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WO2006008127A1 - Procede de production de polymeres de poids moleculaire ultra eleve a l'aide de catalyseurs metallocene non pontes - Google Patents

Procede de production de polymeres de poids moleculaire ultra eleve a l'aide de catalyseurs metallocene non pontes Download PDF

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Publication number
WO2006008127A1
WO2006008127A1 PCT/EP2005/007825 EP2005007825W WO2006008127A1 WO 2006008127 A1 WO2006008127 A1 WO 2006008127A1 EP 2005007825 W EP2005007825 W EP 2005007825W WO 2006008127 A1 WO2006008127 A1 WO 2006008127A1
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Prior art keywords
indenyl
methyl
zirconium dichloride
phenyl
bis
Prior art date
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PCT/EP2005/007825
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German (de)
English (en)
Inventor
Jens Ehlers
Jens Panitzky
Tim Dickner
Jörg SCHOTTEK
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Ticona Gmbh
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Priority to EP05773455A priority Critical patent/EP1771484A1/fr
Publication of WO2006008127A1 publication Critical patent/WO2006008127A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present invention relates to a process for the production of ultra-high molecular weight polymers by polymerization and copolymerization of olefins using catalysts and their catalyst systems. Furthermore, the invention relates to novel catalysts for the polymerization of olefins to ultrahigh molecular weight products.
  • Ultrahigh molecular weight polymers of ethylene are said to have a viscometrically determined molecular weight of greater than 1 ⁇ 10 6 mol / g. Such polymers are widely used because of their exceptional properties such as high abrasion resistance and low sliding friction. That is how you find it
  • ultra high molecular weight polyethylenes are prepared by the low pressure process with heterogeneous so-called Ziegler
  • Catalysts produced Such catalysts are described, for example, in the following patents: EP186995, DE3833445, EP575840 and US20020045537.
  • Other known catalysts for olefin polymerization are so-called “single-site catalysts.”
  • ultrahigh molecular weight polymers can only be produced with them in exceptional cases and under economically unviable conditions.
  • so-called "constrained-geometry" catalysts form ultrahigh molecular weight polyethylenes heterogeneous phase with only moderate activities and morphologies.
  • phenoxy-imine catalysts UHMWPEs are obtained only with low activities in economically unviable temperature ranges, examples of which and also for other metallocenes are disclosed in WO9719959, WO0155231, Adv. Synth. Catal., 2002, 344 , 477-493, EP0798306 and also in EP0643078.
  • single-site catalysts having a suitable ligand structure have now been found which not only allow the production of ultra-high molecular weight polyethylenes but also provide products having improved processability.
  • the present invention is a process for the preparation of ultra-high molecular weight polymers using compounds of the formula I.
  • M 1 represents a transition metal of the 3rd to 6th group of the Periodic Table of the Elements, the oxidation state of which is not equal to zero, and preferably Ti, Zr, Hf, V,
  • R 1 , R 2 , R 3 , R 4 , R 5 are each the same or different and are hydrogen or a halogen atom or a Ci - C 2 o- carbon-containing group, of which two or more can form a cyclic system with each other
  • R 6 , R 7 , R 8 , R 9 , R 10 are each the same or different and are hydrogen or a halogen atom or a Ci - C 2 o- carbon-containing group, of which two or more can form a cyclic system with each other
  • X 1 is hydrogen or a C 1 -C 20 -carbon-containing group or
  • Is halogen, and X 2 is hydrogen or a C 1 -C 2 0 carbon-containing group or
  • Is halogen and m is either 0, 1, 2 or 3, and n is either 0, 1, 2 or 3, and o is either 0, 1, 2 or 3, and p is either 0, 1, 2 or 3 , and the sum of m, n, o and p is always equal to four.
  • radicals C 1 -C 20 -alkyl are preferably selected from C 1 -C 20 -carbon-containing groups.
  • Pentafluorophenyl 3,5-bistrifluoromethylphenyl, pentafluorobenzylidene, 3,5-bistrifluoromethylbenzylidene, tetrafluorophenyl or heptafluoronaphthyl, C 1 -C 20 -alkoxy, more preferably methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy, C 6 -C 20 -aryloxy, particularly preferably phenoxy, Naphthoxy, biphenyloxy, anthracenyloxy, phenanthrenyloxy, C 7 -C 2 o-arylalkyl, more preferably o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-i -propylphenyl
  • M 1 represents a transition metal of groups 3 to 6 of the Periodic Table of the Elements whose oxidation state is not equal to zero, and preferably Ti, Zr, Hf, V, Mo, Sc, Y, Cr and Nb, and
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are each the same or different and equal to hydrogen or a halogen atom or a Ci - C 20 - carbon-containing
  • R 18, R 19, R 20, R 21, R 22, R 23, R 24 are identical or different and each is equal to
  • X 2 is hydrogen or a C 1 -C 20 carbon-containing group or a halogen atom, and m is either 0, 1 or 2, and n is either 0, 1 or 2 and 0 is either 0, 1 or 2, and p is either 0, 1 or 2, and the sum of m, n, o and p is always equal to four.
  • M 1 is a transition metal of Group 4 of the Periodic Table of the Elements whose oxidation state is not zero, and preferably Ti or Zr, and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are the same or are different and the same
  • Group are two or more of which can form a cyclic system with each other, and X 1 is hydrogen or a Ci - C 2 o- carbon-containing group or a
