ES2539455T3 - Complejos de metal de transición de piridildiamido, producción y uso de los mismos - Google Patents

Complejos de metal de transición de piridildiamido, producción y uso de los mismos Download PDF

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ES2539455T3
ES2539455T3 ES09800751.1T ES09800751T ES2539455T3 ES 2539455 T3 ES2539455 T3 ES 2539455T3 ES 09800751 T ES09800751 T ES 09800751T ES 2539455 T3 ES2539455 T3 ES 2539455T3
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hydrocarbyls
mao
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John R. Hagadorn
Catherine A. Faler
Timothy M. Boller
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ExxonMobil Chemical Patents Inc
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

Un complejo de metal de transición de piridildiamido para su uso en polimerización de alqueno que tiene la fórmula general (I)**Fórmula** en la que: M es un metal del Grupo 3, 4, 5, 6, 7, 8, 9, 10, 11 o 12; Z es -(R14)pC-C(R15)q-, donde R14 y R15 se seleccionan independientemente del grupo que consiste en hidrógeno, hidrocarbilos (tal como alquilos), y hidrocarbilos sustituidos, y en la que los grupos adyacentes R14 y R15 pueden unirse para formar un anillo de hidrocarbilo aromático o saturado, sustituido o no sustituido, donde el anillo tiene 5, 6, 7, o 8 átomos de carbono anulares y donde las sustituciones en el anillo pueden unirse para formar anillos adicionales, p es 1 o 2, y q es 1 o 2; R1 y R11 se seleccionan independientemente del grupo que consiste en hidrocarbilos (tal como alquilos y arilos), hidrocarbilos sustituidos (tal como heteroarilos), y grupos sililo; R2 y R10 son cada uno, independientemente, -E(R12)(R13)- siendo E carbono, silicio o germanio, y siendo cada R12 y R13 independientemente seleccionado del grupo que consiste en hidrógeno, hidrocarbilos (tal como alquilos, arilos), alcoxi, sililo, amino, ariloxi, hidrocarbilos sustituidos (tal como heteroarilo), halógeno, y fosfino, R12 y R13 pueden unirse para formar un anillo de hidrocarbilo saturado, sustituido o no sustituido, donde el anillo tiene 4, 5, 6, o 7 átomos de carbono anulares y donde las sustituciones en el anillo pueden unirse para formar anillos adicionales, o R12 y R13 pueden unirse para formar un anillo heterocíclico saturado, o un anillo heterocíclico sustituido saturado donde las sustituciones en el anillo pueden unirse para formar anillos adicionales; R3, R4, y R5 se seleccionan independientemente del grupo que consiste en hidrógeno, hidrocarbilos (tal como alquilos y arilos), hidrocarbilos sustituidos, alcoxi, ariloxi, halógeno, amino, y sililo, y en la que los grupos adyacentes R (R3 & R4, y /o R4 & R5) pueden unirse para formar un anillo heterocíclico o hidrocarbilo sustituido o no sustituido, donde el anillo tiene 5, 6, 7, o 8 átomos anulares y donde las sustituciones en el anillo pueden unirse para formar anillos adicionales; L es un grupo saliente aniónico, donde los grupos L pueden ser iguales o diferentes y cualquiera dos grupos L pueden estar unidos para formar un grupo saliente dianiónico; n es 0, 1, 2, 3, o 4; L' es base de Lewis neutral; y w es 0, 1, 2, 3 o 4.

