EP1373283A1 - Non-metallocenes, leur procede de production et leur utilisation dans la polymerisation d'olefines - Google Patents

Non-metallocenes, leur procede de production et leur utilisation dans la polymerisation d'olefines

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Publication number
EP1373283A1
EP1373283A1 EP02716780A EP02716780A EP1373283A1 EP 1373283 A1 EP1373283 A1 EP 1373283A1 EP 02716780 A EP02716780 A EP 02716780A EP 02716780 A EP02716780 A EP 02716780A EP 1373283 A1 EP1373283 A1 EP 1373283A1
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atom
group
bis
different
same
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German (de)
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Jörg SCHOTTEK
Jörg SCHULTE
Cornelia Fritze
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Celanese Ventures GmbH
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Celanese Ventures GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes

Definitions

  • Non-metallocenes processes for their preparation and their use in the polymerization of olefins
  • the present invention relates to a process for the preparation of special transition metal compounds, new transition metal compounds and their use for the polymerization of olefins
  • metallocenes have been used for olefin polymerization to generate polyolefins with special properties that cannot be achieved with conventional Ziegler catalysts.
  • Metallocenes optionally in combination with one or more co-catalysts, can be used as a catalyst component for the polymerization and copolymerization of olefins.
  • halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex.
  • non-metallocenes are described in the literature, such as, for example, in EP-A-874 005, which are distinguished by advantages in the representability and the cost of the starting materials. The high activities of these complexes represent a further cost-saving factor.
  • the present invention relates to compounds of the formula (I)
  • M 4 is a metal of III. to XII is group of the periodic table of the elements, in particular Ti, Zr, Hf, Ni, V, W, Mn, Rh, Ir, Cu, Co, Fe, Pd, Sc, Cr and Nb
  • R 15 , R 16 are in each case the same or different and are a hydrogen atom or Si (R 12 ) 3 , in which R 12 in each case the same or different is a hydrogen atom or a -C-C 40 carbon-containing group such as C-rC 2 o-alkyl, CrCio -Fluoroalkyl, -C-C 10 alkoxy, C 6 -C 20 aryl ( C 6 -C ⁇ o-fluoroaryl, C 6 -C ⁇ o-aryloxy, C 2 -C 10 alkenyl, C 7 -C 40 - arylalkyl, C 7 -C 40 alkylaryl or C 8 -C 40 arylalkenyl, or R 15 , R 16 are each the same or different and a C 1 -C30 - carbon-containing group such as -C-C 25 alkyl, for example methyl, ethyl , tert-butyl, n-hexyl
  • X can each be the same and different and is an element of the 13-16 group of the Periodic Table of the Elements, preferably boron, carbon, silicon, nitrogen, oxygen and sulfur, with each other cyclic systems such as aromatics or aliphatics, in which one or more C atoms can be replaced by N, O, S, B, particularly preferably form carbon, sulfur, nitrogen and oxygen, which in turn can be substituted by R 15 or R 16 , where at least one X is B, Si, N, Must be 0, S, P
  • L can in each case be the same or different and a hydrogen atom, a -C-hydrocarbon group such as CrCio-alkyl or C 6 -C ⁇ o-aryl, a halogen atom, or OR 9 , SR 9 , OSi (R 9 ) 3 , Si (R 9 ) 3, P (R 9) 2 or N (R 9) 2, wherein R 9 is a halogen atom, a C C ⁇ o alkyl group, a halogenated C 1 -C 1 0 alkyl group, a C 6 -C 20 aryl group or a halogenated C 6 -C 2 o are aryl group,
  • 0 is an integer from 1 to 4, preferably 2,
  • Z denotes a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
  • Z examples are groups M 2 R 10 R 11 , in which M 2 is carbon, silicon, germanium boron or tin and R 10 and R 11, identical or different, are a C 1 -C 20 -hydrocarbon-containing group such as CC 0 alkyl, C 6 -Cu-aryl or trimethylsilyl.
