EP1049705A1 - Metallocenmonohalogenide - Google Patents

Metallocenmonohalogenide

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Publication number
EP1049705A1
EP1049705A1 EP99956012A EP99956012A EP1049705A1 EP 1049705 A1 EP1049705 A1 EP 1049705A1 EP 99956012 A EP99956012 A EP 99956012A EP 99956012 A EP99956012 A EP 99956012A EP 1049705 A1 EP1049705 A1 EP 1049705A1
Authority
EP
European Patent Office
Prior art keywords
butyl
tert
mono
fluorine
zirconium
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Withdrawn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
EP99956012A
Other languages
German (de)
English (en)
French (fr)
Inventor
Carsten Bingel
Hans-Herbert Brintzinger
Hans-Robert-Hellmuth Damrau
Patrik MÜLLER
Jürgen Suhm
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
Targor GmbH
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 Targor GmbH, Basell Polyolefine GmbH filed Critical Targor GmbH
Priority to EP03026592A priority Critical patent/EP1396495B1/de
Publication of EP1049705A1 publication Critical patent/EP1049705A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—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
    • 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
    • C08F4/65912—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/941—Synthetic resins or natural rubbers -- part of the class 520 series having the transition metal bonded directly to carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to specially substituted metallocenes, a process for their preparation and their use in the polymerization of olefins.
  • Metallocenes can be used as a catalyst component for the polymerization and copolymerization of olefins.
  • halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex (EP-A-129368).
  • metallocenes are known per se (US 4,752,597; US 5,017,714; EP-A-320762; EP-A-416815; EP-A-537686; EP-A-669340; HH Brintzinger et al .; Angew. 107 (1995), 1255; HH Brintzinger et al., J. Organomet. Che. 232 (1982), 233).
  • cyclopentadienyl-metal compounds can be reacted with halides of transition metals such as titanium, zirconium and hafnium.
  • the metallocene dihalides formed are in the case of the technically interesting racemic ansa-bis-indenyl-metallocenes which are required for the production of isotactic polypropylene (EP 0485823, EP 0549900, EP 0576970, WO 98/40331 ), usually poorly soluble compounds.
  • a better solubility of the technically interesting metallocenes would be desirable both in the preparation of the polymerization-active cationic metallocene catalyst system in unsupported or supported form and in the purification of the racemic metallocene, ie the catalyst precursor, by crystallization techniques.
  • the task was therefore to find readily soluble metallocenes which, after conversion into the polymerization-active species, show at least the same polymerization performance as the catalyst systems which are prepared from the poorly soluble metallocene dichlorides.
  • M is a metal of III., IV., V. or VI.
  • Subgroup of the periodic table of the elements is, in particular Ti, Zr or Hf, particularly preferably zirconium,
  • R 1 are identical or different and is Si (R 12 ), in which R 12, identical or different, represents a hydrogen atom or a C ⁇ -C 4 o ⁇ carbon-containing group, preferably C ⁇ -C o-alkyl,
  • Ci-Cio-fluoroalkyl C ⁇ -C ⁇ 0 alkoxy, C 6 -C 20 aryl, C 6 -C ⁇ 0 -Fluoraryl, Ce-Cio-aryloxy, C -C ⁇ n alkenyl, C -C 4 o-arylalkyl, C -C 4 o ⁇ alkylyl or C 8 -C 4 o-arylalkenyl,
  • R 1 is a -C-C 30 - carbon-containing group, preferred
  • -CC 5 alkyl such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 25 alkenyl, C 3 -C 5 alkylalkenyl, C 6 -C 24 aryl, C 5 -C 24 -Heteroaryl, C -C 3 n-arylalkyl, C -C 3 o-alkylaryl, fluorine-containing C ⁇ -C 5 alkyl, fluorine-containing C 6 -C 4 aryl, fluorine-containing C -C o-arylalkyl, fluorine-containing C. _C 3 o _ is alkylaryl or -CC -alkoxy,