Description

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Diagrama 1
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En un segundo aspecto de la invención, se proporcionan diversos procesos para sintetizar los complejos del primer aspecto, tal como los mostrados anteriormente. Algunos de estos procesos pueden utilizar productos intermedios 5 que son nuevos en su propio derecho y forman un aspecto adicional de la invención.
Una primera metodología sintética se basa en la inserción formal de una imina en el enlace de metal .carbono de un grupo arilo orto-metalado de un complejo de metal de piridilamido intermediario sintetizado por separado. La inserción de los resultados de imina en la sustitución del enlace de metal-carbono con un enlace de metal-amido. Así, el complejo de metal-ligando original en el que el ligando fue coordinado al metal a través de dos dadores de 10 nitrógeno y un dador de carbono, se refiere como ligandos y complejos NNC, se ha transformado fundamentalmente de modo que ahora se coordina a través de tres dadores de nitrógeno, referido como ligandos y complejos NNN. Un compuesto que contiene un doble enlace de carbono-nitrógeno, tal como la imina R11N=C(R12)(R13), puede ser insertado en un enlace de metal -arilo para formar un complejo NNN con un anillo quelato de cinco miembros y uno siete miembros. R11, R12 y R13 son como se define más arriba. Los complejos de metal de piridilamido intermediarios
15 (NNC) pueden tener actividad de polimerización catalítica por sí mismos. La invención permite que el desempeño de dichos complejos intermediarios sea modificado para llegar a nuevas posibilidades en términos de desempeño de polimerización y estructuras catalizadoras.
Por ejemplo el complejo NNN C5 que se muestra en el Diagrama 1 más arriba puede fabricarse a partir del complejo intermediario NNC que contiene Hf referido como Int-5 en la forma descrita en los ejemplos como "Síntesis de Int-5
20 con ligando tridentado N-N-C". Int-5 es análogo a algunos complejos descritos en US 6.900.321.
Se pueden utilizar otras vías sintéticas, más generales, para la preparación de complejos del tipo mostrado en el Diagrama 1 que emplea piridil diaminas o sus derivados de metales alcalinos térreos o alcalinos en vez de complejos intermediarios NNC. La invención puede utilizar iminas, carbodiimidas, isocianatos, isotiocianatos, o otros reactivos que contienen dobles enlaces de carbono-nitrógeno para producir ligandos tridentados NNN. El uso de
25 iminas es de particular interés, lo que dará ligandos tridentados dadores de piridildiamido. La ecuación V a continuación muestra un ejemplo general de la formación de un complejo NNN a partir de un complejo NNC y un reactivo con un doble enlace carbono-nitrógeno.
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Ejemplos -síntesis de complejos de metal de transición
Síntesis de Int-3 con ligando tridentado N-N-C (no de acuerdo a la invención)
Int-3 (estructura de más abajo) se utiliza como intermediario para fabricar complejos de N-N-N. Se añadió una
5 solución de benceno (5 ml) de ZrBn2Cl2(OEt2) (0,532 g, 1,27 mmol) en gotas durante 30 segundos a una solución de benceno (5 ml) de Int-2 (0,438 g, 1,27 mmol). La solución naranja se calentó a 70 °C durante 2 horas y 45 minutos. Después la solución negra se enfrió a temperatura ambiente (aproximadamente 23 °C). La solución se filtró y se añadió Et2O (1 ml). La concentración hasta 6 ml condujo a la formación de un precipitado cristalino. Se añadió el Et2O adicional (10 ml) el día siguiente. A continuación, el sólido cristalino oscuro se recogió en un disco poroso y se
