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WO2005077988A1 - Catalyseur de polymerisation sur support - Google Patents

Catalyseur de polymerisation sur support Download PDF

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Publication number
WO2005077988A1
WO2005077988A1 PCT/GB2005/000378 GB2005000378W WO2005077988A1 WO 2005077988 A1 WO2005077988 A1 WO 2005077988A1 GB 2005000378 W GB2005000378 W GB 2005000378W WO 2005077988 A1 WO2005077988 A1 WO 2005077988A1
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WO
WIPO (PCT)
Prior art keywords
cocatalyst
polymerisation catalyst
polymerisation
transition metal
polymerisable monomer
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Application number
PCT/GB2005/000378
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English (en)
Inventor
Grant Berent Jacobsen
Brian Stephen Kimberley
Claudine Viviane Lalane-Magne
Sergio Mastroianni
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Ineos Europe Limited
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Publication of WO2005077988A1 publication Critical patent/WO2005077988A1/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
    • C08F210/16—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
    • C08F4/6592—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

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 ⁇ -olefms 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. There have been developed several different families of metallocene complexes.
  • Examples of both the bis (cyclopentadienyl) and mono (cyclopentadienyl) complexes have been described in WO 96/04290 and WO 95/00526 respectively.
  • the above metallocene complexes are utilised for polymerisation in the presence of a cocatalyst or activator.
  • activators are aluminoxanes, in particular methyl aluminoxane or alternatively may be compounds based on boron compounds.
  • Examples of the latter are 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 olefins in solution, slurry or gas phase.
  • the metallocene complex and/or the activator are suitably supported.
  • Typical supports include inorganic oxides e.g. silica or polymeric supports may alternatively be used. Examples of the preparation of supported metallocene catalysts for the polymerisation of olefins maybe 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.
  • 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.
  • Our copending application WO04/020487 discloses that the addition of a polymerisable monomer to the support prior to contact with one or both of the polymerisation catalyst and the cocatalyst results in an improved supported catalyst system which has improved activity and which is stable over extended periods of time.
  • a number of references teach the incorporation of inorganic metal compounds into supported polymerisation catalyst systems. For example MgO and ZnO compounds are disclosed in US 6469111 and CuSO 4 compounds are disclosed in US 6207230.
  • a method for the preparation of a supported polymerisation catalyst system comprising the combination of (i) a porous support pretreated with a source of a transition metal atom, (ii) a polymerisable monomer, (iii) a polymerisation catalyst, and (iv) a cocatalyst, characterised in that the polymerisable monomer is added to the porous support before addition of one or both of the polymerisation catalyst and the cocatalyst.
  • a preferred method according to the present invention comprises the following steps: (i ) addition of a cocatalyst to the pretreated porous support, (ii) addition of a polymerisable monomer, and (iii) addition of a polymerisation catalyst.
  • Other suitable orders of addition according to the present invention include the following: • pretreated support, polymerisation catalyst, monomer and cocatalyst
  • the source of the transition metal atom is preferably an organic or an inorganic metal compound and is preferably a metal salt.
  • the preferred transition metal salts are for example metal salts of iron, copper, cobalt, nickel and zinc.
  • the preferred metal salts are those of iron and copper.
  • the preferred salts are sulphates, nitrates, phosphates or acetates.
  • the most preferred salts are sulphates.
  • acid salts such as acetates and gluconates for example ferrous acetate or ferrous D-gluconate dihydrate. Particularly preferred salts for use in the present invention are ferrous sulphate .
  • the most preferred support material for use with the catalyst system according the present invention are inorganic metal oxides in particular oxides of aluminium, silicon, zirconium, zinc and titanium.
  • Alumina, silica and silica-alumina are preferred metal oxides.
  • Suitable silicas include Crosfield ES70, Davison 948 and Sylopol 948 silicas.
  • the support material is preferably treated with a water solution of the required transition metal salt.
  • the support material may then be further 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°C to 1000°C and preferably at 200 to 850°C in an inert atmosphere under reduced pressure.
  • the support material may be further combined with an organometallic compound preferably an organoamminium 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.
  • Other suitable support materials include Group Ila metal halides for example magnesium chloride or polymeric materials such as finely divided polyolefins for example finely divided polyethylene.
  • the transition metal content on the support material is typically in the range
  • the polymerisable monomer may be added to the porous support at 0.01 to 2 times the pore volume of the support. In the preferred embodiment the polymerisable monomer is added to the porous support at 0.01 - 2 times the pore volume of the support but is preferably less than or equal to the pore volume of the support.
  • 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. Alternatively a combination of one or more monomers may be used for example 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. When using a liquid monomer it may be advantageous that the catalyst components be optionally present in a solution of the polymerisable monomer for example when using 1 -hexene as 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 LIB of the Periodic Table of Elements (ITJPAC 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 mclude transition metal compounds from
