CN1856363A - Ziegler-natta catalyst for polyolefins - Google Patents

Ziegler-natta catalyst for polyolefins Download PDF

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CN1856363A
CN1856363A CNA2004800271807A CN200480027180A CN1856363A CN 1856363 A CN1856363 A CN 1856363A CN A2004800271807 A CNA2004800271807 A CN A2004800271807A CN 200480027180 A CN200480027180 A CN 200480027180A CN 1856363 A CN1856363 A CN 1856363A
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catalyst
product
halogenation
contacted
metatitanic acid
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CN100450620C (en
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D·W·克内佩尔
T·J·科菲
H·恩瑞克斯
S·格雷
K·维齐尼
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Fina Technology Inc
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Fina Technology Inc
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

A Ziegler-Natta type catalyst component can be produced by a process comprising contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A, and contacting reaction product A with a first, second and third halogenating/titanating agents. Catalyst components, catalysts, catalyst systems, polyolefin, products made therewith, and methods of forming each are disclosed. The reaction products can be washed with a hydrocarbon solvent to reduce titanium species [Ti] content to less than about 100 mmol/L.

Description

Be used for polyolefinic Ziegler-Natta catalyst
The cross reference of related application
The application be in being entitled as of submitting on October 13rd, 2000 " be used for Narrow Molecular Weight Distribution to the polyolefinic Ziegler-Natta catalyst of bread molecular weight distribution and preparation method thereof and using method; and polyolefin prepared therefrom (Ziegler-Natta Catalyst For Narrow to Broad MWD of Polyolefins; Method ofMaking; Method of Using; And Polyolefins Made Therewith) " the part continuation application of U.S. Patent application 09/687560, it is included in this by reference, patent application 09/687560 is in the part continuation application of the U.S. Patent application 08/789862 that is entitled as " Ziegler-Natta catalyst (Ziegler-NattaCatalysts for Olefin Polymerization) that is used for olefinic polymerization " of submission on January 28th, 1997, it is No. 6174971, United States Patent (USP) that U.S. Patent application 08/789862 was authorized January 16 calendar year 2001, and it also is included in this by reference.
Background of invention
Technical field
The present invention relates generally to catalyst, prepare the method for the method of catalyst, the method for using catalyst, polymerization and with the polymer of this type of Preparation of Catalyst.More particularly, the present invention relates to polyolefin catalyst and Z-N (Ziegler-Natta) catalyst, the method for preparing this type of catalyst, the method for using this type of catalyst, polyolefin polymerization and polyolefin.
Background technology
Alkene is also referred to as alkene, be contain in the molecule one or more pairs of by the unsaturated hydrocarbons of doubly linked carbon atom.When carrying out polymerization process, alkene can be converted into polyolefin, for example polyethylene and polypropylene.A kind of polymerization commonly used relates to olefinic monomer is contacted with the ziegler-natta type catalyst system.Many ziegler-natta type polyolefin catalysts, their general preparation method and being applied in the polymerization field subsequently are well-known.Usually, these systems comprise the ziegler-natta type polymerization catalyst component; Co-catalyst; With give electron compound.One class ziegler-natta type polymerization catalyst component can be that wherein said transition metal is titanium, chromium or vanadium for example derived from the halide of transition metal and the complex compound of metal hydride and/or metal alkyl, and metal alkyl is organo-aluminum compound normally.This catalytic component comprises the halogenated titanium on the magnesium compound of loading on the alkyl aluminum complexing usually.The many catalyst that mainly is designed to polypropylene and ethene and publication patents of catalyst system of relating to are arranged, and they are well known by persons skilled in the art.The example of this type of catalyst system is at United States Patent (USP) the 4th, 107, and 413,4,294,721,4,439,540,4,114,319,4,220,554,4,460,701,4,562,173,5,066,738 and 6,174, mention that it is by with reference to being included in this in No. 971.
Conventional Ziegler-Natta catalyst comprises the general formula M R that uses xThe transistion metal compound of expression, wherein M is a transistion metal compound, and R is halogen or hydrogen carboxyl, and x is the chemical valence of transition metal.Usually, M is selected from the metal of IV to VII family, and such as titanium, chromium or vanadium, R is chlorine, bromine or alkoxyl.Transistion metal compound commonly used is TiCl 4, TiBr 4, Ti (OC 2H 5) 3Cl, Ti (OC 3H 7) 2Cl 2, Ti (OC 6H 13) 2Cl 2, Ti (OC 2H 5) 2Br 2And Ti (OC 12H 25) Cl 3Transistion metal compound loads on the inert solid usually, for example, loads on the magnesium chloride.
Ziegler-Natta catalyst generally provides with the form that loads on the carrier, that is, be deposited on the solid crystal carrier.Carrier can be not with the inert solid of any component generation chemical reaction of the Ziegler-Natta catalyst of routine.Carrier is magnesium compound normally.Can be used to provide the example of the magnesium compound of support source to catalytic component is the carboxylate of magnesium halide, dialkoxy magnesium, halogenated alkoxy magnesium, zirconyl oxyhalides magnesium, dialkyl magnesium, magnesia, magnesium hydroxide and magnesium.
The character of polymerization catalyst can have influence on the character of the polymer that forms with this catalyst.For example, the form of polymer depends on catalyst form usually.Good polymer morphology comprises the homogeneous and the acceptable bulk density (bulk density) of particle diameter and shape.And, because a variety of causes for example, for fear of stopping up transmission or recirculating line, need farthest reduce the number of minimum polymer beads (that is fine grained (fines)).Very large particle also must reduce as much as possible, to avoid forming block and ropy in polymer reactor.
Another polymer property that influenced by the catalyst system therefor type is molecular weight distribution (MWD), shows the width that molecular length changes in the fixed fluoropolymer resin.For example, in polyethylene, the molecular weight distribution that narrows can improve toughness, promptly improves puncture, stretching and impact property.On the other hand, wider molecular weight distribution can make processing become easily and help melting intensity.
Although about Ziegler-Natta catalyst know a lot, still need continuous effort, at polymer output, catalyst life, catalyst activity and have in generation and make progress aspect the polyolefinic ability of special properties.
Summary of the invention
An embodiment of the invention provide a kind of method for preparing catalyst, and it comprises: the glycol magnesium compound is contacted with halogenating agent, form product A; B) product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B; C) product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C; And d) product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form product D.Second and the 3rd halogenation/metatitanic acid esterifying agent can comprise titanium tetrachloride.Second and the 3rd halogenation/metatitanic acid esterif iotacation step can respectively comprise titanium to the ratio of magnesium in the scope of about 0.1-5.Product A, B and C can each clean with varsol before halogenation/metatitanic acid esterif iotacation step subsequently.Product D can clean with varsol, up to titanium elements [Ti] content less than about 100 mMs/liter.
Another embodiment of the invention provides a kind of polyolefin catalyst, and this catalyst is made by the method that generally comprises following steps: catalytic component of the present invention is contacted with organometallic reagent.Catalytic component makes by said method.Catalyst of the present invention can have fine hair (fluff) form that adapts to polymerization production process, can make poly molecular weight distribution be at least 5.0, and provides homogeneous particle diameter to distribute, and is less less than about 125 microns particle.Activity of such catalysts depends on polymerizing condition.Usually activity of such catalysts is at least 5000 gram PE/ gram catalyst, but activity of such catalysts also can be greater than 50000 gram PE/ gram catalyst or greater than 100000 gram PE/ gram catalyst.
Another embodiment of the invention also provides a kind of polyolefin polymer for preparing by the method that may further comprise the steps: a) under polymerizing condition, one or more olefinic monomers are contacted in the presence of catalyst of the present invention; B) extract polyolefin polymer.In general, monomer is a vinyl monomer, and polymer is a polyolefin.
And another embodiment of the invention provides film, fiber, tubing, textile material or the manufactured goods that comprise by the polymer of the present invention's preparation.Manufactured goods can be to comprise the film of one deck at least, and this layer comprises the polymer by the method preparation that relates to catalyst of the present invention.
Another embodiment of the invention provides a kind of method for preparing catalyst, it comprises: by adding the viscosity of alkyl aluminum control catalyst synthetic solvent, change the precipitation of catalytic component from the catalyst synthetic solvent, wherein the average grain diameter of catalytic component increases along with the increase of alkyl aluminum concentration in the synthetic solvent.This method can further comprise contacts the pre-activator of catalytic component and organic metal, forms catalyst, and wherein the average grain diameter of catalyst increases with the increase of alkyl aluminum concentration in the synthetic solvent.
Another embodiment of the invention provides a kind of method for preparing catalyst, and it comprises: the glycol magnesium compound is contacted with halogenating agent, form product A; B) product A is contacted with first halogenation/metatitanic acid esterification (titanating) agent, form product B; C) product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C; D) product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form product D; And e) the pre-activator of product D and organic metal is contacted, form catalyst.The glycol magnesium compound is the product that comprises the reaction of following material: general formula is the alkyl magnesium compound of MgRR ＇, and wherein R and R ＇ are the alkyl with 1-10 carbon atom, and R and R ＇ can be identical or different; General formula is R " alcohol of OH, wherein, alcohol is straight or branched, R " is the alkyl with 2-20 carbon atom; General formula is AlR  3Alkyl aluminum, wherein at least one R  is alkyl or the alkoxy or halogen with 1-8 carbon atom, wherein each R  can be identical or different.The average grain diameter of catalyst along with alkyl aluminum to the increase of the ratio of alkyl magnesium and increase.
Second and the 3rd halogenation/metatitanic acid esterifying agent can comprise titanium tetrachloride.Second and the 3rd halogenation/metatitanic acid esterif iotacation step can respectively comprise titanium to the ratio of magnesium in the scope of about 0.1-5.Product A, B and C can clean with varsol before halogenation/metatitanic acid esterif iotacation step subsequently.Product D can clean with varsol, up to titanium elements [Ti] content less than about 100 mMs/liter.
Also provide a kind of polyolefin polymer in the another embodiment of the invention: a) under polymerizing condition, one or more olefinic monomers are contacted in the presence of catalyst of the present invention by a kind of method preparation that may further comprise the steps; And b) extracts polyolefin polymer.The average grain diameter of polymer along with used alkyl aluminum in the Preparation of Catalyst to the increase of the ratio of alkyl magnesium and increase.In general, monomer is a vinyl monomer, and polymer is a polyethylene.
And another embodiment of the invention provides film, fiber, tubing, textile material or the manufactured goods that comprise by the polymer of the present invention's preparation.Manufactured goods can be to comprise the film of one deck at least, and this layer comprises the polymer by the present invention's preparation.
Other embodiment comprises that a kind of formation is used in the method for the catalyst in the olefinic polymerization.This method comprises makes chlorinating agent and the reaction of pure magnesium compound, forms magnesium-titanium-pure salt adduct, makes the reaction of magnesium-titanium-pure salt adduct and alkyl chloride compound, forms magnesium chloride support.Make carrier and titanium tetrachloride (TiCl then 4) reaction, be formed for generating polyolefinic high activated catalyst.
In an embodiment of the invention, at first butyl ethyl magnesium (BEM) and alcohol reaction are formed pure magnesium compound, wherein alcohol generally represents that with general formula R OH R is the alkyl that contains for example about 1-20 carbon atom.Then pure magnesium compound is combined with chlorinating agent, wherein chlorinating agent is generally used general formula TiCl n(OR ＇) 4-nExpression, wherein, R ＇ is alkyl, cycloalkyl or aryl, n is 1-3.The result that the alcohol magnesium compound mixes with chlorinating agent forms magnesium-titanium-pure salt adduct.
With alkyl chloride compound and magnesium-titanium-pure salt adduct reaction, form magnesium chloride (MgCl 2) carrier and one or more accessory substances such as ether and/or alcohol.Subsequently, use TiCl 4Handle MgCl 2, form and load on MgCl 2On Ziegler-Natta catalyst.Use the polyolefin of this Preparation of Catalyst to have Narrow Molecular Weight Distribution, thereby can form terminal articles for use as barrier film, fiber and tubing and so on.
Description of drawings
Fig. 1 illustrated with Preparation of Catalyst of the present invention polymer (embodiment 1) and with the settling efficiency curve of the polymer (Comparative Examples 4) of conventional Preparation of Catalyst.
The particle diameter that Fig. 2 has described the catalyst described in Comparative Examples 1A-2A and the embodiment 1A-2A distributes.
The particle diameter that Fig. 3 has described the catalyst described in Comparative Examples 1A-2A and the embodiment 4A distributes.
Fig. 4 has described among the embodiment 4A-10A catalyst yield as the function of PhCOCl consumption.
The particle diameter that Fig. 5-6 has described the catalyst that forms among the embodiment 4A-10A distributes.
Fig. 7 has described among the embodiment 4A-10A average catalyst particle diameter (D as the function of PhCOCl consumption 50).
