WO1995018809A1 - Utilisation d'une solution d'alumoxane sans gel - Google Patents

Utilisation d'une solution d'alumoxane sans gel Download PDF

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Publication number
WO1995018809A1
WO1995018809A1 PCT/US1994/013367 US9413367W WO9518809A1 WO 1995018809 A1 WO1995018809 A1 WO 1995018809A1 US 9413367 W US9413367 W US 9413367W WO 9518809 A1 WO9518809 A1 WO 9518809A1
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WO
WIPO (PCT)
Prior art keywords
solution
alumoxane
gel
free
supported catalyst
Prior art date
Application number
PCT/US1994/013367
Other languages
English (en)
Inventor
Terry John Burkhardt
William Barry Brandley
Original Assignee
Exxon Chemical Patents Inc.
Hoechst Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc., Hoechst Aktiengesellschaft filed Critical Exxon Chemical Patents Inc.
Priority to JP7518473A priority Critical patent/JPH09507515A/ja
Priority to EP95903569A priority patent/EP0739346A1/fr
Publication of WO1995018809A1 publication Critical patent/WO1995018809A1/fr

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Classifications

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

Definitions

  • TITLE USE OF GEL-FREE ALUMOXANE SOLUTION
  • This invention relates generally to polymerization catalysts and more particularly to the use of gel-free alumoxane solution as a cocatalyst for supported catalyst useful in the polymerization of olefins.
  • Alumoxane solution has been known to be a useful cocatalyst with metallocenes in the formation of catalysts.
  • a problem associated with alumoxane is the formation of gel or gel like particles. Problems associated with gelled alumoxane include the gels plugging up reactor lines, enhancing fines or fine formation, creating difficulties in preparation of supported catalysts.
  • US 5,157,137 incorporated by reference, discloses a method for removing gels and providing clear gel-free solutions of alumoxane, and especially methylalumoxane by treating the solution with certain alkali or alkaline earth metals compounds. US '137 discloses that the treatment results in alumoxane solutions that are stable and remain gel-free for extended periods of time.
  • This invention relates to a method in which visually clear, substantially transparent, gel-free alumoxane solution (AO) is used in the preparation of polyolefins comprising the step of removing gels from a gelled alumoxane solution, or alternately separating gels from AO with gels and using the substantially gel-free AO during the polymerization of olefins to polyolefins.
  • AO alumoxane solution
  • the invention further relates to a method for producing a supported catalyst comprising combining visually clear, substantially gel-free alumoxane (AO) obtained by separating gelled-AO from AO containing gelled particles with a dehydrated carrier and at least one metallocene to form a supported catalyst.
  • AO substantially gel-free alumoxane
  • the invention further relates to a method for the polymerization of olefins to polyolefins combining contacting the supported catalyst prepared as described above with at least one olefin under suitable polymerization conditions, wherein the olefin contains from 2 to about 20 carbon atoms.
  • the gel-free alumoxane is preferably methylalumoxane employed in a ratio of aluminum in the alumoxane to transition metal in the metallocene of about 12: 1 to about 1000: 1, preferably in a ratio of about 100: 1 to about 500: 1.
  • a still further embodiment relates to a method for preparing a supported system comprising the steps of:
  • step (b) combing the solution of (a) with a support and a metallocene, said combining step occurring no more than seven days subsequent to the completion of step (a).
  • the invention is useful with any class of transition metal compounds or metallocenes including mono, di, or tri cyclopentadienyl radical systems or derivatives thereof.
  • Monocyclo-pentadienyl moieties include, for example, those as disclosed in US 4,808,561 or US 5,055,438 herein incorporated by reference.
  • Carriers include organic or inorganic support mediums. Particularly preferred carriers include porous, inorganic mediums such as silica, alumina or silica alumina combinations with silica being the most preferred.
  • Supported catalysts made with gel-free alumoxane solutions generally produce polymer having excellent morphology, controlled particle size, generally in granular form, with minimal to no fouling occuring in the reactor during polymerization.
  • U.S. 5,157,137 discloses a method to avoid gels forming in an alumoxane solution. We have found that one can remove the gels and use the gel-free alumoxane solution without further treatment to produce a supported catalyst with excellent performance relative to that produced with gelled alumoxane solutions.
  • the alkali treatment disclosed in US '137 is not necessary for use of the alumoxane solutions especially if the gel-free alumoxane is used immediately upon separation.
  • the alkali treatment disclosed in US '137 adds cost to the alumoxane. By eliminating the treatment, a more cost efficient catalyst may be produced.
  • the present invention describes a method of using alumoxane free of unnecessary additives or additional treatment steps. Since alumoxane will gel over time, it is preferred to use the separated gel-free alumoxane within about 5-7 days after separation, preferably about 3-5 days, and most preferably immediately upon separation to about 2 days for 10 wt.% alumoxane solutions. If employing 30wt.% alumoxane it is generally advised to use the separated alumoxane within about 3-5 days, preferably about 1-3 days and most preferably immediately upon separation to about 1 day.
  • the alumoxane solution may be purchased from a vendor, for example, Ethyl Corporation or Shering Corporation, or can be produced before use via known literature techniques.
  • a preferred embodiment for forming a supported catalyst comprises the steps of contacting a substantially gel-free alumoxane solution, at least one metallocene, and a dehydrated carrier or support medium.
