EP1175424A1 - Compose chimique, procede permettant de le preparer et son utilisation dans un systeme catalytique pour preparer des polyolefines - Google Patents

Compose chimique, procede permettant de le preparer et son utilisation dans un systeme catalytique pour preparer des polyolefines

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Publication number
EP1175424A1
EP1175424A1 EP00920700A EP00920700A EP1175424A1 EP 1175424 A1 EP1175424 A1 EP 1175424A1 EP 00920700 A EP00920700 A EP 00920700A EP 00920700 A EP00920700 A EP 00920700A EP 1175424 A1 EP1175424 A1 EP 1175424A1
Authority
EP
European Patent Office
Prior art keywords
methyl
indenyl
zirconium dichloride
phenyl
dichloride dimethylsilanediyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00920700A
Other languages
German (de)
English (en)
Inventor
Jörg SCHOTTEK
Patricia Becker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Basell Polyolefine GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basell Polyolefine GmbH filed Critical Basell Polyolefine GmbH
Publication of EP1175424A1 publication Critical patent/EP1175424A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/062—Al linked exclusively to C
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention describes a chemical compound which has a neutral structure.
  • this can form a new catalyst system which is advantageously used for the polymerization of olefins.
  • aluminum oxane such as methyl aluminum oxane (MAO) as a cocatalyst can be dispensed with and a high catalyst activity can nevertheless be achieved.
  • MAO methyl aluminum oxane
  • MAO as the most effective cocatalyst to date has the disadvantage of being used in a large excess, which leads to a high undesirable aluminum content in the polymer.
  • EP-A-0 427 697 claims this synthesis principle and a corresponding catalyst system consisting of a neutral metallocene species (eg Cp 2 ZrMe), a Lewis acid (eg B (C 6 F 5 ) 3 ) and aluminum alkyls .
  • a process for the preparation of salts of the general form LMX + XA ⁇ according to the principle described above is disclosed in EP-A-0 520 732.
  • the task was therefore to find a chemical compound with a low tendency to coordinate, which avoids the disadvantages of the prior art and nevertheless enables high polymerization activities.
  • the present invention thus relates to a chemical compound, a process for its preparation and its use in a catalyst system for the production of polyolefins. Furthermore, it relates to a catalyst system containing at least one chemical compound according to the invention as a cocatalyst.
  • R 1 , R 2 are the same or different and a hydrogen atom, a halogen atom, a boron-free -CC-carbon-containing
  • Group such as C 1 -C 2 n-alkyl, C 1 -C 2 o-haloalkyl, C 1 -C 10 alkoxy, C 6 -C 20 aryl, C 5 -C 20 haloaryl, C 6 -C 0 aryloxy , C 7 -C o-arylalkyl, C 7 -C 4 o-haloarylalkyl, C -C 4 o -alkylaryl, C 7 -C 4 o -haloalkylaryl or an Si (R 4 ) 3 group,
  • R 4 is a boron-free -CC 4 o-carbon-containing group such as -C-C 2 o-alkyl, -C-C 2 o-haloalkyl, -C-C ⁇ o-alkoxy, C 6 -C 2 o-aryl, C 5 -C 2 o haloaryl, C 6 -C 20 aryloxy, C 7 -C 4 may be o _ o-haloalkylaryl arylalkyl, C 7 -C 4 o-Halogenarylalky, C 7 -C 40 -alkylaryl, C 7 -C 4,
  • R3 can be identical to or different from R 1 and R 2 , a hydrogen atom, a halogen atom, a C 4 -C 4 -carbon-containing group such as CC ⁇ alkyl, C 1 -C 2 o-haloalkyl, C 1 -C 8 alkoxy, C 6 - C 20 aryl, C 6 -C 0 haloaryl, C 6 -C 20 -Ary- loxy, C 7 -C 4 o ⁇ arylalkyl, C -C 4 o-Halogenarylalky, C 7 -C 4 o ⁇ alkylene laryl , C 7 -C 4 o-haloalkylaryl or an OSi (R 4 ) 3 group,
  • X identically or differently denotes an element from group IV, V or Via of the periodic table of the elements or an NH group
  • M 1 is an element of the purple group of the Periodic Table of the Elements and
  • k is a natural number from 1 to 100 and
  • the index k is the result of Lewis acid-base interactions of the chemical compound according to the invention, these mutually forming dimers, trimers or higher oligomers.
