WO2005075523A1 - Composition de catalyseur - Google Patents

Composition de catalyseur Download PDF

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Publication number
WO2005075523A1
WO2005075523A1 PCT/GB2005/000179 GB2005000179W WO2005075523A1 WO 2005075523 A1 WO2005075523 A1 WO 2005075523A1 GB 2005000179 W GB2005000179 W GB 2005000179W WO 2005075523 A1 WO2005075523 A1 WO 2005075523A1
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Prior art keywords
monoeyclopentadienyl
hydrogen
catalyst component
group
sir
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PCT/GB2005/000179
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English (en)
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Grant Berent Jacobsen
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Ineos Europe Limited
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Publication of WO2005075523A1 publication Critical patent/WO2005075523A1/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/65912—Component covered by group C08F4/64 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
    • C08F4/62—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

Definitions

  • the present invention relates to a catalyst composition comprising a solid catalyst component and a catalyst component in solution, said catalyst composition is particularly suitable for use in the polymerisation of olefms in the gas phase.
  • a catalyst composition comprising a solid catalyst component and a catalyst component in solution
  • said catalyst composition is particularly suitable for use in the polymerisation of olefms in the gas phase.
  • Metallocene catalysts offer the advantage of generally a higher activity than traditional Ziegler catalysts and are usually described as catalysts which are single site in nature.
  • catalysts based on bis (cyclopentadienyl) metal complexes were developed, examples of which may be found in EP 129368 or EP 206794.
  • More recently complexes having a single or mono cyclopentadienyl ring have been developed.
  • Such complexes have been referred to as 'constrained geometry' complexes and examples of these complexes maybe found in EP 416815 or EP 420436. hi both of these complexes the metal atom eg. zirconium is in the highest oxidation state.
  • borates such as trialkyl-substituted ammonium tetraphenyl- or tetrafluorophenyl-borates or triarylboranes such as tris(pentafluorophenyl) borane.
  • Catalyst systems incorporating borate activators are described in EP 561479, EP 418044 and EP 551277.
  • the above metallocene complexes may be used for the polymerisation of olef ⁇ ns in solution, slurry or gas phase. When used in the sluixy or gas phase the metallocene complex and/or the activator are suitably supported.
  • Typical supports include inorganic oxides eg. silica or polymeric supports may alternatively be used.
  • WO 0246246 describes a process for polymerising olefms comprising continuously combining a catalyst component slurry with a catalyst component solution to form a catalyst composition and then polymerising olef ⁇ ns in a reactor.
  • the catalyst component slurry may be a slurry of silica supported methyl aluminoxane and the catalyst component solution may be a solution of a metallocene complex.
  • US 5786291 describes the preparation of supported metallocene catalysts comprising the combination of a silica supported metallocene in solid form with a solution of a different metallocene.
  • the metallocenes disclosed comprise bridged bis(indenyl) complexes.
  • US2002/0103310 describes catalysts comprisng the combination of a solid or a slurry of one or more bulky ligand metallocene catalysts, a support and one or more activators with a solution comprising one or more phenoxide catalyst compounds.
  • WO 03/047751 describes the preparation of bimetallic compounds comprising the combination of a slurry of a non-metallocene catalyst with a solution of a metallocene compound.
  • a first catalyst component comprising a monoeyclopentadienyl metallocene compound in solid form
  • a second catalyst component comprising a monoeyclopentadienyl metallocene compound in solution
  • the control of the resultant polymer properties may be improved by independently controlling the concentration of each of the catalyst components.
  • a catalyst component solution comprising a second monoeyclopentadienyl metallocene compound to form a catalyst composition.
  • the first and second monocylcopentadienyl metallocene compounds may be the same or different.
  • the first and the second monoeyclopentadienyl metallocene compounds are the same.
  • Suitable monoeyclopentadienyl metallocene compounds comprise the general formula:
  • R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R' having up to 20 nonhydrogen atoms, and optionally, two R' groups (where R' is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure;
  • X is hydride or a moiety selected from the group consisting of halo, alkyl, aryl, aryloxy, alkoxy, alkoxyalkyl, amidoalkyl, siloxyalkyl etc.
  • R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system.
  • n is 1 or 2 depending on the valence of M.
  • Suitable monoeyclopentadienyl compounds are (tert-butylamido) dimethyl (tetramethyl- ⁇ 5 - cyclopentadienyl) silanetitanium dichloride and (2- methoxyphenylamido) dimethyl (tetramethyl— ⁇ 5 - cyclopentadienyl) silanetitanium dichloride.
  • Particularly preferred monoeyclopentadienyl metallocene compounds for use in the preparation of the supported catalysts of the present invention may be represented by the general formula:
  • R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R' having up to 20 nonhydrogen atoms, and optionally, two R' groups (where R' is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a 'fused ring structure;