  • the supported catalyst is optionally prepolymerized with alpha olefins.
  • US '894 is silent on the use of gel-free alumoxane.
  • the present invention represents an improvement over that described in US '894.
  • substantially gel-free is defined as a visually clear, substantially transparent alumoxane solution absent of haze and gels.
  • gelled alumoxane is defined as a translucent alumoxane solution containing haze and gels. The color of the alumoxane solution is not relevant here provided the solution is substantially transparent, free of haze and gels.
  • techniques for monitoring the gel particles in the alumoxane solution other than visual, will suffice.
  • alternative monitoring techniques including light beam transmission would be suitable for determining "gel-free" state of alumoxane.
  • a physical separation of the gel-free alumoxane from the gel like material may be achieved by conventional techniques such as physical withdrawal or by extraction by a syringe.
  • the gel particles may be removed by filtration, separating the filtrate from the solution or be removed by other conventional liquid-solid separation techniques such as centrifugation and decanting the liquid.
  • Metallocenes represented by the general formula below may be employed with the gel-free alumoxane solution.
  • the metallocene may be bridged or unbridged, and include heteroatoms in the structure.
  • Preferred metallocenes are represented by the general formula:
  • M 1 is a metal of group 4, 5, or 6 of the Periodic Table
  • R 1 and R 2 are identical or different, are one of a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group a C 8 -C 40 arylalkenyl group, or a halogen atom;
  • R 3 and R 4 are hydrogen atoms
  • R 5 and R 6 are identical or different, preferably identical, are one of a halogen atom, a C 1 -C 10 alkyl group, which may be halogenated, a C 6 -C 10 aryl group, which may be halogenated, a C 2 -C 10 alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, a -NR 2 15 , -SR 15 , -OR 15 , -OSiR 3 15 or -PR 2 15 radical, wherein R 1 5 is one of a halogen atom, a
  • R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 5 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group or R 11 and R 12 , a C 7 -C 40 alkylaryl group, or R 11 and R 13 , together with the atoms binding them, can form ring systems;
  • M 2 is silicon, germanium or tin, or a derivative thereof
  • R 8 and R 9 are identical or different and have the meanings as stated for R 11 ;
  • n and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2;
  • radicals R 10 are identical or different and have the meanings stated for R 11 , R 12 and R 13 or two adjacent R 10 radicals can be joined together to form a ring system.
  • metallocene components include rac-dimethylsilandiylbis (2-methyl-4, 5-benzoindenyl) -zirconium dichloride;
  • Exemplary metallocenes include monocyclopentadienyl titanocenes such as pentamethylcyclopentadienyl titanium trichloride, and the like,
  • the support is dehydrated preferably at about 800°C for about 18-24 hours or until a 1% or less loss on ignition value is obtained.
  • the supported catalyst Prior to use, the supported catalyst is dried to remove essentially all of the residual solvent which may be trapped in the pores of the carrier. This results in a free-flowing supported catalyst.
  • the supported catalyst may be employed under various polymerization conditions. Suitable polymerization conditions include gas phase, or slurry polymerization.
  • the supported catalyst prepared as described herein is contacted with alpha olefins in a slurry
  • the polymerization procedure is as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, triethylaluminum, TEAL, (about 0.8 ml, about 1.5 M in heptane) was added and then the reactor closed and filled with about 750 ml liquid propylene. With the reactor temperature at about 30°C the catalyst (as a 25 wt% oil slurry) was washed in via an addition tube with about 250 ml propylene. The reactor was rapidly heated to about 65°C. After thirty minutes the reactor was cooled and the excess propylene vented. The polymer was removed and dried.
  • TEAL triethylaluminum
  • DMS (MBI) ZrCl 2 dimethylsilandiyl bis(2-methyl-4, 5-benzoindenyl) zirconium dichloride.
  • Gel-free MAO was employed. A freshly separated solution of gel-free MAO, decanted from a solution of gelled MAO was employed.
  • Polymerizations were conducted at about 65°C, under the conditions described above with the catalysts of examples 1, 2 and 3. Polymerizations with the catalysts of examples 1 and 2 resulted in free flowing, granular polymer with minimal to no residue observed on the walls of the reactor. Polymerization with the catalyst of example 3 resulted in polymer clumping and residue detected on the walls of the reactor. The clumping of the polymer made it impractial to determine particle size.
  • the examples demonstrate that the use of gel-free alumoxane solution results in (1) a supported catalyst which produces polyolefins with improved morphology relative to that obtained using gelled alumoxane solution and, (2) minimum to no fouling in the polymerization reactor. This is in contrast to use of gelled alumoxane solution which resulted in a supported catalyst producing polymer clumping on the agitator and walls of the polymerization reactor and wherein the polymer was not free flowing or granular in form.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un procédé d'utilisation d'une solution d'alumoxane sans gel pour préparer des catalyseurs sur supports. Ces derniers produisent des particules de polymères présentant une excellente morphologie et ne provoquant qu'un encrassement très faible, voire même nul, du réacteur pendant la polymérisation.
PCT/US1994/013367 1994-01-11 1994-11-16 Utilisation d'une solution d'alumoxane sans gel WO1995018809A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP7518473A JPH09507515A (ja) 1994-01-11 1994-11-16 ゲルのないアルモキサン溶液の使用
EP95903569A EP0739346A1 (fr) 1994-01-11 1994-11-16 Utilisation d'une solution d'alumoxane sans gel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17985094A 1994-01-11 1994-01-11
US08/179,850 1994-01-11