  • Groups r A - NLA in particular catalysts based on titanium compounds of formula MPvX 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 TiCl 4) TiBr 4 , Ti(OEt) 3 Cl, Ti(OEt) 2 Br 2 and similar.
  • Traditional Ziegler atta catalysts are described in more detail in "Ziegler- ⁇ atta Catalysts and Polymerisation" by J.Boor, Academic Press, New York, 1979.
  • •Vanadium based catalysts include vanadyl halides eg.
  • VC1 4 alkoxy halides and alkoxides such as VOCl 3 , VOCl 2 (OBu), VCl 3 (OBu) and similar.
  • Conventional 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.
  • Other conventional transition metal compounds are those based on magnesium/titanium electron donor complexes described for example in US 4302565.
  • Other suitable 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 maybe illustrated by [2,6-diacetylpyridinebis(2,6- diiso ⁇ ropylanil)FeCl ], 2.6-diacetylpyridinebis (2,4,6-trimethylanil) FeCl 2 and [2,6- diacetylpyridinebis(2,6-diisopropylanil)CoCl2].
  • Other catalysts include derivatives of Group ILIA, FVA 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.
  • anionic or neutral ligand groups which may be cyclic or non-cyclic delocalized ⁇ -bonded anionic ligand groups.
  • ⁇ - 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 INB of the Periodic Table. Included in the term "hydrocarbyl" are CI - 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.
  • Suitable 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.
  • 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 TVA metals for example titanium, zirconium and hafnium.
  • Metallocene complexes may be represented by the general formula: LxMQn where L is a cyclopentadienyl ligand, M is a Group INA metal, Q is a leaving group and x and n are dependent upon the oxidation state of the metal.
  • the Group INA 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 may 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(cyclo ⁇ entadienyl) zirconium dichloride, bis( ⁇ entamethyl)cyclopentadienyl dichloride, or may be bridged eg. ethylene bis(indenyl) zirconium dichloride or dimethylsilyl(indenyl) zirconium dichloride.
  • Other suitable bis(cyclopentadienyl) metallocene complexes are those bis(cyclopentadienyl) diene complexes described in WO 96/04290.
  • Such complexes are bis(cyclopentadienyl) zirconium (2.3-dimethyl-l,3-butadiene) and ethylene bis(indenyl) zirconium 1,4-diphenyl butadiene.
  • Examples of monocyclopentadienyl or substituted monocyclopentadienyl • complexes suitable for use in the present invention are described in EP 416815, EP 418044, EP 420436 and EP 551277.
  • Suitable complexes may be represented by the general formula: CpMX n wherein Cp is a single cyclopentadienyl or substituted cyclopentadienyl group optionally covalently bonded to M through a substituent, M is a Group NLA 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.
  • 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 monocyclopentadienyl complexes are (tert-butylamido) dimethyl (tetramethyl- ⁇ 5 - cyclopentadienyl) silanetitanium dichloride and (2- methoxyphenylamido) dimethyl (tetramethyl ⁇ 5 - cyclopentadienyl) silanetitanium dichloride.
  • Other 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.
  • Another type of 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.
  • Particularly preferred 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;
  • 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 - 1 ,4-ditolyl- 1 ,3 -butadiene; s-trans- ⁇ 4 - 1 ,4-bis(trimethylsilyl)- 1 ,3-butadiene; s- cis- ⁇ 4 -3-methyl-l,3-pentadiene; s-cis- ⁇ 4 -l,4-dibenzyl- 1,3 -butadiene; s-cis- ⁇ 4 -l,3- pentadiene; s-cis- ⁇ 4 -l,4-bis(trimethylsilyl)-
  • 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, tetrahydromdenyl, fluorenyl, terahydrofluorenyl, or octahydrofluorenyl group.
  • Highly preferred Y groups are nitrogen or phosphorus containing groups containing a group corresponding to the formula -N(R 7 )- or -P(R )- wherein R ; is CM 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/g to 1 mmol/g.
  • a supported metallocene catalyst system comprising the combination of (i) a porous support pretreated with a source of a transition metal atom, (ii) a polymerisable monomer, (iii) a metallocene complex, and (iv) a cocatalyst, characterised in that the polymerisable monomer is added to the porous support before addition of one or both of the metallocene complex and the cocatalyst.
  • 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) bora ⁇ ie 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).
  • 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*-H) + d (A d" ) wherein 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.
  • 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 entafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl
  • 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
  • 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) methylammonium . and similar.
  • Particular preferred cocatalysts of this type are alkylammonium tris(pentafluorophenyl) 4-(hydr xyphenyl) 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( ⁇ entaflurophenyl)-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 less than 1 and most preferably in the range 0.3 to 0.8.
  • 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.
  • 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 olef ⁇ n 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-olefms.
  • 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.
  • 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 niost 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 supported catalysts of the present invention.
  • Particularly preferred polymerisation processes are those comprising the polymerisation of ethylene or the copolymerisation of ethylene and ⁇ -olef ⁇ ns 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 ⁇ -olef ⁇ ns 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 less deactivating kinetic profile than similar catalysts prepared without the incorporation of a polymerisable monomer. 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.
  • the supported catalyst systems of the present invention may reduce static levels on the resultant polymers thereby preventing the formation of deposits on the reactor walls and reducing fouling in the reactor. This is particularly the case for processes performed in a fluidised bed reactor and in particular for the copolymerisation of ethylene and alpha-olef ⁇ ns.

