ES2565410T3 - Copoliméro de bloque que presenta flujo y elasticidad alta - Google Patents

Copoliméro de bloque que presenta flujo y elasticidad alta Download PDF

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ES2565410T3
ES2565410T3 ES05723937.8T ES05723937T ES2565410T3 ES 2565410 T3 ES2565410 T3 ES 2565410T3 ES 05723937 T ES05723937 T ES 05723937T ES 2565410 T3 ES2565410 T3 ES 2565410T3
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block
molecular weight
hydrogenation
block copolymer
styrene
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Dale Handlin, Jr.
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Kraton Polymers US LLC
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Abstract

Copolímero de bloque hidrogenado selectivamente que presenta un bloque S y un bloque E1 y que presenta la fórmula general: (S-E1)nX o mezclas de los mismos con uno cualquiera de fórmula general: S-E-S o (S-E1)n o (S-E1)nS, en los que: (a) antes de la hidrogenación el bloque S es un bloque de poliestireno; (b) antes de la hidrogenación el bloque E es un bloque de polidieno, seleccionado de entre el grupo que comprende polibutadieno, poliisopreno y mezclas de los mismos, que presenta un peso molecular comprendido entre 40.000 y 70.000; (c) antes de la hidrogenación el bloque E1 es un bloque de polidieno, seleccionado de entre el grupo que comprende polibutadieno, poliisopreno y mezclas de los mismos, que presenta un peso molecular comprendido entre 20.000 y 35.000; (d) n es un número entero con un valor comprendido entre 2 y 6, y X es un residuo de agente de acoplamiento; (e) el contenido en estireno del copolímero de bloque se encuentra comprendido entre el 13 por ciento y el 25 por ciento. (f) el contenido de vinilo del bloque de polidieno antes de la hidrogenación está comprendido entre el 70 y el 85 por ciento en moles; (g) el copolímero de bloque comprende menos de un 15 por ciento en peso del contenido en unidades de bajo peso molecular que presentan la fórmula general: S-E o S-E1 en la que S, E y E1 son tal como se ha definido anteriormente; (h) tras la hidrogenación aproximadamente del 0 al 10% de los dobles enlaces de estireno se han hidrogenado y por lo menos el 90 % de los dobles enlaces de dieno conjugado se han hidrogenado; (i) el peso molecular de cada uno de los bloques S está comprendido entre 5.000 y 7.000. (j) el índice de fusión del copolímero de bloque es superior o igual a 12 gramos/10 minutos según ASTM D1238 a 230° C y 2,16 kg de peso; y (k) la temperatura de orden-desorden (ODT) del copolímero de bloque se define como la temperatura por encima de la que se puede medir una viscosidad transversal cero mediante reología capilar o reología dinámica utilizando un reómetro BohilnVOR y es inferior a 250 °C.