The particle diameter that Fig. 8 has described the catalyst described in Comparative Examples 1A-2A and embodiment 4A and the 11A distributes.
Fig. 9 has described the fine hair shape particle grain size distribution of the fluoropolymer resin described in Comparative Examples 3A-4A and the embodiment 12A.
Figure 10 has described the fine hair shape particle grain size distribution of the fluoropolymer resin described in Comparative Examples 3A-4A and the embodiment 13A.
The particle diameter that Figure 11 has described the catalyst described in the embodiment 14A distributes.
The particle diameter that Figure 12 has described the catalyst described in the embodiment 15A distributes.
The specific embodiment
According to an embodiment of the invention, the method for preparing catalytic component generally comprises following steps: form metal two alkoxide by metal diaikyl and alcohol, metal halide two alkoxide form product, three the step or more in the multistep product is contacted with one or more halogenations/metatitanic acid esterifying agent, form catalytic component, use pre-Treatment with activating agent catalytic component then as organo-aluminium and so on.
An embodiment of the invention are generally as follows:
1.
2.
3.
4. ；
5.
6.
In above-mentioned general formula, M can generally be an IIA family metal for any suitable metal, is generally Mg.In above-mentioned general formula, " independent separately is the hydrocarbyl portion of alkyl or replacement, and R and R ＇ have 1-20 carbon atom, are generally 1-10 carbon atom, are generally 2-6 carbon atom, can have 2-4 carbon atom for R, R ＇, R ", R  and R "." generally comprise 3-20 carbon atom, R  generally comprises 2-6 carbon atom to R, and R " " generally comprises 2-6 carbon atom and is generally butyl.Also can use R, R ＇, R ", R  and R " " in two or more any combinations, the combination of R group can be identical or different.
At the above-mentioned general formula ClAR  that relates to xEmbodiment in, A can make a chlorine and alkoxyl that the irreducibility oxyphie compound of exchange takes place, R  is the alkyl of alkyl or replacement, x is that the chemical valence of A subtracts 1.The example of A comprises titanium, silicon, aluminium, carbon, tin and germanium, normally titanium or silicon, and x is 3.The example of R  comprises methyl, ethyl, propyl group, isopropyl and has alkyl of 2-6 carbon atom etc.The non-limitative example of available chlorinating agent in the present invention is ClTi (O iPr) 3And ClSi (Me) 3
Metal two alkoxide in the above-mentioned embodiment are chlorinated, and form product " A ".Though the definite composition of product " A " is unknown, believe that it contains the metallic compound of part chlorination, an example can be ClMg (OR ").
Product " A " is contacted with one or more halogenations/metatitanic acid esterifying agent, form product " B ", the example of wherein halogenation/metatitanic acid esterifying agent is TiCl 4And Ti (OBu) 4Combination.Product " B " can be chlorination with the metal of part chlorination and the complex compound of titanium compound.Product " B " can comprise the MgCl of titanium dipping 2Carrier for example, is used as (MCl 2) y(TiCl x(OR) 4-x) zAnd so on compound represent.Product " B " can be used as solid and is precipitated out from catalyst pulp.
Second halogenation/metatitanic acid esterif iotacation step produces product or catalytic component, and " C " also can be complex compound halogenation or partially halogenated metal and titanium compound, but is different from " B ", available (MCl 2) y(TiCl X ＇(OR) 4-x ＇) Z ＇Expression.Wish that the halogenation degree of " C " surpasses the halogenation degree of product " B ".The bigger complex compound that can produce different compounds of halogenation degree.
The 3rd halogenation/metatitanic acid esterif iotacation step produces product or catalytic component, and " D " also can be complex compound halogenation or partially halogenated metal and titanium compound, but is different from " B " and " C ", can use (MCl 2) y(TiCl X "(OR) 4-x ") Z "Expression.Wish that the halogenation degree of " D " surpasses the halogenation degree of product " C ".Halogenation degree more conference produces the complex compound of different compounds.Though provided chemically most possible explanation in this explanation to product, the present invention as claimed in claim is not subject to this theoretical mechanism.
Metal two alkoxide that are applicable to metal diaikyl of the present invention and gained can comprise any can be with the material that produces suitable polyolefin catalyst in the present invention.These metal two alkoxide and metal diaikyl can comprise two alkoxide and the dialkyl group thing of IIA family metal.Metal two alkoxide or metal diaikyl can be magnesium two alkoxide or dialkyl magnesium.The non-limitative example of suitable dialkyl magnesium comprises magnesium ethide, dipropyl magnesium, dibutylmagnesium, butyl ethyl magnesium etc.Butyl ethyl magnesium (BEM) is a kind of suitable dialkyl magnesium.
In the embodiment of this invention, metal two alkoxide can be that general formula is Mg (OR ") 2The compound of magnesium, wherein, R " is to have the alkyl of 1-20 carbon atom or the alkyl of replacement.
Metal two alkoxide can be soluble, normally irreducibility.The irreducibility compound has formation MgCl 2But not the advantage of insoluble material, insoluble material can form by the reduction as the compound of MgRR ＇ and so on, can cause forming having the catalyst that wide particle diameter distributes.In addition, be lower than the Mg (OR ") of MgRR ＇ when activity 2Use is carried out chlorination, when carrying out in the reaction of halogenation/metatitanic acid esterif iotacation step subsequently, can be obtained the more product of homogeneous relating to gentle chlorinating agent, for example, catalyst particle size is better controlled and distributed.
The non-limitative example of spendable metal two alkoxide comprises that butanols magnesium, amylalcohol magnesium, hexanol magnesium, two (2-ethyl hexyl oxy) magnesium and any being applicable to make the soluble alkoxide of system.
As non-limitative example, two alkoxide of magnesium such as two (2-ethyl hexyl oxy) magnesium, can make by alkyl magnesium compound as follows (MgRR ＇) and alcohol (ROH) reaction.
This reaction can at room temperature be carried out, and reactant forms solution.R and R ＇ can be respectively for having any alkyl of 1-10 carbon atom, and R and R ＇ can be identical or different.Suitable MgRR ＇ compound comprises, for example, and magnesium ethide, dipropyl magnesium, dibutylmagnesium and butyl ethyl magnesium.MgRR ＇ compound can be BEM, and wherein RH and R ＇ H are respectively butane and ethane.
In the embodiment of this invention, can use any alcohol that can generate required metal two alkoxide.In general, the alcohol that uses can be that any general formula is R, and " alcohol of OH, wherein, " be the alkyl with 2-20 carbon atom, carbon number can be at least 3, at least 4, at least 5 or at least 6 to R.The non-limitative example of suitable alcohol comprises ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, 2-methyl anyl alcohol, 2-Ethylhexyl Alcohol etc.Believe that nearly all alcohol can use, can use straight or branched, senior branched-chain alcoho, for example 2-ethyl-1-hexanol.
The addition of alcohol can change, for example in a non-exclusionism scope 0-10 equivalent, generally at about 0.5 equivalent (equivalent is with respect to magnesium or metallic compound in the literary composition) to the scope of about 6 equivalents, can be at about 1 equivalent to the scope of about 3 equivalents.
Metal alkyl compound can produce HMW, at the very big material of solution medium viscosity.Can reduce viscosity by the alkyl aluminum that adds as triethyl aluminum (TEAl) and so in reaction, alkyl aluminum can be blocked the association between each metal alkyl molecule.The ratio of alkyl aluminum metal can be 0.01: 1 to 0.5: 1 in 0.001: 1 to 1: 1 scope usually, also can be in 0.03: 1 to 0.2: 1 scope.In addition, can use electron donor (for example, isoamyl ether (DIAE)) further to reduce the viscosity of metal alkyl as ether and so on.Electron donor to the ratio of metal usually in 0: 1 to 10: 1 scope, can be in 0.1: 1 to 1: 1 scope.
The reagent that is used in the step of metal halide alkoxide comprises any halogenating agent that can produce suitable polyolefin catalyst when using in the present invention.Halogenation step can be a chlorinating step, and this moment, halogenating agent contained chlorine (that is, being chlorinating agent).
The halogenation of metallic alkoxide compound is usually in varsol, carry out under inert atmosphere.The non-limitative example of suitable solvent comprises toluene, heptane, hexane, octane etc.In this halogenation step, metal alkoxide to the mol ratio of halogenating agent generally about 6: 1 to about 1: 3 scope, can about 3: 1 to about 1: 2 scope, can about 2: 1 to about 1: 2 scope, also can be about 1: 1.
Halogenation step is generally carried out under about 0 ℃ of temperature to about 100 ℃ of scopes, and the reaction time is in about 0.5 hour to 24 hours scope.Halogenation step can be carried out under about 20 ℃ of temperature to about 90 ℃ of scopes, and the reaction time can be at about 1 hour to about 4 hours scope.
Carried out halogenation step and metal alkoxide by halogenation after, can carry out twice or more times halogenation/metatitanic acid esterification treatment halogenated products " A ".
Halogenation/metatitanic acid the esterifying agent that uses can be two kind of four mixture that replaces titanium compound, and four all four substituting groups that replace in the titanium compound all are identical, and substituting group is halogen or alkoxyl or the phenoxy group with 2-10 carbon atom, such as TiCl 4Or Ti (OR " ") 4Halogenation/metatitanic acid the esterifying agent that uses can be chlorination/metatitanic acid esterifying agent.
Halogenation/metatitanic acid esterifying agent can be single compound or combination of compounds.The inventive method provides a kind of active catalyst after first halogenation/metatitanic acid esterification; But, wish to carry out altogether at least three halogenations/metatitanic acid esterif iotacation step.
The metatitanic acid esterifying agent that first halogenation/metatitanic acid esterifying agent is normally gentle, it can be the mixture of halogenated titanium and organic titanate.First halogenation/metatitanic acid esterifying agent can be TiCl 4And Ti (OBu) 4Mixture, TiCl wherein 4/ Ti (OBu) 4In 0.5: 1 to 6: 1 scope, this ratio also can be 2: 1 to 3: 1.The mixture reaction that it is believed that halogenated titanium and organic titanate forms alkoxyl halogenated titanium, Ti (OR) aX b, wherein, OR and X are respectively alkoxyl and halogen, a+b is the chemical valence of titanium, is generally 4.
Perhaps, first halogenation/metatitanic acid esterifying agent can be single compound.The example of first halogenation/metatitanic acid esterifying agent is Ti (OC 2H 5) 3Cl, Ti (OC 2H 5) 2Cl 2, Ti (OC 3H 7) 2Cl 2, Ti (OC 3H 7) 3Cl, Ti (OC 4H 9) Cl 3, Ti (OC 6H 13) 2Cl 2, Ti (OC 2H 5) 2Br 2And Ti (OC 12H 5) Cl 3
As the step 1 of first halogenation/metatitanic acid esterification by at first under room temperature/environment temperature, making halogenated products " A " in varsol, become the mud state to carry out.The non-limitative example of suitable varsol comprises heptane, hexane, toluene, octane etc.Product " A " is partly soluble at least in varsol.
Add halogenation/metatitanic acid esterifying agent in soluble product " A " after, solid product " B " at room temperature precipitates.The use amount of halogenation/metatitanic acid esterifying agent must be enough to solid product is precipitated from solution.In general, be benchmark in titanium to the ratio of metal, the use amount of halogenation/metatitanic acid esterifying agent is generally about 0.5 to about 5 scope, usually about 1 to about 4 scope, can be to about 2.5 scope about 1.5.
Reclaim precipitated solid product " B " in first halogenation/metatitanic acid esterif iotacation step with suitable recovery technology then, under room temperature/environment temperature, clean then with solvent as hexane and so on.In general, " B " cleans to solid product, up to [Ti] less than about 100 mMs/liter.In the present invention, [Ti] expression can comprise the titanium class of a part that is not product described in the literary composition as any titanium class of second generation Ziegler-Natta catalyst.Then the product " B " of gained is carried out second and the 3rd halogenation/metatitanic acid esterif iotacation step, generate product " C " and " D ".After each halogenation/metatitanic acid esterif iotacation step, can clean solid product, up to [Ti] less than the amount that requires.For example, less than about 100 mMs/liter, less than about 50 mMs/liter, or less than about 10 mMs/liter.After halogenation the last time/metatitanic acid esterif iotacation step, can clean product, up to [Ti] less than the amount that requires.For example, less than about 20 mMs/liter, less than about 10 mMs/liter, or less than about 1.0 mMs/liter.It is believed that lower [Ti] can generate improved catalyst, makes it can be used as second generation Ziegler catalyst material owing to reduced the amount of titanium.It is believed that lower [Ti] is a factor that generates improved catalyst, for example makes catalyst have Narrow Molecular Weight Distribution.
