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WO1999015536A1 - Compose de metal de transition - Google Patents

Compose de metal de transition Download PDF

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Publication number
WO1999015536A1
WO1999015536A1 PCT/EP1998/005687 EP9805687W WO9915536A1 WO 1999015536 A1 WO1999015536 A1 WO 1999015536A1 EP 9805687 W EP9805687 W EP 9805687W WO 9915536 A1 WO9915536 A1 WO 9915536A1
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Prior art keywords
aryl
radicals
alkyl
alkylaryl
carbon
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PCT/EP1998/005687
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German (de)
English (en)
Inventor
Cornelia Fritze
Gerhard Erker
Lothar Duda
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Targor Gmbh
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Publication of WO1999015536A1 publication Critical patent/WO1999015536A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • the present invention relates to a transition metal compound and its
  • aluminoxane a Lewis acid or an ionic compound.
  • these catalysts deliver polymers and copolymers with a narrow molecular weight distribution.
  • Such catalyst systems usually contain an excess of the cocatalyst component, such as an aluminoxane compound.
  • a cocatalyst such as a [Ph 3 C] + or [Me 2 NPh] + salt of a non-coordinating anion, has recently been described.
  • Transitional metal compounds which bring about the polymerization of olefins without the addition of a cocatalyst are also known.
  • catalyst systems mentioned are generally not suitable for the copolymerization of nonpolar olefins with polar functionalized olefins, such as, for example, acrylates.
  • polar functionalized olefins such as, for example, acrylates.
  • polar olefins such as methyl methacrylate (MMA)
  • MMA methyl methacrylate
  • the stereospecific polymerization of MMA using zirconium compounds (macro molecules, 1995, 28, 3067-3073) or lanthanoids (J. Am. Chem. Soc. 1992, 114, 4908) has been described.
  • Block copolymers of ⁇ -olefins CH 2 CHR with acrylates
  • the catalyst compositions described in the previous paragraph mostly include a metal alkyl or metal hydride compound in conjunction with a cocatalyst, or a hydride of a rare earth metal.
  • the object of the present invention was to provide a new class of transition metal compounds which are suitable as catalyst components.
  • the present invention relates to a transition metal compound which contains at least one imidic acid group.
  • Such transition metal compounds can be used as a catalyst component for the production of polymers.
  • a catalyst contains (A) at least one transition metal compound according to the invention which contains at least one imidic acid group in the ligand system and (B) at least one cocatalyst.
  • the present invention furthermore relates to a process for the preparation of the transition metal compound according to the invention and the catalyst and its use. Preparation of polyolefins.
  • the new class of transition metal compounds described here is easily accessible and provides polyolefins in high activity.
  • the transition metal compound according to the invention is preferably an organometallic compound of the formula I.
  • L are the same or different ⁇ ligand, such as unsubstituted or -C-C 2 o-substituted cyclopentadienyl, CC 2 o-substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, or C 2 -C 4 o-alkenyl, C 2 -C 40 -alkadienyl, C 2 -C 0 -alkadienediyl, C 3 -C 40 -alkylalkenyl, C 5 -C 24 -aryl,
  • C 5 -C 24 heteroaryl such as pyridyl, furyl, quinolyl or boratabenzene
  • m is an integer from 0 to 6
  • M is a metal from group 3, 4, 5 or 6 of the Periodic Table of the Elements as well as lanthanides or actinoids
