CA2253449A1 - Use of heat treated alumoxanes in preparing supported catalysts - Google Patents
Use of heat treated alumoxanes in preparing supported catalysts Download PDFInfo
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- CA2253449A1 CA2253449A1 CA002253449A CA2253449A CA2253449A1 CA 2253449 A1 CA2253449 A1 CA 2253449A1 CA 002253449 A CA002253449 A CA 002253449A CA 2253449 A CA2253449 A CA 2253449A CA 2253449 A1 CA2253449 A1 CA 2253449A1
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- alumoxane
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- 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
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
Alumoxanes, and especially methylalumoxane, which provide supported metallocene and/or transition metal catalyst compositions having increased activity, are prepared by heating the alumoxane prior to placing it on the support.
Description
CA 022~3449 1998-11-03 W O 97143320 PCTrUS97/07734 USE OF HEAT TREATED ALUMOXANES
TN PREPARING SUPPORTED CATALYSTS
This invention relates generally to the production of aluminoxanes by reacting This invention relates generally to hydrocarbylalumoxane compositions and more specifically to improved supported alumoxane/metallocene olefin polymerization catalysts and their p.,_~alalion.
Hydrocarbylalumoxanes complexed with transition metal compounds, such as metallocenes, have been found to be very effective olefin polymerization catalysts. Methyl-alumoxanes are especially effective catalyst components in forming both homogeneous and supported catalysts. We have found that the activity and other properties of such supported catalysts is improved by heat treating the methylalumoxanes prior to placing them on the 1 0 support.
In accordance with this invention there is provided a process for preparing a supported alumoxane, said process comprising heat treating an alumoxane and placing the heat treated alumoxane on a support. A supported olefin polymerization catalyst is forrned by also adding a transition metal compound such, as a metallocene, to the support.
Also provided are supported alumoxane and alumoxane cont~inin~ catalyst compositlons.
Hydrocarbylalumoxanes are formed by the partial hydrolysis of hydrocarbyl-aluminum compounds and, especially, trialkylaluminums such as trimethylaluminum.Hydrocarbylalumoxanes may exist in the form of linear, cyclic, caged or polymeric structures with the simplest monomeric compounds being a tetraalkylalumoxane such as tetramethylalumoxane, (CH3)2AlOAl(CH3)2, or tetraethylalumoxane, (C2H5)2AlOAl(C2H5)2.
The compounds pl~r~l-cd for use in olef1n polymerization catalysts are oligomeric m~teri~
sometimes referred to as polyalkylalurnoxanes, which usually contain 4 to 20 of the repeating units:
R
I
~Al-O ~
where R is Cl-C~0 alkyl and especially preferred are polymethylalumoxanes (MAOs).
Although the linear and cyclic alumoxanes are often noted as having the structures CA 022~3449 1998-11-03 W O 97/43320 PCT~US97/07734 R ~Al-O ~mAlR2 and R
~Al-O ~n where m and n are integers of 4 or more, the exact configuration of the alumoxanes remains unknown.
Methylalumoxanes can contain some higher alkyl groups to improve their solubility.
Such modified methylalumoxanes are described, for example, in U.S. Patent No. 5,157,008.
Besides MAO, non-limiting examples of hydrocarbylalumoxanes for use in the invention include ethylalumoxane (EAO), isobutylalumoxane (IBAO), n-propylalumoxane, or n-octyl-alumoxane. The hydrocarbylalumoxanes can also contain up to 20 mole percent ~based on aluminum) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, or alkyl disiloxanes to improve their activity, solubility and/or stability.
The alumoxanes can be prepared as known in the art by the partial hydrolysis of trialkylaluminurn compounds. The trialkylaluminum compounds can be hydrolyzed byreacting them with either free water or water c~ solids, which can be either hydrates or porous materials which have absorbed water. Because it is difficult to conkol the reaction by adding water per se, even with vigorous agitation of the mixture, the free water is usually added in the form of a solution or a dispersion in an organic solvent. Suitable hydrates include salt hydrates such as, for example, CuSO4-5H2O, Al2(SO4)3- 1 8H2O, FeSO4-7H2O, AlCl3-6H2O, Al(NO3)3-9H2O, MgSO4-7H2O, MgCl2-6H2O, ZnSO4-7H20, Na2SO4-10H20, Na3PO4-12H20, LiBr-2H20, LiCl-lH20, LiI-2H20, LiI-3H20, KF-2H20, or NaBr-2H20 and alkali metal or ~lk~line earth metal hydroxide hydrates such as, for example, NaOH-H2O, NaOH-2H2O, Ba(OH)2-8H2O, KOH-2H2O, CsOH- 1 H2O, or LiOH- lH2O. Mixtures of any of the above hydrates can be used. The 30 mole ratios of free water or water in the hydrate or in porous materials such as alumina or CA 022~3449 1998-11-03 silica to total alkyl aluminum compounds in the mixture can vary widely, such as for example from 2: 1 to 1 :4, with ratios of from 4:3 to 1 :3.5 being preferred.
Such hydrocarbylalumoxanes and processes for pl~p~ lg hydrocarbylalumoxanes are described, for example, in U.S. PatentNos. 4,908,463; 4,924,018; 5,003,095; 5,041,583;
5,066,631; 5,099,050; 5,157,008; 5,157,137; 5,235,081; 5,248,801, and 5,371,260, whose entire teachings are incorporated herein by reference. The methylalumoxanes contain varying amounts, of from 5 to 35 mole percent, of the alurninum value as unreacted trimethylahlminl~m Preferably, the all-mimlm content as trimethylalllminllm is less than 23 mole percent of the total aluminum value, and, more preferably, less than 20 mole percent.
