[go: up one dir, main page]

WO2000069869A1 - Catalyseurs de polymerisation - Google Patents

Catalyseurs de polymerisation Download PDF

Info

Publication number
WO2000069869A1
WO2000069869A1 PCT/GB2000/001385 GB0001385W WO0069869A1 WO 2000069869 A1 WO2000069869 A1 WO 2000069869A1 GB 0001385 W GB0001385 W GB 0001385W WO 0069869 A1 WO0069869 A1 WO 0069869A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
diacetylpyridinebis
polymerisation
acetylacetonate
heterohydrocarbyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2000/001385
Other languages
English (en)
Inventor
George Johan Peter Britovsek
Vernon Charles Gibson
Stefan Klaus Spitzmesser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Chemicals Ltd
Original Assignee
BP Chemicals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BP Chemicals Ltd filed Critical BP Chemicals Ltd
Priority to AU39811/00A priority Critical patent/AU3981100A/en
Publication of WO2000069869A1 publication Critical patent/WO2000069869A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/90—Antimony compounds
    • C07F9/902—Compounds without antimony-carbon linkages
    • 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
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B

Definitions

  • the present invention relates to transition metal complex compounds, to polymerisation catalysts based thereon and to their use in the polymerisation and copolymerisation of olefins.
  • 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 solution process 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.
  • These processes are generally operated at relatively low pressures (for example 10-50 bar) and low temperature (for example 50 to 150°C).
  • relatively low pressures for example 10-50 bar
  • low temperature for example 50 to 150°C.
  • metallocene catalysts for example biscyclopentadienylzirconiumdichloride activated with alumoxane
  • 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.
  • W098/27124 discloses that ethylene may be polymerised by contacting it with certain iron or cobalt complexes of selected 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis(imines). Cationic versions of these complexes are disclosed, but only including monodentate anionic ligands into which ethylene can insert.
  • WO 98/11144 discloses catalyst compositions comprising complexes of Group IVB,VB and VIII metals in which the ligands include chelating ligands where at least one atom from O, N, P or S is directly bound to the metal, plus a neutral Lewis base. However no permanent ligands of the type claimed below are disclosed.
  • Our own copending application GB9903402.7 discloses certain vanadium and titanium complexes of selected 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis(imines), but only in the neutral form.
  • An object of the present invention is to provide a novel catalyst suitable for polymerising and oligomerising monomers, for example, olefins such as ⁇ -olefins containing from 2 to 20 carbon atoms, and especially for polymerising ethylene alone, propylene alone, or for copolymerising ethylene or propylene with other 1 -olefins such as C 2-2 o ⁇ -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 or propylene with higher 1 -olefins to provide homopolymers and copolymers having controllable molecular weights.
  • the catalysts of the present invention there can be made a wide variety of products such as, for example, liquid polyolefins, oligomers, linear ⁇ -olefins, branched ⁇ -olefins, resinous or tacky polyolefins, solid polyolefins suitable for making flexible film and solid polyolefins having high stiffness.
  • the present invention provides a complex having the Formula (I)
  • R 1 to R 7 are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl or SiR' 3 where each R' is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl;
  • B is a chelating ligand comprising at least one atom from O, S, N and P bound directly to M;
  • X is a monodentate monoanionic ligand;
  • L is a ligand datively bonded to M;
  • n is greater or equal to 1, m is greater or equal to 0 and q is greater or equal to 0, provided that n and m are integers or zero which satisfy the valency of the metal; and D is a compatible non-coordinating anion.
  • R 6 and R 7 are preferably independently selected from substituted or unsubstituted alicyclic, heterocyclic or aromatic groups, for example, phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2-t-butylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, 2,6- trifluoromethylphenyl, 4-bromo-2,6-dimethylphenyl, 3,5 dichloro2,6-diethylphenyl, and 2,6,bis(2,6-dimethylphenyl)phenyl, cycl
  • R 19 to R 28 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; when any two or more of R 1 to R 5 and R 19 to R 28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents.
  • the ring systems P and Q are preferably independently 2,6-hydrocarbylphenyl or fused-ring polyaromatic, for example, 1-naphthyl, 2-naphthyl, 1-phenanthrenyl and 8- quinolinyl. More preferably the ring systems P and Q are independently 2,4,6- hydrocarbylphenyl.
  • R 19 , R 20 , R 21 and R 22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. More preferably at least one of R 19 and R 20 , and at least one of R 21 and R 22 , is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. Most preferably R 19 , R 20 , R 21 and R 22 are all independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.
  • R , R , R and R are preferably independently selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert.- butyl, n-pentyl, neopentyl, n-hexyl, 4-methylpentyl, n-octyl, phenyl and benzyl.
  • R 1 , R 2 , R 3 , R 4 , R 6 and R 19 to R 28 are preferably independently selected from hydrogen and Ci to C 8 hydrocarbyl, for example, methyl, ethyl, n-propyl, n-butyl, t- butyl, n-hexyl, n-octyl, phenyl and benzyl.
  • R 6 is a group having the formula -NR 29 R 30 and R 7 is a group having the formula -NR R , wherein R to R are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; when any two or more of R to R , R and R to R are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents.
