EP1368385A1 - Compose de metal de transition utilise comme constituant de catalyseur et son utilisation pour produire des polyolefines - Google Patents

Compose de metal de transition utilise comme constituant de catalyseur et son utilisation pour produire des polyolefines

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Publication number
EP1368385A1
EP1368385A1 EP02716778A EP02716778A EP1368385A1 EP 1368385 A1 EP1368385 A1 EP 1368385A1 EP 02716778 A EP02716778 A EP 02716778A EP 02716778 A EP02716778 A EP 02716778A EP 1368385 A1 EP1368385 A1 EP 1368385A1
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EP
European Patent Office
Prior art keywords
aryl
alkyl
group
radicals
fluorine
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EP02716778A
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German (de)
English (en)
Inventor
Jörg SCHOTTEK
Jörg SCHULTE
Cornelia Fritze
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Celanese Ventures GmbH
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Celanese Ventures GmbH
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Publication of EP1368385A1 publication Critical patent/EP1368385A1/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

Definitions

  • the present invention relates to transition metal compounds (non-metallocenes) containing oxazoline groups in the ligand system as a catalyst component for the polymerization of olefins and to processes for their preparation and use in the polymerization of olefins.
  • metallocenes in particular have been used for olefin polymerization in order to produce polyolefins with new property profiles.
  • Metallocenes can be used in combination with one or more cocatalysts as a catalyst component for the polymerization and copolymerization of olefins.
  • the often multi-stage synthesis and use of metallocenes still represents a significant cost factor today.
  • WO 96/23010 describes transition metal complexes containing diimine groups as ligands, their preparation and their use in olefin polymerization.
  • WO 00/69923 discloses individual organometallic complexes which, however, are not the subject of the present invention.
  • EP-A0942010 describes further transition metal complexes containing oxazoline derivatives as ligands and their use in the polymerization of olefins
  • non-metallocene complexes described in the literature are not always distinguished by an outstanding polymerization activity and, in particular, it has not yet been possible to produce isotactic polypropylene with sufficient tacticity. It was therefore the task of synthesizing new transition metal complexes which are simple and inexpensive to produce and which show high polymerization activity and stereo- and regioselectivity in the polymerization of olefins.
  • ligand structures can be built up from substituted or unsubstituted oxazoline derivatives, which can react by reaction with a transition metal compound to form a transition metal complex which is suitable for the polymerization of olefins.
  • the present invention relates to the use of compounds of the formula (I)
  • M 1 is a metal from the group of the elements Ti, Zr, Hf, Ni, V, W, Mn, Rh, Ir, Cu, Co, Fe, Pd, Sc, Cr and Nb
  • R 1 , R 2 are in each case identical or different, are a hydrogen atom, or are Si (R 12 ) 3 , in which R 12 in each case are, identically or differently, a hydrogen atom or a group containing C 1 -C 0 -carbon, in particular CrC 20 -alkyl, Cio-fluoroalkyl, Ci-Cio-alkoxy, C 6 -C 20 aryl, C 6 -C ⁇ 0 fluoroaryl, C 6 -C 10 aryloxy, C 2 -C ⁇ 0 alkenyl, C 7 -C 40 arylalkyl, C 7 -C 0 alkylaryl or C 8 -C 0 arylalkenyl, or R 1 , R 2 are in each case identical or different, a Ci-Cso - carbon-containing group, in particular C 1 -C 25 -alkyl, particularly preferably methyl, ethyl , n-propyl, i-prop
  • X can be the same or different and a hydrogen atom, a C 1 -C 1 0 carbon-containing group, in particular CrCio-alkyl or C 6 -C ⁇ 0 aryl, a halogen atom or OR 9 , SR 9 , OSi (R 9 ) 3 , Si (R 9) mean 3) P (R 9) 2 or N (R 9) 2, wherein R 9 is a halogen atom, a d-Cio-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 aryl group, or the radicals or the radicals X are a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-triflu
  • Y is an OR 10 , SR 10 , OSi (R 10 ) 3 , Si (R 10 ) 3 , P (R 10 ) 2 or N (R 10 ) 2 , in which the individual R 10 are the same or different.
  • p can be 1, 2, 3 or 4
  • Z is a bridging structural element of the formula M 2 R 13 R, in which M 2 is carbon, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium, boron, aluminum or tin and R 13 and R 14 can be identical or different and a hydrogen atom, a -CC 24 -hydrocarbon-containing group, especially CrC-io-alkyl, particularly preferably methyl, ethyl, n-propyl, i-propyl, tert-butyl, n-hexyl, cyclohexyl or octyl, C 2 -C ⁇ 0 -Alkenyl, C 3 -C 10 alkylalkenyl, C 6 -C 24 aryl, C 5 -C 2 heteroaryl, C 7 -C 2 arylalkyl, C 7 -C 2 alkylaryl, fluorine-containing CrC 2 alkyl, fluorine-containing C 6 -C 2 aryl, fluorin
