WO1997018218A1 - Aluminoxane process and product - Google Patents
Aluminoxane process and product Download PDFInfo
- Publication number
- WO1997018218A1 WO1997018218A1 PCT/US1996/018244 US9618244W WO9718218A1 WO 1997018218 A1 WO1997018218 A1 WO 1997018218A1 US 9618244 W US9618244 W US 9618244W WO 9718218 A1 WO9718218 A1 WO 9718218A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- product
- stabilizing agent
- aluminum compound
- mao
- hydrocarbyl aluminum
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 20
- -1 lithium halide Chemical class 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 47
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 41
- 239000007787 solid Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000007872 degassing Methods 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 229910007928 ZrCl2 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- LWBWGOJHWAARSS-UHFFFAOYSA-N diethylalumanyloxy(diethyl)alumane Chemical compound CC[Al](CC)O[Al](CC)CC LWBWGOJHWAARSS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- ZBOGUDPFEVIZIQ-UHFFFAOYSA-N toluene;dihydrochloride Chemical compound Cl.Cl.CC1=CC=CC=C1 ZBOGUDPFEVIZIQ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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 Table
- 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
Definitions
- a process for making an aluminoxane comprising reacting water which contains a stabilizing agent with a hydrocarbyl aluminum compound in an organic solvent so as to produce an aluminoxane product. Also provided is a new stable aluminoxane product prepared by this novel process.
- Hydrocarbylaluminoxanes may exist in the form of linear, cyclic, caged or polymeric structures with the simplest compounds being a tetraalkylaluminoxane such as tetramethylaluminoxane, (CH 3 ) 2 A10A1(CH 3 ) 2 , or tetraethylaluminoxane, (C 2 H 5 ) 2 AlOAl-
- the compounds preferred for use in olefin polymerization catalysts usually contain about 4 to 20 ofthe repeating units:
- R is C,-C Intel alkyl and is preferably methyl.
- R is C,-C Intel alkyl and is preferably methyl.
- the exact structure of aluminoxanes has not been defined and they may contain linear, cyclic, caged and/or cross-linked species.
- Methylaluminoxanes normally have lower solubility in organic solvents than higher alkylaluminoxanes and the methylaluminoxane solutions tend to be cloudy or gelatinous due to the separation of particles and agglomerates.
- higher alkyl groups e.g.
- C 2 to C 20 can be included such as by hydrolyzing a mixture of trimethylaluminum with a C 2 to C 20 alkylaluminum compound such as, for example, triethylaluminum, tri-n-propyl-aluminum, triisobutyl- aluminum, tri-n-hexylaluminum, tri-n-octylaluminum or a triarylaluminum.
- methylaluminoxane any hydrocarbyl aluminum compound or mixture of compounds capable of reacting with water to form an aluminoxane can be used. This includes, for example, 1
- This invention relates generally to the preparation of aluminoxanes and more particularly to the preparation of hydrocarbylaluminoxanes, such as methylaluminoxane, by reacting a hydrocarbyl aluminum compound with water which contains a stabilizing agent, such as a metal salt, which solution is dispersed in an organic solvent.
- a stabilizing agent such as a metal salt
- Vandenberg, U. S. 3,219,591 reported the catalytic activity of compounds formed by the reaction of trialkyl aluminum with limited amounts of water in the polymerization of epichlorohydrin and other oxiranes. Shortly thereafter, Manyik, et al. U.S. 3,242,099 reported the use of aluminoxanes, made by reacting 0.85 - 1.05 moles of water with hydrocarbyl aluminum compounds such as triisobutylaluminum, as co-catalysts with certain transition metal compounds in the polymerization of mono-unsaturated alpha- olefins; e.g. ethylene and propylene. Isobutylaluminoxane was also made by adding an equal mole quantity of water to a heptane solution of triisobutylaluminum.
- Schoenthal, et al. U.S. 4,730,071 show the preparation of methylaluminoxane by dispersing water in toluene using an ultrasonic bath to cause the dispersion and then adding a toluene solution of trimethylaluminum to the dispersion.
- Schoenthal, et al. U.S. 4,730,072 is similar except it uses a high speed, high shear-inducing impeller to form the water dispersion.
