# US 2021/0340413 A1 · Phthalonitrile adhesive formulations and related methods > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2021/0340413 A1 - Document ID: US20210340413A1 - Status: Published application - Kind: A1 - Application number: 16/863,052 - Filed: 2020-04-30 - Published: 2021-11-04 - Earliest claimed: 2020-04-30 - Assignees: The Boeing Company - Applicants: The Boeing Company - Inventors: Ashley M. Dustin; Andrew P. Nowak; Gregory P. Nowak; Kevin J. Drummey; Michael Ventuleth - Web page: https://patentgrep.com/patent/US20210340413A1 ## CPC - C09J 11/06: organic - C08G 73/024: {Polyamines containing oxygen in the form of ether bonds in the main chain} - C08K 5/315: Compounds containing carbon-to-nitrogen triple bonds - C09J 179/02: Polyamines - C08K 3/013: Fillers, pigments or reinforcing additives - C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators} - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract Provided herein are phthalonitrile adhesive formulations and methods of making and using the adhesive formulations. An illustrative adhesive formulation comprises a phthalonitrile additive selected from a group consisting of 1,2-dicyanobenzene; a derivative of 1,2-dicyanobenzene; and combinations thereof; a bisphthalonitrile compound; and a curing agent; wherein the phthalonitrile additive does not comprise an ether functional group and does not comprise a thioether functional group. ## Claims ### Claim 1 An adhesive formulation comprising: (a) a phthalonitrile additive selected from a group consisting of 1,2-dicyanobenzene; a derivative of 1,2-dicyanobenzene; and combinations thereof; (b) a bisphthalonitrile compound; and (c) a curing agent, wherein the phthalonitrile additive does not comprise an ether functional group and does not comprise a thioether functional group. ### Claim 2 (depends on 1) The adhesive formulation of claim 1, wherein the derivative comprises at least one phthalonitrile moiety and a functional group. ### Claim 3 (depends on 2) The adhesive formulation of claim 2, wherein the functional group comprises a hydrogen bond donor. ### Claim 4 (depends on 3) The adhesive formulation of claim 3, wherein the hydrogen bond donor is an N—H bond of the functional group. ### Claim 5 (depends on 3) The adhesive formulation of claim 3, wherein the functional group comprises an amine group; an amide group; an oxalamide group; a urea group; a urethane group; or combinations thereof. ### Claim 6 (depends on 5) The adhesive formulation of claim 5, wherein the functional group is monofunctional. ### Claim 7 (depends on 5) The adhesive formulation of claim 5, wherein the functional group is multifunctional comprising one or more of the amine group; the amide group; the oxalamide group; the urea group; the urethane group; or combinations thereof. ### Claim 8 (depends on 1) The adhesive formulation of claim 1, wherein the phthalonitrile additive comprises a single phthalonitrile moiety or two phthalonitrile moieties. ### Claim 9 (depends on 1) The adhesive formulation of claim 1, wherein the phthalonitrile additive is selected from a group consisting of 1,2-dicyanobenzene; 4-aminophthalonitrile; 4-phenylureaphthalonitrile; toluene bisureaphthalonitrile; methylene diphenylureaphthalonitrile; and combinations thereof. ### Claim 10 (depends on 1) The adhesive formulation of claim 1, wherein the phthalonitrile additive is present in the adhesive formulation at an amount in a range of from 2 mol % to 30 mol %. ### Claim 11 (depends on 1) The adhesive formulation of claim 1, wherein the bisphthalonitrile compound is an oligomer. ### Claim 12 (depends on 1) The adhesive formulation of claim 1, wherein the bisphthalonitrile compound comprises an aromatic ether linking group and a ketone linking group. ### Claim 13 (depends on 12) The adhesive formulation of claim 12, wherein the aromatic linking group is provided by a bisphenol and the ketone linking group is provided by a benzophenone. ### Claim 14 (depends on 1) The adhesive formulation of claim 1, wherein a portion of the phthalonitrile moieties in the adhesive formulation are crosslinked to form a prepolymer of the phthalonitrile additive and the bisphthalonitrile compound in the adhesive formulation. ### Claim 15 An adhesive formulation comprising: (a) a phthalonitrile additive selected from a group consisting of 1,2-dicyanobenzene; a derivative of 1,2-dicyanobenzene; and combinations thereof; (b) a bisphthalonitrile compound; (c) a curing agent; (d) a prepolymer of the phthalonitrile additive and the bisphthalonitrile compound; and (e) a solvent, wherein the phthalonitrile additive does not comprise an ether functional group and does not comprise a thioether functional group. ### Claim 16 (depends on 15) The adhesive formulation of claim 15, wherein the derivative comprises at least one phthalonitrile moiety and a functional group. ### Claim 17 (depends on 16) The adhesive formulation of claim 16, wherein the functional group comprises a hydrogen bond donor. ### Claim 18 (depends on 15) The adhesive formulation of claim 15 characterized by a shear viscosity which is at least 1.5 times greater than that of a comparative adhesive formulation that does not comprise the phthalonitrile additive. ### Claim 19 (depends on 15) The adhesive formulation of claim 15, characterized by a shear viscosity in a range of from 1,000 cP. to 100,000 cP. ### Claim 20 (depends on 15) The adhesive formulation of claim 15, wherein the prepolymer, together with the phthalonitrile additive, the bisphthalonitrile compound, and the curing agent, are present at an amount in a range of from 25 weight % to 80 weight %. ### Claim 21 (depends on 15) The adhesive formulation of claim 15, further comprising an additive selected from a group consisting of a filler, a dispersant, a flow agent, a cure promoter, and a surfactant. ### Claim 22 (depends on 15) The adhesive formulation of claim 15, further comprising a filler having an aspect ratio of greater than 2. ### Claim 23 (depends on 15) A prepreg comprising a fibrous material and the adhesive formulation of claim 15 impregnated into the fibrous material. ### Claim 24 (depends on 15) An adhesive article comprising a substrate and a layer of the adhesive formulation of claim 15 on a surface of the substrate. ### Claim 25 (depends on 1) A thermoset polymer formed by curing the adhesive formulation of claim 1. ### Claim 26 (depends on 15) A thermoset polymer formed by curing the adhesive formulation of claim 15. ### Claim 27 (depends on 1) A method of using the adhesive formulation of claim 1, the method comprising: heating the adhesive formulation of claim 1 at a temperature and for a period of time to achieve partial curing of the phthalonitrile additive and the bisphthalonitrile compound to form a prepolymer; and adding a solvent. ### Claim 28 (depends on 15) A method of using the adhesive formulation of claim 15, comprising heating the adhesive formulation of claim 15 according to a curing profile to form a thermoset polymer.