PROCEDIMIENTO PARA LA PREPARACION DE UN PRODUCTO POLIMERO CON UN CATALIZADOR QUE CONSISTE EN UN PAR IONICO

• Main Authors: HLATKY, GREGORY GEORGE, TURNER, HOWARD WILLIAM
• Format: Patent
• Language: Spanish
• Published: 16.07.2005
• Edition: 7
• Subjects: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAININGELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN,SULFUR, SELENIUM OR TELLURIUM; CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOIDCHEMISTRY; CHEMISTRY; COMPOSITIONS BASED THEREON; MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVINGCARBON-TO-CARBON UNSATURATED BONDS; METALLURGY; ORGANIC CHEMISTRY; ORGANIC MACROMOLECULAR COMPOUNDS; PERFORMING OPERATIONS; PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL; THEIR PREPARATION OR CHEMICAL WORKING-UP; THEIR RELEVANT APPARATUS; TRANSPORTING

LA INVENCION SE REFIERE A UN CATALIZADOR PREPARADO COMBINANDO UN PRIMER COMPUESTO FORMADO POR UN COMPUESTO DE BIS(CICLOPENTADIENIL)ZIRCONIO QUE TIENE UNA DE LAS SIGUIENTES FORMULAS: DONDE (A-CP) ES, BIEN (CP)(CP*) O CP - A'' - CP*, Y CP Y CP* SON RADICALES CICLOPENTADIENILO SUSTITUIDOS O SIN SUSTITUIR, IGUALES O DISTINTOS; A'' ES UN GRUPO DE PUENTE COVALENTE; L ES UNA OLEFINA, DIOLEFINA O LIGANDO ARINO; ZR ES ZIRCONIO; X 1 Y X 2 SE SELECCIONAN INDEPENDIENTEMENTE A PARTIR DEL GRUPO FORMADO POR RADICALES HIDRURO, RADICALES HIDROCARBILO, RADICALES HIDROCARBILO SUSTITUIDOS, RADICALES ORGANOMETALOIDES Y SIMILARES; X'' 1 Y X'' 2 ESTAN UNIDOS ENTRE SI Y UNIDOS AL ATOMO DE ZIRCONIO FORMANDO UN CICLO METALICO, EN EL CUAL EL ZIRCONIO, X'' 1 Y X'' 2 FORMAN UN ANILLO HIDROCARBOCICLI CO QUE CONTIENE DE APROX. 3 A 20 ATOMOS DE CARBONO; Y R ES UN SUSTITUYENTE EN UNO DE LOS RADICALES CICLOPENTADIENILO, QUE ESTA UNIDO ASIMISMO AL ATOMO DE ZIRCONIO. DICHO PRIMER COMPUESTO SE COMBINA CON UN SEGUNDO COMPUESTO QUE COMPRENDE UN CATION CAPAZ DE DONAR UN PROTON Y UN ANION LABIL, VOLUMINOSO, QUE CONTIENE UN UNICO ATOMO DE BORO Y DIVERSOS RADICALES AROMATICOS, CAPAZ DE ESTABILIZAR EL CATION ZIRCONIO QUE TIENE FORMALMENTE UN NUMERO DE COORDINACION DE 3 Y UNA VALENCIA DE +4, FORMADO COMO RESULTADO DE DICHO SEGUNDO COMPUESTO, DE FORMULA GENERAL: DONDE: L ES UNA BASE DE LEWIS NEUTRA; H ES UN ATOMO DE HIDROGENO; [L'' - H] + ES UN ACIDO DE BRONSTED; B ES BORO EN ESTADO DE VALENCIA 3; AR 1 Y AR 2 SON RADICALES HIDROCARBONADOS AROMATICOS O AROMATICOS SUSTITUIDOS, IGUALES O DISTINTOS, QUE PUEDEN ESTAR UNIDOS ENTRE SI A TRAVES DE UN GRUPO DE PUENTE ESTABLE; Y X 3 Y X 4 SE SELECCIONAN INDEPENDIENTEMENTE A PARTIR DEL GRUPO FORMADO POR RADICALES HIDRURO, RADICALES HALURO, RADICALES HIDROCARBILO, RADICALES HIDROCARBILO SUSTITUIDOS, RADICALES ORGANOMETALOIDES, Y SIMILARES. MUCHOS DE LOS CATALIZADORES FORMADOS DE ESTA MANERA SON ESTABLES Y AISLABLES, Y SE PUEDEN RECUPERAR Y ALMACENAR. DICHOS CATALIZADORES SE PUEDEN PREFORMAR Y SE PUEDEN UTILIZAR A CONTINUACION PARA POLIMERIZAR OLEFINAS, DIOLEFINAS Y/O COMPUESTOS ACETILENICAMENTE INSATURADOS, BIEN SOLOS O COMBINADOS ENTRE SI O CON OTROS MONOMEROS; O BIEN SE PUEDEN FORMAR DICHOS CATALIZADORES IN SITU DURANTE LA POLIMERIZACIO, MEDIANTE ADICION DE LOS COMPONENTES SEPARADOS A LA REACCION DE POLIMERIZACION. EL CATALIZADOR SE FORMA CUANDO LOS DOS COMPONENTES SE COMBINAN EN UN DISOLVENTE O DILUYENTE ADECUADO, A UNA TEMPERATURA COMPRENDIDA ENTRE APROX. -100 Y 300 C. LOS CATALIZADORES ASI PREPARADOS PROPORCIONAN UN CONTROL MEJORADO DEL PESO MOLECULAR POLIMERICO Y NO ESTAN SOMETIDOS A UNA INVERSION DEL EQUILIBRIO. DICHOS CATALIZADORES SON ASIMISMO MENOS PIROFORICOS QUE LOS CATALIZADORES DE POLIMERIZACION DE OLEFINAS DE ZIEGLER-NATTA CONVENCIONALES. A catalyst is prepared by combining a first compound consisting of a bis(cyclopentadienyl)zirconium compound having one of the following general formulae:Wherein:(A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp* and Cp and Cp* are the same or different substituted or unsubstituted cyclopentadienyl radicals;A' is a covalent bridging group;L is an olefin, diolefin or aryne ligand;Zr is zirconium;X1 and X2 are, independently, selected from the group consisting of hydride radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals, organometalloid radicals and the like;X'1 and X'2 are joined and bound to the zirconium atom to form a metallacycle, in which the zirconium, X'1 and X'2 form a hydrocarbocyclic ring containing from about 3 to about 20 carbon atoms; andR is a substituent on one of the cyclopentadienyl radicals which is also bound to the zirconium atom. With a second compound comprising a cation capable of donating a proton and a bulky, labile anion containing a single boron atom, and a plurality of aromatic radicals capable of stabilizing the zirconium cation formally having a coordination number of 3 and a valence of +4 which is formed as a result of the combination, said second compound having the general formula:         [L'-H]+[BAr1Ar2X3X4]-Wherein:L' is a neutral Lewis base;H is a hydrogen atom;[L'-H]+ is a Bronsted acid;B is boron in a valence state of 3;Ar1 and Ar2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals which may be linked to each other through a stable bridging group; andX3 and X4 are, independently, selected from the group consisting of hydride radicals, halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals, organometalloid radicals and the like. Many of the catalysts thus formed are stable and isolable and may be recovered and stored. The catalysts may be preformed and then used to polymerize olefins, diolefins and/or acetylenically unsaturated compounds either alone or in combination with each other or with other monomers or the catalysts may be formed in situ during polymerization by adding the separate components to the polymerization reaction. The catalyst will be formed when the two components are combined in a suitable solvent or diluent at a temperature within the range from about -100°C to about 300°C. The catalysts thus prepared afford better control of polymer molecular weight and are not subject to equilibrium reversal. The catalysts thus produced are also less pyrophoric than the more conventional Ziegler-Natta olefin polymerization catalysts.