  • radicals R 1 can be linked to one another in such a way that the radicals R 1 and the atoms of the cyclopentadienyl ring connecting them form a C 4 -C 4 ring system, which in turn can be substituted,
  • R 2 are the same or different and Si (R 12 ) 3 , in which R 12 is the same or different is a hydrogen atom or a C ⁇ -C 4 o-carbon-containing group, preferably C ⁇ -C 0 alkyl,
  • R 2 is a C 1 -C 8 carbon-containing group, preferably C 1 -C 25 alkyl, such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C -C 25 alkenyl, C 3 -C 5 alkylalkenyl, C 6 -C 24 aryl, C 5 -C 24 heteroaryl, C 7 -C 30 arylalkyl, C 7 -C 30 alkylaryl, fluorine-containing C ⁇ -Cs-alkyl, fluorine-containing C 6 -C 4 aryl, fluorine-containing C. 7 -C 3 o-arylalkyl, fluorine-containing C 7 _C 3 o-alkylaryl or -C-C ⁇ 2 alkoxy,
  • radicals R 2 can be linked to one another in such a way that the radicals R 2 and the atoms of the cyclopentadienyl ring connecting them form a C 4 -C 4 ring system, which in turn can be substituted,
  • R 3 is a C 1 -C 40 - carbon-containing group, preferably C 1 -C 5 alkyl, such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C -C 25 alkenyl, C 3 -C 15 - Alkylalkenyl, C 6 -C 24 aryl, C 5 -C heteroaryl such as pyridyl, furyl or quinolyl, C 7 -C 3 o-arylalkyl, C 7 -C 3 o-alkylaryl, fluorine-containing c ⁇ ⁇ C 5 - Is alkyl, fluorine-containing C 6 -C 4 aryl, fluorine-containing C 7 -C 30 arylalkyl or fluorine-containing C 7 _C 3 o-alkylaryl,
  • X is a halogen atom, in particular chlorine,
  • n 1 to 3, preferably 1,
  • B denotes a bridging structural element between the two cyclopentadienyl rings.
  • B are groups M 3 R 13 R 14 , in which M 3 is carbon, silicon, germanium or tin and R 13 and R 14, the same or different, are a C 1 -C 8 -hydrocarbon-containing group such as Ci-Cin-alkyl, C 6 -Ci 4 aryl or trimethylsilyl.
  • B is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, Si (CH 3 ) (SiR 20 R 1 R 22 ), (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 -
  • R 20 R 21 R 22 identically or differently, mean a Cj_-C o-hydrocarbon-containing group such as C ⁇ -C ⁇ o-alkyl or C 6 ⁇ Ci 4 -aryl.
  • B can also form a mono- or polycyclic ring system with one or more radicals R 1 and / or R 2 .
  • Bridged metallocene compounds of the formula (I) are preferred, in particular those in which k is 1 and one or both cyclopentadienyl rings are substituted in such a way that they represent an index 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 2 o-carbon-containing groups, such as Ci-Cig-alkyl or C 6 -Ci8-aryl, where two or more substituents of the indeyl ring together can form a ring system.
  • Bridged metallocene compounds of the formula (II) are particularly preferred.
  • M is Ti, Zr or Hf, particularly preferably zirconium,
  • R 3 identical or different, is a C 1 -C 30 - carbon-containing
  • R 5 , R 7 are the same or different and a hydrogen atom, a -C-C 20 - carbon-containing group, preferably Ci-Cis-alkyl, such as methyl, ethyl, n-butyl, cyclohexyl or octyl, C 2 -C ⁇ o-alkenyl, C 3 -C-alkylalkenyl, C ß- Cis-aryl, Cs-Ci ⁇ -heteroaryl such as pyridyl, - furyl or quinolyl, C 7 -C 2 o-arylalkyl, C 7 -C 2 o-alkylaryl, fluorine-containing
  • R 8 and R 9 are the same or different and mean a hydrogen atom, halogen atom or a -C-C 2 o - carbon-containing group, preferably a linear or branched Ci-Cis-alkyl group, such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 0 -alkenyl, C 3 -C 5 -alkylalkenyl, a Cö-Cis-aryl group, which may optionally be substituted, in particular phenyl, tolyl, xylyl, tert. -Butylphenyl, ethylphenyl, di-tert.