  • X are the same or different and are a CrC o-carbon-containing group, such as CC 40 alkyl, for example methyl, ethyl, tert-butyl, cyclohexyl or octyl, -C-C 0 - haloalkylene, C 6 -C 40 -aryl, CC 40 -Alkylaryl, C 2 -C 40 -AIkenyI, -C-C ⁇ 2 - alkoxyalkyl, C 5 -C 2 o-aryloxyalkyl, CC 2 o-alkylamine, C5-C 20 arylamine, C 1 -C 2 0- alkylphosphine, C 5 -C 2 o-arylphosphine, CrC 2 o-alkyl sulfide or C 5 -C 2 o-aryl sulfide, in particular methyl, ethyl, isopropyl, butyl,
  • Alkylamine, C 5 -C 20 arylamine, C ⁇ -C 20 alkylphosphine, C 5 -C 2 o-arylphosphine, CC 2 o-alkyl sulfide or C 5 -C 2 o-aryl sulfide, or X are halogen, OH, SH, NH 2 or PH 2 , n is 0, 1, 2, 3, 4 or 5, R 1 , R 2, independently of one another, are the same or different
  • Hydrogen atom a SiR 5 3 group, in which R 5, the same or different, represents a hydrogen atom or a C 1 -C 20 carbon-containing group such as C 1 -C 2 o -alkyI, d-cio-haloalkyl, CrCio-alkoxy, C 5 -C 20 aryl, C 5 -C ⁇ 0 haloaryl, C 5 -C 10 aryloxy, C 2 -C 10 alkenyl, C 6 -C 0 arylalkyl, C 6 -C 0 alkylaryl or C 7 -C 0 - Arylalkenyl, or a CC o - carbon-containing group such as CrC 40 -
  • Alkyl e.g. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 40 alkenyl, C 3 -C 40 alkylalkenyl, C 5 -C 2 aryl, C 5 -C 24 heteroaryl such as pyridyl, furyl or Quinolyl, C 6 -C 30 arylalkyl, C 6 -C 3 o-alkylaryl, halogen-containing dC ⁇ alkyl, halogen-containing C 5 -C 2 aryl, halogen-containing C 6 -C 3 o-arylalkyl, halogen-containing C 6 -C 3 o-alkylaryl, C 2 C ⁇ alkoxyalkyl, C 5 -C 20 aryloxyalkyl, C 2 -C 20 - alkenyloxyalkyl, C ⁇ -C 20 alkylamine, C 5 -
  • Aryl sulfide, C 2 -C 20 alkenyl sulfide, CrC 20 oxoalkyI, C 5 -C 20 oxoaryl, C 1 -C 2 0 carboxyalkyl, C 5 -C 2 o-carboxyaryl or one or more radicals R 1 and R 2 can be linked to L in such a way that the residues R 1 , R 2 and L and the atoms connecting them form a C 3 -C 24 ring system, which in turn can be substituted with CrC 2 o-carbon-containing residues, or two or more residues R 1 and R 2 can be linked to one another such that the radicals R 1 and R 2 or two or more radicals R 1 or two or more radicals R 2 and the atoms connecting them form a C 3 -C 2 ring system, which in turn can be substituted with -C 20 carbon-containing radicals, and p is 1, 2, 3 or 4.
  • M in formula I is particularly preferably a transition metal of group 3, 4, 5 or 6 of the periodic table of the elements and lanthanoids or actinoids to the at least one ⁇ ligand, e.g. a cyclopentadienyl ligand is attached.
  • the central metal atom in formula I is particularly preferably an element from group 4 of the periodic table of the elements, such as titanium, zirconium or hafnium, to which one or two cyclopentadienyl ligands are bonded.
  • Cyclopentadienyl unsubstituted cyclopentadienyl and substituted cyclopentadienyl groups such as methylcyclopentadienyl, Trifluoromethylcyclopentadienyl, Pyridylcyclopentadie- nyl, Phenylcyclopentdienyl, Tetramethylcyclopentadienyi, indenyl, 2-methylindenyl, are 2-methyl-4-phenylindenyl, tetrahydroindenyl, benzoindenyl, fluorenyl, Benzofluore- nyl, tetrahydrofluorenyl to understand Octahydrofluorenylreste .
  • the indenyl ring is preferably substituted, although two or more substituents on the indenyl ring can together form a ring system.
  • the ⁇ ligands e.g. B. Cyclopentadienyl ligands can be bridged or unbridged, single and multiple bridging - also via ring systems - are possible.
  • a transition metal compound of the formula (I) is particularly preferably a metal locene which can be bridged or unbridged.
  • metallocene also includes compounds with more than one metallocene fragment, so-called multinuclear metallocenes. These can have any substitution pattern and bridging variant.
  • the individual metallocene fragments of such multinuclear metallocenes can be either of the same type or different from one another.
  • Examples of such multinuclear metallocenes are e.g. B. described in (EP-A-632063, JP-A-04/80214, JP-A-04/85310 or EP-A-654476).
