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WO1999019335A1 - Nouveaux catalyseurs de polymerisation - Google Patents

Nouveaux catalyseurs de polymerisation Download PDF

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Publication number
WO1999019335A1
WO1999019335A1 PCT/GB1998/003027 GB9803027W WO9919335A1 WO 1999019335 A1 WO1999019335 A1 WO 1999019335A1 GB 9803027 W GB9803027 W GB 9803027W WO 9919335 A1 WO9919335 A1 WO 9919335A1
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WIPO (PCT)
Prior art keywords
formula
groups
catalyst
chromium
complex
Prior art date
Application number
PCT/GB1998/003027
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English (en)
Inventor
Vernon Charles Gibson
Claire Newton
Gregory Adam Solan
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Bp Chemicals Limited
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Application filed by Bp Chemicals Limited filed Critical Bp Chemicals Limited
Priority to AU93594/98A priority Critical patent/AU9359498A/en
Publication of WO1999019335A1 publication Critical patent/WO1999019335A1/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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • 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
    • C08F10/02—Ethene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not

Definitions

  • the present invention relates to novel polymerisation catalysts based on organic transition metal complexes and to a polymerisation process using the catalysts.
  • the use of Ziegler-Natta catalysts for example, those catalysts produced by activating titanium halides with organometallic compounds such as triethylaluminium, is fundamental to many commercial processes for manufacturing polyolefins. Over the last twenty or thirty years, advances in the technology have led to the development of Ziegler-Natta catalysts which have such high activities that olefin polymers and copolymers containing very low concentrations of residual catalyst can be produced directly in commercial polymerisation processes.
  • the quantities of residual catalyst remaining in the produced polymer are so small as to render unnecessary their separation and removal for most commercial applications.
  • Such processes can be operated by polymerising the monomers in the gas phase, or in solution or in suspension in a liquid hydrocarbon diluent. Polymerisation of the monomers can be carried out in the gas phase (the "gas phase process"), for example by fluidising under polymerisation conditions a bed comprising the target polyolefin powder and particles of the desired catalyst using a fluidising gas stream comprising the gaseous monomer.
  • the (co)polymerisation is conducted by introducing the monomer into a solution or suspension of the catalyst in a liquid hydrocarbon diluent under conditions of temperature and pressure such that the produced polyolefin forms as a solution in the hydrocarbon diluent.
  • the temperature, pressure and choice of diluent are such that the produced polymer forms as a suspension in the liquid hydrocarbon diluent.
  • Commodity polyethylenes are commercially produced in a variety of different types and grades. Homopolymerisation of ethylene with transition metal based catalysts leads to the production of so-called "high density" grades of polyethylene. These polymers have relatively high stiffness and are useful for making articles where inherent rigidity is required. Copolymerisation of ethylene with higher 1-olefins (eg butene, hexene or octene) is employed commercially to provide a wide variety of copolymers differing in density and in other important physical properties. Particularly important copolymers made by copolymerising ethylene with higher 1- olefins using transition metal based catalysts are the copolymers having a density in the range of 0.91 to 0.93.
  • 1-olefins eg butene, hexene or octene
  • linear low density polyethylene are in many respects similar to the so called “low density” polyethylene produced by the high pressure free radical catalysed polymerisation of ethylene.
  • Such polymers and copolymers are used extensively in the manufacture of flexible blown film.
  • metallocene catalysts for example biscyclopentadienylzirconiumdichloride activated with alumoxane
  • metallocene catalysts of this type suffer from a number of disadvantages, for example, high sensitivity to impurities when used with commercially available monomers, diluents and process gas streams, the need to use large quantities of expensive alumoxanes to achieve high activity, and difficulties in putting the catalyst on to a suitable support.
  • An object of the present invention is to provide a novel catalyst suitable for polymerising olefins, and especially for polymerising ethylene alone or for copolymerising ethylene with higher 1-olefins.
  • a further object of the invention is to provide an improved process for the polymerisation of olefins, especially of ethylene alone or the copolymerisation of ethylene with higher 1-olefins to provide homopolymers and copolymers having controllable molecular weights.
  • polyolefins such as, for example, liquid polyolefins, resinous or tacky polyolefins, solid polyolefins suitable for making flexible film and solid polyolefins having high stiffness.
