WO2002038637A1 - Procede de copolymerisation de propylene et/ou d"ethylene au moyen de 1-olefines sur des catalyseurs a supports metallocenes - Google Patents

Procede de copolymerisation de propylene et/ou d"ethylene au moyen de 1-olefines sur des catalyseurs a supports metallocenes Download PDF

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Publication number
WO2002038637A1
WO2002038637A1 PCT/EP2001/012264 EP0112264W WO0238637A1 WO 2002038637 A1 WO2002038637 A1 WO 2002038637A1 EP 0112264 W EP0112264 W EP 0112264W WO 0238637 A1 WO0238637 A1 WO 0238637A1
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Prior art keywords
borate
phenyl
alkyl
methyl
aryl
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PCT/EP2001/012264
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German (de)
English (en)
Inventor
Jürgen Suhm
Hans-Herbert Brintzinger
Sarah Reybuck
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Basell Polypropylen Gmbh
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Priority to AU2002219055A priority Critical patent/AU2002219055A1/en
Publication of WO2002038637A1 publication Critical patent/WO2002038637A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • Y is an element of I. to VI. Main group or the I. to VIII. Subgroup of the periodic table means
  • d corresponds to the difference a-z, but d is greater than or equal to 1, are polymerized.
  • Metallocene catalysts with high activity are used for the production of poly (1-olefins) with a defined molar mass distribution, uniform stereo and regional regularity and controlled co-monomer incorporation.
  • a frequently occurring disadvantage of the heterogeneous, supported metallocene / cation activator systems [MAO, Tris (pentafluorophenyDboran, Trityltetra (pentafluorophenyl.borat and N, N-Dimethylaniliniumtetr (pentafluorophenyDborat]) is the loss of stereo- and regio-regularity however, the activity due to interactions of the metallocene / cation activator system with the surface of the carrier material.
  • reaction c) requires large amounts of expensive aluminoxane, which has a disruptive effect in the polymer formed.
  • the object of the present invention was therefore to provide an improved process for the copolymerization of propene and / or ethene with 1-olefins which avoids the above disadvantages of the prior art and in particular enables high comonomer incorporation rates.
  • Suitable transition metal compounds A) are in principle all those which chemically react with components B), if appropriate in combination with a further component C), an active catalyst being formed.
  • transition metal compounds A) are Transition metal complexes with 'a ligand of the general formulas FI to F-IV
  • transition metal is selected from the elements Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt or an element of the rare earth metals. Compounds with nickel and palladium as the central metal are preferred.
  • R 6A for hydrocarbon or substituted hydrocarbon residues
  • R 5A for hydrogen, hydrocarbon or substituted hydrocarbon radicals, R 6A and R 5A can also together form a ring system.
  • R 8A for hydrocarbon or substituted hydrocarbon radicals
  • R 16A and ⁇ R17A independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals
  • transition metal compounds are those with a ligand of the general formula F-V
  • R 8B C x - to Cio-alkyl, C 3 - to C 10 -cycloalkyl, C 6 - bis
  • transition metal compounds A) are furthermore those with at least one cyclopentadienyl-type ligand, which are commonly referred to as metallocene complexes (two or more cyclopentadienyl-type ligands) or half-sandwich complexes (a cyclopentadienyl yp ligand).
  • the catalyst system according to the invention contains at least one or more metallocene complexes.
  • Particularly suitable metallocene complexes are those of the general formula
  • Tantalum as well as elements of the III. Subgroup of the periodic table and the lanthanoids,
  • R 9 to R 13 are hydrogen, ⁇ to Cio-alkyl, 5- to 7-membered can carry as substituent cycloalkyl 'in turn is a Ci to Cio-alkyl, C 6 - to C 5 aryl or arylalkyl and wherein proceedingsenf lls two adjacent radicals together can also represent saturated or unsaturated cyclic groups having 4 to 15 carbon atoms, or Si (R 14 ) with
  • R 16 , R 17 and R 18 are the same or different and a water
  • M 2 is silicon, germanium or tin
  • R 19 Ci to Cio alkyl, C 6 to C 5 aryl,
  • R 20 is hydrogen, -C ⁇ to Cio-alkyl, C 6 - to cis-aryl, which in turn can be substituted with Ci- to C 4 alkyl groups or C 3 - to C 10 cycloalkyl
  • radicals X can be the same or different, they are preferably the same.
  • X is chlorine, C 1 -C 4 -alkyl or phenyl, n is the number 2 and
  • M stands for titanium, zirconium or hafnium
  • X is chlorine, C 1 -C 4 -alkyl or phenyl
  • n is the number 2
  • R 1 to R 5 are hydrogen, C 1 -C 4 -alkyl or Si (R 8 ) 3 ,
  • R 9 to R 13 are hydrogen, Ci to C 4 alkyl or Si (R 14 ) 3 .
  • Examples of particularly suitable compounds include: bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-butylethyldiryl) zirconium dichloridyldiryldiumchloride as well as the corresponding dimethyl zirconium compounds.
  • R 1 and R 9 ' are the same and represent hydrogen or Ci to Cio alkyl groups
  • R 5 and R 13 are the same and for hydrogen, a methyl
  • R 2 , R 3 , R 10 and R 11 have the meaning
  • R 2 and R 10 have hydrogen or two adjacent radicals R 2 and R 3 and R 10 and R 11 together represent cyclic groups containing 4 to 12 carbon atoms, R 16 R16 R 16
  • R 15 stands for - M 2 - or - c - c -
  • X represents chlorine, Ci to C4 alkyl or phenyl.
  • Examples of particularly suitable complex compounds Ic are dimethylsilanediylbis (indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-methyl-4-ethyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4-a-acenaphth-indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2,5, 6-trimethyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2, 4, 7-trimethyl-indenyl) zirconium dichloride
  • X represents chlorine, C 1 -C 4 -alkyl or phenyl.
  • M 3 is an element of III.
  • Main group of the periodic table means, in particular B, Al or Ga, preferably B,
  • Qi to Q z for single negatively charged radicals such as Ci to C 28 alkyl, C 6 to Cis aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl, each having 6 to 20 C atoms in the aryl and 1 to 28 C Atoms in the alkyl radical, C 3 - to Cio-cycloalkyl, which can optionally be substituted with Ci- to Cio-alkyl groups, halogen, Ci- to C 8 -alkoxy, C ⁇ - to Cis-aryloxy, silyl or mercaptyl groups
  • Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable.
  • the triphenylmethyl cation, the silver cation and the 1, 1 '-dimethylferrocenyl cation should be mentioned in particular. They preferably have non-coordinating counterions, in particular boron compounds, as they are also mentioned in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate.
  • Examples include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis (phenyl) aluminate, ferrocenium tetrakis (pentafluorophenyl) borate and / or ferrocenium aluminum tetrakis (pentafluorophenyl).
  • Ionic compounds as component B) with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO 91/09882, the preferred cation is N, N-dimethylanilinium.
  • the molar ratio of transition metal compound A): cation-forming compound B) is preferably 1: 3 to 1: 9, particularly preferably 1: 4 to 1: 8, in particular 1: 5 to 1: 7, very particularly preferably 1: 6.
  • the catalyst system according to the invention can, as a further component C), optionally also an organometallic compound, preferably a metal compound of the general formula IV
  • M 1 is an alkali metal, an alkaline earth metal or a metal of III.
  • Main group of the periodic table, i. H . Means boron, aluminum, gallium, indium or thallium, R 21 is hydrogen, Ci to C 10 alkyl, C 6 to C 5 aryl,
  • Alkylaryl or arylalkyl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
  • R 22 and R 23 are hydrogen, halogen, Ci to -C ⁇ 0 alkyl,
  • s and t are integers from 0 to 2
  • oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and include in EP-A 284 708 and US A 4,794,096.
  • component C) is present together with A) and / or B), in this case it is not identical to components A) and in particular B).
  • M 1 means lithium, magnesium or aluminum
  • Particularly preferred metal compounds of the formula IV are n-butyl lithium, n-butyl-n-octyl magnesium, n-butyl-n-heptyl magnesium, tri-n-hexyl aluminum, tri-iso-butyl aluminum, triethyl aluminum and trimethyl aluminum.
  • the catalyst system used in the process according to the invention comprises, in addition to the components A), B), C) and, where appropriate, the compounds IV to VI, a carrier substance.
  • Suitable carrier substances are, for example, organic polymers, but preferably porous inorganic materials.
  • the carrier materials used are preferably finely divided carriers which have a particle diameter in the range from
  • Suitable organic carriers are such as fine-particle polymers, for example fine-particle polyethylene or fine-particle polypropylene.
  • suitable inorganic carriers are aluminum trioxide, silicon dioxide, titanium dioxide or their mixed oxides, aluminum phosphate or magnesium chloride.
  • silica gels come the formula Si0 2 ⁇ a A1 2 0 3 is used, wherein a is a number ranging from 0 to 2, preferably 0 to 0.5, is.
  • the carrier particles can be used in granular form and spray-dried in microscopic form. Products of this type are commercially available, for example silica gel 332 from Grace or ES 70 X from Crosfield.
  • Preferred inorganic carrier materials are acidic, inorganic metal or semimetal oxides with very high porosity, which are described, for example, in WO-A-97/47662.
  • the carrier materials can be pretreated thermally or chemically (e.g. with metal alkyl compounds) in order to achieve a specific property profile of the carrier (e.g. water and / or OH group content).
  • a specific property profile of the carrier e.g. water and / or OH group content
  • the catalyst system used in the process according to the invention is generally obtained by reacting a transition metal compound A) with a cation former B). This reaction can be carried out in a homogeneous, liquid phase or in the presence of a carrier material, organic solvents being generally used as suspending agents.
  • the compound thus obtained can be used directly in suspension as a catalyst. 'But it is also possible to isolate the compound and use it as such as a catalyst e.g. B. in gas phase processes, it can also be brought back into suspension after isolation and then used as a catalyst.