As the step 1 of second halogenation/metatitanic acid esterification by making the solid product, the solid product " B " that from the first metatitanic acid esterif iotacation step, reclaim in varsol, become the mud state to carry out.Can use the varsol that is applicable in first halogenation/metatitanic acid esterif iotacation step.Second with the 3rd halogenation/metatitanic acid esterif iotacation step can use with first halogenation/metatitanic acid esterif iotacation step in different compound or combination of compounds.Second with the 3rd halogenation/metatitanic acid esterif iotacation step can use with first halogenation/metatitanic acid esterif iotacation step in identical but reagent that concentration is higher, but this not necessarily.Second and the 3rd halogenation/metatitanic acid esterifying agent can be halogenated titanium, such as titanium tetrachloride (TiCl 4).Halogenation/metatitanic acid esterifying agent is joined in the slurry.Reinforced can under environment temperature/room temperature, carrying out, but also can under the temperature and pressure different, carry out with environmental condition.
In general, second and the 3rd halogenation/metatitanic acid esterifying agent comprise titanium tetrachloride.Common second and the 3rd halogenation/metatitanic acid esterif iotacation step respectively comprise titanium to the ratio of magnesium in about scope of 0.1 to 5, ratio also can be about 2.0, ratio can be about 1.0.As the 3rd halogenation/metatitanic acid esterification step 1 at room temperature, in slurry, carry out, but also can carry out being different under the temperature and pressure of environmental condition.
The amount of the amount of employed titanium tetrachloride or other halogenation/metatitanic acid esterifying agent can represent that also equivalent is the amount with respect to the titanium of magnesium or metallic compound with equivalent here.Second and the 3rd halogenation/metatitanic acid esterif iotacation step in the amount of titanium general respectively about 0.1 to the scope of about 5.0 equivalents, can be to the scope of about 4 equivalents about 0.25, normally about 0.3 to the scope of about 3 equivalents, hope be about 0.4 to the scope of about 2.0 equivalents.In a specific embodiment, use second and the 3rd halogenation/metatitanic acid esterif iotacation step in titanium tetrachloride amount respectively about 0.45 to the scope of about 1.5 equivalents.
Catalytic component " D " by method for preparing can make up with organometallic catalyst component (a kind of " pre-activator "), forms the pre-activated catalyst system that is applicable to olefinic polymerization.Usually, the pre-activator that uses with the catalytic component that contains transition metal " D " is an organo-metallic compound, such as alkyl aluminum, alkyl aluminium hydride, alkyl aluminum lithium, zinc alkyl, alkyl magnesium etc.
Pre-activator is organo-aluminum compound normally.The pre-activator of organo-aluminium normally general formula is AlR 3Alkyl aluminum, wherein, at least one R is alkyl or the halogen with 1-8 carbon atom, each R can be identical or different.The pre-activator of organo-aluminium can be a trialkylaluminium, for example, and trimethyl aluminium (TMA), triethyl aluminum (TEAl) and triisobutyl aluminium (TiBAl).Aluminium to the ratio of titanium in about 0.1: 1 to 2: 1 scope, normally 0.25: 1 to 1.2: 1.
Randomly, Ziegler-Natta catalyst can be prepolymerized.In general, the prepolymerization process process by at catalyst with after co-catalyst contacts, small amounts of monomer contacted with catalyst and work.The prepolymerization process process prescription is at United States Patent (USP) the 5th, 106, and 804,5,153,158 and 5,594, in No. 071, it is by with reference to being included in this.
Catalyst of the present invention can be used on any method that is used for the alpha-olefin of homopolymerization or copolymerization any kind.For example, catalyst of the present invention can be used for catalyzed ethylene, propylene, butylene, amylene, hexene, 4-methylpentene and other the alpha-olefin that has two carbon atoms at least, and their mixture.Above-mentioned copolymer can produce required result, and for example, the MWD of broad and multimodal distribute, such as bimodal and three peak character.Catalyst of the present invention can be used for polymerising ethylene and produces polyethylene.
The present invention can use various polymerization techniques, for example, and list and/or multiloop technology, the batch technology that does not relate to the loop type reactor or continuous processing.The example that can be used to carry out multiloop technology of the present invention is the double loop system, wherein, polymerisation is carried out in first loop, the polyolefin of gained has lower MW than the polyolefin that second loop polymerization reactions is produced in this loop, thereby makes the gained resin have wider molecular weight distribution and/or have bimodality.Perhaps, another example that can be used to carry out multiloop technology of the present invention is the double loop system, wherein polymerisation is carried out in first loop, the polyolefin of gained has higher MW than the polyolefin that second loop polymerization reactions is produced in this loop, thereby makes the gained resin have wider molecular weight distribution and/or bimodality.
Polymerization process can be, for example, body phase, slurry are mutually or gas-phase polymerization.Catalyst of the present invention can be used in the slurry phase-polymerization.Polymerizing condition (for example, temperature and pressure) depends on the type of employed equipment in the polymerization process and the type of the polymerization technique that adopted, and these conditions are well known in the art.In general, temperature is in about 50-110 ℃ scope, and pressure is in the scope of about 10-800psi.
The activity of such catalysts of embodiment of the present invention gained depends on polymerization and condition to small part, for example, and the temperature of employed equipment and reaction.For example, produce in the poly by way of example at polymerising ethylene, general activity of such catalysts is at least 5000 gram PE/ gram catalyst, but activity also can surpass 50000 gram PE/ gram catalyst, and activity can surpass 100000 gram PE/ gram catalyst.
In addition, the catalyst of gained of the present invention can make the fine hair form of polymer be improved.Thereby catalyst of the present invention can obtain the big polymer beads of even size distribution, and tiny particle (less than about 125 microns) only exists with low concentration, for example, and less than 2% or less than 1%.Catalyst of the present invention comprises the powder that has the big of high powder accumulation density and be easy to shift, and this catalyst is to adapt to polymerization production process.In general, catalyst of the present invention reduces the granule in the polymer, and bulk density (B.D.) increases, and wherein, the B.D. value is greater than about 0.31 gram/cubic centimetre, can be greater than about 0.33 gram/cubic centimetre, even can be greater than about 0.35 gram/cubic centimetre.
Olefinic monomer can join in dilution in the polymerization zone, and described dilution is nonactive heat exchanging agent, and it is a liquid under reaction condition.The example of this type of diluent is hexane and iso-butane.For the copolyreaction of ethene and another kind of alpha-olefin such as butylene or hexene, the amount of second alpha-olefin can be 0.01-20 mole %, can be between about 0.02-10 mole %.
Randomly, electron donor can add with halogenating agent, first halogenation/metatitanic acid esterifying agent or halogenation subsequently/metatitanic acid esterifying agent.In second halogenation/metatitanic acid esterif iotacation step, wish to use electron donor.The electron donor that is used in the preparation polyolefin catalyst is well-known, can use any suitable electron donor that can produce appropriate catalyst in the present invention.Electron donor is also referred to as Louis (Lewis) alkali, is the organic compound that oxygen, nitrogen, phosphorus or the sulphur of duplet can be provided to catalyst.
Electron donor can be simple function or polyfunctional compound, can be selected from aliphatic series or aromatic carboxylic acid and their Arrcostab, aliphatic ether or cyclic ethers, ketone, vinyl esters, acryloyl group derivative (particularly alkyl acrylate or alkyl methacrylate) and silane.The example of suitable electron donor is a n-butyl phthalate.One class example of suitable electron donor is that general formula is RSi (OR ＇) 3Alkyl silicyl alkoxide, for example, methyl silicane base three ethylates [MeSi (OEt 3)], wherein, R and R ＇ are the alkyl with 1-5 carbon atom, R and R ＇ can be identical or different.
For polymerization process, interior electron donor can be used for the synthetic of catalyst, and external electronic donor or stereoselectivity controlling agent (SCA) activating catalyst when being used in polymerisation.Interior electron donor can be used in halogenation or halogenation/metatitanic acid esterif iotacation step in the formation reaction of catalyst.The compound that electron donor is used to prepare conventional support type Ziegler-Natta catalyst component in being suitable as comprises ether, diether, ketone, lactone, the electronic donor compound capable with N, P and/or S atom and the ester of special defects.Specially suitablely be: the ester of phthalic acid, such as diisobutyl phthalate, dioctyl phthalate, diphenyl phthalate and phthalic acid benzyl butyl ester; The ester of malonic acid is such as malonic acid diisobutyl ester and diethyl malonate; New pentane acid alkyl ester and neopentanoic acid aryl ester; Maleic acid Arrcostab, maleic acid cycloalkyl ester and maleic acid aryl ester; Alkyl carbonate and aryl carbonates, such as, carbonic acid diisobutyl ester, carbonic acid ethyl phenyl ester and diphenyl carbonate; Succinate is such as single-ethyl succinate and diethyl succinate.
The external electronic donor that can be used in the preparation catalyst of the present invention includes organic silicon compound, is SiR such as general formula m(OR ＇) 4-mAlkoxy silane, wherein R is selected from alkyl, cycloalkyl, aryl and vinyl; R ＇ is an alkyl; M is 0-3, and R and R ＇ can be identical; When m is 0,1 or 2 o'clock, R ＇ group can be identical or different; When m was 2 or 3, the R group can be identical or different.
The optional self-drifting of external electronic donor of the present invention is:
Figure A20048002718000221
Silane compound, wherein, R 1And R 4All be contain link to each other with silicon primary, the alkyl or cycloalkyl of the second month in a season or tertiary carbon atom, R 1And R 4Identical or different; R 2And R 3It is alkyl or aryl.R 1Can be methyl, isopropyl, cyclopenta, cyclohexyl or the tert-butyl group; R 2And R 3Can be methyl, ethyl, propyl group or butyl, and not need identical; R 4Also can be methyl, isopropyl, cyclopenta, cyclohexyl or the tert-butyl group.Concrete external electronic donor is cyclohexyl methyl dimethoxy silane (CMDS), diisopropyl dimethoxy silane (DIDS), cyclohexyl isopropyl dimethoxy silane (CIDS), dicyclopentyl dimethoxyl silane (CPDS) or di-t-butyl dimethoxy silane (DTDS).
Use the poly MWD of above-mentioned Preparation of Catalyst to be at least 5.0, can be greater than about 6.0.
Polyolefin of the present invention is suitable for use in the various application, for example, is used in the extrusion, produces the product of wide range.These extrusions comprise, for example, blown film is extruded, casting film is extruded, the slit band shape is extruded, blowing, tubing is extruded and foaming plate is extruded.These technologies can comprise that individual layer is extruded or be multi-layer co-extruded.
The terminal articles for use that can use the present invention to make comprise, for example, and film, fiber, tubing, textile material, manufactured goods, diaper composition, feminine hygiene articles, automobile component and medical material.
All lists of references of being quoted in the literary composition comprise research paper, and all U.S. and other national patent and patent application are included in this one by one and intactly by reference.
First group of embodiment
The present invention has been carried out general description, following embodiment shows its enforcement and advantage just for some embodiment of the present invention is described.The mode by exemplary illustration that should be understood that provides embodiment, and embodiment is not intended to limit by any way the scope of specification of the present invention or claim.
The synthetic schemes following (all ratios are with respect to BEM) that is used for synthetic this type of catalyst:
Think that best prescription is X=0.5 to 2, before pre-activated catalyst C, clean 0-2 time with TEAl.In order to make the metatitanic acid esterification more effective, carried out following improvement for Preparation of Catalyst:
As implied above, TiCl 4Feed in raw material and in two steps, finish wherein X and Y=0.5-1.0.Catalyst C generally cleans once or twice, and twice cleaning simultaneously finished after Y, to shift out the soluble titanium class as second generation Ziegler catalyst class.
Embodiment 1:
In the case that a purging with nitrogen gas is crossed, 1412.25 gram (2.00 moles) BEM-1,27.60 gram (0.060 mole) TEAl (in heptane, concentration is 24.8%) and 189.70 gram (1.20 moles) DIAE are joined in 3 liters of round-bottomed flasks.Then vial is flowed down at nitrogen by sleeve pipe and transfer in 20 liters of Buchi reactors.Then with flask with about 400 milliliters of hexane wash, cleaning solution is transferred in the reactor.The speed setting of agitator is at 350rpm.
In 1 litre flask, add 2-Ethylhexyl Alcohol (543.60 gram, 4.21 moles) and add a cover.Before then in joining reactor, be diluted to volume with hexane and be 1 liter altogether.The service property (quality) flow controller is transferred to this solution in the reactor by sleeve pipe.The original top temperature is 25.3 ℃, and the maximum temperature that reaches is 29.6 ℃.After reinforced (about 2 hours), with 400 milliliters of hexane wash bottles, cleaning solution is transferred in the reactor.Reactant mixture is 350rpm at rotating speed, is to stir and spend the night under the condition of 0.5 crust at nitrogen pressure, close heat exchanger.
