CN1418893A - Polyolefine catalyst, its making method, using method, and polymer made from said catalyst - Google Patents
Polyolefine catalyst, its making method, using method, and polymer made from said catalyst Download PDFInfo
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- CN1418893A CN1418893A CN 01137456 CN01137456A CN1418893A CN 1418893 A CN1418893 A CN 1418893A CN 01137456 CN01137456 CN 01137456 CN 01137456 A CN01137456 A CN 01137456A CN 1418893 A CN1418893 A CN 1418893A
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Abstract
The Ziegler-Natta catalyst can make molecular weight distribution of polyolefine produced by said catalyst be broadened, at the same time said catalyst can retain high activity and good villus state, generally, the production method of said catalyst is characterized by that it uses organic aluminium preactivating agent to contact with catalyst component, in which the production method of catalyst component includes the following steps: 1). using halogenating agent to contact with soluble dioxyalkyl magnesim compound whose general formula is Mg(OR'')2 to form reaction product A; B) using first halogenating/titanizing agent to contact with reaction product A to form reaction product B; C) using second halogenating/titanizing agent to contact with reaction product B to form catalyst component.
Description
See related application
This application is a continuation-in-part application of U.S. patent application entitled "Ziegler-Natta catalyst for olefin polymerization" filed on 28/1 1997, serial No. 08/789,862, which is incorporated herein by reference.
Technical Field
The present invention relates to a catalyst, a method for producing the catalyst, a method for using the catalyst, a polymerization method, and a polymer produced by the catalyst. In another aspect, the present invention relates to a polyolefin catalyst, a method of making the catalyst, a method of using the catalyst, a polymerization reaction of a polyolefin, and a polyolefin. In yet another aspect, the present invention also relates to Ziegler-Natta catalysts, methods of making the catalysts, methods of using the catalysts, polymerization of polyolefins, and polyolefins.
Background
Ziegler-type polyolefin catalysts, their usual production methods and their subsequent use methods have been widely known in the polymerization field since the beginning of the 50 th century.
However, although not a few are known for ziegler-type catalysts, there is a constant search for methods to improve their polymer yield, catalyst life, catalyst activity, and their ability to make polyolefins having certain properties.
U.S. patent 4,255,544 issued on 10/3 1981 to Kimura et al discloses a process for the polymerization of ethylene using a catalyst comprising: (A) a reaction product of a magnesium compound and a titanium halide, (B) an organoaluminum compound wherein component A is obtained by reacting a magnesium dialkoxide with a halogen-containing silicon compound and an alcohol to obtain a solid substance, and then reacting the solid substance with a titanium halide in the presence of a silicon compound having an alkoxy group.
Published in 1990, 4/3, Job et al, U.S. Pat. No. 4,914,069, discloses a process for the preparation of an olefin polymer catalyst component having improved activity and selectivity, which process comprises: (a) halogenating a magnesium compound containing at least one aryloxy, alkyl, or carbonate or alkoxy group with a first halide of tetravalent titanium and a first electron donor; (b) contacting the resulting product with a second halide of tetravalent titanium; (c) the resulting treated halogenated product is washed with an inert hydrocarbon liquid. In this process, a second electron donor is used in step (a) or (b), and the product of step (b) is contacted with a third halide of tetravalent titanium at a temperature of 40-140 ℃ in step (b2), followed by washing the treated product in step (c).
U.S. patent 5,155,187 issued on 10/13 of 1992 to Shelly discloses a polymerization process using a catalyst which is generally the 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.
U.S. patent 5,610,246 issued to Buehler et al, 3/11/1997, discloses a process for the polymerization of propylene using a silica supported catalyst. The catalyst comprises the product resulting from contacting silica with, in any order: (1) at least one hydrocarbon-soluble magnesium-containing compound; (2) a first modified compound selected from the group consisting of: silicon halides, boron halides, aluminum halides, and mixtures thereof, followed by a specially modified second compound.
Us patent 5,631,334 issued on 20/5/1997 in Zandona discloses a process for the manufacture of a catalyst solid for the (co) polymerization of at least one olefin, which comprises precipitating magnesium together with at least one transition metal.
However, despite the advances in the art, none of these prior art disclose or suggest that increasing the amount of titanating agent in the second titanation step in the manufacture of a catalyst increases the molecular weight distribution of the product polyolefin produced from the catalyst.
Accordingly, there is a need in the art for polyolefin catalysts.
There is also a need in the art for a method of making a polyolefin catalyst.
There is also a need in the art for a process for the polymerization of olefins.
There is also a need in the art for polyolefins having a broad molecular weight distribution.
There is also a need in the art for polyolefin catalysts that facilitate the production of polyolefins having increased molecular weight distributions, which catalysts also have high activity and good fluff morphology.
These and other needs in the art will become apparent to those skilled in the art upon a reading of the specification, including its drawings and claims.
Disclosure of Invention
It is an object of the present invention to provide a polyolefin catalyst.
It is another object of the present invention to provide a method for producing the polyolefin catalyst.
It is another object of the present invention to provide a process for the polymerization of olefins.
It is another object of the present invention to provide polyolefins having a broad molecular weight distribution.
It is another object of the present invention to provide a polyolefin catalyst which facilitates the production of polyolefins of various molecular weight distributions, and which also has high activity and excellent fluff morphology.
According to an embodiment of the present invention, there is provided a catalyst component produced by a method comprising the steps of: a) with the general formula Mg (OR')2Is contacted with a halogenating agent capable of replacing an alkoxy group with a halogen to form reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing from 1 to 20 carbon atoms; b) contacting reaction product a with a first halogenating/titanating agent to form reaction product B; d) a second halogenating/titanating agent is contacted with reaction product B to form the catalyst component. Typically, the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium to magnesium in the second halogenating/titanating step is from about 0.1 to about 5. The ratio of titanium to magnesium in the second halogenation/titanation step is preferably about 2.0.