  • Compounds in which X is an oxygen atom or an NH group are particularly preferred.
  • R 1 and R 2 are particularly preferably a boron-free C 1 -C 40 hydrocarbon radical which can be halogenated, preferably perhalogenated, with halogen such as fluorine, chlorine, bromine or iodine, in particular a halogenated, in particular perhalogenated C 1 -C 3 o-alkyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated C ⁇ -C o-aryl group such as pentafluorophenyl, 2, 4, 6-trifluorophenyl, heptachloronaphtyl, heptafluoronaphthyl, heptafluorotolyl, 3-heptafluorotolyl , 5-bis (trifluoromethyl) phenyl-, 2, 4, 6-tris (trifluoromethyl-phenyl, nonafluorobiphen
  • R 1 and R 2 are radicals such as phenyl, naphthyl, anisyl, Methyl, ethyl, isopropyl, butyl, tolyl, biphenyl or 2, 3-dimethylphenyl, with R 1 and R 2 particularly preferably the radicals pentafluorophenyl, phenyl, biphenyl, bisphenylmethylene, 3 , 5-bis (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, nonafluorobiphenyl, bis (pe ntafluorophenyDmethylene and 4-methylphenyl.
  • R 1 and R 2 particularly preferably the radicals pentafluorophenyl, phenyl, biphenyl, bisphenylmethylene, 3 , 5-bis (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, nonafluorobiphenyl, bis (pe ntafluoroph
  • R 3 is particularly preferably a boron-free C 1 -C 4 -hydrocarbon residue which can be halogenated, preferably perhalogenated, with halogen such as fluorine, chlorine, bromine or iodine, in particular a halogenated, in particular perhalogenated C 3 -C 3 o- Alkyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated C 6 -C 3 o-aryl group such as pentafluorophenyl, 2, 4, 6-trifluorophenyl, heptachloronaphtyl, heptafluoronaphthyl, heptafluorotolyl, 3 , 5-bis (trifluoromethyl) phenyl-, 2, 4, 6-tris (trifluoromethyl-phenyl, nonafluorobiphenyl- or 4- (tri
  • R 3 are radicals such as phenyl, naphthyl, anisyl, methyl, Ethyl, isopropyl, butyl, tolyl, biphenyl or 2, 3-dimethyl-phen yl.
  • Particularly preferred for R 3 are methyl, ethyl, isopropyl, butyl-pentafluorophenyl, phenyl, biphenyl, Bisphenylmethylene, 3,5-bis (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, nonafluorobiphen yl-, bis (penta-fluorophenyDmethylene and 4-methyl-phenyl.
  • Non-limiting examples to illustrate the formula I can also be non-fluorinated):
  • the compounds of the formula (I) according to the invention are prepared from organoaluminum or organoboron compounds of the formula (II).
  • R 5 is a hydrogen atom or a boron-free C ⁇ -C 4 o carbon-containing group such as C ⁇ -C n-alkyl, Cg-C o-aryl, C 7 -C 4 o-arylalkyl, C -C 4 o-alkylaryl or halogen atom can be,
  • Y is boron or aluminum.
  • Nonlimiting examples of the preferred compounds of formula (II) are:
  • Trimethyl aluminum triethyl aluminum, triisobutyl aluminum, tri-hexyl aluminum,
  • Trioctyl aluminum tri-n-butyl aluminum, tri-n-propyl aluminum, triisoprene aluminum,
  • the compound of the formula (I) according to the invention is prepared by reacting the compound of the formula (II) with compounds of the formula (III).