  • X is a halogen atom, in particular chlorine,
  • Y is an element of the 6th main group of the periodic table of the
  • 1, 1 ' identical or different, are an integer between zero and 4, preferably 1 or 2, particularly preferably equal to 1, B denotes a bridging structural element between the two idyl radicals.
  • Examples of B are groups M 3 R 13 R 14 , in which M 3 is carbon, silicon, germanium or tin, preferably carbon and silicon, and R 13 and R 14 are identical or different hydrogen, a C 1 -C 2 -hydrocarbon-containing Group such as Ci-Cio-alkyl, C 6 -Ci 4 aryl or trimethylsilyl mean.
  • B is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 C, (C6H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si,
  • R 20 R 21 R 22 identical or different, mean a C 1 -C 2 -hydrocarbon-containing group such as C 1 -C 10 alkyl or C 6 -C 4 aryl.
  • Bridged metallocene compounds of the formula (II) are very particularly preferred,
  • M zirconium
  • R 3 is a C ⁇ -C 3 o - carbon-containing group, preferred
  • C 3 -C ⁇ o-alkyl such as iso-propyl, tert-butyl, cyclohexyl or octyl, C 6 -C 24 aryl, C 5 -C 24 heteroaryl such as pyridyl, furyl or quinolyl, C 7 -C 3 o- arylalkyl, C 7 -C 30 -alkylaryl, fluorinated C6-C 4 aryl, fluorinated C 7 -C3o arylalkyl or fluorinated C 7 _C 3 is o-alkylaryl,
  • R 4 , R 6 are the same or different and a hydrogen atom or a C 1 -C 2 alkyl group, preferably an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl or octyl are, particularly preferably methyl or ethyl,
  • R 5 , R 7 are hydrogen atoms
  • R 8 and R 9 are identical or different and are a hydrogen atom
  • Halogen atom or a -CC 2 o ⁇ carbon-containing group preferably a linear or branched
  • Cx-Cs-alkyl group such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 6 alkenyl, C 3 -C 6 alkylalkenyl, a C6 "Ci8 aryl group which may optionally be substituted, in particular Phenyl, tolyl, xylyl, tert-butylphenyl, ethylphenyl, di-tert-butylphenyl, naphthyl, acenaphthyl, phenanthrenyl or anthracenyl, C 5 -C 8 heteroaryl such as pyridyl, furyl or quinolyl, C 7 -Ci 2 arylalkyl, C 7 -Ci 2 -alkylaryl, fluorine-containing Ci-Cs-alkyl, fluorine-containing C 6 -Ci 8 _ aryl,
  • 1, 1 ' is an integer between zero and 4, preferably 1 or 2, particularly preferably equal to 1,
  • B denotes a bridging structural element between the two indenyl radicals, B preferably being (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (C 6 H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, CH 2 CH 2 / CH (CH 3 ) CH 2 , CH (CH 9 ) C (CH 3 ) 2 , CH 2 , C (CH 3 ) 2 , (C 6 H 5 ) 2 C, particularly preferably (CH) Si , CH and CH 2 is CH 2 .
  • a significantly better solubility is said to mean that the molar concentrations in the organic solvent at least double, preferably more than fourfold and very particularly preferably more than eightfold.
  • Another advantage is that the compounds of the invention are better
  • Inert organic solvents for metallocenes are usually aliphatic or aromatic hydrocarbons, but also halogen-containing, oxygen-containing or nitrogen-containing hydrocarbons.
  • Non-limiting examples of the individual classes of solvents are heptane, toluene, dichlorobenzene, methylene chloride, tetrahydrofuran or triethylamine.
  • mixtures of the metallocenes of the formula (II) and the corresponding pseudo-meso metallocenes of the formula (Ha) can also be used in the catalyst preparation for catalyst preparation.
