ES2596717T3 - Composición de catalizador para la polimerización de olefina y procedimiento de preparación de poliolefina usando la misma - Google Patents

Composición de catalizador para la polimerización de olefina y procedimiento de preparación de poliolefina usando la misma Download PDF

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ES2596717T3
ES2596717T3 ES11769056.0T ES11769056T ES2596717T3 ES 2596717 T3 ES2596717 T3 ES 2596717T3 ES 11769056 T ES11769056 T ES 11769056T ES 2596717 T3 ES2596717 T3 ES 2596717T3
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alkyl
ketal
acetal
aryl
ether group
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Bun-Yeoul Lee
Ji-Hae Park
Seung-Hyun Do
Young-Kook Kim
In-Sung Nam
Seung-Woong Yoon
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Lotte Chemical Corp
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Abstract

Una composición de catalizador para la polimerización de olefinas, que comprende: un compuesto de metal de transición representado por la siguiente fórmula 1; y un compuesto de metal de transición representado por la siguiente fórmula 2:**Fórmula** en la que M unido a Q1 y Q2 es un metal de transición del Grupo 4; Q1 y Q2 son independientemente un halógeno, alquilo C1-C20, alquenilo C2-C20, alquinilo C2-C20, arilo C6-C20, alquil C1-C20 arilo C6-C20, aril C6-C20 alquilo C1-C20, alquilamido C1-C20 o arilamido C6-C20; R1, R2, R3, R4, R5, R6, R7, R8, R9 y R10 son independientemente hidrógeno; alquilo C1-C20 con o sin un grupo acetal, cetal o éter; alquenilo C2-C20 con o sin un grupo acetal, cetal o éter; alquil C1-C20 arilo C6-C20 con o sin un grupo acetal, cetal o éter; aril C6-C20 alquilo C1-C20 con o sin un grupo acetal, cetal o éter; o sililo C1-C20 con o sin un grupo acetal, cetal o éter; y R11, R12 y R13 son independientemente hidrógeno; alquilo C1-C20 con o sin un grupo acetal, cetal o éter; alquenilo C2-C20 con o sin un grupo acetal, cetal o éter; alquil C1-C20 arilo C6-C20 con o sin un grupo acetal, cetal o éter; aril C6-C20 alquilo C1-C20 con o sin un grupo acetal, cetal o éter; sililo C1-C20 con o sin un grupo acetal, cetal o éter; alcoxi C1-C20; o ariloxi C6-C20, en la que M unido a X es uno cualquiera seleccionado entre los elementos de los Grupos 3 a 10 de la tabla periódica; X es alquilo C1-C20, alquilsililo C1-C20, sililalquilo C1-C20, cicloalquilo C3-C20, arilo C6-C20, aril C6-C20 alquilo C1-C20, alquil C1-C20 arilo C6-C20, arilsililo C6-C20, sililarilo C6-C20, alcoxi C1-C20, alquilsiloxi C1-C20, ariloxi C6-C20, halógeno o amina; n es un número entero de 1 a 5; Cp1 y Cp2 son independientemente un ligando con una cadena principal de ciclopentadienilo; B es dimetilsilileno, dietilsilileno, difenilsilileno o etileno; y q es un número entero de 0 a 4.

