CA1296348C - Process for the preparation of aluminoxanes - Google Patents
Process for the preparation of aluminoxanesInfo
- Publication number
- CA1296348C CA1296348C CA000543358A CA543358A CA1296348C CA 1296348 C CA1296348 C CA 1296348C CA 000543358 A CA000543358 A CA 000543358A CA 543358 A CA543358 A CA 543358A CA 1296348 C CA1296348 C CA 1296348C
- Authority
- CA
- Canada
- Prior art keywords
- water
- aluminoxanes
- solvent
- solution
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
- C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
-
- 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
Abstract
A B S T R A C T
PROCESS FOR THE PREPARATION OF ALUMINOXANES
Process for preparing aluminoxanes fron trialkylaluminium compounds and an ultrasonically produced water dispersion.
PROCESS FOR THE PREPARATION OF ALUMINOXANES
Process for preparing aluminoxanes fron trialkylaluminium compounds and an ultrasonically produced water dispersion.
Description
PRDCESS FOR THE PgEPARATIOM OF ALUMINOXANES
This invention relates ~o a process for the preparation of alumlnoxanes - also referred to as alumoxanes - which are useful in ccmbination with transition metal co~pcunds to prepare polymerization catalysts.
AlumLnoxanes find use as ccmponents in polymerization and oligomerization catalysts. Alumunoxanes have been prepared by reacting a hydrocarbon solution containing trialkylaluminium with hydrated crystalline salts such as CuSO4.5H2O as described in "Mech~nism of Stereochemical Control in Propylene Polymerization with Soluble Grcup 4B Metallocene-Methylalumoxane Catalysts, J. Am.
Chem Soc., 1984, 106. 6355-6364), and A12tS04)3.9H20 a in "Zirconium Catalysts Polymerize Olefins Faster," Chem. & Eng.
News, July 4, 1983~ 29-30 and U.S. patent specification 4,544,762.
This technique requires guarding against the possibility of contam~
inating the alumLnoKanes with small amounts of the crystalline salts which can act as poisons when the aluminoxanes are used in polymerization catalysts. In U.S. patent specification 3,300,458, a method is descriked for preparing aluminoxanes which consists of contacting triaIkylaluminium dissolved in a hydrocarbon solvent with a second hydrccarbon s~ream which has been saturated with water by contacting the solvent with water in a solvent saturator.
In this technique, however, since the amount of water present in the hydrocarbon is small, being limited by the solubility of water in the solvent, relatively large amounts of solvent are required to prepare the aluminoxanes. Manyik et al in "A Soluble Chromium-based Catalyst for Ethylene Trimerization or Polymeriza~ion", Journal of Catalysis, 47, 197-209, (1977) also describe the use of water wetted solvent and further describes the use of the direct addition of water to a dilute solution of trialkylalumlnium. Hawever, the water addition must be done very slowly in order to prepare the aluminsxane rather than aluminium hydroxide.
3~8 It is an object of the present invention to use a manimal amount of solvent and to allow for a relatively rapid reaction rate to be used over a broad ranye of temperatures.
Accord mgly, the invention provide~ a process for the prepara-tion of alumincxanes which process comprises mixing a first solutionof a triaLkylalumLnium ccmpound in a liquid, dry, inert hydrocarbon solvent with a second solution of a liquid, inert, hydrocarbon solvent having water ultrasonically dispersed therein wherein the trialkylalumLmum cc~pound and the water react to produce an I o aluminoxane.
The aluminoxanes are well-known in the art and are polymeric aluminium compounds which can be represented by the general formLla (R-Al-O)n which is a cyclic compound and R(R-Al-O)n ~ , which is a linear compound. In the general formula, R is preferably an alkyl group having in the range of fm m 1 to 5 carbon atcms, such as, for e~ample, methyl, ethyl, prcpyl, butyl and pentyl and n is an integer mm l to about 20. Generally, in the preparation of aluminoxanes from trialkylaluminium and water, a mixture of the linear and cyclic campounds is obtained.
The aluminoxanes are prepared according to the invention by reacting a Cl bo C5 triaLkyl~luminium co~pound ~ ~ ) in a suit~ble solvent with ~ater which has been ultrasonically dispersed in a suitable solvent. Illustrat ve examples of suitable trialkylaluminium compounds are trimethylaluminium, triethylaluminium, tri-isopropyl-aluminium, tri-n-propylaluminium, tri-isobutylaluminium and tri-n-pentylaluminiuml. Methyl and ethyl groups are preferred. Methyl yluups are particularly preferred.