  • Suitable ligands B are the following: ⁇ - diketonate, ⁇ -diketiminate, dithioacetylacetonate, carboxylate, carbamate, thiocarboxylate, dithiocarboxylate, thiocarbamate, dithiocarbamate, xanthate, thioxanthate, phosphinate, thiophosphinate, dithiophosphinate, dialkyldithiophosphate, amidinate, bisimidazolate, phosphate, sulphurdiiminate, amidate, tropolonate, oxalate, oxalate ester, nitrate, nitrite, carbonate, squarate, croconate, sulphinate, sulphate, sulphite, fluorosulphate, hydroxamate, thiohydroxamate, and dithiohydroxamate.
  • Particularly suitable ligands B are ⁇ -diketonates or ⁇ -diketiminate, for example acetylacetonate or substituted acetylacetonates such as fluorinated derivatives.
  • the atom or group represented by X in the compounds of Formula (I) and (II) can be, for example, selected from selected from halide, 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.
  • Examples are for example, chloride, bromide; hydride; hydrocarbyloxide, for example, methoxide, ethoxide, isopropoxide, phenoxide; carboxylate, for example, formate, acetate, benzoate; hydrocarbyl, for example, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl; substituted hydrocarbyl; heterohydrocarbyl; tosylate; and triflate.
  • X is selected from halide, hydride and hydrocarbyl. Chloride is particularlyy preferred.
  • Illustrative but non-limiting examples of the ligand L are primary, secondary and tertiary amines, amides, phosphoramides, phosphines, phosphites, ethers, thioethers, nitriles, carbonyl compounds, for example, esters, ketones, aldehydes, carbon monoxide, carbon dioxide, sulphoxides, sulphones and boroxines.
  • Illustrative but non-limiting examples of the compatible, non-coordinating anion D are BF 4 " , SbF 6 " , PF 6 " and tetrakis(aryl)borates e.g.
  • M is Fe, Co or V, particularly Fe.
  • complexes of the present invention include 2,6-diacetylpyridinebis(2,6-diisopropylanil)Fe(acetylacetonate) + SbF ⁇ " 2,6-diacetylpyridinebis(2-tert.-butylanil)Fe(acetylacetonate) + SbF 6 " 2,6-diacetylpyridinebis(2,3-dimethylanil)Fe(acetylacetonate) + SbF ⁇ '
  • the present invention further provides a polymerisation catalyst comprising (1) a compound having the Formula (I) as hereinbefore defined, and (2) an activating quantity of at least one activator compound.
  • the activator compound for the catalyst of the present invention is suitably selected from organoaluminium compounds and hydrocarbylboron compounds.
  • Suitable organoaluminium compounds include compounds of the formula A1R 3 , where each R is independently C ⁇ -C ⁇ 2 alkyl or halo.
  • Examples include trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium (TLBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, and alumoxanes.
  • 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 trimethylaluminium. Such compounds can be linear, cyclic or mixtures thereof.
  • alumoxanes are generally believed to be mixtures of linear and cyclic compounds.
  • the cyclic alumoxanes can be represented by the formula [R 1 AlO] s and the linear alumoxanes by the formula R 17 (R 18 AlO) s wherein s is a number from about 2 to 50, and wherein R 16 , R 17 , and R 18 represent hydrocarbyl groups, preferably Ci to C ⁇ alkyl groups, for example methyl, ethyl or butyl groups.
  • Alkylalumoxanes such as methylalumoxane (MAO) and trialkylaluminiums such as trimethylaluminium (TMA), triethylaluminium (TEA), tri- isobutylaluminium (TLBA) are preferred.
  • MAO methylalumoxane
  • TMA trimethylaluminium
  • TEA triethylaluminium
  • TLBA tri- isobutylaluminium
  • alkylalumoxanes and trialkylaluminium compounds are particularly preferred, such as MAO with TMA or TIBA.
  • alkylalumoxane as used in this specification includes alkylalumoxanes available commercially which may contain a proportion, typically about 10wt%, but optionally up to 50wt%, of the corresponding trialkylaluminium; for instance, commercial MAO usually contains approximately 10wt% trimethylaluminium (TMA), whilst commercial MMAO contains both TMA and TLBA.
  • TMA trimethylaluminium
  • alkylalumoxane quoted herein include such trialkylaluminium impurities, and accordingly quantities of trialkylaluminium compounds quoted herein are considered to comprise compounds of the formula A1R 3 additional to any A1R 3 compound incorporated within the alkylalumoxane when present.
  • hydrocarbylboron compounds examples include boroxines, trimethylboron, triethylboron, dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate, sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl] borate, H + (OEt 2 )[(bis-3,5- trifluoromethyl)phenyl]borate, trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.
  • 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 the quantity employed is sufficient to provide 0.1 to 20,000 atoms, preferably 1 to 2000 atoms of aluminium or boron per atom of metal M in the compound of Formula (I).
  • polymerisation catalysts can be prepared from neutral complexes of selected 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis(imines) and an activator as disclosed in WO99/12981.
  • the best catalyst activities have been generated with MAO as activator, because MAO is able to abstract a ligand to generate a cation and also alkylate the metal centre.
  • MAO is expensive, and cheaper activators are desirable.
  • the catalysts of the present invention can also include one or more other types of catalyst, such as those of the type used in conventional Ziegler-Natta catalyst systems, metallocene-based catalysts, monocyclopentadienyl- or constrained geometry based catalysts, or heat activated supported chromium oxide catalysts (eg Phillips-type catalyst).
  • the catalysts of the present invention can be unsupported or supported on a support material, for example, silica, alumina, MgCl 2 or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, or p oly(amino styrene) .
  • a support material for example, silica, alumina, MgCl 2 or zirconia
  • a polymer or prepolymer for example polyethylene, polypropylene, polystyrene, or p oly(amino styrene) .
