WO2002004528A2 - Support de catalyseur fragmentable - Google Patents

Support de catalyseur fragmentable Download PDF

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Publication number
WO2002004528A2
WO2002004528A2 PCT/EP2001/007780 EP0107780W WO0204528A2 WO 2002004528 A2 WO2002004528 A2 WO 2002004528A2 EP 0107780 W EP0107780 W EP 0107780W WO 0204528 A2 WO0204528 A2 WO 0204528A2
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nanoparticles
polymerization
catalyst
carrier
monomer
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PCT/EP2001/007780
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German (de)
English (en)
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WO2002004528A3 (fr
Inventor
Matthias Koch
Markus Klapper
Klaus MÜLLEN
Aurélie FALCOU
Nikolay Nenov
Kristina Margarit-Puri
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MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.
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Priority to AU2001276387A priority Critical patent/AU2001276387A1/en
Publication of WO2002004528A2 publication Critical patent/WO2002004528A2/fr
Publication of WO2002004528A3 publication Critical patent/WO2002004528A3/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
    • 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
    • C08F110/02—Ethene
    • 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+
    • 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
    • C08F4/6592—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 invention relates to fragmentable supports for polymerization catalysts and catalysts supported therewith and a process for their preparation.
  • the supported catalysts can e.g. be used for olefin polymerizations.
  • Polymerization catalysts such as transition metal catalysts for the polymerization of olefins, have long been known. Commonly used examples are Ziegler-Natta catalysts and metallocene aluminoxane type catalysts.
  • the use of metallocenes for olefin polymerizations offers the particular advantages that the catalysts are available in a large, structural variety and can also be custom-made for specific requirements.
  • the tacticity of the polymer formed can be controlled via metallocene catalysts.
  • the metallocenes are well-defined catalyst structures, the single-site catalysts in particular delivering advantageous products, for example with a narrow molecular weight division and constant incorporation of the comonomers.
  • metallocenes are soluble in the solvents usually used for the polymerization of olefins.
  • a morphology check of the product is therefore not possible or only with difficulty.
  • the solubility of the catalyst has in particular the consequence that the desired polyolefin product is mostly obtained as dust, with the result that the product is difficult to process further and that there is a risk of reactor fouling.
  • supported catalysts are usually used. The activity and productivity of such supported catalysts also depends on the type of support used. Cross-linked polymers or inorganic support materials, such as silica gel, are usually used as the support material for transition metal catalysts (WO 94/28034, EP-A-295312, WO98 / 01481).
  • the supported catalysts with a size in the ⁇ m range that are usually used in a heterogeneous polymerization reaction are incorporated into the product or the polymer is formed around the catalyst / support granule.
  • the polymer formed thus contains inclusions of inorganic material, which can be disadvantageous in many areas of application of the polymers, for example in the formation of films.
  • catalyst supports based on crosslinked polymers have also been used in the prior art (WO99 / 5031 1; EP-A-0 614 468).
  • irreversibly cross-linked microparticles formed from polystyrene and divinylbenzene, are used, as is the case with S.B. Roscoe et al., Science 280 (1998), 270-273.
  • supported catalysts made using such polymer microparticles have relatively low activity.
  • the irreversibly crosslinked and therefore non-fragmentable polymer supports form inclusions, which are likewise disadvantageous in many applications.
  • catalyst supports which consist of fragmentable polymers (WO99 / 60035). Soluble polymers were produced for this purpose, which are reversibly crosslinked, for example via a Diels-Alder reaction. When using such Materials for supported catalysts in polymerization reactions, fragmentation of the support up to the soluble individual molecular chains of the polymer can occur. While considerable advantages such as high productivity can be achieved and the risk of inclusions of the carrier material is eliminated, it was found that a further improvement of the system would be desirable for some applications. In particular, the bulk density of polymers obtained with such supported catalysts is often below the desirable range.
  • An object of the present invention was therefore to provide a support for polymerization catalysts and a supported catalyst and a process for their preparation in which the disadvantages of the prior art are at least partially eliminated and by which supported catalysts can be obtained with high productivity.
  • the product formed should be essentially free of interfering inclusions and at the same time have a high bulk density.
  • nanoparticles formed from an irreversibly cross-linked polymer and b) reversible cross-linking of the nanoparticles, whereby fragmentable carrier microparticles are formed.
  • irreversibly crosslinked means that such crosslinking is not solved under the conditions prevailing when the supported polymerization catalyst is used.
  • An irreversibly crosslinked polymer thus retains its integrity under the polymerization conditions prevailing when the supported catalyst is used and is not fragmented.