Non-limiting examples of olefin polymerization catalysts include metallocenes and/or transition metal compounds. As used in the specification and claims, the term "metallocene" includes metal derivatives which contain at least one cyclopentadienyl moiety.
Suitable metallocenes are well known in the art and include the metallocenes of (3roups 3, 4, 5, 6, lathanide and actinide metals, for example, the metallocenes which are described in U.S. Patent Nos. 2,864,843; 2,983,740; 4,665,046; 4,874,880; 4,892,851; 4,931,417;
4,952,713; 5,017,714; 5,026,798; 5,036,034; 5,064,802; 5,081,231; 5,145,819; 5,162,278;
5,245,019; 5,268,495; 5,276,208; 5,304,523; 5,324,800; 5,329,031; 5,329,033; 5,330,948, 5,347,025; 5,347,026; and 5,347,752.
Non-limiting, illustrative examples of such metallocenes are bis(cyclopentadienyl)-zirconium dimethyl, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)-zirconium monomethylmonochloride, bis(cyclopentadienyl)titanium dichloride, bis-(cyclopentadienyl)titanium difluoride, cyclopentadienylzirconium tri-(2-ethylhexanoate), (biscyclopentadienyl)zirconium hydrogen chloride, bis(cyclopentadienyl)hafnium dichloride, racemic and meso dimethylsilanylene-bis(methylcyclopentadienyl)hafnium dichloride, racemic dimethylsilanylene-bis(indenyl)hafnium dichloride, racemic ethylene-bis(indenyl)-zirconium dichloride, (~5-indenyl)hafnium trichloride, (~ 5Me5)hafnium trichloride, racemic dimethylsilanylene-bis(indenyl)thorium dichloride, racemic dimethylsilanylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride, racemic dimethylsilanylene-bis(indenyl)-uranium dichloride, racemic dimethylsilanylene-bis(2,3,5-trimethyl-1-cyclopentadienyl)-zirconium dichloride, racemic dimethylsilanylene(3-methylcyclopentadienyl)hafnium dichloride, racemic dimethylsilanylene-bis(1 -(2-methyl-4-ethyl)indenyl) zirconium . .
CA 022~3449 1998-11-03 W O 97/43320 PCT~US97/07734 dichloride; racemic dimethylsilanylene-bis(2-methyl-4,5,6,7-tetrahydro- 1 -indenyl)-zirconium dichloride, bis(pentamethylcyclopentadienyl)thorium dichloride, bis(penta-methylcyclopentadienyl)uraniumdichloride,(tert-butylamido)dimethyl(tetramethyl-tl5-cyclo-pentadienyl)silanetitanium dichloride, (tert-butylamido)dimethyl(tetramethyl-rl5-cyclopenta-S dienyl)silanechromium dichloride, (tert-butylamido)dimethyl(-rl5-cyclopentadienyl)silane-titanium dichloride, (tert-butylamido)dimethyl(tetramethyl-r~5-cyclopentadienyl)silane-methyltitanium bromide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)- l ,2-ethane-diyluranium dichloride, (tert-butylamido)(tetramethyl-l15-cyclopentadienyl)- 1 ,2-ethane-diyltitanium dichloride, (methylamido)(tetramethyl-~5-cyclopentadienyl) 1,2 ethane diylcerium dichloride, (methylamido)(tetramethyl-~5-cyclopentadienyl)- 1 ,2-ethane-diyltitanium dichloride, (ethylamido)(tetramethyl-~5-cyclopentadienyl)methylenetitanium dichloride, (tert-butylamido)dibenzyl(tetramethyl-rl5-cyclopentadienyl)-silanebenzyl-vanadium chloride, (benzylamido)dimethyl(indenyl)silanetitanium dichloride, and (phenyl-phosphido)dimethyl(tetramethyl-rl5-cyclopentadienyl)silanebenzyltitanium chloride.
Suitable transition metal compounds include the well known Ziegler-Natta catalyst compounds of Group 4-6 metals. Non-limiting illustrative examples of such transition metals include TiCI4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)Cl3, Ti(OC4H9)3CI, Ti(OC3H,)2Cl2, Ti(OCl7)2Br2, VCI4, VOCI3 VO(OC2H5)3, ZrC14, ZrCI3(OC2H5), Zr(OC2H5)4, or Cl(OC4H9)3 .
As known in the art the solid support can be any particulate solid, and particularly porous supports. Non-limiting examples include talc, magnesium halides, zeolites, inorganic oxides, and resinous support m~teri~l such as polyolefins. A ple~ d support material is an inorganic oxide in finely divided form. Such inorganic oxide support materials include Group IIA, IIIA, IVA or IVB metal oxides such as silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides that may be employed either alone or incombination with the silica, alumina or silica-alumina are magnesia, titania, or zirconia.
Other suitable support materials are finely divided polyolefins such as finely divided polyethylene.
The specific particle size, surface area, pore diameter, and pore volume of the support materials are selected as known in the art. For example, particle sizes of from 0.1 to 600 micrometers, surface area of from 50 to 1000m2/g, pore diameters of from 50-500 , ' ~ ' , ~
an~ u-~ls and pore vo1umes of from 0.3 to 5.0 cc/g. The supports can be dehydrated either rhemirqlly or by heating at IGlll~a~ s of from -100 to lOOO C in a dry inert gas for 1-24 hours as is known in the art.