- Edwards, et al. U.S. 4,722,736 describe an aluminoxane process in which water is introduced below the surface of a solution of hydrocarbyl aluminum adjacent to a stirrer which serves to immediately disperse the water in the hydrocarbon solution.
- a problem associated with free water addition to trialkylaluminum to produce aluminoxane solutions in organic solvents is that the solutions may produce gel and/or small particles which aggregate to form gel on standing. Even when the particles and/or gel are removed by filtration, additional gel can form in the solution after 2 or 3 weeks, especially when originally-prepared dilute solutions are concentrated to contain higher aluminoxane contents which are convenient for storage, shipment and use.
- trialkylaluminum, triarylaluminum, or mixed alkyl-aryl aluminum are convenient for storage, shipment and use.
- the preferred hydrocarbyl aluminum compounds are the alkyl aluminum compounds, especially trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, or trioctylaluminum. Of these, the more preferred are the tri-C ] . 4 -alkylaluminum compounds.
- methylaluminoxane and ethyl- aluminoxane are the more difficult to prepare because of the extreme reactivity of trimethylaluminum and triethylaluminum with water.
- the most reactive is trimethyl ⁇ aluminum and, accordingly, the preferred use of the process ofthe invention is to make methylaluminoxane.
- the reaction is carried out in an inert solvent.
- Any inert solvent can be used.
- the preferred solvents are aliphatic and aromatic hydrocarbons. Aromatic hydrocarbons are more preferred such as toluene, xylene, ethylbenzene, cumene, or mesitylene.
- the most preferred solvent is toluene.
- the concentration of the hydrocarbyl aluminum compounds in the inert solvent can range from about 1-30 weight percent. A preferred concentration is about 5-10 weight percent, more preferably 10-15 weight percent.
- the stabilizing agents are combined with the water used to hydrolyze the hydrocarbyl aluminum compounds.
- the term "stabilizing agent" as used herein includes any water soluble inorganic compound which is effective to provide alkylaluminoxanes having improved solubility in organic solvents when added to the water used to hydrolyze the hydrocarbyl aluminum compound.
- Preferred are water soluble (at least 1 gram/100 mL H 2 O at 25°C) metal salts and their ammonium analogs and especially alkali and alkaline earth metal halides.
- Non-limiting examples of such compounds include, NaBr, NaF, NaCl, LiCl, LiBr, LiF, Lil, Kcl, MgCl 2 , or Mgl.
- Halide salts of other metals as well as ammonium and metal nitrates, nitrites, sulfates, sulfites, phosphates, phosphites, borates, and carbonates can be used, for example Na 2 S0 4 , LiB0 2 , LiCO 3 , LiN0 2 , Li 2 SO MgSO 4 , NaNO 3 , NaNO 2 , NaPO 3 , Na 2 SO 3 , Al 2 (SO 4 ) 3 , or Na 3 PO 4 .
- Hydroxides such as LiOH, Ba(OH) 2 , KOH, CsOH, or NaOH can also be used.
- the stabilizing agents are added to make from about 0.05 percent by weight up to saturated solutions in water. Preferably from about 0.1 to 50 percent by weight aqueous solutions of stabilizing agents are used to hydrolyze the hydrocarbyl aluminum compounds.
- the stabilizing agent containing aqueous solutions can be combined with the hydrocarbyl aluminum compound in an inert organic solvent by any suitable manner such as the various ways which are known in the art.
- the process which is described in U.S. Patent No. 4,908,463 where water dispersed in an organic solvent is mixed with a solution ofthe hydrocarbyl aluminum in a "T-shaped" reactor.
- the amount of water dispersed in the solvent is preferably from about 0.25 to 5.0 weight percent, based on the weight of solvent. A more preferred amount is about 0.5 to 3.0 weight percent and most preferred is about 1.0 to 2.5 weight percent.
- the reactants are combined in proportions to provide from about 0.5 to 4.0 moles of hydrocarbyl aluminum compound per mole of water and from about 5.0 to 10,000 moles of hydrocarbyl aluminum compound per mole of stabilizing agent and, preferably, from about 50 to 5,000 moles of hydrocarbyl aluminum compound per mole of stabilizing agent.