Start heat exchanger, and be set at 25 ℃.In 21 litre flasks, add chlorination three isopropyl titanates (774.99 and 775.01 grams, totally 2.00 moles), obtain two liters material altogether.The service property (quality) flow controller by sleeve pipe with the substance transfer in each bottle in reactor.The temperature of initial head space (head space) is 24.6 ℃, and temperature is up to 25.9 ℃ in the reinforced process of second bottle.For bottle 1 and bottle 2, the reinforced time was respectively 145 minutes and 125 minutes.Behind reinforced the end, with 200 milliliters of hexanes each bottle is washed, cleaning solution is transferred in the reactor.Reactant mixture is that 350rmp and nitrogen pressure are to stir under 0.5 condition of clinging to spend the night at rotating speed.Close heat exchanger.
TiCl 4/ Ti (OBu) 4Preparation
Use standard schlenk systems technology prepares the mixture of titanium tetrachloride/four butanols titaniums in 5 liters of round-bottomed flasks.In 1 liter of pressure bottle, restrain (1.99 moles) Ti (OBu) with 680.00 with hexane 4Being diluted to cumulative volume is 1 liter.This solution is transferred in the reactor by sleeve pipe then.With 200 milliliters of hexane wash bottles, cleaning solution is transferred in the reactor.In 1 liter of graduated cylinder, with hexane with 440 milliliters of (～760 gram, 4.00 moles) TiCl 4Being diluted to cumulative volume is 1 liter.Solution in 5 liters of flasks is stirred, at N 2Under the pressure, by sleeve pipe with TiCl 4Drips of solution is added in the reactor.Behind reinforced the end, with 200 milliliters of hexane wash 1L graduated cylinders, cleaning solution is transferred in the reactor.After 1 hour, with hexane reactant mixture being diluted to cumulative volume is 4L, and is stored in the flask, up to use.
Start heat exchanger, and be set at 25 ℃.By sleeve pipe and mass flow controller with TiCl 4/ Ti (OBu) 4Mixture is transferred in 20 liters of reactors.Initial head space temperature is 24.7 ℃, and in 225 minutes reinforced processes, temperature is up to 26.0 ℃.After reinforced,, and it was stirred 1 hour with 1 liter of hexane wash vessel.
Close agitator, and made the solution sedimentation 30 minutes.By reactor being pressurized to 1 crust, reduce dip-tube, the solution decant is come out, and guarantee not have the lucite pipe of solid catalyst by connecting.According to following steps catalyst is cleaned 3 times then.Use the pressure vessel of poised state, take by weighing 2.7 kilograms of hexanes in container, transfer in the reactor then.Start agitator, catalyst mixture was stirred 15 minutes.Close agitator then, made the mixture sedimentation 30 minutes.Repeat this step.After adding hexane for the third time, the slurry sedimentation is spent the night, close heat exchanger.
Decant goes out supernatant liquor, adds 2.0 kilograms of hexanes in reactor.Stirring restarts, and rotating speed is 350rpm, starts heat exchanger, and is set at 25 ℃.In one 1 liter graduated cylinder, add 440 milliliters of (760 grams, 4.00 moles) titanium tetrachlorides.With hexane with TiCl 4Be diluted to 1 liter, half solution is transferred in the reactor by sleeve pipe and mass flow controller.In reinforced process, the original top temperature has raise 0.5 ℃ for 24.7 ℃.Totally 45 minutes reinforced time.After 1 hour, close agitator, made the solid sedimentation 30 minutes.Decant goes out supernatant liquor, according to above-mentioned steps with the hexane cleaning catalyst once.After cleaning is finished, 2.0 kilograms of hexanes are transferred in the reactor, restart to stir.According to using 500 remaining ml solns to finish TiCl with the similar mode of aforesaid way 4The second time reinforced.After reinforced, with 400 milliliters of hexane wash graduated cylinders, cleaning solution joins in the Buchi reactor.After reaction 1 hour, close agitator, made the solid sedimentation 30 minutes.Decant goes out supernatant liquor then, with hexane catalyst is cleaned three times.Then 2.0 kilograms of hexanes are transferred in the reactor.
In one 1 liter pressure bottle, add 144.8 gram (312 mM) TEAl (in hexane, concentration is 25.2%).Add a cover for this bottle, and be diluted to 1 liter with hexane.The service property (quality) flow controller is transferred to this solution in the reactant mixture by sleeve pipe then.In 120 minutes reinforced process, the color transition of slurry is a dark-brown.Initial head temperature is 24.5 ℃, and maximum temperature reaches 25.3 ℃.After reinforced, with 400 milliliters of hexane wash bottles, cleaning solution is transferred in the reactor.After reaction 1 hour, close agitator, made catalyst sedimentation 30 minutes.Decant goes out supernatant liquor, according to above-mentioned steps catalyst is cleaned once then.After cleaning, in reactor, add 2.7 kilograms of hexanes.Then with in gallon pressure bottle of the substance transfer to three in the reactor.With 1.0 kilograms and 0.5 kilogram of hexane wash Buchi reactor, cleaning solution joins in the pressure bottle.Estimated catalyst output is 322 grams.
In one embodiment, the percetage by weight of composition is: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti7.9%.For the observed scope of each element be: Cl 48.6-55.1%; Al 2.3-2.5%; Mg 11.8-14.1%; Ti 6.9-8.7%.The scope of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti 2.0-14.0%.
Table 1 has been enumerated and has been added TiCl 4/ Ti (OBu) 4, clean, add for the first time TiCl for three times 4, once clean and add TiCl for the second time 4And after three cleanings subsequently, to [Ti] of sample in measurement gained.Decant sample 1-4 is corresponding to adding TiCl 4/ Ti (OBu) 4Afterwards, decant sample 5 and 6 is corresponding to adding for the first time TiCl 4Afterwards.Decant sample 7-10 is corresponding to adding for the second time TiCl 4Afterwards.
Table 1
The decant sample Ti (ppm) MM/liter
1 2.1 21000 306.9
2 0.8 8000 116.9
3 0.2 2000 29.2
4 0.1 1000 14.6
5 2 20000 292.3
6 0.4 4000 58.5
7 1.9 19000 277.7
8 0.4 4000 58.5
9 0.0925 925 13.5
10 0.0064 64 0.9
Comparative Examples 1:
Comparative Examples 1 according to embodiment 1 in similarly mode prepare, different is to save metatitanic acid esterif iotacation step for the third time, and the metatitanic acid esterif iotacation step is used the TiCl of 1/4th amounts for the second time 4Carry out.
Comparative Examples 2:
Comparative Examples 2 according to embodiment 1 in similarly mode prepare, that different is the second and the 3rd titanate esters step is used 0.5 equivalent in each metatitanic acid esterif iotacation step TiCl 4Carry out.
Comparative Examples 3:
Comparative Examples 3 according to Comparative Examples 1 in similarly mode prepare, that different is the TiCl that uses in the metatitanic acid esterif iotacation step in the second time 4Amount approximately be 4 times used in the Comparative Examples 1.After the metatitanic acid esterification second time, carry out a hexane and clean.In one embodiment, the percetage by weight of composition is: Cl 57.0%; Al 2.0%; Mg 9.5% and Ti 10.0%.The scope of each element can be: Cl 55.0-57.0%; Al 2.0-2.6%; Mg 8.9-9.5%; Ti10.0-11.0%.
Comparative Examples 4:
Comparative Examples 4 according to Comparative Examples 3 in similarly mode prepare, different is after second time metatitanic acid esterif iotacation step, carries out twice hexane and cleans.In one embodiment, the percetage by weight of composition is: Cl 53.0%; Al 2.3%; Mg 9.7% and Ti 9.5%.The scope of each element can be: Cl 52.6-53.0%; Al 2.0-2.3%; Mg 9.7-10.6%; Ti 8.7-9.5%.
Table 2 has been enumerated the catalyst of preparation.
Table 2
Catalyst X Wash number Y Wash number
Comparative Examples 1 0.5 0 0 NA
Comparative Examples 2 0.5 1 0.5 2
Embodiment 1 1.0 1 1.0 2
Comparative Examples 3 2.0 1 0 NA
Comparative Examples 4 2.0 2 0 NA
Table 3 has provided the MWD data with the polymer of embodiment 1 and Comparative Examples 1-4 preparation.For given catalyst/co-catalyst system, these data show by increasing wash number or increase TiCl 4Carry out metatitanic acid esterif iotacation step for the third time, can obtain narrower MWD.In general, the MWD of fluoropolymer resin inherence increases in the following order, i.e. Comparative Examples 1＜Comparative Examples 2＜Comparative Examples 4＜embodiment 1＜Comparative Examples 3.
Table 3
Catalyst Co-catalyst Wash number behind the X Wash number behind the Y SR5 (HLMI/MI 5) D (Mw/Mn)
Comparative Examples 1 TEAl 0 0 10.9 6.2
Comparative Examples 2 TEAl 1 2 10.9 NA
Embodiment 1 TEAl 1 2 12.6 6.8
Comparative Examples 3 TEAl 1 NA 11.8-12.8 5.9-6.8
Comparative Examples 4 TEAl 2 NA 10.8-12.0 6.0-6.3
Embodiment 1 TIBAl 1 2 11.9 7.0
Comparative Examples 3 TIBAl 1 NA 12.2-13.6 6.9-7.3
Comparative Examples 4 TIBAl 2 NA 11.4-11.8 6.6-7.5
As shown in table 4, each catalyst provides granule (less than 125 microns particle) less powder; But, provide fine hair usually with high-bulk-density by the catalyst of the present invention of two steps metatitanic acid esterif iotacation step preparation.
Table 4
Catalyst D 50(micron) Fine hair D 50(micron) The % fines B.D. (gram/cubic centimetre)
Comparative Examples 1 9.4 260 0.0 0.38
Comparative Examples 2 7.8 237 0.6 0.40
Comparative Examples 4 10.1 287 1.6 0.34
Embodiment 1 9.2 264 0.6 0.38
These character have material impact for the settling efficiency of polymer, are confirmed by settling efficiency curve shown in Figure 1 as the laboratory.Showing initial 10 milliliters of fine hair with the polymer of the present invention of the Preparation of Catalyst of the present invention of embodiment 1 rapidly disappears from solution, mean and the polymer phase ratio of the conventional catalyst preparation of using Comparative Examples 4 that this polymer has the rate of settling and better polymer morphology faster.
The viscosity control of synthetic solvent
Have been found that by in the catalyst building-up process, changing solution viscosity, can change the precipitation of catalytic component from solution.Have been found that the precipitation that changes catalytic component, can influence the gained catalyst and with the particle diameter of the polymer of this Preparation of Catalyst.Can change the viscosity of catalyst synthetic solvent according to the relative quantity of the alkyl aluminum that exists.Therefore, can change catalyst and with the particle diameter of the polymer of this Preparation of Catalyst according to the relative quantity of used alkyl aluminum.
Alkyl aluminum with the difference amount prepares catalyst in synthetic solvent, and this catalyst is tested with the polymer fine hair with this Preparation of Catalyst.Embodiment 2 has described synthetic schemes used in Preparation of Catalyst, and table 5 has been represented the size of gained catalyst and polymer.
Embodiment 2:
Used synthetic schemes following (all ratios are with respect to BEM):
1.
2.
3.
4. ；
5.
7.
In 1 liter of Buchi reactor, prepare four kinds of catalyst, Y=Z=1 in this synthetic schemes according to this general synthetic schemes.Change the amount of TEAl in the first step reaction, research is to the influence of catalyst particle size.In each catalyst is synthetic, adjust the relative quantity of 2-Ethylhexyl Alcohol, to prevent that titanium complex is by any unreacted alkyl aluminum or alkyl magnesium reduction.Following table listed synthetic catalyst, used BEM, TEAl and 2-Ethylhexyl Alcohol relative quantity, catalyst average grain diameter and with the average grain diameter of the polyvinyl resin of each Preparation of Catalyst.
Following table provides the particle size distribution data that obtains for each catalyst.As shown in Table, average particle size distribution increases with the increase of TEAl amount.
Table 5
Catalyst BEM TEAl 2-Ethylhexyl Alcohol BEM∶ TEAl Catalyst Polymer fine hair
Equivalent Equivalent Equivalent Ratio D 50(micron) D 50(micron)
101 1.0 0.03 2.09 1.0∶0.03 13.0 399
102 1.0 0.3 2.9 1.0∶0.3 16.1 420
103 1.0 0.5 3.5 1.0∶0.5 18.3 418
104 1.0 1.0 5.0 1.0∶1.0 21.7 504
As shown in table 5, the average grain diameter of catalyst and gained fine hair shape particle all increases with the increase of TEAl amount in the synthetic initial soln of catalyst.By changing the relative quantity of alkyl aluminum, can change the viscosity of catalyst synthetic solvent.Thereby the variation of solution viscosity can change the precipitation character that catalytic component precipitates from solution, and this can influence catalytic component and with the average grain diameter of the polymer of this Catalyst Production.As can be seen from the table, the average grain diameter of catalytic component increases with the increase of alkyl aluminum concentration in the synthetic solvent.It can also be seen that, increase with the increase of the average grain diameter of the fluoropolymer resin of this Catalyst Production with alkyl aluminum concentration in the synthetic solvent.