Publications (1)

Publication Number Publication Date
WO1995018809A1 true WO1995018809A1 (fr) 1995-07-13

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EP (1) EP0739346A1 (fr)
JP (1) JPH09507515A (fr)
CN (1) CN1149297A (fr)
CA (1) CA2180981A1 (fr)
WO (1) WO1995018809A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043180A (en) * 1994-11-17 2000-03-28 The Dow Chemical Company Supported catalyst component, supported catalyst, their preparation, and addition polymerization process

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0295312A1 (fr) * 1986-12-30 1988-12-21 Mitsui Petrochemical Industries, Ltd. Catalyseur a l'etat solide pour la polymerisation d'olefines et procede de preparation
EP0393358A2 (fr) * 1989-03-23 1990-10-24 Idemitsu Kosan Company Limited Procédé de préparation d'une solution homogène d'aluminoxane
EP0442300A2 (fr) * 1990-02-14 1991-08-21 Witco GmbH Procédé de préparation de solutions de méthylaluminoxanes oligomériques
WO1993019073A1 (fr) * 1992-03-18 1993-09-30 Ethyl Corporation Procede permettant d'eliminer des matieres formant un gel presentes dans des methylaluminoxanes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0295312A1 (fr) * 1986-12-30 1988-12-21 Mitsui Petrochemical Industries, Ltd. Catalyseur a l'etat solide pour la polymerisation d'olefines et procede de preparation
EP0393358A2 (fr) * 1989-03-23 1990-10-24 Idemitsu Kosan Company Limited Procédé de préparation d'une solution homogène d'aluminoxane
EP0442300A2 (fr) * 1990-02-14 1991-08-21 Witco GmbH Procédé de préparation de solutions de méthylaluminoxanes oligomériques
WO1993019073A1 (fr) * 1992-03-18 1993-09-30 Ethyl Corporation Procede permettant d'eliminer des matieres formant un gel presentes dans des methylaluminoxanes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043180A (en) * 1994-11-17 2000-03-28 The Dow Chemical Company Supported catalyst component, supported catalyst, their preparation, and addition polymerization process

Also Published As

Publication number Publication date
EP0739346A1 (fr) 1996-10-30
CA2180981A1 (fr) 1995-07-13
JPH09507515A (ja) 1997-07-29
CN1149297A (zh) 1997-05-07

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