WO2000018773A1 - Compose chimique - Google Patents

Compose chimique Download PDF

Info

Publication number
WO2000018773A1
WO2000018773A1 PCT/EP1999/007056 EP9907056W WO0018773A1 WO 2000018773 A1 WO2000018773 A1 WO 2000018773A1 EP 9907056 W EP9907056 W EP 9907056W WO 0018773 A1 WO0018773 A1 WO 0018773A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
indenyl
zirconium dichloride
dichloride dimethylsilanediyl
phenyl
Prior art date
Application number
PCT/EP1999/007056
Other languages
German (de)
English (en)
Inventor
Hans Bohnen
Patricia Becker
Jörg SCHOTTEK
Original Assignee
Targor 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 Targor Gmbh filed Critical Targor Gmbh
Publication of WO2000018773A1 publication Critical patent/WO2000018773A1/fr

Links

Classifications

    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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) can be dispensed with as a cocatalyst and nevertheless high catalyst activity can be achieved.
  • MAO as the most effective cocatalyst to date has the disadvantage of being used in large excess, which leads to a high undesirable aluminum content in the polymer.
  • EP-A-0 427 697 claims this synthetic principle and a corresponding catalyst system consisting of a neutral metallocene species (eg Cp 2 ZrMe 2 ), 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 and to a method for producing this chemical compound.
  • a catalyst system containing at least one metallocene and at least one chemical compound according to the invention as cocatalyst.
  • the catalyst system can additionally contain a further organometallic compound and can also be fixed on a support material.
  • a process for the production of polyolefins is also described.
  • R 1 , R 2 are the same or different and a hydrogen atom, a halogen atom, a boron-free C 1 -C 4 o-carbon-containing group such as C 1 -C 8 -alkyl.
  • R 3 are the same or different and are a hydrogen atom, a halogen atom, a C 1 -C 4 o -carbon-containing group such as C 1 -C 8 -alkyl, C 1 -C 8 -haloalkyl, C 1 -C 20 alkoxy, C 6 -C 20 aryl , C 6 -C 20 haloaryl, C 6 -C 20 aryloxy, C -C 4 o-arylalkyl, CC 4 o-haloarylalky, C -C 4 o-alkylaryl, C 7 -C 4 o-haloalkylaryl or a CH (SiR 4 ) group means
  • R 4 are the same or different and are a hydrogen atom, a halogen atom, a C 1 -C 4 o -carbon-containing group such as C 1 -C 20 alkyl, C 1 -C 2 o haloalkyl, C 1 -C 10 alkoxy,
  • C 6 -C 20 aryl, C 6 -C 20 haloaryl, C 6 -C 20 aryloxy, C -C 4 o-arylalkyl, C 7 -C o-haloarylalky, C 7 -C 4 o-alkylaryl, C 7 -C o-haloalkylaryl means
  • X identically or differently denotes an element of the group 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.
  • 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.
  • R 1 and R 2 are particularly preferably a boron-free C 1 -C 4 -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 8 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, trifluoromethyl, trifluoromethyl tyDphenyl-, 2, 4, 6-tris (trifluoromethyl) phenyl, nonafluorobiphenyl- or
  • R 1 Also preferred for R 1 are residues such as phenyl, naphthyl, anisyl, methyl, ethyl, iso - propyl, butyl, tolyl, biphenyl, or 2, 3-Dirnethyl-phenyl particularly preferred for R 1, the radicals pentafluorophenyl, phenyl, biphenyl, 3, 5-bis (trifluoromethyl) henyl-, 4- (. trifluoromethyl) phenyl, nonafluorobiphenyl and 4-methylphenyl.
  • residues such as phenyl, naphthyl, anisyl, methyl, ethyl, iso - propyl, butyl, tolyl, biphenyl, or 2, 3-Dirnethyl-phenyl particularly preferred for R 1, the radicals pentafluorophenyl, phenyl, biphenyl, 3, 5-bis (trifluoromethyl) henyl-
  • the compounds of the formula [I) according to the invention are composed of organoboron compounds of the formula (II)