  • the present invention provides a polymerisation catalyst comprising (1) a complex chromium compound comprising the monomeric skeletal unit depicted in Formula W, or dimers of such units;
  • N 1 is a nitrogen atom
  • Q is a nitrogen atomN 2 or an oxygen atom O
  • R 20 and R 21 are organic groups
  • R 22 is hydrogen or an organic group
  • two or more of R 20 , R 21 R 22 and R 23 can optionally be linked to one another
  • the bonds between R 23 and N 1 or Q can be independently single or double bonds
  • k is the nominal negative charge on the bidentate ligand and is 1 or 2
  • n is the number of the defined bidentate ligands attached to the chromium atom and is 1 or 2
  • X is the oxidation state of the chromium and is 2 or 3
  • the chromium compound can optionally comprise one or more neutral molecules coordinated to the chromium, for example, solvent molecules.
  • neutral molecules are ethers, amines, nitriles and esters, for example, tetrahydrofuran, acetonitrile, formdimethylamide and methyl benzoate.
  • the complex chromium compound of Formula W can comprise, for example, the monomeric unit depicted in any one of Formulae A, B, C, D, E or F or dimers of such units:
  • R 2 , R 5 , R 8 , R 1 , R 14 and R 16 are organic groups comprising at least a saturated or unsaturated chain;
  • R 1 , R 3 , R 4 , R 6 , R 7 , R 11 , R 13 , and R 18 are organic groups;
  • R 9 , R 12 , R 15 and R 17 are independently hydrogen or organic groups;
  • two or more of the defined R groups are optionally linked to one another within the respective Formula A, B, C, D, E, or F;
  • N 1 and N 2 are nitrogen atoms;
  • O is an oxygen atom;
  • X is the oxidation state of the chromium; in Formulae A and C, X is 3; in Formula B, D, E and F, X is 2 or 3;
  • Z is a univalent atom or group;
  • p represents the number of atoms or groups of
  • One embodiment of the present invention provides a polymerisation catalyst comprising (1) a complex chromium compound comprising the monomeric unit depicted in Formula A, B or C or dimers of such units:
  • an activating quantity of an activator compound selected from organoaluminium compounds and hydrocarbylboron compounds selected from organoaluminium compounds and hydrocarbylboron compounds.
  • Formulae W, A, B, C, D, E and F defined above relate to the monomeric unit of the chromium complex catalyst of the present invention.
  • the present invention also provides catalysts comprising dimers of these units.
  • R groups R 1 to R 18 and R 20 to R 23 can be, for example, an organic group selected from aliphatic, alicyclic, aromatic, carbocyclic or heterocyclic systems.
  • the nitrogen atoms N 1 and N 2 can form, for example, part of hetero-organic ring systems or hetero-organic chains.
  • Such systems can comprise, for example, straight or branched chain units, and can contain suitable substituents or functional groups, for example halogen, nitrile, fluoroalkyl and nitro groups.
  • R 1 , R 3 , R 4 , R 6 , R 7 , R", R 13 , R 18 , R 20 , R 21 and R 22 can each consist of a monovalent organic group pendant from the defined nitrogen atom N 1 or N 2 , and can, if desired, be further bonded to one or more of the other defined R groups.
  • R 9 , R 12 , R 15 , R 17 and R 22 are independently hydrogen or organic groups and can, if desired, be further bonded to one or more of the other defined R groups.
  • R 1 , R 3 , R 4 , R 6 , R 7 , R 9 , R 11 , R 12 , R 13 , R 15 , R 17 , R 18 , R 20 , R 21 and R 22 can be independently selected from, for example, aliphatic groups, for example, methyl, ethyl, propyl, butyl, butenyl, hexyl, cyclohexyl, cyclohexenyl or octyl; or alkyaryl groups, for example, benzyl, phenylethyl or phenylpropyl; or aryl groups, for example, phenyl, naphthyl, 2,6- dimethylphenyl, 2,4-diethylphenyl, 2,6-diisopropyl or 4-chlorophenyl.
  • aliphatic groups for example, methyl, ethyl, propyl, butyl, butenyl, hexyl
  • R 23 , R 2 , R 5 , R 8 , R 10 , R 14 and R 16 are organic groups comprising at least a saturated or unsaturated chain linking N 1 with N 2 or O.
  • the group R 23 , R 2 , R 5 , R 8 , R 10 , R 14 and R 16 comprises a saturated chain
  • said chain comprises at least one carbon atom.
