# US 9,751,991 B1 · Renewable resins and thermoplastics from eugenol > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,751,991 B1 - Document ID: US9751991B1 - Status: Granted - Kind: B1 - Application number: 14/688,109 - Filed: 2015-04-16 - Granted: 2017-09-05 - Earliest claimed: 2015-04-16 - Assignees: The United States of America as represented by the Secretary of the Navy - Applicants: The United States of America as Represented by the Secretary of the Navy - Inventors: Benjamin G. Harvey - Web page: https://patentgrep.com/patent/US9751991B1 ## CPC - C08G 64/24: and phenols - C08G 64/045: {containing aliphatic unsaturation} - Y02P 20/584: Recycling of catalysts - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract An eugenol, an abundant natural phenol and the primary component of clove oil, which is converted to a thermoset resin via a high yield, two-step reaction. Modest heating yields a thermoset material with thermal stability above 350° C., a glass transition temperature of 187° C. and water uptake of only 1.8%. ## Claims ### Claim 1 A method for manufacturing thermoplastics or resins from a bisphenol, comprising: isolating eugenol synthetically or from at least one renewable resource; reacting said eugenol with at least one metathesis catalyst to form an unsaturated bisphenol; converting said unsaturated bisphenol to a thermosetting resin or a thermoplastic polymer; or first hydrogenating said unsaturated bisphenol to produce a saturated bisphenol and then converting said saturated bisphenol to a resin or thermoplastic polymer; purifying said resins or thermoplastic polymers; and combining and curing said resins or thermoplastic polymers or resins and thermoplastic polymers with support material to produce composite materials of thermoplastic polymers, resins, or blends of thermoplastic polymers and resins. ### Claim 2 (depends on 1) The method according to claim 1, further comprising hydrogenating said unsaturated bisphenol with at least one hydrogenating catalyst under a H2 environment to yield a saturated bisphenol. ### Claim 3 (depends on 1) The method according to claim 1, wherein said resin is a cyanate ester and/or epoxy resins and further comprising combining and curing said resins or thermoplastic polymers with support material to produce composite materials having a low water uptake of less than 1.8% and glass transition temperature greater than 186° C. ### Claim 4 (depends on 1) The method according to claim 1, wherein said resin is cyanate esters and/or epoxy resins. ### Claim 5 (depends on 1) The method according to claim 1, wherein said one metathesis catalyst is a homogeneous and/or heterogeneous catalyst. ### Claim 6 (depends on 5) The method according to claim 5, further comprising separating said heterogeneous catalyst by filtration. ### Claim 7 (depends on 5) The method according to claim 5, further comprising separating said homogeneous catalyst by extraction of said bisphenol into water with a base and reprecipitation of said bisphenol with at least one acid. ### Claim 8 (depends on 5) The method according to claim 5 further comprising using at least one solvent under pressure of about 0.1-100 atm and with at least one catalyst. ### Claim 9 (depends on 8) The method according to claim 8, wherein said at least one solvent is a mixture of alcohol and THF and said catalyst is selected from the group consisting of Ni, Pd, Pt, Ru, Cu, and any combination thereof. ### Claim 10 (depends on 5) The method according to claim 5, wherein said homogeneous catalysts are olefin metathesis catalysts based on Ru, Re, Mo, W, and any combination thereof. ### Claim 11 (depends on 5) The method according to claim 5, wherein said heterogeneous catalysts are olefin metathesis catalysts on inorganic or polymer supports based on Ru, Re, Mo, W and any combination thereof. ### Claim 12 (depends on 1) The method according to claim 1, wherein said resins are selected from the group consisting of cyanate esters, epoxy resins, benzoxazines, and any combination thereof. ### Claim 13 (depends on 1) The method according to claim 1, wherein said thermoplastic polymers are selected from the group consisting of polycarbonates prepared with reagents including polysulfones, polyethers, poly ether ether ketones (PEEK), polyesters, alkylphenolics, polyarylates, and any combination thereof. ### Claim 14 (depends on 1) The method according to claim 1, wherein said support material is selected from the group consisting of carbon fiber, carbon nanotubes, graphene, glass fibers, metal oxides, clay, nanofibers, and any combination thereof. ### Claim 15 (depends on 1) The method according to claim 1, wherein said curing temperature for resins ranges from about 50° C. to about 350° C. and said resins are dicyanate esters. ### Claim 16 (depends on 1) The method according to claim 1, wherein said thermoplastic polymers are melt-pressed with said support materials to yield composite materials or tougheners for thermosetting resins. ### Claim 17 (depends on 1) The method according to claim 1, wherein a thermosetting resin and said thermoplastic resin prepared from eugenol are thermally cured to generate a homogenous network. ### Claim 18 A method for manufacturing thermoplastics or resins from phenol, comprising: isolating eugenol synthetically or from at least one renewable resource; reacting said eugenol with at least one metathesis catalyst to form an unsaturated bisphenol; converting said unsaturated bisphenol to a thermosetting resin or a thermoplastic polymer; or first hydrogenating said unsaturated bisphenol to produce a saturated bisphenol and then converting said saturated bisphenol to a thermosetting resin or thermoplastic polymer; purifying said resins or thermoplastic polymers; and combining and curing said resins or thermoplastic polymers or resins and thermoplastic polymers with support material to produce composite materials of thermoplastic polymers, resins, or blends of thermoplastic polymers and resins; and wherein said composite materials are recycled back to eugenol phenols and bisphenols via a controlled pyrolysis process. ### Claim 19 (depends on 18) The method according to claim 18, further comprising hydrogenating said unsaturated bisphenol with at least one hydrogenating catalyst under a H2 environment to yield a saturated bisphenol. ### Claim 20 (depends on 18) The method according to claim 18, wherein said resin is a cyanate ester and/or epoxies and further comprising combining and curing said resins or thermoplastic polymers with support material to produce composite materials having a low water uptake of less than 1.8% and glass transition temperature greater than 186° C. ### Claim 21 (depends on 18) The method according to claim 18, wherein said pyrolysis process is at a temperature range of about 250° C. to about 450° C. ### Claim 22 (depends on 18) The method according to claim 18, wherein said pyrolysis process is in the presence of a hydrolysis catalyst. ### Claim 23 (depends on 18) The method according to claim 18, wherein recycled said phenols or bisphenols are purified by distillation, sublimation, crystallization, or column chromatography.