  • Is halogen, and X 2 is hydrogen or a C 1 -C 2 0 carbon-containing group or
  • the compounds of the formula I according to the invention are particularly suitable as constituents of catalyst systems for the preparation of polyolefins by polymerization of at least one olefin in the presence of a catalyst which comprises at least one cocatalyst and at least one compound according to the invention.
  • Another component of the present invention is a process for the polymerization of ethylene using the invention
  • Catalysts polymerization being understood to mean both the homopolymerization of ethylene and the copolymerization of ethylene with other olefins.
  • other olefins are 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-olefin.
  • Octene, styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinylnorbornene,
  • ethylene is preferably homopolymerized, or ethylene is copolymerized with one or more 1-olefins having 2 to 8 C atoms, such as propene, 1-butene, 1-pentene, 1-hexene, styrene, norbornene or butadiene.
  • the polymerization is preferably at a temperature from -20 to 300 0 C 1 0 to 200 0 C, most preferably at 20 to 100 0 C performed.
  • the pressure is 0.5 to 2000 bar, preferably 1 to 64 bar.
  • the polymerization can be in solution, in
  • Suitable solvents for the polymerization are, for example, aliphatic hydrocarbons such as pentane, hexane and the like or aromatic
  • Hydrocarbons such as benzene, toluene, xylene and the like, or ethers such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether and ethyl phenyl ether, also halogenated solvents such as dichloromethane, trichloromethane, chlorobenzene, bromobenzene and the like. It can also mixtures of different solvents in different
  • Quantity ratios are used according to the invention.
  • the present invention further provides catalyst systems for the preparation of polyolefins by polymerization of at least one olefin in the presence of at least one compound of the formula I.
  • These catalyst systems comprise, in addition to at least one compound of the formula I, at least one cocatalyst.
  • the cocatalyst which forms the catalyst system together with at least one transition metal compound of the formula I contains at least one compound from
  • Type of an aluminoxane or a Lewis acid or an ionic compound which, by reaction with the transition metal compound, converts them into a cationic compound.
  • aluminoxane is preferably a compound of general formula IV
  • aluminoxanes may be e.g. cyclic as in formula V.
  • Such aluminoxanes are described, for example, in JACS 1 17 (1995), 6465-74, Organometallics 13 (1994), 2957-2969.
  • radicals R in the formulas IV, V, VI and VII may be the same or different and represent a C ⁇
  • radicals R are the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl. If the radicals R are different, then they are preferably methyl and hydrogen,
  • aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, that an aluminum hydrocarbon compound and / or a Hydridoaluminium- hydrocarbon compound with water (gaseous, solid, liquid or bound - for example, as water of crystallization) in an inert solvent (such as toluene) is reacted.
  • aluminoxane having different alkyl groups R two different trialkylaluminums (AIR3 + AIR'3) are reacted with water according to the desired composition and reactivity (see S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0, 302,424). ,
  • the preferred Lewis acid is at least one borane or organoaluminum compound containing C 1 -C 20 carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, e.g. Methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, ToIyI, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl,
  • C 1 -C 20 carbon-containing groups such as branched or unbranched alkyl or haloalkyl, e.g. Methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, ToIyI, benzyl groups, p-fluorophenyl, 3,5-diflu
  • Pentachlorophenyl pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di (trifluoromethyl) phenyl.
  • Lewis acids are trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane,
  • Tris (4-fluorophenyl) borane tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyl) borane, tris ( 3,5-difluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Particularly preferred is tris (pentafluorophenyl) borane.
  • ionic cocatalysts it is preferred to use compounds which contain a non-coordinating anion, for example Tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF ", CF3SO3 or CIO4-.
  • a non-coordinating anion for example Tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF ", CF3SO3 or CIO4-.
  • a cationic counterion protonated Lewis bases such as methylamine, aniline, N, N-dimethylbenzylamine and their derivatives, N 1 N-dimethylcyclohexylamine and their derivatives, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, Triethylamine, tri-n-butylamine,
  • Methyldiphenylamine pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene or triphenylcarbenium used.
  • N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
  • borane or carborane compounds such as e.g.
  • cocatalyst systems are combinations of at least one of the abovementioned amines and optionally a carrier with organometallic compounds as described in patent WO 99/40129.
  • the carriers mentioned in WO 99/40129 with organometallic compounds are likewise part of the present invention.
  • Preferred constituents of these cocatalyst systems are the compounds of the formulas A and B, Formula A
  • R 5 25 represents a hydrogen atom, a halogen atom, a Ci-C 20 carbon-containing