In one aspect of the invention, the heat treated ~ rnoY~n~ is collll,lll~d with the support in the plestllcG of an inert organic solvent. The dry support can be added to a solution of the ---~oY~ -~ or vice versa. Al~n~1i~ely, the qt~lmoYqn~ can be combined with a solvent slurry of the carrier. The coating ~ c and pressure is not critical and ambient con~litirJnc can be used but, plGÇ. .ably the lt~ G is ,,,~;n~ ed at from 25 to 250 C, more preferably 60 to 150-C, ard the pressure at from 135.8 to 3548.9 kPa (5 to 500 psig), plG~.ably 135.8 to 446.1 kPa (5 to 50 psig), such as by using a closed system. An inert gas can be used to further increase the pressure.
Non-lin~iting ~Y~ of organic solvents for use in the process include qlirhq~ir h~/d.~lJons such as pentane, isop~,n~c, hexane, cyclohexane, heptane, octane, decane, dodecqn~, h~ ler~n~., or ~-d~-f, with those having carbon numbers of S to 10 being prGr,~lGd, and arol"àlic hyd,~l,(ns such as benzene, chlurobc.~.lc, toluene, xylene, or cumene, with those having carbon llull~b~ of 6 to 20 being l.r~Ç~ ,d. The aromatic solvents are IJçGrcllGd. The amount of solvent used is not critical and is generally chosen to be from 0.5 to 50, ~lefe.~bly 5 to 50 times, the total weight of coating material and carrier.
The olefin polyl,l~.iLalion catalyst can be combined with the support either before, after or s;.. ~ o~ly with the ql ""o~ . The catalyst can also be pre-reacted with the qhlmoYqnP.
The total loading of the catalyst system Culll~Oll.,.lb on the support and the relative pr(Jpolliû~ of catalyst ~ can vary over a wide range and are chosen based on theparticular materials and the pol~ Ld;on applirq~ion which are involved. For example, - metal catalysts are usually employed in amounts of from 0.01 to 10 mmoles/g ofsupport and the catalyst culll~ol~ b are generally used in proportions to provide mole ratios of metal atom in the catalyst to ~ .. atom in the qln-nnYqn~ of from 0.0002:1 to 0.2:1, although greater or lesser amounts can be used.
The ~ollGd catalyst systems which are prepared according to the process of the invention are useful in plUdUCillg olefin polymers and especially ethylene polymers, propylene polymers, ethylene/a-olefm copolymers, and styrene polymers and copolymers.
A~R ,~"'-'' !~H~T
IPEA/EP
.. . , . ....... ....... . , .. , . ... ~, . .... ...
CA 022~3449 1998-11-03 WO 97/43320 PCTrUS97/07734 In accordance with the invention, a solution of the hydrocarbylalumoxane is heattreated at a temperature of at least 35~C and preferably from 45 to 1 50~C for at least 0.5 hour and preferably from 1 to 20 hours prior to applying it to the support.
The invention is further illustrated by, but is not intended to be limited to, the S following examples.
Example 1 Approximately 600 grarns of a clear, 30% by weight solution of methylalumoxane (MAO) in toluene was transferred under nitrogen to a clean, dry, 2 liter reactor which was equipped with an agitator. The agitator was turned on and heated to a temperature of 55~C
by means of a circulating oil heating bath. Samples were taken at I hour, 3 hours and 7 hours after the reactor reached 55~C. No gel or any appreciable hazing of the MAO solution was observed either right after the samples were taken or after being stored in a freezer for one week. Any slight hazing disappeared after the samples were warmed to room temperature.
Example 2 Example 1 was repeated, except that the treating telllpeldlule was 85~C. The seven hour sample showed a slight hazing but no gel appeared. After storage in a freezer, some gel appeared in the seven hour sample. The hazing and gel disappeared after the samples were warmed to room t~ peld~ure.
Example 3 Example 1 was repeated, except that the treating temperature was 80~C with no agitation. After 8 hours a slight hazing was observed. At 36 hours, a second, clear layer was formed at the top of the reactor (approximately 1 -2-deep) but the bulk of the material was not gelled. The material was removed after 46 hours of heating and stored in a freezer.
Preparation of Supported Catalysts Supported catalysts were prepared by placing 18.6 gram samples of the heat treated MAO on 11.1 grams of vacuum dried (200~C) silica along with 0.62 grams of the metallocene catalyst using 87 grams of toluene as the solvent. After several washes, the dried catalyst product recovery was from 16.4 to 16.9 grams.
Polymerization Activitv Testin~
Samples of the supported catalysts were used to polymerize ethylene in accor~lce with the following procedure.
The reactor is heated to 130-C, under a flow of nitrogen, for at least I hour prior to polymerization. The reactor is then sealed and purged three times with high pressure nitrogen and cooled to 81.5-C. Isobutane (500 mL) is then added to the reactor and the t~ ; is controlled at 81.5 C. Ethylene is then added to the reactor to bring the total pressure to 2169.9 kPa (300 psig). The catalyst is prepared in the drybox, by weighing out 25 mg catalyst into the barrel of a syringe. The plunger is replaced. 1 mL of a 25% (w/w) of TIBA in toluene is added to the reactor. A 14 gauge needle is added to the end of the catalyst syringe and is then stuck into a septum sealed vial. Hexene (6.75 g) is weighed into a syringe, needle added, and stored in the same sealed bottle. The hexene is then added to the reactor through the catalyst addition bomb and rinsed in with approximately 250 mL of isobutane. The catalyst is then added in a similar fashion and rinsed in with the r,.. ~i.. ;.. g isobutane. The pressure of the reactor is increased to 3066.2 kPa (430 psig) and ...~ Fd there feeding ethylene on demand. Once the alu~'~ gets back to 81.5-C, the pol~.l.e.iLation is timed for I hour. When the polyll-~,l iLa~ion is complete, the isobutane and ethylene are vented off, the reactor is opened, and the polymer is scooped out. The polymer is then weighed and the activity C~IG~
The tests were colllpaled with two samples of methyl~ moY~ which had not been heat treated. The results are shown in Table 1.