  • the catalysts can be formed in situ in the presence of the support material, or the support material can be pre-impregnated or premixed, simultaneously or sequentially, with one or more of the catalyst components.
  • the catalysts of the present invention can if desired be supported on a heterogeneous catalyst, for example, a magnesium halide supported Ziegler Natta catalyst, a Phillips type (chromium oxide) supported catalyst or a supported metallocene catalyst.
  • Formation of the supported catalyst can be achieved for example by treating the transition metal compounds of the present invention with alumoxane or trialkylaluminium in a suitable inert diluent, for example a volatile hydrocarbon, slurrying a particulate support material with the product and evaporating the volatile diluent.
  • a suitable inert diluent for example a volatile hydrocarbon
  • the produced supported catalyst is preferably in the form of a free-flowing powder.
  • the quantity of support material employed can vary widely, for example from 100,000 to 1 grams per gram of metal present in the transition metal compound.
  • a supported catalyst is to slurry the transition metal compounds of the present invention in a suitable inert diluent, for example a volatile hydrocarbon, with a particulate support material and evaporating or filtering the volatile diluent.
  • a suitable inert diluent for example a volatile hydrocarbon
  • the produced supported catalyst is preferably in the form of a free-flowing powder.
  • the quantity of support material employed can vary widely, for example from 100,000 to 1 grams per gram of metal present in the transition metal compound.
  • This type of supported catalyst can be activated by trialkylaluminium activators in the polymerisation reactor or vessel. This type of process enables more controlled exotherms on catalyst injections into polymerisation reactors, and avoids agglomerate formation and sheeting in gas phase and slurry phase reactors.
  • 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 polymerisation catalyst of the present invention.
  • a preferred process comprises the steps of : a) preparing a prepolymer-based catalyst by contacting one or more 1 -olefins with a catalyst, and b) contacting the prepolymer-based catalyst with one or more 1 -olefins, wherein the catalyst is as defined above.
  • the polymerisation conditions can be, for example, solution phase, slurry phase, gas phase or bulk phase, with polymerisation temperatures ranging from -100°C to +300°C, and at pressures of atmospheric and above, particularly from 140 to 4100 kPa.
  • 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 or stirred bed conditions.
  • Suitable monomers for use in the polymerisation process of the present invention are, for example, ethylene and C 2- o ⁇ -olefins, specifically propylene, 1-butene, 1- pentene, 1-hexene, 4-methylpentene-l, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- undecene, 1-dodeene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1- heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.
  • Other monomers include methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene.
  • Preferred monomers for homopolymerisation processes are ethylene and propylene.
  • the catalysts and process of the invention can also be used for copolymerising ethylene or propylene with each other or with other 1 -olefins such as 1-butene, 1-hexene, 4-methylpentene-l, and octene, or with other monomeric materials, for example, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene.
  • polymerization or copolymerization is typically carried out under conditions that substantially exclude oxygen, water, and other materials that act as catalyst poisons.
  • polymerization or copolymerization can be carried out in the presence of additives to control polymer or copolymer molecular weights.
  • 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, bulk 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.
  • the polymerisation process of the present invention provides polymers and copolymers, especially ethylene polymers, at remarkably high productivity (based on the amount of polymer or copolymer produced per unit weight of complex employed in the catalyst system). This means that relatively very small quantities of transition metal complex are consumed in commercial processes using the process of the present invention. It also means that when the polymerisation process of the present invention is operated under polymer recovery conditions that do not employ a catalyst separation step, thus leaving the catalyst, or residues thereof, in the polymer (e.g. as occurs in most commercial slurry and gas phase polymerisation processes), the amount of transition metal complex in the produced polymer can be very small.
  • Slurry phase polymerisation conditions or gas phase polymerisation conditions are particularly useful for the production of high or low density grades of polyethylene, and polypropylene.
  • the polymerisation conditions can be batch, continuous or semi-continuous.
  • one or more reactors may be used, e.g. from two to five reactors in series. Different reaction conditions, such as different temperatures or hydrogen concentrations may be employed in the different reactors.
  • the catalyst is generally metered and transferred into the polymerisation zone in the form of a particulate solid either as a dry powder (e.g. with an inert gas) or as a slurry.
  • This solid can be, for example, a solid catalyst system formed from the one or more of complexes of the invention and an activator with or without other types of catalysts, or can be the solid catalyst alone with or without other types of catalysts.
  • the activator can be fed to the polymerisation zone, for example as a solution, separately from or together with the solid catalyst.
  • 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 one or more support materials. Most preferably the catalyst system is supported on the 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.