The inert solvents that can be used to dissolve the triaIkyl-aluminium or disperse the water are well kncwn and include the saturated aliphatic ccmpounds such as butane, pentane, hexane, heptane, octane, isoctane and the purified kerosenes; the cyclo-aliphatics such as cyclobutane, cyclopentane, cyclohexane, cyclo-heptane, methylcyclopentane and dimethylcycl~pent~ne; alkenes such as butene, hexene and octene; cycloaLkenes such as cyclohexene; and the aromatic sclvents such as benzene, toluene and xylene. The major requiremints in the selection of a solvent are that it be liquid at the reaction temperature, tha~ it does not reach with the trialkylalumunium compound or with water or mterfere with any subsequent reaction wherein the alumdncNanes are used in polymer-ization catalysts. The solvents must be cKygen-free. HydrcKyl groups, ether groups, carboxyl groups, keto grcups and the like adversely affect preparation of the aluminoxanes.
The aluminoxanes can be prGduced over a wide range of tempera-tures, fr~m above the melting point of the solvent to up to the boilmg point at the pressure used. Generally, temperatures below about 50 ~C are used. Relatively low temperatures can be utilized with the appropriate solvent, say, -100 C or lower. Pressures are not critical and will typically vary from atmospheric to about 35 bar.
IS There are numerous pieces of equipment available commercially containing ultrasonic transducers that can be used to ultrasonically disper~e the water in the solvent. The ultrasonic baths that æe rea~ily available commercially provide suitable means for dispersmg the water in the solvent. The amount of water to be dispersed in the organic solvent ranges from just above the limits of solubility of water in the solvent to less than about 5% by weight. There are several alternative methods that can be used to prepare the alumlnoxanes accor~ing to the present invention. The preferred method is to first ultrasonically disperse the water in a suitable solvent, and, while maintaining the ultrasonic power, add the solution of triaLkylaluminlum to the water dispersion, allowing the trialkylalumunium to react with the water to produce the aluminoxane.
Alternatively, the ultrasonic pcwer can be shut off prior to adding (with mixing) the triaLkylaluminium solution. The key here is to carry out the reaction prior to the breakup of the water dispersion.
The disper~ion can be maLntained for relatively long periods of time by cooling the dispersion. Very satisfactory results have been obtained by cooling the dispersion to dry ice (-78.5 C) temperatures.
The above reaction should be carried out in an inert, ~or example nitrogen or argon atlmosphere~
After reaction, the solvent can be stripped and the aluminoxane isolated as a stable white pcwder. Preferably, however, the aluminoxane is left dissolved in the solvent, which can then be reacted with suitable transition met 1 ccmpounds to form polymer-S ization ca~alysts.
In ~eneral, the molar ratio of trialkylaluminium to water will be about 1:1 although væ iations of this ratio can occur without adversely affecting the aluminQKane product, i.e., the Al/water molar ratio can vary between 0.65:1 to 2:1, pre~erably 0.75:1 to 1.25:1.
The follcwing examples further illustrate the invention.
Example 1 The following represents a typical preparation of an aluminoxane at ambient conditions by the process of the instant mvention.
Dry toluene t20 ml) was placed in a bottle fitted with a ni~rogen purge system and the bottle was placed in an ultrasonic bath (Branson). The ultrasonic was started and water (4 mTQl) was added through a hypodermic syringe. After a five min period of sonification, 4 mmol of trimethylal~mLnium (as a 25% by weight solution of trimethylaluminium in toluene) was added. Sonification was continued during the reaction to prepare the alumincKane as evidenced by gas e~olution.
Exa~le 2 Exa~ple 1 was repeated in substantially the same manner except that the ultrasc mc bath was maintained at 0 C.
Ex~n~le 3 EXample 1 was repeated in substantially the same manner except that the ultrasonic bath was maintained at a temperature of 50 C.
Example 4 Dry toluene (20 ml) was plaoe d Ln a bottle fitted with a nitrogen purge system and the bottle was placed in the ultrasonic bath. Water (4 mmol) was injected and sonification was continued for SL~ m m. The ~Qttle was then rencved and chilled in a dry-ice acetone mLxture. After chilling, 4 mmol of trim~ethylaluminium (as a 3 ~
25~ by we1ght solution in toluene) ~as injected and the reaction to the alumunL ~ne was allowed to go to ca~?letiQn.