Another embodiment of the present invention provides a polyolefin catalyst prepared by a process generally comprising the steps of: a) the catalyst components of the present invention are contacted with an organoaluminum preactivating agent. The catalyst component is prepared by a method comprising the following steps: i) with the general formula Mg (OR')2Is contacted with a halogenating agent capable of replacing an alkoxy group with a halogen to form reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms; ii) contacting reaction product a with a first halogenating/titanating agent to form reaction product B; iii) contacting the reaction product B with a second halogenating/titanating agent to form the catalyst component. The amount of the second halogenating/titanating agent used is determined by the desired molecular weight distribution of the polymer to be produced with the catalyst.Typically, the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium to magnesium in the second halogenating/titanating step is from about 0.1 to about 5. The ratio of titanium to magnesium in the second halogenation/titanation step is preferably about 2.0. The catalyst of the present invention has a fluff morphology suitable for polymerization manufacturing processes which provides polyethylene having a molecular weight distribution of at least 5.0 and provides a uniform particle size distribution and a small amount of particles having a particle size of less than 125 microns. The activity of the catalyst depends on the polymerization conditions. Typically, the catalyst has an activity of at least 6,000 grams of polyethylene per gram of catalyst, but may have an activity in excess of 100,000 grams of polyethylene per gram of catalyst.
In yet another embodiment of the present invention, there is provided a polyolefin polymer made by a process comprising the steps of a) contacting one or more α -olefins with each other under polymerization conditions in the presence of the catalyst of the present invention, and b) discharging the polyolefin polymer, the monomer typically being ethylene monomer and the polymer typically being polyethylene.
Another embodiment of the present invention is to provide a catalyst system comprising the catalyst of the present invention and an inert support. The inert carrier is typically a magnesium compound.
Another embodiment of the present invention provides a method of forming a catalyst component. In general, the catalyst component of the invention is prepared by a process comprising the steps of: i) with the general formula Mg (OR')2With magnesium dialkoxide and halides(ii) a halogenating agent capable of replacing an alkoxy group with a halogen to form a reaction product "A", wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing from 1 to 20 carbon atoms; ii) contacting the reaction product "A" with a first halogenating/titanating agent to form a reaction product "B"; iii) contacting the reaction product "B" with a second halogenating/titanating agent to form the catalyst component.
Another embodiment of the present invention is to provide a method of making a catalyst for producing a polyolefin having a desired molecular weight distribution ("MWD"). The method generally comprises the steps of: a) an organoaluminum preactivating agent is contacted with the catalyst component of the present invention.
Yet another embodiment of the present invention is to provide an α -olefin polymerization process to produce a polyolefin having a desired molecular weight distribution ("MWD") generally comprising the steps of a) contacting one or more α -olefin monomers with each other under polymerization conditions in the presence of the catalyst of the present invention, and b) withdrawing a polyolefin polymer, the monomers preferably being ethylene and the polymer preferably being polyethylene.
These and other objects will be apparent to those skilled in the art from this specification, including its drawings and claims.
Drawings
Figure 1 is a catalyst/fluff morphology particle size distribution plot.
Detailed Description
The method for producing the catalyst component of the present invention generally comprises the steps of: the catalyst is prepared by forming a metal dialkoxide from a metal dialkyl and an alcohol, halogenating the metal dialkoxide, halogenating/titanating in two or more steps to form a catalyst, then treating the catalyst component with a pre-activator such as an organoaluminum, and then heat treating the pre-activated catalyst. Increasing the amount of halogenation/titanation agent used in the second halogenation/titanation step increases the molecular weight distribution of the product polyolefin produced from the catalyst. Thus, the molecular weight distribution of the product polyolefin can be altered.
The mechanism proposed by 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″+TlCl4/Ti(OR″″)4→″B″；
4.″B″+TiCl4→″C″；
5. "C" + TEAL → preactivated catalyst;
6. heat treatment of preactivated catalysts
In the above formula, M may be any suitable metal, preferably group IIA, most preferably Mg. In the above formula, R, R ', R' and R 'are each a single hydrocarbyl or substituted hydrocarbyl moiety, and R' contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. R "typically contains 3 to 20 carbon atoms, R'" typically contains 2 to 6 carbon atoms, R "" typically contains 2 to 6 carbon atoms, and is typically butyl. Any combination of two or more of R, R ', R' may be the same, or the R groups may be different from each other.
ClAR' ″ in the above formulaxIn which A is preferably a non-reducing oxophilic compound capable of replacing an alkoxy group with a chloride ion, R' "is preferably hydrocarbyl or substituted hydrocarbyl, and x is the valence of A minus 1. Examples of a include titanium, silicon, aluminum, carbon, tin and germanium, with titanium and silicon being most preferred and x being most preferred 3. Examples of R' "include methyl, ethyl, propyl, isopropyl and the like containing 2 to 6 carbon atoms.
When the exact composition of product "a" is unknown, it is believed to contain a partially chlorinated metal compound, an example of which is ClMg (OR' "). The reaction product "B" may be a complex of a chlorinated or partially chlorinated metal with a titanium compound, for example, may be a complex of (MCl)2)y·(TiClx(OR)4-x)z′The complex represented. The second chlorination/titanation produces the reaction product, catalyst component "C", which may also be a complex of a chlorinated and partially chlorinated metal with a titanium compound, but unlike product "B", may be prepared from (MCl)2)y·(TiClx′(OR)4-x′)z′The complex represented. "product C" is expected to be more chlorinated than "product B". A greater degree of chlorination can produce different complexes of different compounds. While these descriptions of the reaction products now provide the most likely chemical explanations, the invention as recited in the claims is not limited by these theoretical mechanisms.
The metal alkyls and resulting metal dialkoxides suitable for use in the present invention include any metal alkyls and metal dialkoxides that produce suitable polyolefin catalysts when used in the present invention. Preferred metal dialkoxides and dialkyl metals include metal dialkoxides and metal dialkoxides of group IIA metals. More preferred metal dialkoxides or dialkyl metals are magnesium dialkoxides or magnesium dialkyls.