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, (C 6 H 5 ) 2 Ge, (CH 3 ) 3 Si-Si (CH 3 ) ] (C 6 H 5 ) 2 Sn, (CH 2 ) 4 Si, CH 2 Si (CH 3 ) 2) oC 6 H 4 or 2,2 ' - (C 6 H) 2 , and 1, 2- (1-methyl-ethanediyl) -, 1, 2- (1, 1-dimethyl-ethanediyl) - and 1, 2- (1, 2-dimethyl-ethanediyl).
  • Z can also form a mono- or polycyclic ring system with one or more radicals R
  • Ph stands for substituted or unsubstituted phenyl, Et for ethyl and Me for methyl.
  • X particularly preferably represents a radical -CR- where R each independently of one another is hydrogen or a CrC 4 o-carbon-containing group such as CrC 20 - alkyl, such as methyl, ethyl, tert-butyl, n-hexyl, cyclohexyl or octyl, C ⁇ -C ⁇ 0 fluoroalkyl, CC 10 alkoxy, C 6 -C 24 aryl, fluorine-containing C 6 -C 24 aryl, C 5 -C 24 heteroaryl, C 6 -C ⁇ o- fluoroaryl, C 5 -C ⁇ o- Aryloxy, C 2 -C 25 alkenyl, C 3 -C 5 alkylalkenyl, C 7 -C 40 arylalkyl, fluorine-containing C 7 -C 3 o-arylalkyl, C 7 -C 40 alkylaryl, fluorine-containing C 7 -C 3 is
  • Bridged metal compounds of the formula (I) are preferred, in particular those in which v is 1 and the five-membered ring is fused with a six-membered ring.
  • R 15 , R 16 , X have the meaning given above,
  • R 3 are in each case identical or different and are a hydrogen atom, O-Si (R 12 ) 3 or Si (R 12 ) 3 , in which R 12 in each case the same or different is a hydrogen atom or a CrC 40 carbon-containing group such as C 1 -C 20 - alkyl, C C ⁇ o-fluoroalkyl, CrCio-alkoxy, C 6 -C 20 aryl, C 6 -C 10 -Fluoraryl, C 6 -C 0 - aryloxy, C 2 -C-to-alkenyl, C 0 -C 4 -arylalkyl , C 7 -C 4 o -Alkylaryl or C 8 -C 0 arylalkenyl, or R 3 are the same or different and a CC 30 - carbon-containing group such as -CC 25 alkyl, z.
  • R 3 radicals can in each case be linked to one another in such a way that the R 3 radicals and the atoms connecting them form a C 4 -C 24 ring system which in turn can be substituted,
  • J is in each case independently of one another a halogen atom, in particular chlorine,
  • Alkyl groups C 1 -C 8 alkyl group, in particular methyl, ethyl, tert-butyl, or substituted or unsubstituted phenolates, i in each case, identically or differently, is an integer between 1 and 8, preferably
  • I is an integer from 1 to 5, preferably 1 to 3, depending on the valence of the atom X
  • m is an integer from 1 to 5, preferably 1 to 3, depending on the
  • Valence of the atom X, y is an integer from 1 to 4, preferably 2.
  • the ring system is preferably substituted with R 3 , R 15 or R 16 , in particular in 2-, 4-, 7-, 2, 4, 5-, 2, 4, 6-, 2, 4, 7-, 2, 4 , 5, 6, 7- or 2, 4, 5, 6-position, with C r C 20 - carbon-containing groups, such as -CC 8 -alkyl or C 6 -C 18 -aryl, with two or more substituents of the cyclic system together can form a ring system.
  • B are groups M 3 R 13 R 14 wherein M 3 is silicon or carbon and R 13 and R 14 are the same hydrocarbon group as C ⁇ -C ⁇ mean 0 alkyl, C 6 -C 1 aryl or trimethylsilyl.
  • B is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 3 Si-Si (CH 3 ).