Can measure the amount of alkyl aluminum to the ratio of alkyl magnesium according to alkyl aluminum, it can change to about 10: 1 scope at about 0.01: 1.Poly MWD with above-mentioned Catalyst Production is at least 4.0, can be greater than about 6.0.
Catalyst 101 in the table 5 is identical with the foregoing description 1.In one embodiment, the percetage by weight of composition is: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti 7.9%.The scope of each element can be: Cl40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti 2.0-14.0%.
Catalyst 102 in the table 5 has in one embodiment: Cl 47.0%; Al 3.4%; Mg 13.1% and Ti 4.0%.The scope of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti2.0-14.0%.
Catalyst 103 in the table 5 has in one embodiment: Cl 50.0%; Al 2.4%; Mg 12.1% and Ti 3.9%.The scope of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti2.0-14.0%.
Catalyst 104 in the table 5 has in one embodiment: Cl 53.0%; Al 3.1%; Mg 12.8% and Ti 4.2%.The scope of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0%; Ti 2.0-14.0%.
Polyolefin of the present invention is suitable for use in the various application, for example, is used in the extrusion, produces the product of wide range.These extrusions comprise that for example, blown film is extruded, casting film is extruded, the slit band shape is extruded (silt tape extrusion), blowing, tubing is extruded and foaming plate is extruded.These technologies can comprise that individual layer is extruded or be multi-layer co-extruded.The terminal articles for use that can use the present invention to make comprise, for example, and film, fiber, tubing, textile material, manufactured goods, diaper composition, feminine hygiene articles, automobile component and medical material.
According to the embodiment of an alternative of the present invention, use to comprise that the method for some reactions forms polyolefin polymerization catalyst.The first, alkyl magnesium compound (that is Mg (R, *) 2, R wherein *Can be identical or different alkyl with about 1-20 carbon atom), BEM for example, according to following reaction and the alcohol soluble magnesium alkoxide of formation that reacts:
Wherein, R is the alkyl that contains for example about 1-20 carbon atom.The alcohol of representing with general formula R OH can be branching or non-branching.The example of suitable alcohol is a 2-Ethylhexyl Alcohol.Any suitable reaction condition and charging sequence that is used for BEM and alcohol reactant are converted into pure magnesium compound can adopt.In one embodiment, alcohol is joined in the BEM solution, form reactant mixture, this process maintains under environment temperature and the environmental pressure.Reactant mixture is stirred time enough, form soluble pure magnesium compound.
The pure magnesium compound of gained is mixed with the chlorinating agent of gentleness, form magnesium-titanium-pure salt adduct, this process is carried out according to following equation:
Wherein R ＇ is alkyl, cycloalkyl or aryl, and n is 1-3, and m is at least 1, also can be greater than 1.Wish that n is 1.Reaction reagent comprises TiCl n(OR ＇) 4-n, wherein, R ＇=alkyl or aryl, n are 1, perhaps Ti (O iPr) 3Cl, wherein iPr represents isopropyl.Any suitable condition that is used to form magnesium-titanium-pure salt adduct may be utilized and carries out this process.In one embodiment, this process is carried out under environment temperature and environmental pressure.Reactant is mixed the sufficiently long time, form magnesium-titanium-pure salt adduct.It is believed that why adduct can form, is because magnesium-titanium-alkoxide cpd is to have sterically hinderedly, and the chlorine atom in the titanium compound is difficult to and magnesium alkoxide ligand exchange position.In essence, but adduct not exclusively is converted into MgCl basically 2
Subsequently, with magnesium-titanium-pure salt adduct and alkyl chloride compound, make adduct be converted into MgCl 2Carrier.Reactions steps is as follows:
Wherein, R " be the alkyl that contains for example about 2-18 carbon atom, " TiMgCl 2" MgCl of expression titanium dipping 2Carrier." can be branching or nonbranched, wish R in some embodiments " be nonbranched to though R.Possible alkyl chloride compound comprises chlorobenzoyl chloride, chloromethyl ethyl ether and tertiary butyl chloride, and in some specific embodiment, chlorobenzoyl chloride is desirable.The amount that joins the alkyl chloride in the magnesium alkoxide adduct can surpass the required amount of reaction.(for example, the ratio of amount BEM) can change (that is, about 1: 1 ratio is to about 20: 1 ratio) to the amount of chlorobenzoyl chloride in the scope of about 1-20, or about 1-10, wishes to change in the scope of about 4-8 to Mg in the reactant mixture.Reaction can be carried out under the condition of any suitable precipitation magnesium chloride support.In one embodiment, with the sufficiently long time of reaction mixture refluxed, make MgCl 2Carrier precipitation.In the embodiment that uses tertiary butyl chloride, reactant can heat in the process that refluxes.In the embodiment that uses chlorobenzoyl chloride or chloromethyl ethyl ether, reactant can maintain room temperature in the process that refluxes.Also can produce one or more accessory substances (as shown in above-mentioned reaction) by this reaction as ether and so on.It is believed that at precipitation MgCl 2Process in have Ti, play main effect for producing high activated catalyst.
With MgCl 2After carrier separates, can clean carrier with for example hexane, to remove any pollutant that remains on the carrier from reactant mixture.Use TiCl then 4Handle MgCl 2Carrier forms catalyst pulp, and this process is carried out according to following equation:
This processing procedure can be carried out under any suitable condition that is used to form catalyst pulp, for example, carries out under environment temperature and environmental pressure.With for example hexane cleaning catalyst slurry, dry then.Can activate in advance with alkyl aluminum compound such as triethyl aluminum (TEAL) catalyst, to prevent the catalytic erosion polymer reactor gained.More particularly, when titanium chloride in the catalyst and alkyl aluminum compound reaction, titanium chloride is converted into the alkyl titanium.In addition, when titanium chloride is exposed in the moisture, may be converted into HCl, the result causes the corrosion to polymer reactor.
Second group of embodiment
The present invention has been carried out general description, following embodiment provides as the specific embodiment of the present invention, and is used for showing its enforcement and advantage.The mode by exemplary illustration that should be understood that provides embodiment, and embodiment is not intended to limit by any way the scope of specification of the present invention or claim.
Unless indication is arranged in addition, all experimental embodiment use standard Schlenk systems technology to carry out under inert atmosphere.Several catalyst (sample C-M) have been prepared according to the inventive method.In addition, prepared the catalyst of two class routines, be called sample A and sample B, wherein sample B is according to No. 5563225 preparation of United States Patent (USP), and they are used for making comparisons with other catalyst sample.Required chemical compound lot among the embodiment, i.e. 2-Ethylhexyl Alcohol, chlorobenzoyl chloride, n-butyl chloride, tertiary butyl chloride, chloromethyl ethyl ether, ClTi (O iPr) 3And TiCl 4, available from Aldrich chemical company, and the form when receiving kinds of goods is used.The n-heptane solution that contains 15.6 weight %BEM and 0.04 weight %Al is buied from Akzo Nobel.Use Malvem Mastersizer to measure catalyst particle size and distribute, comprise average grain diameter D 50, and all particle diameters distributions given here are basic calculation with the volume averaging value.
Hexane is buied from Phillips, and for purifying, with the speed of 12 ml/min from 3A molecular sieve column, F200 alumina column, filled the post of BASF R3-11 copper catalyst and passed through.Use autoclave in the presence of each catalyst sample, to carry out vinyl polymerization.The capacity of this reactor is 4 liters, and is furnished with four and mixes dividing plate, and dividing plate has two relative spiral propellers.Add ethene and hydrogen in reactor, the back pressure regulator (dome loaded back pressure) of operative installations in vault kept reaction pressure simultaneously, uses steam and cooling water to keep reaction temperature.In reactor, add hexane as diluent.Unless indication is arranged in addition, is aggregated under the described condition of table 3A and carries out.Obtain the poly fine hair shape particle grain size distribution of gained by using CSC Scientific vibrating sieving machine to screen analysis based on quality.Short grained percentage is defined as the percetage by weight less than 125 microns fine hair shape particle.
Comparative Examples 1A
Prepare Comparative Examples catalyst sample A by in 1 liter of reactor, adding the n-heptane solution that contains 15.6 weight %BEM (70.83 grams, 100 mMs).Then, in the solution that contains BEM, slowly add 26.45 gram (203 mM) 2-Ethylhexyl Alcohols.Reactant mixture was stirred 1 hour at ambient temperature.Then, slowly adding 77.50 gram (100 mM) concentration in said mixture is the ClTi (OiPr) of 1.0M 3Hexane solution.Reactant mixture was stirred 1 hour at ambient temperature, form [Mg (O-2-ethylhexyl) 2ClTi (OiPr) 3] adduct.Then, in gained solution, add TNBT (34.04 grams, 100 moles) and TiCl 4The hexane solution (250 milliliters) of the mixture of (37.84 grams, 200 mMs).Reactant mixture was stirred 1 hour at ambient temperature, form white precipitate.Make the precipitation sedimentation, decant goes out supernatant liquor.With about 200 milliliters of hexane washing and precipitating three times.Make to be deposited in about 150 milliliters of hexanes to be muddy again, add 50 milliliters and contain TiCl 4The hexane solution of (18.97 grams, 100 mMs).Slurry was stirred 1 hour at ambient temperature.Make the solid sedimentation, decant goes out supernatant liquor.Clean solid once with 200 milliliters of hexanes.In precipitation, add about 150 milliliters of hexanes then.Contain TiCl with 50 milliliters 4The hexane solution of (18.97 grams, 100 mMs) is handled catalyst once more.Slurry was stirred 1 hour at ambient temperature.Make the solid sedimentation, decant goes out supernatant liquor.With twice of 200 milliliters of hexane cleaning catalyst.In precipitation, add about 150 milliliters of hexanes.By with 7.16 gram (15.6 mM) concentration be that the n-heptane solution of the TEAL of 25 weight % reacts at ambient temperature and obtained final catalyst in 1 hour.
Comparative Examples 2A
By add 330 ml concns in 1 liter of flask is that n-heptane solution, 13.3 molar concentrations of the dibutylmagnesium of 15 weight % are that the pentane solution of the four aluminium isobutyl alkane (tetraisobutylaluminoxane) of 20 weight %, 3 milliliters of isoamyl ethers and 153 milliliters of hexanes prepare Comparative Examples catalyst sample B.Mixture was stirred 10 hours at 50 ℃.Then, add 0.2 milliliter of TiCl 4And the mixture of tertiary butyl chloride (96.4 milliliters) and DIAE (27.7 milliliters).Mixture was stirred 3 hours at 50 ℃.Make the precipitation sedimentation, decant goes out supernatant liquor.At room temperature clean solid three times with hexane (100 milliliters).Make solid in 100 milliliters of hexanes, be muddy again.In 20 minutes, anhydrous HCl is joined in the reactant mixture.Cross filter solid, and clean twice with 100 milliliters of hexanes.Solid is suspended in the hexane again.With 50 milliliters of pure TiCl 4Join in the slurry, and mixture was stirred 2 hours at 80 ℃.Decant goes out supernatant liquor, with 100 milliliters of hexane cleaning catalysts ten times.At N 2Stream and 50 ℃ of following dry catalysts.
Embodiment 1A
Prepare catalyst sample C according to the present invention according to following steps: in 250 milliliter of three neck round-bottomed flask being furnished with dropping funel, barrier film and condenser pipe, add the n-heptane solution that contains 15.6 weight %BEM (17.71 grams, 25 mMs).Then, in the solution that contains BEM, slowly add 6.61 gram (51 mM) 2-Ethylhexyl Alcohols.Reactant mixture was stirred 1 hour at ambient temperature.Then, in this solution, add 19.38 gram (25 mM) ClTi (O iPr) 3(1M is in hexane).Reactant mixture was stirred 1 hour at ambient temperature, form [Mg (O-2-ethylhexyl) 2ClTi (O iPr) 3] adduct.Then, add 18.51 gram (200 mM) tertiary butyl chlorides in gained solution, making tertiary butyl chloride is about 8: 1 to the mol ratio of BEM.Reactant mixture was heated 24 hours down at reflux temperature (promptly about 80 ℃), form MgCl 2Precipitation (that is, obtaining catalyst carrier).Make the white precipitate sedimentation, decant goes out lurid supernatant liquor.With about 100 milliliters of hexane washing and precipitating three times.In precipitation, add about 100 milliliters of hexanes then, in gained solution, slowly add TiCl then 4(9.485 grams, 50 mMs).Slurry was stirred 1 hour at ambient temperature.Make the solid sedimentation, decant goes out supernatant liquor.With 50 milliliters of hexane cleaning catalysts 4 times.