  • R 6 is a hydrogen atom or a boron-free -C-o-carbon-containing group such as -C-C o-alkyl, C 6 -C 2 o-aryl, C -C 4 o-arylalkyl, C 7 -C 4 o-alkylaryl can,
  • R 1 represents the radicals listed under formula (I) and
  • X identically or differently represents an element of the group Via of the Periodic Table of the Elements or an NH group, preferably an oxygen atom or an NH group.
  • the compound of the formula (I) according to the invention is prepared by dehydrating the compound of the formula (II). This can be done by heating, dehydrating reagents and other dehydrating processes. Such methods are known to the person skilled in the art.
  • the chemical compounds of the formula (I) according to the invention can be used together with an organometallic transition compound as a catalyst system.
  • an organometallic transition compound e.g. Metallocene compounds used.
  • This can e.g. 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, polynuclear cyclopentadienyl complexes as described for example in EP-A-0 632 063, ⁇ -ligand-substituted tetrahydropentenes as described for example in EP-A-0 659 758 or ⁇ Ligand-substituted tetrahydro
  • 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, e.g. at D.H. McConville, et al, Macro-molecules, 1996, 29, 5241 and D.H. McConville, et al, J. Am.
  • Preferred metallocene compounds are unbridged or bridged compounds of the formula (III),
  • M is a metal of III., IV., V. or VI. Subgroup of the
  • Periodic table of the elements in particular Ti, Zr or Hf,
  • R 10 are the same or different and are a hydrogen atom or
  • SiR 3 1 in which R 12, identical or different, is a hydrogen atom or a C 4 -C 4 -carbon-containing group, preferably C 1 -C 20 alkyl, C 1 -C 4 fluoroalkyl, C 1 -C 0 alkoxy, C 3 - C o-aryl, C6 _ C ⁇ o-fluoroaryl, C 6 -C ⁇ 0 aryloxy, C 2 -C ⁇ 0 alkenyl, C 7 -C 40 aryl alkyl, C 7 -C 0 alkylaryl or Cs-C o- Arylalkenyl, or R 10 is a C 1 -C 3 carbon-containing group, preferably C 1 -C 5 alkyl, such as methyl, ethyl, tert.
  • R 12 is a hydrogen atom or a C 4 -C 4 -carbon-containing group, preferably C 1 -C 20 alkyl, C 1 -C 4 fluoroalkyl
  • R 11 are the same or different and are a hydrogen atom or SiR 3 12 , in which R 12 is the same or different a hydrogen atom or a -C-C4o ⁇ carbon-containing group, preferably C ⁇ -C 2 o-alkyl, C ⁇ -C 10 - fluoroalkyl, C ⁇ -C ⁇ 0 alkoxy,
  • C6-Ci4-aryl C 6 -C ⁇ 0 fluoroaryl, C 6 -C ⁇ o-aryloxy, C -C ⁇ o-alkenyl, C -C 4 o-arylalkyl, C -C4o ⁇ alkylaryl or Cs-C4o-arylalkenyl, or R 11 a C ⁇ -C 3 o - carbon-containing group, preferably c ⁇ _ C25 _ alkyl, such as methyl, ethyl, tert.
  • L 1 can be the same or different and a hydrogen atom, a C ⁇ -C ⁇ o-hydrocarbon group such as C ⁇ -C ⁇ 0 alkyl or C 6 -C ⁇ 0 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 ) 2 mean, wherein R 16 is a
  • Halogen atom, a C ⁇ -C ⁇ o alkyl group, a halogenated C ⁇ -C ⁇ o-alkyl group, a C 6 ⁇ C o aryl group or a halogenated C 6 -C 2 o aryl group, or L 1 are 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 group containing C C-C o-hydrocarbon such as
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH, 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 ) Si, CH Si (CH 3 ) 2 , oC 6 H or 2, 2 '- (C 6 H 4 ) 2 .
  • Z can also form a mono- or polycyclic ring system with one or more R 10 and / or R 11 radicals.
  • Chiral bridged metallocene compounds of the formula (III) 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 the 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 or 2, 4, 5, 6-position, with C ⁇ -C o- carbon-containing groups, such as C ⁇ -C ⁇ o-alkyl or Cg-C o _ aryl, where two or more substituents of the indenyl ring together can form a ring system.
  • Chiral bridged metallocene compounds of the formula (III) can be used as pure racemic or pure eso compounds. Mixtures of a racemic compound and a meso compound can also be used.
