Phthalonitrile adhesive formulations and related methods

Patent metadata

Field	Value
Publication number	US-11746262-B2
Application number	US-202016863052-A
Country	US
Kind code	B2
Filing date	Apr 30, 2020
Priority date	Apr 30, 2020
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

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.

First claim

What is claimed is:

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.

2. The adhesive formulation of claim 1 , wherein the phthalonitrile additive is the derivative of 1,2-dicyanobenzene and the derivative comprises at least one phthalonitrile moiety and a functional group comprising a hydrogen bond donor, wherein the functional group is directly covalently bound to the benzene of the at least one phthalonitrile moiety.

3. The adhesive formulation of claim 2 , wherein the hydrogen bond donor is an N-H bond of the functional group and the N of the N-H bond is directly covalently bound to the benzene of the at least one phthalonitrile moiety.

4. 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.

5. The adhesive formulation of claim 4 , wherein the functional group is monofunctional.

6. The adhesive formulation of claim 4 , 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.

7. The adhesive formulation of claim 1 , wherein the phthalonitrile additive comprises a single phthalonitrile moiety or two phthalonitrile moieties.

8. 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.

9. 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 %.

10. The adhesive formulation of claim 1 , wherein the bisphthalonitrile compound is an oligomer.

11. The adhesive formulation of claim 1 , wherein the bisphthalonitrile compound comprises an aromatic ether linking group and a ketone linking group.

12. The adhesive formulation of claim 11 , wherein the aromatic ether linking group is provided by a bisphenol and the ketone linking group is provided by a benzophenone.

13. The adhesive formulation of claim 1 , wherein a portion of phthalonitrile moieties in the adhesive formulation are crosslinked to form a prepolymer of the phthalonitrile additive and the bisphthalonitrile compound in the adhesive formulation.

14. 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.

15. The adhesive formulation of claim 14 , wherein the phthalonitrile additive is the derivative of 1,2-dicyanobenzene and the derivative comprises at least one phthalonitrile moiety and a functional group comprising a hydrogen bond donor, wherein the functional group is directly covalently bound to the benzene of the at least one phthalonitrile moiety.

16. The adhesive formulation of claim 15 , wherein the hydrogen bond donor is an N-H bond of the functional group and the N of the N-H bond is directly covalently bound to the benzene of the at least one phthalonitrile moiety.

17. The adhesive formulation of claim 14 , 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 %.

18. The adhesive formulation of claim 14 , further comprising an additive selected from a group consisting of a filler, a dispersant, a flow agent, a cure promoter, and a surfactant.

19. A prepreg comprising a fibrous material and the adhesive formulation of claim 14 impregnated into the fibrous material.

20. An adhesive article comprising a substrate and a layer of the adhesive formulation of claim 14 on a surface of the substrate.

21. A thermoset polymer formed by curing the adhesive formulation of claim 1 .

22. A thermoset polymer formed by curing the adhesive formulation of claim 14 .

23. A method of using an adhesive formulation, 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.

24. A method of using an adhesive formulation, the method comprising heating the adhesive formulation of claim 14 according to a curing profile to form a thermoset polymer.

25. The adhesive formulation of claim 1 , wherein the phthalonitrile additive is selected from a group consisting of 4-aminophthalonitrile; 4-phenylureaphthalonitrile; toluene bisureaphthalonitrile; methylene diphenylureaphthalonitrile; and combinations thereof.

26. The adhesive formulation of claim 1 , wherein the phthalonitrile additive is 4-phenylureaphthalonitrile.

27. The adhesive formulation of claim 14 , wherein the phthalonitrile additive is selected from a group consisting of 4-aminophthalonitrile; 4-phenylureaphthalonitrile; toluene bisureaphthalonitrile; methylene diphenylureaphthalonitrile; and combinations thereof.

28. The adhesive formulation of claim 14 , wherein the phthalonitrile additive is 4-phenylureaphthalonitrile.

Assignees

• Boeing Co

Inventors

• Dustin Ashley M
• Nowak Andrew P
• Nowak Gregory P
• Drummey Kevin J
• Ventuleth Michael

Classifications

• C09J11/06 Primary

  organic · CPC title

• C08G73/024

  Polyamines containing oxygen in the form of ether bonds in the main chain · CPC title

• C08K5/315

  Compounds containing carbon-to-nitrogen triple bonds · CPC title

• C09J179/02

  Polyamines · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title