Supported group 8-10 transition metal Olefin polymerization catalysts
AssigneeEastman Chemical Company
InventorsPeter Borden Mackenzie, Leslie Shane Moody, Christopher Moore Killian, Gino Georges Lavoie
Life of this patent
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Abstract
Methods for preparing olefin polymers, and catalysts for preparing olefin polymers are disclosed. The polymers can be prepared by contacting the corresponding monomers with a Group 8-10 transition metal catalyst and a solid support. The polymers are suitable for processing in conventional extrusion processes, and can be formed into high barrier sheets or films, or low molecular weight resins for use in synthetic waxes in wax coatings or as emulsions.
Claims47
A catalyst for the polymerization of olefins comprising a complex comprising (a) a ligand of the formula X, (b) a group 8-10 transition metal, and optionally (c) a Bronsted or Lewis acid,
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- R1 and R6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl;
- N represents nitrogen;
- and
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- wherein the complex is attached to a solid support, and wherein the solid support, the optional Bronsted or Lewis acid, and the complex are combined in any order to form said catalyst.
A catalyst for the polymerization of olefins comprising the reaction product of a compound of formula XII, a compound Y and a solid support:
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- R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- Q represents an alkyl, chloride, iodide or bromide;
- W represents an alkyl, chloride, iodide or bromide;
- N represents nitrogen;
- and
- M represents Ni(II), Pd(II), Co(II), or Fe(II);
- and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W− to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
A process for the preparation of supported catalysts comprising contacting a group 8-10 transition metal complex of a ligand of the formula X, a solid support, and optionally a Bronsted or Lewis acid,
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- wherein R1 and R6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl;
- N represents nitrogen;
- and
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- wherein the complex is attached to a solid support, and wherein the solid support, the optional Bronsted or Lewis acid, and the complex are combined in any order to form said supported catalyst.
A process for the preparation of supported catalysts comprising contacting a compound of formula XII, a compound Y and a solid support:
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- R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl,
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- Q represents an alkyl, chloride, iodide or bromide;
- W represents an alkyl, chloride, iodide or bromide,
- N represents nitrogen;
- and
- M represents Ni(II), Pd(II), Co(II), or Fe(II);
- and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W− to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
A process for the polymerization of olefins, comprising contacting one or more monomers of the formula RCH═CHR8 with a catalyst comprising a group 8-10 transition metal complex of a ligand of the formula X and optionally a Bronsted or Lewis acid,
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- wherein R and R8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
- R1 and R6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl;
- N represents nitrogen;
- and
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- wherein the complex is attached to a solid support, and wherein the solid support, the optional Bronsted or Lewis acid, and the complex are combined in any order.
A process for the polymerization of olefins, comprising contacting one or more monomers of the formula RCH═CHR8 with the reaction product of a compound of formula XII, a compound Y and a solid support:
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- wherein R and R8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
- R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- Q represents an alkyl, chloride, iodide or bromide;
- W represents an alkyl, chloride, iodide or bromide;
- N represents nitrogen;
- and
- M represents Ni(II), Pd(II), Co(II), or Fe(II);
- and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W− to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
A process for the polymerization of olefins, comprising contacting one or more monomers of the formula RCH═CHR8 with a supported catalyst formed by combining a compound of formula XII:
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- with a solid support which has been pre-treated with a compound Y,
- wherein R and R8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
- R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- Q represents an alkyl, chloride, iodide or bromide;
- W represents an alkyl, chloride, iodide or bromide;
- N represents nitrogen;
- and
- M represents Ni(II), Pd(II), Co(II), or Fe(II);
- and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W− to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
A process for the copolymerization of ethylene and a comonomer of the formula CH2═CH(CH2)nCO2R1 which comprises contacting ethylene and a comonomer of the formula CH2═CH(CH2)nCO2R1 with a supported catalyst formed by combining silica with a compound of the formula XII and optionally a compound Y;
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- wherein R1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl or silyl;
- n is an integer greater than 3;
- R1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- Q represents an alkyl, chloride, iodide or bromide;
- W represents an alkyl, chloride, iodide or bromide;
- N represents nitrogen;
- and
- M represents Ni(II), Pd(II), Co(II), or Fe(II);
- and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W− to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
A polyethylene composition comprising a blend of polyethylene polymers, wherein said blend has an average degree of branching of from 5 to 120 alkyl branches per 1000 carbon atoms, wherein any individual component of said blend has a degree of branching of from 0 to 150 alkyl branches per 1000 carbon atoms, wherein said polymers are prepared in one reaction vessel, solely from ethylene, and wherein said polymers are prepared utilizing a Group 8-10 transition metal catalyst which has been reacted with a solid support and optionally a compound Y, in any order, wherein Y is selected from the group consisting of methylaluminoxane and other aluminum sesquioxides having the formulas R73Al, R72AlCl, and R7AlCl2,wherein R7 is alkyl.
A Group 8-10 transition metal catalyst having an improved rate for the co-polymerization of one or more olefin monomers of the type RCH═CHR8 with one or more functional olefin monomers of the formula CH2═CH(CH2)nJ, in an olefin polymerization reaction which comprises combining said catalyst with a solid support, and optionally a Bronsted or Lewis acid in any order, prior to the utilization of said catalyst in said olefin polymerization reaction.
- wherein R and R8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
- n is an interger between 1-20;
- J is a group selected from ester, acyl, acid halide, aldehyde, alkyl amide, aryl, alkylamine, aryl amine, alkyl amido, aryl amido, alkyl imido, aryl imido, ether, nitrile, alcohol, keto, amino, amido, imido, alkoxy thiol, thioalkoxy, acid, urea, sulfonamido, and sulfoester.
A ethylene homopolymer with a CDBl of less than 50%.
A polyalkene with a CDBl of less than 50%, which contains about 80 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 30 to about 90 ethyl branches, about 4 to about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl or longer branches.
A polyalkene with a CDBl of less than 50% which contains about 20 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 4 to about 20 ethyl branches, 1 to about 12 propyl branches, 1 to about 12 butyl branches, 1 to about 10 amyl branches, and 0 to about 20 hexyl or longer branches.
A process for the copolymerization of one or more olefin, monomers of the type RCH═CHR8 with one or more functional olefin monomers of the formula CH2═CH(CH2)nJ comprising a catalyst, in an olefin polymerization reaction which comprises combining a complex of the formula XII, a solid support, and optionally a compound Y, prior to the utilization of said catalyst in said olefin polymerization reaction.
- wherein R and R8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
- n is an interger between 1-20;
- J is a group selected from ester, acyl, acid halide, aldehyde, alkyl amide, aryl, alkylamine, aryl amine, alkyl amido, aryl amido, alkyl imido, aryl imido, ether, nitrile, alcohol, keto, amino, amido, imido, alkoxy thiol, thioalkoxy, acid, urea, sulfonamido, and sulfoester;
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- R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
- A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16;
- in addition, A and B may be linked by a bridging group;
- Q represents an alkyl, chloride, iodide or bromide;
- W represents an alkyl, chloride, iodide or bromide;
- N represents nitrogen;
- and
- M represents Ni(II), Pd(II), Co(II), or Fe(II);
- and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W− to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
Dependencies are inferred from the claim text.