  • said saturated chain can have the formula (CR 30 R 31 ) n wherein each of the substituents R 30 and R 31 is independently hydrogen or an organic or inorganic substituent, and n is an integer from 1 to 10, preferably from 1 to 5, most preferably from 2 to 4.
  • R 23 , R 2 , R 5 , R 8 , R 10 , R 14 and R 16 comprise an unsaturated chain
  • said chain comprises at least two carbon atoms.
  • the unsaturated chain preferably comprises or forms part of an aromatic ring system or a system of conjugated double bonds.
  • the bridging groups R 23 , R 2 , R 5 , R 8 , R 10 , R 14 and R 16 can comprise, for example, hydrocarbyl or heterohydrocarbyl groups. They can comprise, for example, straight or branched chain aliphatic or cycloaliphatic, aromatic or heterocyclic groups.
  • Such groups can be derived from, for example, benzene, naphthalene, phenanthrene, cyclohexane, cyclohexene, cyclopentane, pyridine, pyrimidine, quinoline, isoquinoline, acenapthene, pyrazole, thiazole, furan, tetrahydrofuran and substituted derivatives of these types.
  • one or more of the organic groups R to R are further bonded to one or more other of these organic groups within the respective Formulae A, B, C, D, E, F or W, they form ring systems including one or more of the nitrogen atoms N 1 and N 2 .
  • Such ring systems may, if desired, comprise one or more hetero atoms in addition to the one or more defined nitrogen atoms. Examples of such hetero atoms are nitrogen, silicon, sulphur and oxygen.
  • the ring systems can include, for example, straight or branched chain hydrocarbon or heterohydrocarbyl units. Further ring systems can be fused thereto, for example, units derived from benzene, naphthalene, phenanthrene, cyclohexane, cyclohexene, cyclopentane, pyridine, pyrimidine, quinoline, isoquinoline, acenapthene, pyrazole, thiazole, furan, tetrahydrofuran and subststiuted derivatives thereof.
  • the ring systems can contain suitable substituents or functional groups, for example halogen, nitrile, fluoroalkyl and nitro groups.
  • Ligand B 13 Ligand B 14 - PyrroHde-imine Imine-amide
  • Formulae Al, A2 and A3 illustrate units of the Formula A type
  • Formulae Bl, B2, B3 and B4 illustrate Formula B type
  • Formula Cl illustrates a unit of the Formula C type. Illustrations of Formula D and E types are shown later in this specification.
  • one or more of the hydrogen atoms pendant from the carbon atoms of the organic groups can be replaced by other atoms or groups, for example, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, naphthyl, acetyl, carboxyl, pyridino; silyl, for example, trimethylsilyl, triethylsilyl: and suitable inorganic atoms or groups (eg halogen).
  • R 10 , R 11 , R 12 and R 13 are suitably selected from hydrogen, hydrocarbyl and heterohydrocarbyl. Preferably they are hydrogen or alkyl groups containing 1 to 6 carbon atoms.
  • the atom(s) or group(s) represented by Z in the units of Formula A and C are preferably selected from halide, sulphate, nitrate, thiolate, thiocarboxylate, BF 4 " , PF 6 " , hydride, hydrocarbyloxide, carboxylate, hydrocarbyl, substituted hydrocarbyl, and heterohydrocarbyl.
  • Examples of such atoms or groups are chloride, bromide, methyl , ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, tosylate, triflate, formate, acetate, phenoxide and benzoate.
  • the chromium compound complex units forming component (1) of the catalyst of the present invention may exist in the form of monomeric or dimeric forms.
  • the solid crystalline complexes generally exist in the dimeric state.
  • Complex B5 illustrated below is a complex chromium compound unit having a similar structure to that of Formula B2 above, but is substituted with isopropyl groups in the 2,6-positions on the phenyl substituents, and has two methyl groups on the group bridging the nitrogen atoms.
  • the solid form of Complex B5 is a crystalline dimer having the Formula B6 (shown below): Formula B6
  • the activator compound for the catalyst of the present invention is suitably selected from organoaluminium compounds and hydrocarbylboron compounds.
  • organoaluminium compounds include trialkyaluminium compounds, for example, trimethylaluminium, triethylaluminium, tributylaluminium, tri-n- octylaluminium, ethylaluminium dichloride, diethylaluminium chloride and alumoxanes. Dialkyl aluminium halides are particularly preferred.