  • any associated and absorbed hydrocarbons are substantially removed, or degassed, from the polymer by, for example, pressure let-down or gas purging using fresh or recycled steam, nitrogen or light hydrocarbons (such as ethylene). Recovered gaseous or liquid hydrocarbons may be recycled to the polymerisation zone.
  • 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.
  • the polymerisation diluent is compatible with the polymer(s) and catalyst(s), and may be an alkane such as hexane, heptane, isobutane, or a mixture of hydrocarbons or paraffins.
  • the particles are 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.
  • 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.
  • liquid monomer such as propylene is used as the polymerisation medium.
  • Such methods generally involve agitating (e.g. by stirring, vibrating or fluidising) a bed of catalyst, or a bed of the target polymer (i.e. 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 (e.g. recycled gaseous monomer) and/or volatile liquid (e.g.
  • 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 in the polymerisation zone is small in relation to the quantity of polymer present. 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.
  • 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 (e.g. nitrogen or inert hydrocarbons such as methane, ethane, propane, butane, pentane or hexane) 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 (i.e. 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 then returned to 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 catalyst can be contacted with water, alcohols, acetone, or other suitable catalyst deactivators a manner known to persons of skill in the art.
  • Homopolymerisation of ethylene with the catalysts of the invention may produce 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
  • Particularly important copolymers made by copolymerising ethylene with higher 1 -olefins with the catalysts of the invention are the copolymers having a density in the range of 0.91 to 0.93.
  • copolymers which are generally referred to in the art as 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.
  • Propylene polymers produced by the process of the invention include propylene homopolymer and copolymers of propylene with less than 50 mole % ethylene or other alpha-olefin such as butene-1, pentene-1, 4-methylpentene-l, or hexene-1, or mixtures thereof. Propylene polymers also may include copolymers of propylene with minor amounts of a copolymerizable monomer. Typically, most useful are normally-solid polymers of propylene containing polypropylene crystallinity, random copolymers of propylene with up to about 10 wt.% ethylene, and impact copolymers containing up to about 20 wt.% ethylene or other alpha-olefin. Polypropylene homopolymers may contain a small amount (typically below 2 wt.%) of other monomers to the extent the properties of the homopolymer are not affected significantly.
  • Propylene polymers may be produced which are normally solid, predominantly isotactic, poly ⁇ -olefins. Levels of stereorandom by-products are sufficiently low so that useful products can be obtained without separation thereof.
  • useful propylene homopolymers show polypropylene crystallinity and have isotactic indices above 90 and many times above 95. Copolymers typically will have lower isotactic indices, typically above 80-85.
  • propylene polymers with melt flow rates from below 1 to above 1000 may be produced in a reactor.
  • polypropylenes with a MFR from 2 to 100 are typical. Some uses such as for spunbonding may use a polymer with an MFR of 500 to 2000.
  • Peroxide compounds may be added to ethylene or propylene polymers.
  • peroxides can be used to give cross-linking in the polymer.
  • peroxide compounds may be added during extrusion for controlled rheology to increase the melt flow rate of polymer.
  • Peroxide acts to break long polymer chains and has the effect of both increasing MFR and narrowing the molecular weight distribution (Mw/Mn) or polydispersity.
  • a typical reactor polypropylene powder with an MFR of 2g/10 min. by controlled rheology treatment with peroxide in an extruder may form a polymer with an MFR of 20-40.
  • the final polymer MFR may be controlled as known in the art.
  • additives are typically incorporated into the polymer formulation such as acid scavengers, antioxidants, stabilizers, and the like. Generally, these additives are incorporated at levels of about 25 to 2000 ppm, typically from about 50 to about 1000 ppm, and more typically 400 to 1000 ppm, based on the polymer.
  • polymers or copolymers made according to the invention in the form of a powder are conventionally compounded into pellets.
  • uses for polymer compositions made according to the invention include use to form fibres, extruded films, tapes, spunbonded webs, moulded or thermoformed products, and the like.
  • the polymers may be blown into films, or may be used for making a variety of moulded or extruded articles such as pipes, and containers such as bottles or drums.
  • Specific additive packages for each application may be selected as known in the art.
  • supplemental additives include slip agents, anti-blocks, anti-stats, mould release agents, primary and secondary anti-oxidants, clarifiers, nucleants, uv stabilizers, and the like.
  • Classes of additives are well known in the art and include phosphite antioxidants, hydroxylamine (such as N,N-dialkyl hydroxylamine) and amine oxide (such as dialkyl methyl amine oxide) antioxidants, hindered amine light (uv) stabilizers, phenolic stabilizers, benzofuranone stabilizers, and the like.
  • Various olefin polymer additives are described in U.S. patents 4,318,845, 4,325,863, 4,590,231, 4,668,721, 4,876,300, 5,175,312, 5,276,076, 5,326,802, 5,344,860, 5,596,033, and 5,625,090.
  • the parent tridentate 2,6 bis(imino)pyridine dichloro complexes 1 - 3 were prepared according to the literature. AgSbF ⁇ and Ag acac were purchased from Aldrich. Acetonitrile (MeCN), pentane and dichloromethane (DCM) were distilled over CaH ; diethylether (Et 2 O) was distilled over sodium prior to use.
  • the cationic Fe and Co complexes 4 - 11 were prepared as shown in schemes 1 and 2.