- the invention is further illustrated by, but is not intended to be limited to, the following examples.
- An aqueous LiCl solution was prepared which contained 0.35 pounds (158.9 grams) of anhydrous LiCl salt in 3 gallons (1 1.36 liters) of solution.
- This salt solution was fed into a flow-through sonicating hom at a rate of 0.15 lbs. (68.1 gms) per hour and emulsified with toluene fed at a rate of 10 pounds (4.54 Kg) per hour.
- This emulsion was then reacted with a 12 weight percent trimethylaluminum (TMA) in toluene stream fed at a rate of 1 1 pounds (5.38 Kg) per hour.
- TMA-to-water mol ratio was 2.2 to 1.
- reaction mixture was then discharged into an eductor, mixed with methylaluminoxane (MAO) product solution from a pump-around loop, and finally discharged into the vapor space of a degassing vessel.
- MAO methylaluminoxane
- the toluene feed to the sonication horn was maintained at a temperature of -2°C.
- the TMA feed stream was maintained at a temperature of 5°C.
- degassing vessel was maintained at a temperature of 20°C.
- a sample ofthe new MAO was taken from the product stream during the run and was filtered.
- the solids produced from the reaction appear to filter easier than those formed by the standard MAO plain-water process.
- the filtered crude was then batch flashed to concentrate the product.
- the crude product was concentrated by flashing ofthe solvent using a 104°C wall temperature, a 60°C bulk temperature, and a vacuum of 100 mm Hg.
- the resulting solution was 8.86 weight percent Al.
- the TMA content of the solution was 4.84 weight percent TMA.
- the sample contained less than 20 ppm Cl.
- the aluminum content equates to a 15 weight percent solution of MAO. This 15 weight percent MAO solution was isolated from the flash pot as a clear liquid.
- the increased stability ofthe new MAO was demonstrated by placing a 15 weight percent solution in an oven at 60°C for 4 days, along with a 30 weight percent solution of conventional plain- water prepared MAO. After the 4 days the MAO was cloudy, but the new MAO was still clear. The oven temperature was then increased to 65°C for two more days. The new MAO remained clear. The oven temperature was then raised to 80°C. After one day at 80°C the new MAO was still clear, but regular MAO was completely gelled. After the oven test, the 15 weight percent MAO solution was used in a polymerization test to determine if it was active as a co-catalyst. Three mL of the 15 weight percent MAO solution were added to 100 mL of toluene.
- the polymerization test was repeated with standard plain-water prepared MAO. A change was made in the volume of MAO solution added based on the calculated weight percent MAO. Two mL of 23 weight percent MAO was added to 100 mL of toluene and then 0.25 mL ofthe zirconcene dichloride toluene solution was added. The reaction was performed under the same conditions for the same length of time as the above polymerization test. The polyethylene was collected, washed and dried. The final yield was 7.88 grams. Allowing for experimental error, this result equates to approximately the same degree of reactivity as the new MAO which has been heat aged. This demonstrates that the improved stability of the MAO prepared in accordance with the process of the invention is achieved without loss of activity.
- MAO was prepared using the same LiCl salt solution as in Example 1 , but the feed rates and temperatures were somewhat different.
- the salt solution was fed at a rate of 0.16 lbs (72.6 gms)/hr.
- the toluene stream was fed at 1 1.6 lbs (5.26 Kg)/hr.
- the TMA stream was fed at 1 1.6 lbs (5.26 Kg)/hr.
- a sample ofthe MAO was taken from the second run and was filtered and flashed under the same conditions as the first run sample of Example 1.
- the final weight percent Al of this sample was 1 1.4.
- the sample contained 7.96 weight percent TMA and 0.01 weight percent Cl. These results equate to an 18 weight percent MAO solution. This solution was clear upon leaving the flash pot. A portion of the sample was placed in an oven at 65°C for two days and it remained clear ang gel free. The oven was then increased to 80°C, and a sample of standard 10 weight percent MAO was placed in the oven. After one day the new MAO was still clear, but the 10 weight percent MAO began turning cloudy. The solids filtered from the sample from Example 2 were analyzed.
- the solids contained 1 1.5 weight percent Al, no detectable TMA, 0.35 weight percent Cl, and a gas/Al mole ratio of 1.47. This ratio is approximately equivalent to that of standard plain- water prepared MAO. These results indicate that these solids could be a higher molecular weight MAO.
- An experiment was conducted to determine if the solids could be used as both an activator and a support for a metallocene catalyst. The solid was rinsed from the bottle with toluene and collected on a coarse frit. The solids were then washed with isopentane and a fine white powder resulted. The solid was removed from the frit and slurried with toluene.
- the vessel was then placed in an oil bath at 80°C and the slurry was stirred at this temperature. Ethylene was applied to the vessel at a continuous pressure of 60 psig while being maintained at 80°C. After 10 minutes, the vessel was removed from the oil bath and the pressure on the vessel was released. The polyethylene produced from this reaction was washed, filtered, and dried. The final yield of polyethylene was 2.1 grams.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2237434 CA2237434A1 (en) | 1995-11-13 | 1996-11-12 | Aluminoxane process and product |
EP96939700A EP1021450A1 (en) | 1995-11-13 | 1996-11-12 | Aluminoxane process and product |
JP9519059A JP2000500460A (en) | 1995-11-13 | 1996-11-12 | Aluminoxane method and products |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/556,479 US5693838A (en) | 1995-11-13 | 1995-11-13 | Aluminoxane process and product |
US08/556,479 | 1995-11-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997018218A1 true WO1997018218A1 (en) | 1997-05-22 |
Family
ID=24221495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/018244 WO1997018218A1 (en) | 1995-11-13 | 1996-11-12 | Aluminoxane process and product |
Country Status (4)
Country | Link |
---|---|
US (2) | US5693838A (en) |
EP (1) | EP1021450A1 (en) |
JP (1) | JP2000500460A (en) |
WO (1) | WO1997018218A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010052239A1 (en) * | 2008-11-10 | 2010-05-14 | Borealis Ag | Process for the preparation of an unsupported, solid metallocene catalyst system and its use in polymerization of olefins |
WO2010052237A1 (en) * | 2008-11-10 | 2010-05-14 | Borealis Ag | Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins |
Families Citing this family (90)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5073600A (en) * | 1989-10-12 | 1991-12-17 | Shell Oil Company | Dispersant viscosity index improvers |
US6207130B1 (en) * | 1997-04-11 | 2001-03-27 | Rice University | Metal-exchanged carboxylato-alumoxanes and process of making metal-doped alumina |
US6322890B1 (en) * | 1998-03-30 | 2001-11-27 | Wm. Marsh Rice University | Supra-molecular alkylalumoxanes |
US6245868B1 (en) | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
US7244498B2 (en) * | 2002-06-12 | 2007-07-17 | Tda Research, Inc. | Nanoparticles modified with multiple organic acids |
CN101724110B (en) | 2002-10-15 | 2013-03-27 | 埃克森美孚化学专利公司 | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
US7459500B2 (en) | 2002-11-05 | 2008-12-02 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
US7579407B2 (en) | 2002-11-05 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
US6953764B2 (en) | 2003-05-02 | 2005-10-11 | Dow Global Technologies Inc. | High activity olefin polymerization catalyst and process |
US7399874B2 (en) | 2004-10-29 | 2008-07-15 | Exxonmobil Chemical Patents Inc. | Catalyst compound containing divalent tridentate ligand |
ATE502093T1 (en) * | 2004-12-21 | 2011-04-15 | Dow Global Technologies Inc | POLYPROPYLENE-BASED ADHESIVE COMPOSITION |