Description

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En la fórmula 1-a, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 y R13 son como se han definido en la fórmula 1.
A este respecto, el compuesto precursor de fórmula 1-a puede prepararse mediante un procedimiento que comprende: (a) hacer reaccionar un derivado de tetrahidroquinolina representado por la siguiente fórmula 1-b con alquil litio y añadir dióxido de carbono para preparar un compuesto representado por la siguiente fórmula 1-c; y (b) hacer reaccionar el compuesto de fórmula 1-c con alquil litio, añadir un compuesto representado por la siguiente fórmula 1-d y, después, tratar con un ácido:
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<Ejemplo comparativo iv-2: Polimerización usando catalizador no soportado>
Los procedimientos se realizaron de la misma manera que se ha descrito en el Ejemplo iv-1, a excepción de que se añadió dicloruro de bisindenilcirconio a un volumen total de 7,5°µmol sin usar el compuesto de metal de transición E4, para proporcionar un polietileno (95 g).
<Ejemplo iv-5: Polimerización usando catalizador soportado>
Se purgó un autoclave (capacidad: 2 l, acero inoxidable) con nitrógeno a la temperatura ambiente y se llenó con 1 l de n-hexano como disolvente para la polimerización. Después, se añadieron secuencialmente 2°mmol de triisobutil aluminio (suministrado por Aldrich) y 0,1 g del catalizador soportado del Ejemplo iii-1.
El autoclave se calentó hasta 70 ºC, se le proporcionó gas de etileno y se mantuvo a la presión parcial del etileno de 700 kPa para permitir una reacción de polimerización durante una hora.
Después de la finalización de la reacción de polimerización, la solución resultante se enfrió a la temperatura ambiente y se retiró el gas de etileno sobrante. Posteriormente, el polvo de polietileno dispersado en el disolvente se separó por filtración y se secó en un horno de vacío a 80 ºC durante al menos 15 horas para producir un polietileno (120 g).
<Ejemplo iv-6: Polimerización usando catalizador soportado>
Los procedimientos se realizaron de la misma manera que se ha descrito en el Ejemplo iv-5, a excepción de que se usó el catalizador soportado del Ejemplo iii-2 en lugar del catalizador soportado del Ejemplo iii-1, para proporcionar un polietileno (90 g).
<Ejemplo iv-7: Polimerización usando catalizador soportado>
Los procedimientos se realizaron de la misma manera que se ha descrito en el Ejemplo iv-5, a excepción de que se inyectó 1-hexeno adicional (10 ml) después de la adición de n-hexano como disolvente para la polimerización al autoclave, para proporcionar un polietileno (80 g).
<Ejemplo iv-8: Polimerización usando catalizador soportado>
Los procedimientos se realizaron de la misma manera que se ha descrito en el Ejemplo iv-6, a excepción de que se inyectó 1-hexeno adicional (10 ml) después de la adición de n-hexano como disolvente para la polimerización al autoclave, para proporcionar un polietileno (65 g).
<Ejemplo iv-9: Polimerización usando catalizador soportado>
Los procedimientos se realizaron de la misma manera que se ha descrito en el Ejemplo iv-5, a excepción de que se usó el catalizador soportado del Ejemplo iii-3 (añadiendo secuencialmente 0,05 g del catalizador soportado que contenía el compuesto de metal de transición E-4 y 0,05 g del catalizador soportado que contenía dicloruro de bisindenilcirconio) en lugar del catalizador soportado del Ejemplo iii-1, para proporcionar un polietileno (100 g).
<Ejemplo comparativo iv-3: Polimerización usando catalizador soportado>
Los procedimientos se realizaron de la misma manera que se ha descrito en el Ejemplo iv-5, a excepción de que se usaron 0,1 g del catalizador soportado del Ejemplo Comparativo iii-1 en lugar del catalizador soportado del Ejemplo iii-1, para proporcionar un polietileno (90 g).
<Ejemplo comparativo iv-4: Polimerización usando catalizador soportado>
Los procedimientos se realizaron de la misma manera que se ha descrito en el Ejemplo iv-5, a excepción de que se usaron 0,1 g del catalizador soportado del Ejemplo Comparativo iii-2 en lugar del catalizador soportado del Ejemplo iii-1, para proporcionar un polietileno (90 g).
[Tabla 1]
Catalizador
Actividad (kg-PE)/(mmolmetal)(hora) Peso molecular (Pm) (x103) Distribución de peso molecular (Pm/Pn) Punto de fusión (ºC)
Ejemplo iv1
(E-4) + (Ind2ZrCl2) 29,9 445 4.21 134
Ejemplo iv2
(E-6) + (Ind2ZrCl2) 25,3 421 3,83 133
Ejemplo iv3
(E-4) + (Ind2ZrCl2) 34,7 310 4,64 78
Ejemplo iv4
(E-6) + (Ind2ZrCl2) 29,3 290 4,03 86
18
(continuación)
Catalizador
Actividad (kg-PE)/(mmolmetal)(hora) Peso molecular (Pm) (x103) Distribución de peso molecular (Pm/Pn) Punto de fusión (ºC)
Ejemplo comparativo iv-1
(E-4) 29,3 883 2,18 135
Ejemplo comparativo iv-2
(Ind2ZrCl2) 25,3 284 2,84 135
[Tabla 2]
Catalizador
Actividad (kg-PE)/(mmolmetal)(hora) Peso molecular (Pm) (x103) Distribución de peso molecular (Pm/Pn) Punto de fusión (ºC)
Ejemplo iv-5
Ejemplo iii-1 1,2 426 7,85 135
Ejemplo iv-6
Ejemplo iii-2 0,9 386 7,24 134
Ejemplo iv-7
Ejemplo iii-1 0,8 280 8,35 128
Ejemplo iv-8
Ejemplo iii-1 0,7 265 7,51 130
Ejemplo iv-9
Ejemplo iii-3 1,0 410 6,57 135
Ejemplo comparativo iv-3
Ejemplo comparativo iii-1 0,9 3207 2,96 135
Ejemplo comparativo iv-4
Ejemplo comparativo iii-2 0,6 299 2,50 135
5 Como puede observarse a partir de las Tablas 1 y 2, en comparación con los Ejemplos Comparativos de los que las poliolefinas tenían una distribución de peso molecular reducida a 2 a 3, los Ejemplos que usaron los catalizadores de la presente invención proporcionaron poliolefinas con un mayor peso molecular y una distribución de peso molecular más amplia dentro del intervalo que no afecta a la actividad catalítica de los catalizadores.
Además, la presente invención hizo posible preparar poliolefinas con un amplio intervalo de propiedades al cambiar 10 el punto de fusión a través de la copolimerización olefina-olefina.
19

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