  • X is a neutral ⁇ 4 bonded diene group having up to 30 non-hydrogen atoms, which forms a ⁇ -complex with M;
  • Y is -O-, -S-, -NR*-, -PR*-, M is titanium or zirconium in the + 2 formal oxidation state;
  • Suitable X groups include s-trans- ⁇ 4 -l,4-diphenyl-l,3-butadiene, s- trans- ⁇ 4 -3-methyl-l ,3-pentadiene; s-trans- ⁇ 4 -2,4-hexadiene; s-trans- ⁇ 4 - 1,3-pentadiene; s-trans- ⁇ 4 -l,4-ditolyl-l,3-butadiene; s-trans- ⁇ -l,4-bis(trimethylsilyl)-l,3-butadiene; s- cis- ⁇ 4 -3 -methyl- 1,3-pentadiene; s-cis- ⁇ -l,4-dibenzyl-l,3-butadiene; s-cis- ⁇ 4 -l, 3- pentadiene; s-cis- ⁇ 4 - l,4-bis(trimethylsilyl)-l,3-butadiene,
  • R' is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, or phenyl or 2 R' groups (except hydrogen) are linked together, the entire C 5 R' group thereby being, for example, an indenyl, tetrahydroindenyl, fluorenyl, terahydrofluorenyl, or octahydrofluorenyl group.
  • Highly preferred Y groups are nitrogen or phosphorus containing groups containing a group corresponding to the formula -N(R )- or -P(R )- wherein R is C ⁇ - 10 hydrocarbyl.
  • Most preferred compounds are amidosilane - or amidoalkanediyl compounds Most preferred compounds are those wherein M is titanium. Specific compounds suitable for use in the present invention are those disclosed in WO 95/00526 and are incorporated herein by reference. A particularly preferred compound for use in the method of the present invention is (t-butylamido) (tetramethyl- ⁇ 5 - cyclopentadienyl) dimethyl silanetitanium - ⁇ 4 -1.3 - pentadiene.
  • Cp is a ligand from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl and substituted fluorenyl
  • M is a Group 4 metal selected from hafnium, titanium or zirconium
  • PI is a phosphinimine ligand
  • L is an actvatable ligand
  • m 1 and n is 1 or 2
  • q is 1 or 2
  • the preferred Group 4 metal is titanium.
  • Preferred phosphinimine ligands are those wherein each R is a hydrocarbyl radical and a particularly preferred phosphinimine ligand is tri-(tertiary butyl) phosphinimine.
  • the activatable ligands are those which may be activated by a cocatalyst for polymerisation. Suitable ligands are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C ⁇ in hydrocarbyl radical, a C*_ ⁇ o alkoxy radical and similar.
  • the preferred phosphinimine complexes for use in the present invention are those wherein the Cp is cyclopentadienyl and the activatable ligand is halide for example chloride.
  • the catalyst component solid of the present invention preferably comprises a support material.
  • Suitable support materials include inorganic metal oxides or alternatively polymeric supports may be used for example polyethylene, polypropylene, clays, zeolites, etc.
  • the most preferred support material for use with the solid catalyst component of the present invention is silica.
  • Suitable silicas include Ineos ES70 and Grace, Davison 948 silicas.
  • the support material may be subjected to a heat treatment and/or chemical treatment to reduce the water content or the hydroxyl content of the support material.
  • chemical dehydration agents are reactive metal hydrides, aluminium alkyls and halides.
  • the support material Prior to its use the support material may be subjected to treatment at 10O°C to 1000°C and preferably at 200 to 850°C in an inert atmosphere under reduced pressure.
  • the supports are preferably pretreated with an organometallic compound preferably an organoaluminium compound and most preferably a trialkylaluminium compound in a dilute solvent.
  • the support material is pretreated with the organometallic compound at a temperature of -20°C to 150°C and preferably at 20°C to 100°C.
  • the catalyst component solid and the catalyst component solution may suitably also comprise a cocatalyst.
  • the catalyst component- solid comprises a cocatalyst.
  • Suitable cocatalysts for use in the method of the present invention are those typically used with the aforementioned monoeyclopentadienyl metallocene compounds.
  • Suitable cocatalysts include aluminoxanes such as methyl aluminoxane (MAO), boranes such as tris(pentafluorophenyl) borane and borates.
  • Aluminoxanes are well known in the art and preferably comprise oligomeric linear and/or cyclic alkyl aluminoxanes.
  • Aluminoxanes may be prepared in a number of ways and preferably are prepare by contacting water and a trialkylaluminium compound, for example trimethylaluminium, in a suitable organic medium such as benzene or an aliphatic hydrocarbon.
  • a preferred aluminoxane is methyl aluminoxane (MAO).
  • Other suitable cocatalysts are organoboron compounds in particular triarylboron compounds.
  • a particularly preferred triarylboron compound is tris(pentafluorophenyl) borane.
  • Other compounds suitable as cocatalysts are compounds which comprise a cation and an anion. The cation is typically a Bronsted acid capable of donating a proton and the anion is typically a compatible non-coordinating bulky species capable of stabilizing the cation.
  • Such cocatalysts may be represented by the formula:
  • L* is a neutral Lewis base (L*-H) + d is a Bronsted acid
  • a d ⁇ is a non-coordinating compatible anion having a charge of d "
  • d is an integer from 1 to 3.
  • the cation of the ionic compound may be selected from the group consisting of acidic cations, carbonium cations, silylium cations, oxonium cations, organometallic cations and cationic oxidizing agents.
  • Suitably preferred cations include trihydrocarbyl substituted ammonium cations eg.
  • N.N-dialkylanilinium cations such as N,N-dimethylanilinium cations.
