Abstract: Catalysts and catalytic processes for the synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, which are carried out in a diluent or in the absence of a diluent. In an aspect, ethylene and CO2 can be contacted with a Group 8-11 transition metal precursor compound or a Group 8-11 transition metal metalalactone compound in the presence of a metal-treated chemically-modified solid oxide (MT-CMSO) or a metal-treated solid oxide (MT-SO), to form a metal acrylate. As the catalytic activity wanes in either the presence or absence of a diluent, pressure cycling—that is, pressurizing the reaction system with CO2 and an olefin such as ethylene for a time period, releasing the pressure, then re-pressurizing with CO2 and ethylene—can rejuvenate the catalyst and restore its declining catalytic activity.

Abstract: This disclosure provides processes for forming acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic processes, and catalyst systems for effecting the processes. For example, there is provided a catalyst system for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the catalyst system comprising: (a) a transition metal precursor compound comprising a Group 8-11 transition metal and at least one first ligand; (b) optionally, at least one second ligand; and (c) an anionic polyaromatic resin with associated metal cations. The catalyst system can further comprise (d) an olefin; (e) carbon dioxide (CO2); and (f) a diluent. Methods of regenerating the anionic polyaromatic resin with associated metal cations are described.

Abstract: This disclosure provides for catalyst systems and processes for forming an ?,?-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: This disclosure provides for routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a metal-treated chemically-modified solid oxide such as a sulfur oxoacid anion-modified solid oxide, a phosphorus oxoacid anion-modified solid oxide, or a halide ion-modified solid oxide, to provide a reaction mixture; and (2) applying reaction conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or the salt thereof. Methods of regenerating the metal-treated chemically-modified solid oxide are described.

Abstract: This disclosure provides for processes to form a porous crosslinked polyphenoxide resin, using a templating process which can increase the porosity, pore size, active sites, and the like of the resin, as compared with a non-templated crosslinked polyphenoxide resin. The process includes contacting a phenol or polyphenol compound with formaldehyde and an aqueous base in the presence of a basic particulate template to form a templated crosslinked polyphenol resin. The templated crosslinked polyphenol resin can then be contacted with an aqueous acid to remove the basic particulate template and form a porous crosslinked polyphenol resin. This porous crosslinked polyphenol resin can subsequently be contacted with a metal-containing base to form a promoter for acrylate and acrylic acid formation from CO2 and ethylene coupling.

Abstract: This disclosure provides processes for forming acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic processes, and catalyst systems for effecting the processes. For example, there is provided a catalyst system for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the catalyst system comprising: (a) a transition metal precursor compound comprising a Group 8-11 transition metal and at least one first ligand; (b) optionally, at least one second ligand; and (c) an anionic polyaromatic resin with associated metal cations. The catalyst system can further comprise (d) an olefin; (e) carbon dioxide (CO2); and (f) a diluent. Methods of regenerating the anionic polyaromatic resin with associated metal cations are described.

Abstract: This disclosure provides for catalyst systems and processes for forming an ?,?-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: Disclosed is a continuous process for producing ?,?-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO2), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an ?,?-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.

Abstract: This disclosure provides routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. In an aspect, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order a group 8-11 transition metal precursor compound comprising at least one first ligand, at least one second ligand, an olefin, carbon dioxide, a diluent, and an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: This disclosure provides for catalyst systems and processes for forming an ?,?-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: The present invention discloses processes for oligomerizing an olefin feedstock containing C4 to C20 alpha olefins using a catalyst system containing a metallocene compound, an organoaluminum compound, and a suspension of a chemically-treated solid oxide. The liquid medium for the suspension of the chemically-treated solid oxide can be an alpha-olefin oligomer product formed by the oligomerization process.

Abstract: Disclosed is a continuous process for producing ?,?-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO2), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an ?,?-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.

Abstract: This disclosure provides for routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a metal-treated chemically-modified solid oxide such as a sulfur oxoacid anion-modified solid oxide, a phosphorus oxoacid anion-modified solid oxide, or a halide ion-modified solid oxide, to provide a reaction mixture; and (2) applying reaction conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or the salt thereof. Methods of regenerating the metal-treated chemically-modified solid oxide are described.

Abstract: Processes for producing an ?,?-unsaturated carboxylic acid, such as acrylic acid, or a salt thereof, using treated solid oxides are disclosed. The treated solid oxides can be calcined solid oxides, metal-treated solid oxides, or metal-treated chemically-modified solid oxides, illustrative examples of which can include sodium-treated alumina, calcium-treated alumina, zinc-treated alumina, sodium-treated sulfated alumina, sodium-treated fluorided silica-coated alumina, and similar materials.

Abstract: This disclosure provides for catalyst systems and processes for forming an ?,?-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: This disclosure provides for routes of synthesis of ?,?-unsaturated carboxylic acids and their salts, including acrylic acid. For example, disclosed is a process for producing an ?,?-unsaturated carboxylic acid or its salt, comprising: (1) contacting a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a sulfur oxoacid anion-substituted polyaromatic resin or a phosphorus oxoacid anion-substituted polyaromatic resin with associated metal cations to provide a mixture; and (2) applying reaction conditions to the mixture suitable to produce the ?,?-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: Disclosed is a continuous process for producing ?,?-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO2), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an ?,?-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.

Abstract: This disclosure provides routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. In an aspect, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order a group 8-11 transition metal precursor compound comprising at least one first ligand, at least one second ligand, an olefin, carbon dioxide, a diluent, and an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: This disclosure provides for routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Abstract: The present invention discloses processes for oligomerizing an olefin feedstock containing C4 to C20 alpha olefins using a catalyst system containing a metallocene compound, an organoaluminum compound, and a suspension of a chemically-treated solid oxide. The liquid medium for the suspension of the chemically-treated solid oxide can be an alpha-olefin oligomer product formed by the oligomerization process.