ES2094174T3 - Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores. - Google Patents

Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores.

Info

Publication number
ES2094174T3
ES2094174T3 ES91113752T ES91113752T ES2094174T3 ES 2094174 T3 ES2094174 T3 ES 2094174T3 ES 91113752 T ES91113752 T ES 91113752T ES 91113752 T ES91113752 T ES 91113752T ES 2094174 T3 ES2094174 T3 ES 2094174T3
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ES
Spain
Prior art keywords
catalysts
radicals
sub
metal
component
Prior art date
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Expired - Lifetime
Application number
ES91113752T
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English (en)
Other versions
ES2094174T5 (es
Inventor
Howard William Turner
Gregory George Hlatky
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
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Publication of ES2094174T3 publication Critical patent/ES2094174T3/es
Publication of ES2094174T5 publication Critical patent/ES2094174T5/es
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Polymerization Catalysts (AREA)
  • Polymerisation Methods In General (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Steroid Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

SE PREPARA UN CATALIZADOR AL COMBINAR UN PRIMER COMPUESTO CONSISTENTE EN UN COMPUESTO DE METAL BIS (CICLOPENTADIENILO) TENIENDO UNO DE LA SIGUIENTE FORMULA GENERAL: DONDE: M ES UN METAL SELECCIONADO DEL GRUPO QUE CONSISTE EN TITANIO, ZIRCONIO Y HAFNIO; (A-CP) ES BIEN (CP) (CP ELEVADO *) O CP ADO * Y CP Y CP ELEVADO * SON LO MISMO DIFERENTES RADICALES CICLOPENTADIENILAS SUSTITUIDAS O NO SUSTITUIDAS; A'' ES UN GRUPO FORMADOR DE PUENTE COVALENTE; L ES UNA OLEFINA, DIOLEFINA O LIGANTE ARINO; X SUB 1 Y X SUB 2 SON INDEPENDIENTEMENTE, SELECCIONADAS DEL GRUPO QUE CONSISTE EN RADICALES HIDRIDAS, RADICALES HIDROCARBILAS, RADICALES HIDROCARBILAS SUSTITUIDAS, RADICALES ORGANOMETALOIDAS Y SIMILARES; X'' SUB 1 Y X'' SUB 2 ESTAN JUNTAS Y UNIDAS AL ATOMO DE METAL PARA FORMAR UN METALOCICLO, EN EL QUE EL ATOMO DE METAL, X'' SUB 1 Y X'' SUB 2 FORMAN UN ANILLO HIDROCARBOCICLICO CONTENIENDO DE ALREDEDOR DE 3 A ALREDEDOR DE 20 ATOMOS DE CARBONO; Y R ES UN SEGUNDO COMPUESTO QUE ES UN COMPUESTO DE INTERCAMBIO DE IONES COMPRENDIENDO UN CATION QUE REACCIONARA IRREVERSIBLEMENTE CON UN LIGADOR EN DICHO PRIMER COMPONENTE Y UN ANION QUE ES UN SOLO COMPLEJO DE COORDINACION COMPRENDIENDO UNA PLURALIDAD DE RADICALES LIPOFILICOS COVALENTEMENTE COORDINADAS Y PROTEGIENDO UN METAL CON CARGA CENTRAL O ATOMO METALOIDE, CUYO ANION ES VOLUMINOSO Y ESTABLE A LAS REACCIONES QUE INVOLUCRAN EL ION BUSCADOR DEL SEGUNDO COMPONENTE. DESPUES DE LA COMBINACION DEL PRIMER Y SEGUNDO COMPONENTE, EL CATION DEL SEGUNDO COMPONENTE REACCIONA CON UNO DE LOS LIGADORES DEL PRIMER COMPONENTE, GENERANDO ASI UN PAR ION CONSISTENTE EN UN CATION DE METAL DEL METAL DEL GRUPO IV-B CON UN NUMERO DE COORDINACION FORMAL DE 3 Y UNA VALENCIA DE +4 Y EL ANION ANTES MENCIONADO, CUYO ANION ES COMPATIBLE CON Y NO COORDINANDO HACIA EL CATION DE METAL FORMADO DEL PRIMER COMPONENTE. UNOS SEGUNDOS COMPONENTES APROPIADOS PUEDEN ESTAR REPRESENTADOS POR LA SIGUIENTE FORMULA GENERAL: DONDE: L'' ES UNA BASE NEUTRAL LEWIS; H ES UN ATOMO DE HIDROGENO [L''-H] ES UN ACIDO BRONSTED; M'' ES UN METAL O METALOIDE SELECCIONADO DE LOS GRUPOS SUBTENDIDOS POR GRUPOS V-B A V-A DE LA TABLA DE ELEMENTOS PERIODICOS; POR EJ., GRUPOS V-B, VI-B, VII-B, VIII, I-B, II-B III-A, IV-A Y V-A; Q SUB 1 A Q SUB N SON INDEPENDIENTEMENTE SELECCIONADAS DEL GRUPO QUE CONSISTE EN RADICALES HIDRIDAS, RADICALES DIALQUILAMIDO, RADICALES ARILOXIDA Y ALCOXIDA, HIDROCARBILO Y RADICALES HIDROCARBILOS SUSTITUIDAS Y RADICALES ORGANOMETALOIDAS SELECCIONADAS INDEPENDIENTEMENTE DE LAS RADICALES SIGUIENTES: M ES UN ENTERO DE 1 A 7; N ES UN ENTERO DE 2 A 8; Y N TALIZADORES ASI FORMADOS SON ESTABLES Y SE PUEDEN AISLAR Y PUEDEN RECUPERARSE Y ALMACENARSE. LOS CATALIZADORES SE PUEDEN FORMAR Y DESPUES USAR PARA POLIMERIZAR OLEFINAS, DIOLEFINAS Y/O COMPUESTOS ACETILENICALMENTE NO SATURADOS BIEN SOLOS O EN COMBINACION UNO CON OTRO O CON OTROS MONOMEROS O SE PUEDEN FORMAR LOS CATALIZADORES IN SITU DURANTE LA POLIMERIZACION AL AÑADIR LOS COMPONENTES SEPARADOS A LA REACCION DE POLIMERIZACION. LOS CATALIZADORES SE FORMARAN CUANDO SE COMBINEN LOS DOS COMPONENTES EN UN DISOLVENTE APROPIADO O DILUYENTE A UNA TEMPERATURA DENTRO DE UN PROMEDIO DE ALREDEDOR DE -100 C A ALREDEDOR DE 300 C.LOS CATALIZADORES ASI PREPARADOS AFRONTAN UN MEJOR CONTROL DE PESO MOLECULAR DE POLIMERO Y NO ESTAN SUJETOS A REVERSION DE EQUILIBRIO. LOS CATALIZADORES ASI PRODUCIDOS SON TAMBIEN MENOS PIROFONICOS QUE LOS CATALIZADORES DE POLIMERIZACION ZIEGLER-NATTA MAS CONVENCIONALES. CIERTOS DE ESTOS CATALIZADORES TAMBIEN PRODUCEN HOMOPOLIMEROS DE OLEFINAS-(ALFA) TENIENDO PESOS MOLECULARES RELATIVAMENTE ALTOS. CIERTOS DE ESTOS CATALIZADORES PRODUCEN TAMBIEN COPOLIMEROS CONTENIENDO SIGNIFICATIVAMENTE MAS COMONOMERO, MUCHOS DE DICHOS COPOLIMEROS PUEDEN SE ELASTOMERICOS.
ES91113752T 1987-01-30 1988-01-27 Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores. Expired - Lifetime ES2094174T5 (es)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US880087A 1987-01-30 1987-01-30
US8800 1987-01-30
US13348087A 1987-12-22 1987-12-22
US133480 1987-12-22

Publications (2)

Publication Number Publication Date
ES2094174T3 true ES2094174T3 (es) 1997-01-16
ES2094174T5 ES2094174T5 (es) 2005-06-01

Family

ID=26678640

Family Applications (5)

Application Number Title Priority Date Filing Date
ES99201940T Expired - Lifetime ES2237031T3 (es) 1987-01-30 1988-01-27 Procedimiento para la preparacion de un producto polimero con un catalizador que consiste en un par ionico.
ES93201186T Expired - Lifetime ES2150931T5 (es) 1987-01-30 1988-01-27 Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores.
ES93201185T Expired - Lifetime ES2094461T3 (es) 1987-01-30 1988-01-27 Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores.
ES99201939T Expired - Lifetime ES2229620T3 (es) 1987-01-30 1988-01-27 Producto polimerico preparado con un catalizador que comprende un par de iones.
ES91113752T Expired - Lifetime ES2094174T5 (es) 1987-01-30 1988-01-27 Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores.

Family Applications Before (4)

Application Number Title Priority Date Filing Date
ES99201940T Expired - Lifetime ES2237031T3 (es) 1987-01-30 1988-01-27 Procedimiento para la preparacion de un producto polimero con un catalizador que consiste en un par ionico.
ES93201186T Expired - Lifetime ES2150931T5 (es) 1987-01-30 1988-01-27 Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores.
ES93201185T Expired - Lifetime ES2094461T3 (es) 1987-01-30 1988-01-27 Catalizadores, metodo para preparar estos catalizadores y metodo para usar dichos catalizadores.
ES99201939T Expired - Lifetime ES2229620T3 (es) 1987-01-30 1988-01-27 Producto polimerico preparado con un catalizador que comprende un par de iones.

Country Status (20)

Country Link
EP (6) EP0468537B2 (es)
JP (5) JP2965572B2 (es)
KR (1) KR960015192B1 (es)
AT (5) ATE145218T1 (es)
AU (1) AU617990B2 (es)
BR (1) BR8805026A (es)
CA (3) CA1339142C (es)
CZ (1) CZ57988A3 (es)
DE (6) DE3856574T3 (es)
DK (1) DK548888A (es)
ES (5) ES2237031T3 (es)
FI (1) FI101477B (es)
HU (1) HU211065B (es)
IL (1) IL85097A (es)
NO (1) NO179589C (es)
PL (1) PL159196B1 (es)
PT (1) PT86672A (es)
RU (2) RU2139291C1 (es)
WO (1) WO1988005793A1 (es)
YU (2) YU45838B (es)

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