Supported group 8-10 transition metal olefin polymerization catalysts

A catalyst for the polymerization of olefins comprising the reaction product of a compound of formula XII, a compound Y1 and a solid support:

• wherein R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
• A and B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16 of the Periodic Table;
• in addition, A and B1 may be linked to each other by a bridging group;
• Q represents an alkyl, chloride, iodide or bromide;
• W1 represents an alkyl, chloride, iodide or bromide;
• N represents nitrogen;
• M represents Ni(II), Pd(II), Co(II), or Fe(II);
• and Y1 is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W1− 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,

• wherein R1 and R6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl;
• N represents nitrogen;
• and
• A and B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16 of the Periodic Table;
• in addition, A and B1 may be linked to each other by a bridging group;
• wherein the complex is attached to a solid support, and wherein the solid support, the 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 the reaction product of a compound of formula XII, a compound Y1 and a solid support:

• wherein R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
• A and B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16 of the Periodic Table;
• in addition, A and B1 may be linked to each other by a bridging group;
• Q represents an alkyl, chloride, iodide or bromide;
• W1 represents an alkyl, chloride, iodide or bromide;
• N represents nitrogen;
• M represents Ni(II), Pd(II), Co(II), or Fe(II);
• and Y1 is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W1− 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,

• 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 B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16;
• in addition, A and B1 may be linked to each other 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 Y1 and a solid support:

• 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 B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16;
• in addition, A and B may be linked to each other by a bridging group;
• Q represents an alkyl, chloride, iodide or bromide;
• W1 represents an alkyl, chloride, iodide or bromide;
• N represents nitrogen;
• and
• M represents Ni(II), Pd(II), Co(II), or Fe(II);
• and Y1 is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W1− 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:

• with a solid support which has been pre-treated with a compound Y1,
• 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 B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16;
• in addition, A and B1 may be linked to each other by a bridging group;
• Q represents an alkyl, chloride, iodide or bromide;
• W1 represents an alkyl, chloride, iodide or bromide;
• N represents nitrogen;
• and
• M represents Ni(II), Pd(II), Co(II), or Fe(II);
• and Y1 is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W1− 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 Y1;

• wherein R1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl or silyl;
• n is an integer greater than 3;
• R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
• A and B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16;
• in addition, A and B1 may be linked to each other by a bridging group;
• Q represents an alkyl, chloride, iodide or bromide;
• W1 represents an alkyl, chloride, iodide or bromide;
• N represents nitrogen;
• and
• M represents Ni(II), Pd(II), Co(II), or Fe(II);
• and Y1 is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W1− 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 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 combining said olefin monomers with said functional olefin monomers with a catalyst which comprises a complex of the formula XII, a solid support, and optionally a compound Y1;

• wherein R and R8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to each other to form a cyclic olefin;
• n is an integer between 1-20;
• J is a group selected from the group consisting of 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;
• R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl;
• A and B1 are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is from Group 15 or 16;
• in addition, A and B1 may be linked to each other by a bridging group;
• Q represents an alkyl, chloride, iodide or bromide;
• W1 represents an alkyl, chloride, iodide or bromide;
• N represents nitrogen;
• and
• M represents Ni(II), Pd(II), Co(II), or Fe(II);
• and Y1 is selected from the group consisting of a neutral Lewis acid capable of abstracting Q− or W1− 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.