WO2006056734A1 - Catalyseurs de polymerisation a support - Google Patents

Catalyseurs de polymerisation a support Download PDF

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Publication number
WO2006056734A1
WO2006056734A1 PCT/GB2005/004211 GB2005004211W WO2006056734A1 WO 2006056734 A1 WO2006056734 A1 WO 2006056734A1 GB 2005004211 W GB2005004211 W GB 2005004211W WO 2006056734 A1 WO2006056734 A1 WO 2006056734A1
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hydrogen
polymerisation
supported
polymerisation catalyst
ethylene
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PCT/GB2005/004211
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English (en)
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Grant Berent Jacobsen
Brian Stephen Kimberley
Sergio Mastroianni
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Ineos Europe Limited
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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
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • 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

Definitions

  • the present invention relates to supported catalysts suitable for the polymerisation of olefins and in particular to supported metallocene catalysts providing advantages for operation in gas phase processes for the polymerisation of ethylene or the copolymerisation of ethylene and ⁇ -olefins having from 3 to 10 carbon atoms.
  • 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.
  • metallocene complexes There have been developed several different families of metallocene complexes. In earlier years 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 may be found in EP 416815 or EP 420436. In both of these complexes the metal atom eg. zirconium is in the highest oxidation state.
  • activators are aluminoxanes, in particular methyl aluminoxane or alternatively may be compounds based on boron compounds.
  • borates such as trialkyl-substituted ammonium tetraphenyl- or tetrafluorophenyl-borates or triarylboranes such as tris(pentafluorophenyl) borane.
  • the above metallocene complexes may be used for the polymerisation of olefins in solution, slurry 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.
  • Examples of the preparation of supported metallocene catalysts for the polymerisation of olefins may be found in WO 94/26793, WO 95/07939, WO 96/00245, WO 96/04318, WO 97/02297 and EP 642536.
  • WO 98/27119 describes supported catalyst components comprising ionic compounds comprising a cation and an anion in which the anion contains at least one substituent comprising a moiety having an active hydrogen.
  • supported metallocene catalysts are exemplified in which the catalyst is prepared by treating the aforementioned ionic compound with a trialkylaluminium compound followed by subsequent treatment with the support and the metallocene.
  • WO 98/27119 also describes a method for activating a substantially inactive catalyst precursor comprising (a) an ionic compound comprising a cation and an anion containing at least one substituent comprising a moiety having an active hydrogen, (b) a +transition metal compound and optionally, (c) a support by treatment with an organometallic compound thereby forming an active catalyst.
  • Various methods have been utilised to prepare supported catalysts of this type.
  • WO 98/27119 describes several methods of preparing the supported catalysts disclosed therein in which the support is impregnated with the ionic compound.
  • the volume of the ionic compound may correspond from 20 volume percent to greater than 200 volume percent of the total pore volume of the support. In a preferred preparative route the volume of the solution of the ionic compound does not exceed substantially, and is preferably equal to, the total pore volume of the support.
  • Such methods of preparation may be referred to as incipient precipitation or incipient wetness techniques.
  • US 6225423 describes the reaction product of a transition metal compound with an unsaturated organic compound such as 1-hexene and wherein the reaction product is then contacted in a suitable solvent with a carrier material.
  • US 5912202 describes the contact between a single site catalyst precursor with an activating cocatalyst before, during or after contact of the single site precursor with a weakly coordinating electron donor that does not substantially polymerise during the contacting stage.
  • Macromolecular Rapid Communications 1998, 19. 505 - 509 describes the preparation of a number of silica supported metallocene catalysts. Exemplified systems described the addition of a metallocene/1-hexene solution to a silica supported aluminoxane or the addition of a metallocene to silica supported aluminoxane followed by addition of 1-hexene.
