CN1149297A - Use of gel-free alumoxane solution - Google Patents

Use of gel-free alumoxane solution Download PDF

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Publication number
CN1149297A
CN1149297A CN94194816A CN94194816A CN1149297A CN 1149297 A CN1149297 A CN 1149297A CN 94194816 A CN94194816 A CN 94194816A CN 94194816 A CN94194816 A CN 94194816A CN 1149297 A CN1149297 A CN 1149297A
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Prior art keywords
gel
solution
aikyiaiurnirsoxan beta
loaded catalyst
agglomerative
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T·J·伯克哈特
W·B·布兰得利
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Hoechst AG
ExxonMobil Chemical Patents Inc
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Hoechst AG
Exxon Chemical Patents Inc
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

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Abstract

Disclosed is a method of using gel-free alumoxane solution in the preparation of supported catalysts. These supported catalysts produce polymer particles with excellent morphology and minimal to no reactor fouling during polymerization.

Description

Do not contain the application of the aluminoxanes solution of gel
Invention field
In general, the present invention relates to polymerizing catalyst, more particularly, the present invention relates to not contain of the application of the aluminoxanes solution of gel as the promotor of load type catalyst for olefinic polymerization.
Background of invention
Known that aluminoxanes solution is a kind of useful promotor when preparing catalyzer with metallocenes.The problem relevant with aikyiaiurnirsoxan beta is to generate gel or gellike particle.Some problems relevant with the gelling aikyiaiurnirsoxan beta are gel blocking reactor line, and fine particle increases or generates fine particle, and the preparation loaded catalyst is encountered difficulties.The US5157137 that incorporates into as a reference discloses the particularly method of methylaluminoxane solution of the aluminoxanes solution that does not contain gel that some basic metal of a kind of usefulness or alkaline earth metal compound treatment soln remove gel and make cleaning.It is stable and the aluminoxanes solution that still do not contain gel for a comparatively long period of time that US5157137 discloses this processing.
It has been observed by the present inventors that the use of agglomerative aikyiaiurnirsoxan beta can be made polymerization reactor dirty.The loaded catalyst technology of various use aluminoxanes solutions is known.It seems and all do not have application and the application that does not contain the aikyiaiurnirsoxan beta of gel open or differentiation gelling aikyiaiurnirsoxan beta.
Summary of the invention
The present invention relates to a kind of like this method, in this method, use the aluminoxanes solution that does not contain gel (AO) of the substantial transparent of range estimation cleaning to prepare polyolefine, this method may further comprise the steps, from the agglomerative aluminoxanes solution, remove gel or from the AO that contains gel separating gel, generate in the polyolefinic process in olefinic polymerization then and use this to be substantially free of the AO of gel.
The invention still further relates to a kind of method for preparing loaded catalyst, this method comprises using the aikyiaiurnirsoxan beta that is substantially free of gel (AO) of isolating the range estimation cleaning that agglomerative AO obtains from contain gelling particulate AO to mix with the carrier and at least a metallocenes that dewater, makes loaded catalyst.
The invention still further relates to a kind of olefinic polymerization and generate polyolefinic method, this method comprises that the loaded catalyst of above-mentioned preparation contacts under the polymerizing condition that is fit to at least a alkene, and wherein alkene contains 2 to about 20 carbon atoms.
The aikyiaiurnirsoxan beta that does not contain gel is preferably methylaluminoxane, and the transition metal in the aluminium in the used aikyiaiurnirsoxan beta and the metallocenes is than being about 12: 1 to about 1000: 1, preferred about 100: 1 to about 500: 1.
Another embodiment of the present invention relates to the polyolefinic method of the controlled particle diameter of a kind of preparation, and this method may further comprise the steps:
Remove gel from the agglomerative aluminoxanes solution, the aluminoxanes solution that will not contain gel then mixes with the carrier and at least a metallocenes of dehydration, makes loaded catalyst.