EX~u~le S
l-Octene 150 ml) was placed in a nitrogen purged bottle which was placed in an ultrasonlc bath at ambient ~emperature. Approxi-mately 4 m~ol of water was injected. After 3 mun of sc m fication to disperse the water about 4 mmol of trimethylal~Lniun (as a 25% by weight solution in toluene) was added aDd thR reaction to the alum m cxane was allowed to go to co~pl~tion.
Example 6 Part A - Oligomerization catalysts aocording to the teachings of oo-pending Canadian patent application Serial No. 544,409 were prepared and tested.
To the al~mlnox_ne soluti~ns of Examples 1-5, 0.5 m~ol of bis(cyclopentadienyl)zirccnium dichlQride were added with stirring to prepare the catalysts. To e~?les 1-4 were ad~ed 50 ml of l-octene, Example 5 already oontaining l-oc~ene frcm the alumunoxan=
preparation. The resultant mixtures w~re heated to 40 C for 30 mun before removing samples for gas chromatographic analysis. The conversions of l-octene to oligomers, presented in table 1 herein-after, are highest where the alumuncxanes had been prepared at a temperature in the range of frcm -100 C to ~50 C.
~BLE 1 ; ~ _ Aluminc~an from Exam~le % Conversion of l-octene _r , .,, _ __ . .
1 49.8 2 65.0 3 11.7 4 93.5 61.9 ~/~
~`3~.
Part B - Various amounts of water were used to prepare the _ aluminoxane and the results on the dimerization catalysts ~7ere measuredO
The catalysts were prepared as follows: 20 ml of dry toluene were placed in a boktle fitted with a nitrogen purge system and the bottle was placed in an ultrasonic bath (Branson~ The ultrasonic was started and the designated ancunt of water was added through a hypodermQc syringe. After a five minute period of sonification, 4 mmol of trimethylaluminium (as a 25% by weight solution in toluene) was added. After the reaction was oompleted (as evidenced by termination of gas evolution~, 50 ml of l-octene and 0.5 mmol of bis(cyclcpentadienyl)zirconium dichloride was added and ~he mixture was heated to 40 C. After 30 min, samples were removed for analysis.
The results, presented in table 2 hereinafter, show that the conversions of l-octene are highest when the mDlar ratio Al to water ranges from 0.65:1 to 2:1.
I~BLE 2 Water, Al/water Conversion mmol molar ratioof l-octene, %
3.0 0.75 37 3.2 0.8 57 3!6 0.9 72 3.9 0.975 67 4.0 1.0 49 4.2 1.05 29 4.7 1.175 12 ~ ~r~
This invention relates ~o a process for the preparation of alumlnoxanes - also referred to as alumoxanes - which are useful in ccmbination with transition metal co~pcunds to prepare polymerization catalysts.
AlumLnoxanes find use as ccmponents in polymerization and oligomerization catalysts. Alumunoxanes have been prepared by reacting a hydrocarbon solution containing trialkylaluminium with hydrated crystalline salts such as CuSO4.5H2O as described in "Mech~nism of Stereochemical Control in Propylene Polymerization with Soluble Grcup 4B Metallocene-Methylalumoxane Catalysts, J. Am.
Chem Soc., 1984, 106. 6355-6364), and A12tS04)3.9H20 a in "Zirconium Catalysts Polymerize Olefins Faster," Chem. & Eng.
News, July 4, 1983~ 29-30 and U.S. patent specification 4,544,762.
This technique requires guarding against the possibility of contam~
inating the alumLnoKanes with small amounts of the crystalline salts which can act as poisons when the aluminoxanes are used in polymerization catalysts. In U.S. patent specification 3,300,458, a method is descriked for preparing aluminoxanes which consists of contacting triaIkylaluminium dissolved in a hydrocarbon solvent with a second hydrccarbon s~ream which has been saturated with water by contacting the solvent with water in a solvent saturator.
In this technique, however, since the amount of water present in the hydrocarbon is small, being limited by the solubility of water in the solvent, relatively large amounts of solvent are required to prepare the aluminoxanes. Manyik et al in "A Soluble Chromium-based Catalyst for Ethylene Trimerization or Polymeriza~ion", Journal of Catalysis, 47, 197-209, (1977) also describe the use of water wetted solvent and further describes the use of the direct addition of water to a dilute solution of trialkylalumlnium. Hawever, the water addition must be done very slowly in order to prepare the aluminsxane rather than aluminium hydroxide.