  • Alumoxanes are well known in the art as typically the oligomeric compounds which can be prepared by the controlled addition of water to an alkylaluminium compound, for example t ⁇ methylaluminium. Such compounds can be linear, cyclic or mixtures thereof. Commercially available alumoxanes are generally believed to be mixtures of linear and cyclic compounds.
  • the cyclic alumoxanes can be represented by the formula [R ,33 AlO] s and the linear alumoxanes by the formula R 34 ( /r R > 35 A, lO) s wherein s is a number from about 2 to 50, and wherein R , R , and R represent hydrocarbyl groups, preferably d to C 6 alkyl groups, for example methyl, ethyl or butyl groups.
  • hydrocarbylboron compounds are dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate, sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate, tris(pentafluorophenyl) boron H+(OEt2)[(bis-3,5-trifluoromethyl)phenyl]borate, and trityltetra(pentafluorophenyl)borate.
  • the quantity of activating compound selected from organoaluminium compounds and hydrocarbylboron compounds to be employed is easily determined by simple testing, for example, by the preparation of small test samples which can be used to polymerise small quantities of the monomer(s) and thus to determine the activity of the produced catalyst. It is generally found that, for the organoaluminium activators the quantity employed is sufficient to provide 1 to 20,000 atoms, preferably 1 to 2000 atoms of aluminium per chromium atom in the compound of Formula W, A, B, C, D, E or F.
  • the catalyst of the present invention can , if desired, be supported on a support material, for example, silica, alumina, or zirconia, or on a polymer or prepolymer, for example polyethylene or polystyrene.
  • a support material for example, silica, alumina, or zirconia
  • a polymer or prepolymer for example polyethylene or polystyrene.
  • Methods of preparation of supported catalysts are well known in the art.
  • the quantity of support material employed can vary widely, for example from 100,000 to 1 grams per gram of metal present in the defined chromium complex compound.
  • the present invention further provides a process for the polymerisation and copolymerisation of 1-olefins comprising contacting the monomeric olefin under polymerisation conditions with the catalyst of the present invention.
  • the polymerisation conditions can be, for example, solution phase, slurry phase or gas phase.
  • the catalyst can be used to polymerise ethylene under high pressure/high temperature process conditions wherein the polymeric material forms as a melt in supercritical ethylene.
  • the polymerisation is conducted under gas phase fluidised bed conditions.
  • Suitable monomers for use in the polymerisation process of the present invention are, for example, ethylene, propylene, butene, hexene, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene (the monomers in this list which are not 1-olefins can be used as comonomers if desired).
  • the process can be, for example, homopolymerisation or copolymerisation of monomer selected from one or more of ethylene, propylene, 1-butene, 1 -hexene, 4-methylpentene-l and octene.
  • Preferred monomers for homopolymerisation processes are ethylene and propylene.
  • the catalyst is useful for copolymerising ethylene with other 1-olefins such as propylene, 1-butene, 1-hexene, 4-methylpentene-l, and octene.
  • Slurry phase polymerisation conditions or gas phase polymerisation conditions are particularly useful for the production of high, medium and low density grades of polyethylene.
  • the polymerisation conditions can be batch, continuous or semi-continuous.
  • the catalyst is generally fed to the polymerisation zone in the form of a particulate solid.
  • This solid can be, for example, an undiluted solid catalyst system formed from the chromium complex of the present invention and an activator, or can be the solid complex alone. In the latter situation, the activator can be fed to the polymerisation zone, for example as a solution, separately from or together with the solid complex.
  • the catalyst system or the transition metal complex component of the catalyst system employed in the slurry polymerisation and gas phase polymerisation is supported on a support material.
  • the catalyst system is supported on a support material prior to its introduction into the polymerisation zone.
  • Suitable support materials are, for example, silica, alumina, zirconia, talc, kieselguhr, or magnesia.
  • Impregnation of the support material can be carried out by conventional techniques, for example, by forming a solution or suspension of the catalyst components in a suitable diluent or solvent, and slurrying the support material therewith. The support material thus impregnated with catalyst can then be separated from the diluent for example, by filtration or evaporation techniques.
  • the solid particles of catalyst, or supported catalyst are fed to a polymerisation zone either as dry powder or as a slurry in the polymerisation diluent.
  • a polymerisation zone is fed to a polymerisation zone as a suspension in the polymerisation diluent.
  • the polymerisation zone can be, for example, an autoclave or similar reaction vessel, or a continuous loop reactor, e.g. of the type well-know in the manufacture of polyethylene by the Phillips Process.
  • the polymerisation process of the present invention is carried out under slurry conditions the polymerisation is preferably carried out at a temperature above 0°C, most preferably above 15°C.
  • the polymerisation temperature is preferably maintained below the temperature at which the polymer commences to soften or sinter in the presence of the polymerisation diluent. If the temperature is allowed to go above the latter temperature, fouling of the reactor can occur. Adjustment of the polymerisation within these defined temperature ranges can provide a useful means of controlling the average molecular weight of the produced polymer.
  • a further useful means of controlling the molecular weight is to conduct the polymerisation in the presence of hydrogen gas which acts as chain transfer agent. Generally, the higher the concentration of hydrogen employed, the lower the average molecular weight of the produced polymer.
  • hydrogen gas as a means of controlling the average molecular weight of the polymer or copolymer applies generally to the polymerisation process of the present invention.
  • hydrogen can be used to reduce the average molecular weight of polymers or copolymers prepared using gas phase, slurry phase or solution phase polymerisation conditions.
  • the quantity of hydrogen gas to be employed to give the desired average molecular weight can be determined by simple "trial and error" polymerisation tests.
  • Such methods generally involve agitating (eg by stirring, vibrating or fluidising) a bed of catalyst, or a bed of the target polymer (ie polymer having the same or similar physical properties to that which it is desired to make in the polymerisation process) containing a catalyst, and feeding thereto a stream of monomer at least partially in the gaseous phase, under conditions such that at least part of the monomer polymerises in contact with the catalyst in the bed.
  • the bed is generally cooled by the addition of cool gas (eg recycled gaseous monomer) and/or volatile liquid (eg a volatile inert hydrocarbon, or gaseous monomer which has been condensed to form a liquid).
  • the polymer produced in, and isolated from, gas phase processes forms directly a solid in the polymerisation zone and is free from, or substantially free from liquid.
  • any liquid is allowed to enter the polymerisation zone of a gas phase polymerisation process the quantity of liquid is small in relation to the quantity of polymer present in the polymerisation zone. This is in contrast to “solution phase” processes wherein the polymer is formed dissolved in a solvent, and “slurry phase” processes wherein the polymer forms as a suspension in a liquid diluent.
  • the gas phase process can be operated under batch, semi-batch, or so-called “continuous” conditions. It is preferred to operate under conditions such that monomer is continuously recycled to an agitated polymerisation zone containing polymerisation catalyst, make-up monomer being provided to replace polymerised monomer, and continuously or intermittently withdrawing produced polymer from the polymerisation zone at a rate comparable to the rate of formation of the polymer, fresh catalyst being added to the polymerisation zone to replace the catalyst withdrawn form the polymerisation zone with the produced polymer.
  • Gas phase fluidised bed polymerisation conditions are preferred in the polymerisation process of the present invention..
  • the process can be operated, for example, in a vertical cylindrical reactor equipped with a perforated distribution plate to support the bed and to distribute the incoming fluidising gas stream through the bed.
  • the fluidising gas circulating through the bed serves to remove the heat of polymerisation from the bed and to supply monomer for polymerisation in the bed.
  • the fluidising gas generally comprises the monomer(s) normally together with some inert gas (eg nitrogen) and optionally with hydrogen as molecular weight modifier.
  • the hot fluidising gas emerging from the top of the bed is led optionally through a velocity reduction zone (this can be a cylindrical portion of the reactor having a wider diameter) and, if desired, a cyclone and or filters to disentrain fine solid particles from the gas stream.
  • the hot gas is then led to a heat exchanger to remove at least part of the heat of polymerisation.
  • Catalyst is preferably fed continuously or at regular intervals to the bed.
  • the bed comprises fluidisable polymer which is preferably similar to the target polymer.
  • Polymer is produced continuously within the bed by the polymerisation of the monomer(s).
  • Preferably means are provided to discharge polymer from the bed continuously or at regular intervals to maintain the fluidised bed at the desired height.
  • the process is generally operated at relatively low pressure, for example, at 10 to 50 bars, and at temperatures for example, between 50 and 120 °C.
  • the temperature of the bed is maintained below the sintering temperature of the fluidised polymer to avoid problems of agglomeration.
  • the heat evolved by the exothermic polymerisation reaction is normally removed from the polymerisation zone (ie, the fluidised bed) by means of the fluidising gas stream as described above.
  • the hot reactor gas emerging from the top of the bed is led through one or more heat exchangers wherein the gas is cooled.
  • the cooled reactor gas, together with any make-up gas, is then recycled to the base of the bed.
  • the volatile liquid can condense out.
  • the volatile liquid is separated from the recycle gas and reintroduced separately into the bed.
  • the volatile liquid can be separated and sprayed into the bed.
  • the volatile liquid is recycled to the bed with the recycle gas.
  • the volatile liquid can be condensed from the fluidising gas stream emerging from the reactor and can be recycled to the bed with recycle gas, or can be separated from the recycle gas and sprayed back into the bed.
  • the catalyst, or one or more of the components employed to form the catalyst can, for example, be introduced into the polymerisation reaction zone in liquid form, for example, as a solution in an inert liquid diluent.
  • the transition metal component, or the activator component, or both of these components can be dissolved or slurried in a liquid diluent and fed to the polymerisation zone.
  • the liquid containing the component(s) is sprayed as fine droplets into the polymerisation zone.
  • the droplet diameter is preferably within the range 1 to 1000 microns.
  • EP-A-0593083 discloses a process for introducing a polymerisation catalyst into a gas phase polymerisation.
  • the methods disclosed in EP-A-0593083 can be suitably employed in the polymerisation process of the present invention if desired.
  • the present invention further provides a novel complex chromium compound having the Formula A, or a dimer thereof:
  • R is an organic group" comprising at least a saturated or unsaturated chain; R and R are organic groups; two or more of the defined R groups are optionally linked to one another; N and N are nitrogen atoms; X is the oxidation state of the chromium; Z is a univalent atom or group.
  • the present invention further provides a novel complex chromium compound having the Formula B, or a dimer thereof:
  • R 5 is an organic group comprising at least a saturated or unsaturated chain
  • R 4 and R 6 are organic groups
  • R 9 is hydrogen or an organic groups
  • two or more of the defined R groups are optionally linked to one another
  • N 1 and N 2 are nitrogen atoms
  • X is the oxidation state of the chromium and is 3
  • p represents the number of atoms or groups of Y present in the complex unit
  • n is 1 or 2
  • the present invention further provides a novel complex chromium compound having the Formula D, or a dimer thereof:
  • R 10 is an organic group comprising at least a saturated or unsaturated chain
  • the present invention further provides a novel complex chromium compound having the Formula E, or a dimer thereof:
  • R 14 is an organic group comprising at least a saturated or unsaturated chain;
  • R 13 is an organic group;
  • R 15 is hydrogen or an organic group; two or more of the defined R groups are optionally linked to one another;
  • N 1 is a nitrogen atom;
  • O is an oxygen atom;
  • X is the oxidation state of the chromium and is 2;
  • p represents the number of atoms or groups of Y present in the complex unit;
  • n is 1 or 2; and
  • the chromium compound in addition to the defined ligand or ligands, can optionally comprise one or more neutral molecules coordinated to the chromium, for example, solvent molecules.
  • neutral molecules are ethers, amines, nitriles and esters, for example, tetrahydrofuran, acetonitrile, formdimethylamide and methyl benzoate.
  • the atom(s) or group(s) represented by Z in the units of Formula A are preferably selected from halide, sulphate, nitrate, thiolate, thiocarboxylate, BF 4 " , PF 6 " , hydride, hydrocarbyloxide, carboxylate, hydrocarbyl, substituted hydrocarbyl, and heterohydrocarbyl.
  • Examples of such atoms or groups are chloride, bromide, methyl , ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, tosylate, triflate, formate, acetate, phenoxide and benzoate; and the atom(s) or group(s) represented by Y in the units of Formula B, D and E can be, if desired, selected from the same atoms of groups as the Z atoms or groups listed above.
  • Y can be derived from, for example a dicarboxylic acid, a diol, a hydrocarbyl diradical, or an inorganic dibasic acid (eg sulphate).
  • a dicarboxylic acid e.g., when the Y group has a valency of 2
  • Y can be derived from, for example a dicarboxylic acid, a diol, a hydrocarbyl diradical, or an inorganic dibasic acid (eg sulphate).