  • R 25 may also be an -OSiR 3 group, wherein R is the same or different and has the same meaning as R 25 .
  • R j25 has the same meaning as mentioned above, and R 26 is a hydrogen atom or a boron-free C 1 -C 4 -carbon-containing group, such as
  • C- 20 alkyl, C 6 -C 2 o-aryl, C 7 -C 20 arylalky, C 7 -C 2 o-alkylaryl and X 3 may be an element of the 16th group of the Periodic Table of the Elements or an NR group wherein R is o-hydrocarbon radical such as CiC 2 o alkyl or CiC 2 is a hydrogen atom or a Ci ⁇ C2o-aryl, and L is equal to an element of the 16th group of the Periodic Table of the elements or an NR group, wherein R is a hydrogen atom or a Ci-C 20 - hydrocarbon radical such as Ci-C 20 alkyl or CrC 2 o-aryl, f is an integer from 0 to 3, g is an integer from 0 to 3, where z + y are not 0, h is an integer of 1 to 10.
  • the organometallic compounds are combined with an organometallic compound of the formula IV to VII and or VIII [M2R27 ( .)
  • M ⁇ is an element of the 1st, 2nd and 13th group of the Periodic Table of the Elements, R27 are the same or different is and a hydrogen atom, a halogen atom, a
  • C1-C40-carbon-containing group in particular C1-C20-alkyl, C3-C15-aryl, C7-C20-aryl-alkyl or C7-C20-alkyl-aryl group, r is a whole Number of 1 to 3 and k is an integer of 1 to 4.
  • the organometallic compounds of the formula F are preferably neutral Lewis acids in which M is lithium, magnesium and / or aluminum, in particular aluminum.
  • Examples of the preferred organometallic compounds of the formula F are trimethylaluminum, triethylaluminum, trisodium isopropylaluminum, trihexylaluminum, trioctylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisoprenaluminum, dimethylaluminum monochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum sesqui chloride, ethylaluminum sesquichloride, dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, dimethylaluminum (trimethylsiloxide), dimethylaluminum (triethylsiloxide
  • the catalysts of the invention can be used homogeneously and also heterogeneously supported.
  • the carrier component of the catalyst system may be any organic or inorganic inert
  • Solid especially a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g., polyolefins).
  • a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g., polyolefins).
  • Suitable inorganic oxides can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements.
  • oxides preferred as the carrier include silica, alumina and mixed oxides of the elements calcium,
  • Other inorganic oxides which can be used alone or in combination with the last-mentioned preferred oxide supports are, for example, MgO, ZrO 2 , TiO 2 or B 2 O 3 , to name only a few.
  • the support materials used have a specific surface area in the range of 10 to 1000 m 2 / g, a pore volume in the range of 0.1 to 5 ml / g and an average particle size of 1 to 500 microns.
  • the support material used is inherently low in moisture content or residual solvent content, dehydration may occur or avoid drying before use. If this is not the case, as with the use of silica gel as a carrier material, dehydration or drying is recommended.
  • the thermal dehydration or drying of the support material can be carried out under vacuum and simultaneous inert gas overlay (eg nitrogen). The drying temperature is in the range between 100 and
  • the parameter pressure is not decisive in this case.
  • the duration of the drying process can be between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the conditions chosen, equilibration can be achieved with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
  • Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane or organometallic compounds of aluminum, boron and magnesium, for example trimethylaluminum, triethylaluminum, triisobutylaluminum, triethylborane, dibutylmagnesium.
  • the chemical dehydration or inertization of the carrier material is carried out, for example, by reacting under air and moisture exclusion a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent for reaction.
  • suitable solvents include aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene.
  • the inertization is carried out at temperatures between 25 ° C and 120 0 C, preferably between 50 and 70 0 C. Higher and lower temperatures are possible.
  • the duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours.
  • the support material is isolated by filtration under inert conditions, one or more times with suitable inert solvents as before have been washed and then in inert gas or on
  • Organic support materials such as finely divided polyolefin powders (e.g., polyethylene, polypropylene, or polystyrene) may also be used, and should also be free from the use of adherent moisture, residual solvents, or others
  • Impurities are cleaned by appropriate cleaning and drying operations.
  • the supported catalyst system At least one of the compounds of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, preferably a soluble reaction product, an adduct or a mixture being obtained.
  • a suitable solvent preferably a soluble reaction product, an adduct or a mixture being obtained.
  • the resulting formulation is then mixed with the dehydrated or inertized support material, the solvent removed and the resulting supported catalyst system dried to ensure that the solvent is completely or mostly removed from the pores of the support material.
  • the supported catalyst is obtained as a free-flowing powder.