  • Ph stands for substituted or unsubstituted phenyl, Et for ethyl and Me for methyl.
  • M is Ni, Co, Fe Ti or Zr
  • R 15 , R 16 are each a hydrogen atom or linear or branched C C ⁇ 2 ⁇
  • alkyl groups preferably an alkyl group such as methyl, ethyl, n-butyl, n-hexyl, isoproppyl, isobutyl, isopentyl, cyclohexyl, cyclopentyl or octyl, particularly preferably methyl is ethyl, isopropyl or cyclohexyl,
  • R 3 are in each case identical or different and represent a hydrogen atom, halogen atom or a CrC 2 o - carbon-containing group, preferably a linear or branched C 1 -C 8 -alkyl group, such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 6 alkenyl, C 3 -C 6 alkylalkenyl, a C 6 -C 18 aryl group which may optionally be substituted, in particular phenyl, tolyl, xylyl, tert-butylphenyl, ethylphenyl, naphthyl, acenaphthyl, phenanthrenyl or Anthracenyl, C 5 -C 18 heteroaryl, C 7 -C 2 arylalkyl, C 7 -C-
  • J is chlorine or methyl
  • X can in each case be the same and different and is a carbon, nitrogen, oxygen, boron and sulfur, with each other cyclic systems such as aromatics or aliphatics, in which one or more C atoms can be replaced by N, O, S, B, form, in particular carbon, nitrogen and oxygen, which in turn can be substituted by R 15 , R 16 or R 3 , where at least one X must be B, Si, N, O, S, P, i is the same or different an integer between 3 and 4, preferably the same
  • I is 1 or 2, depending on the valence of the atom X
  • m is 1 or 2, depending on the valence of the atom X
  • B denotes a bridging structural element between the cyclic systems, B preferably being Si (Me) 2 , Si (Ph) 2 , Si (Et) 2 , Si (MePh),
  • B is: Si (Me) 2 , Si (Ph) 2 , Si (Et) 2 , Si (MePh), Si (C 4 H 8 ), CH 2 , CMe 2 , CHMe, CH 2 CH 2 , (CH 3 ) 3 Si-Si (CH 3 ).
  • the present invention also relates to a catalyst system which contains the chemical compound of the formula (II) according to the invention.
  • the metal complexes of the formulas (II) according to the invention are particularly suitable as a constituent of catalyst systems for the production of polyolefins by polymerizing at least one olefin in the presence of a catalyst which contains at least one cocatalyst and at least one metal complex.
  • the cocatalyst which together with a transition metal complex of the formula II according to the invention forms the catalyst system, contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound, which converts this into a cationic compound by reaction with a metal complex.
  • a compound of the general formula (III) is preferred as the aluminoxane
  • aluminoxanes can e.g. cyclic as in formula (IV)
  • radicals R in the formulas (III), (IV), (V) and (VI) can be identical or different and a C 1 -C 6 -hydrocarbon group such as a C 1 -C 6 -alkyl group, a C 6 -
  • the radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
  • radicals R are different, they are preferably methyl and hydrogen
  • Butyl preferably 0.01 to 40% (number of radicals R) are contained.
  • the 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).
  • the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains groups containing C 1 -C 2 o -carbon, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) phenyl.
  • organoboron or organoaluminum compound which contains groups containing C 1 -C 2 o -carbon, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl,
  • Lewis acids are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentane) Tris (tolyl) borane, tris (3,5-dimethylphenyl) borane, tris (3,5-difluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.
  • Compounds which contain a non-coordinating anion such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 -, CF3SO3 - or CIO 4 - are preferably used as ionic cocatalysts.
  • a non-coordinating anion such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 -, CF3SO3 - or CIO 4 - are preferably used as ionic cocatalysts.
  • Protonated Lewis bases such as methylamine, aniline, N, N-dimethylbenzylamine and derivatives, N, N-dimethylcyclohexylamine and 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- DimethyIanilin, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene or triphenylcarbenium used.