Embodiment 2A
Step according to embodiment 1A is carried out, and forms catalyst sample D, and different is accelerates reaction rate by add more the tertiary butyl chloride of volume in flask.Specifically, add 37.02 gram (400 mM) tertiary butyl chlorides in the solution in flask, and solution was heated 24 hours at 55 ℃.Tertiary butyl chloride/BEM mol ratio of containing of solution is about 16: 1 (is 16 equivalents with respect to BEM) like this.As what expect, embodiment 2A compares with embodiment 1A, obtains higher output.
Following table 1A has listed the composition of the catalyst that forms among Comparative Examples 1A and 2A and embodiment 1A and the 2A.
Table 1A
Catalyst sample Mg (weight %) Ti (weight %) Al (weight %) Cl (weight %)
A 11.92 6.8 2.7 51.71
B 22.8 2.3 - 66.7
C 13.17 3.6 0.8 48.05
D 11.01 4.9 - 47.77
The amount of Mg and Cl is similar to corresponding amount among the sample A among sample C and the D.Among sample C and the D between the amount of the amount of Ti Ti in sample A and B.
For embodiment 1A and 2A, the usefulness proton magnetic resonance (PMR) ( 1H NMR) and and gas chromatography-mass spectrum (GCMS) analyze and to detect Ti (O iPr) 3ClMg (OR) 2] nAccessory substance with the tertiary butyl chloride reaction.Find that main accessory substance is a 2-Ethylhexyl Alcohol, rather than the tert-butyl group 2-ethylhexyl ether or the tert-butyl group-2-isopropyl ether of expection.Based on this result, suppose certain reduction reaction takes place in the mixture, may form isobutene, from reaction, remove.Figure 1A has illustrated that the particle diameter of sample A-D distributes.Sample A and B catalyst all have narrow particle diameter and distribute.The average grain diameter of sample B catalyst is bigger slightly than the average grain diameter of sample A catalyst.The bimodal distribution that has broad with the catalyst sample C and the D of tertiary butyl chloride preparation.
Embodiment 3A
Step according to embodiment 1A is carried out, and different is adds uncle's chlorine, n-butyl chloride rather than tertiary butyl chloride in flask, forms n-butyl chloride/BEM mol ratio be about 16: 1 solution of (is 16 equivalents with respect to BEM).Unfortunately, after 24 hours, n-butyl chloride can not precipitate [Ti (O 50 ℃ of heating iPr) 3ClMg (OR) 2] nAccording to hypothesis, this observed result has shown that mechanism of chlorination relates to a disassociation and eliminates (E1) step, and this step needs a stable carbocation.
Embodiment 4A
Prepare catalyst sample K according to following steps: in 500 milliliter of three neck round-bottomed flask being furnished with dropping funel, barrier film and condenser pipe, add n-heptane solution and 100 milliliters of hexanes of containing 15.6 weight %BEM (8.85 grams, 12.5 mMs).Then, in the solution that contains BEM, slowly add 3.31 gram (25 mM) 2-Ethylhexyl Alcohols, reactant mixture was stirred 1 hour at ambient temperature.Then, in said mixture, slowly add 9.69 gram (12.5 mM) ClTi (OiPr) 3, reactant mixture was stirred 1 hour at ambient temperature.Then, in this solution, add 17.6 gram (125 mM) chlorobenzoyl chlorides (PhCOCl), make PhCOCl be about 10: 1 (is 10 equivalents with respect to BEM) the mol ratio of BEM.Reactant mixture was stirred 2 hours at ambient temperature, form MgCl 2Precipitation.Make the white precipitate sedimentation, decant goes out supernatant liquor.With 100 milliliters of hexane washing and precipitating three times.In precipitation, add about 100 milliliters of hexanes then, in this solution, slowly add TiCl then 4(4.25 grams, 25 mMs).The gained slurry was stirred 1 hour at ambient temperature.Make the light yellow solid sedimentation, decant goes out the yellow clear liquid in upper strata.With 50 milliliters of hexane cleaning catalysts 3 times.
Obviously, form MgCl by PhCOCl 2The reaction of carrier need not heated as the reaction of carrying out with tertiary butyl chloride.And as shown in Figure 3, it is suitable with the particle diameter distribution of catalyst sample A and B that the particle diameter of the catalyst sample K that use PhCOCl forms distributes.
Embodiment 5A-10A
Step according to embodiment 4A prepares six samples (sample E-J) again, and the use amount of different is PhCOCl each time is all different, makes that the molar equivalent with respect to BEM changes in the scope of 1.2-7.2.
Fig. 4 has shown catalyst yield, and it is as the function of PhCOCl use amount among the embodiment 4A-410.Catalyst yield increases along with the increase of PhCOCl concentration earlier, keeps constant at about 7.0 equivalent place then, obtains the maximum production of about 1.7 grams.Following table 2A has listed the composition of the catalyst that forms among the embodiment 4A-10A.
Table 2A
Catalyst sample The equivalent of PhCOCl Ti (weight %) Al (weight %) Mg (weight %) Cl (weight %)
E 1.2 5.0 ＜0.2 13.02 51.34
F 2.4 3.8 ＜0.2 12.55 47.55
G 3.6 3.1 ＜0.2 12.47 40.24
H 4.8 2.7 ＜0.2 12.48 41.07
I 6.0 2.6 ＜0.2 12.39 43.02
J 7.2 2.6 ＜0.2 10.87 43.03
K 10 2.6 ＜0.2 11.30 42.35
A - 6.8 2.7 11.92 51.71
B - 2.3 - 22.8 66.7
As show as shown in the 2A, being elevated in the process of 6.0 equivalents in PhCOCl concentration, the content of titanium descends, and the content of titanium keeps constant when higher equivalent.The Ti content of catalyst sample H-K and the corresponding content of catalyst sample B are similar, and is lower than the corresponding content of catalyst sample A.Can relate to benzoic ether product or unreacted PhCOCl to the possible explanation of Ti content decline.NMR and GCMS analyze and have confirmed that the main accessory substance of chlorination reaction is benzoic acid 2-Octyl Nitrite and isopropyl benzoate.These esters and unreacted PhCOCl are lewis bases, can both with the titanium or the magnesium complexing of short of electricity.It is believed that forming this type of complex compound will make more titanium be extracted out from carrier.Also believe, with MgCl 2The complexing of carrier has prevented TiCl 4The extension keyed jointing takes place in metatitanic acid esterification subsequently.After what is interesting is that content as PhCOCl is greater than 7 equivalents, it is constant that the content of titanium keeps.This numerical value is corresponding to all ClTi (O iPr) 3And Mg (OR) 2All be chlorinated.More than this PhCOCl amount, it is constant that the amount of ester also keeps, and shows in the amount of ester titanium in the final catalyst of decision to play an important role.
Catalyst sample E-H that the PhCOCl of use variable concentrations forms and the particle diameter of I-K distribute, and are illustrated respectively among Fig. 5 and Fig. 6.The catalyst sample E that forms with the PhCOCl (is 1.2 equivalents with respect to BEM) of least concentration shows wide bimodal distribution.Improve the content of PhCOCl, produce catalyst, and therefore improved catalyst form with narrower Unimodal Distribution.In addition, as shown in Figure 7, average grain diameter (D 50) slightly descend along with the increase of PhCOCl concentration.Suppose PhCOCl and ester products can both with the growth in MgCl 2Complexing takes place in the unsaturated magnesium site on the carrier.As mentioned above, these lewis bases help the carrier from growth to extract titanium.Equally, it is believed that the dynamics that carrier forms can change because lacking the titanium complexing.
Embodiment 11A
Prepare catalyst sample L according to following steps: in 250 milliliter of three neck round-bottomed flask being furnished with dropping funel, barrier film and condenser pipe, add the n-heptane solution and the 30 milliliters of hexanes (30 milliliters) that contain 15.6 weight %BEM (4.43 grams, 6.25 mMs).Then, in the solution that contains BEM, slowly add 1.66 gram (12.5 mM) 2-Ethylhexyl Alcohols, reactant mixture was stirred 1 hour at ambient temperature.Then, in said mixture, slowly add ClTi (OiPr) 3The solution of (concentration is 1M in hexane, 4.85 grams, 6.25 mMs) stirred reactant mixture 1 hour at ambient temperature.Then, in this solution, add the hexane solution (25 milliliters) that contains chloromethyl ethyl ether (CMEE) (9.45 grams, 100 mMs), make CMEE be about 8: 1 (is 8 equivalents with respect to BEM) the mol ratio of BEM.Reactant mixture was stirred 1 hour at ambient temperature, form MgCl 2Precipitation.Make the white precipitate sedimentation, decant goes out supernatant liquor.With 50 milliliters of hexane washing and precipitating three times.In precipitation, add 30 milliliters of hexanes then, in this solution, slowly add TiCl then 4The hexane solution (30 milliliters) of (2.13 grams, 125 mMs).The gained slurry was stirred 1 hour at ambient temperature.Make the light yellow solid sedimentation, decant goes out yellow supernatant liquor.Use 50 milliliters of hexane cleaning catalysts 3 times then.
The particle diameter that Fig. 9 has described the catalyst based sample L of CMEE, the catalyst based sample K of PhCOCl and catalyst sample A and B distributes.The catalyst based sample of CMEE has than sample A, sample B and the wide slightly particle diameter distribution of the catalyst based sample K of PhCOCl.The shoulder breadth of the particle diameter distribution of peaks that CMEE is catalyst based is about 7 microns.
Comparative Examples 3A
Carrying out vinyl polymerization in the presence of catalyst sample A and the TEAl co-catalyst and under the listed condition of table 3A.
Comparative Examples 4A
Carrying out vinyl polymerization in the presence of catalyst sample B and the TEAl co-catalyst and under the listed condition of table 3A.
Embodiment 12A
Use is carried out vinyl polymerization by the catalyst sample C and the D of tertiary butyl chloride preparation under the listed condition of table 3A.Fig. 9 has illustrated the fine hair shape particle grain size distribution of the polymer for preparing among embodiment 12A and Comparative Examples 3A and the 4A.The particle diameter that uses catalyst sample C and D to obtain distributes very wide.On the contrary, the distribution relative narrower that obtains by catalyst sample A and B.Fine hair by sample C and D preparation contains more granule than the fine hair by sample A and B preparation.Fine hair by sample C and D preparation has relative low bulk density.
Table 3A
Diluent Hexane
Temperature (℃) 80
H 2/C 2 2/8
Pressure (psig) 125
Co-catalyst TEAL (0.75 mM/liter)
Following table 4A has listed the character of the fluoropolymer resin that uses catalyst sample A, B, C and D preparation.
Table 4A
Catalyst sample The Mg base is active Resin density (gram/cubic centimetre) Melt index, 2.1 kilograms (10 gram/minute) Melt index, 5.0 kilograms (10 gram/minute) SR 2 (HLMI /MI 2) SR 5 (HLMI/ MI 5) Wax (%)
A 20,694 0.9647 3.75 12.06 35.6 11.1 1.4
B 10,000 0.9584 0.47 1.4 29.5 10.2 1.3
C 18,766 0.9574 0.59 1.6 28.1 10.3 0.7
D 41,390 0.9578 1.06 3.2 30.0 9.8 0.6
Earlier the polymer dissolution that forms with catalyst with by this catalyst extracts remaining Mg in acid, comes to determine the magnesium base activity of each catalyst sample like this.Determine catalyst activity according to remaining Mg content.As show as shown in the 4A, the corresponding activity of the magnesium base specific activity catalyst sample A of catalyst sample C is lower slightly, than the corresponding active height of catalyst sample B.The specific activity catalyst sample A of catalyst sample D and B's is corresponding active high.The ratio of melt index is calculated the shear loading of the polymer for preparing with catalyst sample by the melt index (HLMI) of determining high load capacity.Shear loading by the shear loading of the polymer of catalyst sample C and D preparation and sample B polymer is similar, but more lower slightly than the shear loading of sample A polymer.The amount of the wax (wax) of preparation all is suitable for all polymer.
Embodiment 13A
Use is carried out vinyl polymerization by the catalyst sample E-K of chlorobenzoyl chloride preparation under the listed condition of table 3A.Figure 10 A has illustrated the fine hair shape particle grain size distribution of the polymer (sample G-K) for preparing among this embodiment.Average grain diameter (the D of PhCOCl base resin 50) to compare with the average grain diameter of sample B resin with sample A be bigger.
Among the following table 5A form of PhPOCl catalyst sample and form with the polymer of PhCOCl catalyst sample formation are compared.
Table 5A
The catalyst form Polymer morphology
Catalyst sample D10 (micron) D50 (micron) D90 (micron) D90-D10 D 50(micron) Granule (%)
F 10.08 19.12 30.94 20.86 617.9 4.6
G 9.87 16.76 24.89 15.02 658.0 1.8
H 10.37 19.77 30.42 20.05 532.1 4.4
I 9.58 15.89 23.39 13.81 533.4 1.7
J 9.32 14.38 20.35 11.03 378.3 8.1
K 5.74 12.56 21.74 16.00 404 2.2
A 5.29 10.85 18.32 13.03 292 1.0
B 7.26 14.24 22.67 15.14 286 0.2
Based on replicating principle, the form of polymer is relevant with catalyst form.But as if for embodiment F-K, the form of polymer does not correspond to catalyst form (that is, disproportionate), and for sample A and B, two kinds of forms are seemingly corresponding.