r~r ~ J~=ET
l ~_ ~ i ,',_ D
., CA 022~3449 1998-11-03 W 097/43320 PCTrUS97107734 Table I
Sample ID~ lA lB lC 3A 3B Comp. 1 Comp. 2 Grams Sample 24 25 25 24 Rxn Time 45 60 55 50 60 40 60 Activity 6733 7370 7529 6294 7215 6963 6060 Fouling None None None None - - -Morphology Good Good Good Good Bulk Density .357 .353 .352 .362 gm/ml 10' IA, lB, lC Example 1 samples (55~C) where A = I hr, B = 3 hr, and C = 7 hr samples 3A, 3B Example 3 samples (85~C) where A = I hr, and B = 3 hr samples The results show that up to a 25 percent increase in activity over the comparisons could be achieved by using the process ofthe invention, depending upon the heating time and tem~ dlule.
15The process of heat treatment is believed to provide a more stable MAO product.
MAO is found to gel after time under normal storage conditions and more quickly at elevated temperatures. The formation of gel leads to variabilities in perforrnance and unfeasible processing in plants. The process of heat treatment reduces the arnount of gel forrnation and increases the activity of supported catalysts produced using the pretreated MAO products of 20 the invention.
TN PREPARING SUPPORTED CATALYSTS
This invention relates generally to the production of aluminoxanes by reacting This invention relates generally to hydrocarbylalumoxane compositions and more specifically to improved supported alumoxane/metallocene olefin polymerization catalysts and their p.,_~alalion.
Hydrocarbylalumoxanes complexed with transition metal compounds, such as metallocenes, have been found to be very effective olefin polymerization catalysts. Methyl-alumoxanes are especially effective catalyst components in forming both homogeneous and supported catalysts. We have found that the activity and other properties of such supported catalysts is improved by heat treating the methylalumoxanes prior to placing them on the 1 0 support.
In accordance with this invention there is provided a process for preparing a supported alumoxane, said process comprising heat treating an alumoxane and placing the heat treated alumoxane on a support. A supported olefin polymerization catalyst is forrned by also adding a transition metal compound such, as a metallocene, to the support.
Also provided are supported alumoxane and alumoxane cont~inin~ catalyst compositlons.
Hydrocarbylalumoxanes are formed by the partial hydrolysis of hydrocarbyl-aluminum compounds and, especially, trialkylaluminums such as trimethylaluminum.Hydrocarbylalumoxanes may exist in the form of linear, cyclic, caged or polymeric structures with the simplest monomeric compounds being a tetraalkylalumoxane such as tetramethylalumoxane, (CH3)2AlOAl(CH3)2, or tetraethylalumoxane, (C2H5)2AlOAl(C2H5)2.
The compounds pl~r~l-cd for use in olef1n polymerization catalysts are oligomeric m~teri~
sometimes referred to as polyalkylalurnoxanes, which usually contain 4 to 20 of the repeating units:
R
I
~Al-O ~
where R is Cl-C~0 alkyl and especially preferred are polymethylalumoxanes (MAOs).
Although the linear and cyclic alumoxanes are often noted as having the structures CA 022~3449 1998-11-03 W O 97/43320 PCT~US97/07734 R ~Al-O ~mAlR2 and R
~Al-O ~n where m and n are integers of 4 or more, the exact configuration of the alumoxanes remains unknown.
Methylalumoxanes can contain some higher alkyl groups to improve their solubility.
Such modified methylalumoxanes are described, for example, in U.S. Patent No. 5,157,008.
Besides MAO, non-limiting examples of hydrocarbylalumoxanes for use in the invention include ethylalumoxane (EAO), isobutylalumoxane (IBAO), n-propylalumoxane, or n-octyl-alumoxane. The hydrocarbylalumoxanes can also contain up to 20 mole percent ~based on aluminum) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, or alkyl disiloxanes to improve their activity, solubility and/or stability.
The alumoxanes can be prepared as known in the art by the partial hydrolysis of trialkylaluminurn compounds. The trialkylaluminum compounds can be hydrolyzed byreacting them with either free water or water c~ solids, which can be either hydrates or porous materials which have absorbed water. Because it is difficult to conkol the reaction by adding water per se, even with vigorous agitation of the mixture, the free water is usually added in the form of a solution or a dispersion in an organic solvent. Suitable hydrates include salt hydrates such as, for example, CuSO4-5H2O, Al2(SO4)3- 1 8H2O, FeSO4-7H2O, AlCl3-6H2O, Al(NO3)3-9H2O, MgSO4-7H2O, MgCl2-6H2O, ZnSO4-7H20, Na2SO4-10H20, Na3PO4-12H20, LiBr-2H20, LiCl-lH20, LiI-2H20, LiI-3H20, KF-2H20, or NaBr-2H20 and alkali metal or ~lk~line earth metal hydroxide hydrates such as, for example, NaOH-H2O, NaOH-2H2O, Ba(OH)2-8H2O, KOH-2H2O, CsOH- 1 H2O, or LiOH- lH2O. Mixtures of any of the above hydrates can be used. The 30 mole ratios of free water or water in the hydrate or in porous materials such as alumina or CA 022~3449 1998-11-03 silica to total alkyl aluminum compounds in the mixture can vary widely, such as for example from 2: 1 to 1 :4, with ratios of from 4:3 to 1 :3.5 being preferred.