  • Triphenylcarbenium tetrakis (pentafluorophenyl) borate Triphenylcarbenium tetrakis (pentafluorophenyl) borate
  • Triphenylcarbenium tetrakis (phenyl) aluminate Triphenylcarbenium tetrakis (phenyl) aluminate
  • N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
  • Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
  • Combinations of at least one of the amines mentioned above and optionally a support with organo-element compounds as described in patent WO 99/40129 are also important as cocatalyst systems.
  • the carriers with elemental organic compounds mentioned in WO 99/40129 are also part of the present invention.
  • R "L7 are the same or different is a hydrogen atom, a halogen atom, a CrC o-carbon-containing group, in particular C ⁇ -C2o-alkyl, C ⁇ ⁇ C 20 - haloalkyl, C ⁇ -C 10 alkoxy, C 6 -C 20 aryl , C 6 -C 20 haloaryl, C 6 -C 20 aryloxy, C 7 -C 0 arylalkyl, C 7 -C 0 haloarylalkyl, C 7 -C 40 alkylaryl or C 7 -C 40 - haloalkylaryl.
  • R 7 can also be a -OSiR 18 3 group, in which R 18 can be the same or different and has the same meaning as R 17 .
  • cocatalysts are generally compounds which are formed by the reaction of at least one compound of the formula (C) and / or (D) and / or (E) with at least one compound of the formula (F).
  • R 80 each identically or differently represents a hydrogen atom or a boron-free Cr
  • C 40 carbon-containing group such as C r C 20 alkyl, C 6 -C 20 aryl, C 7 -C 0 aryl alkyl,
  • R 17 has the same meaning as mentioned above,
  • X 1 is an element of VI. Main group of the Periodic Table of the Elements or an NR group, in which R is a hydrogen atom or a C 1 -C 20 hydrocarbon radical such as CrC 20 alkyl or CrC 20 aryl,
  • D is an element of VI.
  • Main group of the periodic table of the elements or an NR group wherein R is a hydrogen atom or a C 1 -C 20 hydrocarbon radical such as CrC 20 alkyl or -C-C 20 aryl, v is an integer from 0 to 3, s is an integer Is an integer from 0 to 3, h is an integer from 1 to 10,
  • B is boron
  • AI is aluminum.
  • the elemental organic compounds are combined with an organometallic compound of the formula III to V and or VII [M40R 9b] d, where M40 is an element of I., II. And III. Main group of the Periodic Table of the Elements is, R19 is the same or different and is a hydrogen atom, a halogen atom, a C1-C40 carbon-containing group, in particular C1-C20-alkyl, C6-C40-aryl, C7-C40-aryl-alkyl or C7-C40-alkyl-aryl group means, b is an integer from 1 to 3 and d is an integer from 1 to 4. Examples of the cocatalytically active compounds of the formulas A and B are
  • the organometallic compounds of the formula VII are preferably neutral Lewis acids in which M ⁇ O is lithium, magnesium and / or aluminum, in particular aluminum.
  • Examples of the preferred organometallic compounds of the formula XII are trimethylaluminium, triethylaluminium, triisopropylaluminum, trihexylaluminium, trioctylaluminium, tri-n-butylaluminium, trin-propylaluminum, triisoprenaluminium, dimethylaluminium monochloride, diethyl, diammonium chloride, diethylaluminium chloride, , Diethyl aluminum hydride, diisopropyl aluminum hydride, dimethyl aluminum (trimethylsiloxide), dimethyl aluminum (triethylsiloxide), phenylalane, pentafluorophenylalane and o-tolylalane.
  • the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g. polyolefins).
  • Suitable inorganic oxides can be found in the II-VI main group of the periodic table and the III-IV subgroup of the periodic table of the elements.
  • preferred oxides as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures, and hydrotalcites.
  • Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, ZrO 2 , TiO 2 or B 2 O 3 , to name just a few.