  • metallocene compounds examples are:
  • Dimethylsilanediylbis (2-methyl-4- (4-ethylphenyl-indenyl) zirconium dimethyl Dimethylsilanediylbis (2-methyl-4- (4-trifluoromethyl-phenyl-indenyl) zirconium dimethyl Dimethylsilanediylbis 2-methyl-4- (4-methoxy-phenyl-indenyl) - zirconium dimethyl Dimethylsilanediylbis 2-ethyl-4- (4-tert-butyl-phenyl-indenyl) - zirconiumdimethyl Dimethylsilanediylbis 2-ethyl-4- (4-methyl- phenyl-indenyl) - zirconium dimethyl 1 dimethylsilanediylbis 2-ethyl-4- (4-ethyl-phenyl-indenyl) zirconium-diethyl dimethylsilanediylbis 2-ethyl-4-
  • Methylethylidenebis (2-ethyl-4- (4'-tert.-butyl-phenyl) -indenyl) zirconium dichloride
  • Methylethylidenebis (2-ethyl-4- (4'-tert.-butyl-phenyl) -indenyl) hafnium dichloride
  • Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-trimethylsilylphenyl -indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- ( 4'-trimethylsilylphenyl-indenyl) zirconium dichloride
  • Methylphenylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-ter-butylphenyl-indenyl) zirconium dichloride methylidene (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirconium dichloride
  • Dimethylsilanediylbis 2 -methyl-4-oxapentalen) zirconium dichloride Dimethylsilanediylbis 2-methyl-5-oxapentalen) zirconium dichloride Dimethylsilanediylbis 2-methyl-6-oxapentalen) zirconium dichloride Dimethylsilanediylbis 2, oxonediumdichloride
  • 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 (III) in any stoichiometric ratio.
  • the catalyst system according to the invention can additionally contain an aluminum compound of the formula (IV)
  • the radicals R 20 in formula (IV) can be the same or different and a halogen atom, a hydrogen atom, a C ⁇ -C o-carbon-containing group, preferably C ⁇ -C o-alkyl, C ⁇ -C o-haloalkyl, C 6 ⁇ C 2 o-aryl, C 6 -C 2 o-haloaryl, C 7 -C o ⁇ arylalkyl, C -C 4 o-halo-arylalkyl, C 7 -C 4 o-alkylaryl or C 7 -C 4 o-haloalkylaryl , mean.
  • Preferred for R 20 are C ⁇ -C 6 alkyl groups, particularly preferred for R 20 are C ⁇ -C 4 alkyl groups.
  • the compound of formula (IV) can be added in any stoichiometric ratio.
  • a molar ratio B: M between the compounds of the formulas (I) and the formula (III) of 0.01 to 10,000 is used.
  • a molar ratio of 0.1 to 1000 is preferred, and a molar ratio of 1 to 100 is very particularly preferably used.
  • a compound of formula (IV) 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, very particularly preferably a molar ratio of 1 to 100 is 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 (III) is dissolved or suspended in an aliphatic or aromatic solvent.
  • a compound of the formula (IV) 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 A- 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 2 or B0 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 has a naturally low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as with the use of silica gel as a carrier material, dehydration or drying is recommended.
  • the thermal dehydration or drying of the carrier material can be carried out under vacuum and at the same time with an inert gas blanket (eg nitrogen).
  • the drying temperature is 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 selected conditions the equilibrium with the Hydroxyl groups can occur on the support surface, which normally takes between 4 and 8 hours.
  • Dehydration or drying of the carrier material is also possible 5 chemically by reacting the adsorbed water and the hydroxyl groups on the surface with suitable inerting agents. Through 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 effects.
  • 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, for example, trimethylalu-