  • a preferred method of production of a supported catalyst of transition metal compound A), preferably those 'of the general formula I, in particular those of formula Ic with cation-forming compound B) is as follows.
  • the carrier substance preferably inorganic, porous oxides, in particular silica gel, is optionally deactivated with organometallic compounds of the formula IV, preferably organoaluminum compounds, and this precursor is isolated and with the cation-forming compound B), preferably that of the formulas II- and III or Bronsted acids with non- nucleophilic anion, in an organic solvent, preferably aliphatic or aromatic C 6 - to C 3 o-hydrocarbon, in particular toluene.
  • Transition metal component A preferably metallocenes of the formula I, in particular those of the formula Ic, and added to the mixture 4 the solvent is removed immediately or after an exposure time of up to 48 h, preferably up to 10 h, in particular up to 90 minutes.
  • propene and / or ethene are polymerized with 1-olefins.
  • the polymerization process according to the invention is preferably used for the copolymerization of propene and / or ethene with C 4 -C 1 -alk-1-enes.
  • C 4 to C 1 -alk-1-enes are but-1-enes, pent-1-enes, 4-methyl-pent-1-enes, hex-1-enes, hept-1-enes or oct-1 -en or mixtures of these C 4 - to -C -alk-1-enes preferred.
  • Copolymers of ethene or propene are particularly preferred, the proportion of ethene or propene in the copolymers being at least 50 mol%.
  • the copolymers of propene are, in particular, those copolymers which contain ethene or but-1-ene or mixtures thereof as further monomers.
  • the polymerization process according to the invention is preferably used to prepare those polymers which
  • the polymerization according to the invention can be carried out continuously or batchwise in the processes customary for the polymerization of olefins, such as solution processes, suspension processes, stirred gas phase processes or gas phase fluidized bed processes.
  • olefins such as solution processes, suspension processes, stirred gas phase processes or gas phase fluidized bed processes.
  • Inert hydrocarbons such as isobutane or the monomers themselves can be used as solvents or suspending agents.
  • Suitable reactors include continuously operated stirred tanks, loop reactors or fluidized bed reactors, it also being possible to use a number of several reactors connected in series (reactor cascade).
  • the copolymerization with the aid of the process according to the invention is generally carried out at temperatures in the range from -50 to 300 ° C., preferably in the range from 0 to 150 ° C., and at pressures generally in the range from 0.5 to 3000 bar, preferably in Range from 1 to 80 bar.
  • antistatic agents and molecular weight regulators for example hydrogen, can also be used.
  • the deactivated carrier was finally suspended with 20 L of toluene, 290.6 g (90 ⁇ mol / g SiO 2 ) N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate were added and the mixture was heated to 85 ° C. At this temperature the suspension was stirred for 30 minutes. Thereafter, 50.3 g of rac-dimethylsilanediyl bis (2-methyl-phenylindenyl) zirconium dichloride (20 ⁇ mol / g Si0 2 ). The mixture was then stirred at 85 ° C. for a further 90 minutes. The color of the suspension changed from white to turquoise and then to black-violet. The catalyst was then dried in vacuo at 85 ° C.
  • the copolymerization was carried out in a 1 L autoclave.
  • the reactor temperature was 65 ° C, the pressure 29 bar, the polymerization time 60 minutes.
  • the propene (350 g) was placed in the reactor with 4 mmol of triisobutylaluminum (2 mol / L in heptane). Then 3.5 g of ethene were added.
  • the catalyst from Example 1 was metered into the 1-olefin / ethene mixture at 25 ° C. using argon overpressure.
  • the ethene-propene copolymer obtained had an ethene content of 2.5% by weight.
  • a toluene solution of the catalyst was placed in a vessel containing MAO and injected into the polymerization reactor after an equilibration time of 15 minutes.
  • a standard catalyst solution was added to a toluene solution of borane or borate in the presence of an Al (i-Bu) 3 scavenger and equilibrated for 3 minutes before injection into the polymerization reactor.
  • the polymerization times varied in order to keep the polymerization conversion low in all cases.
  • the polymerization was terminated by adding an acidic methanol solution.
  • the polymers were filtered, washed with acidic methanol and dried at 40 ° C for at least 3 days.
  • the comonomer incorporation was determined by means of 13C NMR spectroscopy.
  • Example 5 The procedure was as described in Example 5. The ethene / hexene ratios were kept constant. In Examples 6 to 9 and Comparative Example 2, the catalyst solids from Examples 1 to 4 and Comparative Example 1 were used. The respective rates of incorporation of 1-hexene based on the total monomer content were determined on the copolymers obtained.
  • the copolymer obtained had a proportion of incorporated 1-hexene of 56.2 mol%.
  • Catalyst solid from Example 2 The copolymer obtained has a 56.5 mol% proportion of incorporated 1-hexene.
  • Catalyst solid from comparative example 1 The copolymer obtained had a proportion of 1-hexene incorporated of 10 44.5 mol%.