Such hydrocarbylalumoxanes and processes for pl~p~ lg hydrocarbylalumoxanes are described, for example, in U.S. PatentNos. 4,908,463; 4,924,018; 5,003,095; 5,041,583;
5,066,631; 5,099,050; 5,157,008; 5,157,137; 5,235,081; 5,248,801, and 5,371,260, whose entire teachings are incorporated herein by reference. The methylalumoxanes contain varying amounts, of from 5 to 35 mole percent, of the alurninum value as unreacted trimethylahlminl~m Preferably, the all-mimlm content as trimethylalllminllm is less than 23 mole percent of the total aluminum value, and, more preferably, less than 20 mole percent.
Non-limiting examples of olefin polymerization catalysts include metallocenes and/or transition metal compounds. As used in the specification and claims, the term "metallocene" includes metal derivatives which contain at least one cyclopentadienyl moiety.
Suitable metallocenes are well known in the art and include the metallocenes of (3roups 3, 4, 5, 6, lathanide and actinide metals, for example, the metallocenes which are described in U.S. Patent Nos. 2,864,843; 2,983,740; 4,665,046; 4,874,880; 4,892,851; 4,931,417;
4,952,713; 5,017,714; 5,026,798; 5,036,034; 5,064,802; 5,081,231; 5,145,819; 5,162,278;
5,245,019; 5,268,495; 5,276,208; 5,304,523; 5,324,800; 5,329,031; 5,329,033; 5,330,948, 5,347,025; 5,347,026; and 5,347,752.
Non-limiting, illustrative examples of such metallocenes are bis(cyclopentadienyl)-zirconium dimethyl, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)-zirconium monomethylmonochloride, bis(cyclopentadienyl)titanium dichloride, bis-(cyclopentadienyl)titanium difluoride, cyclopentadienylzirconium tri-(2-ethylhexanoate), (biscyclopentadienyl)zirconium hydrogen chloride, bis(cyclopentadienyl)hafnium dichloride, racemic and meso dimethylsilanylene-bis(methylcyclopentadienyl)hafnium dichloride, racemic dimethylsilanylene-bis(indenyl)hafnium dichloride, racemic ethylene-bis(indenyl)-zirconium dichloride, (~5-indenyl)hafnium trichloride, (~ 5Me5)hafnium trichloride, racemic dimethylsilanylene-bis(indenyl)thorium dichloride, racemic dimethylsilanylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride, racemic dimethylsilanylene-bis(indenyl)-uranium dichloride, racemic dimethylsilanylene-bis(2,3,5-trimethyl-1-cyclopentadienyl)-zirconium dichloride, racemic dimethylsilanylene(3-methylcyclopentadienyl)hafnium dichloride, racemic dimethylsilanylene-bis(1 -(2-methyl-4-ethyl)indenyl) zirconium . .
CA 022~3449 1998-11-03 W O 97/43320 PCT~US97/07734 dichloride; racemic dimethylsilanylene-bis(2-methyl-4,5,6,7-tetrahydro- 1 -indenyl)-zirconium dichloride, bis(pentamethylcyclopentadienyl)thorium dichloride, bis(penta-methylcyclopentadienyl)uraniumdichloride,(tert-butylamido)dimethyl(tetramethyl-tl5-cyclo-pentadienyl)silanetitanium dichloride, (tert-butylamido)dimethyl(tetramethyl-rl5-cyclopenta-S dienyl)silanechromium dichloride, (tert-butylamido)dimethyl(-rl5-cyclopentadienyl)silane-titanium dichloride, (tert-butylamido)dimethyl(tetramethyl-r~5-cyclopentadienyl)silane-methyltitanium bromide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)- l ,2-ethane-diyluranium dichloride, (tert-butylamido)(tetramethyl-l15-cyclopentadienyl)- 1 ,2-ethane-diyltitanium dichloride, (methylamido)(tetramethyl-~5-cyclopentadienyl) 1,2 ethane diylcerium dichloride, (methylamido)(tetramethyl-~5-cyclopentadienyl)- 1 ,2-ethane-diyltitanium dichloride, (ethylamido)(tetramethyl-~5-cyclopentadienyl)methylenetitanium dichloride, (tert-butylamido)dibenzyl(tetramethyl-rl5-cyclopentadienyl)-silanebenzyl-vanadium chloride, (benzylamido)dimethyl(indenyl)silanetitanium dichloride, and (phenyl-phosphido)dimethyl(tetramethyl-rl5-cyclopentadienyl)silanebenzyltitanium chloride.
Suitable transition metal compounds include the well known Ziegler-Natta catalyst compounds of Group 4-6 metals. Non-limiting illustrative examples of such transition metals include TiCI4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)Cl3, Ti(OC4H9)3CI, Ti(OC3H,)2Cl2, Ti(OCl7)2Br2, VCI4, VOCI3 VO(OC2H5)3, ZrC14, ZrCI3(OC2H5), Zr(OC2H5)4, or Cl(OC4H9)3 .