  • the chemical dehydration or inertization of the carrier material is carried out, for example, by suspending the carrier material in a suitable solvent with the inert substance while excluding air and moisture.
  • reagent in pure form or dissolved in a suitable solvent to react.
  • suitable solvents are e.g. 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
  • the support material is isolated by filtration under inert conditions, one or more times with
  • Organic carrier materials such as finely divided polyolefin powder 35 (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. 40
  • 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 III is placed in an aliphatic or aromatic solvent such as toluene, heptane, tetrahydrofuran or diethyl ether. Then one or more compounds of the formula (IV) 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. This is followed by the addition of one or more compounds of the formula (I) 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 (IV) and the formula (III) of 0.1 to 10000 is preferred, a molar ratio of 1 to 100 being very particularly preferably used.
  • a molar ratio B: M1 between the compounds of the formula (I) and the formula (III) of 0.1 to 1000 is preferred, and a molar ratio of 1 to 100 is very particularly preferably used.
  • the preparation thus obtained is then mixed with the dehydrated or inertized carrier material, the solvent is removed and the resulting supported metallocene 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.
  • 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 (III).
  • polymerisation is understood to mean homopolymerization as well as copolymerization.
  • olefins examples include 1-olefins having 2 to 40, 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 methyl norbornene.
  • propene or ethene are preferably homopolymerized, or Propene with ethene and / or with one or more 1-olefins with 4 to 20 C atoms, such as hexene, and / or one or more 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 / propene / 1,4-hexadiene terpolymers.
  • 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 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.
  • 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 catalyst according to the invention.
  • Triad tacticity (TT) and the proportion of 2-1-inserted propene units (RI), which can be determined from the 13 C-NMR spectra, are particularly characteristic of the stereo and region specificity of polymers, in particular of polypropylene.
  • RI (%) 0.5 la, ß (Ia, a + Ia, ß + Ia, d) • 100,
  • 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 by using the catalyst system according to the invention with high productivity with technically relevant process parameters without formation of deposits.
  • 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).
  • a 300 ml polymerization autoclave (Parr 4560) is filled with 150 ml of heptane under an argo atmosphere. Then 1.1 ml of TIBA (20%) are added and the mixture is stirred at 20 ° C. for 20 minutes. The reactor is then heated to 50 ° C. and 0.25 ml of the catalyst solution prepared in Example 2 are injected. An ethylene pressure of 10 bar is then applied and it is polymerized for 40 hours at a constant ethylene pressure. The result is 10.5 g of polyethylene powder.
  • the catalyst activity was 7.8 kg PE / g metallocene x h
  • 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% triisobutyl aluminum solution in Varsol diluted with 30 cm 3 Exxol was 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 was kept at 60 ° C. for 1 hour by cooling. The polymerization was stopped by venting the remaining propylene. The polymer was dried in a vacuum drying cabinet. The result is 1.55 kg of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 113 kg PP / g metallocene x h.