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

Abstract

L"invention concerne un procédé de copolymérisation de propylène et/ou d"éthylène au moyen de 1-oléfines sur des catalyseurs métallocènes, selon lequel ces monomères sont polymérisés en présence d"un système catalyseur contenant comme composants actifs des composants pouvant être obtenus par réaction de A) un composé de métaux de transition avec B) un composé formant des cations, de formule générale (II) dans laquelle M3 représente un élément du groupe principal (III) de la classification périodique des éléments, X?1, X2 et X3¿ désignent hydrogène, alkyle C1-C10, aryle C6-C15, alkylaryle, arylalkyle, halogénure d"alkyle ou halogénure d"aryle, avec respectivement 1 à 10 atomes de carbone dans le reste alkyle et 6 à 20 atomes de carbone dans le reste aryle, ou fluor, chlore, brome ou iode, et/ou de formule générale (III) dans laquelle Y représente un élément des groupes principaux I à VI ou des sous-groupes I à VIII de la classification périodique des éléments, Q¿1? à Qz représentent des restes à une seule charge négative tels que alkyle C1-C28, aryle C6-C15, alkylaryle, arylalkyle, halogénure d"alkyle, halogénure d"aryle, avec respectivement 6 à 20 atomes de carbone dans le reste aryle et 1 à 28 atomes de carbone dans le reste alkyle, cycloalkyle C3-C10, qui peut être éventuellement substitué avec des groupes alkyle C1-C10, halogène, alcoxy C1-C28, aryloxy C6-C15, des groupes silyle ou mercaptyle, a représente un nombre entier compris entre 1 et 6, z représente un nombre entier compris entre 0 et 5 et d correspond à la différence a-z, d étant néanmoins supérieur ou égal à 1.
PCT/EP2001/012264 2000-11-09 2001-10-24 Procede de copolymerisation de propylene et/ou d"ethylene au moyen de 1-olefines sur des catalyseurs a supports metallocenes WO2002038637A1 (fr)

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DE10055618.3 2000-11-09
DE10055618 2000-11-09

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Cited By (3)