In an embodiment of the invention, the magnesium dialkyl [ MgRR '] may be any magnesium dialkyl wherein R and R' are as described above. Of course, R and R' may be the same or different. Non-limiting examples of suitable dialkylmagnesium include diethylmagnesium, dipropylmagnesium, dibutylmagnesium, butylethylmagnesium, and the like. Butylethylmagnesium (BEM) is the preferred magnesium dialkyl.
In an embodiment of the invention, the metal dialkoxide is preferably of the formula Mg (OR')2Wherein R' is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms.
The metal dialkoxide is most preferably soluble and non-reducing. The advantage of the non-reducing compound is that it forms MgCl2Rather than soluble Ti formed by reduction of compounds such as MgRR+3The latter tend to form catalysts having a broad particle size distribution. In addition, Mg (OR')2Is less reactive than MgRR' and it is chlorinated with a weak chlorinating agent, then simultaneously chlorinated/titanized with a weak agent and second chlorinated/titanized with a stronger agentIs a stepwise and sequential stronger reaction which results in a more uniform product, i.e. better control of catalyst particle size and particle size distribution.
Non-limiting examples of preferred types of metal dialkoxides that are suitable for use include dibutoxymagnesium, dipentyloxymeagnesium, dihexyloxymagnesium, bis (2-ethylhexyloxy) magnesium, and any alkoxide suitable to render the system soluble. The most preferred type of metal alkoxide is magnesium bis (2-ethylhexyloxy).
By way of non-limiting example, magnesium dialkoxides, such as magnesium bis (2-ethylhexoxide), can be prepared by reacting an alkyl magnesium compound (MgRR '), such as Butyl Ethyl Magnesium (BEM), with an alcohol (R' OH), such as 2-ethylhexanol, represented by the formula:
in the case of BEM, RH and R' H are respectively butane and ethane. The reaction was carried out at room temperature and the reactants formed a solution.
In embodiments of the present invention, any alcohol that produces the desired metal dialkoxide may be used. Although it is contemplated that almost any alcohol can be used, including straight or branched chain alcohols, it is preferred to use a higher branched chain alcohol, such as 2-ethyl-1-hexanol. In general, the alcohol used may be any alcohol of the formula R "OH, wherein R" is an alkyl group containing from 4 to 20 carbon atoms, preferably containing at least 3 carbon atoms, more preferably containing at least 4 carbon atoms, still more preferably containing at least 5 carbon atoms, and most preferably containing at least 6 carbon atoms. Non-limiting examples of suitable alcohols include butanol, isobutanol, 2-ethylhexanol, and the like. The preferred alcohol is 2-ethylhexanol.
The amount of the alcohol to be added to the slurry is usually about 0.5 to 4 equivalents (equivalents relative to the total amount of the magnesium or metal compound), preferably about 1 to 3 equivalents.
Metal alkyl compounds are highly associated due to electron deficient bonding, which results in highly viscous high molecular weight forms in solution. This high viscosity can be reduced by the addition of an alkyl aluminium such as triethyl aluminium. Aluminum alkyls disrupt the association between individual metal alkyl molecules. The ratio of aluminium alkyl to metal is preferably from 0.001: 1 to 1: 1, more preferably from 0.01 to 0.1: 1, most preferably from 0.03: 1 to 0.05: 1. In addition, electron donors such as ethers, for example, diisoamyl ether (DIAE), may be used to further reduce the viscosity of the metal alkyl. The preferred range of the ratio of electron donor to metal is 0: 1 to 10: 1, more preferably 0.1: 1 to 1: 1.
The reagents used in the step of halogenating the metal alkoxide include any halogenating agent which, when used in the present invention, produces a suitable polyolefin catalyst. The halogenation step is preferably a chlorination step, and the preferred halogenating agent is a chloride.
Preferred chlorinating agents have the general formula ClAR' ″xOr ClAOR' ″xWherein A is a non-reducing oxophilic compound capable of replacing one with a chloride ionAn alkoxy group, R' ″ is alkyl, and x is the valence of A minus 1. Examples of A are titanium, silicon, aluminum, carbon, tin and germanium, with titanium and silicon being most preferred, and x being 3. Examples of R' "are methyl, ethyl, propyl, isopropyl and the like containing 2 to 6 carbon atoms. Chlorination effective for the present inventionAn example of an agent is ClTi (O)iPr)3And ClSi (Me)3. R "" is typically butyl.
Halogenation of the metal alkoxide is typically carried out in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane, and the like. The preferred solvent is hexane.
The molar ratio of metal alkoxide to halogenating agent in the halogenation step is generally in the range of about 6: 1 to about 1: 3, and preferably in the range of about 3: 1 to about 1: 2. A more preferred range is from about 2: 1 to about 1: 2, and a most preferred range is about 1: 1.
The halogenation step is generally carried out at a temperature ranging from about 0 ℃ to about 100 ℃ for a reaction time ranging from about 0.5 hours to about 24 hours. The halogenation step is preferably conducted at a temperature in the range of about 20 to about 90 c and the reaction time is preferably about 1 to about 4 hours.
Once the halogenation step is conducted and the metal alkoxide is halogenated, the product "a" is subjected to one or more halogenation/titanation steps.
The halogenating/titanating agent is preferably a tetra-substituted titanium compound, all four substituents being the same and the substituent being a halide, or an alkoxy or phenoxy group containing 2 to 10 carbon atoms, e.g. TiCl4OR Ti (OR "")4. The halogenation/titanation agent is preferably a chlorination/titanation agent.
The preferred chlorinating/titanating agents may be a single compound or a mixture of compounds. The process of the present invention provides an activated catalyst after the first chlorination/titanation step; however, it is preferred that at least two chlorination/titanation steps each use a different compound or combination of compounds and that a stronger chlorinating/titanating agent be used with each successive chlorination/titanation step.