Landscapes

  • 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. Associé à un composé organométallique, il peut constituer un nouveau système catalyseur pouvant avantageusement être utilisé aux fins de polymérisation d'oléfines. Cela permet de renoncer à l'utilisation d'oxanne d'aluminium tel que de l'oxanne méthylaluminium (MAO) comme cocatalyseur tout en obtenant une activité catalytique élevée.
PCT/EP1999/007056 1998-09-26 1999-09-22 Compose chimique WO2000018773A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19844195A DE19844195A1 (de) 1998-09-26 1998-09-26 Chemische Verbindung enthaltend Elemente der Gruppe IIIa des Periodensystems der Elemente und deren Verwendung als Co-Katalysator bei der Polymerisation von Olefinen
DE19844195.9 1998-09-26

Publications (1)

Publication Number Publication Date
WO2000018773A1 true WO2000018773A1 (fr) 2000-04-06

Family

ID=7882336

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/007056 WO2000018773A1 (fr) 1998-09-26 1999-09-22 Compose chimique

Country Status (2)

Country Link
DE (1) DE19844195A1 (fr)
WO (1) WO2000018773A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL116248B2 (en) * 1979-12-31 1981-05-30 Wyzsza Szkola Pedagog Method of polymerization of olefines
US4552859A (en) * 1984-08-06 1985-11-12 Stauffer Chemical Company Olefin polymerization catalyst and process
EP0495099A1 (fr) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Copolymeres olefines et leur production
DE19733017A1 (de) * 1997-07-31 1999-02-04 Hoechst Ag Chemische Verbindung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL116248B2 (en) * 1979-12-31 1981-05-30 Wyzsza Szkola Pedagog Method of polymerization of olefines
US4552859A (en) * 1984-08-06 1985-11-12 Stauffer Chemical Company Olefin polymerization catalyst and process
EP0495099A1 (fr) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Copolymeres olefines et leur production
DE19733017A1 (de) * 1997-07-31 1999-02-04 Hoechst Ag Chemische Verbindung

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CARDIN, CHRISTINE J. ET AL: "Dimesitylboryl compounds. Part 9. Crystal structure of oxybis(dimesitylborane)", J. CHEM. RES., SYNOP. (1983), (4), 93, XP000866130 *
CHEMICAL ABSTRACTS, vol. 88, no. 6, 6 February 1978, Columbus, Ohio, US; abstract no. 38222, MESHKOVA, I. N. ET AL: "Alkylaluminoxanes as cocatalysts of ethylene polymerization" XP002127783 *
CHEMICAL ABSTRACTS, vol. 99, no. 4, 25 July 1983, Columbus, Ohio, US; abstract no. 23113, NOWAKOWSKA, MARIA ET AL: "Polymerization of olefins" XP002127782 *
CHEMISCHE BERICHTE, vol. 88, 1955, pages 1761 - 1763, XP000867025 *
VYSOKOMOL. SOEDIN., SER. B (1977), 19(11), 849-52 *

Also Published As

Publication number Publication date
DE19844195A1 (de) 2000-03-30

Similar Documents

Publication Publication Date Title
EP1250363B1 (fr) Compose chimique, procede permettant de le preparer et de l'utiliser dans des systemes catalyseurs pour produire des polyolefines
EP1023334B1 (fr) Systeme catalyseur
EP1175262B1 (fr) Systeme catalyseur
EP1003753B1 (fr) Composes contenant du bore et de l'aluminium
EP0824113B2 (fr) Système catalytique sur support, procédé pour sa préparation et son utilisation pour la polymérisation d'oléfines
EP0824112B1 (fr) Composé chimique supporté
EP1290002B1 (fr) Produits chimiques pouvant etre utilises comme co-catalyseurs, leur procede de preparation et leur utilisation dans des systemes de catalyse pour produire des polyolefines
DE19962814A1 (de) Neues Katalysatorsystem und dessen Verwendung
WO1999033881A1 (fr) Systeme de catalyseur supporte pour la polymerisation d'olefines
WO1999040129A1 (fr) Systeme de catalyseur
DE19622207A1 (de) Chemische Verbindung
EP1272532B1 (fr) Compose chimique salin, procede pour sa production et son utilisation dans des systemes catalytiques pour la production de polyolefines
WO1999061488A1 (fr) Systeme de catalyseur
WO2000035973A1 (fr) Compose metal de transition neutre, zwitterionique, contenant du bore
EP1175424A1 (fr) Compose chimique, procede permettant de le preparer et son utilisation dans un systeme catalytique pour preparer des polyolefines
WO2000020466A9 (fr) Systeme catalyseur
WO2000018773A1 (fr) Compose chimique
DE19632557A1 (de) Chemische Verbindung
DE19632558A1 (de) Geträgerte chemische Verbindung
DE19845240A1 (de) Katalysatorsystem
DE19647070A1 (de) Geträgerte chemische Verbindung
DE19857377A1 (de) Übergangsmetallverbindung
DE19900585A1 (de) Verfahren zur Aufreinigung von Metallocenen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase