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WO2002090365A1 - Nouveaux catalyseurs de polymerisation - Google Patents

Nouveaux catalyseurs de polymerisation Download PDF

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Publication number
WO2002090365A1
WO2002090365A1 PCT/GB2002/002144 GB0202144W WO02090365A1 WO 2002090365 A1 WO2002090365 A1 WO 2002090365A1 GB 0202144 W GB0202144 W GB 0202144W WO 02090365 A1 WO02090365 A1 WO 02090365A1
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Prior art keywords
complex
hydrocarbyl
substituted
heterohydrocarbyl
hydrogen
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PCT/GB2002/002144
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English (en)
Inventor
Vernon Charles Gibson
Peter Kok Yong Goh
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Bp Chemicals Limited
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Publication of WO2002090365A1 publication Critical patent/WO2002090365A1/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
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages

Definitions

  • the present invention relates to novel polymerisation catalysts based on organic transition metal complexes and to a polymerisation process using the catalysts.
  • 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 polyolef ⁇ ns. 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 olefm 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 polyolefm 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 polyolefm 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).
  • 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 (e.g. 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 e.g. 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.
  • WO 98/42664 discloses as polymerisation catalysts compounds having the general Formula (0) shown below in which M is a transition metal and R 1 may be anthracenyl.
  • EP 0874005A and WO 98/30609 also disclose compounds with similar generic formulas as Formula (0).
  • Our own WO 99/19335 discloses such compounds where M is Cr, R 1 is t-Bu.
  • An object of the present invention is to provide a novel complex and catalyst prepared therefrom suitable for polymerising olef ⁇ ns, 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 olef ⁇ ns, 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 complex having the formula (I)
  • M is a transition metal, lanthanide or actinide and T is its oxidation state
  • X represents an atom or group covalently or ionically bonded to M
  • b is the valency of the atom or group X
  • L is a group datively bound to M, and n is from 0 to 4
  • Z is oxygen, sulphur or a group represented by NR 10 or PR 10
  • D is a group datively bound to M, comprising a neutral donor selected from NR n R 12 , PR n R 12 , OR 11 or SR ⁇
  • R 5 to R 12 are all 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, and any two or more of each R 5 to R
  • the complex of the invention has the formula (II)
  • R 5 to R 7 , M, T, L, n, b, X, Z and D are as defined above, and R 1 to R 4 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, and any two or more of R to R and R 10 to R 12 may be linked to form cyclic substituents.
  • R 1 is a cyclic hydrocarbyl group, more preferably R 1 is a polycyclic hydrocarbyl, and most preferably R 1 is anthracenyl, naphthyl, triptycenyl or phenanthrenyl, all of which may optionally be substituted, preferably with - alkyl groups.
  • the polycyclic hydrocarbyl group may be unsubstituted or substituted with one or more Cj-C 6 alkyl groups and is preferably selected from anthracenyl, naphthyl, triptycenyl and phenanthrenyl.
  • a particularly preferred group R 1 has the following Structure A:
  • R 13 to R 16 are each independently hydrogen or methyl. Most preferably R 13 to R 16 are all hydrogen or R to R are all methyl.
  • M is Ti[II], Ti[IH], Ti[TV], Fe[H], Fe[III], Co[II], Co[ ⁇ i], Ni[II], Cr[II], Cr[III], Mn[II], Mn[ ⁇ i], Mn[IV], Ta[II], Ta[III], Ta[IV], Rh[II], Rh[Hl], Y[II], ⁇ [i ⁇ i], scfii], sc[i ⁇ ], Ru[iij, RU[I ⁇ J, RU[ ⁇ V], Pdprj, zr[ ⁇ ], zrp ⁇ j, Zr[rv], Hftrrj,
  • M is Ti[II], Ti[III], Ti[IV], Ta[II], Ta[HI], Ta[IV], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[ ⁇ i], Hf[IV], V[H], V[III], V[IV], Nb[II], Nb[III], Nb[IV] or Nb[V].
  • M is Ti[III] or Ti[IV].
  • Z is oxygen
  • D is PR ⁇ R 12 then preferably R ⁇ and R 12 are both phenyl.
  • D is NR n R 12 where R ⁇ and R 12 are as defined above. More preferably R 11 and R 12 are each independently a hydrogen or hydrocarbyl group.
  • the atom or group represented by X in the complexes of Formula (I) or (II) can be, for example, selected from halide, sulphate, nitrate, thiolate, thiocarboxylate, BF “ , PF 6 " , hydride, hydrocarbyloxide, carboxylate, hydrocarbyl, substituted hydrocarbyl and heterohydrocarbyl, ⁇ -diketonates, or mixtures thereof.
  • the atoms or groups X are halide, 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; or triflate. More preferably X is selected from halide, hydride, hydrocarbyloxide and hydrocarbyl. Chloride, isopropoxide or mixtures thereof are particularly preferred.
  • the group L may be an ether, such as tetrahydrofuran or diethylether; an alcohol such as ethanol or butanol; a primary, secondary or tertiary amine; or a phosphine.
  • an ether such as tetrahydrofuran or diethylether
  • an alcohol such as ethanol or butanol
  • a primary, secondary or tertiary amine such as a phosphine.
  • R to R are all independently selected from hydrogen or hydrocarbyl.
  • the most preferable complex is of the Formula (II), above, where M is Ti(IV), Z is oxygen, R 1 is Structure A, all of R 2 to R 7 are hydrogen, R 13 to R 16 are all methyl and D is NMe 2 , the three X groups consist of 2 CI groups and one O'Pr group, and L is tetrahydrofuran.