Landscapes

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

Abstract

L'invention concerne un complexe destiné à la polymérisation de 1-oléfines, et représenté par la formule (I), dans laquelle M est Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II[, Ru[III], Ru[IV], V[II], V[III], V[IV], V[V], Ti[II], Ti[III] ou Ti[IV]; et R1 à R7 sont chacun sélectionnés indépendamment parmi hydrogène, halogène, hydrocarbyle, hydrocarbyle substitué, hétérohydrocarbyle, hétérohydrocarbyle substitué ou SiR'¿3?, chaque R' étant sélectionné indépendamment parmi hydrogène, hydrogène, halogène, hydrocarbyle, hydrocarbyle substitué, hétérohydrocarbyle, hétérohydrocarbyle substitué; B est un ligand chélateur comprenant au moins un atome de O, S, N et P lié directement à M; X est un ligand mono-anionique monodenté; L est un ligand lié de manière bipolaire à M; n est plus grand ou égal à 1, m est plus grand ou égal à 0 et q est plus grand ou égal à 0, à condition que n et m soient des entiers satisfaisant la valence du métal; et D est un anion non coordonnant compatible.
PCT/GB2000/001385 1999-05-15 2000-04-12 Catalyseurs de polymerisation Ceased WO2000069869A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39811/00A AU3981100A (en) 1999-05-15 2000-04-12 Polymerisation catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9911245.0 1999-05-15
GBGB9911245.0A GB9911245D0 (en) 1999-05-15 1999-05-15 Polymerisation catalysts