  • reversible crosslinking denotes a chemical and / or physical crosslinking of polymer chains or latex particles, which is dissolved or reversed under the polymerization conditions in which the supported catalysts are used. The crosslink bonds were thus cleaved when the supported catalyst was used and the support was fragmented.
  • Usual polymerization conditions in particular olefin polymerization conditions in which the supported catalysts are used, have reaction temperatures of from -50 ° C. to 300 ° C., in particular from 0 ° C. to 150 ° C.
  • Such polymerizations will Usually carried out in organic solvents, such as isobutane or hexane, in suspensions, in liquid monomers or in the gas phase, for example in a stirred gas phase or in a gas phase fluidized bed. Irreversible crosslinks remain intact under the reaction conditions, while reversible crosslinks are released.
  • polymer as used herein encompasses both homopolymers in which a single monomer has been reacted and copolymers in which two or more different monomers have been reacted to form the product.
  • the carrier is preferably formed from an organic polymer.
  • the (non-decomposable) nanoparticles formed from an irreversibly crosslinked polymer and thus resistant in the course of a polymerization reaction carried out later using the carrier preferably have an average particle size of 10 nm to 400 nm, in particular 30 nm to 150 nm.
  • the size of the nanoparticles is adjusted in particular so that it lies below the wavelength of visible light in order not to cause scattering centers in the later product.
  • the size of the nanoparticles made of irreversibly crosslinked polymer can be determined by suitable selection of the manufacturing conditions, e.g. Spray drying can be set. However, it is also possible to bring larger particles to the desired size by means of suitable comminution processes, such as grinding or spray drying.
  • Partially fragmentable carrier microparticles are then produced from these nanoparticles by reversible crosslinking, which preferably have a size of 1 ⁇ m to 800 ⁇ m, more preferably 10 ⁇ m to 400 ⁇ m and most preferably 30 ⁇ m to 300 ⁇ m.
  • This Carrier microparticles have the size required to carry out heterogeneous catalysis.
  • the two-stage process according to the invention has the effect that a material is obtained in which there are deliberately two different types of linkages.
  • Nanoparticle spheres are reversibly cross-linked to one another to make them larger and suitable as a carrier for heterogeneous catalysis
  • carrier microparticles To form carrier microparticles.
  • the reversible cross-links or bonds are then broken under the conditions of use of the carrier, so that the carrier microparticle breaks down into the nanoparticles.
  • a fragmentable carrier material is obtained, which is defined to a predetermined extent and up to a predetermined extent
  • Step (a) of the method according to the invention comprises the production of irreversibly cross-linked polymeric nanoparticles.
  • the irreversible crosslinking can be formed, for example, by copolymerization of monomers and crosslinking agents or / and subsequent irreversible crosslinking of polymer chains.
  • the nanoparticles can be formed from any polymers, for example from polymers that are formed by polyaddition, polycondensation or radical polymerization.
  • the nanoparticles are preferably produced by reacting at least one monomer which has at least one olefinically unsaturated bond with at least one crosslinking agent which has at least two olefinically unsaturated bonds.
  • Suitable olefinically unsaturated monomers preferably have the formula I.
  • R 1 , R 2 , R 3 and R 4 independently of one another are hydrogen, halogen, in particular F, a branched or unbranched alkyl, alkenyl, aralkyl or aryl radical which may optionally contain and / or be substituted by heteroatoms.
  • All alkyl, alkenyl, aralkyl and aryl groups mentioned herein preferably have from 1 to 30 carbon atoms, in particular from 1 to 16 carbon atoms.
  • Suitable heteroatoms which may be contained in the radicals are, for example, O, S, N, P etc.
  • Suitable substituents which the groups may have are in particular -OH, -NH 2 , -CN, -COOH, and acid derivatives, such as such as acid amides, esters, etc.
  • At least one of the radicals R 1 , R 2 , R 3 and R 4 is preferably a substituted or unsubstituted phenyl, pyrenyl, naphthyl or alkenyl.
  • Preferred monomers I are styrene, butadiene and isoprene.
  • the properties of the polymer formed, for example the polarity of the polymeric supports, can be modified in a desired manner by the choice of the residues, for example by introducing polar groups, such as, for example, acrylic acid or methacrylic acid esters or nitriles.
  • polar groups such as, for example, acrylic acid or methacrylic acid esters or nitriles.
  • a support in which styrene has been used as monomer I can preferably be used for a styrene polymerization.
  • crosslinking agent Any agent with which two polymer chains can be crosslinked or which one can be used as the crosslinking agent Introduces branching point in a polymer.
  • Crosslinking agents are preferably used which have at least two olefinically unsaturated bonds which are not conjugated.