  • at least two of R 2 to R 7 are linked to form a cyclic substituent.
  • R 6 and R 7 are linked to form a cyclic substituent, forming a complex of the Formula (III), below:
  • R 1 to R 5 , M, T, L, n, b, X, Z and D are as defined above, and R 17 to R 20 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, and any two or more of the R groups may be linked to form cyclic substituents.
  • R to R and/or R to R are each independently selected from hydrogen or hydrocarbyl.
  • M is Ti( ⁇ V)
  • Z is oxygen
  • R 1 is Structure A
  • R 9 ⁇ to R are all hydrogen and D is NHPh, the three X groups consist of 2 CI groups and one O'Pr group, and L is tetrahydrofuran.
  • a second aspect of the invention provides a polymerisation catalyst comprising a) a complex as defined above, and, optionally, b) an effective amount of at least one activator compound.
  • the activator compound for the catalyst of the present invention when required, 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 (TIBA), tri-n-octylaluminium, methylamminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylamminium 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 21 AlO] s and the linear alumoxanes by the formula R 22 (R 23 AlO) s wherein s is a number from about 2 to 50, and wherein R , R , and R represent hydrocarbyl groups, preferably C ⁇ to C 6 alkyl groups, for example methyl, ethyl or butyl groups.
  • Alkylalumoxanes such as methylalumoxane (MAO) are preferred.
  • 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 TIBA.
  • 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 in the transition metal compound.
  • An alternative class of activators comprise salts of a cationic oxidising agent and a non-coordinating compatible anion.
  • cationic oxidising agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb 2+ .
  • non- coordinating compatible anions are BF 4 " , SbCl 6 " , PF 6 " , tetrakis(phenyl)borate and tetrakis(pentafluorophenyl)borate.
  • the polymerisation catalyst of the present invention may also comprise (3) a neutral Lewis base.
  • Neutral Lewis bases are well known in the art of Ziegler-Natta catalyst polymerisation technology.
  • classes of neutral Lewis bases suitably employed in the present invention are unsaturated hydrocarbons, for example, alkenes (other than 1-olefins) or alkynes, primary, secondary and tertiary amines, amides, phosphoramides, phosphines, phosphites, ethers, thioethers, nitriles, carbonyl compounds, for example, esters, ketones, aldehydes, carbon monoxide and carbon dioxide, sulphoxides, sulphones and boroxines.
  • 1-olefins are capable of acting as neutral Lewis bases, for the purposes of the present invention they are regarded as monomer or comonomer 1-olefins and not as neutral Lewis bases er se.
  • alkenes which are internal olefins, for example, 2-butene and cyclohexene are regarded as neutral Lewis bases in the present invention.
  • Preferred Lewis bases are tertiary amines and aromatic esters, for example, dimethylaniline, diethylaniline, tributylamine, ethylbenzoate and benzylbenzoate.
  • components (1), (2) and (3) of the catalyst system can be brought together simultaneously or in any desired order.
  • components (2) and (3) are compounds which interact together strongly, for example, form a stable compound together, it is preferred to bring together either components (1) and (2) or components (1) and (3) in an initial step before introducing the final defined component.
  • components (1) and (3) are contacted together before component (2) is introduced.
  • the quantities of components (1) and (2) employed in the preparation of this catalyst system are suitably as described above in relation to the catalysts of the present invention.
  • the quantity of the neutral Lewis Base [component (3)] is preferably such as to provide a ratio of component (l)xomponent (3) in the range 100:1 to 1:1000, most preferably in the range 1 : 1 to 1 :20.
  • Components (1), (2) and (3) of the catalyst system can be brought together, for example, as the neat materials, as a suspension or solution of the materials in a suitable diluent or solvent (for example a liquid hydrocarbon), or, if at least one of the components is volatile, by utilising the vapour of that component.
  • the components can be brought together at any desired temperature. Mixing the components together at room temperature is generally satisfactory. Heating to higher temperatures e.g. up to 120°C can be carried out if desired, e.g. to achieve better mixing of the components. It is preferred to carry out the bringing together of components (1), (2) and (3) in an inert atmosphere (e.g. dry nitrogen) or in vacuo.
  • an inert atmosphere e.g. dry nitrogen
  • the catalyst on a support material can be achieved, for example, by preforming the catalyst system comprising components (1), (2) and (3) and impregnating the support material preferably with a solution thereof, or by introducing to the support material one or more of the components simultaneously or sequentially.
  • the support material itself can have the properties of a neutral Lewis base and can be employed as, or in place of, component (3).
  • An example of a support material having neutral Lewis base properties is poly(aminostyrene) or a copolymer of styrene and aminostyrene (i.e. vinylaniline).
  • the catalysts of the present invention can if desired comprise more than one of the defined complexes.
  • the catalysts of the present invention can also include one or more other types of transition metal compounds or catalysts, for example, nitrogen containing catalysts such as those described in WO 99/12981.