  • the preferred ionic compounds used as cocatalysts are those wherein the cation of the ionic compound comprises a hydrocarbyl substituted ammonium salt and the anion comprises an aryl substituted borate.
  • Typical borates suitable as ionic compounds include: tri ethyl ammonium tetraphenylbor ate triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, trimethyl ammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluoroph
  • a preferred type of cocatalyst suitable for use with the transition metal compounds of the present invention comprise ionic compounds comprising a cation and an anion wherein the anion has at least one substituent comprising a moiety having an active hydrogen.
  • Suitable cocatalysts of this type are described in WO 98/27119 the relevant portions of which are incorporated herein by reference.
  • Examples of this type of anion include: triphenyl(hydroxyphenyl) borate tri (p-tolyl)(hydroxyphenyl) borate tris (pentafluorophenyl)(hydroxyphenyl) borate tris (pentafluorophenyl)(4-hydroxyphenyl) borate
  • Examples of suitable cations for this type of cocatalyst include triethylammonium, triisopropylammonium, diethylmethylammonium, dibutylethylammonium and similar.
  • Particularly suitable are those cations having longer alkyl chains such as dihexyldecylmethylammonium, dioctadecylmethylammonium, ditetradecylmethylammonium, bis(hydrogentated tallow alkyl) methyl ammonium and similar.
  • Particular preferred cocatalysts of this type are alkylammonium tris(pentafluorophenyl) 4-(hydroxyphenyl) borates.
  • a particularly preferred cocatalyst is bis(hydrogenated tallow alkyl) methyl ammonium tris (pentafluorophenyl) (4- hydroxyphenyl) borate.
  • a preferred compound is the reaction product of an alkylammonium tris(pentaflurophenyl)-4-(hydroxyphenyl) borate and an organometallic compound, for example triethylaluminium.
  • the preferred method according to the present invention comprises
  • a catalyst component solution comprising a second monoeyclopentadienyl metallocene compound to form a catalyst composition.
  • a catalyst component solid comprising (i) a first monoeyclopentadienyl metallocene compound, (ii) a cocatalyst, and (iii) a support with
  • the catalyst compositions of the present invention may be suitable for the polymerisation of olefm monomers selected from (a) ethylene, (b) propylene (c) mixtures of ethylene and propylene and (d) mixtures of (a), (b) or (c) with one or more other alpha-olefins.
  • a process for the polymerisation of olefin monomers selected from (a) ethylene, (b) propylene (c) mixtures of ethylene and propylene and (d) mixtures of (a), (b) or (c) with one or more other alpha-olefins said process performed in the presence of a polymerisation catalyst composition as hereinbefore described
  • the catalyst compositions of the present invention are most suitable for use in slurry or gas phase processes.
  • the preferred process is a gas phase process.
  • a slurry process typically uses an inert hydrocarbon diluent and temperatures from about 0 C up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerisation medium.
  • Suitable diluents include toluene or alkanes such as hexane, propane or isobutane. Preferred temperatures are from about 30°C up to about 200°C but preferably from about 60°C to 100°C. Loop reactors are widely used in slurry polymerisation processes. Gas phase processes for the polymerisation of olefins, especially for the homopolymerisation and the copolymerisation of ethylene and ⁇ -olefins for example 1- butene, 1-hexene, 4-methyl-l-pentene are well known in the art. Typical operating conditions for the gas phase are from 20°C to 100°C and most preferably from 40°C to 85°C with pressures from subatmospheric to 100 bar.
  • Particularly preferred gas phase processes are those operating in a fluidised bed. Examples of such processes are described in EP 89691 and EP 699213 the latter being a particularly preferred process for use with the catalyt compositions of the present invention.
  • Particularly prefened polymerisation processes are those comprising the polymerisation of ethylene or the copolymerisation of ethylene and ⁇ -olefins having from 3 to 10 carbon atoms.
  • a process for the polymerisation of ethylene or the copolymerisation of ethylene and ⁇ - olefins having from 3 to 10 carbon atoms said process performed under polymerisation conditions in the presence of a polymerisation catalyt composition as hereinbefore described.
  • the prefened ⁇ -olefins are 1-butene, 1-hexene, 4-methyl-l-pentene and 1- octene.
  • Example 2 To 2 g of the above supported catalyst component from Example 1 (two days after its preparation) was added 0.397ml (0.068 mmol) of an heptane solution of
  • Example 1 comparative
  • Example 2 was tested for ethylene - 1-hexene copolymerisation as follows: A 2.5 1 double jacketed thermostatic stainless steel autoclave was purged with nitrogen at 70°C for at least one hour. 150g of PE pellets previously dried under vacuum at 80°C for 12 hours were introduced and the reactor was then purged three times with nitrogen (7 bar to atmospheric pressure). -0.13 g of TEA treated silica (1.5 mmol TEA/g) was added under pressure and allowed to scavenge impurities for at least 15 minutes under agitation.
  • TEA treated silica 1.5 mmol TEA/g
  • the gas phase was then composed (addition of ethylene, 1- hexene and hydrogen) and a mixture of supported catalyst (-0.1 g) and silica/TEA (-0.1 g) was injected.
  • a constant pressure of ethylene and a constant pressure ratio of ethylene/co-monomer were maintained during the run.
  • the run was terminated by venting the reactor and then purging the reactor 3 times with nitrogen.