  • the crosslinking agent preferably has the formula II
  • R 6 , R 7 , R 8 and R 9 each independently represent hydrogen, halogen, in particular F, an alkyl, alkenyl, aralkyl or aryl radical which is branched or unbranched and which may contain and / or be substituted by heteroatoms and R 5 represents a direct chemical bond or an alkyl, alkenyl, aralkyl or aryl radical which can be linear or branched and can optionally contain or / and be substituted by heteroatoms.
  • Preferred crosslinking agents are divinylbenzene, divinylnaphthalene and diisopropenylbenzene.
  • the insoluble nanoparticles which carries at least one further functional group in addition to a polymerizable group, in particular an olefinically unsaturated group.
  • This functional group can be the functional group desired later, for example a hydroxyl group, an amine group, etc., or it can be a substitutable group Leaving group, for example a halogen, especially chlorine, bromine, iodine.
  • the further functionalizing monomer preferably has the formula III
  • R 1 and R 2 are as defined above,
  • A is a direct chemical bond or a linking group and B is a functional group, especially a functional group
  • A is in particular a group
  • n is an integer from 0 to 8.
  • A can also be a saturated, unsaturated or aromatic linking group which may optionally contain heteroatoms and may be substituted.
  • B is preferably selected from halogen, in particular bromine, chlorine, iodine and C, - Cg alkoxy.
  • Particularly preferred compounds of the formula III are bromostyrene, chloromethylstyrene, methoxymethylstyrene and methoxystyrene.
  • Nucleophilically substitutable leaving groups for example tosylate, trifluoroacetate, acetate or azide, can also be used as substitutable leaving group B.
  • the substitutable leaving group X can also be an organometallic functional group such as Li or Mg X 4 , where X 4 represents halogen, in particular fluorine, chlorine, bromine or iodine.
  • the proportion of the monomer is preferably 20-80% by weight, more preferably 30-60% by weight, the proportion of the crosslinker II preferably 2-30% by weight, more preferably 5-20% by weight and the proportion of the functional monomer III is preferably from 0 to 60% by weight, more preferably from 30 to 60% by weight, based on the total weight of the polymer.
  • the addition of an additional crosslinking agent can be dispensed with.
  • a copolymer is prepared from 40-50% by weight of styrene, 5-15% by weight of divinylbenzene and 40-50% by weight of p-bromostyrene.
  • At least one of the monomers used has the formula Ia in step (a)
  • R 10 is a linking group, in particular a direct chemical bond or an alkyl, alkenyl, aralkyl or aryl group, which may be linear or branched and optionally contain heteroatoms or / and can be substituted and C is a polyether radical.
  • the radical C preferably comprises a linking group which connects the polyether radical to the rest of the molecule.
  • C preferably has the formula OR 13 -O- [R 11 -O-] m -R 12 , where R 12 is hydrogen, an alkyl, alkenyl, aralkyl or aryl radical, which can be linear or branched and optionally contain heteroatoms or / and can be substituted.
  • R 13 is preferably a linking group, for example an alkyl, alkenyl, aralkyl or aryl group.
  • Each occurrence of R 11 is independently an alkyl, alkenyl, aralkyl or aryl group, which can be straight-chain or branched and optionally contains or is substituted by further heteroatoms.
  • m is preferably 1-20, particularly preferably 2-10.
  • radical C are polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol etc. and block and mixed copolymers containing PEG or / and PPG.
  • Such monomers containing a polyether substituent are preferably reacted together with a monomer I and chloromethylstyrene as the functionalized monomer.
  • the production of the insoluble nanoparticles is carried out in the presence of a block copolymer. This block copolymer can be embedded in the nanoparticles formed or covalently bonded to and in the nanoparticles.
  • Preferred block copolymers are so-called polymeric surfactants, such as polystyrene-polyethylene glycol block copolymers (so-called Goldschmidt polymers), polyalkane-polyethylene glycols (e.g. Unithox) or other hydrophilic-hydrophobic block copolymers.
  • polymeric surfactants such as polystyrene-polyethylene glycol block copolymers (so-called Goldschmidt polymers), polyalkane-polyethylene glycols (e.g. Unithox) or other hydrophilic-hydrophobic block copolymers.
  • the insoluble nanoparticles in step (a) of the invention are preferably produced by emulsion polymerization.
  • one or more monomers, one or more crosslinking agents and optionally one or more functionalizing monomers are reacted in the presence of an emulsifier.
  • emulsifiers are, for example, ionic surfactants such as SDS (sodium dodecyl sulfate) or sodium dioctyl sulfosuccinate as well as non-ionic surfactants such as ethoxylated polyalkanes (e.g. Unithox from Baker Petrolite).
  • the emulsifier in particular the ionic surfactants, is removed again, for example by centrifugation or filtration.
  • the addition of a separate low molecular weight emulsifier can be dispensed with.