  • metallocenes according to the invention are:
  • Methylidenebis (2-methyl-indenyl) zirconium monochloro-mono- (2,4-di-tert-butyl-phenolate) isopropylidenebis (2-methyl-indenyl) -zirconium monochloro-mono- (2,4-di - tert - butyl phenolate)
  • Methylidenebis (2-methyl-4- (1-naphthyl) -indenyl) zirconium monochloro-mono- (2,4-di-tert-butyl-phenolate) isopropylidenebis (2-methyl-4- (1-naphthyl) -indenyl) -zirconium-mo-nochloro-mono- (2,4-di-ter-butyl-phenolate)
  • Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) zirconium monochloro-mono- (2,4-di-tert-butyl-phenolate)
  • Dimethylsilanediylbis (2-methyl-4,5-diisopropyl-indenyl) -zirconium- monochloro-mono- (2,4-di-tert-butyl-phenolate)
  • Dimethylsilanediylbis (2-methyl-4- (tert-butyl-phenyl-indenyl) zirconium monochloro-mono- (2,4-di-tert-butyl-phenolate)
  • Dimethylsilanediylbis (2-methyl-4- (4-methyl -phenyl-indenyl) -zirconium-monochloro-mono- (2, -di-tert.-butyl-phenolate) dimethylsilanediylbis (2-methyl-4- (4-ethyl-phenyl-indenyl) -zirconium-monochloro-mono- ( 2,4-di-tert-butyl-phenolate) dimethylsilanediylbis (2-methyl-4- (4-trifluoromethyl-phenyl-indeyl) zirconium monochloro-mono- (2,4-di-tert-butyl -phenolate)
  • Dimethylsilanediylbis (2-methyl-4- (4-methoxy-phenyl-indenyl) zirconium monochloro-mono- (2,4-di-tert-butyl-phenolate)
  • Dimethylsilanediylbis (2-ethyl-4- (4-tert -butyl-phenyl-indenyl) -zirconium-monochloro-mono- (2,4-di-tert.-butyl-phenolate) dimethylsilanediylbis (2-ethyl-4- (4-ethyl-phenyl-indenyl) -zirconium-monochloro- mono- (2,4-di-tert-butyl-phenolate) dimethylsilanediylbis (2-ethyl-4- (4-trifluoromethyl-phenyl-inde- nyl) zirconium monochloro-mono- (2,4-di-ter
  • Dimethylsilanediylbis (2-methyl-4- (4'-tert. -Butyl-phenyl) -indenyl) -zirconium monochloro-mono- (2,4-di-tert-butyl-phenolate)
  • Dimethylsilanediylbis (2-methyl-4 - (3 ', 5' -di-tert-butyl-phenyl) -indenyl) zirconium monochloro-mono- (2, 4-di-tert-butyl-phenolate) methylidenebis (2-methyl-4- ( 4'-tert.-butyl-phenyl) -indenyl) zirconium monochloro-mono- (2, 4-di-tert-butyl-phenolate) isopropylidenebis (2-methyl-4- (4 '-tert.
  • Methylidenebis (2-n-propyl-4- (4'-tert.-butyl-phenyl) -indenyl) zirconium monochloro-mono- (2,4-di-tert-butyl-phenolate) isopropylidenebis (2-n -propyl-4- (4'-tert.
  • Zirconium-monochloro-mono-neopentyl has examples of the metallocenes according to the invention.
  • the present invention furthermore relates to a process which can be carried out industrially for the preparation of the compounds of the formulas (I) and (II).
  • pseudo-rac M 1 is equal to a cation or a cation fragment such as Li, Na, K, MgCl, MgBr, Mgl and the other radicals are defined as above.
  • Metallocene dichloride of the formula III are preferably used as metallocenes: (EP 0485823, EP 0549900, EP 0576970, WO 98/22486, WO 98/40331).
  • the compound M ⁇ YR 3 can be prepared by deprotonating the compound HYR 3 with a suitable base, such as, for example, butyl lithium, methyl lithium, sodium hydride, potassium hydride, sodium, potassium or Grignard compounds in an inert solvent or solvent mixture.
  • a suitable base such as, for example, butyl lithium, methyl lithium, sodium hydride, potassium hydride, sodium, potassium or Grignard compounds in an inert solvent or solvent mixture.
