Fluorinated transition metal catalysts and formation thereof

A method comprising:

• providing an inorganic support composition, wherein the inorganic support composition comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• and
• contacting the inorganic support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

A catalyst system comprising:

• an inorganic support composition, wherein the inorganic support composition comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• and
• an organometallic catalyst compound, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

A polymerization process comprising:

• introducing a supported catalyst system comprising a fluorinated support composition and transition metal compound into a polymerization vessel, wherein the supported catalyst system is formed by a process comprising:
• providing a support material comprising silica-alumina prepared by cogel methods;
• contacting the support material with a fluorinating agent selected from ammonium fluoride containing compounds to form a fluorinated support;
• contacting the fluorinated support with a transition metal compound to form a supported catalyst system;
• and
• contacting the supported catalyst system with an olefin monomer within the polymerization vessel to form a polyolefin.

A method of forming catalyst systems comprising:

• contacting an alumina-silica support composition with ammonium bifluoride in the presence of water to form a first fluorinated support composition;
• heating the first fluorinated support composition in an oxygen containing atmosphere to a temperature of from about 200° C. to about 800° C. to form a second fluorinated support composition, wherein the second fluorinated support composition comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• and
• contacting the second fluorinated support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

A method of forming catalyst systems for commercial production comprising:

• contacting a commercial quantity of alumina-silica support composition with an aqueous fluorinating agent to form a first fluorinated support composition;
• heating the first fluorinated support composition in an oxygen containing atmosphere to a temperature of from about 200° C. to about 600° C. to form a second fluorinated support composition, wherein the second fluorinated support composition comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• and
• contacting the second fluorinated support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

A method of forming catalyst systems comprising:

• contacting an alumina-silica support composition with a fluorinating agent in the presence of water within a muffle furnace to form a first fluorinated support composition;
• heating the first fluorinated support composition in an oxygen containing atmosphere to a temperature of from about 200° C. to about 800° C. to form a second fluorinated support composition, wherein the second fluorinated support composition comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• and
• contacting the second fluorinated support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency.

A polymerization process comprising:

• contacting an inorganic support composition with a fluorinating agent to form a fluorinated support, wherein the fluorinating agent comprises an organofluorine compound having the formula R4nAlF3-n and wherein each R is independently selected from alkyls, aryls and combinations thereof and n is 1 or 2;
• contacting the fluorinated support with a transition metal compound to form a supported catalyst system;
• and
• contacting an olefin monomer with the supported catalyst composition to form a polyolefin.

A method of forming polyolefins comprising:

• introducing an inorganic support material to a reaction zone, wherein the inorganic support material comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• introducing a transition metal compound to the reaction zone;
• contacting the transition metal compound with the inorganic support material for in situ activation/heterogenization of the transition metal compound to form a catalyst system;
• introducing an olefin monomer to the reaction zone;
• and
• contacting the catalyst system with the olefin monomer to form a polyolefin.

A method of forming polyolefins comprising:

• identifying desired polymer properties;
• providing a transition metal compound;
• selecting a support material capable of producing the desired polymer properties, wherein the support material comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• contacting the transition metal compound with the support material to form an active supported catalyst system, wherein the contact of the transition metal compound with the support material occurs in proximity to contact with an olefin monomer;
• and
• contacting the active supported catalyst system with the olefin monomer to form a polyolefin, wherein the polyolefin comprises the desired polymer properties.

A method of forming polyolefins comprising:

• identifying a desired polymer molecular weight;
• providing a transition metal compound;
• providing a support material comprising a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof and wherein a fluorine to aluminum ratio of the support material is capable of producing the desired polymer molecular weight;
• contacting the transition metal compound with the support material to form an active supported catalyst system, wherein the contact of the transition metal compound with the support material occurs in proximity to contact with an olefin monomer;
• and
• contacting the active supported catalyst system with the olefin monomer to form a polyolefin, wherein the polyolefin comprises the desired polymer molecular weight.

A method of forming copolymers comprising:

• providing a transition metal compound represented by the formula [L]mM[A]n, wherein L is a bulky ligand comprising bis-indenyl, A is a leaving group, M is a transition metal and m and n are such that the total ligand valency corresponds to the transition metal valency;
• providing a support material comprising a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof;
• contacting the transition metal compound with the support material to form an active supported catalyst system, wherein the contact of the transition metal compound with the support material occurs in proximity to contact with monomer;
• and
• contacting the active supported catalyst system with a plurality of monomers to form an copolymer.

A catalyst system comprising:

• an inorganic support material comprising a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof, wherein the inorganic support material comprises an acid strength (pKa) of less than about 4.8;
• and
• a transition metal compound, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to a transition metal valency.

A method of forming a catalyst system comprising:

• providing an inorganic support material comprising a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof, wherein the inorganic support material comprises an acid strength (pKa) of less than about 4.8;
• and
• contacting the inorganic support material with a transition metal compound to form the catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to a transition metal valency.

A method of forming polyolefins comprising:

• introducing an inorganic support material to a reaction zone, wherein the inorganic support material comprises a bonding sequence selected from Si—O—Al—F, F—Si—O—Al, F—Si—O—Al—F and combinations thereof and an acid strength (pKa) of less than about 4.8;
• introducing a transition metal compound to the reaction zone;
• contacting the transition metal compound with the inorganic support material for in situ activation/heterogenization of the transition metal compound to form a catalyst system;
• introducing an olefin monomer to the reaction zone;
• and
• contacting the catalyst system with the olefin monomer to form a polyolefin.

A method of forming a catalyst composition for olefin polymerization:

• providing an inorganic support composition, wherein the inorganic support composition comprises aluminum, fluorine and silica;
• contacting the inorganic support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency;
• and
• contacting the inorganic support composition, the transition metal compound, the supported catalyst system or combinations thereof with at least one compound represented by the formula XRn, wherein X is selected from Group 12 to 13 metals, lanthanide series metals or combinations thereof and each R is independently selected from alkyls, alkoxys, aryls, aryloxys, halogens, hydrides, Group 1 or 2 metals, organic nitrogen compounds, organic phosphorous compounds and combinations thereof and n is from 2 to 5.

A method of forming a catalyst composition for olefin polymerization:

• providing an inorganic support composition, wherein the inorganic support composition comprises aluminum, fluorine and silica;
• contacting the inorganic support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency;
• and
• contacting the inorganic support composition, the transition metal compound, the supported catalyst system or combinations thereof with a plurality of compounds, wherein the plurality of compounds comprise a first compound comprising an organo aluminum compound and a second compound comprising boron.

A polymerization process comprising:

• providing an inorganic support composition, wherein the inorganic support composition comprises aluminum, fluorine and silica;
• contacting the inorganic support composition with a transition metal compound to form a supported catalyst system, wherein the transition metal compound is represented by the formula [L]mM[A]n;
• wherein L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that a total ligand valency corresponds to the transition metal valency;
• contacting the inorganic support composition, the transition metal compound, the supported catalyst system or combinations thereof with at least one compound represented by the formula XRn, wherein X is selected from Group 12 to 13 metals, lanthanide series metals or combinations thereof and each R is independently selected from alkyls, alkoxys, aryls, aryloxys, halogens, hydrides, Group 1 or 2 metals, organic nitrogen compounds, organic phosphorous compounds and combinations thereof and n is from 2 to 5;
• and
• contacting the supported catalyst system with an olefin monomer to form a polyolefin.