  • a process for the preparation of a free-flowing and optionally prepolymerized supported catalyst system comprises the following steps: a) preparation of a mixture of at least one compound of formula I and at least one cocatalyst in a suitable solvent or suspending agent, b) application of those obtained from step a) C) removing the majority of solvent from the resulting mixture; d) isolating the supported catalyst system; e) optionally pre-polymerizing the resulting supported catalyst system with one or more olefinic monomer (s) to form a prepolymerized supported To obtain catalyst system.
  • Preferred solvents in step a) are hydrocarbons and hydrocarbon mixtures which are liquid at the chosen reaction temperature and in which the individual components preferentially dissolve.
  • the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of Compound of formula I and cocatalyst is soluble in the chosen solvent.
  • suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Very particular preference is given to toluene.
  • a molar ratio of aluminum to the transition metal in the compound of the formula I is preferably set from 10: 1 to 1000: 1, very particularly preferably a ratio of from 50: 1 to 500: 1.
  • the compound of formula I is dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the compound of formula I separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Preferably, toluene is used.
  • the pre-activation time is 1 minute to 200 hours. The preactivation can take place at room temperature (25 ° C.). The use of higher temperatures can shorten the required duration of pre-activation in individual cases and cause an additional increase in activity.
  • Higher temperature in this case means a range between 50 and 100 ° C.
  • an inert carrier material usually silica gel, which is present in the form of a dry powder or as a suspension in one of the abovementioned solvents ,
  • the carrier material is used as a powder.
  • the order of addition is arbitrary.
  • the preactivated metallocene cocatalyst solution or the metallocene cocatalyst mixture can be added to the initially introduced carrier material, or else the carrier material can be introduced into the initially introduced solution.
  • Cocatalyst mixture can exceed 100% of the total pore volume of the carrier material used or up to 100% of the total pore volume.
  • Cocatalyst mixture is brought into contact with the carrier material may vary in the range between 0 and 100 0 C. Lower or higher temperatures are also possible. Subsequently, the solvent is completely or for the most part of the supported carrier material.
  • Catalyst system removed wherein the mixture can be stirred and optionally also heated.
  • both the visible portion of the solvent and the proportion in the pores of the carrier material is removed.
  • the removal of the solvent can be carried out in a conventional manner using vacuum and / or inert gas purging.
  • the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 0 C.
  • the free solvent is the visible amount of solvent in the mixture.
  • residual solvent is meant the portion trapped in the pores.
  • Catalyst system to be dried only to a certain residual solvent content, the free solvent has been completely removed. Subsequently, the supported catalyst system can be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
  • a low-boiling hydrocarbon such as pentane or hexane
  • the supported catalyst system as illustrated may be used either directly for the polymerization of olefins or prepolymerized prior to its use in a polymerization process with one or more olefinic monomers.
  • the execution of the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
  • an olefin preferably an ⁇ -olefin (for example, vinylcyclohexane, styrene or phenyldimethylvinylsilane) as a modifying component or an antistatic agent (as described in US Serial No. 08 / 365,280) may be added.
  • an olefin preferably an ⁇ -olefin (for example, vinylcyclohexane, styrene or phenyldimethylvinylsilane)
  • an antistatic agent as described in US Serial No. 08 / 365,280
  • Component is preferably between 1: 1000 to 1000: 1, most preferably 1: 20 to 20: 1.
  • Another component of the present invention are unbridged catalysts of the formula IX
  • M 1 represents a transition metal of Group 4 of the Periodic Table of the Elements whose oxidation state is not equal to zero, and preferably Ti or Zr
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 28 , R 29 R 30 , R 31 are the same or different and are each hydrogen or a halogen atom or a C 1 -C 20 carbon-containing group, two or more of which may form a cyclic system with one another, and
  • X 1 is hydrogen or a C 1 -C 20 carbon-containing group or a halogen atom
  • X 2 is hydrogen or a C 1 -C 20 -carbon group or a halogen atom.
  • Compounds of the formula IX are very particularly preferably used in the process according to the invention for the preparation of ultrahigh molecular weight polymers.
  • This bridged metallocene was chosen as a comparative substance for the polymerizations.
  • This bridged metallocene was chosen as a comparative substance for the polymerizations.
  • Exxsol 1.5 l of Exxsol are introduced into a 2 l steel autoclave and 15 mmol of an aluminum alkyl (for example triisobutylaluminum) are added. Subsequently, the reactor is brought to the desired temperature and built up an ethylene pressure of 7-15 bar. At the start of the polymerization, 9-18 ⁇ mol of the respective catalyst (see Table 1) are suspended in Exxsol. It is usually polymerized for one hour and the reaction is stopped by reducing the ethylene pressure. The polymer is filtered off and dried in vacuo at 8O 0 C. Finally, the yield and the molecular weight are determined.
  • an aluminum alkyl for example triisobutylaluminum

