# US 9,040,615 B2 · Compositions of polyesters and fibrous clays > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,615 B2 - Document ID: US9040615B2 - Status: Granted - Kind: B2 - Application number: 13/296,205 - Filed: 2011-11-14 - Published: 2012-11-22 - Granted: 2015-05-26 - Earliest claimed: 2004-12-22 - Assignees: E. I. Du Pont de Nemours and Company - Applicants: David T. Williamson; Thomas M. Herrod; William M. Simmons; Henry Max Schleinitz - Inventors: David T. Williamson; Thomas M. Herrod; William M. Simmons; Henry Max Schleinitz - Web page: https://patentgrep.com/patent/US9040615B2 ## CPC - C09D 167/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09D167/06 takes precedence) - C08K 3/346: {Clay} - C08K 9/04: Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)} - C08L 67/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) - C08K 3/013: Fillers, pigments or reinforcing additives - C08K 5/0016: {Plasticisers} - C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins - Y10T 428/31786: Of polyester [e.g., alkyd, etc.] - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Compositions of thermoplastic polyesters containing dispersed nanoparticles of fibrous clay are made by polymerizing the polyester precursors in the presence of exfoliated fibrous clay that has not been organically modified. The compositions have good physical properties and can be melt molded into various articles. Many of these articles may be coated (painted) and are especially useful for appearance parts such as visible exterior automotive body parts. ## Claims ### Claim 1 A process for manufacturing a thermoplastic polyester nanocomposite composition via a condensation polymerization, the process comprising the steps of: (i) mixing exfoliated fibrous clay with at least one thermoplastic polyester precursor composition wherein the components of the precursor composition are selected from the group consisting of a) at least one diacid or diester and at least one diol; b) at least one polymerizable polyester monomer; c) at least one linear polyester oligomer; and d) at least one macrocyclic polyester oligomer, and, optionally, a polymerization catalyst in addition to the exfoliated fibrous clay, and (ii) subsequently polymerizing said at least one polyester precursor in the absence of a solvent, wherein said exfoliated fibrous clay is a nano-sized clay that has not been organically modified prior to mixing. ### Claim 2 (depends on 1) The process as recited in claim 1 wherein the fibrous clay content in the composition so produced is 0.1 to 20 weight percent, based on the total weight of said clay and said polyester precursor composition. ### Claim 3 (depends on 1) The process as recited in claim 1 wherein said polyester consists essentially of repeat units derived from one or more of terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid, and repeat units derived from one or more of HO(CH2)nOH, 1,4-cyclohexanedimethanol, HO(CH2CH2O)mCH2CH2OH, and HO(CH2CH2CH2CH2O)zCH2CH2CH2CH2OH, wherein n is an integer of 2 to 10, m is an average of 1 to 4, and z is an average of about 7 to about 40. ### Claim 4 (depends on 1) The process as recited in claim 1 wherein said polyester is poly(ethylene terephthalate), poly(1,3-propylene terephthalate), poly(1,4-butylene terephthalate), or poly(1,4-cylohexyldimethylene terephthalate), or a modified version thereof. ### Claim 5 (depends on 1) The process as recited in claim 1 wherein the polymerization of the polyester precursor is carried out as a continuous process. ### Claim 6 (depends on 1) The process as recited in claim 1 wherein the polymerization of the polyester precursor is carried out as a batch or semibatch process. ### Claim 7 (depends on 1) The process as recited in claim 1 wherein no polyester polymerization catalyst is added in addition to the fibrous clay. ### Claim 8 (depends on 1) The process as recited in claim 1 wherein one or more solid particulate fillers are present during polymerization, with the proviso that said solid particulate fillers do not interfere with the polymerization. ### Claim 9 (depends on 1) The process as recited in claim 1 comprising the additional step of subjecting said composition in the liquid state to shear stress. ### Claim 10 (depends on 1) The process as recited in claim 1 wherein said fibrous clay is first mixed with at least a portion of said at least one diol to form a slurry and said slurry is thereafter mixed with said at least one diacid and the remainder of said at least one diol; and wherein said the slurry formed by mixing the fibrous clay with at least a portion of said at least one diol has 9 to 12 weight percent solids in the form of said fibrous clay. ### Claim 11 (depends on 10) The process as recited in claim 10 wherein said slurry is added after 75 percent of a stoichiometric amount of water or alcohol produced from the condensation polymerization has been removed from the polymerization process.