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  • Chemical & Material Sciences (AREA)
  • 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 préparation d'une composition de catalyseur de polymérisation consistant à combiner un composant de catalyseur solide comprenant un premier composé de monocyclopentadiényl métallocène avec une solution de composant de catalyseur comprenant un second composé de monocyclopentadiényl métallocène. Les complexes de monocyclopentadiényl métallocène peuvent être identiques ou différents et par combinaison du premier composant de catalyseur sous forme solide avec le second composant de catalyseur en solution, le contrôle des propriétés du polymère obtenu peut être amélioré par contrôle, de manière indépendante, de la concentration de chacun des composants de catalyseur.
PCT/GB2005/000179 2004-02-04 2005-01-19 Composition de catalyseur WO2005075523A1 (fr)

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GB0402427A GB0402427D0 (en) 2004-02-04 2004-02-04 Catalyst composition
GB0402427.9 2004-02-04

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5783512A (en) * 1996-12-18 1998-07-21 The Dow Chemical Company Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same
US6486273B1 (en) * 1999-07-19 2002-11-26 Nova Chemicals (International) S.A Mixed phosphinimine catalyst
US6538080B1 (en) * 1990-07-03 2003-03-25 Bp Chemicals Limited Gas phase polymerization of olefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6538080B1 (en) * 1990-07-03 2003-03-25 Bp Chemicals Limited Gas phase polymerization of olefins
US5783512A (en) * 1996-12-18 1998-07-21 The Dow Chemical Company Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same
US6486273B1 (en) * 1999-07-19 2002-11-26 Nova Chemicals (International) S.A Mixed phosphinimine catalyst

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