3~8 It is an object of the present invention to use a manimal amount of solvent and to allow for a relatively rapid reaction rate to be used over a broad ranye of temperatures.
Accord mgly, the invention provide~ a process for the prepara-tion of alumincxanes which process comprises mixing a first solutionof a triaLkylalumLnium ccmpound in a liquid, dry, inert hydrocarbon solvent with a second solution of a liquid, inert, hydrocarbon solvent having water ultrasonically dispersed therein wherein the trialkylalumLmum cc~pound and the water react to produce an I o aluminoxane.
The aluminoxanes are well-known in the art and are polymeric aluminium compounds which can be represented by the general formLla (R-Al-O)n which is a cyclic compound and R(R-Al-O)n ~ , which is a linear compound. In the general formula, R is preferably an alkyl group having in the range of fm m 1 to 5 carbon atcms, such as, for e~ample, methyl, ethyl, prcpyl, butyl and pentyl and n is an integer mm l to about 20. Generally, in the preparation of aluminoxanes from trialkylaluminium and water, a mixture of the linear and cyclic campounds is obtained.
The aluminoxanes are prepared according to the invention by reacting a Cl bo C5 triaLkyl~luminium co~pound ~ ~ ) in a suit~ble solvent with ~ater which has been ultrasonically dispersed in a suitable solvent. Illustrat ve examples of suitable trialkylaluminium compounds are trimethylaluminium, triethylaluminium, tri-isopropyl-aluminium, tri-n-propylaluminium, tri-isobutylaluminium and tri-n-pentylaluminiuml. Methyl and ethyl groups are preferred. Methyl yluups are particularly preferred.
The inert solvents that can be used to dissolve the triaIkyl-aluminium or disperse the water are well kncwn and include the saturated aliphatic ccmpounds such as butane, pentane, hexane, heptane, octane, isoctane and the purified kerosenes; the cyclo-aliphatics such as cyclobutane, cyclopentane, cyclohexane, cyclo-heptane, methylcyclopentane and dimethylcycl~pent~ne; alkenes such as butene, hexene and octene; cycloaLkenes such as cyclohexene; and the aromatic sclvents such as benzene, toluene and xylene. The major requiremints in the selection of a solvent are that it be liquid at the reaction temperature, tha~ it does not reach with the trialkylalumunium compound or with water or mterfere with any subsequent reaction wherein the alumdncNanes are used in polymer-ization catalysts. The solvents must be cKygen-free. HydrcKyl groups, ether groups, carboxyl groups, keto grcups and the like adversely affect preparation of the aluminoxanes.
The aluminoxanes can be prGduced over a wide range of tempera-tures, fr~m above the melting point of the solvent to up to the boilmg point at the pressure used. Generally, temperatures below about 50 ~C are used. Relatively low temperatures can be utilized with the appropriate solvent, say, -100 C or lower. Pressures are not critical and will typically vary from atmospheric to about 35 bar.
IS There are numerous pieces of equipment available commercially containing ultrasonic transducers that can be used to ultrasonically disper~e the water in the solvent. The ultrasonic baths that æe rea~ily available commercially provide suitable means for dispersmg the water in the solvent. The amount of water to be dispersed in the organic solvent ranges from just above the limits of solubility of water in the solvent to less than about 5% by weight. There are several alternative methods that can be used to prepare the alumlnoxanes accor~ing to the present invention. The preferred method is to first ultrasonically disperse the water in a suitable solvent, and, while maintaining the ultrasonic power, add the solution of triaLkylaluminlum to the water dispersion, allowing the trialkylalumunium to react with the water to produce the aluminoxane.
Alternatively, the ultrasonic pcwer can be shut off prior to adding (with mixing) the triaLkylaluminium solution. The key here is to carry out the reaction prior to the breakup of the water dispersion.
The disper~ion can be maLntained for relatively long periods of time by cooling the dispersion. Very satisfactory results have been obtained by cooling the dispersion to dry ice (-78.5 C) temperatures.
The above reaction should be carried out in an inert, ~or example nitrogen or argon atlmosphere~
After reaction, the solvent can be stripped and the aluminoxane isolated as a stable white pcwder. Preferably, however, the aluminoxane is left dissolved in the solvent, which can then be reacted with suitable transition met 1 ccmpounds to form polymer-S ization ca~alysts.