  • the carrier materials used have a specific surface area in the range from 10 to 1000 m / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 ⁇ m.
  • Carriers with a specific surface area in the range from 50 to 500 ⁇ m, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 ⁇ m are preferred.
  • Carriers with a specific surface area in the range from 200 to 400 m 2 / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 ⁇ m are particularly preferred.
  • the carrier material used naturally has a low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as is the case when using silica gel as the carrier material, dehydration or drying is recommended.
  • the thermal dehydration or drying of the carrier material can take place under vacuum and at the same time inert gas blanket (eg nitrogen).
  • the drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical.
  • the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established 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, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium.
  • the chemical dehydration or inertization of the carrier material is carried out, for example, by suspending the carrier material in a suitable manner with the exclusion of air and moisture Solvent with the inerting reagent in pure form or dissolved in a suitable solvent to react.
  • suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene.
  • the inerting takes place at temperatures between 25 ° C and 120 C, preferably between 50 and 70 ° 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, washed one or more times with suitable inert solvents, as have already been described above, and then dried in an inert gas stream or in vacuo.
  • Organic carrier materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be freed of adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.
  • polyolefin powders e.g. polyethylene, polypropylene or polystyrene
  • At least one of the transition metal compounds of the formula II described above is brought into contact with at least one cocatalyst component in a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.
  • the preparation thus obtained is then mixed with the dehydrated or rendered inert carrier material, the solvent removed and the resulting supported transition metal compound catalyst system dried to ensure that the solvent is completely or largely removed from the pores of the carrier material.
  • the supported catalyst is obtained as a free-flowing powder.
  • a method for preparing a free-flowing and optionally prepolymerized transition metal compound catalyst system comprises the following steps: a) Preparation of a transition metal compound / cocatalyst mixture in a suitable solvent or suspending agent, the transition metal compound component having one of the structures described above. b) applying the transition metal compound / cocatalyst mixture to a porous, preferably inorganic, dehydrated carrier c) removing the main proportion of solvent from the resulting mixture d) isolating the supported catalyst system e) optionally pre-polymerizing the obtained supported catalyst system with one or more olefinic monomer (s) to obtain a prepolymerized supported catalyst system.
  • Transition metal compound and cocatalyst components in the chosen one are Transition metal compound and cocatalyst components in the chosen one
  • Solvent is soluble.
  • 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.
  • Toluene is very particularly preferred.
  • Aluminoxane and transition metal compound can be varied over a wide range.
  • a molar ratio of aluminum to is preferred
  • Transition metal in the transition metal compounds from 10: 1 to 1000: 1, very particularly preferably a ratio of 50: 1 to 500: 1.
  • the transition metal compound 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 transition metal compound separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Toluene is preferably used.
  • the preactivation time is 1 minute to 200 hours.
  • the preactivation can take place at room temperature (25 ° C).
  • the application of higher temperatures can, in individual cases, the required preactivation time shorten and cause an additional increase in activity.
  • a higher temperature means a range between 50 and 100 ° C.
  • the preactivated solution or the transition metal compound / cocatalyst mixture is then combined with an inert support material, usually silica gel, which is in the form of a dry powder or as a suspension in one of the abovementioned solvents.
  • the carrier material is preferably used as a powder.
  • the order of addition is arbitrary.
  • the preactivated transition metal compound-cocatalyst solution or the transition metal compound-cocatalyst mixture can be metered into the support material provided, or the support material can be introduced into the solution presented.
  • the volume of the preactivated solution or of the transition metal compound / cocatalyst mixture can exceed 100% of the total pore volume of the support material used or can be up to 100% of the total pore volume.
  • the temperature at which the preactivated solution or the transition metal compound / cocatalyst mixture is brought into contact with the support material can vary in the range between 0 and 100 ° C. However, lower or higher temperatures are also possible.