  • R 1 and R 2 have the meaning described under formula (I),
  • X is an oxygen, sulfur or an NH group, preferably oxygen or an NH group
  • R 6 is hydrogen, -CC 4 o-carbon-containing group or a p-toluenesulfonic acid radical.
  • Non-limiting examples of the compound of formula (III) are:
  • Pentaflourophenol phenol, bis (pentafluorophenyl) carbinol, bis (phenyl) carbinol, pentafluoroaniline, tris (pentaflourophenyl) silanol, bis (nonafluorodiphenyl) carbinol, tris (nonafluorodi - phenyl) silanol, nonafluorophenyl, nonafluorodiphenyl, nonafluorodiphenyl phenyl) silanol, 3,5 bis (trifluoromethyl) aniline, 3,5 bis (trifluoromethyl) phenol, bis (2, 3, 4 trifluorophenyl) carbinol, bis (3, 5 trifluoromethylphenyl) carbinol, 2, 3, 4, Trifluorophenol, 2, 3, 4, trifluoroaniline, tris (2, 3, 4 trifluorophenyl) silanol, 2, 4, 6 trifluoroaniline, 2,
  • one or more compounds of the formula (II) are placed in a reaction vessel.
  • the compounds can either be dissolved or suspended in a solvent, or else be in bulk.
  • Aliphatic or aromatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decanoate, petreleomether, toluene, benzene, o-xylene serve as solvents.
  • One or more compounds of the formula (II) are initially introduced at temperatures between -100 ° C. and 300 ° C.
  • one or more compounds of the formula (III) are added. These can also be dissolved or suspended in a solvent, but can also be in substance.
  • the solvents already described above are used as solvents, preferably the same solvent is used.
  • the addition takes place over a period of 1 minute to 96 hours. An addition time of 10 minutes to 8 hours is preferred.
  • the temperature of the sample is between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 100 ° C are preferred. Temperatures between -80 ° C and 40 ° C are particularly preferred.
  • the temperature is chosen so that at least one reactant is in the liquid phase. Furthermore, the reaction is carried out at normal pressure.
  • cooling is carried out with an intensive cooler, which is optionally operated with refrigerants.
  • the reaction temperature is between -100 ° C and 200 ° C.
  • a reaction temperature between -80 ° C and 150 ° C is preferred.
  • a reaction temperature between -80 ° C and 40 ° C is particularly preferred.
  • At least one reactant is preferably in the liquid phase.
  • the reaction time is between 1 minute and up to 96 hours. A reaction time of 10 minutes to 8 hours is preferred.
  • the resulting compounds of formula (I) can be obtained in step B) using known technologies such as e.g. Distillation, recrystallization, extraction or sublimation can be isolated.
  • the chemical compounds of formula (I) according to the invention can be used together with an organometallic transition compound as a catalyst system, which is also the subject of the present invention.
  • Metallocene compounds for example, are used as the organometallic transition compound.
  • These can be, for example, bridged or unbridged biscyclopentadienyl complexes, as described, for example, in EP-A-0 129 368, EP-A-0 561 479, EP-A-0 545 304 and EP-A-0 576 970, monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes, which are described, for example, in EP-A-0 416 815, multinuclear cyclopentadienyl complexes, as described for example in EP-A-0 632 063, ⁇ -ligand-substituted tetrahydropentalenes, as described for example in EP-A-0 659 758 or ⁇ -
  • Organometallic compounds can also be used in which the complexing ligand contains no cyclopentadienyl ligand. Examples of this are diamine complexes of III. And IV. Subgroup of the Periodic Table of the Elements, as described, for example, in DH McConville, et al, Macromolecules, 1996, 29, 5241 and DH McConville, et al, J. Am. Chem. Soc, 1996, 118, 10008. In addition, diimine complexes of subgroup VIII of the Periodic Table of the Elements (for example Ni 2+ or Pd 2+ complexes), as described by Brookhart et al, J. Am. Chem. Soc. 1995, 117, 6414 and, Brookhart et al, J.