  • US 6458904 describes the preparation of supported metallocene catalysts by contacting a metallocene complex with an alk-1-ene followed by reaction of this mixture with an ionic compound followed by addition to a support material.
  • Prepolymerisation is a well known method, in particular in the gas phase, for improving the morphology of the final polymers.
  • a substantially dry formed catalyst is prepolymerised, optionally in a solvent, by treatment with a monomer to produce a prepolymerised catalyst.
  • porous 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 supported catalysts according to the method 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 100 0 C to 1000 0 C and preferably at 200 to 850 0 C in an inert atmosphere under reduced pressure.
  • the porous 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 0 C to 150 0 C and preferably at 20 0 C to 100 0 C.
  • Suitable supports may be those described in our published application WO 04/055062. This application describes the use of supports pretreated with a source of a transition metal atom for example metal salts of iron or copper.
  • Polymerisable monomers suitable for use in the method of the present invention include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, styrene, butadiene, and polar monomers for example vinyl acetate, methyl methacrylate, etc.
  • Preferred " monomers are ethylene, propylene, 1-butene or 1-hexene.
  • ethylene/ 1 -hexene ethylene/ 1 -hexene.
  • the preferred polymerisable monomer for use in the present invention is 1-hexene.
  • the polymerisable monomer is suitably used in liquid form or alternatively may be used in a suitable solvent.
  • the polymerisable monomer and polymerisation catalyst are typically used in a ratio of 1 : 1 to 250: 1 and most preferably in the ratio 20: 1 to 80: 1.
  • the polymerisation catalyst component according to the present invention may suitably be any polymerisation catalyst used in conjunction with a porous support in the present of a suitable cocatalyst.
  • the polymerisation catalyst may typically be a transition metal compound of Groups IIIA to HB of the Periodic Table of Elements (IUPAC Version). Examples of such transition metal compounds are traditional Ziegler Natta, vanadium and Phillips-type catalysts well known in the art. .
  • the traditional Ziegler Natta catalysts include transition metal compounds from Groups IVA - VIA, in particular catalysts based on titanium compounds of formula MRx where M is titanium and R is halogen or a hydrocarbyloxy group and x is the oxidation state of the metal.
  • Such conventional type catalysts include TiCU, TiBr 4 , Ti(OEt)3Cl, Ti(OEt) 2 Br 2 and similar.
  • Traditional Ziegler Natta catalysts are described in more detail in "Ziegler-Natta Catalysts and Polymerisation" by J.Boor, Academic Press, New York, 1979.
  • Vanadium based catalysts include vanadyl halides eg. VCl 4 , and alkoxy halides and alkoxides such as VOCl 3 , VOCl 2 (OBu), VCl 3 (OBu) and similar.
  • chromium catalyst compounds referred to as Phillips type catalysts include CrO 3 , chromocene, silyl chromate and similar and are described in US 4124532, US 4302565.
  • transition metal compounds are those based on magnesium/titanium electron donor complexes described for example in US 4302565.
  • transition metal compounds are those based on the late transition metals (LTM) of Group VIII for example compounds containing iron, nickel, manganese, ruthenium, cobalt or palladium metals. Examples of such compounds are described in WO 98/27124 and WO 99/12981 and may be illustrated by [2,6-diacetyl ⁇ yridinebis(2,6- diisopropylanil)FeCl2], 2.6-diacetylpyridinebis (2,4,6-trimethylanil) FeCl 2 and [2,6- diacetylpyridinebis(2,6-diisopropylanil)CoCl2].
  • LTM late transition metals
  • catalysts include derivatives of Group IIIA, IVA or Lanthanide metals which are in the +2, +3 or +4 formal oxidation state.
  • Preferred compounds include metal complexes containing from 1 to 3 anionic or neutral ligand groups which may be cyclic or non-cyclic delocalized ⁇ -bonded anionic ligand groups. Examples of such ⁇ - bonded anionic ligand groups are conjugated or non-conjugated, cyclic or non-cyclic dienyl groups, allyl groups, boratabenzene groups, phosphole and arene groups.
  • ⁇ -bonded is meant that the ligand group is bonded to the metal by a sharing of electrons from a partially delocalised ⁇ -bond.
  • Each atom in the delocalized ⁇ -bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl, substituted metalloid radicals wherein the metalloid is selected from Group IVB of the Periodic Table. Included in the term "hydrocarbyl” are Cl - C20 straight, branched and cyclic alkyl radicals, C6 - C20 aromatic radicals, etc. In addition two or more such radicals may together form a fused ring system or they may form a metallocycle with the metal.
  • anionic, delocalised ⁇ -bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, etc. as well as phospholes and boratabenzene groups.