Another embodiment relates to a kind of method for preparing loaded catalyst, and this method may further comprise the steps:
(a) buy the agglomerative aluminoxanes solution from the seller;
(b) from described aluminoxanes solution, remove gel;
(c) aluminoxanes solution that is substantially free of gel with (b) mixes with carrier and metallocenes, makes loaded catalyst.
Another embodiment relates to a kind of method for preparing loaded catalyst, and this method may further comprise the steps:
(a) from agglomerative AO solution, isolate gel, make the AO solution that is substantially free of gel;
(b) solution with (a) mixes with carrier and metallocenes, and described mixing step carries out in 7 days after (a) step is finished.
The present invention is suitable for any kind transistion metal compound or metallocenes, comprises one, two or three cyclopentadienyl system or derivatives thereofs.One cyclopentadiene part for example comprises those disclosed in US4808561 or 5055438, incorporates the present invention here as a reference into.
Carrier comprises organic carrier and inorganic carrier.Particularly preferred carrier comprises the porous inorganic carrier, and as silicon oxide, aluminum oxide or silica-alumina, silicon oxide is most preferred.
Usually made fabulous form, controllable grain size, be generally granular polymkeric substance with not containing the loaded catalyst that aluminoxanes solution makes, reactor seldom or is not made dirty in polymerization process.
Detailed description of preferred embodiments
US4808561,5240894 and 4921825 discloses the whole bag of tricks of making promotor carrying transition metal component or metallocenes with aikyiaiurnirsoxan beta.The many relevant documents of aikyiaiurnirsoxan beta as promotor of using in the preparation loaded catalyst are arranged.Above-mentioned reference only is representational.Though existing relevant production does not contain the whole bag of tricks of aikyiaiurnirsoxan beta, it seems does not all have application or advantage at not containing gel aikyiaiurnirsoxan beta or methylaluminoxane (MAO).
In this specialty, it is the common means that stirring agglomerative solution distributes all uniform particles.We find, can make the loaded catalyst of production reunion polymkeric substance with equally distributed gelling aluminoxanes solution.
US5157137 discloses the method for avoiding generating gel in aluminoxanes solution.We find, can remove gel, and use the aluminoxanes solution that does not contain gel that does not need further to handle to make loaded catalyst, and compare with the loaded catalyst of agglomerative aluminoxanes solution production, and the former has fabulous performance.Disclosed alkaline purification is not necessarily used in US5157137, if when separation does not contain the aluminoxanes solution of gel with regard to using immediately.By cancelling this processing, can be made into catalyzer cheaply.The invention discloses a kind of method of not using the aikyiaiurnirsoxan beta of additive or other treatment step.For 10% (weight) aluminoxanes solution,, preferably in 3-5 days, most preferably just be separated in about 2 days because aikyiaiurnirsoxan beta is preferably used the separated aikyiaiurnirsoxan beta that does not contain gel through after a while can gelling in about 5-7 days after separation.If use 30% (weight) aluminoxanes solution, the separated aikyiaiurnirsoxan beta in about 3-5 days is used in suggestion usually, preferably about 1-3 days, most preferably just has been separated to about 1 day.
Aluminoxanes solution can from seller such as Ethyl Corporation or SheringC0rporation buys or can be before use by known technical literature production.
The present inventor finds, can produce the polymer beads of fabulous form by the silica supported catalyzer that the aikyiaiurnirsoxan beta that does not contain gel makes.In addition, in Preparation of Catalyst, the use that does not contain the aluminoxanes solution of gel can make the minimum or reactor of not making dirty in the polymerization process.In addition, the use that does not contain the aikyiaiurnirsoxan beta of gel can make polymkeric substance seldom or not reunite.Use the Comparative Examples of gelling aikyiaiurnirsoxan beta to make to make reactor to make dirty and the catalyzer of polymer lumps.