  • M 1 M is a metal from group 3, 4, 5 or 6 of the periodic table of the elements and also lanthanoids or actinoids, in particular titanium, zirconium or hafnium
  • R 3 are the same or different and a hydrogen atom, a SiR 8 3 group, wherein R 8 the same or different is a hydrogen atom or a CrC 4 o- carbon-containing group such as -C-C 2 o-alkyl, C ⁇ -C ⁇ 0 -fluoroalkyl, d -Cio-alkoxy, C 5 -C 20 aryl, C 5 -C ⁇ 0 fluoroaryl, C 5 -C ⁇ 0 aryloxy, C 2 -C 10 alkenyl, C 6 -C 0 arylalkyl, C 6 -C 0 alkylaryl or C 7 -C 4 o-arylalkenyl, or a C 1 -C 3 0 - carbon-containing group as is C ⁇ -C 25
  • Heteroaryl e.g. B. pyridyl, furyl or quinolyl, C 6 -C 3 o-arylalkyl, C 6 -C 30 alkylaryl, fluorine-containing CrC 25 alkyl, fluorine-containing C 5 -C 2 aryl, fluorine-containing C ⁇ -C 30 arylalkyl, fluorine-containing C. 6 -C 30 alkylaryl or -CC 2 alkoxy or two or more radicals R 4 can be linked together so that the radicals R 4 and the atoms of the cyclopentadienyl ring connecting them are a C -C 2 -
  • Form ring system which in turn can be substituted with C 20 -C 20 carbon-containing radicals
  • bridges Z are groups M 2 RR ß , where M 2 is carbon, silicon, germanium or tin and R and R ß, the same or different, are a C 1 -C 20 - carbon-containing group such as a CC 2 o-alkyl, C 5 - C 24 aryl or a CC 2 o heteroalkyl, C 5 -C 24 heteroaryl group.
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , (CH 3 ) 3 C (CH 3 ) C, 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, (CH 3 ) 3 Si (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 3 and / or R 4 .
  • transition metal compounds according to the invention are:
  • the titanocenes and the hafnocenes are also important.
  • the transition metal compound according to the invention can be prepared, for example, by reacting a metal halide with an anionic ligand system and is intended to be illustrated by way of example in the reaction scheme below.
  • M 1 , R 2 , R 3 , a have the same meaning as indicated above in formulas II and III, M 3 is an alkali metal, shark is a halogen such as fluorine or chlorine,
  • R 7 , R 8 independently of one another, the same or different, represent a hydrogen or an SiR 5 3 group, wherein R 5, identical or different, represents a hydrogen atom or a dC o-carbon-containing group such as -C-C 2 o-alkyl, Ci-Cio-haloalkyl, CrC 10 alkoxy, C 5 -C 20 aryl, C 5 -C ⁇ o-haloaryl, C 5 -C ⁇ 0 aryloxy, C 2 -C ⁇ 0 - alkenyl, C 6 -C o-arylalkyl, C 6 -C 0 alkylaryl or C 7 -C 0 arylalkenyl, or a -C-C 0 - carbon-containing group such as -C-C 0 alkyl, z .
  • R 5 identical or different, represents a hydrogen atom or a dC o-carbon-containing group such as -C-C 2 o-alky
  • C 2 o-oxoaryl, -C-C 2 o-carboxyalkyl, C 5 -C 2 o-carboxyaryl and R 9 are, independently of one another, the same or different, a CrC 0 - carbon-containing group such as CC 40 alkylidene, for.
  • reaction of compounds IV in inert solvents with the M 3 R 8 leads to the dialkali metal adduct VIl, which can be isolated or can be reacted directly with transition metal halides with elimination of salt to give the compounds of the formula VI or VII.
  • the reaction takes place at temperatures from -50 ° C to + 150 ° C, preferably at 0 ° C to 100 ° C in organic solvents, such as
  • the reaction takes from 1 minute to 24 hours, preferably from 5 minutes to 5 hours.
  • transition metal compound according to the invention can also be used without isolation of
  • the transition metal compounds according to the invention are highly active catalyst components for olefin polymerization. Depending on the substitution pattern of the ligands, the transition metal compounds can be obtained as a mixture of isomers.
  • the transition metal compounds are preferably used isomerically pure, but can also be used as a mixture of isomers.
  • the present invention further relates to a method for producing a
  • Polyolefins by polymerizing one or more olefins in the presence of a catalyst system containing at least one transition metal compound according to the invention and at least one cocatalyst.
  • the term polymerization is understood to mean homopolymerization as well as copolymerization.
  • the term olefins is understood to mean functionalized and unfunctionalized olefins.
  • olefins examples include 1-olefins having 1 to 20 carbon atoms, such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, cyclic or acyclic Dienes such as 1, 3-butadiene, isoprene, 1, 4-hexadiene, norbornadiene, vinyl norbornene, 5-ethylidene norbomene or cyclic monoolefins such as norbornene or tetracyclododecene, vinyl alcohol, vinyl acetate, ⁇ , ß-unsaturated carbonyl compounds such as, ß-unsaturated esters or Ketones, carboxamides, vinyl ketones or acrylates such as methyl methacrylate, butyl methacrylate, allyl methacrylate of the nitriles.
