DK2603534T3 - Modificeret katalysatorbærestof - Google Patents

Modificeret katalysatorbærestof Download PDF

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DK2603534T3
DK2603534T3 DK11743250.0T DK11743250T DK2603534T3 DK 2603534 T3 DK2603534 T3 DK 2603534T3 DK 11743250 T DK11743250 T DK 11743250T DK 2603534 T3 DK2603534 T3 DK 2603534T3
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group
catalyst system
metallocene
carbon atoms
supported catalyst
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Christopher Willocq
Martine Slawinski
Aurélien Vantomme
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Total Res & Technology Feluy
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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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
    • C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
    • 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
    • C08F4/02—Carriers therefor
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • 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
    • C08F210/00—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • C08F4/65912—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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Claims (14)

  1. MODIFICERET KATALYSATORBÆRESTOF Patentkrav
    1. Understøttet katalysatorsystem, der omfatter: (a) et copræci pite ret silica- og titandioxidholdigt bærestof, der omfatter en alumoxan, og (b) mindst én metallocen, hvor det understøttede katalysatorsystem har et Ti-indhold på fra 0,1 vægtprocent til 10 vægtprocent.
  2. 2. Understøttet katalysatorsystem ifølge krav 1 med et Ti-indhold på fra 1 til 10 vægtprocent.
  3. 3. Understøttet katalysatorsystem ifølge et hvilket som helst af de foregående krav, hvor metallocenen er valgt blandt formlerne (I) og (II): (Ar)2MQ2 (I) R"(Ar)2MQ2 (II) hvor metallocenerne ifølge formel (I) er ikke-brobundne metallocener, og metallocenerne ifølge formel (II) er brobundne metallocener; hvor metallocenen ifølge formel (I) eller (II) har to Ar bundet til M, som kan være ens eller forskellige fra hinanden; hvor Ar er en aromatisk ring, gruppe eller molekyledel, og hvor hvert Ar uafhængigt af hinanden er valgt fra gruppen bestående af cyclopentadienyl, indenyl, tetrahydroindenyl eller fluorenyl, hvor hver af grupperne eventuelt kan være substitueret med én eller flere substituenter, der uafhængigt af hinanden hver især er valgt fra gruppen bestående af hydrogen, halogen og et hydrocarbyl med 1 til 20 carbonatomer, og hvor hydrocarbylet eventuelt indeholder ét eller flere atomer, som er valgt fra gruppen, der omfatter B, Si, S, O, F og P; hvor M er et overgangsmetal, som er valgt fra gruppen bestående af titan, zirconium, hafnium og vanadium; og fortrinsvis er zirconium; hvor hvert Q uafhængigt af hinanden er valgt fra gruppen bestående af halogen; et hydrocarboxy med 1 til 20 carbonatomer og et hydrocarbyl med 1 til 20 carbonatomer, og hvor hydrocarbylet eventuelt indeholder ét eller flere atomer, som er valgt fra gruppen, der omfatter B, Si, S, O, F og P; og hvor R" er en divalent gruppe eller molekyledel, der danner bro med de to Ar-grupper og er valgt fra gruppen bestående af en Ci-C2o-alkylen, et germanium, et silicium, en siloxan, en alkylphosphin og en amin, og hvor R" eventuelt er substitueret med én eller flere substituenter, som uafhængigt af hinanden hver især er valgt fra gruppen, der omfatter et hydrocarbyl med 1 til 20 carbonatomer, og hvor hydrocarbylet eventuelt indeholder ét eller flere atomer, som er valgt fra gruppen, der omfatter B, Si, S, O, F og P.
  4. 4. Understøttet katalysatorsystem ifølge krav 3, hvor metallocenen er valgt blandt (I) og (II), hvor hvert Ar uafhængigt af hinanden er valgt blandt et indenyl og et tetrahydroindenyl, idet hvert Ar fortrinsvis er ens.