Description

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Se tomaron muestras de tal modo que se pudiese determinar el peso molecular del bloque de estireno y los bloques de butadieno e isopreno. Se determinó asimismo la cantidad de butadieno con la configuración 1,2 antes de la hidrogenación y la eficiencia del acoplamiento. Se analizó el copolímero de bloque hidrogenado con respecto al flujo de fusión y la ODT. Los resultados del análisis se presentan a continuación en la tabla 1.
Ejemplo 2
Se preparó un copolímero de bloque hidrogenado mediante polimerización aniónica de estireno y a continuación butadieno en presencia de un agente de control de la microestructura seguido por el acoplamiento y tras ello la hidrogenación: se preparó un polímero dibloqueaniónico, S-B-Li cargando 348 kg de ciclohexano y 26 kg de estireno en un reactor. Se aumentó la temperatura del reactor hasta 40 °C. Se eliminaron las impurezas añadiendo pequeñas cantidades iguales de s-butil-litio hasta que aparecieron los primeros indicios de color. Se añadieron 3.160 mililitros de una disolución de una solución de s-butil-litio en ciclohexano al 12 % en peso y se dejó que el estireno completase la polimerización a 60 °C. Se determinó que el peso molecular del poliestireno producido en esta reacción era de 6.200 mediante GPC. La temperatura se mantuvo a 60 °C, se añadieron 450 g de 1,2dietoxipropano y a continuación se añadieron 90 kg de butadieno con un ritmo que permitiese que la temperatura permaneciera a 60 °C. Una muestra recogida al final de la polimerización del butadieno presentó un contenido en estireno del 22 % en peso y un contenido en vinilo del 81 % basándose en una 1H NMR y un peso molecular global de 30.200 determinado por GPC. Se dejó polimerizar el butadieno y a continuación se añadieron 363 g de TESi, y se dejó que la reacción de acoplamiento procediera durante 60 minutos a 60 °C. Se añadió metanol (15 g, 0,1 moles por mol de Li) para finalizar la reacción. El producto final presentó una eficiencia de acoplamiento del 89 % y el 65 % de las especies acopladas eran lineales y el 35 % restante era radial con 3 ramas.
Se hidrogenó una muestra del polímero hasta una concentración de olefina residual de 0,17 meq/g en presencia de 20 ppm de un catalizador de Ni/disolución de un octanoato de níquel - trietilo de aluminio (Al/Ni = 2,1 mol/mol). Tras la hidrogenación en dichas condiciones, un 89 % del polímero permaneció acoplado. Se eliminó el catalizador lavando con ácido fosfórico acuoso y se recuperó el polímero mediante destilación por arrastre de vapor, en unas condiciones típicas para los polímeros hidrogenados. Se tomaron muestras de tal modo que se pudiese determinar el peso molecular del bloque de estireno y de los bloques de butadieno. Se determinó asimismo la cantidad de butadieno con la configuración 1,2 antes de la hidrogenación y la eficiencia del acoplamiento. Se analizó el copolímero de bloque hidrogenado con respecto al flujo de fusión y la ODT. Los resultados del análisis se presentan a continuación en la tabla 1.
Ejemplo 3
Se preparó un copolímero de bloque hidrogenado mediante polimerización aniónica de estireno y a continuación butadieno en presencia de un agente de control de la microestructura seguido por el acoplamiento y tras ello la hidrogenación: se preparó un polímero dibloqueaniónico, S-B-Li cargando 243 kg de ciclohexano y 20 kg de estireno en un reactor. Se aumentó la temperatura del reactor hasta 40 °C. Se eliminaron las impurezas añadiendo pequeñas cantidades iguales de s-butil-litio hasta que aparecieron los primeros indicios de color. Se añadieron 2.500 mililitros de una disolución de una solución de s-butil-litio en ciclohexano al 12 % en peso y se dejó que el estireno completase la polimerización a 60 °C. Se determinó que el peso molecular del poliestireno producido en esta reacción era de 6.100 mediante GPC. La temperatura se mantuvo a 60 °C, se añadieron 210 g de 1,2dietoxipropano y a continuación se añadieron 60 kg de butadieno con un ritmo que permitiese que la temperatura permaneciera a 60 °C. Una muestra recogida al final de la polimerización del butadieno presentó un contenido en estireno del 22 % en peso y un contenido en vinilo del 76 % basándose en una 1H NMR y un peso molecular global de 27.700 determinado por GPC. Se dejó polimerizar el butadieno y a continuación se añadieron 243 g de TESi, y se dejó que la reacción de acoplamiento procediera durante 60 minutos a 60 °C. El producto final presentó una eficiencia de acoplamiento del 94 % y el 62 % de las especies acopladas eran lineales y el 38 % restante era radial con 3 ramas.