  • Ethylene, propylene, vinyl alcohol, methacrylate, methyl vinyl ketone, ethyl vinyl ketone, octyl vinyl ketone, phenyl vinyl ketone or ethylene, propylene, vinyl alcohol, methacrylate, methyl vinyl ketone, ethyl vinyl ketone, octyl vinyl ketone, phenyivinyl ketone with one another and / or with one or more are preferred in the process according to the invention acyclic 1-olefins with 4 to 20 C atoms and / or with one or more dienes with 4 to 20 C atoms, such as 1, 3-butadiene, copolymerized.
  • the copolymerization can take place statistically or in blocks.
  • the polymerization is preferably carried out at a temperature of from -78 to 250.degree. C., particularly preferably from 50 to 200.degree.
  • the pressure is preferably 0.5 to 2000 bar, particularly preferably 5 to 64 bar.
  • a prepolymerization can be carried out with the aid of the catalyst according to the invention.
  • the prepolymerization is preferably carried out using the (or one of the) monomer (s) used in the polymerization.
  • the polymerization can be in solution, in bulk, in suspension, in the gas phase or be carried out in a supercritical medium, continuously or discontinuously, in one or more stages.
  • a preferred embodiment is gas phase polymerization and suspension polymerization.
  • the catalyst used in the process according to the invention preferably contains a transition metal compound. Mixtures of two or more transition metal compounds can also be used, e.g. for the production of polyolefins with a broad or multimodal molecular weight distribution.
  • any compound is suitable as a cocatalyst in the process according to the invention which, because of its Lewis acidity, can convert the neutral transition metal compound into a cation and stabilize it ("unstable coordination").
  • the cocatalyst or the anion formed from it should not undergo any further reactions with the cation formed (EP 427 697).
  • An aluminum compound and / or a boron compound is preferably used as the cocatalyst.
  • the boron compound preferably has the formula R 12 X NH 4-X BR 13 4 , R 12 X PH 4 .
  • X BR 13 4 , R 12 3 CBR 13 or BR 13 3 where x is a number from 1 to 4, preferably 3, the radicals R 12 are the same or different, preferably the same, and d-Cio-alkyl or C 6 -Ci8 aryl, or two radicals R 12 together with the atoms connecting them form a ring, and the radicals R 13 are the same or different, preferably the same, and are C 6 -Ci 8 aryl which can be substituted by alkyl, haloalkyl or Fluorine can be substituted.
  • R 12 stands for ethyl, propyl, butyl or phenyl and R 13 for phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP 277 003, EP 277 004 and EP 426 638).
  • An aluminum compound such as aiuminoxane and / or an aluminum alkyl is preferably used as the cocatalyst.
  • An aiuminoxane in particular of the formula Xa for the linear type and / or of the formula Xb for the cyclic type, is particularly preferably used as cocatalyst,
  • the radicals R 14 are the same or different and are hydrogen or a CrC 2 o-hydrocarbon group such as a -CC 8 alkyl group, a C ⁇ -cis-aryl group or benzyl and p is an integer of 2 to 50, preferably 10 to 35.
  • the R 14 radicals are preferably the same and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
  • R 14 radicals are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in a number fraction of from 0.01 to 40% (of the R 14 radicals).
  • the processes for producing the aluminoxanes are known.
  • the exact spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings combine to form larger two-dimensional or three-dimensional structures.
  • all aluminoxane solutions have in common a changing content of unreacted aluminum starting compound, which is present in free form or as an adduct.
  • the preactivation of the transition metal compound is preferably carried out in solution.
  • the transition metal compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon.
  • An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon.
  • Toluene is preferably used.
  • the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total amount of solution.
  • the transition metal compound can be used in the same concentration, but it is preferably used in an amount of 10 "4 to 1 mol per mol of aiuminoxane.
  • the preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes.
  • the temperature is from -78 to 150 ° C, preferably 0 to 80 ° C.
  • the transition metal compound is preferably used in a concentration, based on the transition metal, of 10 "3 to 10 " 8 , preferably 10 "4 to 10 " 7 mol of transition metal per dm 3 solvent or per dm 3 reactor volume.
  • the aiuminoxane is preferably used in a concentration of 10 "6 to 10 " 1 mol, preferably 10 "5 to 10 " 2 mol per dm 3 solvent or per dm 3 reactor volume.