  • Phospholes are anionic ligands that are phosphorus containing analogues to the cyclopentadienyl groups. They are known in the art and described in WO 98/50392.
  • the boratabenzenes are anionic ligands that are boron containing analogues to benzene. They are known in the art and are described in Organometallics, 14, 1, 471 - 480 (1995).
  • the preferred polymerisation catalyst of the present invention is a bulky ligand compound also referred to as a metallocene complex containing at least one of the aforementioned delocalized ⁇ -bonded group, in particular cyclopentadienyl ligands.
  • metallocene complexes are those based on Group IVA metals for example titanium, zirconium and hafnium.
  • Metallocene complexes may be represented by the general formula:
  • L is a cyclopentadienyl ligand
  • M is a Group IVA metal
  • Q is a leaving group
  • x and n are dependent upon the oxidation state of the metal.
  • the Group IVA metal is titanium, zirconium or hafnium
  • x is either 1 or 2 and typical leaving groups include halogen or hydrocarbyl.
  • the cyclopentadienyl ligands may be substituted for example by alkyl or alkenyl groups or rriay comprise a fused ring system such as indenyl or fluorenyl. Examples of suitable metallocene complexes are disclosed in EP 129368 and EP 206794. Such complexes may be unbridged eg.
  • bis(cyclopentadienyl) zirconium dichloride bis(pentamethyl)cyclopentadienyl dichloride, or may be bridged eg. ethylene bis(indenyl) zirconium dichloride or dimethylsilyl(indenyl) zirconium dichloride.
  • bis(cyclopentadienyl) metallocene complexes are those bis(cyclopentadienyl) diene complexes described in WO 96/04290.
  • Examples of such complexes are bis(cyclopentadienyl) zirconium (2.3-dimethyl-l,3-butadiene) and ethylene bis(indenyl) zirconium 1,4-diphenyl butadiene.
  • CpMX n wherein Cp is a single cyclopentadienyl or substituted cyclopentadienyl group optionally covalently bonded to M through a substituent, M is a Group VIA metal bound in a ⁇ 5 bonding mode to the cyclopentadienyl or substituted cyclopentadienyl group, X each occurrence is hydride or a moiety selected from the group consisting of halo, alkyl, aryl, aryloxy, alkoxy, alkoxyalkyl, amidoalkyl, siloxyalkyl etc. having up to 20 non-hydrogen atoms and neutral Lewis base ligands having up to 20 non-hydrogen atoms or optionally one X together with Cp forms a metallocycle with M and n is dependent upon the valency of the metal.
  • Particularly preferred monocyclopentadienyl complexes have the 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. having up to 20 non- hydrogen atoms and neutral Lewis base ligands having up to 20 non-hydrogen atoms
  • Y is -O-, -S-, -NR*-, -PR*-
  • M is hafnium, titanium or zirconium
  • 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 monocyclopentadienyl complexes are (tert-butylamido) dimethyl (tetramethyl- ⁇ 5 - cyclopentadienyl) silanetitanium dichloride and (2- methoxyphenylamido) dimethyl (tetramethyl- ⁇ 5 - cyclopentadienyl) silanetitanium dichloride.
  • Suitable monocyclopentadienyl complexes are those comprising phosphinimine ligands described in WO 99/40125, WO 00/05237, WO 00/05238 and WO00/32653.
  • a typical examples of such a complex is cyclopentadienyl titanium [tri (tertiary butyl) phosphinimine] dichloride.
  • polymerisation catalyst suitable for use in the present invention are monocyclopentadienyl complexes comprising heteroallyl moieties such as zirconium (cyclopentadienyl) tris (diethylcarbamates) as described in US 5527752 and WO 99/61486.
  • metallocene complexes 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;
  • v. 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;
  • 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.
  • 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 -l,3-pentadiene; s- trans- ⁇ 4 -l,4-ditolyl-l,3-butadiene; s-trans- ⁇ 4 -l,4-bis(trimethylsilyl)-l,3-butadiene; s-cis- ⁇ 4 -3-methyl-l,3-pentadiene; s-cis- ⁇ 4 -l,4-dibenzy ⁇ -l,3-butadiene; s-cis- ⁇ 4 -l,3-pentadiene; s-cis- ⁇ 4 -l,4-bis(trimethylsilyl)-l,3-butad
  • 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 4 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 M O hydrocarbyl.
  • Most preferred complexes are amidosilane - or amidoalkanediyl complexes. Most preferred complexes are those wherein M is titanium.
  • Specific complexes suitable for use in the preparation of the supported catalysts of the present invention are those disclosed in WO 95/00526 and are incorporated herein by reference.
  • a particularly preferred complex for use in the preparation of the supported catalysts of the present invention is (t-butylamido) (tetramethyl- ⁇ 5 - cyclopentadienyl) dimethyl silanetitanium - ⁇ 4 -1.3 -pentadiene.
  • the loading (transition metal) in the supported catalysts of the present invention is typically in the range 0.1 ⁇ mol/gto 1 mmol/g.