WO2007005364A2 (en) * | 2005-07-01 | 2007-01-11 | Albemarle Corporation | Haloaluminoxane compositions |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
DE102006004429A1 (en) * | 2006-01-31 | 2007-08-02 | Advanced Micro Devices, Inc., Sunnyvale | Forming metallization layers for high-density integrated circuit component interconnection, also deposits dielectric material of low permitivity |
ES2634440T3 (en) | 2006-05-17 | 2017-09-27 | Dow Global Technologies Llc | Polymerization process of polyethylene in high temperature solution |
EP2121776B1 (en) * | 2007-03-07 | 2012-12-12 | Dow Global Technologies LLC | Tethered supported transition metal complex |
TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
TW200936619A (en) | 2007-11-15 | 2009-09-01 | Univation Tech Llc | Polymerization catalysts, methods of making, methods of using, and polyolefin products made therefrom |
EP2212359B1 (en) * | 2007-11-19 | 2013-08-28 | Dow Global Technologies LLC | Long chain branched propylene-alpha-olefin copolymers |
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 |
US8309749B2 (en) | 2009-06-11 | 2012-11-13 | W R Grace & Co-Conn | Process of making aluminoxane and catalysts containing thus prepared aluminoxane |
BR112012009098B1 (en) | 2009-10-19 | 2018-05-22 | Sasol Technology PTY | OLIGOMERIZATION OF POLYMER-REDUCED OLEPHINIC COMPOUNDS |
WO2011078923A1 (en) | 2009-12-23 | 2011-06-30 | Univation Technologies, Llc | Methods for producing catalyst systems |
EP2354184B1 (en) | 2010-01-29 | 2012-08-22 | Borealis AG | Polyethylene moulding composition with improved stress crack/stiffness relationship and impact resistance |
EP2528970B1 (en) | 2010-01-29 | 2015-07-29 | Borealis AG | Improving homogeneity in polyethylene blends |
EP2354183B1 (en) | 2010-01-29 | 2012-08-22 | Borealis AG | Moulding composition |
RU2554881C2 (en) | 2010-02-18 | 2015-06-27 | Юнивейшн Текнолоджиз, Ллк | Methods of controlling polymerisation reactor operation |
WO2011103402A1 (en) | 2010-02-22 | 2011-08-25 | Univation Technologies, Llc | Catalyst systems and methods for using same to produce polyolefin products |
EP2386581B1 (en) | 2010-05-07 | 2014-03-26 | Borealis AG | Preparation of a solid catalyst system |
EP2386583A1 (en) | 2010-05-07 | 2011-11-16 | Borealis AG | Process for the preparation of a solid metallocene catalyst system and its use in polymerisation of olefins |
EP2386582B1 (en) | 2010-05-07 | 2016-02-17 | Borealis AG | Preparation of a solid catalyst system |
CN103261239B (en) | 2010-10-21 | 2016-04-06 | 尤尼威蒂恩技术有限责任公司 | Polyethylene and production method thereof |
MY161763A (en) | 2010-11-30 | 2017-05-15 | Univation Tech Llc | Catalyst composition having improved flow characteristics and methods of making and using the same |
RU2587080C2 (en) | 2010-11-30 | 2016-06-10 | Юнивейшн Текнолоджиз, Ллк | Methods for polymerisation of olefins using extracted metal carboxylates |
CN103534279B (en) | 2011-05-13 | 2016-08-17 | 尤尼威蒂恩技术有限责任公司 | The carbon monoxide-olefin polymeric being spray-dried and the polymerization using it |
WO2013028283A1 (en) | 2011-08-19 | 2013-02-28 | Univation Technologies, Llc | Catalyst systems and methods for using same to produce polyolefin products |
BR112014010906B1 (en) | 2011-11-08 | 2020-12-01 | Univation Technologies, Llc | method for producing a polyolefin |
EP2750797B1 (en) | 2011-11-08 | 2020-04-01 | Univation Technologies, LLC | Methods of preparing a catalyst system |
WO2014074981A1 (en) | 2012-11-12 | 2014-05-15 | Univation Technologies, Llc | Recycle gas cooler systems for gas-phase polymerization processes |