The first chlorinating/titanating agent is preferably a weak titanating agent and a blend of titanium halide and organic titanate is preferred. The first chlorinating/titanating agent is more preferably TiCl4And Ti (OBu)4Of a blend of (1), TiCl4/Ti(OBu)4From about 0.5: 1 to about 6: 1, and most preferably from about 2: 1 to about 3: 1. It is believed that the blend of titanium halide and organotitanate reacts to form titanium alkoxide halide, Ti (OR)aXbWhere OR and X are alkoxy and halide, respectively, a + b is the valence of titanium, typically 4, and both a and b may be fractional, for example a ═ 2.5, b ═ 1.5.
Alternatively, the first chlorinating/titanating agent may be a single compound. An example of the first chlorinating/titanating agent as a single compound is Ti (OC)2H5)3Cl、Ti(OC2H5)3Cl、Ti(OC3H7)2Cl2、Ti(OC3H7)3Cl、Ti(OC4H9)Cl3、Ti(OC6H13)2Cl2、Ti(OC2H5)2Br2And Ti (OC)12H5)Cl3。
The first halogenation/titanation step is generally carried out in the following manner: the halogenated product "a" is first slurried 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.
After addition of the halogenation/titanation agent to the soluble product "A" at room temperature, the solid product "B" precipitates out.
The amount of halogenation/titanation agent used must be sufficient to precipitate the solid product from solution. Generally, the halogenating/titanating agent is used in an amount, based on the titanium to metal ratio, generally in the range of from about 0.5 to about 5, preferably in the range of from about 1 to about 4, and most preferably in the range of from about 1.5 to about 2.5.
The solid product "B" precipitated in the first titanation step is then recovered by any suitable recovery technique and washed with a hydrocarbon solvent.
Compounds suitable for use as the second halogenating/titanating agent include those suitable for use as the first halogenating/titanating agent, except that the second halogenating/titanating agentStronger agents are preferred. The stronger second halogenating/titanating agent is preferably a titanium halide, more preferably titanium tetrachloride [ TiCl ]4]。
The second halogenation/titanation step is generally carried out in the following manner: the solid product "B" recovered from the first titanation step is slurried in a hydrocarbon solvent. The listed hydrocarbon solvents suitable for the first halogenation/titanation step are all usable. The slurry is then heated slightly to a temperature in the range of about 50-90 c and titanium tetrachloride is added.
Typically, the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium to magnesium contained in the second halogenating/titanating step is from about 0.1 to about 5. The ratio of titanium to magnesium contained in the second halogenation/titanation step is preferably about 2.0.
The amount of titanium tetrachloride may also be expressed in terms of equivalents, which herein are the amount of titanium relative to magnesium or metal compound. The amount of titanium used in the second halogenation/titanation step is generally from about 0.1 to about 5.0 equivalents, preferably from about 0.25 to about 4 equivalents, more preferably from about 0.5 to about 3 equivalents, and most preferably from about 0.75 to about 2.0 equivalents. In a particularly preferred embodiment, the amount of titanium tetrachloride used in the second halogenation/titanation step is about 1.0 equivalent.
By increasing the amount of halogenation/titanation agent used in the second halogenation/titanation step, the molecular weight distribution of the polyolefin produced can be broadened. That is, the molecular weight distribution of the polyolefin produced by the catalyst widens as the amount of carbon tetrachloride is increased.
The catalyst component "C" prepared by the above process can be combined with an organoaluminum cocatalyst component ("preactivator") to form a preactivated catalyst system suitable for olefin polymerization. In general, the cocatalyst used with the transition metal containing the catalyst component "C" is an organometallic compound of a metal of groups Ia, IIa, IIIa, such as aluminum alkyl, aluminum alkyl hydride (aluminum alkyl hydrides), lithium aluminum alkyl, zinc alkyl, magnesium alkyl, etc.
The preactivating agent is preferably an organoaluminum compound. The organoaluminum preactivating agent is preferably of the formula AlR ^3Wherein R is an alkyl group having 1 to 8 carbon atoms or a halide. More preferably, the organoaluminum preactivating agent is trialkylAluminum alkyls such as Trimethylaluminum (TMA), Triethylaluminum (TEAL) and triisobutylaluminum (TiBAl). The most preferred preactivating agent is TEAl. The ratio of Al to titanium is from 0.1: 1 to 2: 1, preferably from 0.25: 1 to 1.2: 1.
Alternatively, the electron donor may be added with the halogenating agent, the weak first halogenating/titanating agent, or the stronger second halogenating/titanating agent. Most preferred is the use of an electron donor in the second halogenation/titanation step.
The electron donors useful for the preparation of polyolefins are well known and any suitable electron donor that provides a suitable catalyst may be used in the present invention.
The electron donor, also known as a Lewis base, is an organic compound of oxygen, nitrogen, phosphorus, or sulfur that provides an electron pair to the catalyst.
The electron donor may be a monofunctional or polyfunctional compound, preferably selected from aliphatic or aromatic carboxylic acids and their alkyl, aliphatic or cyclic ethers, ketones, vinyl esters, acryloyl derivatives, in particular alkyl acrylates or methacrylates and silanes. A preferred example of a suitable electron donor is di-n-butyl phthalate. More preferred examples of suitable electron donors are of the formula RSi (OR')3Alkylsilylalkoxides of (C) such as methyltriethoxysilane [ MeSi (OEt)3)]Wherein R and R' are alkyl groups containing 1 to 5 carbon atoms, which may be the same or different.