  • Suitable cocatalysts for use in the method of the present invention are those typically used with the aforementioned polymerisation catalysts.
  • Aluminoxanes such as methyl aluminoxane (MAO)
  • boranes such as tris(pentafluorophenyl) borane and borates.
  • Aluminoxanes are well known in the art and preferably comprise oHgomeric 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).
  • cocatalysts are organoboron compounds in particular triarylboron compounds.
  • a particularly preferred triarylboron compound is tris(pentafluorophenyl) borane.
  • 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 " , and 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. triethylammonium, tripropylammonium, tri(n-butyl)ammonium and similar. Also suitable are 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: triethylammonium tetraphenylborate triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluoropheny
  • a preferred type of cocatalyst suitable for use with the metallocene complexes 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
  • 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) methylammonium and similar.
  • Particular preferred cocatalysts of this type are alkylammonium tris(pentafluorophenyl) 4-(hydroxyphenyl) borates.
  • a particularly preferred cocatalyst is bis(hydrbgenated 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 metal with respect to the organometallic compound is aluminium and the preferred metal for the ionic activator is boron whereby the molar ratio of Al/B is less than 2 and is preferably in the range 0.5 to 1.5.
  • the molar ratio of metallocene complex to cocatalyst employed in the method of the present invention may be in the range 1:10000 to 100:1.
  • a preferred range is from 1 :5000 to 10:1 and most preferred from 1:10 to 10:1. It is advantageous in this method of the present invention that the ionic compound is dried before contact with the organometallic compound. This enables lower ratios of organometallic compound to the ionic compound to be used without any detrimental effects on activity.
  • Suitable solvents for use in the method of the present invention include for example toluene, hexene, heptane or similar.
  • the supported catalyst systems of the present invention are most suitable for operation in processes which typically employ supported polymerisation catalysts.
  • the supported catalysts of the present invention may be suitable 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.
  • 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.
  • 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 supported polymerisation catalyst system as hereinbefore described.
  • the supported systems of the present invention are however most suitable for use in slurry or gas phase processes.
  • a slurry process typically uses an inert hydrocarbon diluent and temperatures from about O 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 0 C up to about 200 0 C but preferably from about 6O 0 C to 100 0 C.
  • Loop reactors are widely used in slurry polymerisation processes.
  • Typical operating conditions for the gas phase are from 20 0 C to 100 0 C and most preferably from 4O 0 C to 85 0 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 supported catalysts of the present invention.
  • Particularly preferred 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 present of a supported catalyst system prepared as hereinbefore described.
  • the preferred ⁇ -olefins are 1-butene, 1-hexene, 4-methyl-l-pentene and 1-octene.
  • the supported catalysts prepared according to the present invention may also be suitable for the preparation of other polymers for example polypropylene, polystyrene, etc.
  • a free flowing powder is produced which typically may have a similar particle size to the starting porous support material.
  • the resultant supported catalysts are- stable at room temperature over extended periods of time and exhibit a reduction in the peak exotherm allowing the loading of the active species to be reduced without risking overheating of the catalyst particles. It is also an advantage of the method of the present invention that supported catalysts may be suitably prepared in a one-pot procedure ie. a preparation carried out without the need for washing steps and typically wherein the contact between the support material, cocatalyst, polymerisation catalyst and monomer is performed in a single reaction vessel.
  • Example 2 The catalyst of Example 1 was tested for ethylene - 1-hexene copolymerisation as follows:
  • a 250 ml 1 double jacketed thermostatic stainless steel autoclave was purged with nitrogen at 70 0 C for at least one hour.
  • 70 g of NaCl was introduced as the seed bed and the reactor was then purged three times with nitrogen (7 bar to atmospheric pressure).
  • ⁇ 0.15 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.
  • 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.

