ES2644733T3 - Composiciones de mezcla de polietileno y película - Google Patents

Composiciones de mezcla de polietileno y película Download PDF

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ES2644733T3
ES2644733T3 ES13867708.3T ES13867708T ES2644733T3 ES 2644733 T3 ES2644733 T3 ES 2644733T3 ES 13867708 T ES13867708 T ES 13867708T ES 2644733 T3 ES2644733 T3 ES 2644733T3
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boron
tetra
borate
phenyl
tetrakis
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Patrick Lam
Victoria Ker
Karen Grabow
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Nova Chemicals International SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/02—Anti-static agent incorporated into the catalyst
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Description

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Es bien conocido en la técnica que el alquilaluminoxano puede desempeñar funciones dobles tanto como alquilante como activador. Por lo tanto, un activador de alquilaluminoxano se usa a menudo en combinación con ligandos activables tales como halógenos.
5 Como alternativa, el activador de catalizador de la presente invención puede ser una combinación de un agente alquilante (que también puede servir como secuestrante) con un activador capaz de ionizar el grupo 4 del catalizador metálico del catalizador de fosfinimina (es decir, un activador iónico). En este contexto, el activador puede elegirse de entre uno o más de alquilaluminoxano y/o un activador iónico, puesto que un alquilaluminoxano puede servir tanto como activador como agente alquilante.
Cuando están presentes, el agente alquilante puede seleccionarse del grupo que consiste en (R4)p MgX22-p, en la que X2 es un haluro y cada R4 se selecciona independientemente del grupo que consiste en radicales alquilo C1-10 y p es 1 o 2; R4Li, en el que R4 es como se ha definido anteriormente, (R4)qZnX22-q, en la que R4 es como se ha definido anteriormente, X2 es halógeno and q is 1 o 2; (R4)s Al2X23-s, en la que R4 es como se ha definido
15 anteriormente, X2 es halógeno y s es un número entero de 1 a 3. Preferiblemente, en los compuestos anteriores, R4 es un alquilo C1-4 y X2 es cloro. Los compuestos comercialmente disponibles incluyen trietilaluminio (TEAL), cloruro de dietilaluminio (DEAC), dibutilmagnesio ((Bu)2Mg), y butiletilmagnesio (BuEtMg o BuMgEt). Los alquilaluminoxanos también se pueden usar como alquilantes.
El activador iónico puede seleccionarse entre el grupo que consiste en: (i) compuestos de la fórmula [R5]+[B(R6)4]-en la que B es un átomo de boro, R5 es un catión aromático C5-7 cíclico o un catión de trifenilmetilo y cada R6 se selecciona independientemente del grupo que consiste en radicales fenilo que están no sustituidos o sustituidos con de 3 a 5 sustituyentes seleccionados del grupo que consiste en un átomo de flúor, un radical alquilo o alcoxi C1-4 que está no sustituido o sustituido por un átomo de flúor; y un radical sililo de la fórmula --Si--(R7)3; en la que cada R7 se 25 selecciona independientemente de entre el grupo que consiste en un átomo de hidrógeno y un radical alquilo C1-4; y
(ii) compuestos de la fórmula [(R8)tZH]+[B(R6)4]-en la que B es un átomo de boro, H es un átomo de hidrógeno, Z es un átomo de nitrógeno o un átomo de fósforo, t es 2 o 3 y R8 se selecciona del grupo que consiste en radicales alquilo C1-8, un radical fenilo que está no sustituido o sustituido con hasta tres radicales alquilo C1-4 o un R8 tomado junto con el átomo de nitrógeno puede formar un radical de anilinio y R6 es como se ha definido anteriormente; y (iii) compuestos de la fórmula B(R6)3 en la que R6 es como se ha definido anteriormente.
En los compuestos anteriores preferentemente R6 es un radical pentafluorofenilo, y R5 es un catión trifenilmetilo, Z es un átomo de nitrógeno y R8 is un radical alquilo C1-4 o R8 tomado junto con el átomo de nitrógeno forma un radical de anilinio que está sustituido con dos radicales alquilo C1-4.
35 Ejemplos de compuestos capaces de ionizar el catalizador de fosfinimina incluyen los siguientes compuestos: trietilamonio tetra(fenil)boro, tripropilamonio tetra(fenil)boro, tri(n-butil)amonio tetra(fenil)boro, trimetilamonio tetra(ptolil)boro, trimetilamonio tetra(o-tolil)boro, tributilamonio tetra(pentafluorofenil)boro, tripropilamonio tetra (o,pdimetilfenil)boro, tributilamonio tetra(m,m-dimetilfenil)boro, tributilamonio tetra(p-trifluorometilfenil)boro, tributilamonio tetra(pentafluorofenil)boro, tri(n-butil)amonio tetra (o-tolil)boro, N,N-dimetilanilinio tetra(fenil)boro, N,N-dietilanilinio tetra(fenil)boro, N,N-dietilanilinio tetra(fenil)n-butilboro, N,N-2,4,6-pentametilanilinio tetra(fenil)boro, di(isopropil)amonio tetra(pentafluorofenil)boro, diciclohexilamonio tetra(fenil)boro, trifenilfosfonio tetra)fenil)boro, tri(metilfenil)fosfonio tetra(fenil)boro, tri(dimetilfenil)fosfonio tetra(fenil)boro, borato de tropillio tetraquispentafluorofenilo, borato de trifenilmetilio tetraquispentafluorofenilo, borato de benceno (diazonio)
45 tetraquispentafluorofenilo, borato de tropilio feniltrispentafluorofenilo, borato de trifenilmetilio feniltrispentafluorofenilo, borato de benceno (diazonio) feniltrispentafluorofenilo, tropilio tetraquis(2,3,5,6tetrafluorofenil)borato, trifenilmetilio tetraquis (2,3,5,6-tetrafluorofenil)borato, benceno (diazonio) tetraquis(3,4,5trifluorofenil)borato, tropilio tetraquis (3,4,5-trifluorofenil)borato, benceno (diazonio) tetraquis(3,4,5trifluorofenil)borato, tropilio tetraquis (1,2,2-trifluoroetenil)borato, trofenilmetilio tetraquis (1,2,2-trifluoroetenil)borato, benceno(diazonio) tetraquis (1,2,2-trifluoroetenil)borato, tropilio tetraquis (2,3,4,5-tetrafluorofenil)borato, trifenilmetilio tetraquis(2,3,4,5-tetrafluorofenil)borato, y benceno (diazonio)tetraquis (2,3,4,5-tetrafluorofenil)borato.
Los activadores comercialmente disponibles que son capaces de ionizar el catalizador de fosfinimina incluyen:
55 borato de N,N-dimetilaniliniotetraquispentafluorofenilo ("[Me2NHPh][B(C6F5)4]"); borato de trifenilmetilio tetraquispentafluorofenilo ("[Ph3C][B(C6F5)4]"); y trispentafluorofenilboro.
En una realización de la invención, los compuestos activadores iónicos pueden usarse en cantidades que proporcionan una relación molar del metal de transición del grupo 4 y el boro que será de 1:1 a 1:6.
Opcionalmente, se pueden usar mezclas de alquilaluminoxanos y activadores iónicos como activadores para el catalizador de fosfinimina.
En la presente invención, el sistema catalizador de la polimerización comprenderá, preferentemente, un soporte
65 inerte (nota: los términos "soporte" y "soporte inerte" se usan indistintamente en la presente invención). En una realización particular de la invención, el sistema de catalizador de la polimerización comprende un catalizador de
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Claims (1)

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ES13867708.3T 2012-12-24 2013-12-12 Composiciones de mezcla de polietileno y película Active ES2644733T3 (es)

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CA2800056 2012-12-24
CA2800056A CA2800056A1 (en) 2012-12-24 2012-12-24 Polyethylene blend compositions
PCT/CA2013/001024 WO2014100889A1 (en) 2012-12-24 2013-12-12 Polyethylene blend compositions and film

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EP (1) EP2935456B1 (es)
JP (1) JP2016510349A (es)
KR (1) KR102135812B1 (es)
CN (1) CN104937025B (es)
BR (1) BR112015015290B1 (es)
CA (2) CA2800056A1 (es)
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