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JPWO2005051963A1 (ja) * 2003-11-28 2007-12-06 北興化学工業株式会社 ホスホニウムボレート化合物の製造方法、新規なホスホニウムボレート化合物およびその使用方法
EP2070953A1 (fr) * 2007-12-11 2009-06-17 Total Petrochemicals Research Feluy Activation de supports basés sur des complexes de phosphonium
WO2014078919A1 (fr) 2012-11-26 2014-05-30 Braskem S.A. Catalyseur métallocène supporté sur support hybride, procédé d'obtention de celui-ci, procédé de polymérisation pour l 'obtention d'un homopolymère ou d'un copolymère d'éthylène à distribution de masse molaire large ou bimodale, utilisation du catalyseur de métallocène supporté et polymère d'éthylène à distribution de masse molaire large ou bimodale

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WO1991009882A1 (fr) * 1990-01-02 1991-07-11 Exxon Chemical Patents Inc. Catalyseurs en alliage organometallique ionique supportes de polymerisation d'olefines
EP0591756A2 (fr) * 1992-09-22 1994-04-13 Idemitsu Kosan Company Limited Catalyseurs de polymérisation et procédé de production de polymères
EP0768320A1 (fr) * 1995-09-29 1997-04-16 Nippon Oil Co. Ltd. Composante catalytique et catalyseur
WO1999041289A1 (fr) * 1998-02-11 1999-08-19 The Dow Chemical Company Procede ameliore de polymerisation d'olefines
WO2001048035A2 (fr) * 1999-12-23 2001-07-05 Basell Polyolefine Gmbh Compose chimique, procede permettant de le preparer et de l'utiliser dans des systemes catalyseurs pour produire des polyolefines

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Publication number Priority date Publication date Assignee Title
WO1991009882A1 (fr) * 1990-01-02 1991-07-11 Exxon Chemical Patents Inc. Catalyseurs en alliage organometallique ionique supportes de polymerisation d'olefines
EP0591756A2 (fr) * 1992-09-22 1994-04-13 Idemitsu Kosan Company Limited Catalyseurs de polymérisation et procédé de production de polymères
EP0768320A1 (fr) * 1995-09-29 1997-04-16 Nippon Oil Co. Ltd. Composante catalytique et catalyseur
WO1999041289A1 (fr) * 1998-02-11 1999-08-19 The Dow Chemical Company Procede ameliore de polymerisation d'olefines
WO2001048035A2 (fr) * 1999-12-23 2001-07-05 Basell Polyolefine Gmbh Compose chimique, procede permettant de le preparer et de l'utiliser dans des systemes catalyseurs pour produire des polyolefines

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2005051963A1 (ja) * 2003-11-28 2007-12-06 北興化学工業株式会社 ホスホニウムボレート化合物の製造方法、新規なホスホニウムボレート化合物およびその使用方法
JP4841954B2 (ja) * 2003-11-28 2011-12-21 北興化学工業株式会社 ホスホニウムボレート化合物の製造方法、新規なホスホニウムボレート化合物およびその使用方法
US8124809B2 (en) 2003-11-28 2012-02-28 Hokko Chemical Industry Co., Ltd. Process for producing phosphonium borate compound, novel phosphonium borate compound, and method of using the same
US8604249B2 (en) 2003-11-28 2013-12-10 Hokko Chemical Industry Co., Ltd. Process for producing phosphonium borate compound, novel phosphonium borate compound, and method of using the same
EP1688424B1 (fr) * 2003-11-28 2016-01-13 Hokko Chemical Industry Co., Ltd. Compose de borate de phosphonium et procede d'utilisation
EP2070953A1 (fr) * 2007-12-11 2009-06-17 Total Petrochemicals Research Feluy Activation de supports basés sur des complexes de phosphonium
US8338324B2 (en) 2007-12-11 2012-12-25 Total Petrochemicals Research Feluy Activating supports based on phosphonium complexes
WO2014078919A1 (fr) 2012-11-26 2014-05-30 Braskem S.A. Catalyseur métallocène supporté sur support hybride, procédé d'obtention de celui-ci, procédé de polymérisation pour l 'obtention d'un homopolymère ou d'un copolymère d'éthylène à distribution de masse molaire large ou bimodale, utilisation du catalyseur de métallocène supporté et polymère d'éthylène à distribution de masse molaire large ou bimodale

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