Abstract

L'invention concerne une méthode pour préparer un système de catalyseurs de polymérisation à support. Cette méthode comprend les étapes consistant à: (i) ajouter un cocatalyseur à un support poreux dans un solvant approprié, (ii) ajouter un catalyseur de polymérisation au produit de l'étape (i) dans un solvant approprié, (iii) ajouter un monomère polymérisable au produit de l'étape (ii), et (iv) retirer le solvant. L'utilisation de la méthode de l'invention permet d'obtenir une poudre à fluage doux pouvant typiquement présenter une taille particulaire analogue à celle du support poreux de départ. Les catalyseurs à support obtenus sont stables à température ambiante, pendant des périodes prolongées, et sont particulièrement appropriées à une utilisation en phase gazeuse.
PCT/GB2005/004211 2004-11-25 2005-11-01 Catalyseurs de polymerisation a support WO2006056734A1 (fr)

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GB0425954A GB0425954D0 (en) 2004-11-25 2004-11-25 Supported polymerisation catalysts

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5968864A (en) * 1996-12-20 1999-10-19 Fina Technology, Inc. Catalyst efficiency for supported metallocene catalyst
EP1541598A1 (fr) * 2003-12-01 2005-06-15 Maruzen Petrochemical Co., Ltd. Catalyseur pour la polymérisation d'oléfine, méthode pour la production de polymère d'oléfine à l'aide de ce catalysateur
WO2005082949A1 (fr) * 2004-02-25 2005-09-09 Ineos Europe Limited Catalyseurs de polymerisation supportes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5968864A (en) * 1996-12-20 1999-10-19 Fina Technology, Inc. Catalyst efficiency for supported metallocene catalyst
EP1541598A1 (fr) * 2003-12-01 2005-06-15 Maruzen Petrochemical Co., Ltd. Catalyseur pour la polymérisation d'oléfine, méthode pour la production de polymère d'oléfine à l'aide de ce catalysateur
WO2005082949A1 (fr) * 2004-02-25 2005-09-09 Ineos Europe Limited Catalyseurs de polymerisation supportes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAMFJORD T ET AL: "Supported metallocene catalysts prepared by impregnation of MAO-modified silica by a metallocene / monomer solution", 1998, MACROMOLECULAR: RAPID COMMUNICATIONS, WILEY VCH VERLAG, WEINHEIM, DE, PAGE(S) 505-509, ISSN: 1022-1336, XP002325547 *

Also Published As

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