US4808561,4921825 and 5240894 discloses the whole bag of tricks of producing loaded catalyst.Disclosed technological improvement is to produce the loaded catalyst embodiment preferred in US5240894.Produce the loaded catalyst preferred embodiment and comprise the contacted step of the carrier that is substantially free of gel aluminoxanes solution, at least a metallocenes and dehydration.Loaded catalyst can with the alpha-olefin prepolymerization.US5240894 does not mention the aikyiaiurnirsoxan beta that use does not contain gel.The present invention represents a kind of improvement to the US5240894 disclosed method.
" be substantially free of gel " and refer to the aluminoxanes solution of the substantial transparent of the range estimation cleaning that does not have spray and gel.On the other hand, the agglomerative aikyiaiurnirsoxan beta refers to contain the transparent aluminoxanes solution of spray and gel.The color of aluminoxanes solution is inessential, here as long as the solution substantial transparent does not contain spray and gel.With regard to the present invention, those skilled in the art will appreciate that except estimating, to also have the technology of gel particle in many monitoring aluminoxanes solutions to meet the demands.For example, the alternative Monitoring techniques that comprises the light beam transmission is suitable for measuring the state of aikyiaiurnirsoxan beta " not containing gel ".In case aluminoxanes solution becomes agglomerative or muddy, preferably allow material sedimentation in the container.Can make the aikyiaiurnirsoxan beta physical sepn from the gellike material that does not contain gel with traditional technology such as physical sepn or with method of extraction.The available gel particle that removes by filter separates or removes leaching thing from solution with other traditional liquid-solid isolation technique such as centrifugation or decant liquid.
The metallocenes that following general formula is represented can use with the aluminoxanes solution that does not contain gel.
Cp mMR nX qIn the formula, C pBe the cyclopentadienyl rings or derivatives thereof, M is the 4th, 5 or 6 group 4 transition metals, and R is alkyl or the-oxyl that 1-20 carbon atom arranged, and X is a halogen, m=1-3, and n=0-3, q=0-3, and m+n+q equals the oxidation shape of transition metal.Metallocenes can be that bridging is drunk or bridging not, can contain heteroatoms in structure.
Preferred metallocenes is represented with following general formula:
Figure A9419481600071
In the formula, M 1Be periodictable the 4th, 5 or 6 family's metals, R 1And R 2For identical or different, be hydrogen atom, C 1-C 10Alkyl, C 1-C 10Alkoxyl group, C 6-C 10Aryl, C 6-C 10Aryloxy, C 2-C 10Alkenyl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 8-C 40Aralkenyl or halogen atom; R 3And R 4Be hydrogen atom; R 5And R 6For identical or different, preferred identical, be halogen atom, C 1-C 10Alkyl (can by halogenated), C 6-C 10Aryl (can by halogenated), C 2-C 10Alkenyl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 8-C 40Aralkenyl ,-NR 2 15, SR 15, OR 15, OSiR 3 15Or PR 2 15, R wherein 15Be halogen atom, C 1-C 10Alkyl or C 6-C 10Aryl;
R 7For
Figure A9419481600073
=BR 11,=AlR 11,-Ge-,-Sn-,-O-,-S-,=SO ,=SO 2,=NR 11,=CO, PR 11Or=P (O) R 11R wherein 11, R 12And R 13Be identical or different, be hydrogen atom, halogen atom, C 1-C 20Alkyl, C 1-C 20Fluoro-alkyl, C 6-C 30Aryl, C 6-C 30Fluorinated aryl, C 1-C 20Alkoxyl group, C 2-C 20Alkenyl, C 7-C 40Aralkyl, C 8-C 40Aralkenyl, C 7-C 40Alkaryl or R 11And R 12, C 7-C 40Alkaryl or R 11And R 13Constitute ring system with the atom that links them; M 2Be Si, Ge or Sn, or derivatives thereof; R 8And R 9Be identical or different, R is arranged 11Implication; M and n are identical or different, are 0,1 or 2, and m+n is 0,1 or 2; And R 10For identical or different, R is arranged 11, R 12And R 13Implication, or two adjacent R 10Can be associated in and constitute ring system together.