  • the solvent is then completely or largely removed from the supported catalyst system, and the mixture can be stirred and optionally also heated. Both the visible portion of the solvent and the portion in the pores of the carrier material are preferably removed.
  • the solvent can be removed in a conventional manner using vacuum and / or purging with inert gas. During the drying process, 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 ° C.
  • the free solvent is the visible proportion of solvent in the mixture. Residual solvent is the proportion that is enclosed in the pores.
  • the supported catalyst system can also be dried only to a certain residual solvent content, the free solvent having been removed completely.
  • the supported catalyst system can then be used with a low boiling point Hydrocarbon such as pentane or hexane are washed and dried again.
  • the supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before being used in a polymerization process.
  • the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
  • a small amount of an olefin, preferably an ⁇ -olefin (for example vinylcyclohexane, styrene or phenyldimethylvinylsilane) can be added as a modifying component or an antistatic (as described in US Serial No. 08/365280) during or after the preparation of the supported catalyst system.
  • the molar ratio of additive to compound of formula (I) is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
  • the present invention also relates to a process for the preparation of a polyolefin by polymerizing one or more olefins in the presence of the catalyst system according to the invention.
  • the term polymerisation is understood to mean homopolymerization as well as copolymerization.
  • olefins examples include 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclododecene or methylnorbornene.
  • 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norborn
  • Ethene or propene are preferably homopolymerized in the process according to the invention, or propene with ethene and / or with one or more 1-olefins having 4 to 20 C atoms, such as butene, hexene, styrene or vinylcyclohexane, and / or one or more dienes 4 to 20 carbon atoms, such as 1,4-butadiene, norbornadiene, ethylidene norborons or ethyl norbornadiene, copolymerized.
  • 1-olefins having 4 to 20 C atoms, such as butene, hexene, styrene or vinylcyclohexane, and / or one or more dienes 4 to 20 carbon atoms, such as 1,4-butadiene, norbornadiene, ethylidene norborons or ethyl norbornadiene, copolymerized.
  • copolymers examples include ethene / propene copolymers, ethene / norbomen, ethene / styrene or ethene / propene / 1,4-hexadiene terpolymers.
  • the polymerization is carried out at a temperature of 0 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 50 to 80 ° C.
  • the pressure is 0.5 to 2000 bar, preferably 5 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • the catalyst system shown according to the invention can be used as the only catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably in combination with at least one alkyl compound of the elements from I to III.
  • Main group of the periodic table e.g. an aluminum, magnesium or lithium alkyl or an aluminoxane can be used.
  • the alkyl compound is added to the monomer or suspending agent and is used to purify the monomer from substances which can impair the catalyst activity. The amount of alkyl compound added depends on the quality of the monomers used. If necessary, hydrogen is added as a molecular weight regulator and / or to increase the activity.
  • the catalyst system can be fed neat to the polymerization system or inert components such as paraffins, oils or waxes can be added for better meterability.
  • an antistatic can also be metered into the polymerization system together with or separately from the catalyst system used.
  • the polymers shown with the catalyst system according to the invention have a uniform grain morphology and have no fine grain fractions. No deposits or caking occur in the polymerization with the catalyst system according to the invention.
  • a solution of 85 g of NaOH in 170 ml of water is added to 20.0 g (169 mmol) of benzimidazole and the mixture is stirred at 50 ° C. for 30 min. Then 3.4 g (10 mmol) of tetrabutylammonium bromide and 16.1 g (85 mmol) of 1,2-dibromoethane are added and the mixture is stirred at 50 ° C. for 30 min. A precipitate forms after 2 h. The suspension is stirred at RT overnight and then at 4 ° C. for 3 h stored. The precipitate thus obtained is filtered off and stirred with ethanol.