EP4039366A1 (en) | 2012-12-28 | 2022-08-10 | Univation Technologies, LLC | Supported catalyst with improved flowability |
KR102143409B1 (en) | 2013-01-30 | 2020-08-14 | 유니베이션 테크놀로지즈, 엘엘씨 | Processes for making catalyst compositions having improved flow |
CN105143285B (en) | 2013-02-07 | 2019-03-08 | 尤尼威蒂恩技术有限责任公司 | The preparation of polyolefin |
ES2644669T3 (en) | 2013-03-15 | 2017-11-29 | Univation Technologies, Llc | Ligands for catalysts |
CN105143281B (en) | 2013-03-15 | 2018-06-01 | 尤尼威蒂恩技术有限责任公司 | For three tooth nitrogen class ligands of olefin polymerization catalysis |
CN105308007B (en) | 2013-06-05 | 2017-07-21 | 尤尼威蒂恩技术有限责任公司 | Protect phenolic group |
EP3033389B1 (en) | 2013-08-14 | 2017-10-11 | Borealis AG | Propylene composition with improved impact resistance at low temperature |
JP6190961B2 (en) | 2013-08-21 | 2017-08-30 | ボレアリス・アクチェンゲゼルシャフトBorealis Ag | High flow polyolefin composition having high rigidity and toughness |
US9890275B2 (en) | 2013-08-21 | 2018-02-13 | Borealis Ag | High flow polyolefin composition with high stiffness and toughness |
EP2853563B1 (en) | 2013-09-27 | 2016-06-15 | Borealis AG | Films suitable for BOPP processing from polymers with high XS and high Tm |
EP2860031B1 (en) | 2013-10-11 | 2016-03-30 | Borealis AG | Machine direction oriented film for labels |
EP2865713B1 (en) | 2013-10-24 | 2016-04-20 | Borealis AG | Blow molded article based on bimodal random copolymer |
EP3060589B9 (en) | 2013-10-24 | 2018-04-18 | Borealis AG | Low melting pp homopolymer with high content of regioerrors and high molecular weight |
CN105722869B (en) | 2013-10-29 | 2017-09-12 | 北欧化工公司 | Solid single-point catalyst with high polymerization activity |
BR112016009549B1 (en) | 2013-11-22 | 2021-07-27 | Borealis Ag | LOW EMISSION PROPYLENE HOMOPOLYMER WITH HIGH FLUIDITY INDEX |
BR112016011829B1 (en) | 2013-12-04 | 2022-01-18 | Borealis Ag | COMPOSITION OF POLYPROPYLENE, FIBER AND MELT BLOWN, ARTICLE AND USE OF POLYPROPYLENE COMPOSITION |
EP3083777B1 (en) | 2013-12-18 | 2019-04-24 | Borealis AG | Bopp film with improved stiffness/toughness balance |
EP3094660B1 (en) | 2014-01-17 | 2018-12-19 | Borealis AG | Process for preparing propylene/1-butene copolymers |
WO2015117958A1 (en) | 2014-02-06 | 2015-08-13 | Borealis Ag | Soft copolymers with high impact strength |
WO2015117948A1 (en) | 2014-02-06 | 2015-08-13 | Borealis Ag | Soft and transparent impact copolymers |
EP2907841A1 (en) | 2014-02-14 | 2015-08-19 | Borealis AG | Polypropylene composite |
CN114957529A (en) | 2014-04-02 | 2022-08-30 | 尤尼威蒂恩技术有限责任公司 | Continuous compositions and methods of making and using the same |
ES2659731T3 (en) | 2014-05-20 | 2018-03-19 | Borealis Ag | Polypropylene composition for automotive interior applications |
SG11201701260WA (en) | 2014-08-19 | 2017-03-30 | Univation Tech Llc | Fluorinated catalyst supports and catalyst systems |
BR112017003314A2 (en) | 2014-08-19 | 2018-01-23 | Univation Tech Llc | fluorinated catalyst supports and catalyst systems |
CN106714967B (en) | 2014-08-19 | 2020-07-17 | 尤尼威蒂恩技术有限责任公司 | Fluorination catalyst support and catalyst system |
EP3268399B1 (en) | 2015-03-10 | 2021-01-20 | Univation Technologies, LLC | Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes |
SG11201708410UA (en) | 2015-04-20 | 2017-11-29 | Univation Tech Llc | Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom |
US10252967B2 (en) | 2015-04-20 | 2019-04-09 | Univation Technologies, Llc | Bridged bi-aromatic ligands and transition metal compounds prepared therefrom |
WO2016176135A1 (en) | 2015-04-27 | 2016-11-03 | Univation Technologies, Llc | Supported catalyst compositions having improved flow properties and preparation thereof |