The example of particularly preferred metallocene components comprises two (2-methyl-4, the 5-benzo indenyl) zirconium dichlorides of racemize-dimethylsilane two bases; Two (the 2-methyl indenyl) zirconium dichlorides of racemize-dimethylsilane two bases; Two (2-methyl-4, the 6-di-isopropyl indenyl) zirconium dichlorides of racemize-dimethylsilane two bases and two (2-methyl-4-phenyl indenyl) zirconium dichlorides of racemize-dimethylsilane two bases.
Illustrative metallocenes comprises that the monocyclopentadienyl titanium is luxuriant as pentamethyl-cyclopentadienyl titanous chloride etc., dimetylsilyl (tetramethyl-ring pentadienyl) (tertiary butyl amido) zirconium dimethyl (or zirconium dichloride) etc.; The bicyclic pentadiene zirconium is luxuriant as bicyclic pentadiene zirconium dichloride etc.
According to the preferred embodiment of preparation loaded catalyst, carrier is below 1% or 1% at about 800 ℃ of following about 18-24hr of dehydration or up to ignition loss preferably.Before using, with the loaded catalyst drying, remove basically might be adsorbed on residual solution in the carrier duct.Can obtain free-pouring loaded catalyst like this.
In case make loaded catalyst, it just can use under various polymerizing conditions.The polymerizing condition that is fit to comprises vapour phase polymerization or slurry polymerization.In preferred embodiments, in the slurry polymerization reactor, contact with alpha-olefin as prepared loaded catalyst disclosed herein.
Further specify the present invention with following non-limiting examples.
Experiment
All experiments are all carried out in the reactor that nitrogen wash is crossed.All solvents are all bought by commercial source, all through nitrogen purge or distillation and dry on the activatory molecular sieve.Aluminum alkyls is bought from commercial source with 20-25% (weight) solution.MAO buys from Shering Corporation with 30% (weight) toluene solution.
Polymerization procedure is as follows.In 2 liters of autoclaves of cleaning exsiccant that a usefulness propylene steam flush is crossed, triethyl aluminum (TEAL) (about 0.8ml, about 1.5M n-heptane solution) is added closed reactor, and about 750ml liquid propene of packing into then.When temperature of reaction during at about 30 ℃, by filling tube with about 250ml propylene washing catalyst (being 25% (weight) slurry oil).Reactor is heated to about 65 ℃ rapidly.30min is later on reactor cooling and the excessive propylene of emptying.Take out polymkeric substance and dry.
Carry out polymer analysis by US5026798 and 5017714 methods of describing.On industrial DSC instrument, measure the DSC fusing point and be called second fusing point.
DMS (MBI) ZrCl 2Two (2-methyl-4, the 5-benzo indenyl) zirconium dichlorides of=dimethylsilane two bases.
DMS (MBI) ZrCl 2Preparation
Diethylmethyl (2-naphthyl methyl) malonic ester (1)
Under heating, 5.15g (224mmol) sodium is dissolved in the 150ml dehydrated alcohol, at room temperature add 37.3ml (217mmol) methyl-malonic ester.Under 0 ℃ the solution of 50g (217mmol) 2-brooethyl naphthalene (96% purity) in 270ml ethanol is slowly being splashed into, and with the mixture heating up 4-5hr that refluxes.Pour into it in the frozen water and use ethyl acetate extraction.Also vaporize with the organic phase that dried over sodium sulfate merges.After drying under the oil pump vacuum, under 0 ℃, the oily residue is stirred with hexane, subsequent crystallisation goes out 55g (81%) compound 1.
Synthesizing of 2-methyl-3-naphthyl propionic acid (2)
The solution of 23.7g (422mmol) potassium hydroxide in 50ml water is added to 33.2g (105mmol) compound 1 in 70ml alcoholic acid solution, and with the mixture heating up 4hr that refluxes.Stripping goes out after the solvent, and solid residue is absorbed in the ethyl acetate, adds entry, and with hydrochloric acid the pH value is adjusted to 1.With the ethyl acetate extraction water for several times.After drying on the sal epsom, evaporate the organic phase that merges fully.Residue stirs with hexane and carries out crystallization.For decarboxylation, beige solid is heated down at 175 ℃, till gas is all emitted.Make 21g (94%) product 2 beige solids.