  • the present invention is illustrated in the following Examples which describe the preparation of chromium complex compounds, their activation with organmetallic activators to form polymerisation catalaysts and the use of these catalaysts to polymerise ethylene in accordance with the present invention.
  • a summary of the polymerisation tests is provided Tables 1 and 2.
  • the Formula A4 compound is a dimer comprising two units in accordance with the Formula A complex of the present invention.
  • 1.3 Polymerisation of ethylene using a catalyst prepared from the Formula A4 complex and DEAC A 1.8 M solution of diethylaluminium chloride (DEAC) in toluene (0.33 ml, 0.6 mmol) was added via syringe to a stirred suspension of the Formula A4 complex (26 mg, 0.06 mmol) in toluene (40 ml).
  • DEAC is commercially available from Aldrich.
  • the produced catalyst solution was degassed under reduced pressure and back-filled with an atmosphere of ethylene.
  • Tetrahydrofuran (THF) 40 ml was added to a mixture of the lithium salt of "Intermediate IB7(b)" (1.13 g, 2.7 mmol) and CrCl 3 .(THF) 3 (1.00 g, 2.7 mmol) in a Schlenk vessel. The mixture was stirred overnight at room temperature during which time the solution became olive green. The THF was removed under reduced pressure, then pentane (40 ml) was added and the solution sti ⁇ ed. Filtration of the lithium salts and drying of the filtrate overnight gave the complex of Formula A8 (1.16 g, 80%). Microanalysis, FAB Mass spectrum and single crystal X-ray diffraction confirm the structure of the complex. The single crystal X-ray diffraction study revealed the structure to be dimeric in the solid state (see Figure 1).
  • Activity is expressed as g mmol "1 h "1 bar “1 .
  • the chromium complex (“procatalyst”) was dissolved in toluene (40 ml) in a Schlenk tube and the co-catalyst diethylaluminium chloride ("DEAC", 1.8 molar in toluene or "DMAC”, 1.0 molar in toluene) was added.
  • the Schlenk tube was then purged with ethylene and the contents magnetically stirred and maintained under ethylene (1 bar) for the duration of the polymerization. After 0.5 to 1 hour the polymerization was terminated by the addition of aqueous hydrogen chloride.
  • the insoluble, solid, polyethylene was recovered by filtration, washed with methanol (50 ml) and dried (vacuum oven at 50 °C).
  • a 1 litre reactor was baked out under a nitrogen flow for at least 1 hour at >85°C.
  • the reactor was then cooled to 35°C.
  • Isobutane 500ml was then added and the reactor boxed in nitrogen and left for at least 1 hour.
  • Ethylene was introduced into the reactor until a pre-determined over-pressure was achieved.
  • the pre-formed catalyst solution in toluene was then injected under nitrogen.
  • the reactor pressure was maintained constant throughout the polymerization run by computer controlled addition of ethylene.
  • the polymerization time was 1 hour.
  • Upon termination of the polymerisation the reactor contents were isolated, washed with aqueous HCl, methanol and dried in a vacuum oven at 50°C.

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Abstract

L'invention concerne un catalyseur de polymérisation comprenant (1) le composé de Formule (W), ou ses dimères; dans laquelle N représente azote, Q représente azote ou oxygène, X représente l'état d'oxydation de Cr et Y représente un atome ou un groupe ayant une valence de m, p représente zéro ou un entier de manière que p = (X - nk)/m, et (2) un composé activateur choisi parmi des composés organoaluminiques et hydrocarbylboriques. Le catalyseur peut être utilisé pour la polymérisation ou la copolymérisation des 1-oléfines. L'invention concerne également certains nouveaux complexes de chrome.
PCT/GB1998/003027 1997-10-11 1998-10-08 Nouveaux catalyseurs de polymerisation WO1999019335A1 (fr)

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AU93594/98A AU9359498A (en) 1997-10-11 1998-10-08 Novel polymerisation catalysts

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GB9721559A GB9721559D0 (en) 1997-10-11 1997-10-11 Novel polymerisation catalysts
GB9721559.4 1997-10-11

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WO2002050138A3 (fr) * 2000-12-20 2003-09-12 Bp Chem Int Ltd Nouveaux catalyseurs de polymerisation
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