  5. 5. Understøttet katalysatorsystem ifølge et hvilket som helst af de foregående krav, hvor alumoxanen er en oligomer, lineær eller cyklisk alumoxan valgt blandt R-(AI(R)-0)x-AIR2 (III) for oligomere, lineære alumoxaner og (-AI(R)-0-)y (IV) for oligomere, cykliske alumoxaner; hvor x er 1 -40; hvor y er 3-40; og hvor hvert R uafhængigt af hinanden er valgt blandt et C-i-Ce-alkyl, fortrinsvis methyl.
  6. 6. Fremgangsmåde til fremstilling af det understøttede katalysatorsystem ifølge et hvilket som helst af de foregående krav, hvilken fremgangsmåde omfatter følgende trin: a) copræcipitering af præcursorerne af titandioxid og silica i opløsning til dannelse af en gel b) ældning af gelen c) vaskning af gelen til fjernelse af uønskede salte d) tørring af gelen til dannelse af det copræcipiterede silica- og titandioxidholdige bærestof e) behandling af det copræcipiterede silica- og titandioxidholdige bærestof med et katalysatoraktiveringsmiddel, som er alumoxan.
  7. 7. Fremgangsmåde ifølge krav 6, hvor prækursoren af titandioxid er valgt blandt én eller flere af forbindelserne med den almene formel RnTi(OR')m, (RO)nTi(OR')m, hvor R og R' er ens eller forskellige og er valgt blandt hydrocarbylgrupper indeholdende fra 1 til 12 carbonatomer, halogener og hydrogen, og hvor n er 0 til 4, m er 0 til 4, og m+n er lig med 4.
  8. 8. Fremgangsmåde ifølge krav 7, hvor prækursoren af titandioxid er valgt blandt én eller flere i gruppen bestående af tetraalkoxider af titanoxid med den almene formel Ti(OR')4, hvor hvert R er ens eller forskelligt og kan være en alkyl- eller cycloalkylgruppe, der hver især har fra 3 til 5 carbonatomer.
  9. 9. Fremgangsmåde ifølge et hvilket som helst af kravene 6 til 8, hvor prækursoren af silica er valgt blandt én eller flere i gruppen silicatsalte, såsom natriumsilicat, og forbindelser med den almene formel RnSi(OR')m eller (RO)nSi(OR')m, hvor R og R' er ens eller forskellige og er valgt blandt hydrocarbylgrupper indeholdende fra 1 til 12 carbonatomer, halogener og hydrogen, og hvor n er 0 til 4, m er 0 til 4, og m+n er lig med 4.
  10. 10. Fremgangsmåde til fremstilling af en polyolefin, der omfatter trinnet med polymerisering af en olefin i nærværelse af et understøttet katalysatorsystem ifølge et hvilket som helst af kravene 1 til 5.
  11. 11. Fremgangsmåde ifølge krav 10, hvor polymeriseringen udføres: -ved en gasfasefremgangsmåde, fortrinsvis udført i en fluid-bed-reaktor, og/eller -ved en opslæmningsfasefremgangsmåde, fortrinsvis i én eller flere opslæmningsloop-reaktorer, navnlig i to opslæmnings-loop-reaktorer, der er serieforbundet.
  12. 12. Fremgangsmåde ifølge krav 10 eller 11, hvor polyolefinen er polypropylen, og hvor fremgangsmåden omfatter trinnet med polymerisering af propylen ved en bulkfremgangsmåde, fortrinsvis i en loop-reaktor.
  13. 13. Fremgangsmåde ifølge et hvilket som helst af kravene 10 eller 11, hvor olefinen er -ethylen, eventuelt copolymeriseret med en alpha-olefin-comonomer med fra 3 til 10 carbonatomer, fortrinsvis 1-hexen; eller -propylen, eventuelt copolymeriseret med en alpha-olefin-comonomer med fra 4 til 10 carbonatomer eller ethylen, fortrinsvis ethylen.
  14. 14. Polyolefin, der kan opnås ifølge et hvilket som helst af kravene 10 til 13.
DK11743250.0T 2010-08-13 2011-08-16 Modificeret katalysatorbærestof DK2603534T3 (da)

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CN103068857A (zh) 2013-04-24
EA201370034A1 (ru) 2013-06-28
US9403920B2 (en) 2016-08-02
KR101465911B1 (ko) 2014-11-26
KR20130049807A (ko) 2013-05-14
WO2012020145A1 (en) 2012-02-16
EP2603534A1 (en) 2013-06-19
CN103068857B (zh) 2015-12-09
EA024095B1 (ru) 2016-08-31
US20130225772A1 (en) 2013-08-29
EP2603534B1 (en) 2015-07-01

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