10 lavó con Et2O (10 ml), después se secó a presión reducida para proporcionar el producto como un sólido gris. Rendimiento: 40 g, 54%. 1H RMN (250 MHz, CD2Cl2): δ 8,00-7,68 (4H, m), 7,37-7,15 (6H, m), 5,15 (2H, m), 3,60 (4H, q), 3,46 (1H, sept), 1,35 (6H, d), 1,16 (6H, d), 1,08 (6H, t).
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Síntesis de Int-4 con ligando tridentado N-N-C (no de acuerdo a la invención)
15 Int-4 (estructura de más abajo) se utiliza como intermediario para fabricar complejos N-N-N. Se añadió dietil éter (15 ml) a ZrBn2Cl2(OEt2) (0,217 g, 0,519 mmol) para formar una solución amarilla turbia. A -68 ° C se añadió gota a gota una solución de imina Int-1 (0,178 g, 0,519 mmol) en Et2O (4 ml). La mezcla se dejó calentar lentamente a temperatura ambiente (aproximadamente 23 °C) durante varias horas. Después de agitar durante toda la noche se había formado una solución oscura. Los elementos volátiles se eliminaron por evaporación y el sólido se suspendió
20 en pentano. El sólido gris se recogió en una frita, se lavó con pentano, y después se secó a presión reducida. Rendimiento: 0,24 g, 61%. 1H RMN (250 MHz, C6D6): δ 8,22 (1H, d), 6,5-7,3 (ca. 14H, m), 5,88 (1H, d), 4,93 (1H, dd), 4,32 (1H, sept), 3,48 (1H, dd), 3,32 (4H), 2,8-2,1 (2H, m), 1,64 (3H, d), 1,32 (3H, d), 1,28 (3H, d), 1,21 (3H, d), 1,03 (6H, t).
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25 Síntesis de Int-5 con ligando tridentado N-N-C (no de acuerdo a la invención)
Int-5 (estructura de más abajo) se utiliza como intermediario para fabricar complejos N-N-N. Se añadió benceno (4 ml) a una combinación de Int-2 (0,281 g, 0,815 mmol) y HfBn2Cl2(OEt2)1,5 (0,442 g, 0,815 mmol). La solución naranja se calentó hasta 60 °C durante 75 minutes. Los elementos volátiles después se evaporaron hasta casi sequedad. Después se añadió benceno adicional (5 ml) y el sólido suspendido se recolectó en un disco poroso , se lavó con 30 benceno (5 ml), y se secó bajo presión reducida. Rendimiento: 0,467 g, 86,0%. 1H RMN (250 MHz, CD2Cl2): δ 8,00
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Tabla 1: Polimerización de etileno y 1-octeno utilizando Int-3 y C1
Ejemplo
catalizador activador (1000 equivalentes) Temperatura (°C) actividad (g/mmol cat/h/bar) % en peso de octeno Mw Mn Mw/Mn
1
Int-3 MAO 50 5076 4 450,668 97,606 4,6
2
Int-3 MAO 80 15626 4 180,608 53,629 3,4
3
Int-3 MAO 80 14607 5 252,141 77,375 3,3
4
Int-3 MAO 110 18076 4 132,804 48,142 2,8
5
Int-3 MAO 110 20210 13 129,407 48,292 2,7
6
C1 MAO 50 29207 3 133,973 60,086 2,2
7
C1 MAO 50 25620 3 110,680 50,435 2,2
8
C1 MAO 80 46641 5 72,715 37,599 1,9
9
C1 MAO 80 42145 4 74,381 40,141 1,9
10
C1 MAO 110 30894 5 55,531 23,382 2,4
11
C1 MAO 110 31797 3 59,355 26,909 2,2
Ejemplo 2: Polimerización de mezcla de etileno y 1-octeno utilizando Int-3 y C3
Las polimerizaciones se realizaron en un reactor de presión paralelo como se describe más arriba, pero con las siguientes características específicas. Se añadió activador MAO (1000 equivalentes por equivalente de catalizador) 5 como una solución de tolueno al 1 % en peso. Las concentraciones de catalizador fueron 0,00800 mM (40 nanomoles de catalizador utilizado). No se utilizaron agentes de barrido de trialquil aluminio. Los datos se muestran en la Tabla 2. El catalizador C3 se forma por la reacción def PhCH=N`Pr con el catalizador Int-3. Los datos que se muestran indican que C3 tiene una mayor actividad para la formación de copolímeros de etileno-octeno que Int-3 a 50 °C, pero es menos activo a temperaturas superiores. El catalizador Int-3 no está de acuerdo a la invención; el
10 catalizador C3 está de acuerdo a la invención.
25
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Tabla 2: Polimerización de etileno y 1-octeno utilizando Int-3 y C3
Ejemplo
catalizador activador (1000 equivalentes) Temperatura (°C) actividad (g/mmol cat/h/bar) % en peso de octeno Mw Mn Mw/Mn
1
Int-3 MAO 50 5076 4 450,668 97,606 4,6
2
Int-3 MAO 80 15626 4 180,608 53,629 3,4
3
Int-3 MAO 80 14607 5 252,141 77,375 3,3
4
Int-3 MAO 110 18076 4 132,804 48,142 2,8
5
Int-3 MAO 110 20210 3 129,407 48,292 2,7
6
C3 MAO 50 14125 3 184,000 94,143 2,0
7
C3 MAO 50 20104 2 188,145 102,570 1,8
8
C3 MAO 80 5887 3 163,568 75,673 2,2
9
C3 MAO 80 5128 2 142,768 73,769 1,9
10
C3 MAO 110 1224 3 129,461 30,544 4,2
11
C3 MAO 110 829 3 125,633 31,788 4,0
Ejemplo 3: Polimerización de mezcla de etileno y 1-octeno utilizando C8
Las polimerizaciones se realizaron en el reactor de presión paralelo como se describe más arriba, pero con las siguientes características específicas. Se utilizó isohexano como disolvente. Se añadió 5 tetraquis(pentafluorofenil)borato de N,N-dimetilanilinio, abreviado como dmah-NCA, activador (1,0 equivalentes por equivalente de catalizador) como una solución de tolueno 20 mM. Las concentraciones de catalizador fueron 0,00400 mM (20 nanomoles de catalizador utilizado). Se utilizó tri-n-octilaluminio (0,100 ml de solución 0,010 M en isohexano) como agente de barrido. Los datos se muestran en la Tabla 3. Los datos mostrados indican que C8 con el activador de anión no coordinante dmah-NCA es un catalizador activo para la polimerización de una mezcla de
10 etileno 1-octeno.
Tabla 3: Polimerización de etileno y 1-octeno utilizando C8
Ejemplo
catalizador activador (1,0 equivalente) T (°C) actividad (g/mmol cat/h/bar) Mw Mn Mw/Mn
1
C8 dmah-NCA 50 14034 630778 338252 630778
2
C8 dmah-NCA 80 22582 544394 283986 544394
3
C8 dmah-NCA 80 22197 492637 262243 492637
4
C8 dmah-NCA 110 157 337119 175278 337119
5
C8 dmah-NCA 1110 182 369850 174061 369850
Ejemplo 4: Polimerización de propileno utilizando, C1, C2, C3, y C5
Las polimerizaciones se realizaron en un reactor de presión paralelo en forma análoga a aquella que se describe más arriba para las polimerizaciones de etileno-octeno, pero con las siguientes características específicas. Se utilizó 15 isohexano como disolvente. Se utilizó propileno (1,0 ml) en vez de 1-octeno. El volumen total fue 5,10 ml. Se añadió
26
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activador MAO (700 equivalentes por equivalente de catalizador) como una solución de tolueno 1% en peso. Las concentraciones de catalizador fueron 0,01600 mM (80 nanomoles de catalizador utilizado). No se utilizaron agentes de barrido de trialquil aluminio. Se dejó que las reacciones procedieran durante 20 minutos. Los datos se muestran en la Tabla 4. Los datos mostrados indican que los complejos de piridildiamido C1, C2, C3, y C5 con activador MAO son catalizadores activos para la polimerización de propileno.
Tabla 4: Polimerización de propileno utilizando C1, C2, C3, y C5
Ejemplo
Catalizador activador (700 Equivalentes) T (°C) actividad (g/mmol cat/hr) Mw Mn Mw/Mn
1
C1 MAO 70 4961 25962 11153 2,3
2
C1 MAO 70 5133 26942 11876 2,3
3
C1 MAO 85 2155 14837 6731 2,2
4
C1 MAO 85 2216 15834 7051 2,2
5
C1 MAO 100 1089 9231 4465 2,1
6
C1 MAO 100 981 7954 4121 1,9
7
C2 MAO 70 3780 19399 8710 2,2
8
C2 MAO 70 3891 19649 8669 2,3
9
C2 MAO 85 2297 7941 4190 1,9
10
C2 MAO 85 2388 8549 4480 1,9
11
C2 MAO 100 2644 28432 4495 6,3
12
C2 MAO 100 2508 27754 4385 6,3
13
C3 MAO 70 1780 10548 5534 1,9
14
C3 MAO 70 3158 77692 10657 7,3
15
C3 MAO 85 1435 8698 4618 1,9
16
C3 MAO 85 1453 10089 5092 2
17
C3 MAO 100 857 5636 3388 1,7
18
C3 MAO 100 889 5870 3500 1,7
19
C5 MAO 70 3462 59630 12391 4,8
20
C5 MAO 70 2369 18887 7990 2,4
21
C5 MAO 85 2377 21442 8483 2,5
22
C5 MAO 85 3726 45757 13980 3,3
23
C5 MAO 100 2321 14701 6458 2,3
24
C5 MAO 100 2315 14819 6514 2,3
27

Claims (1)

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