2-methyl-6,7-benzo 1-Indanone (3) synthetic
The 22ml thionyl chloride is added in 21g (98mmol) compound 2, removes steam, and with the mixture heating up 30min that refluxes.Steam excessive thionyl chloride then.Under the oil pump vacuum, from volatile compound, simply tell residue, it is dissolved in the methylene dichloride as under the inert gas at Ar then.Solution slowly is added drop-wise to 26g (196mmol) aluminum chloride in the suspension of 60ml methylene dichloride, and 30min then refluxes mixture heating up.It is poured in the ice, use dichloromethane extraction then.Also evaporate with the organic phase that dried over sodium sulfate merges.The oily residue of chromatographic separation black on 600g silica gel 60.8.6g (45%) compound 3 can flow out (light yellow solid) with hexane/ethyl acetate (9: 3) moving phase mixture.
2-methyl-4,5-benzindene (4) synthetic
At room temperature, 2.2g (59.5mmol) sodium borohydride is divided several parts be added to 7.8g (39.7mmol) indone (compound 3) and in the solution of 400ml tetrahydrofuran (THF)/carbinol mixture (2: 1), then mixture stirred 14hr.Pour into solution in the hydrochloric acid frozen water and use extracted with diethyl ether.The organic phase that washes merging with water is used dried over sodium sulfate several times then.The orange oil that stays after the solvent stripping gone out is dissolved in the 240ml toluene, then solution with 570ml (3.15mmol) tosic acid at 80 ℃ of heating 15min down.At room temperature wash with water several times, with dried over sodium sulfate and evaporation.Chromatogram separating residual thing on 300g silica gel 60.4.7g (65%) indenes 4 flows out with hexane/isopropyl ether (20: 1) moving phase mixture.
1H-NMR composes (360MHz, CDCl 3): 8.02 (1, d), 7.84 (1, m), 7.59 (1, d), 7.52 (1, d), 7.38-7.48 (2, m), 7.06 (1, m), 3.42 (2, s), 2.25 (3, d).
Synthesizing of two (2-methyl-4, the 5-benzo indenyl) silane (5) of dimethyl
At room temperature, 10.2ml (25.5mmol) 2.5M n-buli hexane solution is added in the solution of 4.6g (25.5mmol) compound 4 in the 50ml tetrahydrofuran (THF), 1hr then refluxes mixture heating up.Then this red solution at room temperature is added drop-wise to 1.55g (12mmol) dimethyldichlorosilane(DMCS) in the solution of 10ml tetrahydrofuran (THF), and with the mixture heating up 5-6hr that refluxes.Reaction soln is poured in the frozen water, and with extracted with diethyl ether several times.Also evaporate with the organic phase that dried over sodium sulfate merges.Residue is dry under the oil pump vacuum.Chromatographic separation on 300g silica gel 60.Moving phase mixture with hexane/3% ethyl acetate flows out the unreacted starting compound 4 of 500mg at last.Flow out ligand system compound 5 together with identical moving phase subsequently.Stripping goes out after the solvent, and ligand system is crystallization from hexane.Output be 1.7g (34%, or by the reaction indene compound 4 count 44%).