  • nitrogen containing catalysts such as those described in WO 99/12981.
  • examples of such other catalysts include 2,6-diacetylpyridinebis(2,4,6-trimethyl anil)FeCl 2 .
  • 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 (e.g. 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 poly(aminostyrene).
  • a support material for example, silica, alumina, MgCl 2 or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, or poly(aminostyrene).
  • 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 complexes of the present invention with alumoxane in a suitable inert diluent, for example a volatile hydrocarbon, slurrying a particulate support material with the product and evaporating the volatile diluent.
  • 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 complex.
  • the precursor components of the catalyst may be added directly to the polymerisation reactor together with the 1-olefin to be polymerised.
  • 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 system, and b) contacting the prepolymer-based catalyst with one or more 1-olefins, wherein the catalyst system is as defined above.
  • the term "catalyst” is intended to include "prepolymer- based catalyst” 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 fmidised bed or stirred bed conditions.
  • Suitable monomers for use in the polymerisation process of the present invention are, for example, ethylene and C 3-20 ⁇ -olefins, specifically propylene, 1-butene, 1- pentene, 1-hexene, 4-methylpentene-l, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1- heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.
  • Other monomers include methyl mefhacrylate, 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.
  • 1-olefins such as 1-butene, 1- hexene, 4-methylpentene-l, and octene
  • monomeric materials for example, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene.
  • 1-olefins with dienes particularly non- conjugated dienes, such as 1,4 pentadiene, 1,5-hexadiene, cyclopentadiene and ethylene norbornadiene is also possible, particular, ethylene/ 1-olefin/diene terpolymers may be made by the process of the invention where the diene is as above and the other 1- olefin is preferably propylene.
  • polymerisation or copolymerisation is typically carried out under conditions that substantially exclude oxygen, water, and other materials that act as catalyst poisons. Also, polymerisation or copolymerisation 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 maybe 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 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.
  • solution phase processes wherem the polymer is formed dissolved in a solvent
  • 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 gas phase fluidised bed polymerisation process of the present invention it is desirable to provide additional cooling of the bed (and thereby improve the space time yield of the process) by feeding a volatile liquid to the bed under conditions such that the liquid evaporates in the bed thereby absorbing additional heat of polymerisation from the bed by the "latent heat of evaporation" effect.
  • 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 method of condensing liquid in the recycle gas stream and returning the mixture of gas and entrained liquid to the bed is described in EP-A-0089691 and EP-A- 0241947. It is preferred to reintroduce the condensed liquid into the bed separate from the recycle gas using the process described in our US Patent 5541270, the teaching of which is hereby incorporated into this specification.
  • 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.
  • Copolymerisation of ethylene with higher 1-olefins can 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 with the catalysts of the invention are the copolymers having a density in the range of 0.91 to 0.93.
  • These 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-olefm 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-olefm. 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.
  • minor amounts of 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.
  • 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 50°C. Isobutane (0.5 litre) and triisobutylaluminium were then added and the reactor was boxed in nitrogen. The alkyl aluminium was allowed to scavenge for poisons in the reactor for at least 1 hour. The reactor was allowed to equilibriate at the desired temperature and ethylene was introduced into the reactor until a predetermined over-pressure was achieved, then the catalyst solution (7.8 mmol of II, 600 equivalents MAO in toluene) was injected under nitrogen. The reactor pressure was maintained constant throughout the polymerisation run by computer controlled addition of additional ethylene. The polymerisation time was 1 hour. Upon termination of the run the reactor contents were isolated, washed with acidified methanol (50ml)
  • Absolute ethanol (15 mL) was added to a mixture of 3-anthracenyl-2- hydroxybenzaldehyde (1.00 g, 3.35 mmol) andN-mesityl-l,2-phenylenediamine (0.76 g, 3.35 mmol). After the addition of a few drops of formic acid, the solution was refluxed for 18 hours. Upon cooling to room temperature, the suspension was filtered and the yellow solid was washed with cold pentane and dried under vacuum overnight (1.10 g, 65 %).
  • Absolute ethanol (20 mL) was added to a mixture of 3-anthracenyl-2- hydroxybenzaldehyde (1.09 g, 3.64 mmol) and NN-dimethylethylenediamine (0.4 mL, 3.64 mmol). After the addition of a few drops of formic acid, the solution was refluxed for 18 hours. Upon cooling to room temperature, the product was crystallized from ethanol. After filtration the yellow solid was washed with cold pentane and dried under vacuum overnight (0.66 g, 49 %).