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Abstract

L'invention concerne un procédé permettant de produire des polymères de poids moléculaire ultra élevé, par polymérisation et copolymérisation d'oléfines, à l'aide de catalyseurs, ainsi que leurs systèmes catalyseurs.
PCT/EP2005/007825 2004-07-21 2005-07-19 Procede de production de polymeres de poids moleculaire ultra eleve a l'aide de catalyseurs metallocene non pontes WO2006008127A1 (fr)

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EP05773455A EP1771484A1 (fr) 2004-07-21 2005-07-19 Procede de production de polymeres de poids moleculaire ultra eleve a l'aide de catalyseurs metallocene non pontes

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DE102004035308.5 2004-07-21
DE200410035308 DE102004035308A1 (de) 2004-07-21 2004-07-21 Verfahren zur Herstellung von ultrahochmolekularen Polymeren unter Verwendung von unverbrückten Metallocen-Katalysatoren

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Cited By (9)

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US7619047B2 (en) 2006-02-22 2009-11-17 Chevron Phillips Chemical Company, Lp Dual metallocene catalysts for polymerization of bimodal polymers
US8034886B2 (en) 2005-11-04 2011-10-11 Ticona Gmbh Process for manufacturing high to ultra high molecular weight polymers using novel bridged metallocene catalysts
US8877672B2 (en) 2013-01-29 2014-11-04 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8895679B2 (en) 2012-10-25 2014-11-25 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8937139B2 (en) 2012-10-25 2015-01-20 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US9034991B2 (en) 2013-01-29 2015-05-19 Chevron Phillips Chemical Company Lp Polymer compositions and methods of making and using same
WO2021033966A1 (fr) * 2019-08-22 2021-02-25 한화솔루션 주식회사 Composé de métal de transition, catalyseur le comprenant et son procédé de préparation

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US7910763B2 (en) 2005-09-15 2011-03-22 Chevron Phillips Chemical Company Lp Process for preparing a monocyclopentadienyl compound
US7521572B2 (en) 2005-09-15 2009-04-21 Chevron Phillips Chemical Company, Lp Polymerization catalysts and process for producing bimodal polymers in a single reactor
US8034886B2 (en) 2005-11-04 2011-10-11 Ticona Gmbh Process for manufacturing high to ultra high molecular weight polymers using novel bridged metallocene catalysts
US7652160B2 (en) 2006-02-02 2010-01-26 Cheveron Phillips Chemical Company, L.P. Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching
US7732542B2 (en) 2006-02-02 2010-06-08 Chevron Phillips Chemical Company, Lp Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching
US7517939B2 (en) 2006-02-02 2009-04-14 Chevron Phillips Chemical Company, Lp Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching
US7619047B2 (en) 2006-02-22 2009-11-17 Chevron Phillips Chemical Company, Lp Dual metallocene catalysts for polymerization of bimodal polymers
US8895679B2 (en) 2012-10-25 2014-11-25 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8937139B2 (en) 2012-10-25 2015-01-20 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8877672B2 (en) 2013-01-29 2014-11-04 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US9034991B2 (en) 2013-01-29 2015-05-19 Chevron Phillips Chemical Company Lp Polymer compositions and methods of making and using same
US9394385B2 (en) 2013-01-29 2016-07-19 Chevron Phillips Chemical Company Lp Polymer compositions and methods of making and using same
US9637573B2 (en) 2013-01-29 2017-05-02 Chevron Phillips Chemical Company Lp Polymer compositions and methods of making and using same
WO2021033966A1 (fr) * 2019-08-22 2021-02-25 한화솔루션 주식회사 Composé de métal de transition, catalyseur le comprenant et son procédé de préparation

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