As known in the art the solid support can be any particulate solid, and particularly porous supports. Non-limiting examples include talc, magnesium halides, zeolites, inorganic oxides, and resinous support m~teri~l such as polyolefins. A ple~ d support material is an inorganic oxide in finely divided form. Such inorganic oxide support materials include Group IIA, IIIA, IVA or IVB metal oxides such as silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides that may be employed either alone or incombination with the silica, alumina or silica-alumina are magnesia, titania, or zirconia.
Other suitable support materials are finely divided polyolefins such as finely divided polyethylene.
The specific particle size, surface area, pore diameter, and pore volume of the support materials are selected as known in the art. For example, particle sizes of from 0.1 to 600 micrometers, surface area of from 50 to 1000m2/g, pore diameters of from 50-500 , ' ~ ' , ~
an~ u-~ls and pore vo1umes of from 0.3 to 5.0 cc/g. The supports can be dehydrated either rhemirqlly or by heating at IGlll~a~ s of from -100 to lOOO C in a dry inert gas for 1-24 hours as is known in the art.
In one aspect of the invention, the heat treated ~ rnoY~n~ is collll,lll~d with the support in the plestllcG of an inert organic solvent. The dry support can be added to a solution of the ---~oY~ -~ or vice versa. Al~n~1i~ely, the qt~lmoYqn~ can be combined with a solvent slurry of the carrier. The coating ~ c and pressure is not critical and ambient con~litirJnc can be used but, plGÇ. .ably the lt~ G is ,,,~;n~ ed at from 25 to 250 C, more preferably 60 to 150-C, ard the pressure at from 135.8 to 3548.9 kPa (5 to 500 psig), plG~.ably 135.8 to 446.1 kPa (5 to 50 psig), such as by using a closed system. An inert gas can be used to further increase the pressure.
Non-lin~iting ~Y~ of organic solvents for use in the process include qlirhq~ir h~/d.~lJons such as pentane, isop~,n~c, hexane, cyclohexane, heptane, octane, decane, dodecqn~, h~ ler~n~., or ~-d~-f, with those having carbon numbers of S to 10 being prGr,~lGd, and arol"àlic hyd,~l,(ns such as benzene, chlurobc.~.lc, toluene, xylene, or cumene, with those having carbon llull~b~ of 6 to 20 being l.r~Ç~ ,d. The aromatic solvents are IJçGrcllGd. The amount of solvent used is not critical and is generally chosen to be from 0.5 to 50, ~lefe.~bly 5 to 50 times, the total weight of coating material and carrier.
The olefin polyl,l~.iLalion catalyst can be combined with the support either before, after or s;.. ~ o~ly with the ql ""o~ . The catalyst can also be pre-reacted with the qhlmoYqnP.
The total loading of the catalyst system Culll~Oll.,.lb on the support and the relative pr(Jpolliû~ of catalyst ~ can vary over a wide range and are chosen based on theparticular materials and the pol~ Ld;on applirq~ion which are involved. For example, - metal catalysts are usually employed in amounts of from 0.01 to 10 mmoles/g ofsupport and the catalyst culll~ol~ b are generally used in proportions to provide mole ratios of metal atom in the catalyst to ~ .. atom in the qln-nnYqn~ of from 0.0002:1 to 0.2:1, although greater or lesser amounts can be used.
The ~ollGd catalyst systems which are prepared according to the process of the invention are useful in plUdUCillg olefin polymers and especially ethylene polymers, propylene polymers, ethylene/a-olefm copolymers, and styrene polymers and copolymers.
A~R ,~"'-'' !~H~T
IPEA/EP
.. . , . ....... ....... . , .. , . ... ~, . .... ...
CA 022~3449 1998-11-03 WO 97/43320 PCTrUS97/07734 In accordance with the invention, a solution of the hydrocarbylalumoxane is heattreated at a temperature of at least 35~C and preferably from 45 to 1 50~C for at least 0.5 hour and preferably from 1 to 20 hours prior to applying it to the support.
The invention is further illustrated by, but is not intended to be limited to, the S following examples.
Example 1 Approximately 600 grarns of a clear, 30% by weight solution of methylalumoxane (MAO) in toluene was transferred under nitrogen to a clean, dry, 2 liter reactor which was equipped with an agitator. The agitator was turned on and heated to a temperature of 55~C
by means of a circulating oil heating bath. Samples were taken at I hour, 3 hours and 7 hours after the reactor reached 55~C. No gel or any appreciable hazing of the MAO solution was observed either right after the samples were taken or after being stored in a freezer for one week. Any slight hazing disappeared after the samples were warmed to room temperature.
Example 2 Example 1 was repeated, except that the treating telllpeldlule was 85~C. The seven hour sample showed a slight hazing but no gel appeared. After storage in a freezer, some gel appeared in the seven hour sample. The hazing and gel disappeared after the samples were warmed to room t~ peld~ure.
Example 3 Example 1 was repeated, except that the treating temperature was 80~C with no agitation. After 8 hours a slight hazing was observed. At 36 hours, a second, clear layer was formed at the top of the reactor (approximately 1 -2-deep) but the bulk of the material was not gelled. The material was removed after 46 hours of heating and stored in a freezer.
Preparation of Supported Catalysts Supported catalysts were prepared by placing 18.6 gram samples of the heat treated MAO on 11.1 grams of vacuum dried (200~C) silica along with 0.62 grams of the metallocene catalyst using 87 grams of toluene as the solvent. After several washes, the dried catalyst product recovery was from 16.4 to 16.9 grams.
Polymerization Activitv Testin~
Samples of the supported catalysts were used to polymerize ethylene in accor~lce with the following procedure.
The reactor is heated to 130-C, under a flow of nitrogen, for at least I hour prior to polymerization. The reactor is then sealed and purged three times with high pressure nitrogen and cooled to 81.5-C. Isobutane (500 mL) is then added to the reactor and the t~ ; is controlled at 81.5 C. Ethylene is then added to the reactor to bring the total pressure to 2169.9 kPa (300 psig). The catalyst is prepared in the drybox, by weighing out 25 mg catalyst into the barrel of a syringe. The plunger is replaced. 1 mL of a 25% (w/w) of TIBA in toluene is added to the reactor. A 14 gauge needle is added to the end of the catalyst syringe and is then stuck into a septum sealed vial. Hexene (6.75 g) is weighed into a syringe, needle added, and stored in the same sealed bottle. The hexene is then added to the reactor through the catalyst addition bomb and rinsed in with approximately 250 mL of isobutane. The catalyst is then added in a similar fashion and rinsed in with the r,.. ~i.. ;.. g isobutane. The pressure of the reactor is increased to 3066.2 kPa (430 psig) and ...~ Fd there feeding ethylene on demand. Once the alu~'~ gets back to 81.5-C, the pol~.l.e.iLation is timed for I hour. When the polyll-~,l iLa~ion is complete, the isobutane and ethylene are vented off, the reactor is opened, and the polymer is scooped out. The polymer is then weighed and the activity C~IG~
The tests were colllpaled with two samples of methyl~ moY~ which had not been heat treated. The results are shown in Table 1.
r~r ~ J~=ET
l ~_ ~ i ,',_ D
., CA 022~3449 1998-11-03 W 097/43320 PCTrUS97107734 Table I
Sample ID~ lA lB lC 3A 3B Comp. 1 Comp. 2 Grams Sample 24 25 25 24 Rxn Time 45 60 55 50 60 40 60 Activity 6733 7370 7529 6294 7215 6963 6060 Fouling None None None None - - -Morphology Good Good Good Good Bulk Density .357 .353 .352 .362 gm/ml 10' IA, lB, lC Example 1 samples (55~C) where A = I hr, B = 3 hr, and C = 7 hr samples 3A, 3B Example 3 samples (85~C) where A = I hr, and B = 3 hr samples The results show that up to a 25 percent increase in activity over the comparisons could be achieved by using the process ofthe invention, depending upon the heating time and tem~ dlule.
15The process of heat treatment is believed to provide a more stable MAO product.
MAO is found to gel after time under normal storage conditions and more quickly at elevated temperatures. The formation of gel leads to variabilities in perforrnance and unfeasible processing in plants. The process of heat treatment reduces the arnount of gel forrnation and increases the activity of supported catalysts produced using the pretreated MAO products of 20 the invention.
Claims (10)
1. A process of preparing a supported olefin polymerization catalyst of increased activity, which process comprises:
a) heating a solution of an alumoxane in an aromatic hydrocarbon solvent at a temperature of from 45 to 150°C for at least 3 hours; and b) placing on a catalyst support (i) heat-treated alumoxane from a) and (ii) a metallocene and/or a transition metal catalyst composition, to thereby form a supported catalyst having increased olefin polymerization activity.
a) heating a solution of an alumoxane in an aromatic hydrocarbon solvent at a temperature of from 45 to 150°C for at least 3 hours; and b) placing on a catalyst support (i) heat-treated alumoxane from a) and (ii) a metallocene and/or a transition metal catalyst composition, to thereby form a supported catalyst having increased olefin polymerization activity.
2. The process of claim 1 wherein said alumoxane is a methylalumoxane.
3. The process of claim 1 wherein (ii) in b) is a metallocene.
4. The process of claim 1 wherein said support comprises silica particles.
5. The process of claim 1 wherein said solution in a) is a 30% by weight solution.
6. The process of claim 1 wherein said solution in a) is a 30% by weight solution of a methylalumoxane, wherein (ii) in b) is a metallocene, and wherein said support comprises silica particles.
7. A supported catalyst of any of the preceding claims having an activity greater than if the alumoxane used in b) is not heated as specified in a).
8. A heat-treated composition formed by heating a solution of an alumoxane in an aromatic hydrocarbon solvent at a temperature of from 45 to 150°C for at least 3 hours so that a supported metallocene olefin polymerization catalyst made using said heat-treated composition has an activity greater than if the alumoxane solution had not been heated.
9. The heat-treated composition of claim 8 wherein said alumoxane is a methylalumoxane.
10. The heat-treated composition of claim 8 wherein said solution is a 30%
by weight solution of a methylalumoxane.
by weight solution of a methylalumoxane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US644,764 | 1996-05-10 | ||
| US08/644,764 US5739368A (en) | 1996-05-10 | 1996-05-10 | Use of heat treated alumoxanes in preparing supported catalysts |
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| Publication Number | Publication Date |
|---|---|
| CA2253449A1 true CA2253449A1 (en) | 1997-11-20 |
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| CA002253449A Abandoned CA2253449A1 (en) | 1996-05-10 | 1997-05-07 | Use of heat treated alumoxanes in preparing supported catalysts |
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|---|---|
| US (1) | US5739368A (en) |
| EP (1) | EP0897394B1 (en) |
| JP (1) | JP2000510888A (en) |
| CA (1) | CA2253449A1 (en) |
| DE (1) | DE69724116T2 (en) |
| ES (1) | ES2205216T3 (en) |
| WO (1) | WO1997043320A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693838A (en) * | 1995-11-13 | 1997-12-02 | Albemarle Corporation | Aluminoxane process and product |
| US5856255A (en) * | 1996-01-22 | 1999-01-05 | Albemarle Corporation | Preparation of supported auxiliary catalysts at elevated temperature and pressure in a closed vessel |
| US6034024A (en) * | 1996-05-10 | 2000-03-07 | Albemarle Corporation | Heat treated alumoxanes |
| EP1037931B1 (en) | 1997-12-08 | 2004-02-04 | Albemarle Corporation | Catalyst compositions of enhanced productivity |
| US6677265B1 (en) | 1997-12-08 | 2004-01-13 | Albemarle Corporation | Process of producing self-supported catalysts |
| US6551955B1 (en) | 1997-12-08 | 2003-04-22 | Albemarle Corporation | Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use |
| US6346586B1 (en) * | 1999-10-22 | 2002-02-12 | Univation Technologies, Llc | Method for preparing a supported catalyst system and its use in a polymerization process |
| US7220804B1 (en) * | 2000-10-13 | 2007-05-22 | Univation Technologies, Llc | Method for preparing a catalyst system and its use in a polymerization process |
| PL1856374T3 (en) * | 2005-02-04 | 2012-03-30 | Oxane Mat Inc | A composition and method for making a proppant |
| US7491444B2 (en) * | 2005-02-04 | 2009-02-17 | Oxane Materials, Inc. | Composition and method for making a proppant |
| US8012533B2 (en) * | 2005-02-04 | 2011-09-06 | Oxane Materials, Inc. | Composition and method for making a proppant |
| US7867613B2 (en) * | 2005-02-04 | 2011-01-11 | Oxane Materials, Inc. | Composition and method for making a proppant |
| EP2119732A1 (en) | 2008-05-16 | 2009-11-18 | Borealis Technology Oy | Metallocene catalyst compositions with improved properties, process for its preparation and use for preparing polyolefin homo- or copolymers |
| BR112012015322A2 (en) * | 2009-12-22 | 2019-09-24 | Oxane Mat Inc | proppant and method for forming the proppant |
| WO2011078923A1 (en) | 2009-12-23 | 2011-06-30 | Univation Technologies, Llc | Methods for producing catalyst systems |
| EP2588501B1 (en) * | 2010-07-01 | 2016-03-23 | Total Research & Technology Feluy | Modified catalyst supports |
| EP2663400A4 (en) | 2011-01-14 | 2014-07-30 | Grace W R & Co | Process of making modified metallocene catalyst, catalyst produced and use thereof |
| WO2014078919A1 (en) | 2012-11-26 | 2014-05-30 | Braskem S.A. | Metallocene catalyst supported by hybrid supporting means, process for producing same, polimerization process for producing an ethylene homopolymer or copolymer with broad or bimodal molar mass distribution, use of the supported metallocene catalyst and ethylene polymer with broad or bimodal molar mass distribution |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988002378A1 (en) * | 1986-09-24 | 1988-04-07 | Mitsui Petrochemical Industries, Ltd. | Process for polymerizing olefin |
| JP2538595B2 (en) * | 1987-05-13 | 1996-09-25 | 三井石油化学工業株式会社 | Solid catalyst for olefin polymerization |
| JP2583244B2 (en) * | 1987-10-14 | 1997-02-19 | 三菱化学株式会社 | Method for producing ethylene copolymer |
| US4925821A (en) * | 1987-12-17 | 1990-05-15 | Exxon Chemical Patents Inc. | Method for utilizing triethyaluminum to prepare an alumoxane support for an active metallocene catalyst |
| US5229478A (en) * | 1988-06-16 | 1993-07-20 | Exxon Chemical Patents Inc. | Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system |
| US5001205A (en) * | 1988-06-16 | 1991-03-19 | Exxon Chemical Patents Inc. | Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst |
| US5441920A (en) * | 1989-03-21 | 1995-08-15 | Exxon Chemical Patents Inc. | Silicon-bridged transition metal compounds |
| US5227440A (en) * | 1989-09-13 | 1993-07-13 | Exxon Chemical Patents Inc. | Mono-Cp heteroatom containing Group IVB transition metal complexes with MAO: supported catalysts for olefin polymerization |
| US5602067A (en) * | 1992-12-28 | 1997-02-11 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
| US5756416A (en) * | 1995-11-28 | 1998-05-26 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition having improved comonomer reactivity |
-
1996
- 1996-05-10 US US08/644,764 patent/US5739368A/en not_active Expired - Lifetime
-
1997
- 1997-05-07 CA CA002253449A patent/CA2253449A1/en not_active Abandoned
- 1997-05-07 WO PCT/US1997/007734 patent/WO1997043320A1/en active IP Right Grant
- 1997-05-07 ES ES97922711T patent/ES2205216T3/en not_active Expired - Lifetime
- 1997-05-07 DE DE69724116T patent/DE69724116T2/en not_active Expired - Lifetime
- 1997-05-07 JP JP09540938A patent/JP2000510888A/en not_active Ceased
- 1997-05-07 EP EP97922711A patent/EP0897394B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000510888A (en) | 2000-08-22 |
| EP0897394A1 (en) | 1999-02-24 |
| EP0897394B1 (en) | 2003-08-13 |
| DE69724116D1 (en) | 2003-09-18 |
| WO1997043320A1 (en) | 1997-11-20 |
| DE69724116T2 (en) | 2004-06-09 |
| ES2205216T3 (en) | 2004-05-01 |
| US5739368A (en) | 1998-04-14 |
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