  • a solution of 38 g of NaOH in 76 ml of water is added to 10.0 g (76 mmol) of 2-methylbenzimidazole and the mixture is stirred at 50 ° C. for 30 min. Then 1.5 g (5 mmol) of tetrabutylammonium bromide and 7.1 g (38 mmol) of 1,2-dibromoethane are added and the mixture is stirred at 50 ° C. for 30 min. A precipitate forms after 5 h. The suspension is stirred at RT overnight and then stored at 4 ° C. for 3 h. The precipitate thus obtained is filtered off and stirred with ethanol.
  • N.N'-benzotriazole methane 250 mg (0.999 mmol) of N.N'-benzotriazole methane are placed in 12 ml of THF, and 308 mg (0.905 mmol) of nickel dibromide * DME are added in portions at room temperature. It is stirred at this temperature overnight. The precipitate is isolated on a G4 frit and washed twice with 5 ml of THF. The desired Ni complex is isolated in a yield of 380 mg.
  • Example 16 Ethylene bis (N, N'-2,3-dihydro-1H-benzimidazolyl) zirconium dichloride
  • Example 17 Ethylene bis (N, N'-2,3-dihydro-1H-benzimidazolyl) titanium dichloride
  • Example 18 Ethylene bis (N, N s -2,3-d ⁇ hydro-2,2-dimethyl-1 H-benzimidazolyl) zirconium dichloride
  • Example 19 Ethylene bis (N, N'-2,3-dihydro-2,2-dimethyl-1 f -benzimidazolyl) titanium dichloride

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  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne des composés organométalliques qui présentent une structure de ligand constituée à partir d'hétérocycles substitués ou non substitués. Par réaction avec des halogénures métalliques, on produit de nouveaux complexes métalliques appelés non métallocènes, lesquels peuvent être, après avoir été intégrés dans un système catalyseur, utilisés dans la polymérisation d'oléfines.
EP02716780A 2001-02-17 2002-02-15 Non-metallocenes, leur procede de production et leur utilisation dans la polymerisation d'olefines Withdrawn EP1373283A1 (fr)

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DE10107524 2001-02-17
DE10107524 2001-02-17
PCT/EP2002/001612 WO2002066486A1 (fr) 2001-02-17 2002-02-15 Non-metallocenes, leur procede de production et leur utilisation dans la polymerisation d'olefines

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US7041856B2 (en) * 2001-10-23 2006-05-09 Sumitomo Chemical Company, Limited Coupling catalyst and process using the same
CN100351014C (zh) * 2004-07-29 2007-11-28 中国石油化工股份有限公司 一种非茂金属催化剂及其制备方法
GB0420396D0 (en) 2004-09-14 2004-10-13 Bp Chem Int Ltd Polyolefins
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
US8877672B2 (en) 2013-01-29 2014-11-04 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
CN109485760A (zh) * 2017-09-11 2019-03-19 中国石油化工股份有限公司 负载型非茂金属催化剂、其制备方法及其应用

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DE2261455A1 (de) * 1972-12-15 1974-06-20 Bayer Ag Insektizide und akarizide mittel
CA2241812A1 (fr) * 1995-09-28 1997-04-03 Cornelia Fritze Systeme de catalyseur avec support, processus de preparation et utilisation pour la polymerisation des olefines
JPH09220476A (ja) * 1996-02-16 1997-08-26 Ube Ind Ltd 新規遷移金属化合物及びオレフィン重合用触媒
DE19606167A1 (de) * 1996-02-20 1997-08-21 Basf Ag Geträgerte Katalysatorsysteme
DE19622207A1 (de) * 1996-06-03 1997-12-04 Hoechst Ag Chemische Verbindung
US6217164B1 (en) * 1997-12-09 2001-04-17 Brother Kogyo Kabushiki Kaisha Ink jet recorder
US6180552B1 (en) * 1999-04-07 2001-01-30 Equistar Chemicals, L.P. Transition metal complexes containing neutral, multidentate azacyclic ligands
DE60011286T2 (de) * 1999-11-15 2005-07-14 Therasense, Inc., Alameda Übergangsmetall-komplexverbindungen mit einer bidentaten ligande mit einem imidazol-ring

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