WO2016195824A1 (en) | 2015-05-29 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Polymerization process using bridged metallocene compounds supported on organoaluminum treated layered silicate supports |
WO2016196334A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Single reactor production of polymers in gas or slurry phase |
WO2016197037A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Catalyst system comprising supported alumoxane and unsupported alumoxane particles |
EP3303422B1 (en) | 2015-06-05 | 2021-03-17 | ExxonMobil Chemical Patents Inc. | Production of heterophasic polymers in gas or slurry phase |
EP3353217A4 (en) | 2015-09-24 | 2018-11-07 | ExxonMobil Chemical Patents Inc. | Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports |
BR112020010103B1 (en) | 2017-12-18 | 2024-01-02 | Dow Global Technologies Llc | HAFNOCENE-TITANOCENE CATALYST SYSTEM, METHOD FOR MAKING HAFNOCENOTITANOCENE CATALYST SYSTEM AND METHOD FOR MAKING A POLYETHYLENE COMPOSITION |
EP3728350B1 (en) | 2017-12-18 | 2024-03-13 | Dow Global Technologies LLC | Zirconocene-titanocene catalyst system |
US11384170B2 (en) | 2017-12-21 | 2022-07-12 | Borealis Ag | Process for the preparation of solid catalyst |
JP7249349B2 (en) | 2017-12-27 | 2023-03-30 | ボレアリス エージー | Ziegler-Natta catalyst and its preparation |
EA202091168A1 (en) | 2017-12-28 | 2020-11-24 | Бореалис Аг | CATALYST AND ITS PRODUCTION |
SG11202008088YA (en) | 2018-03-19 | 2020-10-29 | Univation Tech Llc | Ethylene/1-hexene copolymer |
CN111886262B (en) | 2018-03-26 | 2023-05-23 | 陶氏环球技术有限责任公司 | Spray-dried zirconocene catalyst system |
CA3180366A1 (en) | 2020-05-29 | 2021-12-02 | Bethany M. NEILSON | Attenuated post-metallocene catalysts |
US20230151126A1 (en) | 2020-05-29 | 2023-05-18 | Dow Global Technologies Llc | Attenuated post-metallocene catalysts |
CA3180287A1 (en) | 2020-05-29 | 2021-12-02 | Rhett A. BAILLIE | Chemically converted catalysts |
US20230242695A1 (en) | 2020-05-29 | 2023-08-03 | Dow Global Technologies Llc | Chemically converted catalysts |
US20230151127A1 (en) | 2020-05-29 | 2023-05-18 | Dow Global Technologies Llc | Attenuated hybrid catalysts |
BR112022021802A2 (en) | 2020-05-29 | 2022-12-13 | Dow Global Technologies Llc | METHODS FOR PRODUCING A CATALYST AND A POLYOLIFIN POLYMER, ATENUATED POST-METAL CENTER CATALYST, METHOD OF FEEDING A POST-METAL CENTER CATALYST, AND, MULTIMODAL CATALYST SYSTEM |
WO2021247244A2 (en) | 2020-06-03 | 2021-12-09 | Exxonmobil Chemical Patents Inc. | Process for production of thermoplastic vulcanizates using supported catalyst systems and compositions made therefrom |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0645393A1 (en) * | 1993-09-20 | 1995-03-29 | Albemarle Corporation | Aluminoxanes having increased catalytic activity |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU624219B2 (en) * | 1989-02-16 | 1992-06-04 | Idemitsu Kosan Company Limited | Process for preparation of aluminoxane |
US5093295A (en) * | 1989-03-23 | 1992-03-03 | Idemitsu Kosan Company Limited | Process for producing homogeneous aluminoxane solution |
US5206401A (en) * | 1990-06-08 | 1993-04-27 | Akzo Chemicals Inc. | Method of making alkylaluminoxane |
US5041585A (en) * | 1990-06-08 | 1991-08-20 | Texas Alkyls, Inc. | Preparation of aluminoxanes |
US5041583A (en) * | 1990-06-28 | 1991-08-20 | Ethyl Corporation | Preparation of aluminoxanes |
US5157008A (en) * | 1991-08-01 | 1992-10-20 | Ethyl Corporation | Hydrocarbon solutions of alkylaluminoxane compounds |
US5329032A (en) * | 1992-03-18 | 1994-07-12 | Akzo Chemicals Inc. | Polymethylaluminoxane of enhanced solution stability |
US5739368A (en) * | 1996-05-10 | 1998-04-14 | Albemarle Corporation | Use of heat treated alumoxanes in preparing supported catalysts |
-
1995
- 1995-11-13 US US08/556,479 patent/US5693838A/en not_active Expired - Fee Related
-
1996
- 1996-11-12 EP EP96939700A patent/EP1021450A1/en not_active Withdrawn
- 1996-11-12 JP JP9519059A patent/JP2000500460A/en active Pending
- 1996-11-12 WO PCT/US1996/018244 patent/WO1997018218A1/en not_active Application Discontinuation
-
1997
- 1997-12-01 US US08/980,890 patent/US5902891A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0645393A1 (en) * | 1993-09-20 | 1995-03-29 | Albemarle Corporation | Aluminoxanes having increased catalytic activity |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010052239A1 (en) * | 2008-11-10 | 2010-05-14 | Borealis Ag | Process for the preparation of an unsupported, solid metallocene catalyst system and its use in polymerization of olefins |
WO2010052237A1 (en) * | 2008-11-10 | 2010-05-14 | Borealis Ag | Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins |
EP2186831A1 (en) * | 2008-11-10 | 2010-05-19 | Borealis AG | Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins |
EP2186832A1 (en) * | 2008-11-10 | 2010-05-19 | Borealis AG | Process for the preparation of an unsupported, solid metallocene catalyst system and its use in polymerization of olefins |
US8394733B2 (en) | 2008-11-10 | 2013-03-12 | Borealis Ag | Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins |
US8420562B2 (en) | 2008-11-10 | 2013-04-16 | Borealis Ag | Process for the preparation of an unsupported, solid metallocene catalyst system and its use in polymerization of olefins |
Also Published As
Publication number | Publication date |
---|---|
EP1021450A1 (en) | 2000-07-26 |
US5693838A (en) | 1997-12-02 |
JP2000500460A (en) | 2000-01-18 |
US5902891A (en) | 1999-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5693838A (en) | Aluminoxane process and product | |
US5157137A (en) | Method of making gel free alkylaluminoxane solutions | |
EP0463555B1 (en) | Preparation of aluminoxanes | |
EP0405221B1 (en) | Alkylaluminoxane process | |
US5157008A (en) | Hydrocarbon solutions of alkylaluminoxane compounds | |
EP0372617B2 (en) | Synthesis of methylaluminoxanes | |
US6194340B1 (en) | Method of stabilizing hydrocarbylaluminoxanes | |
EP0621279B1 (en) | Siloxy-aluminoxane compositions | |
CA1258265A (en) | Process for the preparation of alumoxanes | |
US4968827A (en) | Alkylaluminoxane process | |
US5086024A (en) | Catalyst system for polymerization of olefins | |
EP0633264B1 (en) | Tertiary amino-aluminoxane halides | |
WO1997014700A1 (en) | Liquid clathrate aluminoxane compositions | |
WO1998047929A1 (en) | Liquid clathrate aluminoxane compositions | |
US5099050A (en) | Preparation of aluminoxanes | |
EP0315234A1 (en) | Process for preparation of aluminoxanes | |
EP0744414B1 (en) | Aluminoxanate compositions | |
CS378589A3 (en) | Process for preparing mixture of linear and cyclic alkyl aluminooxanes | |
CA2237434A1 (en) | Aluminoxane process and product | |
JP4544660B2 (en) | Method for producing aluminoxane | |
CA2015549C (en) | Synthesis of methylaluminoxanes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2237434 Country of ref document: CA Ref country code: CA Ref document number: 2237434 Kind code of ref document: A Format of ref document f/p: F |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1997 519059 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1996939700 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1996939700 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1996939700 Country of ref document: EP |