  • Non-limiting examples of suitable solvents are hydrocarbons which can be halogenated, such as benzene, toluene, xylene, mesitylene, ethylbenzene, chlorobenzene, dichlorobenzene, fluorobenzene, decalin, tetralin, pentane, hexane, cyclohexane, ethers such as diethyl ether, di-n- Butyl ether, MTBE, THF, DME, anisole, triglyme, dioxane, amides such as DMF, dimethylacetamide, NMP, sulfoxides such as DMSO, phosphoramides such as hexamethylphosphoric triamide, urea derivatives such as DMPU, ketones such as acetone, ethyl methyl ketone, esters such as acetic acid and ethyl acetate any mix of those fabrics.
  • hydrocarbons which can be
  • Solvents or solvent mixtures in which the subsequent reaction with the metallocene dichloride can likewise be carried out directly are preferred.
  • Non-limiting examples of these are toluene, hexane, heptane, xylene, tetrahydrofuran (THF), dirthhoxyethane (DME), toluene / THF, heptane / DME or toluene / DME.
  • the compounds of the HYR 3 type are preferably the substance classes of the alcohols, the phenol, the primary and secondary amines and the primary and secondary anilines.
  • Compounds of type HYR 3 preferably contain only one functional group HY and the rest R 3 is defined as described above.
  • the process according to the invention is generally carried out in a temperature range from 0 ° C. to + 200 ° C., preferably in a temperature range from 40 ° C. to 140 ° C., particularly preferably at a temperature between 60 ° C. and 110 ° C.
  • the molar ratio of reagent M 1 -YR 3 to the metallocene halide, in particular to the metallocene dichloride (for example of the formula III) is in general between 5: 1 to 0.8: 1, preferably between 2: 1 and 0.9: 1.
  • the concentration of metallocene dichloride (for example of the formula III) or of reagent M 1 -YR 3 in the reaction mixture is generally in the range between 0.001 mol / 1 and 8 mol / 1, preferably in Range between 0.01 and 3 mol / 1, particularly preferably in the range between 0.05 mol / 1 and 2 mol / 1.
  • the duration of the reaction of metallocene dichloride (for example of the formula III) with reagent M x -YR 3 is generally in the range from 5 minutes to 1 week, preferably in the range from 15 minutes to 48 hours.
  • monoaryloxymonochlorozirconocenes of the formula (II) can also be prepared according to the process described in German patent application 199 12576.7 dated March 19, 1999, the disclosure of which is also the subject of the present description.
  • the metallocenes of the formulas I and II according to the invention are highly active catalyst components for olefin polymerization. Depending on the substitution pattern of the ligands, the metallocenes can be obtained as a mixture of isomers. The metallocenes are preferably used isomerically pure for the polymerization.
  • the pseudo-rac isomeric metallocenes of the formula II are preferably used.
  • the metallocenes of the formulas I and II according to the invention are particularly suitable as a constituent of catalyst systems for the preparation of polyolefins by polymerizing at least one olefin in the presence of a catalyst which comprises at least one cocatalyst and at least one metallocene.
  • the term polymerization 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.
  • 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
  • Ethylene or propylene are preferably homopolymerized, or ethylene is copolymerized with one or more cyclic olefins, such as norbornene, and / or one or more dienes having 4 to 20 carbon atoms, such as 1,3-butadiene or 1,4-hexadiene .
  • cyclic olefins such as norbornene
  • dienes having 4 to 20 carbon atoms, such as 1,3-butadiene or 1,4-hexadiene .
  • Examples of such copolymers are ethylene / norbornene copolymers, ethylene / propylene copolymers and ethylene / propylene / 1,4-hexadiene copolymers.
  • the polymerization is carried out at a temperature of from -60 to 300 ° C., preferably from 50 to 200 ° C., very particularly preferably from 50 to 80 ° C.
  • the pressure is 0.5 to 2000 bar, preferably 5 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • a preferred embodiment is gas phase and bulk polymerization.
  • the catalyst used preferably contains one of the metallocene compounds according to the invention. Mixtures of two or more metallocene compounds can also be used, e.g. B. for the production of polyolefins with broad or multimodal molecular weight distribution.