Synthesizing of racemize-dimethylsilane two (2-methyl-4,5-benzo indenyl) zirconium dichlorides (6) of two bases
At room temperature, Ar as inert gas under, 4.0ml (10.2mmol) 2.5MJ base lithium hexane solution is added to 1.7g (4.1mmol) compound 5 in the solution of 20ml tetrahydrofuran (THF), then mixture is at room temperature stirred 14hr.Hexane wash is used in the residue oil pump vacuum-drying that stays after solvent steamed then.The filbert powder that obtains 40-50 ℃ of following drying with the oil pump vacuum several hours is being added to 1.0g (4.0mmol) zirconium tetrachloride in the suspension of 25ml methylene dichloride then under-78 ℃.After room temperature, stripping goes out solvent with mixture heating up, with 20ml toluene extraction leftover, so that remove the meso-form compound from Metallocenic compound 6.Residue with the extraction of 40ml dichloromethane extraction toluene.Solution concentration is arrived more small volume, then-35 ℃ of following crystallizations.To amount to 970mg (42%) zirconium cyclopentadinyl compound 6 is divided into several parts and separates as pure racemoid.Racemoid 1H-NMR composes (300MHz, CDCl 3): 7.96 (2, m), 7.78 (2, m), 7.60 (2, d), 7.48-7.56 (4, m), 7.36 (2, d), 7.27 (2, s ,-Ind-H), 2.37 (6, s, Ind-CH 3), 1.36 (6, s, Si-CH 3).Mass spectrum: 574M +, proofread and correct explanation, proofread and correct the isotropic substance model.
Use the MAO that does not contain gel.The new isolating MAO that does not contain gel that use is obtained by agglomerative MAO solution decant.
Embodiment 1
Under agitation, (30% (weight) MAO 5.3ml) is added to metal DMS (MBI) ZrCl to the clear solution in MAO upper strata that does not contain gel that decant is obtained 2(0.05g) in the filtering solution of toluene (75ml).Solution Cheng Hong behind the 10min-orange and cleaning.The silicon oxide (6.0g, Davison 948, in about 800 ℃ of dehydrations down) that will dewater is added in the solution, then stir about 15min.Evaporate the about 2.5min of these slurries under about 40 ℃ on rotatory evaporator, this moment, slurries reached " mud " stage.At about 45 ℃ of inferior horns, after the 20min drying, reclaim and obtain light orange solid (6.59g).
Embodiment 2
Under agitation, (30% (weight) MAO 10.6ml) is added to metal DMS (MBI) ZrCl to the supernatant liquid that the decant that cleans is obtained 2(0.1g) in the filtering solution in toluene (50ml).Behind the 10min solution become reddish orange with the cleaning.The silicon oxide (2.0g, Divison 948,800 ℃ of dehydrations down) that will dewater is added in the solution, then stir about 15min.Filter this slurries, under 50 ℃ on rotatory evaporator drying solid.Filtrate is added back on the dried solid repeatedly.After 60 ℃ of following dryings, obtain reddish orange solid (2.53g) at last.
The correlated MAO Preparation of catalysts that contains gel:
Embodiment 3
Under agitation, (30% (weight) MAO 5.3ml) is added to metal DMAS (MBI) ZrCl to the agglomerative MAO slurries that will be obtained by even stirring in bottle 2(0.05g) in the filtering solution in toluene (75ml).Solution is reddish orange behind the 5min, and is muddy slightly.The silicon oxide (6.0g, Davison 948,800 ℃ of dehydrations down) that will dewater is added in the solution.Evaporate the about 25min of these slurries under about 44 ℃ on rotatory evaporator, this moment, slurries reached " mud " stage.Behind dry more about 35min under about 46 ℃, reclaim and obtain light orange solid (7.2g).
Under about 65 ℃, the catalyzer with embodiment 1,2 and 3 carries out polymerization under these conditions.The polymerization of carrying out with the catalyzer of embodiment 1 and 2 obtains the free flowing granule polymkeric substance, on reactor wall seldom or do not have a residue.The polymerization of carrying out with the catalyzer of embodiment 3 makes polymer lumps, and residue is arranged on reactor wall.Polymer lumps makes that the mensuration granularity is impossible.
Polymerization result is listed following table 1 and 2 in.