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , C (C 6 H 5 ) 2 , (C 6 H 4 ) 2 , (C 12 H ⁇ ) 2 , (C 20 H ⁇ 2 ) 2 , NH, N-CH 3 , N- (C S H 5 ), NC 3 H 7 , 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 s H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, (C 6 H 5 ) 2 Ge, (C 6 H 5 ) 2 Sn, (CH 2 ) 4 Si, CH 2 Si (CH 3 ) 2 , oC 6 H 4 , 2,6 bispyridines, or 2,2 ' - (C 6 H) 2 and 1, 2- (methyl -ethanediyl) -, 1,
  • CrC 40 carbon-containing group includes in particular the residues CrC 2 o-alkyl, in particular methyl, ethyl, n-propyl, i-propyl, tert-butyl, n-hexyl, cyclohexyl or Octyl, Ct-C 10 - fluoroalkyl, -C-C ⁇ 0 alkoxy, C 6 -C 20 aryl, C 6 -C 10 fluoroaryl, C 6 -C ⁇ 0 aryloxy, C 2 -C ⁇ 0 - alkenyl, C 7 -C 40 arylalkyl, C 7 -C 4 o-alkylaryl or C 8 -C 40 arylalkenyl understood.
  • C 1 -C 30 - carbon-containing group includes in particular the residues C 1 -C 25 -alkyl, in particular methyl, ethyl, n-propyl, i-propyl, tert-butyl, n-hexyl , Cyclohexyl or octyl, C 2 -C 25 alkenyl, C 3 -C 15 alkylalkenyl, C 6 -C 24 aryl, C 5 -C 24 heteroaryl, C 7 -C 30 arylalkyl, C 7 -C 30 Alkylaryl, fluorine-containing CC 25 alkyl, fluorine-containing C 6 -C 24 aryl, fluorine-containing C -C 30 arylalkyl, fluorine-containing C 7 -C 30 alkylaryl or -CC 12 alkoxy understood.
  • CrC 4 hydrocarbon-containing group includes in particular the residues Ci-Cio-alkyl, in particular methyl, ethyl, n-propyl, i-propyl, tert-butyl, n-hexyl, cyclohexyl or octyl, C 2 -C ⁇ o alkenyl, C 3 -C ⁇ 0 -Alkylalkenyl, C 6 -C 2 aryl, C 5 -C 4 -heteroaryl, C 7 -C 24 - aralkyl, C 7 -C 24 -alkylaryl, fluorinated CrC ⁇ alkyl, fluorine-containing C 6 -C 24 aryl, fluorine-containing C 7 -C 4 arylalkyl, fluorine-containing C 7 -C 24 alkylaryl or -CC 12 alkoxy understood.
  • M 1 is Ni, Pd, Co, Fe, Ti, Zr or Hf,
  • R 1 , R 2 are each the same or different, are a hydrogen atom or Si (R 12 ) 3 , in which R 2 are the same or different a hydrogen atom or a C- ⁇ -C 40 - carbon-containing group, in particular CC 20 alkyl, CrCio- Fluoroalkyl, d-Cio-alkoxy, C 6 -C 2 o-aryl, C 6 -C 10 -fluoroaryl, C 6 -C ⁇ o-aryloxy, C z -C ⁇ 0 -alkenyl, C 7 - C 40 arylalkyl, C 7 -C 4 o-alkylaryl or C 8 -C 4 o-arylalkenyl, or R 1 , R 2 are in each case the same or different, a -C-C 30 - carbon-containing group, in particular CrC 25 -alkyl, particularly preferably methyl, ethyl, n-propyl, i-propy
  • X 1 , X 2 can in each case be the same or different and a hydrogen atom, a C 1 -C 8 -carbon-containing group, in particular C 1 -C 10 -alkyl or C 6 -C 10 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 Ci-C ⁇ alkyl group, a halogenated C ⁇ -C ⁇ 0 alkyl group, a C 6 -C 20 aryl group or a halogenated C 6 -C 20 aryl group, or the radicals X1, X2 are a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl.
  • R 15 each identically or differently represents a hydrogen atom, a C 1 -C 2 -hydrocarbon-containing group, in particular Ci-Cio-alkyl, particularly preferably methyl, ethyl, n-propyl, i-propyl, tert-butyl, n- Hexyl, cyclohexyl or octyl, C 2 -C 10 alkenyl, C 3 -C 0 alkylalkenyl, C 6 -C 2 aryl, C 5 -C 24 heteroaryl, C 7 -C 24 arylalkyl, C 7 -C 24 -alkylaryl, fluorine-containing -C 24 alkyl, fluorine-containing C 6 -C 24 -aryl, fluorine-containing C -C
  • the present invention furthermore relates to catalyst systems for the preparation of polyolefins by polymerizing at least one olefin in the presence of at least one compound of the formula (I).
  • these catalyst systems contain at least one cocatalyst.
  • the cocatalyst which, together with at least one transition metal compound of the formula I, forms the catalyst system contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound which, by reaction with the transition metal compound, converts it into a cationic compound.
  • a compound of general formula IX is preferred as the aluminoxane
  • aluminoxanes can e.g. cyclic as in formula X
  • aluminoxanes are described, for example, in JACS 117 (1995), 6465-74, Organometailics 13 (1994), 2957-2969.
  • the radicals R in the formulas IX, X, XI and XII can be the same or different and a C-
  • 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 hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as, for example, toluene).
  • the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C -] - C20 carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as e.g. Methyl, propyl,
  • Pentachlorophenyl pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5
  • 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 (pentafluorophenyl) borane, tris (tolis), borane 5-dimethylphenyl) borane, tris (3,5-difluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.
  • Protonated Lewis bases such as e.g. Methylamine, aniline, N, N-dimethylbenzylamine and their derivatives, N, N-dimethylcyclohexylamine and their derivatives, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Pyridine, p-bromo-NN-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene or triphenylcarbenium are used.
  • Methylamine, aniline, N, N-dimethylbenzylamine and their derivatives, N, N-dimethylcyclohexylamine and their derivatives dimethylamine, diethylamine
  • 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.
  • Borane or carborane compounds such as e.g.
  • 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.
  • Preferred components of these cocatalyst systems are the compounds of the formulas (A) and (B),
  • R .17 is a hydrogen atom, a halogen atom, a CC 0 carbon-containing
  • R 17 can also be a -OSiR 3 group, in which R is 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 16 is a hydrogen atom or a boron-free C 4 -C 4 -carbon-containing group such as d
  • X 4 is an element of VI , Main group of the Periodic Table of the Elements or an NR group, in which R represents a hydrogen atom or a C 1 -C 2 o
  • Hydrocarbon radical such as -CC 20 alkyl or C 1 -C 20 aryl
  • D is an element of VI.
  • Is hydrocarbon radical such as CrC 20 alkyl or CC 20 aryl
  • f is an integer from 0 to 3
  • g is an integer from 0 to 3
  • z + y are not equal to 0
  • h is an integer from 1 to 10.
  • the elemental organic compounds are combined with an organometallic compound of the formulas IX to XII and or XIII [M 5 R 19 q] [ ⁇ , where M 5 is an element of I., II. And III.
  • M 5 is an element of I., II. And III.
  • Main group of the periodic table of the Elements is, R " I9 is the same or different and is a hydrogen atom, a halogen atom, a C-
  • the organometallic compounds of the formula XIII 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 IX are trimethylaluminium, triethylaluminium, tri-isopropylaluminum, trihexylaluminium, trioctylaluminium, tri-n-butylaluminium, trin-propylaluminium, triisoprenealuminium, dimethylaluminiumalidiumaluminium, dimethylalidiumalidiumalidiumaluminium chloride, diethylaluminium monoalidium chloride, diethyl aluminum diol monomethyl chloride , Diethyl aluminum hydride, diisopropyl aluminum hydride, dimethyl aluminum (trimethylsiloxide), dimethyl aluminum (triethylsiloxide), phenylalane, pentafluorophenylalane and o-tolyla
  • EP-A-811627, WO97 / 11775 and DE-A-19606167 to use compounds.
  • the carrier component of the catalyst system 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 groups 2,3,4,5,13,14,15 and 16 of the periodic table of the elements.
  • preferred oxides as carriers include silicon dioxide, aluminum oxide and mixed oxides of the elements calcium,
  • 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 2 / 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.
  • Dehydration or drying of the carrier material is also possible chemically by reacting the adsorbed water and the hydroxyl groups on the surface with suitable inerting agents.
  • suitable inerting agents As a result of the reaction with the inerting reagent, the hydroxyl groups can be completely or partially converted into a form which does not lead to any negative interaction with the catalytically active centers.
  • 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 trimethylaluminium, triethylaluminium, triisobutylaluminum, Triethylborane, dibutylmagnesium.
  • the chemical dehydration or inertization of the carrier material takes place, for example, by reacting a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent with exclusion of air and moisture.
  • 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 20 ° 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
  • the supported catalyst system In order to prepare 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, a soluble reaction product, an adduct or a mixture preferably being obtained. The preparation thus obtained is then mixed with the dehydrated or inertized carrier material, the solvent is removed and the resulting supported catalyst system is 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 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 the formula (I) and at least one cocatalyst in a suitable solvent or
  • Suspending agents b) applying the mixture obtained from step a) to a porous, preferably inorganic, dehydrated support, c) removing the main proportion of solvent from the resulting mixture d) isolating the supported catalyst system e) optionally prepolymerizing the obtained supported catalyst system with one or more olefinic ones Monomer (s) to obtain a prepolymerized supported catalyst system.
  • Preferred solvents in step a) are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve.
  • the solubility of the individual components is not a requirement if it is ensured that the reaction product of the compound of the formula (I) and cocatalyst is soluble in the solvent selected.
  • 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.
  • the amounts of aluminoxane and compound of the formula (I) used in the preparation of the supported catalyst system can be varied over a wide range.
  • a molar ratio of aluminum to the transition metal in the compound of the formula (I) of 10: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 50: 1 to 500: 1.
  • 30% strength is preferred toluene solutions used; the use of 10% solutions is also possible.
  • 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 the formula (I) 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). In individual cases, the use of higher temperatures can shorten the required preactivation time and cause an additional increase in activity. In this case, a higher temperature means a range between 50 and 100 C.
  • the preactivated solution or the mixture is then combined with an inert carrier 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 non-metallocene cocatalyst solution or the non-metallocene cocatalyst mixture can be metered into the support material provided, or the support material can be introduced into the solution provided.
  • the volume of the preactivated solution or of the non-metallocene 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 non-metallocene 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 washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
  • the supported catalyst system shown can either be used directly for the polymerization of olefins or before being used in one Polymerization process are prepolymerized with one or more olefinic monomers.
  • 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 non-metallocene component is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
  • the catalyst systems represented by the process according to the invention are particularly suitable for producing a polyolefin by polymerizing one or more olefins.
  • 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 norbomadiene and cyclic olefins such as norbomene, tetracyclododecene or methyl norbornene.
  • propene or ethene is preferably homopolymerized, or propene with ethene and / or with one or more 1-olefins having 4 to 20 C atoms, such as butene hexene or vinylcyclohexane, and / or one or more dienes having 4 to 20 C -Atoms, such as 1,4-butadiene, norbornadiene, ethylidene norbones or ethyl norbomadiene, copolymerized.
  • Examples of such copolymers are ethene / propene copolymers 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 - 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 can be used as the only catalyst component for the polymerization of olefins having 2 to 20 C atoms, or preferably in combination with at least one alkyl compound of the elements from the 1st to 111th main group of the periodic table, such as 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.
  • 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.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne des composés de métal de transition (non métallocènes) contenant des groupes oxazoline dans le système de ligand, utilisés comme constituants de catalyseur dans la polymérisation d'oléfines, ainsi que leur utilisation dans la polymérisation d'oléfines.
EP02716778A 2001-02-17 2002-02-15 Compose de metal de transition utilise comme constituant de catalyseur et son utilisation pour produire des polyolefines Withdrawn EP1368385A1 (fr)

Applications Claiming Priority (3)

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DE10107525 2001-02-17
DE10107525 2001-02-17
PCT/EP2002/001602 WO2002066522A1 (fr) 2001-02-17 2002-02-15 Compose de metal de transition utilise comme constituant de catalyseur et son utilisation pour produire des polyolefines

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EP1368385A1 true EP1368385A1 (fr) 2003-12-10

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US (1) US20040133009A1 (fr)
EP (1) EP1368385A1 (fr)
JP (1) JP2004529994A (fr)
CN (1) CN1491235A (fr)
WO (1) WO2002066522A1 (fr)

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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
CN101323650B (zh) * 2007-06-13 2010-11-03 中国石油天然气股份有限公司 一种烯烃聚合催化剂及其制备方法和应用
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