety having 2 to 6 carbon atoms, x is A- A catalyst characterized in that the monovalent formula is ClAR ''' _x . The method of claim 13, And the second chlorinated / titanate agent is a titanium halide. delete The method of claim 13, The organoaluminum preactivator And R ^ is an alkyl or halide having from 1 to 8 carbon atoms, R ^ may be the same or different and at least one R ^ is an aluminum alkyl of the general formula AlR ^ _{3 wherein} alkyl. delete delete The method of claim 13, The catalyst is A uniform particle size with a fluff shape that can be modified to suit the polymerization production process, providing polyethylene having a molecular weight distribution of at least 7.0, having an activity of at least 6,000 gPE / g of catalyst, and having a low particle level of less than 125 microns Providing a distribution. In a polymer produced by a process comprising the step of contacting together at least one α-olefin monomer together in the presence of a catalyst under polymerization conditions: The catalyst component of the catalyst, i) a soluble magnesium dialkoxide compound of the general formula Mg (OR '') ₂ wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms to form reactant A, one halogen Contacting with a halogenating agent exchangeable with an alkoxide of; ii) contacting reaction product A with a first halogen / titanate agent to form reaction product B; And iii) contacting reaction product B with a second halogenated / titanate agent to form a catalyst component, Wherein said first halogen / titanate agent is a blend of Ti (OPr) ₄ / TiCl ₄ . The method of claim 31, wherein Wherein said catalyst is prepared in a process further comprising contacting said catalyst component with an organoaluminum agent. delete The method of claim 31, wherein And said polymer is polyethylene. The method of claim 31, wherein Soluble magnesium dialkoxide compound R and R 'are alkyl groups of 1 to 10 carbon atoms and alkyl magnesium compounds of the general formula MgRR' which may be the same or different, and the alcohol is linear or branched and R '' is 4 to 20 carbon atoms A polymer, characterized in that the reaction product of a reaction comprising an alcohol of the general formula R''OH, which is an alkyl group. delete delete delete 36. The method of claim 35 wherein And wherein said reaction further comprises aluminum alkyl. delete The method of claim 31, wherein The first halogenation / I chloride titanate Ti (OPr) ₄ is the ratio of TiCl ₄ to 0.5: Polymer according to claim 1 blend of within the range of Ti (OPr) ₄ / TiCl ₄ in the: 1-6. delete delete delete The method of claim 31, wherein The halogenating agent is A is a non-reducing oxyphilic compound selected from the group consisting of titanium, silicon, aluminum, carbon, tin and germanium, R ''' _x is a hydrocarbyl moiety having 2 to 6 carbon atoms, x is A-1 And a general formula ClAR ''' _x . The method of claim 31, wherein And wherein the second chlorinated / titanate agent is a titanium halide. delete 33. The method of claim 32, The organoaluminum preactivator A polymer, wherein R ^ is an alkyl having 1 to 8 carbon atoms, or a halide, R ^ may be the same or different and at least one R ^ is an alkyl alkyl of the general formula AlR ^ ₃ , wherein Al ^ is alkyl. delete delete a) a soluble magnesium dialkoxide compound of the general formula Mg (OR '') ₂ , wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms, Contacting with a halogenating agent exchangeable with one alkoxide; b) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And c) contacting reaction product B with a second halogenated / titanate agent to form a catalyst component, Wherein said first halogenated / titanate agent is Ti (OPr) ₄ / TiCl ₄ . The method of claim 51, Soluble magnesium dialkoxide compound R and R 'are alkyl groups of 1 to 10 carbon atoms and alkyl magnesium compounds of the general formula MgRR' which may be the same or different, and the alcohol is linear or branched and R '' is 4 to 20 carbon atoms A reaction product of a reaction comprising an alcohol of the general formula R''OH, which is an alkyl group. delete delete delete delete delete delete delete delete A process for preparing a catalyst comprising the step of contacting a catalyst component with an organoaluminum preactivator, The catalyst component, i) a soluble magnesium dialkoxide compound of the general formula Mg (OR '') ₂ wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms to form reactant A, one halogen Contacting with a halogenating agent exchangeable with an alkoxide of; ii) contacting reaction product A with a first halogen / titanate agent to form reaction product B; And iii) a process comprising contacting reaction product B with a second halogenated / titanate agent, Said first halogen / titanate agent is a blend of Ti (OPr) ₄ / TiCl ₄ . 62. The method of claim 61, Process according to claim 1 blend of within the range of Ti (OPr) ₄ / TiCl ₄ in the: first halogenating / I chloride titanate Ti (OPr) _4, the ratio of TiCl ₄ to 0.5: 1-6. delete 62. The method of claim 61, Soluble magnesium dialkoxide compound R and R 'are alkyl groups of 1 to 10 carbon atoms and alkyl magnesium compounds of the general formula MgRR' which may be the same or different, and the alcohol is linear or branched and R '' is 4 to 20 carbon atoms A reaction product of a reaction comprising an alcohol of the general formula R " OH, which is an alkyl group. delete delete delete 65. The method of claim 64, Said reaction further comprising aluminum alkyl. delete 62. The method of claim 61, And an electron donor is added to said halogenating agent, said first halogenated / titanate agent, or said second halogenated / titanate agent. delete delete 62. The method of claim 61, Halogenating agent A is a non-reducing oxyphilic compound selected from the group consisting of titanium, silicon, aluminum, carbon, tin and germanium, R ''' _x is a hydrocarbyl moiety having 2 to 6 carbon atoms, x is A- Wherein the monovalent formula is ClAR ''' _x . delete delete delete delete 62. The method of claim 61, And 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 0: 1 to 10: 1. In an α-olefin polymerization process comprising the step (a) of contacting at least one α-olefin monomer together in the presence of a catalyst under polymerization conditions, The catalyst component of the catalyst i) a soluble magnesium dialkoxide compound of the general formula Mg (OR '') ₂ , wherein R '' is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms, to form a reaction product A, Contacting with a halogenating agent exchangeable with one alkoxide; ii) contacting reaction product A with a first halogenated / titanate agent to form reaction product B; And iii) contacting reaction product B with a second halogenated / titanate agent to form reaction product C, And wherein said first halogenated / titanate is a blend of Ti (OPr) ₄ / TiCl ₄ . The method of claim 79, Wherein said process further comprises (b) extracting a polyolefin polymer. The method of claim 80, Wherein said polymer has a molecular weight distribution of 7.0 or less. The method of claim 80, Wherein said polymer is polyethylene. delete delete delete delete delete delete delete delete delete