The support of the catalyst system of the present invention may be an inert solid which is chemically unreactive with any conventional Ziegler-Natta catalyst component. The carrier is preferably a magnesium compound. Examples of magnesium compounds used to provide a support for the catalyst component are magnesium halides, dialkoxymagnesiums, alkoxymagnesium halides and magnesium carboxylates. The preferred magnesium compound is magnesium chloride (MgCl)2)。
Alternatively, the Ziegler-Natta catalyst may be prepolymerized. The prepolymerization is carried out by contacting the catalyst with a small amount of the monomer after the catalyst has been contacted with the cocatalyst. A description of the prepolymerization process can be found in U.S. Pat. nos. 5,106,804; 5,135,158, respectively; and 5,594,071, incorporated herein by reference.
For example, the catalysts of the present invention are useful for catalyzing the polymerization of ethylene, propylene, butenes, pentenes, hexenes, 4-methylpentenes and other α -olefins having at least 2 carbon atoms, and mixtures thereof.
The activity of the catalysts of the invention depends on the method and the conditions of the polymerization, such as the apparatus used and the temperature of the reaction. The catalyst activity is typically at least 5,000 grams of polyethylene per gram of catalyst (gPE/g), but may be greater than 100,000 grams of polyethylene per gram of catalyst.
In addition, the catalysts prepared according to the invention provide polymers with excellent fluff morphology. Thus, the catalyst of the present invention provides large polymer particles having a uniform particle size distribution, wherein small, extremely fine particles (less than about 125 microns) are present only in low concentrations. The catalyst of the present invention comprises a large powder which is easily converted, has a high powder bulk density, and is suitable for polymerization manufacturing processes.
The polymerization process may be bulk, slurry or gas phase. The catalysts synthesized as described above are preferably used in slurry polymerization. The polymerization conditions (e.g., temperature and pressure) depend on the type of apparatus used in the polymerization process and the type of polymerization process used, and are well known in the art. The temperature range is typically about 50-100 deg.C and the pressure range is typically about 10-800 lb/in2。
The olefin monomer may be fed to the polymerization zone in the presence of a diluent which is a non-reactive heat carrier liquid at the reaction conditions, examples of such diluents are hexane and isobutane, for the copolymerization of ethylene and another α -olefin (e.g. butene or hexene), the second α -olefin content may be in the range of 0.01 to 20 mole%, preferably 0.02 to 10 mole%.
For the polymerization process, it is preferable to include an internal electron donor and an external electron donor in the catalyst synthesis, or a stereoregular Selectivity Control Agent (SCA), so as to activate the catalyst at the polymerization reaction. The internal electron donor can be used in the catalyst formation reaction in the chlorination or chlorination/titanation step. Compounds suitable as internal electron donors for the preparation of conventional supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, N, P and/or S atom containing electron donors and specific classes of esters. Particularly suitable are phthalic acid esters, such as diisobutyl phthalate, dioctyl phthalate, diphenyl phthalate and benzylbutyl phthalate; malonic esters such as diisobutyl malonate and diethyl malonate; alkyl and aryl neopentanoates; alkyl, cycloalkyl and aryl maleates; alkyl and aryl carbonates, such as diisobutyl carbonate, ethylphenyl carbonate and diphenyl carbonate; succinic acid esters such as monoethyl succinate and diethyl succinate.
External electron donors useful in preparing the catalysts of the invention include organosilane compounds. For example of the formula SiRm(OR′)4-mWherein R is selected from the group consisting of alkyl, cycloalkyl, aryl, and vinyl; r' is alkyl; m is 0 to 3, wherein R may be the same as R'; when m is 0, 1 or 2, the radicals R' may be identical or different; when m is 2 or 3, the R groups may be the same or different.
The external electron donor of the present invention is preferably selected from silane compounds represented by the following formula:
wherein R1 and R4 are both alkyl or cycloalkyl groups containing a primary, secondary or tertiary carbon atom attached to the silicon, and R1 and R4 may be the same or different; r2 and R3 are alkyl or aryl. R1 may be methyl, isopropyl, cyclopentyl, cyclohexyl, or tert-butyl; r2 and R3 may be methyl, ethyl, propyl, or butyl, and need not be the same; r4 can also be methyl, isopropyl, cyclopentyl, cyclohexyl or tert-butyl. Specific external donors are Cyclohexylmethyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS), Cyclohexylisopropyldimethoxysilane (CIDS), dicyclopentyldimethoxysilane (CPDS) or di-tert-butyldimethoxysilane (DTDS).
The molecular weight distribution of the polyethylene produced with the above catalyst is at least 5.0, preferably at least 6.0, more preferably at least 6.5, still more preferably 7.0.
Examples
The invention generally described above, the following examples are intended only to illustrate certain embodiments of the invention, and to demonstrate the practice and advantages of such embodiments. It is to be understood that these examples are given by way of illustration and are not intended to limit the specification or the appended claims in any way.
Preparation of the catalyst
This example illustrates a morphology-controlled polyethylene catalyst that facilitates fine tuning of the intrinsic Molecular Weight Distribution (MWD) of the polymer produced from the catalyst. By adjusting the molecular weight distribution, a single catalyst system can be used to produce various grades of polymer for applications ranging from injection molding (narrow MWD) to blown film (broad MWD).
The catalyst was produced as follows:
step 1
BuEtMg/DIAE/TEAL (1: 0.6: 0.03) + 2-ethylhexanol (2.09) was used to prepare soluble intermediate A.
Step 2
From intermediate A +1.0 ClTi (OPr)3To obtain a soluble intermediate B.
Step 3
From intermediate B + Ti (OBu)4/TiCl4(2.0: 1.0) to obtain a solid precatalyst.
Step 4
With precatalyst + TiCl4(0.25 or 1.00) + TEAL to produce the final catalyst.
Polymerisation reaction
The reactor design for polymerizing ethylene (autoclave industry) has a capacity of 4 liters and is equipped with four mixing baffles and two counter-pitched mixing propellers. Ethylene and hydrogen were passed into the reaction vessel through a Teledyne-Hastings phase comparator (Raydit) mass flow controller while maintaining the internal reaction pressure constant with a dome equipped with a back pressure regulator. The reaction temperature was maintained by adjusting the steam and cooling water (in the reactor jacket) using a Kammer valve connected to a Barber-Coleman controller.