Se hidrogenó una muestra del polímero hasta una concentración de olefina residual de 0,17 meq/g en presencia de 10 ppm de un catalizador de Ni/disolución de un octanoato de níquel - trietilo de aluminio (Al/Ni = 2,1 mol/mol). Tras la hidrogenación en dichas condiciones, un 89 % del polímero permaneció acoplado. Se eliminó el catalizador lavando con ácido fosfórico acuoso y se recuperó el polímero mediante destilación por arrastre de vapor, en unas condiciones típicas para los polímeros hidrogenados.
Se tomaron muestras de tal modo que se pudiese determinar el peso molecular del bloque de estireno y los bloques de butadieno. Se determinó asimismo la cantidad de butadieno con la configuración 1,2 antes de la hidrogenación y la eficiencia del acoplamiento. Se analizó el copolímero de bloque hidrogenado con respecto al flujo de fusión y la ODT. Los resultados del análisis se presentan a continuación en la tabla 1.
Ejemplo 4
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Se preparó un polímero mediante el procedimiento de los ejemplos 2 y 3 en los que se cambiaron las cargas de estireno y butadieno de tal modo que el bloque de estireno presentó un peso molecular de 6.200, el peso molecular global antes del acoplamiento fue de 33.200, el contenido en vinilo fue del 78 % y el grado de acoplamiento fue del 97 %. Tras la hidrogenación la eficiencia de acoplamiento fue del 96 % y la insaturación residual fue de 0,1 meq/g.
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Ejemplo 5
Se preparó un polímero según el procedimiento de los ejemplos 2 y 3 con la excepción de que se utilizó metiltrimetoxisilano como agente de acoplamiento. Se cambiaron las cargas de estireno y butadieno de tal modo que
10 el bloque de estireno presentó un peso molecular de 6.200, el peso molecular global antes del acoplamiento fue de 32.800, el contenido en vinilo fue de 76 y el grado de acoplamiento fue de 94.
Ejemplo 6
15 Se preparó un polímero según el procedimiento de los ejemplos 2 y 3 con la excepción de que se utilizó tetrametoxisilano como agente de acoplamiento. Se cambiaron las cargas de estireno y butadieno de tal modo que el bloque de estireno presentó un peso molecular de 6.100, el peso molecular global antes del acoplamiento fue de 34.500, el contenido en vinilo fue de 76 y el grado de acoplamiento fue de 95.
20 Ejemplos comparativos I, II y III
Se prepararon los copolímeros de bloque hidrogenados comparativos I y II y se analizaron de un modo sustancialmente idéntico al ejemplo 2 con la excepción de que el peso molecular del bloque de estireno era superior a al peso molecular máximo de la presente invención. Se preparó el ejemplo comparativo III mediante la
25 polimerización secuencial del estireno, a continuación butadieno, después estireno seguido por la hidrogenación. Los resultados del análisis se presentan a continuación en la tabla 1.
Tabla 1
Ejemplo #
Bloque S peso mol. (k) Bloque E1peso mol. (k) Bloque E peso mol. (k) Eficiencia de acoplamiento 1,2-butadieno en el bloque E % ODT °C Índice de fusión
1
6,4 27,7 91 68 250 18
2
6,2 24,0 89 81 230 81
3
6,1 21,6 94 76 230 72
4
6,2 27,0 97 78 240 17
5
6,2 26,6 94 76 <250 31
6
6,1 28,5 95 76 <250 20
I
7,5 30,8 84 67 260 10
II
7,9 26,8 92 69 300+ 6
III
7,2 55,8 8,5* 68 300+ 7
Los valores del peso molecular indicados son pesos moleculares reales determinados utilizando cromatografía de exclusión por tamaños y estándares de poliestireno. Se determinaron las ODT utilizando un reómetro BohlinVOR. Método de prueba del índice de fusión [230 °C, 2,16 kg, ASTM D-1238]
30
Los ejemplos 1 a 4 y los ejemplos comparativos I a III demostraron que el peso molecular del bloque S puede tener un efecto significativo en el índice de fusión y/o la ODT.
35 Ejemplos 5 - 7
Se prepararon películas a partir de algunos de los polímeros de la tabla 1 añadiendo antiadherente al 0,15 % y el estabilizante Ethanox 330 al 0,02 % seguido por la extrusión en una línea de película colada Davis Standard a 230 °C. Los polímeros 2 y 3 proporcionaron unas presiones de extrusión bajas y formaron películas lisas y
40 transparentes gracias a su fluencia elevada. En el ejemplo III se obtuvieron unas películas más rugosas con una contrapresión de extrusión elevada. Las propiedades relacionadas con la tracción y la histéresis de dichas películas determinadas en la dirección de extrusión según ASTMD412 se representan en la tabla 2. Todas presentaron una resistencia y una elasticidad excelentes, tal como se demuestra mediante la elevada recuperación del primer ciclo y una baja deformación remanente permanente tras la elongación hasta un 300 %.
11
imagen9
imagen10
imagen11

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