Solid acids as catalysts for the preparation of hydrocarbon resins
AssigneeEastman Chemical Company
InventorsLaura M. Babcock, Dennis G. Morrell
Life of this patent
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Abstract
Solid acids are used as catalysts for the polymerization of a feed stream containing at least one of pure monomer, C5 monomers, and C9 monomers to produce hydrocarbon resins. Freely-associated water may be removed from the solid acid catalyst prior to use. Resins with softening points (Ring and Ball) in the range of about 5° C. to 170° C. can be prepared. These catalysts offer advantages over the traditional Friedel-Crafts polymerization catalysts since the acid sites are an integral part of the solid. The solid acid catalysts are relatively nonhazardous, reusable catalysts which eliminate or at least reduce contamination of the resulting resin products with acid residues or by-products.
Claims71
A process for making a hydrocarbon resin, comprising polymerizing a feed stream comprising C5 monomers in the presence of a solid acid catalyst to produce a hydrocarbon resin, wherein substantially all freely-associated water has been removed from the solid acid catalyst, and wherein the solid acid catalyst comprises as an active catalyst at least one member selected from the group consisting of acid activated clay, silica-alumina, amorphous silica-alumina, Brønsted acid on silica, Brønsted acid on silica-alumina, zeolites, mesoporous silica-alumina, Brønsted acid on mesoporous silica, and Brønsted acid on mesoporous silica-alumina, wherein water removal from the solid acid catalyst comprises calcining the solid acid catalyst at a temperature of about 100° C. to 400° C. to form the active catalyst, wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 2000, a weight average molecular weight (Mw) of about 500 to 3500, a Z average molecular weight (Mz) of about 700 to 15,000, and a polydispersity (pID) as measured by Mw/Mn between about 1.2 and 5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
A process for making a hydrocarbon resin, comprising polymerizing a feed stream comprising pure monomer in the presence of a solid acid catalyst to produce a hydrocarbon, resin, wherein substantially all freely-associated water has been removed from the solid acid catalyst, and wherein the solid acid catalyst comprises as an active catalyst at least one member selected from the group consisting of modified clays, Brønsted acid on clay, amorphous silica-alumina, Brønsted acid on silica, Brønsted acid on silica-alumina, zeolites, mesoporous silica-alumina, Brønsted acid on mesoporous silica, and Brønsted acid on mesoporous silica-alumina, wherein water removal from the solid acid catalyst comprises calcining the solid acid catalyst at a temperature of about 100° C. to 400° C. to form the active catalyst, wherein the hydrocarbon resin has a number average molecular weight (Mn) ranging from about 400 to 2000, a weight average molecular weight (Mw) ranging from about 500 to 5000, a Z average molecular weight (Mz) ranging from about 500 to 10,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC), and wherein the solid acid catalyst has a pKa<0.
A process for making a hydrocarbon resin, comprising polymerizing a feed stream comprising C9 monomers in the presence of a solid acid catalyst to produce a hydrocarbon resin, wherein substantially all freely-associated water has been removed from the solid acid catalyst, and wherein the solid acid catalyst comprises as an active catalyst at least one member selected from the group consisting of acid activated clay, silica-alumina, amorphous silica-alumina, Brønsted acid on silica, Brønsted acid on silica-alumina, zeolites, mesoporous silica-alumina, Brønsted acid on mesoporous silica, and Brønsted acid on mesoporous silica-alumina, wherein water removal from the solid acid catalyst comprises calcining the solid acid catalyst at a temperature of about 100° C. to 400° C. to form the active catalyst, wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 1200, a weight average molecular weight (Mw) of about 500 to 2000, a Z average molecular weight (Mz) of about 700 to 6000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, where Mn and Mw are determined by size exclusion chromatography (SEC), and wherein the solid acid catalyst has a pKa<0.
A process for making a hydrocarbon resin, comprising polymerizing a feed stream comprising at least one member selected from the group consisting of C5 monomers and C9 monomers in the presence of a solid acid catalyst to produce a hydrocarbon resin, wherein substantially all freely-associated water has been removed from the solid acid catalyst by calcining the solid acid catalyst at a temperature of about 100° C. to 400° C., and wherein the solid acid catalyst comprises as an active catalyst at least one member selected from the group consisting of acid activated clay, silica-alumina, amorphous silica-alumina, Brønsted acid on silica, Brønsted acid on silica-alumina, zeolites, mesoporous silica-alumina, Brønsted acid on mesoporous silica, and Brønsted acid on mesoporous silica-alumina, wherein the active catalyst results in a yield of greater than about 10%, based on monomer, wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 200 to 3000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 5 for C5 monomers and about 1.2 and 3.5 for C9 monomers, where Mn and Mw are determined by size exclusion chromatography (SEC), and wherein the solid acid catalyst has a pKa<0.
A process for making a hydrocarbon resin, comprising polymerizing a feed stream comprising pure monomer in the presence of a solid acid catalyst to produce a hydrocarbon resin, wherein substantially all freely-associated water has been removed from the solid acid catalyst by calcining the solid acid catalyst at a temperature of about 100° C. to 400° C., and wherein the solid acid catalyst comprises as an active catalyst at least one member selected from the group consisting of modified clays, Brønsted acid on clay, amorphous silica-alumina, Brønsted acid on silica, Brønsted acid on silica-alumina, zeolites, mesoporous silica-alumina, Brønsted acid on mesoporous silica, and Brønsted acid on mesoporous silica-alumina, wherein the active catalyst results in a yield of greater than about 10%, based on monomer, wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 200 to 3000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, where Mn and Mw are determined by size exclusion chromatography (SEC), and wherein the solid acid catalyst has a pKa<0.
Dependencies are inferred from the claim text.