  • the other cocatalysts mentioned are used in approximately equimolar amounts to the transition metal compound. In principle, however, higher concentrations are also possible.
  • the aiuminoxane can be prepared in various ways by known methods.
  • One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
  • an inert solvent such as toluene
  • R 14 for example
  • two different aluminum tri-alkyls are reacted with water.
  • cleaning by means of a chemical compound or by means of a physical process can be provided.
  • chemical compounds such as aluminum alkyl e.g. Trimethyl aluminum, triisobutyl aluminum, tributyl aluminum can be used.
  • the cleaning can take place both in the polymerization system itself or the olefin is brought into contact with the Al compound before the addition into the polymerization system and then separated again.
  • catalyst poisons can also be separated from the monomer by freezing, crystallization, distillation or sublimation.
  • a radical inhibitor such as 4-methoxyphenol can also be added to the reaction mixture.
  • Hydrogen can be added in the process according to the invention as a molecular weight regulator and / or to increase the catalyst activity.
  • low molecular weight polyolefins such as waxes can be obtained.
  • the transition metal compound is preferably reacted with the cocatalyst outside the polymerization reactor in a separate step using a suitable solvent. Carrying can be carried out.
  • prepolymerization can be carried out using the transition metal compound.
  • the (or one of the) olefin (s) used in the polymerization is preferably used.
  • the catalyst according to the invention optionally contains, in addition to components (A) and
  • the carrier component is preferably a porous inorganic or organic Solid.
  • the carrier material preferably contains at least one inorganic oxide, such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, ThO 2 , carbonates such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , sulfates such as Na 2 SO, AI 2 (SO 4 ) 3 , BaSO, nitrates such as KNO3, Mg (NO 3 ) 2, AI (NO 3 ) 3 and oxides such as Na 2 O, K 2 O, Li 2 O, in particular silicon oxide and / or aluminum oxide, or it preferably contains at least one polymer, copolymer, crosslinked polymer or polymer blends, such as, for example, polyethylene, polypropylene, polybutene, polystyrene, polystyrene crosslinked with divinyl
  • the carrier material can have a specific surface area in the range from 10 to 1000 m 2 / g, preferably from 150 to 500 m 2 / g.
  • the average particle size of the carrier can be 1 to 500 mm, preferably 5 to 350 mm, particularly preferably 10 to 200 mm.
  • the pore volume of the carrier can be 0.5 to 4.0 ml / g, preferably 1.0 to 3.5 ml / g.
  • a porous structure of the carrier causes a proportion of voids (pore volume) in the carrier particle.
  • the shape of the pores can be irregular, often spherical.
  • the pores can be connected to one another by small pore openings.
  • the pore diameter can be approximately 2 to 100 nm.
  • the particle shape of the porous carrier depends on the aftertreatment and can be irregular or spherical.
  • the carrier particle sizes can e.g. B. can be set arbitrarily by cryogenic grinding and / or screening.
  • the carrier material can be pretreated e.g. by heating at temperatures from 50 ° C to 1000 ° C in an inert gas stream or in vacuum at 0.01 bar to 0.001 bar or by reaction with a chemical compound that reacts with catalyst poisons such as Aluminum-,
  • support materials made of SiO 2 can be functionally be settled.
  • a suspension of SiO 2 (pretreated: 4h; 200 ° C, 0.01 bar) in a suitable solvent such as pentane, hexane, heptane, toluene or dichloromethane is reacted with a silyl chloride compound containing a functional group, heated at boiling temperature for several hours and then washed with a suitable solvent.
  • the reaction temperature is preferably> 50 ° C, in particular 50 ° C to 150 ° C.
  • the reaction time is 1 to 600 minutes, preferably 1 to 2 hours.
  • the silyl chloride compound is preferably used in an equimolar ratio based on the proportion of hydroxyl groups on the surface of the SiO 2 .
  • reaction is carried out under inert conditions.
  • the reaction product is then washed with a solvent.
  • Suitable solvents for the washing process are e.g. If necessary, amines are added to pentane, hexane, heptane, toluene or dichloromethane in order to trap the HCI formed. Then solvent residues are removed in vacuo at 20 to 200 ° C and 0.01 to 0.001 bar.
  • the catalyst can be prepared by mixing the individual components in any order.
  • the catalyst component (A) is mixed with the cocatalyst component (B) and then with the support component (C) or the catalyst component (A) with the support component (C) and then with the cocatalyst component (B) or the support component (C) with the cocatalyst component (B) and then with the catalyst component (A).