  • the monomers of the formula Ia themselves act as nonionic emulsifiers, the hydrophilic part of which consists of a polyether with a large number of oxygen atoms, preferably from 2 to 20, in particular from 3 to 10, oxygen atoms.
  • Even when using block copolymers, especially polymeric surface-active ones Agents can be dispensed with the addition of low molecular weight emulsifiers in the emulsion polymerization.
  • the irreversibly crosslinked nanoparticles obtained in step (a) are reversibly crosslinked in a second step (b), as a result of which fragmentable carrier microparticles are formed.
  • the reversible crosslinking can be brought about by any linkages which are stable enough to hold the particles together during the application of the catalyst and at the same time labile enough to cause the bonds to be broken and thus the carrier to fragment under polymerization conditions.
  • the reversible crosslinking of the nanoparticles is preferably brought about by a Diels-Alder reaction, fragmentation being carried out here by a Retro-Diels-Alder reaction.
  • a suitable reversible crosslinking can also take place through interactions of nucleophilic groups, for example ether groups, on the polymer with cocatalysts, for example aluminoxanes and in particular methylaluminoxanes.
  • nucleophilic groups for example ether groups
  • cocatalysts for example aluminoxanes and in particular methylaluminoxanes.
  • appropriately substituted monomers can be reacted, but it is also possible to first functionalize the nanoparticles before the reversible crosslinking, this procedure being preferred.
  • the diene functions can be applied to the surfaces of the nanoparticles by suitable reactions if reversible crosslinking by means of a Diels-Alder reaction is desired.
  • Such functionalization with diene functions is preferably achieved by reacting the nanoparticles with a cyclopentadienyl compound or / and a fulvene compound.
  • the reaction can be carried out on unsubstituted nanoparticles, for example nanoparticles formed from polystyrene and divinylbenzene, but is preferably carried out on nanoparticles substituted with a leaving group.
  • Such nanoparticles are obtained by copolymerizing at least one of the above-mentioned monomers III, which have a substitutable leaving group included, manufactured.
  • Suitable cyclopentadienyl compounds IV or fulvene compounds IVa have, for example, the formulas
  • R 4 , R 5 , R 16 and R 17 are each independently hydrogen, halogen, C, - C 10 -
  • CR 19 R 20 C means germanium or silicon
  • R 19 , R 20 independently of one another are hydrogen, methyl, ethyl or phenyl and
  • X 2 represents halogen, methyl, methoxy or ethoxy
  • R 18 is independently C, - C 4 alkyl or substituted or unsubstituted phenyl each time it occurs.
  • 1 to 4-fold substituted cyclopentadienes can also be used as the cyclopentadienyl compound IV.
  • Suitable substituents are in particular C 1 -C 10 -alkyl groups, such as methyl, ethyl and the various isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
  • the radicals can also represent substituted or unsubstituted phenyl radicals.
  • one of the radicals is a group - QR i 9 R 2 o ⁇ 2 jst> jn, in which the variable Q is preferably silicon, the variables R 19 and R 20 are preferably methyl and the group X 2 is preferably halogens, methyl, Means methoxy or ethoxy.
  • a group -QR 19 R 20 X 2 of the formula -Si (CH3) 2 X 2 is particularly preferred.
  • Such a group can be used to build a bridged metallocene structure on a Use the copolymer backbone. Most preferred, however, is unsubstituted cyclopentadiene.
  • Suitable fulvene compounds IVa may be unsubstituted or substituted on the five-membered ring, the substituents being the same as those above for the cyclopentadienyl compounds III. Particularly preferred fulvene compounds IVa are unsubstituted on the 5-ring. Preferred fulvene IVa are substituted twice on the methylene carbon by radicals R 18 , preference being given to methyl, ethyl or the different isomers of propyl or phenyl. A particularly preferred Fulven IVa is Dimethylfulven.
  • Suitable processes for reacting polymers with cyclopentadienyl or fulvene compounds are known to the person skilled in the art.
  • functionalization can be obtained by reaction with a strong base, such as butyllithium or elemental alkali metal, such as sodium, and adding the corresponding cyclopentadienyl or fulvene compound.
  • the surface of the nanoparticles is additionally functionalized with hydroxyl groups.
  • Such functionalization can be achieved, for example, by reacting functional bromine groups in the nanoparticles with n-Buü and acetone.
  • a reversible crosslinking by a Diels-Alder reaction can then be obtained, for example, by heating a suspension of the nanoparticles in a suitable solvent, for example toluene, to about 50-100 ° C.
  • a suitable solvent for example toluene
  • the microparticles are shaped during drying, preferably spherical shapes are preferred.
  • Particles obtained in the reversible crosslinking can, if appropriate, be brought to the desired size by known comminution processes.
  • the nanoparticles before the reversible crosslinking or the microparticles after the reversible crosslinking are preferably further functionalized in order to enable non-covalent binding of the catalysts suitable for the polymerization.
  • the catalysts are preferably bound via nucleophilic or charged groups on the support, such as ethers, aluminoxanes, aluminum alkyl or boron compounds.
  • the carrier particles are therefore preferably reacted with an (a) aluminoxane, (b) aluminum alkyl, (c) polyether or / and (d) a boron compound.
  • These functional groups are preferably linked to the polymeric support via hydroxy compounds, which can be introduced as described above.
  • a silica-analogous system is formed in the polymeric supports according to the invention, namely an association of MAO with the oxygen of a hydroxy function (O ⁇ MAO).
  • a polyether provided with a leaving group such as a tosilated polyether, is preferably used as the polyether.
  • the ether OH groups are transetherified.
  • Suitable tosylated polyethers have in particular the formula
  • Tos is a leaving group, in particular tosyl and R 21 each independently represents an alkyl, alkenyl, aralkyl or aryl radical, which can be branched or linear and can optionally contain or / and be substituted by further heteroatoms, o is preferably from 2 to 10.
  • boron compound Suitable boron compounds which are widely used as cocatalysts for polyolefin polymerizations are known to the person skilled in the art. Tris (pentafluourphenyl) boron is particularly preferably used. This is covalently attached to the support and activated by adding a strong base, for example N, N-dimethylaniline.
  • the catalyst for example a metal complex, is preferably bound via non-covalent interactions.
  • the binding can take place through the coordination of nucleophilic groups on the support with a complex of MAO and the metal compound, or through the electrostatic interaction between the negatively charged boron compound on the support and a positively charged metal complex.
  • the non-covalent binding of the catalyst to the support enables universal use for a wide range of polymerization catalysts.
  • Activation by means of a boron compound has the additional advantage that there is no need for any inorganic additives and that catalytic activity is observed only on the supported catalyst, since removal of the boron compound from the support is accompanied by a loss of charge and thus inactivation of the catalyst ,
  • the invention thus further relates to a method for producing a supported polymerization catalyst, which is characterized in that a support prepared as described above is mixed with a polymerization catalyst or a precursor thereof.
  • the catalyst can be applied by simply adding it to the support, in particular by impregnation.
  • Suitable polymerization catalysts are, for example, transition metal catalysts, such as Ziegler-Natta catalysts or metallocene catalysts. In principle, all catalysts suitable for a polymerization reaction can be immobilized according to the invention. Suitable catalysts are described, for example, by G. Hlatky, Chem. Rev. 100 (2000), 1347-1376.
  • Preferred catalysts are monocyclopentadienyl compounds of the formula VI CpM (X 3 ) 3 VI, in which Cp is a substituted or unsubstituted cyclopentadienyl radical,
  • M represents Ti, Zr or Hf and
  • X 3 each time is independently halogen, hydrogen, C, - C 10 alkyl or C, - C 10 alkoxy or amido.
  • the cyclopentadienyl radical is preferably substituted with methyl, ethyl, propyl or butyl.
  • the cyclopentadienyl ring can also be part of a more complicated ring system.
  • Most preferred are mono- or dialkylcyclopentadienyl, substituted or unsubstituted fluorenyl, indenyl or tetrahydroindenyl radicals.
  • catalysts with cyclopentadienyl radicals which have been modified with a chlorodimethylsilyl group can also be used. Such metallocene complexes can be used to prepare bridged supported metallocenes.
  • Suitable catalyst compounds have the formula Via M (X 3 ) 4 , where M in turn means titanium, zirconium or hafnium.
  • Preferred radicals X 3 are halogen, in particular chlorine and methyl.
  • Precursors of polymerization catalysts are, in particular, compounds which are in contact with the support or / and Cocatalyst which form active catalyst species or can be converted into an active catalyst species by simple derivatization steps.
  • the support can first be functionalized with a cocatalyst or activator, such as an aluminum compound, and then a catalyst can then be added.
  • a cocatalyst or activator such as an aluminum compound
  • a catalyst can then be added.
  • an aluminum compound such as an aluminoxane or a trialkyl aluminum compound
  • the invention further relates to a fragmentable support for polymerization catalysts which can be produced by the process described above.
  • a carrier consists in particular of irreversibly cross-linked nanoparticles, which are reversibly cross-linked to carrier micro-particles.
  • Another object of the invention is also the supported catalyst obtainable by reacting the fragmentable support with a polymerization catalyst.
  • a polymerization catalyst obtainable by reacting the fragmentable support with a polymerization catalyst.