  • the cocatalyst which together with a metallocenes of the formulas I and II according to the invention forms the catalyst system, contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound, which converts this into a cationic compound by reaction with a metallocene.
  • a compound of the general formula (VII) is preferred as the aluminoxane
  • aluminoxanes can e.g. cyclic as in formula (VI)
  • radicals R in the formulas (IV), (V), (VI) and (VII) can be the same or different and a -C-C 2 o-hydrocarbon group such as a Ci-C ⁇ -alkyl group, a C 6 -C ⁇ 8 -Aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.
  • 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, methyl and isobutyl or methyl and n-butyl, with hydrogen or isobutyl or n-butyl preferably containing 0.01-40% (number of the radicals R).
  • 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 hydrodaluminum-hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
  • an inert solvent such as toluene
  • AIR 3 + AIR ' 3 two different aluminum trialkyls (AIR 3 + AIR ' 3 ) are reacted with water according to the desired composition and reactivity (see S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0,302,424).
  • the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C 1 -C 2 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3, 5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) phenyl.
  • organoboron or organoaluminum compound which contains C 1 -C 2 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, triflu
  • Lewis acids are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, trifluoroborane,
  • Tris (4-fluorophenyl) borane tris (3, 5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3, 5-dimethylphenyl) borane, tris ( 3, 5-difluorophenyl) borane, [(C 6 F 5 ) 2 BO] 2 A1-Me, [(C 6 F 5 ) 2 BO] 3 A1 and / or tris (3, 4, 5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.
  • Compounds which contain a non-coordinating anion are preferably used as ionic cocatalysts.
  • a non-coordinating anion such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 -, CF 3 S0 3 - or C10 4 ", are preferably used as ionic cocatalysts.
  • Protonated Lewis bases such as, for example, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N are used as the cationic counterion , N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene or the triphenylcarbenium cation.
  • Examples of such ionic compounds are triethylammonium tetra (phenyl) borate, tributylammonium tetra (phenyl) borate, trimethylammonium tetra (tolyl) borate, Tributylammoniumtetra (tolyl) borate, Tributylammoniumtetra (pentafluorophenyl) borate, Tributylammoniumtetra (pentafluorophenyl) aluminate, Tripropylammoniumtetra (dimethylphenyl) borate, Tributylammoniumtetra (trifluoromethylphenyl) borathen, tetrahydrofuran (N) N-diethylanilinium tetra (phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium te
  • Ferrocenium tetrakis (pentafluorophenyl) aluminate Ferrocenium tetrakis (pentafluorophenyl) aluminate.
  • Triphenylcarbenium tetrakis (pentafluorophenyl) borate and / or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferred.
  • 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. 7, 8-dicarbaundecaboran (13),
  • 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.
  • preferred oxides 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 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 2 / g, 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 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 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 takes 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 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, in that a suspension of the
  • 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 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 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 catalyst system is produced according to the invention by mixing at least one metallocene according to the invention, at least one cocatalyst and at least one inertized support.
  • the supported catalyst system At least one of the above-described metallocene components 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 so The preparation obtained is then mixed with the dehydrated or inert 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.
  • a method for the preparation of a free-flowing and optionally prepolymerized supported catalyst system comprises the following steps:
  • Preferred solvents for the preparation of the metallocene / Coka- talysator mixture are hydrocarbons and hydrocarbon - mixtures which are liquid at the chosen reaction temperature and ⁇ in which the individual components preferably dissolve.
  • the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of metallocene and cocatalyst components is soluble in the chosen solvent.
  • suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Toluene is very particularly preferred.
  • a molar ratio of aluminum to transition metal in the metallocene is preferred 10: 1 to 1000: 1, most preferably a ratio of 50: 1 to 500: 1.
  • the metallocene 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 metallocene 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).
  • room temperature 25 ° C
  • the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity.
  • a higher temperature means a range between 50 and 100 ° C.