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  • 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 représenté par la formule (I), dans laquelle M est un métal de transition, un lanthanide ou un actinide et T représente son état d'oxydation ; X représente un atome ou un groupe lié ioniquement ou par covalence à M ; b représente la valence de l'atome ou du groupe X ; L représente un groupe lié par liaison bipolaire à M, et n est compris entre 0 et 4 ; Z représente oxygène, soufre ou un groupe représenté par NR?10 ou PR10¿; D représente un groupe lié par liaison bipolaire à M, comprenant un donneur neutre choisi entre NR?11R12, PR11 R12, OR11 ou SR11; et R5 à R12¿ représentent hydrogène, halogène, hydrocarbyle, hydrocarbyle substitué, hétérohydrocarbyle, hétérohydrocarbyle substitué ou SiR'¿3? où R' représente hydrogène, halogène, hydrocarbyle, hydrocarbyle substitué, hétérohydrocarbyle, hétérohydrocarbyle substitué et au moins deux éléments dans le groupe allant de R?5 à R12¿ peuvent être liés pour former des substituants cycliques. De préférence, R8 et R9 sont liés pour former un noyau de carbone à six éléments qui est substitué par un groupe hydrocarbyle cyclique, de préférence anthracényle, naphtyle, triptycényle ou phénanthrényle. Ces complexes conviennent comme catalyseurs de (co)polymérisation d'oléfines.
PCT/GB2002/002144 2001-05-10 2002-05-09 Nouveaux catalyseurs de polymerisation WO2002090365A1 (fr)