  • the supported catalysts have a high activity of> 400 kg PE / (mol Zr h bar), in particular> 500 kg PE / (mol Zr h bar).
  • the supported catalysts according to the invention enable heterogeneous catalysis due to the microparticles, the carrier particles fragmenting in the course of the polymerization reaction to form the nanoparticles. This achieves high activity and productivity of the catalyst, while at the same time producing a product with a high bulk density can be manufactured. On the other hand, there is no further disintegration of the carrier material down to individual polymer strands due to the irreversible crosslinking of the polymeric nanoparticles.
  • the invention also relates to a copolymer which can be obtained by process steps (a) and (b).
  • a copolymer can also be used for other fields of application except as a support for polymerization catalysts in which partial fragmentation is desired.
  • the supported catalyst according to the invention can be used in particular for the polymerization of olefins.
  • Suitable olefins which can be reacted with are, for example, alpha-olefins, functionalized olefinically unsaturated compounds, such as ester or amide derivatives of acrylic or methacrylic acid, such as acrylate, methacrylate or acrylonitrile.
  • Nonpolar olefinic compounds are preferably reacted, such as linear or branched C 2 -C 12 -alk-1-enes, in particular linear C 2 - C 10 -alk-1-enes, such as ethylene, propylene, but-1-enes, Pent-1-ene, hex-1-ene, hept-1-ene, oct-1-ene, non-1-ene, dec-1-ene or 4-methyl-pent-1-ene or unsubstituted or substituted vinyl aromatic Links.
  • linear or branched C 2 -C 12 -alk-1-enes such as ethylene, propylene, but-1-enes, Pent-1-ene, hex-1-ene, hept-1-ene, oct-1-ene, non-1-ene, dec-1-ene or 4-methyl-pent-1-ene or unsubstituted or substituted vinyl aromatic Links.
  • Examples of preferred vinyl aromatic monomers are styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-phenyl-biphenyl, phenylnaphthalene or phenylanthracene.
  • copolymers from mixtures of different olefins, in particular alpha-olefins.
  • the polymerization of olefins can be in solution, in suspension, in liquid
  • Monomers or be carried out in the gas phase Monomers or be carried out in the gas phase.
  • Customary polymerization conditions are used, that is to say temperatures in the range from -50 to 300 ° C., preferably in the range from 0 to 150 ° C. and pressures in the range from 0.5 to 3000 bar, preferably in the range from 1 to 80 bar.
  • the polyolefins produced using the catalysts supported according to the invention differ from the previously known olefins in that they have a high bulk density and at the same time only have carrier inclusions with a size in the nanometer range. This gives advantageous properties, in particular for film production, from the polyolefins.
  • FIG 1 shows the growth process of polymer particles using different catalyst particles
  • Figure 1 (b) shows polymer growth on a catalyst supported on a soluble support.
  • the catalyst is evenly distributed in the reaction medium and the numerous centers lead to a dust-like product.
  • the advantage here is the high productivity in relation to the catalyst. Similar behavior is observed in homogeneous catalysis.
  • FIG. 1 (c) shows the use of a catalyst on an exclusively reversibly cross-linked support.
  • the carrier dissolves completely, so that numerous, very small active centers are formed and a product with low bulk density, in which many air spaces are enclosed, is obtained.
  • Figure 1 (d) shows polymer growth using a supported catalyst according to the invention using reversibly cross-linked insoluble nanoparticles.
  • the microcarrier particle disintegrates into nanoparticles, which in turn are stable and do not disintegrate further. This results in a product with a high bulk density and small air spaces and at the same time high productivity.
  • FIG. 2 shows the functionalization and reversible crosslinking of the carrier particles according to the invention. Is shown in the first
  • Step functionalization with a diene group for a later Diels-Alder reaction
  • dimethylfulvene for a later Diels-Alder reaction
  • reversible crosslinking of the nanoparticles is then achieved by heating via a Diels-Alder reaction.
  • FIG. 3 shows various possibilities for functionalizing the nanoparticles or reversibly cross-linked microparticles in order to create non-covalent binding sites for one
  • the functionalization can be carried out by reaction with MAO to form O ⁇ MAO adducts, by reaction with a tosylated polyether to form polyether-derivatized particles and by reaction with a strong base, for example dimethylaniline and a boron compound, for example tris (pentafluorophenyl) boron.
  • a strong base for example dimethylaniline and a boron compound, for example tris (pentafluorophenyl) boron.
  • FIG. 4 illustrates the non-covalent binding of a catalyst, for example a metallocene, to the support according to the invention.
  • the binding is done via Interactions between polyether chains on the support, MAO and the metallocene.
  • FIG. 5 illustrates a further possibility of attaching a catalyst non-covalently to the support.
  • a boron activator is covalently bound to the carrier.
  • the catalyst is bound by electrostatic interactions.
  • Another activator, such as MAO, is not required with this procedure.
  • FIG. 6 illustrates a preferred embodiment for the formation of irreversibly cross-linked nanoparticles by reacting styrene, bromostyrene and divinylbenzene in an emulsion polymerization in the presence of SDS.
  • the bromine-functionalized nanoparticles are then coated with n-BuLi,
  • FIG. 7 shows how such nanoparticles can be reversibly crosslinked via a Diels-Alder reaction, as a result of which OH-functionalized microparticles are formed. These microparticles can then be functionalized with MAO, PEO or BPH F 3 as described above in order to serve as a support for catalysts.
  • Rotary evaporator evaporated to give a pale yellow oil. No further cleaning is required.
  • Example 2 Preparation of a non-irreversibly cross-linked copolymer polystyrene-co-4-Br-styrene (comparative example).
  • a copolymer of styrene and 4-bromostyrene in a ratio of 1: 1 (molar ratio) is used as the starting carrier polymer.
  • a mixture of 39 mmol styrene (4.1 g, 4.5 ml), 39 mmol 4-bromostyrene (7.2 g, 5.2 ml), AIBN (0.05 g, 0.3 mmol) and toluene ( 10 ml) is degassed and at 70 ° C for 24
  • the polystyrene-co-4-Br-styrene copolymer (2 g, 6.88 mmol Br units) is dissolved in 200 ml dry THF and the
  • Styrene, 4-Br-styrene and divinylbenzene (DVB) in the amounts given in Table 1 were mixed.
  • the monomers were added to a solution of surfactant (SDS), water and KOH (1 M). After 30 minutes the mixture was heated to 60 ° C and the polymerization was started by adding K 2 S 2 O 8 and then carried out under an argon atmosphere with mechanical stirring (600 rpm) for 24 hours.
  • the particles were separated by centrifugation (3 x 50 min at 1800 rpm in an Ultrafref-15 centrifugal filter device, Biomax-50K NMWL membrane) and freeze-dried.
  • Example 5 Preparation of a carrier using latex particles.
  • Particles formed from 48 mmol styrene units, 48.6 mmol 4-Br-styrene units and 9.6 mmol divinylbenzene units (9% cross-linked) were used as the starting polymer. These nanoparticles were functionalized with diene groups and polyether groups as described in Example 3.
  • tulol 3 ml of tulol are first added to 0.5 g of the carrier material and this suspension is heated to 85 ° C. for 72 hours. After the solution has cooled to room temperature, 1 ml of MAO is added to remove water, which may be added to the PEG
  • Example 7 Ethylene polymerization using the partially fragmentable supported catalyst.
  • Ethene was polymerized in isobutane for 60 minutes at 40 bar and 70 ° C using the catalyst prepared in Example 6. A polyethene with a bulk density of 400 g / l was obtained. The activity of the catalyst was 520 kg PE / (mol Zr h bar) and the productivity 680 g PE / g catalyst. The Al / Zr ratio was 300 with an amount of 33 ⁇ mol Zr / g catalyst.
  • Divinylbenzene (183 mg, 1, 4 mmol) are suspended in 50 ml of THF, cooled to -78 ° C and with 4.3 ml of n-butyllithium solution (1, 6 M) in hexane (6.9 mmol, 1, 1 eq). After a reaction time of 15 minutes, 292 mg acetone (5.0 mmol, 0.8 eq and 267 mg
  • the mixture is poured into 250 ml of methanol and the solvent is almost completely removed on a rotary evaporator.
  • the nanoparticles accumulate and can be filtered. They are cleaned by repeated slurrying with methanol and subsequent filtration. After drying in a high vacuum, the functionalized carrier particles are obtained.
  • the polymer is allowed to settle, the supernatant solution is removed, washed with 10 ml of hexane and the support is dried in vacuo.
  • the polymer is carried in 2 ml of a 1 M solution of
  • the catalyst is not dried, but used as a suspension and has the composition 500 mg polymer, 170 ⁇ mol boron, 50 ⁇ mol metallocene, i.e. 30 ⁇ mol Zr / g cat.
  • Example 10
  • 4-vinyl phenol (1) was prepared according to the method of Corson et al., J. Org. Chem. 23 (1 958), 544-548.
  • Transparent films were produced from propylene polymers which were produced using catalysts supported according to the invention. 100 mg of polypropylene prepared according to the invention was heated in a press at 160 ° C. for 10 minutes and then with a
  • films were formed from polypropylene, which was produced using metallocenes, which were provided on supports which were completely irreversibly crosslinked with divinylbenzene, as described, for example, in WO99 / 5031 1, EP-0 61 4 468 and S.B. Roscoe et al., Science 280 (1,998), 270-273.