Hexane was used as a diluent.
Test variables:
the temperature is 80 DEG C
Reaction time 60 minutes
Pressure 125 lb/in2
Catalyst 0.2 ml slurry (about 10 mg catalyst)
Cocatalyst TEAL @0.25 mmol/l
Flow rate H2/C2@0.25
With respect to the molecular weight distribution of the polymer obtained from the catalyst under standard laboratory scale reactor conditionsThe experimental data are shown in table 1. The table shows shear response (SR5), polydispersity index (M)w/Mn) And cross modulus (cross modulus) (G)c) And (6) measuring the values. From these data, it can be seen that the polymer molecular weight distribution is very narrow.
As the data in Table 1 show, the synthesis of the catalyst was modified by adding 4 times the amount of TiCl in the second titanation step (step 4 above)4(i.e., 1.0 equivalent relative to 0.25 equivalent), the intrinsic molecular weight distribution is significantly broadened. This is shown by the higher shear response, higher polydispersity index (Mw/Mn), and lower cross-modulus of the polymer produced from the modified catalyst under standard polymerization conditions.
Table 1: molecular weight distribution data obtained for catalysts with controlled morphology
| Catalyst and process for preparing same | [TiCl4] (mole) | MI5 (dg/min) | HLMI (dg/min) | SR5 | Mw/Mn | Gc (Pa) |
| Standard (69F) | 0.25 | 1.86 | 19.5 | 10.4 | 5.4 | 1.3E5 |
| After improvement (76F) | 1.00 | 1.54 | 20.4 | 13.2 | 7.0 | 8.9E5 |
After the above modifications, no loss of the good fluff/catalyst morphology was seen with the standard catalyst. As shown in fig. 1, the catalyst/fluff particles have a narrow particle size distribution. In addition, the modified catalyst has few particles (fines) smaller than 125 microns. Finally, the activity of the two catalysts subjected to magnesium analysis was very close (22,000 g polyethylene/g catalyst)
While illustrative embodiments of the invention have been described in detail, it should be understood that various other modifications of the invention are apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.
Claims (91)
1. A catalyst component characterized in that it is prepared by a process comprising the steps of:
a) with halogenating agents and compounds of the formula Mg (OR')2Is capable of replacing an alkoxy group with a halogen to form a reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms;
b) contacting reaction product a with a first halogenating/titanating agent to form reaction product B;
c) contacting reaction product B with a second halogenating/titanating agent to form a catalyst component;
wherein the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium tetrachloride to magnesium compound contained in step c) is from 0.1 to 5.
2. The catalyst component according to claim 1, wherein the soluble dialkoxymagnesium compound is a reaction product obtained by reacting an alkylmagnesium of the formula MgRR ', wherein R and R' are alkyl groups having 1 to 10 carbon atoms, which may be the same or different, with an alcohol of the formula R "OH, wherein R" is an alkyl group having 4 to 20 carbon atoms, which is a linear or branched alcohol.
3. The catalyst component of claim 2 wherein the soluble magnesium compound is magnesium bis (2-ethylhexyloxy).
4. The catalyst component according to claim 2 in which the alkyl magnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium.
5. The catalyst component of claim 2 wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.
6. The catalyst composition of claim 2 wherein the reaction further comprises an aluminum alkyl.
7. The catalyst component according to claim 6, characterized in that the aluminum alkyl is triethylaluminum.
8. The catalyst component according to claim 1, wherein the first chlorinating/titanating agent is a blend of two tetra-substituted titanium compounds, all four substituents being the same and being a halide or an alkoxy group having 2 to 10 carbon atoms or a phenoxy group.
9. The catalyst component of claim 8, wherein the first chlorinating/titanating agent is a blend of a titanium halide and an organotitanate.
10. The catalyst component of claim 9 in which the first chlorinating/titanating agent is TiCl4And Ti (OBu)4Of a blend of (1), TiCl4/Ti(OBu)4Is 0.5: 1-6: 1.
11. The catalyst composition of claim 1 wherein the reaction further comprises an electron donor.
12. The catalyst composition of claim 9 wherein the ratio of electron donor to magnesium is from 0: 1 to 10: 1.
13. The catalyst composition of claim 10 wherein the electron donor is an ether.
14. The catalyst component of claim 1 wherein the halogenating agent has the formula of ClAR'xWherein A is a non-reducing oxophilic compound, R' ″xIs a hydrocarbyl moiety containing 2 to 6 carbon atoms, and x is the valence of A minus 1.
15. A catalyst characterized in that it is prepared by a process comprising the steps of:
a) contacting a catalyst component with an organoaluminum preactivating agent, wherein the catalyst component is prepared by a process comprising the steps of:
i) with halogenating agents and compounds of the formula Mg (OR')2Is capable of replacing an alkoxy group with a halogen to form a reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms;
ii) contacting reaction product a with a first halogenating/titanating agent to form reaction product B;
iii) contacting the reaction product B with a second halogenating/titanating agent to form a catalyst component;
wherein the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium tetrachloride to magnesium compound contained in step iii) is from about 0.1 to about 5.
16. The catalyst of claim 15 wherein the soluble dialkoxy magnesium compound is the reaction product of an alkyl magnesium of the formula MgRR 'wherein R and R' are alkyl groups containing from 1 to 10 carbon atoms, which may be the same or different, and an alcohol of the formula R "OH wherein R" is an alkyl group containing from 4 to 20 carbon atoms.
17. The catalyst of claim 16 wherein the soluble magnesium compound is magnesium bis (2-ethylhexyloxy).
18. The catalyst of claim 16 wherein the alkyl magnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium.
19. The catalyst of claim 16 wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.
20. The catalyst of claim 16 wherein the reaction further comprises an aluminum alkyl.
21. The catalyst of claim 20 wherein the aluminum alkyl is triethylaluminum.
22. The catalyst of claim 15 wherein the first chlorinating/titanating agent is a blend of two tetra-substituted titanium compounds, all four substituents being the same and the substituents being halide or alkoxy or phenoxy groups containing from 2 to 10 carbon atoms.
23. The catalyst of claim 22 wherein the first chlorinating/titanating agent is a blend of a titanium halide and an organotitanate.
24. The catalyst of claim 23 wherein said first chlorinating/titanating agent is TiCl4And Ti (OBu)4Of a blend of (1), TiCl4/Ti(OBu)4Is 0.5: 1-6: 1.
25. The catalyst of claim 16 wherein the reaction further comprises an electron donor.
26. The catalyst of claim 25 wherein the ratio of electron donor to magnesium is from 0: 1 to 10: 1.
27. The catalyst of claim 26 wherein the electron donor is an ether.
28. The catalyst of claim 15 wherein the halogenating agent has the formula ClAR'xWherein A is a non-reducing oxophilic compound, R' ″xIs a hydrocarbyl moiety containing 2 to 6 carbon atoms, and x is the valence of A minus 1.
29. The catalyst of claim 15 wherein the organoaluminum preactivating agent is of the formulaIs AlR ^3Wherein R is an alkyl group having 1 to 8 carbon atoms or a halide, R' may be the same or different, and at least one R is an alkyl group.
30. The catalyst of claim 29 wherein the organoaluminum preactivating agent is a trialkylaluminum.
31. The catalyst of claim 15 wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.
32. The catalyst of claim 15 having a fluff morphology suitable for a polymerization process which provides a polyethylene molecular weight distribution of at least 5.0, an activity of at least 6,000 grams of polyethylene per gram of catalyst, and a uniform particle size distribution and a minor amount of particles having a particle size of less than 125 microns.
33. A polymer characterized in that it is prepared by a process comprising the steps of:
a) contacting one or more α -olefin monomers with each other in the presence of said catalyst under polymerization conditions,
wherein the catalyst is prepared by a process comprising the steps of,
i) with halogenating agents and compounds of the formula Mg (OR')2Is capable of replacing an alkoxy group with a halogen to form a reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms;
ii) contacting reaction product a with a first halogenating/titanating agent to form reaction product B;
iii) contacting the reaction product B with a second halogenating/titanating agent to form a catalyst component;
wherein the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium tetrachloride to magnesium compound contained in step iii) is from about 0.1 to about 5.
34. The polymer of claim 33, wherein said catalyst is prepared by a process further comprising the steps of:
iv) contacting the catalyst component with an organoaluminum preactivating agent.
35. The polymer of claim 33, wherein said monomer is ethylene monomer
36. The polymer of claim 33 wherein said polymer is polyethylene.
37. The polymer of claim 33 wherein the soluble dialkoxy magnesium compound is the reaction product of an alkyl magnesium of the formula MgRR 'wherein R, R' is an alkyl group containing 1 to 10 carbon atoms, which may be the same or different, and an alcohol of the formula R "OH wherein R" is an alkyl group containing 4 to 20 carbon atoms.
38. The polymer of claim 37, wherein the soluble magnesium compound is bis (2-ethylhexyloxy) magnesium.
39. The polymer of claim 37 wherein the alkyl magnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium.
40. The polymer of claim 37, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, or 2-ethylhexanol.
41. The polymer of claim 37, wherein the reaction further comprises an aluminum alkyl.
42. The polymer of claim 41 wherein said aluminum alkyl is triethylaluminum.
43. The polymer of claim 37 wherein the first chlorinating/titanating agent is a blend of two tetra-substituted titanium compounds, all four substituents being the same and the substituents being halide or alkoxy or phenoxy groups containing from 2 to 10 carbon atoms.
44. The polymer of claim 43 wherein the first chlorinating/titanating agent is a blend of a titanium halide and an organotitanate.
45. The polymer of claim 44 wherein said first chlorinating/titanating agent is TiCl4And Ti (OBu)4Of a blend of (1), TiCl4/Ti(OBu)4Is 0.5: 1-6: 1.
46. The polymer of claim 37, wherein the reaction further comprises an electron donor.
47. The polymer of claim 46, wherein the ratio of electron donor to magnesium is from 0: 1 to 10: 1.
48. The polymer of claim 47, wherein said electron donor is an ether.
49. The polymer of claim 37, wherein the halogenating agent has the formula C1 AR' "xWherein A is a non-reducing oxophilic compound, R' ″xIs a hydrocarbyl moiety containing 2 to 6 carbon atoms, and x is the valence of A minus 1.
50. The polymer of claim 37, wherein the organoaluminum preactivating agent is of the formula AlR ^3Wherein R is an alkyl group having 1 to 8 carbon atoms or a halide, R' may be the same or different, and at least one R is an alkyl group.
51. The polymer of claim 50 wherein said organoaluminum preactivating agent is a trialkylaluminum.
52. The polymer of claim 15 wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.
53. A method of forming a catalyst component, characterized in that the method comprises:
a) with halogenating agents and compounds of the formula Mg (OR')2Is capable of replacing an alkoxy group with a halogen to form a reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms;
b) contacting reaction product a with a first halogenating/titanating agent to form reaction product B;
c) contacting reaction product B with a second halogenating/titanating agent to form a catalyst component;
wherein the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium tetrachloride to magnesium compound contained in step c) is from about 0.1 to about 5.
54. The method of claim 56, wherein the soluble dialkoxy magnesium compound is a reaction product obtained by reacting an alkyl magnesium of the formula MgRR ', wherein R and R' are alkyl groups containing 1 to 10 carbon atoms, which may be the same or different, with an alcohol of the formula R "OH, wherein R" is an alkyl group containing 4 to 20 carbon atoms.
55. The method of claim 54 wherein the soluble magnesium compound is magnesium bis (2-ethylhexoxide).
56. The method of claim 54 wherein the alkyl magnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium.
57. The method of claim 54, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, or 2-ethylhexanol.
58. The method of claim 54 wherein the reaction further comprises an aluminum alkyl.
59. The method of claim 54 wherein said aluminum alkyl is triethylaluminum.
60. The method of claim 53 wherein the first chlorinating/titanating agent is a blend of two tetrasubstituted titanium compounds, all four substituents being the same and the substituents being halide or alkoxy groups having from 2 to 10 carbon atoms or phenoxy groups.
61. The method of claim 60 wherein the first chlorinating/titanating agent is a blend of a titanium halide and an organotitanate.
62. The method of claim 61, wherein said first chlorinating/titanating agent is TiCl4And Ti (OBu)4Of a blend of (1), TiCl4/Ti(OBu)4Is 0.5: 1-6: 1.
63. A method for producing a catalyst, characterized by comprising:
a) contacting a catalyst component with an organoaluminum preactivating agent, wherein the catalyst component is prepared by a process comprising the steps of:
i) with halogenating agents and compounds of the formula Mg (OR')2Is capable of replacing an alkoxy group with a halogen to form a reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms;
ii) contacting reaction product a with a first halogenating/titanating agent to form reaction product B;
iii) contacting reaction product B with a second halogenating/titanating agent;
wherein the second halogenating/titanating agent comprises titanium tetrachloride and the ratio of titanium tetrachloride to magnesium compound contained in step iii) is from 0.1 to 5.
64. The method of claim 63 wherein the first chlorinating/titanating agent is a blend of two tetrasubstituted titanium compounds, all four substituents being the same and the substituents being halide or alkoxy groups having from 2 to 10 carbon atoms or phenoxy groups.
65. The method of claim 64 wherein the first chlorinating/titanating agent is a blend of a titanium halide and an organotitanate.
66. The method of claim 65, wherein said first chlorinating/titanating agent is TiCl4And Ti (OBu)4Of a blend of (1), TiCl4/Ti(OBu)4Is 0.5: 1-6: 1.
67. The method of claim 64 wherein the soluble dialkoxy magnesium compound is the reaction product of an alkyl magnesium of the formula MgRR ', wherein R and R' are alkyl groups containing 1 to 10 carbon atoms, which may be the same or different, and an alcohol of the formula R "OH, wherein R" is an alkyl group containing 4 to 20 carbon atoms.
68. The method of claim 67, wherein the soluble magnesium compound is magnesium bis (2-ethylhexoxide).
69. The method of claim 67, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium, or butylethyl magnesium.
70. The method of claim 67, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, or 2-ethylhexanol.
71. The method of claim 67, wherein the reaction further comprises an aluminum alkyl.
72. The method of claim 71 wherein said aluminum alkyl is triethylaluminum.
73. The method of claim 72, wherein the reaction further comprises an electron donor.
74. The method of claim 73, wherein the ratio of electron donor to magnesium is from 0: 1 to 10: 1.
75. The method of claim 74 wherein the electron donor is an ether.
76. The method of claim 63 wherein the halogenating agent has the formula ClAR'xWherein A is a non-reducing oxophilic compound, R' ″xIs a hydrocarbyl moiety containing 2 to 6 carbon atoms.
77. The method of claim 76 wherein the halogenating agent is TiCl/Ti (O)iPr)3The blend of (a).
78. The process of claim 63 wherein the organoaluminum preactivating agent is an aluminum alkyl.
79. The method of claim 63 wherein an electron donor is present in any of steps a), i), ii), or iii) wherein the ratio of electron donor to metal is from 0: 1 to 10: 1.
80.α -Process for the polymerization of olefins, characterized in that it comprises:
a) contacting one or more α -olefin monomers with each other in the presence of a catalyst under polymerization conditions;
wherein the catalyst is prepared by a method comprising the following steps:
i) with halogenating agents and compounds of the formula Mg (OR')2Is capable of replacing an alkoxy group with a halogen to form a reaction product a, wherein R "is a hydrocarbyl or substituted hydrocarbyl group containing 1 to 20 carbon atoms;
ii) contacting reaction product a with a first halogenating/titanating agent to form reaction product B;
iii) contacting reaction product B with a second halogenating/titanating agent to form reaction product C;
wherein the second halogenating/titanating agent comprises titanium tetrachloride and step iii) comprises a titanium tetrachloride to magnesium compound ratio of from 0.1 to 5.
81. The method of claim 80, further comprising:
b) the polyolefin polymer is discharged.
82. A method according to claim 81, wherein the polymer has a molecular weight distribution of at least 5.0.
83. The method of claim 82, wherein the polymer is polyethylene.
84. The method of claim 80, wherein the catalyst is prepared by a process further comprising the steps of:
iv) contacting the reaction product C with an organoaluminum preactivating agent.
85. The method of claim 80 wherein the first halogenating/titanating agent is a blend of two tetra-substituted titanium compounds, all four substituents being the same and the substituents being halide or alkoxy or phenoxy groups having from 2 to 10 carbon atoms.
86. The method of claim 84 wherein the first chlorinating/titanating agent is a blend of a titanium halide and an organotitanate.
87. The method of claim 86 wherein said first chlorinating/titanating agent is TiCl4And Ti (OBu)4Of a blend of (1), TiCl4/Ti(OBu)4Is 0.5: 1-6: 1.
88. The method of claim 80 wherein the halogenating agent of step i) is of the formula ClAR'xWherein A is a non-reducing oxophilic compound, R' ″xIs a hydrocarbyl moiety containing 2 to 6 carbon atoms.
89. The method of claim 88 wherein the halogenating agent is ClTi (O)iPr)3。
90. The process of claim 84 wherein the organoaluminum preactivating agent is triethylaluminum.
91. The method according to claim 84, wherein the electron donor is present in any of i) -iv) and the ratio of electron donor to metal is 0: 1 to 10: 1.
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