Table 1
The result of embodiment 1-3
Embodiment Catalyst amounts a??(mgs) ????DSC ????Mp(℃) ????Mw ????(×10 3) ??MWD
????1 ????588 ????149.5 ????695 ????2.2
????2 ????100 ????149.4 ????704 ????2.4
????3 ????600 ????150.4 ????748 ????2.2
A) each test has roughly the same Zr amount
Table 2
Size-grade distribution
Micron Embodiment 1 polymkeric substance % (weight) Embodiment 2 polymkeric substance % (weight)
????2000 ????2.4 ????0.7
????1400 ????1.6 ????0.4
????1000 ????2.4 ????0.6
????710 ????3.3 ????1.3
????500 ????4.7 ????17.4
????354 ????18.1 ????52.5
????250 ????32.2 ????22.6
????180 ????26.6 ????3.0
????125 ????7.4 ????0.6
????90 ????0.7 ????0.4
????63 ????0.2 ????0.1
????PAN ????0.2 ????0.1
Mean particle size 312.1 micron 376.0 micron
Embodiment proves that the use that does not contain the aluminoxanes solution of gel obtains (1) a kind of like this loaded catalyst, compares with the catalyzer that obtains with the agglomerative aluminoxanes solution, and it makes the polymkeric substance of better form, and (2) polymerization reactor is minimum or do not make dirty.This compares with using the agglomerative aluminoxanes solution, and the latter makes a kind of like this catalyzer, and the polymkeric substance of generation is luming on the agitator He on the polyreaction wall, and wherein polymkeric substance can not unrestricted flow or do not become granule type.
The explanation of embodiment preferred only is used for illustrating the present invention, rather than is used for limiting the present invention.After reading disclosure, those skilled in the art will appreciate that and recognize that the various improvement of the embodiment of being retouched or remodeling will can not run counter to spirit of the present invention and essence.Though here embodiment preferred relates to the heterogeneous polymerization condition, the isolating aikyiaiurnirsoxan beta of gel that do not contain is also applicable to the polymerization in homogeneous phase condition.

Claims (6)

1. one kind prepares polyolefinic method with agglomerative aikyiaiurnirsoxan beta (AO), and this method may further comprise the steps: remove gel, generate in olefinic polymerization and use the AO that is substantially free of gel in the polyolefinic process.
2. method for preparing loaded catalyst, this method may further comprise the steps:
(a) from agglomerative aikyiaiurnirsoxan beta (AO) solution, remove gel and the solution that generates mixed with following component, make loaded catalyst:
(b) Tuo Shui carrier, and
(c) at least a metallocenes.
3. an olefinic polymerization generates polyolefinic method, and this method comprises that the loaded catalyst that the method by claim 2 makes contacts under the polymerizing condition that is fit to at least a alkene.
4. according to the method for claim 3, wherein alkene contains 2 to about 20 carbon atoms.
5. each method in requiring according to aforesaid right, wherein aikyiaiurnirsoxan beta is a methylaluminoxane, methylaluminoxane is to use preferred 100: 1 to 500: 1 in 12: 1 to 1000: 1 by aluminium in the aikyiaiurnirsoxan beta and transition metal ratio in the metallocene components.
6. method for preparing load type catalyst system, this method may further comprise the steps:
(a) go out gel from agglomerative AO solution separating.Make the AO solution that is substantially free of gel;
(b) (a) solution that will not contain gel mixes with carrier and metallocenes, and described mixing step carries out in 7 days after step (a) is finished.
CN94194816A 1994-01-11 1994-11-16 Use of gel-free alumoxane solution Pending CN1149297A (en)

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US4921825A (en) * 1986-12-30 1990-05-01 Mitsui Petrochemical Industries, Ltd. Solid catalyst for olefin polymerization and processes for its production
US5093295A (en) * 1989-03-23 1992-03-03 Idemitsu Kosan Company Limited Process for producing homogeneous aluminoxane solution
DE4004477A1 (en) * 1990-02-14 1991-08-22 Schering Ag Solns. of oligomeric methyl-aluminoxane(s) - by partial hydrolysis of tri:methyl-aluminium with water in hydrocarbon solvent, esp. in rotor-stator reactor
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