  • metallocenes which were provided on supports which were completely irreversibly crosslinked with divinylbenzene, as described, for example, in WO99 / 5031 1, EP-0 61 4 468 and S.B. Roscoe et al., Science 280 (1,998), 270-273.
  • block copolymer SEE-101 0 (polystyrene) 10 - (EO) 10 the block copolymer
  • the block copolymers are dissolved in 25 ml of N, N'-dimethylformamide overnight, then, after adding the same amount of Millipore water, the solvent is spun off. The reaction is carried out in a three-necked flask (100 ml) with an argon inlet, reflux condenser and KPG glass stirrer. A mixture of water, potassium hydroxide solution and emulsifier (block copolymer) is initially introduced, homogenized and argon flowed through.
  • styrene and divinylbenzene crosslinking agent; approx. 10% mol / mol of the amount of monomers
  • crosslinking agent approx. 10% mol / mol of the amount of monomers
  • the system is heated to 70 ° C. by means of a temperature control unit and started at a constant temperature by adding the initiator solution (likewise through which argon flows).
  • the particle size and dispersity are determined by dynamic light scattering (Malvern Zetasizer 4000).
  • nanoparticles produced with emulsifiers SEE 10/10 or Unithox 750
  • emulsifiers SEE 10/10 or Unithox 750 0.25 g are placed in a dried (heated in vacuo for 20 min) and argon-filled Schlenk tube. The calculated amount of MAO is then added and the mixture is stirred at room temperature for 12 h.
  • the intended amount of catalyst dissolved in MAO is added to the reaction mixture.
  • the mixture is stirred for 20 minutes.
  • the catalyst thus obtained is mixed with 40 ml of freshly distilled hexane dried over Na / K / benzophenone in a Schlenk tube.
  • the mixture is stirred for 10 min. After the catalyst has failed, it will Removed hexane with a syringe.
  • the catalyst is dried in vacuo (10 2 bar) for 24 h.

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Abstract

L'invention concerne des supports fragmentables pour des catalyseurs de polymérisation, ainsi que des catalyseurs à support et des procédés pour leur production. Ces catalyseurs à support peuvent être employés par exemple pour les polymérisations d'oléfines.
PCT/EP2001/007780 2000-07-07 2001-07-06 Support de catalyseur fragmentable WO2002004528A2 (fr)

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AU2001276387A AU2001276387A1 (en) 2000-07-07 2001-07-06 Fragmentable catalyst support

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DE10033147.5 2000-07-07
DE2000133147 DE10033147A1 (de) 2000-07-07 2000-07-07 Fragmentierbarer Katalysatorträger

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007045616A1 (fr) * 2005-10-18 2007-04-26 Cinvention Ag Particules thermodurcies et procédés pour la production de celles-ci

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995025129A1 (fr) * 1994-03-17 1995-09-21 Exxon Chemical Patents Inc. Polymere seche par pulverisation pour support de catalyseur
WO1999060035A1 (fr) * 1998-05-15 1999-11-25 Basf Aktiengesellschaft Procede de production de catalyseurs a support

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995025129A1 (fr) * 1994-03-17 1995-09-21 Exxon Chemical Patents Inc. Polymere seche par pulverisation pour support de catalyseur
WO1999060035A1 (fr) * 1998-05-15 1999-11-25 Basf Aktiengesellschaft Procede de production de catalyseurs a support

Non-Patent Citations (2)

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Title
GOUSSE C ET AL: "APPLICATION OF THE DIELS-ALDER REACTION TO POLYMERS BEARING FURAN MOIETIES. 2. DIELS-ALDER AND RETRO-DIELS-ALDER REACTIONS INVOLVING FURAN RINGS IN SOME COPOLYMERS" MACROMOLECULES, AMERICAN CHEMICAL SOCIETY. EASTON, US, Bd. 31, Nr. 2, 27. Januar 1998 (1998-01-27), Seiten 314-321, XP000728691 ISSN: 0024-9297 *
STORK M ET AL: "ETHYLENE POLYMERIZATION USING CROSSLINKED POLYSTYRENE AS SUPPORT FOR ZIRCONOCENE DICHLORIDE/METHYLALUMINOXANE" MACROMOLECULAR: RAPID COMMUNICATIONS, WILEY VCH, WEINHEIM, DE, Bd. 20, Nr. 4, April 1999 (1999-04), Seiten 210-213, XP000835009 ISSN: 1022-1336 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007045616A1 (fr) * 2005-10-18 2007-04-26 Cinvention Ag Particules thermodurcies et procédés pour la production de celles-ci

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