  • the mixture is carried out in a suitable solvent such as pentane, heptane, toluene, dichloromethane or dichlorobenzene.
  • the preparation of the catalyst according to the invention is carried out at -80 to 200 ° C, preferably at -20 to 100X and a contact time between 15 minutes and 25 hours, preferably between 15 minutes and 5 hours.
  • the supported catalyst system produced in this way can be dried in vacuo as a powder or with solvent, resuspended and metered into the polymerization system as a suspension in one of the aforementioned inert suspending agents.
  • a common inert solvent is used.
  • an aliphatic or cycloaliphatic or aromatic hydrocarbon as such, for example, propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane, toluene ethereal solvents such as tetrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.
  • a gasoline or hydrogenated diesel oil fraction can also be used.
  • Polymerization is preferably carried out in liquid, gaseous or supercritical monomers.
  • the monomers are added in gaseous or liquid form.
  • the duration of the polymerization is arbitrary, since that to be used according to the invention
  • Catalyst system shows only a small time-dependent drop in the polymerization activity.
  • the polymers produced with the catalyst according to the invention are suitable for the production of materials by known processes.
  • the functional groups on the surface of the polymers result in advantageous interactions with a large number of polar compounds and materials, such as e.g. good adhesive properties.
  • Example 1 The compounds were characterized by 1 H-HMR, 13 C-NMR and IR spectroscopy.
  • Example 1 The compounds were characterized by 1 H-HMR, 13 C-NMR and IR spectroscopy.
  • Example 1 The compounds were characterized by 1 H-HMR, 13 C-NMR and IR spectroscopy.
  • Example 1 The compounds were characterized by 1 H-HMR, 13 C-NMR and IR spectroscopy.
  • Example 1 The compounds were characterized by 1 H-HMR, 13 C-NMR and IR spectroscopy.
  • Examples 8-11 50 mmol of the metallocene precursor are mixed with tris (pentafluorophenyl) borane in 5 ml
  • precursor weight, weight, weight, weight [gPMVK / mol

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Abstract

L'invention concerne un composé de métal de transition de formule (I), dans laquelle L, m, M, X, n, R1, R2 et p ont la signification mentionnée dans la description.
PCT/EP1998/005687 1997-09-24 1998-09-08 Compose de metal de transition WO1999015536A1 (fr)

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CN112745429B (zh) * 2019-10-31 2022-03-15 中国石油化工股份有限公司 用于制备烯烃-不饱和羧酸共聚物的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0816372A1 (fr) * 1996-06-20 1998-01-07 Hoechst Aktiengesellschaft Composé d'un métal de transition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0816372A1 (fr) * 1996-06-20 1998-01-07 Hoechst Aktiengesellschaft Composé d'un métal de transition

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ARNDT, PERDITA ET AL: "Reactions of lactams with titanocene- and zirconocene-alkyne complexes as elemental steps in catalytic anionic ring-opening polymerization of lactams", CHEM. BER. (1996), 129(10), 1281-1285 CODEN: CHBEAM;ISSN: 0009-2940, 1996, XP002089089 *
CHEMICAL ABSTRACTS, vol. 129, Columbus, Ohio, US; abstract no. 189716j, L. DUDA ET AL.: "formation ofg a constrained-geometry Ziegler catalyst system containing a c1 instead of the usual Si1 connection between the cyclopentadienyl and amido ligand components" XP002089093 *
EUR. J. INORG. CHEM., no. 8, 1998, pages 1153 - 1162 *
GAMBAROTTA, SANDRO ET AL: "Stepwise reduction of carbon dioxide to formaldehyde and methanol: reactions of carbon dioxide and carbon dioxide like molecules with hydridochlorobis(cyclopentadienyl)zirconium(IV)", J. AM. CHEM. SOC. (1985), 107(22), 6278-82 CODEN: JACSAT;ISSN: 0002-7863, 1985, XP002081914 *
KLEI, E. ET AL: "Reactions of an alkenyltitanocene", J. ORGANOMET. CHEM. (1981), 222(1), 79-88 CODEN: JORCAI;ISSN: 0022-328X, 1981, XP002089092 *
KLEI, E. ET AL: "Reactions of titanocene allyls", J. ORGANOMET. CHEM. (1982), 224(4), 327-39 CODEN: JORCAI;ISSN: 0022-328X, 1982, XP002089091 *

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