  • the preactivated solution or the metallocene / cocatalyst mixture is then combined with an inert support material, usually silica gel, which is in the form of a dry powder or as a suspension in one of the abovementioned solvents.
  • the carrier material is preferably used as a powder. The order of addition is arbitrary.
  • the preactivated metallocene cocatalyst solution or the metallocene cocatalyst mixture can be metered into the support material provided, or the support material can be introduced into the solution presented.
  • the volume of the preactivated solution or of the 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 metal-locene-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 proportion of the solvent and also removed the portion in the pores of the carrier material.
  • 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 prepolymerized with one or more olefinic monomers before it is used in a polymerization process.
  • the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
  • an olefin preferably an ⁇ -olefin (for example styrene or phenyldimethylvinylsilane) as an activity-increasing component, or for example an antistatic agent, can be added during or after the preparation of the supported catalyst system.
  • an olefin preferably an ⁇ -olefin (for example styrene or phenyldimethylvinylsilane) as an activity-increasing component, or for example an antistatic agent
  • a mixture of a metal salt of medialanic acid, a metal salt of anthranilic acid and a polyamine is usually used as the antistatic.
  • antistatic agents are described, for example, in EP-A-0, 636, 636.
  • the molar ratio of additive to metallocene component compound (I) is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
  • the present invention also relates to a process for the preparation of a polyolefin by polymerizing one or more olefins in the presence of the catalyst system comprising at least one transition metal component of the metallocenes of the formula I or II according to the invention.
  • polymerisation is understood to mean homopolymerization as well as copolymerization.
  • the compounds of the formulas (I) and (II) according to the invention show at least equivalent, but in some cases higher, activities in the polymerization of olefins than the dihalogen compounds, and the polyolefins obtained show a reduction in the undesirable low molecular weight extractables.
  • the catalyst system shown 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 monomers 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 antistatic can be metered into the polymerization system together with or separately from the catalyst system used.
  • the polymers represented by the catalyst system which contains at least one of the metallocenes of the formulas (I) and / or (II) according to the invention have a uniform grain morphology and have no fine grain proportions. No deposits or caking occur during the polymerization with the catalyst system.
  • 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 I ⁇ , ß (I ⁇ , ⁇ + l ⁇ , ß + I ⁇ , ⁇ ) • 100,
  • the isotactic polypropylene which has been produced with the catalyst system, 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> 153 ° 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 with the catalyst system are distinguished by a significantly higher molar mass than in the prior art. At the same time, such copolymers can be produced with high productivity and technically relevant process parameters without deposit formation by using the catalyst system.
  • the polymers produced by the process are particularly suitable tear-resistant, hard and stiff for producing moldings such as fibers, filaments, injection-molded parts t films, sheets or large hollow bodies (eg pipes).
  • Example la Catalyst representation with (1) and polymerization:
  • a dry 21 reactor was first flushed with nitrogen and then with propylene and filled with 1.5 l of liquid propylene. 2 ml of TEA (20% in Varsol) were added and the mixture was stirred for 15 minutes. The catalyst system prepared above (0.886 g) was then resuspended in 20 ml of heptane and rinsed with 15 ml of heptane. The reaction mixture was heated to the polymerization temperature of 60 ° C and polymerized for 1 hour. The polymerization was stopped by exhaust gases of the rest of propylene. The polymer was dried in a vacuum drying cabinet. The result was 470 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 0.53 kg PP / g catalyst x h. 5
  • a dry 21 reactor was first flushed with nitrogen and then with propylene and filled with 1.5 l of liquid propylene. 2 ml TEA (20% in Varsol) were added and 15
  • the polymer was dried in a vacuum drying cabinet. The result was 410 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 0.46 kg PP / g catalyst x h.

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CN1289337A (zh) 2001-03-28
DE59914158D1 (de) 2007-03-08
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ES2280674T3 (es) 2007-09-16
AU1272100A (en) 2000-06-13
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US7053160B1 (en) 2006-05-30
WO2000031090A1 (de) 2000-06-02
CN100340568C (zh) 2007-10-03
BR9906934A (pt) 2000-10-10
BR9906934B1 (pt) 2010-08-24
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