Following table 6A has listed the character with the polymer of PhCOCl catalyst sample (sample E-K) and catalyst sample A and B preparation.
Table 6A
Catalyst The Mg base is active Resin density (gram/cubic centimetre) Melt index, 2.16 kilograms (10 gram/minute) Melt index, 5.0 kilograms (10 gram/minute) SR 2 (HLMI /MI 2) SR 5 (HLMI/ MI 5) Wax (%)
E 39000 0.9669 8.97 29.25 32.0 9.8 0.8
F 40000 0.9633 3.42 10.39 30.1 9.9 0.2
G 37000 0.9633 4.32 13.05 30.4 10.1 0.3
H 25000 0.9636 2.33 6.60 27.8 9.8 0.3
I 26000 0.9626 2.90 10.89 37.7 10.0 0.2
J 25000 0.9636 4.90 14.48 28.5 9.6 0.3
K 38000 0.9601 1.51 4.16 29.2 10.6 0.5
A 20694 0.9647 3.75 12.06 35.6 11.1 1.4
B 10000 0.9584 0.47 1.4 29.5 10.2 1.3
The magnesium base activity of sample E-K is greater than the corresponding activity of sample A and B.This activity generally descends with the increase of PhCOCl equivalent, but except the sample K, its equivalent that has is 10.The density of the density of sample E-K polymer and sample A and B polymer is similar.The melt flow rate (MFR) of sample E-K polymer and sample A polymer (that is melt index) is bigger than the analog value of sample B polymer.The shear loading of the shear loading of sample E-K polymer and sample B polymer is similar, but more lower slightly than the shear loading of sample A polymer.The amount of the wax of preparation all is suitable for all polymer.
Embodiment 14A
As mentioned above, by cleaning MgCl with hexane 2Precipitation prepares the catalyst based sample I of PhCOCl and (hereinafter is called " sample I 1").This embodiment is to catalyst sample I 1With another in the same manner but omit the prepared catalyst sample I of cleaning step 2Compare.It is believed that province omits cleaning step, can obviously reduce and produce required time and the cost of catalyst.Following table 7A has shown sample I 1And I 2Catalyst form.
Table 7A
Catalyst Whether clean The equivalent of PhCOCl Ti (weight %) Al (weight %) Mg (weight %) Cl (weight %)
I 1 Be 6 2.6 ＜0.2 12.39 43.02
I 2 Not 6 1.8 ＜0.2 11.78 38.21
Cleaning step omits in province, can make Ti content descend about 30%.The catalyst sample I that cleaned 1Be faint yellow.Adding TiCl 4Process in, unwashed catalyst sample I 2Also be very significantly yellow.But, work as TiCl 4During the contact mother liquor, catalyst sample I 2Become colorless at once.That supposes is ester and TiCl 4Complex compound can produce yellow, and PhCOCl and TiCl 4Reaction forms colourless compound.This observed result has supported before to depend on about Ti content the discussion of PhCOCl amount.Be not removed meeting and TiCl if it is believed that excessive PhCOCl and ester 2With carrier surface generation complexing, stoped the deposition of titanium on carrier surface.
As shown in figure 11, sample I 1And I 2Particle diameter to distribute be identical basically.Therefore, catalyst particle size distributes and is not subjected to the influence of cleaning step.This observed result is not surprising, because cleaning step is at MgCl 2Carrier carries out after forming.Use sample I 1And I 2Come polymerising ethylene.Following table 8A has listed for sample I 1And I 2Catalyst and the form of polymer.
Table 8A
The catalyst form Polymer morphology
Whether clean D 10(micron) D 50(micron) D 90(micron) D 90-D 10 D 50(micron) Granule (%)
Be 9.58 15.89 23.39 13.81 533.4 1.7
Not 9.21 15.48 23.02 13.81 239.2 23.7
Table 8A has further confirmed the conclusion that particle diameter distributes and not influenced by cleaning step.After cleaning step omitted in province, the short grained number that forms in the polymer obviously increased.The increase of granule number may be because lower output.Use catalyst sample I 1And I 2The character of the polymer that forms is shown among the following table 9A.
Table 9A
Whether clean The Mg base is active Bulk density (gram/cubic centimetre) Resin density (gram/cubic centimetre) 2.16 kilograms of melt indexs (10 gram/minute) 5.0 kilograms of melt indexs (10 gram/minute) SR 2 (HLMI/ MI 2) SR 5 (HLMI/ MI 5) Wax (%)
Be 26000 0.23 0.9626 2.90 10.89 37.7 10.0 0.2
Not 14800 0.29 0.9557 0.48 1.36 24.8 8.8 0.1
As show as shown in the 9A, the polymerization activity of unwashed catalyst almost is half of the catalyst activity that cleaned.The density of two kinds of polymer almost is the same.But the shear loading data show that unwashed catalyst compares with the catalyst that cleaned and have narrower molecular weight distribution.It is believed that the existence of PhCOCl and ester in the catalyst influences the distribution of avtive spot in the catalyst.
Embodiment 15A
Also studied of the influence of BEM concentration to catalyst property.Use is prepared the catalyst based sample of a PhCOCl (sample L) by the BEM solution of 100 milliliters of hexane dilutions.For needs relatively, use by the BEM solution of 20 milliliters of hexane dilutions to prepare the catalyst based sample of the 2nd PhCOCl (sample M).Figure 12 has shown that the catalyst particle size of catalyst sample L and M distributes.The distribution of two kinds of catalyst is very similar.Catalyst sample L and M and by the polymer of their preparations form and character is listed in the table below respectively among 10A and the 11A.
Table 10A
Catalyst sample Output (g) Ti (weight %) Al (weight %) Mg (weight %) Cl (weight %)
L 0.86 3.5 ＜0.2 12.34 43.23
M 0.81 3.8 ＜0.2 12.55 47.55
Table 11A
Catalyst sample The Mg base is active Resin density (gram/cubic centimetre) Melt index, 2.16 kilograms (10 gram/minute) Melt index, 5 kilograms (10 gram/minute) SR 2 (HLM I/MI 2) SR 5 (HLMI/ MI 5) Wax (%)
L 40000 0.9609 2.07 6.19 28.0 9.4 0.3
M 40000 0.9633 3.42 10.39 30.1 9.9 0.2
Table 10A and 11A show that BEM concentration is to catalysis composition and polymer property not influence basically.
Generally speaking, use alkyl chloride to synthesize new catalyst as n-butyl chloride, tertiary butyl chloride and chloromethyl ethyl ether and so on.The catalyst that is formed by chlorobenzoyl chloride and chloromethyl ethyl ether has gratifying particle diameter distribution, and obtains bimodal distribution with tertiary butyl chloride, can not form MgCl with n-butyl chloride 2The amount that joins the chlorobenzoyl chloride in the magnesium alkoxide adduct by change is come the optimization Preparation of catalysts.As what expect, catalyst yield increases along with the increase of benzoyl chlorine dose, and reaches capacity when chlorobenzoyl chloride is about 7 equivalents with respect to BEM.The particle diameter of catalyst distributes and narrows down along with the increase of benzoyl chlorine dose.
Also carried out an experiment, be used for observing at carrier forming the back omission influence that cleaning step brought.Unwashed catalyst sample shows lower activity and lower shear loading than the sample that cleaned.Also detected of the influence of BEM concentration to catalyst property.Particle diameter distributes, catalyst is formed and polymer property is not subjected to the BEM concentration affects.
Though shown and described embodiments of the present invention, those skilled in the art can make amendment to above-mentioned embodiment under the prerequisite that does not deviate from the present invention's spirit and instruction.Embodiment described in the literary composition only is exemplary, is not intended to limit the present invention.Chemism that is disclosed in the literary composition or theory are based on information and view is given, and do not need fettered by this.Can carry out many variations and modification for the present invention who is disclosed here, these variations and modification are also within the scope of the invention.Therefore, protection scope of the present invention is not limited by above-mentioned specification, but only is subjected to the restriction of claims, and this scope comprises the equivalent of the theme of all authority requirement.

Claims (67)

1. the preparation method of a catalytic component, it comprises:
A) by making the glycol magnesium compound contact the reaction of formation product A with halogenating agent;
B) product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
C) product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C; And
D) product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form catalytic component D.
2. the method for claim 1 is characterized in that, the general formula of described halogenating agent is ClAR  x, wherein A is an irreducibility oxyphie compound, and R  is the hydrocarbyl portion with about 2-6 carbon atom, and x is that the chemical combination price of A subtracts 1.
3. the method for claim 1 is characterized in that, described halogenating agent is ClTi (O iPr) 3
4. the method for claim 1 is characterized in that, described first halogenation/metatitanic acid esterifying agent is the four all identical mixtures that replace titanium compounds of two kinds of its four substituting groups, and described substituting group is halogen or alkoxyl or the phenoxy group with 2-10 carbon atom.
5. method as claimed in claim 4 is characterized in that, described first halogenation/metatitanic acid esterifying agent is the mixture of halogenated titanium and organic titanate.
6. method as claimed in claim 5 is characterized in that, described first halogenation/metatitanic acid esterifying agent is TiCl 4/ Ti (OBu) 4The TiCl of ratio in 0.5: 1 to 6: 1 scope 4And Ti (OBu) 4Mixture.
7. the method for claim 1 is characterized in that, described second and the 3rd halogenation/metatitanic acid esterifying agent comprise titanium tetrachloride.
8. method as claimed in claim 7 is characterized in that, described step c) and step d) comprise separately titanium tetrachloride to the ratio of magnesium about 0.1 to about 5 scope.
9. the method for claim 1 is characterized in that, described product A, B and C clean with varsol before carrying out halogenation/metatitanic acid esterif iotacation step subsequently.
10. method as claimed in claim 9 is characterized in that, described product A, B and C are cleaned with varsol before carrying out halogenation/metatitanic acid esterif iotacation step subsequently, ends less than about 100 mMs/be upgraded to up to titanium elements [Ti] content.
11. the method for claim 1 is characterized in that, with varsol described product D is cleaned, and ends less than about 20 mMs/be upgraded to up to titanium elements [Ti] content.
12. the method for claim 1 is characterized in that, at step a), b), c) or any step d) or multistep in have electron donor, wherein electron donor to the ratio of metal at about 0: 1 to about 10: 1 scope.
13. the method for claim 1 also comprises catalyst of the present invention is placed on the inert carrier.
14. method as claimed in claim 13 is characterized in that, described inert carrier is a magnesium compound.
15. the method for claim 1 also comprises: the pre-activator of D and organic metal is contacted, form the pre-activated catalyst system.
16. a catalyst, described catalyst is made by the method that may further comprise the steps:
A) the pre-activator of catalytic component and organic metal is contacted, wherein said catalytic component is by comprising i), method ii), iii) and iv) makes,
I) the glycol magnesium compound is contacted with halogenating agent, form product A;
Product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
Product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C; And
Product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form catalytic component.
17. catalyst as claimed in claim 16 is characterized in that, the pre-activator of described organic metal is that general formula is AlR 3Alkyl aluminum, wherein at least one R is alkyl or the halogen with 1-8 carbon atom, each R can be identical or different.
18. catalyst as claimed in claim 17 is characterized in that, the pre-activator of described organic metal is a trialkylaluminium.
19. catalyst as claimed in claim 18 is characterized in that, described second and the 3rd halogenation/metatitanic acid esterifying agent comprise titanium tetrachloride.
20. catalyst as claimed in claim 19 is characterized in that, aluminium to the ratio of titanium in 0.1: 1 to 2: 1 scope.
21. method as claimed in claim 16 is characterized in that, described product A, B and C clean with varsol before carrying out halogenation/metatitanic acid esterif iotacation step subsequently.
22. method as claimed in claim 16 is characterized in that, with varsol described catalytic component is cleaned, and ends less than about 20 mMs/be upgraded to up to titanium elements [Ti] content.
23. a polymer, described polymer is made by the method that may further comprise the steps:
A) under polymeric reaction condition, one or more olefinic monomers are contacted in the presence of catalyst,
Wherein, described catalyst is by comprising i), method ii), iii) and iv) makes,
I) the glycol magnesium compound is contacted with halogenating agent, form product A;
Product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
Product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C;
Product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form catalytic component; And
B) extract polyolefin polymer.
24. polymer as claimed in claim 23 is characterized in that, described catalyst is by the method preparation that also comprises v), wherein v) for catalytic component is contacted with organo-aluminium reagent.
25. polymer as claimed in claim 23 is characterized in that, described second and the 3rd halogenation/metatitanic acid esterifying agent comprise titanium tetrachloride.
26. polymer as claimed in claim 23 is characterized in that, described product A, B and C clean with varsol before carrying out halogenation/metatitanic acid esterif iotacation step subsequently.
27. comprise film, fiber, tubing, textile material or the manufactured goods of polymer as claimed in claim 23.
28. the method for an olefinic polymerization, it comprises:
A) under polymeric reaction condition, one or more olefinic monomers are contacted in the presence of catalyst, wherein, described catalyst is by comprising i), method ii), iii) and iv) makes,
I) the glycol magnesium compound is contacted with halogenating agent, form product A;
Product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
Product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C;
Product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form product D;
B) extract polyolefin polymer;
Wherein, at least a product A, B and C clean with varsol before carrying out halogenation/metatitanic acid esterif iotacation step subsequently; And
With varsol product D is cleaned, up to titanium elements [Ti] content less than about 100 mMs/liter.
29. method as claimed in claim 28 is characterized in that, the molecular weight distribution of described polymer is at least 4.0.
30. method as claimed in claim 28 is characterized in that, the bulk density of described polymer is at least 0.31 gram/cubic centimetre.
31. goods, it comprises the polymer by method preparation as claimed in claim 28.
32. a method for preparing catalyst, it comprises:
By adding the viscosity of alkyl aluminum control catalyst synthetic solvent, change the precipitation of catalytic component from the catalyst synthetic solvent, wherein the average grain diameter of catalytic component increases along with the increase of alkyl aluminum concentration in the synthetic solvent.
33. method as claimed in claim 32 also comprises the pre-activator of described catalytic component and organic metal is contacted, and forms catalyst, the average grain diameter of wherein said catalyst increases along with the increase of alkyl aluminum concentration in the synthetic solvent.
34. method as claimed in claim 32 is characterized in that, described catalyst synthetic solvent comprises:
The glycol magnesium compound is contacted with halogenating agent, form product A;
Product A is contacted with a series of halogenations/metatitanic acid esterifying agent, form catalytic component; And
The pre-activator of catalytic component and organic metal is contacted, form catalyst;
Wherein, the average grain diameter of described catalyst increases along with the increase of alkyl aluminum concentration in the synthetic solvent.
35. method as claimed in claim 34 is characterized in that, with solvent to product A and each halogenation/metatitanic acid esterif iotacation step after at least a cleaning the in the product of gained, to remove pollutant.
36. a Preparation of catalysts method, it comprises:
A) the glycol magnesium compound is contacted with halogenating agent, form product A;
B) product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
C) product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C;
D) product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form product D; And
E) the pre-activator of product D and organic metal is contacted, form catalyst;
Wherein, the glycol magnesium compound is the product that comprises the reaction of following material: general formula is the alkyl magnesium compound of MgRR ', and wherein R and R ' are the alkyl with 1-10 carbon atom, and R and R ' can be identical or different; General formula is R " alcohol of OH, wherein, alcohol is straight or branched, R " is the alkyl with 2-20 carbon atom; General formula is AlR  3Alkyl aluminum, wherein at least one R  is alkyl or the alkoxy or halogen with 1-8 carbon atom, wherein each R  can be identical or different; And
The average grain diameter of described catalyst along with alkyl aluminum to the increase of the ratio of alkyl magnesium and increase.
37. method as claimed in claim 36 is characterized in that, described alkyl aluminum to the ratio of alkyl magnesium at about 0.01: 1 to about 10: 1 scope.
38. method as claimed in claim 36 is characterized in that, described step c) and d) comprise separately with titanium tetrachloride as halogenation/metatitanic acid esterifying agent, described titanium tetrachloride to the ratio of magnesium about 0.1 to about 5 scope.
39. method as claimed in claim 36 is characterized in that, described glycol magnesium compound is two (2-ethyl hexyl oxy) magnesium.
40. method as claimed in claim 36 is characterized in that, described alkyl magnesium compound is magnesium ethide, dipropyl magnesium, dibutylmagnesium or butyl ethyl magnesium.
41. method as claimed in claim 36 is characterized in that, described alcohol is selected from ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, 2-methyl anyl alcohol and 2-Ethylhexyl Alcohol.
42. method as claimed in claim 36 is characterized in that, the pre-activator of described organic metal comprises alkyl aluminum.
43. method as claimed in claim 36, it is characterized in that, described first halogenation/metatitanic acid esterifying agent is the four all identical mixtures that replace titanium compounds of two kinds of its four substituting groups, and wherein substituting group is halogen or alkoxyl or the phenoxy group with 2-10 carbon atom.
44. method as claimed in claim 43 is characterized in that, described first halogenation/metatitanic acid esterifying agent is the mixture of halogenated titanium and organic titanate.
45. method as claimed in claim 44 is characterized in that, described first halogenation/metatitanic acid esterifying agent is TiCl 4/ Ti (OBu) 4The TiCl of ratio in 0.5: 1 to 6: 1 scope 4And Ti (OBu) 4Mixture.
46. method as claimed in claim 36 is characterized in that, described reaction also comprises electron donor.
47. method as claimed in claim 46 is characterized in that, described electron donor to the ratio of magnesium at about 0: 1 to about 10: 1 scope.
48. method as claimed in claim 46 is characterized in that, described electron donor is an ether.
49. method as claimed in claim 36 is characterized in that, the general formula of described halogenating agent is ClAR  x, wherein A is an irreducibility oxyphie compound, and R  is the hydrocarbyl portion with about 2-6 carbon atom, and x is that the chemical combination price of A subtracts 1.
50. method as claimed in claim 49 is characterized in that, described halogenating agent is ClTi (OiPr) 3
51. method as claimed in claim 36 is characterized in that, with varsol at least a cleaning the among described product A, B, C and the D, up to titanium elements [Ti] content less than about 100 mMs/liter.
52. method as claimed in claim 36 is characterized in that, at step a), b), c) d) in any step or multistep in have electron donor, described electron donor to the ratio of metal at about 0: 1 to about 10: 1 scope.
53. method as claimed in claim 36 also comprises catalyst of the present invention is placed on the inert carrier.
54. method as claimed in claim 53 is characterized in that, described inert carrier is a magnesium compound.
55. a catalyst, described catalyst is made by the method that may further comprise the steps:
A) the pre-activator of catalytic component and organic metal is contacted, wherein, described catalytic component is by comprising i), method ii), iii) and iv) makes,
I) making general formula is Mg (OR ") 2The glycol magnesium compound and can enough halogen exchange the halogenating agent of an alkoxyl contact, formation product A, wherein R " is alkyl or the substituted hydrocarbon radical with 1-20 carbon atom;
Product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
Product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C; And
Product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form catalytic component;
Wherein, the glycol magnesium compound is the product that comprises the reaction of following material: general formula is the alkyl magnesium compound of MgRR ', and wherein R and R ' are the alkyl with 1-10 carbon atom, and R and R ' can be identical or different; General formula is R " alcohol of OH, wherein, alcohol is straight or branched, R " is the alkyl with 2-20 carbon atom; General formula is AlR  3Alkyl aluminum, wherein at least one R  is alkyl or the alkoxy or halogen with 1-8 carbon atom, wherein each R  can be identical or different; And
The average grain diameter of described catalyst along with alkyl aluminum to the increase of the ratio of alkyl magnesium and increase.
56. catalyst as claimed in claim 55 is characterized in that, the pre-activator of described organic-magnesium is that general formula is AlR 3Alkyl aluminum, wherein at least one R is alkyl or the halogen with 1-8 carbon atom, each R can be identical or different.
57. catalyst as claimed in claim 56 is characterized in that, described organosilicon prepolymer activator is a trialkylaluminium.
58. catalyst as claimed in claim 55 is characterized in that, described second and the 3rd halogenation/metatitanic acid esterifying agent comprise titanium tetrachloride.
59. catalyst as claimed in claim 55 is characterized in that, described aluminium to the ratio of titanium in 0.1: 1 to 2: 1 scope.
60. a polymer, described polymer is made by the method that may further comprise the steps:
A) under polymeric reaction condition, one or more olefinic monomers are contacted in the presence of catalyst, wherein, described catalyst is by comprising i), method ii), iii), iv), v) and vi) makes,
I) making general formula is that the alkyl magnesium compound of MgRR ' and general formula are R " the pure and mild general formula of OH is AlR  3Alkyl aluminum contact, the formation general formula is Mg (OR ") 2Two magnesium alkoxides, wherein R among the formula M gRR ' and R ' be have the alkyl of 1-10 carbon atom and R and R ' can be identical or different, general formula R " alcohol of OH can be straight or branched, R " is the alkyl with 2-20 carbon atom, general formula AlR  3In at least one R  be alkyl or alkoxy or halogen with 1-8 carbon atom, each R  can be identical or different;
The glycol magnesium compound is contacted with halogenating agent, form product A, wherein R " is alkyl or the substituted hydrocarbon radical with 1-20 carbon atom;
Product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
Product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C;
Product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form catalytic component; And
This catalytic component is contacted with organo-aluminium reagent; And
B) extract polyolefin polymer;
Wherein, the average grain diameter of polymer is along with using in step I) in alkyl aluminum the increase of the ratio of alkyl magnesium is increased.
61. polymer as claimed in claim 60 is characterized in that, at least a among product A, B and the C cleaned with varsol before carrying out halogenation/metatitanic acid esterif iotacation step subsequently.
62. polymer as claimed in claim 60 is characterized in that, described monomer is a vinyl monomer.
63. polymer as claimed in claim 60 is characterized in that, described polymer is a polyethylene.
64. polymer as claimed in claim 60 is characterized in that, the molecular weight distribution of described polymer is at least 4.0.
65. polymer as claimed in claim 60 is characterized in that, the bulk density of described polymer is at least 0.31 gram/cubic centimetre.
66. comprise film, fiber, tubing, textile material or manufactured goods as right 60 described polymer.
67. a method of controlling the polyolefin polymer particle diameter, it comprises:
A) under polymerizing condition, one or more olefinic monomers are contacted in the presence of catalyst, wherein, described catalyst is by comprising i), method ii), iii), iv), v) and vi) makes,
I) making general formula is that the alkyl magnesium compound of MgRR ' and general formula are R " the pure and mild general formula of OH is AlR  3Alkyl aluminum contact, the formation general formula is Mg (OR ") 2Solubility two magnesium alkoxides, wherein R among the formula M gRR ' and R ' be have the alkyl of 1-10 carbon atom and R and R ' can be identical or different, general formula R " alcohol of OH can be straight or branched, R " is the alkyl with 2-20 carbon atom, general formula AlR  3In at least one R  be alkyl or alkoxy or halogen with 1-8 carbon atom, each R  can be identical or different;
Ii) make described solubility glycol magnesium compound and can contact with the halogenating agent of an alkoxyl of a halogen exchange, form product A, wherein R " is alkyl or the substituted hydrocarbon radical with 1-20 carbon atom;
Product A is contacted with first halogenation/metatitanic acid esterifying agent, form product B;
Product B is contacted with second halogenation/metatitanic acid esterifying agent, form product C;
Product C is contacted with the 3rd halogenation/metatitanic acid esterifying agent, form catalytic component; And
Described catalytic component is contacted with organo-aluminium reagent; And
B) extract polyolefin polymer;
Wherein, the average grain diameter of polymer is along with using in step I) in alkyl aluminum the increase of the ratio of alkyl magnesium is increased.
CNB2004800271807A 2003-09-22 2004-09-07 Ziegler-natta catalyst for polyolefins Expired - Fee Related CN100450620C (en)

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CN103068484A (en) * 2010-08-23 2013-04-24 弗纳技术股份有限公司 Sequential formation of ziegler-natta catalyst using non-blended components
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US5849655A (en) * 1996-12-20 1998-12-15 Fina Technology, Inc. Polyolefin catalyst for polymerization of propylene and a method of making and using thereof
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US9416202B2 (en) 2010-01-11 2016-08-16 Tina Technology, Inc. Ziegler-Natta catalyst systems and polymers formed therefrom
TWI607027B (en) * 2010-01-11 2017-12-01 芬娜工業技術股份有限公司 Ziegler-natta catalyst systems and polymers formed therefrom
CN102869683A (en) * 2010-04-22 2013-01-09 弗纳技术股份有限公司 Formation of ziegler-natta catalyst using non-blended components
US10351640B2 (en) 2010-04-22 2019-07-16 Fina Technology, Inc. Formation of Ziegler-Natta catalyst using non-blended components
CN103068484A (en) * 2010-08-23 2013-04-24 弗纳技术股份有限公司 Sequential formation of ziegler-natta catalyst using non-blended components
CN105622798A (en) * 2014-11-06 2016-06-01 中国石油化工股份有限公司 Catalyst component for olefin polymerization, preparation method and applications thereof
CN105622798B (en) * 2014-11-06 2018-08-17 中国石油化工股份有限公司 A kind of catalytic component of olefin polymerization, preparation method and applications

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