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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 porte sur un procédé de préparation d'un système catalyseur sur support utilisant une combinaison de: (i) un support poreux prétraité par une source d'un atome de métal de transition; (ii) un monomère polymérisable; (iii) un catalyseur de polymérisation; et (iv) un cocatalyseur. Le procédé se caractérise en ce que le monomère polymérisable est ajouté au support poreux avant l'un du catalyseur de polymérisation ou du cocatalyseur, ou avant les deux. Le monomère polymérisable préféré est du 1-hexène, et la source d'atome de métal de transition préférée est un sel de métal de transition, par exemple un acétate ferreux. En traitant le support par un composé de métal de transition avant l'incorporation du monomère polymérisable, on obtient un système catalyseur de polymérisation sur support présentant une activité améliorée, une réduction du niveau d'éléments statiques sur les polymères résultants, et cela en particulier pour les polymérisations en phase gazeuse.
PCT/GB2005/000378 2004-02-11 2005-02-02 Catalyseur de polymerisation sur support WO2005077988A1 (fr)

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GB0402959.1 2004-02-11
GB0402959A GB0402959D0 (en) 2004-02-11 2004-02-11 Supported polymerisation catalysts

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WO2005077988A1 true WO2005077988A1 (fr) 2005-08-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555053A (zh) * 2022-09-22 2023-01-03 中化泉州石化有限公司 一种配体化合物及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997027224A1 (fr) * 1996-01-26 1997-07-31 Borealis A/S Systeme de catalyseur pour la polymerisation des olefines, sa production et son utilisation
US6184170B1 (en) * 1996-09-24 2001-02-06 Exxon Chemical Patents, Inc. Metallocene catalyst systems
EP1097949A1 (fr) * 1999-11-05 2001-05-09 Japan Polychem Corporation Copolymère éthylène/alpha-oléfine et film obtenu à partir de celui-ci
US20030087754A1 (en) * 2001-02-23 2003-05-08 Nova Chemicals (International) S.A. Catalyst for olefin polymerization

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997027224A1 (fr) * 1996-01-26 1997-07-31 Borealis A/S Systeme de catalyseur pour la polymerisation des olefines, sa production et son utilisation
US6184170B1 (en) * 1996-09-24 2001-02-06 Exxon Chemical Patents, Inc. Metallocene catalyst systems
EP1097949A1 (fr) * 1999-11-05 2001-05-09 Japan Polychem Corporation Copolymère éthylène/alpha-oléfine et film obtenu à partir de celui-ci
US20030087754A1 (en) * 2001-02-23 2003-05-08 Nova Chemicals (International) S.A. Catalyst for olefin polymerization

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAMFJORD, THOR ET AL: "Supported metallocene catalysts prepared by impregnation of MAO-modified silica by a metallocene /monomer solution", MACROMOLECULAR RAPID COMMUNICATIONS (1998), 19(10), 505-509, 1998, XP002222295 *
RYTTER, ERLING ET AL: "Supported metallocene catalysts prepared by impregnation of silica with metallocene / aluminoxane /1- hexene solutions", MACROMOLECULAR RAPID COMMUNICATIONS (2001), 22(17), 1427-1431, 2001, XP001113454 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555053A (zh) * 2022-09-22 2023-01-03 中化泉州石化有限公司 一种配体化合物及其应用

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