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Cited By (13)

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WO2003010207A1 (fr) 2001-07-23 2003-02-06 Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences Catalyseurs de polymerisation ou de copolymerisation d'olefines, leur procede de preparation et leur utilisation
WO2004081020A1 (fr) * 2003-03-14 2004-09-23 Ic Innovations Ltd Complexes de metaux de transition, en particulier complexes de fer, utilises en tant que constituants catalytiques de polymerisation d'olefines
WO2005070976A1 (fr) * 2004-01-22 2005-08-04 Innovene Europe Limited Procede de polymerisation
US7129304B1 (en) 2005-07-21 2006-10-31 Chevron Phillips Chemical Company Lp Dimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7268096B2 (en) 2005-07-21 2007-09-11 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7271121B2 (en) 2005-07-21 2007-09-18 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7727926B2 (en) 2005-07-21 2010-06-01 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and method of using in oligomerization and polymerization
US8288435B2 (en) 2006-12-28 2012-10-16 Actelion Pharmaceuticals Ltd. 2-aza-bicyclo[3.1.0]hexane derivatives as orexin receptor antagonists
WO2014135824A1 (fr) * 2013-03-08 2014-09-12 University Of Hull Complexes de niobium et de tantale en tant que catalyseurs pour la polymérisation d'oléfines
US9586872B2 (en) 2011-12-30 2017-03-07 Chevron Phillips Chemical Company Lp Olefin oligomerization methods
US9944661B2 (en) 2016-08-09 2018-04-17 Chevron Phillips Chemical Company Lp Olefin hydroboration
CN114853930A (zh) * 2022-06-13 2022-08-05 青岛科技大学 一种nno-配位钛锆铪金属催化剂的合成及其制备聚烯烃弹性体的应用
CN116162185A (zh) * 2023-01-04 2023-05-26 万华化学集团股份有限公司 一种茂金属催化剂和制备方法及其在烯烃聚合中的应用

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1426385A4 (fr) * 2001-07-23 2008-03-26 Shanghai Inst Organic Chem Catalyseurs de polymerisation ou de copolymerisation d'olefines, leur procede de preparation et leur utilisation
WO2003010207A1 (fr) 2001-07-23 2003-02-06 Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences Catalyseurs de polymerisation ou de copolymerisation d'olefines, leur procede de preparation et leur utilisation
WO2004081020A1 (fr) * 2003-03-14 2004-09-23 Ic Innovations Ltd Complexes de metaux de transition, en particulier complexes de fer, utilises en tant que constituants catalytiques de polymerisation d'olefines
WO2005070976A1 (fr) * 2004-01-22 2005-08-04 Innovene Europe Limited Procede de polymerisation
US7728161B2 (en) 2005-07-21 2010-06-01 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7271121B2 (en) 2005-07-21 2007-09-18 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7268096B2 (en) 2005-07-21 2007-09-11 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7727926B2 (en) 2005-07-21 2010-06-01 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and method of using in oligomerization and polymerization
US7129304B1 (en) 2005-07-21 2006-10-31 Chevron Phillips Chemical Company Lp Dimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7728160B2 (en) 2005-07-21 2010-06-01 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7977269B2 (en) 2005-07-21 2011-07-12 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US8288435B2 (en) 2006-12-28 2012-10-16 Actelion Pharmaceuticals Ltd. 2-aza-bicyclo[3.1.0]hexane derivatives as orexin receptor antagonists
US9586872B2 (en) 2011-12-30 2017-03-07 Chevron Phillips Chemical Company Lp Olefin oligomerization methods
WO2014135824A1 (fr) * 2013-03-08 2014-09-12 University Of Hull Complexes de niobium et de tantale en tant que catalyseurs pour la polymérisation d'oléfines
US9944661B2 (en) 2016-08-09 2018-04-17 Chevron Phillips Chemical Company Lp Olefin hydroboration
CN114853930A (zh) * 2022-06-13 2022-08-05 青岛科技大学 一种nno-配位钛锆铪金属催化剂的合成及其制备聚烯烃弹性体的应用
CN114853930B (zh) * 2022-06-13 2024-03-01 青岛科技大学 一种nno-配位钛锆铪金属催化剂的合成及其制备聚烯烃弹性体的应用
CN116162185A (zh) * 2023-01-04 2023-05-26 万华化学集团股份有限公司 一种茂金属催化剂和制备方法及其在烯烃聚合中的应用

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