In ~eneral, the molar ratio of trialkylaluminium to water will be about 1:1 although væ iations of this ratio can occur without adversely affecting the aluminQKane product, i.e., the Al/water molar ratio can vary between 0.65:1 to 2:1, pre~erably 0.75:1 to 1.25:1.
The follcwing examples further illustrate the invention.
Example 1 The following represents a typical preparation of an aluminoxane at ambient conditions by the process of the instant mvention.
Dry toluene t20 ml) was placed in a bottle fitted with a ni~rogen purge system and the bottle was placed in an ultrasonic bath (Branson). The ultrasonic was started and water (4 mTQl) was added through a hypodermic syringe. After a five min period of sonification, 4 mmol of trimethylal~mLnium (as a 25% by weight solution of trimethylaluminium in toluene) was added. Sonification was continued during the reaction to prepare the alumincKane as evidenced by gas e~olution.
Exa~le 2 Exa~ple 1 was repeated in substantially the same manner except that the ultrasc mc bath was maintained at 0 C.
Ex~n~le 3 EXample 1 was repeated in substantially the same manner except that the ultrasonic bath was maintained at a temperature of 50 C.
Example 4 Dry toluene (20 ml) was plaoe d Ln a bottle fitted with a nitrogen purge system and the bottle was placed in the ultrasonic bath. Water (4 mmol) was injected and sonification was continued for SL~ m m. The ~Qttle was then rencved and chilled in a dry-ice acetone mLxture. After chilling, 4 mmol of trim~ethylaluminium (as a 3 ~
25~ by we1ght solution in toluene) ~as injected and the reaction to the alumunL ~ne was allowed to go to ca~?letiQn.
EX~u~le S
l-Octene 150 ml) was placed in a nitrogen purged bottle which was placed in an ultrasonlc bath at ambient ~emperature. Approxi-mately 4 m~ol of water was injected. After 3 mun of sc m fication to disperse the water about 4 mmol of trimethylal~Lniun (as a 25% by weight solution in toluene) was added aDd thR reaction to the alum m cxane was allowed to go to co~pl~tion.
Example 6 Part A - Oligomerization catalysts aocording to the teachings of oo-pending Canadian patent application Serial No. 544,409 were prepared and tested.
To the al~mlnox_ne soluti~ns of Examples 1-5, 0.5 m~ol of bis(cyclopentadienyl)zirccnium dichlQride were added with stirring to prepare the catalysts. To e~?les 1-4 were ad~ed 50 ml of l-octene, Example 5 already oontaining l-oc~ene frcm the alumunoxan=
preparation. The resultant mixtures w~re heated to 40 C for 30 mun before removing samples for gas chromatographic analysis. The conversions of l-octene to oligomers, presented in table 1 herein-after, are highest where the alumuncxanes had been prepared at a temperature in the range of frcm -100 C to ~50 C.
~BLE 1 ; ~ _ Aluminc~an from Exam~le % Conversion of l-octene _r , .,, _ __ . .
1 49.8 2 65.0 3 11.7 4 93.5 61.9 ~/~
~`3~.
Part B - Various amounts of water were used to prepare the _ aluminoxane and the results on the dimerization catalysts ~7ere measuredO
The catalysts were prepared as follows: 20 ml of dry toluene were placed in a boktle fitted with a nitrogen purge system and the bottle was placed in an ultrasonic bath (Branson~ The ultrasonic was started and the designated ancunt of water was added through a hypodermQc syringe. After a five minute period of sonification, 4 mmol of trimethylaluminium (as a 25% by weight solution in toluene) was added. After the reaction was oompleted (as evidenced by termination of gas evolution~, 50 ml of l-octene and 0.5 mmol of bis(cyclcpentadienyl)zirconium dichloride was added and ~he mixture was heated to 40 C. After 30 min, samples were removed for analysis.
The results, presented in table 2 hereinafter, show that the conversions of l-octene are highest when the mDlar ratio Al to water ranges from 0.65:1 to 2:1.
I~BLE 2 Water, Al/water Conversion mmol molar ratioof l-octene, %
3.0 0.75 37 3.2 0.8 57 3!6 0.9 72 3.9 0.975 67 4.0 1.0 49 4.2 1.05 29 4.7 1.175 12 ~ ~r~
Claims (8)
1. A process for the preparation of aluminoxanes which process comprises mixing a first solution of a trialkylaluminium compound in a liquid, dry, inert hydrocarbon solvent with a second solution of a liquid, inert, hydrocarbon solvent having water ultrasonically dispersed therein wherein the trialkylaluminium compound and the water react to produce an aluminoxane.
2. A process as claimed in claim 1 wherein the alkyl moiety of the trialkylaluminium compound is an alkyl group having in the range of from 1 to 5 carbon atoms.
3. A process as claimed in claim 2 wherein the alkyl moiety is a methyl or ethyl group.
4. A process as claimed in claim 1, 2 or 3 wherein a molar ratio of trialkylaluminium compound to water in the range of from 0.65:1 to 2:1 is used.
5. A process as claimed in claim 4 wherein the molar ratio is in the range of from 0.75:1 to 1.25:1.
6. A process as claimed in claim 5 wherein the molar ratio is about 1:1.
7. A process as claimed in claim 1, 2 or 3 which is carried out at a temperature in the range of from -100°C to +50°C.
8. A process as claimed in claim 1, 2 or 3 wherein said first solution is added to said second solution while maintaining ultrasonic power.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/896,689 US4730071A (en) | 1986-08-15 | 1986-08-15 | Process for preparing aluminoxanes |
| US896,689 | 1992-06-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1296348C true CA1296348C (en) | 1992-02-25 |
Family
ID=25406643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000543358A Expired - Fee Related CA1296348C (en) | 1986-08-15 | 1987-07-30 | Process for the preparation of aluminoxanes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4730071A (en) |
| EP (1) | EP0258924A3 (en) |
| JP (1) | JPS6356508A (en) |
| AU (1) | AU603370B2 (en) |
| CA (1) | CA1296348C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4730072A (en) * | 1986-08-15 | 1988-03-08 | Shell Oil Company | Process for preparing aluminoxanes |
| DE3731665A1 (en) * | 1987-09-20 | 1989-04-06 | Basf Ag | METHOD FOR THE PRODUCTION OF ALUMOXANES, IN PARTICULAR METHYLALUMOXAN, FROM WATER AND ALUMINUM ORGANYLEN, IN PARTICULAR ALUMINUM TRIMETHYL IN INERT CARBONATES |
| US5043515A (en) * | 1989-08-08 | 1991-08-27 | Shell Oil Company | Ethylene oligomerization catalyst and process |
| US5041584A (en) * | 1988-12-02 | 1991-08-20 | Texas Alkyls, Inc. | Modified methylaluminoxane |
| US4908463A (en) * | 1988-12-05 | 1990-03-13 | Ethyl Corporation | Aluminoxane process |
| US4937363A (en) * | 1989-02-21 | 1990-06-26 | Ethyl Corporation | Falling film aluminoxane process |
| US5103031A (en) * | 1989-02-21 | 1992-04-07 | Ethyl Corporation | Falling film aluminoxane process |
| US4968827A (en) * | 1989-06-06 | 1990-11-06 | Ethyl Corporation | Alkylaluminoxane process |
| US4924018A (en) * | 1989-06-26 | 1990-05-08 | Ethyl Corporation | Alkylaluminoxane process |
| 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 |
| US5041585A (en) * | 1990-06-08 | 1991-08-20 | Texas Alkyls, Inc. | Preparation of aluminoxanes |
| US5206401A (en) * | 1990-06-08 | 1993-04-27 | Akzo Chemicals Inc. | Method of making alkylaluminoxane |
| US5099050A (en) * | 1991-04-15 | 1992-03-24 | Ethyl Corporation | Preparation of aluminoxanes |
| US5157137A (en) * | 1991-07-26 | 1992-10-20 | Ethyl Corporation | Method of making gel free alkylaluminoxane solutions |
| US5235081A (en) * | 1992-03-18 | 1993-08-10 | Ethyl Corporation | Method of removing gel forming materials from methylaluminoxanes |
| US5811618A (en) * | 1991-10-16 | 1998-09-22 | Amoco Corporation | Ethylene trimerization |
| US5248801A (en) * | 1992-08-27 | 1993-09-28 | Ethyl Corporation | Preparation of methylaluminoxanes |
| DE69422462T2 (en) * | 1993-09-20 | 2000-05-31 | Albemarle Corp | Aluminoxanes with increased catalytic activity |
| DE69513803T2 (en) * | 1994-01-11 | 2000-06-29 | Exxon Chemical Patents Inc | ALUMOXANS AND CATALYSTS CONTAINING ALUMOXANS |
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| US5606087A (en) * | 1996-04-19 | 1997-02-25 | Albemarle Corporation | Process for making aluminoxanes |
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| US5663394A (en) * | 1996-07-15 | 1997-09-02 | Albemarle Corporation | High yield aluminoxane synthesis process |
| US6078582A (en) | 1996-12-18 | 2000-06-20 | Bell Atlantic Network Services, Inc. | Internet long distance telephone service |
| US6137869A (en) | 1997-09-16 | 2000-10-24 | Bell Atlantic Network Services, Inc. | Network session management |
| US6574216B1 (en) | 1997-03-11 | 2003-06-03 | Verizon Services Corp. | Packet data network voice call quality monitoring |
| US6870827B1 (en) | 1997-03-19 | 2005-03-22 | Verizon Services Corp. | Voice call alternative routing through PSTN and internet networks |
| US6292479B1 (en) | 1997-03-19 | 2001-09-18 | Bell Atlantic Network Services, Inc. | Transport of caller identification information through diverse communication networks |
| CA2246608A1 (en) * | 1998-09-04 | 2000-03-04 | Bayer Inc. | Gel reduction in high cis-1,4 polybutadiene production process |
| KR100430438B1 (en) | 1998-10-22 | 2004-07-19 | 대림산업 주식회사 | Supported metallocence catalyst, preparing method thereof and preparing method of polyolefin using the same |
| US6150478A (en) | 1999-06-04 | 2000-11-21 | Union Carbide Chemicals & Plastics Technology Corporation | Ultrasonic catalyst feed for fluid bed olefin polymerization |
| US8238538B2 (en) | 2009-05-28 | 2012-08-07 | Comcast Cable Communications, Llc | Stateful home phone service |
| EP2440564A4 (en) | 2009-06-11 | 2014-07-09 | Grace W R & Co | Process of making aluminoxane and catalysts comprising thus prepared aluminoxane |
| ZA201402828B (en) * | 2013-04-17 | 2014-12-23 | China Petroleum & Chem Corp | Catalyst compositions and process for ethylene oligomerization |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3300458A (en) * | 1963-08-19 | 1967-01-24 | Union Carbide Corp | Continuous processes for the production of ethylene polymers and catalysts suitable therefor |
| US3242099A (en) * | 1964-03-27 | 1966-03-22 | Union Carbide Corp | Olefin polymerization catalysts |
| GB1176692A (en) * | 1967-01-25 | 1970-01-07 | Union Carbide Corp | Continuous Processes for the production of Ethylene Polymers and Catalysts suitable therefor |
| JPS5210800B2 (en) * | 1973-12-07 | 1977-03-26 | ||
| US4055634A (en) * | 1974-02-22 | 1977-10-25 | Hoffmann-La Roche, Inc. | Antiperspirants |
| JPS57158792A (en) * | 1981-03-26 | 1982-09-30 | Sumitomo Chem Co Ltd | Preparation of bisdialkylaluminum oxane |
| DE3240383A1 (en) * | 1982-11-02 | 1984-05-03 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING OLIGOMER ALUMINOXANES |
| US4730072A (en) * | 1986-08-15 | 1988-03-08 | Shell Oil Company | Process for preparing aluminoxanes |
| US4658078A (en) * | 1986-08-15 | 1987-04-14 | Shell Oil Company | Vinylidene olefin process |
-
1986
- 1986-08-15 US US06/896,689 patent/US4730071A/en not_active Expired - Lifetime
-
1987
- 1987-07-30 CA CA000543358A patent/CA1296348C/en not_active Expired - Fee Related
- 1987-08-12 EP EP87201534A patent/EP0258924A3/en not_active Ceased
- 1987-08-13 AU AU76838/87A patent/AU603370B2/en not_active Ceased
- 1987-08-13 JP JP62202593A patent/JPS6356508A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0258924A3 (en) | 1989-09-06 |
| AU7683887A (en) | 1988-02-18 |
| EP0258924A2 (en) | 1988-03-09 |
| US4730071A (en) | 1988-03-08 |
| JPS6356508A (en) | 1988-03-11 |
| AU603370B2 (en) | 1990-11-15 |
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