  • Preferred metallocene compounds are unbridged or bridged compounds of the formula (IV), R 0 ,
  • M is a metal of III., IV., V. or VI.
  • Subgroup of the periodic system of the elements is, in particular Ti, Zr or
  • R 10 are the same or different and are a hydrogen atom or Si (R 12 ) 3 , in which R 12 is the same or different a hydrogen atom or a C 1 -C 4 o -carbon-containing group, preferably C 1 -C 20 alkyl, C 1 -C 2 -o -Fluoroalkyl, -C-C ⁇ o-alkoxy, C ⁇ -C 2 o-aryl, C 6 -C ⁇ 0 -Fluoroaryl, C 6 -C ⁇ o-aryloxy, C 2 -C ⁇ 0 -alkenyl, C -C 4 o-arylalkyl , C 7 -C 4 o -arylaryl or Cs-C 4 o-arylalkenyl, or R 10 is a C 1 -C 30 - carbon-containing group, preferably C 1 -C 25 -alkyl, such as methyl, ethyl, tert-butyl
  • R 11 are the same or different and are a hydrogen atom or Si (R 12 ) 3 , in which R 12, identical or different, is a hydrogen atom or a C 1 -C 4 o -carbon-containing group, preferably C 1 -C o -alkyl, C ⁇ -C ⁇ o- fluoroalkyl, Ci-CiRj-alkoxy, Cs-C ⁇ 4 aryl, Cg-Cio-fluoroaryl, C 6 ⁇ C ⁇ o-aryloxy, C -C ⁇ o-nyl alkenyl, C 7 -C 4 o-arylalkyl, C 4 -C o Alkylaryl or Cs-C 4 o-arylalkenyl, or R 11 is a C 1 -C 30 carbon-containing group, preferably C 1 -C 25 -alkyl, such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C
  • radicals R 11 can be linked to one another in such a way that the radicals R 11 and the atoms of the cyclopentadienyl ring connecting them form a C 4 -C 4 ring system, which in turn can be substituted,
  • L 1 can be the same or different and a hydrogen atom, a -C-C ⁇ o-hydrocarbon group such as C ⁇ -C ⁇ o-alkyl or Cg-Cio-aryl, a halogen atom, or OR 16 , SR 16 , OSi (R 16 ) 3 , Si (R 16 ) 3 , P (R 16 ) 2 or N (R 16 ) mean in which
  • R 16 is a halogen atom, a C 3 -C 10 alkyl group, a halogenated C 1 -C 10 alkyl group, a C 6 -C 20 aryl group or a halogenated C 6 -Co aryl group, or L 1 is a toluenesulfonyl, trifluoroacetyl, , Trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group,
  • o 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 13 R 14 , in which M 2 is carbon, silicon, germanium or tin and R 13 and R 14 are identical or different to a C 1 -C 8 -hydrocarbon-containing group such as C ⁇ -C ⁇ o-alkyl , C 6 -C 4 aryl or trimethylsilyl mean.
  • 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, (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 4 ) 2 .
  • Z can also form a mono- or polycyclic ring system with one or more radicals R 10 and / or R 11 .
  • Chiral bridged metallocene compounds of the formula (IV) are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted so that they represent an indenyl ring.
  • the indenyl ring is preferably substituted, in particular in 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 or 2, 4, 5, 6-position, with -C ⁇ Co-carbon-containing groups, such as Ci-Cirj-alkyl or C 5 -C 2 o-aryl, where two or more substituents of the indenyl ring together can form a ring system.
  • Chiral bridged metallocene compounds of the formula (IV) can be used as pure racemic or pure meso compounds. Mixtures of a racemic compound and a meso compound can also be used.
  • metallocene compounds examples are:
  • zirconium dichloride meanings
  • Zirconium monochloro mono neopentyl has examples of the metallocenes according to the invention.
  • corresponding zirconium dimethyl compounds the corresponding zirconium- 4- butadiene compounds, and the corresponding compounds with 1, 2- (1-methyl-ethanediyl) -, 1,2- (1, 1-dimethyl) -ethanediyl) - and 1, 2 (1, 2-dimethyl-ethanediyl) bridge.
  • one or more compounds of the formulas (I) can be reacted with an organometallic transition compound of the formula (IV) in any stoichiometric ratio.
  • the catalyst system according to the invention can additionally contain an aluminum compound of the formula (V)
  • the radicals R 20 in formula (V) may be the same or different and are a halogen atom, a hydrogen atom, a C ⁇ -C 4 o-carbon ⁇ containing group, preferably C ⁇ -C2o ⁇ alkyl, C ⁇ -C rj haloalkyl, C 6 -C o-aryl, C 6 -C o-haloaryl, C 7 -C 4 o-arylalkyl, C 7 -C 4 o-haloarylalkyl, C 7 -C 4 o ⁇ alkylaryl or C 7 -C 4 o -Halogenalkylaryl mean.
  • R 20 are Ci-C ⁇ -alkyl groups, particularly preferred for R 20 are -CC 4 alkyl groups.
  • the compound of formula (V) can be added in any stoichiometric ratio.
  • a molar ratio B: M between the compounds of the formulas (I) and the formula (IV) of 0.01 to 10,000 is used in the preparation of the catalyst system according to the invention.
  • a molar ratio of 0.1 to 1000 is preferred, very particularly preferably a molar ratio of 1 to 100 is used.
  • a compound of formula (V) in an Al: M molar ratio of from 0.01 to 10,000 can also be added.
  • a molar ratio of 0.1 to 1000 is preferred, and a molar ratio of 1 to 100 is very particularly preferably used.
  • the connections can be brought into contact with one another in any conceivable combination.
  • One possible procedure is that an organic transition metal compound of the formula (IV) is dissolved or suspended in an aliphatic or aromatic solvent.
  • a compound of the formula (V) is then added in dissolved or in suspended form.
  • the reaction time is between 1 minute and 24 hours, with a reaction time between 5 minutes and 120 minutes being preferred.
  • the reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C being preferred.
  • An organoboron compound of the formula (I) is then added either in bulk or in dissolved or suspended form.
  • the reaction time is between 1 minute and 24 hours, with a reaction time between 5 minutes and 120 minutes being preferred.
  • the reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C being preferred.
  • the individual components can also be added to the polymerization kettle one after the other in any order.
  • the catalyst systems according to the invention can also be used in supported form.
  • 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 groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements.
  • oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the two elements and corresponding oxide mixtures.
  • Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, Zr0 2 , Ti0 or B 2 0, 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 (e.g. 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 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 120 ° C, preferably between 50 ° C 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 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 from adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.
  • polyolefin powders e.g. polyethylene, polypropylene or polystyrene
  • the catalyst systems according to the invention can be brought into contact with the support in any conceivable combination.
  • a conceivable variant is that an organometallic compound of the formula IV is placed in an aliphatic or aromatic solvent such as toluene, heptane, tetrahydrofuran or diethyl ether. Then one or more compounds of the formula (V) are added either in bulk or in dissolved form.
  • the reaction time is between 1 minute and 24 hours, with a reaction time between 5 minutes and 120 minutes being preferred.
  • the reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C being preferred.
  • one or more compounds of the formula (I) are added either in bulk or in dissolved form.
  • reaction time is between 1 minute and 24 hours, a reaction time between 5 minutes and 120 minutes being preferred.
  • the reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C being preferred. All starting materials can be used in any stoichiometric ratio.
  • a molar ratio ADM 1 between the compounds of the formula (V) and the formula (IV) of 0.1 to 10000 is preferred, and a molar ratio of 1 to 100 is very particularly preferably used.
  • a molar ratio B: M1 between the compounds of the formula (I) and the formula (IV) of 0.1 to 1000 is preferred; a molar ratio of 1 to 100 is very particularly preferably used.
  • the preparation thus obtained is then mixed with the dehydrated or rendered inert carrier material, the solvent is removed and the resulting supported metallocene catalyst system is dried to ensure that the solvent is completely dig or for the most part is removed from the pores of the carrier material.
  • the supported catalyst is obtained as a free-flowing powder.
  • 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, comprising at least one transition metal component of the formula (IV).
  • polymerisation is understood to mean homopolymerization as well as copolymerization.
  • olefins examples include I-01efins with 2 - 40, preferably 2 to 10 carbon atoms, such as ethene, propene, 1-butene,
  • propene or ethene are preferably homopolymerized, or
  • 1-olefins with 4 to 20 C atoms such as hexene
  • dienes with 4 to 20 C atoms such as 1, 4-butadiene, norbornadiene, ethylidene - copolymerized norbones or ethyl norbornadiene.
  • Examples of such copolymers are ethene / propene copolymers or ethene / pro-
  • the polymerization is carried out at a temperature of from -60 ° C. to 300 ° C., preferably from 50 ° C. to 200 ° C., very particularly preferably from 50 ° C. to 80 ° C.
  • the pressure is 0.5 to 2000 bar, preferably 5 to 35 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 5 I. to III.
  • Main group of the periodic table such as an aluminum, magnesium or lithium alkyl or an aluminoxane can be used.
  • the alkyl compound is the monomer or Sus- added pensionsstoff and serves to purify the monomer of substances that 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.
  • 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.
  • the isotactic polypropylene which has been produced with the catalyst system according to the invention, is characterized by a proportion of 2-1-inserted propene units RI ⁇ 0.5% with a triad tacticity TT> 98.0% and a melting point> 156 ° C, where M w / M n of the polypropylene according to the invention is between 2.5 and 3.5.
  • copolymers which can be prepared using the catalyst system according to the invention are distinguished by a significantly higher molar mass compared to the prior art. At the same time, such copolymers can be produced with high productivity and technically relevant process parameters without the formation of deposits by using the catalyst system according to the invention.
  • the polymers produced by the process according to the invention are particularly suitable for producing tear-resistant, hard and rigid moldings such as fibers, filaments, injection molded parts, foils, sheets or large hollow bodies (e.g. pipes).
  • Example 6 Synthesis of bis (nonanfluorodiphenyloxy) methyalan 5 (6) 5.0 ml of trimethyl aluminum (2.1 M in Exxol, 10.5 mmol) are placed in 40 ml of toluene and cooled to -40 ° C. 7.0 g (21.0 mmol) of nonafluorodiphenyl-1-ol in 40 ml of toluene are added dropwise to this solution over a period of 40 minutes. The mixture is stirred at -40 ° C. for 30 minutes and then the reaction solution is allowed to warm to room temperature. The mixture is stirred for one hour at room temperature. The slightly cloudy solution is filtered off via a G4 frit. The result is a clear solution (0.13 M based on Al) of bis (nonanfluorodiphenyloxy) methyalane.
  • a dry 16 dm 3 reactor is first flushed with nitrogen and then with propylene and filled with 10 dm 3 of liquid propene. Then 0.5 cm 3 of a 20% tri-0-sobutylaluminum solution in Varsol diluted with 30 cm 3 Exxol were added to the reactor and the mixture was stirred at 30 ° C. for 15 minutes. The catalyst suspension was then added to the reactor. The reaction mixture was heated to the polymerization temperature of 60 ° C. (4 ° C./min) and the polymerization system lh 5 was kept at 60 ° C. by cooling. The polymerisation was stopped tion by exhausting the remaining porpylene. The polymer was dried in an oven.

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

Abstract

L'invention concerne un composé chimique de structure neutre, qui peut former un nouveau système catalytique lorsqu'il est combiné à un composé organométallique. Ledit système catalytique s'utilise avantageusement pour polymériser des oléfines. L'invention permet de ne plus faire appel à l'utilisation d'oxane d'aluminium du type de l'oxane d'aluminium méthylique (MAO) comme cocatalyseur, tout en parvenant à une activité catalytique élevée.
EP00920700A 1999-04-21 2000-04-13 Compose chimique, procede permettant de le preparer et son utilisation dans un systeme catalytique pour preparer des polyolefines Withdrawn EP1175424A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1999117984 DE19917984A1 (de) 1999-04-21 1999-04-21 Chemische Verbindung, Verfahren zu deren Herstellung und deren Verwendung in Katalysatorsystem zur Herstellung von Polyolefinen
DE19917984 1999-04-21
PCT/EP2000/003315 WO2000064906A1 (fr) 1999-04-21 2000-04-13 Compose chimique, procede permettant de le preparer et son utilisation dans un systeme catalytique pour preparer des polyolefines

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EP1175424A1 true EP1175424A1 (fr) 2002-01-30

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EP (1) EP1175424A1 (fr)
JP (1) JP2002543082A (fr)
AU (1) AU4118100A (fr)
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WO (1) WO2000064906A1 (fr)

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SG74749A1 (en) * 1998-09-09 2000-08-22 Sumitomo Chemical Co Modified aluminium oxy compound polymerization catalyst and process for producing olefin polymer and alkenyl aromatic hydrocaron polymer
DE10025412A1 (de) 2000-05-24 2001-11-29 Basell Polypropylen Gmbh Als Cokatalysator geeignete chemische Produkte, Verfahren zu ihrer Herstellung und ihre Verwendung in Katalysatorsystemen zur Herstellung von Polyolefinen
AU2003257456A1 (en) 2002-07-15 2004-02-02 Basell Polyolefine Gmbh Preparation of supported catalyst systems
GB0520085D0 (en) * 2005-10-03 2005-11-09 Sasol Tech Pty Ltd Oligomerisation of olefinic compounds in the presence of an oligomerisation catalyst, and a catalyst activator including a halogenated -AR group
FR2986717B1 (fr) 2012-02-10 2014-08-08 IFP Energies Nouvelles Composition catalytique et procede d'oligomerisation des olefines utilisant ladite composition catalytique

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DE69114087T2 (de) * 1990-08-21 1996-04-11 Nippon Oil Co Ltd Polyolefine.
JPH04323204A (ja) * 1991-04-22 1992-11-12 Kansai Paint Co Ltd リビング重合体の製造方法
BE1007698A3 (fr) * 1993-11-04 1995-10-03 Solvay Systeme catalytique utilisable pour la polymerisation des alpha-olefines et procede pour cette polymerisation.
JPH07173223A (ja) * 1993-12-21 1995-07-11 Tokuyama Corp 低立体規則性ポリプロピレンの製造方法
US5908903A (en) * 1995-12-27 1999-06-01 Basf Aktiengesellschaft Metallocene catalyst systems containing lewis bases
JP3537248B2 (ja) * 1996-01-24 2004-06-14 出光興産株式会社 オレフィン重合用触媒及びそれを用いたオレフィン系重合体の製造方法
JPH09255710A (ja) * 1996-03-27 1997-09-30 Mitsui Petrochem Ind Ltd オレフィン重合用触媒およびオレフィンの重合方法
JP3761670B2 (ja) * 1997-05-20 2006-03-29 住友化学株式会社 アルミニウム化合物、オレフィン重合用触媒およびオレフィン重合体の製造方法
FR2769245B1 (fr) * 1997-10-02 1999-10-29 Atochem Elf Sa Support solide activateur des catalyseurs metallocenes en polymerisation des olefines, son procede de preparation, systeme catalytique et procede de polymerisation correspondants
CA2235175A1 (fr) * 1998-04-17 1999-10-17 Bayer Inc. Processus de polymerisation olefinique et systeme catalyseur connexe

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WO2000064906A1 (fr) 2000-11-02
AU4118100A (en) 2000-11-10
DE19917984A1 (de) 2000-11-09

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