Publications (1)

Publication Number Publication Date
WO2000069869A1 true WO2000069869A1 (fr) 2000-11-23

Family

ID=10853477

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2000/001385 Ceased WO2000069869A1 (fr) 1999-05-15 2000-04-12 Catalyseurs de polymerisation

Country Status (3)

Country Link
AU (1) AU3981100A (fr)
GB (1) GB9911245D0 (fr)
WO (1) WO2000069869A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1260515A1 (fr) * 2001-05-23 2002-11-27 SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) Complexes catalytiques et leur utilisation pour la polymérisation des alpha-oléfines
WO2003042131A1 (fr) * 2001-11-15 2003-05-22 Stichting Voor De Technische Wetenschappen Catalyseur d'hydrogenation et processus d'hydrogenation catalysee
RU2248374C1 (ru) * 2004-01-29 2005-03-20 Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук Двухкомпонентный нанесенный катализатор полимеризации этилена, способ его приготовления (варианты) и способ получения полиэтилена с использованием этого катализатора
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
US7294681B2 (en) 2002-10-15 2007-11-13 Exxonmobil Chemical Patents Inc. Mutliple catalyst system for olefin polymerization and polymers produced therefrom
US7442819B2 (en) 2004-07-09 2008-10-28 E. I. Du Pont De Nemours And Company Catalysts for olefin polymerization or oligomerization
US7541402B2 (en) 2002-10-15 2009-06-02 Exxonmobil Chemical Patents Inc. Blend functionalized polyolefin adhesive
US7550528B2 (en) 2002-10-15 2009-06-23 Exxonmobil Chemical Patents Inc. Functionalized olefin polymers
CN102464677A (zh) * 2010-11-17 2012-05-23 中国科学院化学研究所 一类不对称吡啶二亚胺铁或钴配合物催化剂及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998027124A1 (fr) * 1996-12-17 1998-06-25 E.I. Du Pont De Nemours And Company Polymerisation de l'ethylene a l'aide de complexes specifiques contenant du fer ou du cobalt, nouvelles pyridihebis(imines) et nouveaux complexes de pyridinebis(imines) avec du fer et du cobalt
WO1998049208A1 (fr) * 1997-04-25 1998-11-05 Bp Chemicals Limited Nouveaux composes et leur utilisation dans un procede de polymerisation
WO1999002472A1 (fr) * 1997-07-11 1999-01-21 E.I. Du Pont De Nemours And Company Production d'alpha-olefines
WO1999012981A1 (fr) * 1997-09-05 1999-03-18 Bp Chemicals Limited Catalyseurs de polymerisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998027124A1 (fr) * 1996-12-17 1998-06-25 E.I. Du Pont De Nemours And Company Polymerisation de l'ethylene a l'aide de complexes specifiques contenant du fer ou du cobalt, nouvelles pyridihebis(imines) et nouveaux complexes de pyridinebis(imines) avec du fer et du cobalt
WO1998049208A1 (fr) * 1997-04-25 1998-11-05 Bp Chemicals Limited Nouveaux composes et leur utilisation dans un procede de polymerisation
WO1999002472A1 (fr) * 1997-07-11 1999-01-21 E.I. Du Pont De Nemours And Company Production d'alpha-olefines
WO1999012981A1 (fr) * 1997-09-05 1999-03-18 Bp Chemicals Limited Catalyseurs de polymerisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BENVENUTI F ET AL: "NOVEL POLYMER-SUPPORTED BETA-DIKETONATE NICKEL CATALYSTS FOR ALPHA-OLEFIN ACTIVATION", POLYMERS FOR ADVANCED TECHNOLOGIES,GB,JOHN WILEY AND SONS, CHICHESTER, vol. 9, no. 2, 1 February 1998 (1998-02-01), pages 113 - 120, XP000733424, ISSN: 1042-7147 *
BROOKER, SALLY ET AL: "Six and seven coordinate manganese(II) complexes of Schiff base ligands derived from the condensation of 2,6-diacetylpyridine with ethanolamine (L1) or propanolamine (L2): x-ray crystal structures of [MnL1Cl2].H2O an [{MnL2(NCS)2}x]", J. CHEM. SOC., DALTON TRANS. (1990), (8), 2397-401, XP000929321 *
YATSIMIRSKY, ANATOLY K. ET AL: "Kinetics and mechanism of ester hydrolysis by metal complexes of 2,6-diacetylpyridine dioxime", INORG. CHIM. ACTA (1998), 273(1,2), 167-174, XP000925567 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1260515A1 (fr) * 2001-05-23 2002-11-27 SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) Complexes catalytiques et leur utilisation pour la polymérisation des alpha-oléfines
BE1014196A3 (fr) * 2001-05-23 2003-06-03 Solvay Complexes catalytiques et leur utilisation pour la polymerisation des alpha-olefines.
US6670434B2 (en) 2001-05-23 2003-12-30 Solvay Polyolefins Europe-Belgium (Societe Anonyme) Catalytic complexes and their use for polymerizing alpha-olefins
WO2003042131A1 (fr) * 2001-11-15 2003-05-22 Stichting Voor De Technische Wetenschappen Catalyseur d'hydrogenation et processus d'hydrogenation catalysee
US7294681B2 (en) 2002-10-15 2007-11-13 Exxonmobil Chemical Patents Inc. Mutliple catalyst system for olefin polymerization and polymers produced therefrom
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
US7524910B2 (en) 2002-10-15 2009-04-28 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US7541402B2 (en) 2002-10-15 2009-06-02 Exxonmobil Chemical Patents Inc. Blend functionalized polyolefin adhesive
US7550528B2 (en) 2002-10-15 2009-06-23 Exxonmobil Chemical Patents Inc. Functionalized olefin polymers
US8957159B2 (en) 2002-10-15 2015-02-17 Exxonmobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
RU2248374C1 (ru) * 2004-01-29 2005-03-20 Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук Двухкомпонентный нанесенный катализатор полимеризации этилена, способ его приготовления (варианты) и способ получения полиэтилена с использованием этого катализатора
US7442819B2 (en) 2004-07-09 2008-10-28 E. I. Du Pont De Nemours And Company Catalysts for olefin polymerization or oligomerization
US7683149B2 (en) 2004-07-09 2010-03-23 E. I. Du Pont De Nemours And Company Catalysts for olefin polymerization or oligomerization
CN102464677A (zh) * 2010-11-17 2012-05-23 中国科学院化学研究所 一类不对称吡啶二亚胺铁或钴配合物催化剂及其制备方法与应用
CN102464677B (zh) * 2010-11-17 2014-08-13 中国科学院化学研究所 一类不对称吡啶二亚胺铁或钴配合物催化剂及其制备方法与应用

Also Published As

Publication number Publication date
GB9911245D0 (en) 1999-07-14
AU3981100A (en) 2000-12-05

Similar Documents

Publication Publication Date Title
EP1123303B1 (fr) Catalyseur de polymerisation
EP1117670B1 (fr) Catalyseurs de polymerisation
US6465386B1 (en) Polymerization catalyst
WO2000058320A1 (fr) Catalyseurs de polymérisation à pyridine.imine
EP1131361B8 (fr) Catalyseurs de polymerisation
US20030104929A1 (en) Polymerisation catalyst
US6762258B2 (en) Metal complexes as catalyst component for olefin polymerization
EP1099714A1 (fr) Catalyseur de polymérisation
US7163990B2 (en) Polymerization catalyst
WO2001074830A1 (fr) Catalyseur de polymerisation
WO2002090365A1 (fr) Nouveaux catalyseurs de polymerisation
WO2000069869A1 (fr) Catalyseurs de polymerisation
EP1125952A1 (fr) Méthode de préparation de catalyseur
WO2001012684A1 (fr) Procede de polymerisation
US6492293B1 (en) Polymerisation catalyst
US6828398B2 (en) Polymerization catalyst
US20040087436A1 (en) Novel polymerisation catalysts
WO2000047586A1 (fr) Complexes metalliques utiles en tant que catalyseur de polymerisation

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 09695916

Country of ref document: US

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP