Poly(etherimide-phthalonitrile) adhesives and related methods

Patent metadata

Field	Value
Publication number	US-11795357-B2
Application number	US-202117411191-A
Country	US
Kind code	B2
Filing date	Aug 25, 2021
Priority date	Aug 25, 2021
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

Phthalonitrile adhesive formulations are provided. Such an adhesive formulation may comprise an etherimide-phthalonitrile oligomer having formulawherein R1 is an unsubstituted or substituted aryl group or an unsubstituted or substituted cycloalkyl group; R2 is an unsubstituted or substituted aryl group and n has a value of from 1 to 30. Also provided are methods of making and using the adhesive formulations.

First claim

What is claimed is:

1. An adhesive formulation comprising:
an etherimide-phthalonitrile oligomer having formula

wherein R 1 is an unsubstituted or substituted aryl group or an unsubstituted or substituted cycloalkyl group; R 2 is an unsubstituted or substituted aryl group and n has a value of from 1 to 30.

2. The adhesive formulation of claim 1 , wherein R 1 is monocyclic, or polycyclic having two or more unfused monocyclic rings.

3. The adhesive formulation of claim 1 , wherein R 1 is unsubstituted or substituted benzene, or unsubstituted or substituted cyclohexane.

4. The adhesive formulation of claim 1 , wherein R 1 is polycyclic having two or more unfused monocyclic rings, wherein neighboring unfused monocyclic rings are connected directly or connected via an oxygen, a sulfone, or an unsubstituted or substituted alkyl group.

5. The adhesive formulation of claim 1 , wherein R 2 is monocyclic, or polycyclic having two or more unfused monocyclic rings.

6. The adhesive formulation of claim 1 , wherein R 2 is unsubstituted benzene.

7. The adhesive formulation of claim 1 , wherein R 2 is polycyclic having two or more unfused monocyclic rings, wherein neighboring unfused monocyclic rings are connected directly or connected via one or more groups selected from a group consisting of a ketone group, an ether group, a urethane group, a urea group, an amide group, an imide group, an ester group, an oxamide group, a sulfone group, an alkyl group, and an alkylene group, wherein any group may be unsubstituted or substituted.

8. The adhesive formulation of claim 1 , wherein R 2 is polycyclic having two unfused monocyclic rings connected directly or connected via a sulfone group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkylene group.

9. The adhesive formulation of claim 1 , wherein R 1 is unsubstituted or substituted benzene; or unsubstituted or substituted cyclohexane; or polycyclic having two or more unfused monocyclic rings, wherein neighboring unfused monocyclic rings are connected directly or connected via an oxygen, a sulfone, or an unsubstituted or substituted alkyl group; and
wherein R 2 is unsubstituted benzene; or polycyclic having two unfused monocyclic rings connected directly or connected via a sulfone group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkylene group.

10. The adhesive formulation of claim 1 , wherein the etherimide-phthalonitrile oligomer is

11. The adhesive formulation of claim 1 , further comprising a bisphthalonitrile compound.

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

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

14. The adhesive formulation of claim 1 , wherein a portion of phthalonitrile moieties in the etherimide-phthalonitrile oligomer are crosslinked, forming a prepolymer.

15. The adhesive formulation of claim 14 , further comprising a liquid medium.

16. The adhesive formulation of claim 15 , further comprising a filler.

17. The adhesive formulation of claim 15 , the adhesive formulation in the form of a paste having a shear viscosity of greater than 1,000 cps as measured at room temperature and 100 Hz.

18. The adhesive formulation of claim 15 , the adhesive formulation in the form of a spray having a shear viscosity of less than 300 cps as measured at room temperature and 100 Hz.

19. A method of making an adhesive formulation, the method comprising:
inducing crosslinking in a portion of phthalonitrile moieties of an etherimide-phthalonitrile oligomer having formula

wherein R 1 is an unsubstituted or substituted aryl group or an unsubstituted or substituted cycloalkyl group; R 2 is an unsubstituted or substituted aryl group and n has a value of from 1 to 30, to form a prepolymer; and
combining the prepolymer with a liquid medium to form an adhesive formulation.

20. The method of claim 19 , further comprising synthesizing the etherimide-phthalonitrile oligomer by reacting a bisimide monomer, a diol, and a phthalonitrile endcapper, wherein the bisimide monomer has formula

the diol has formula HO—R 2 —OH; and
the phthalonitrile endcapper has formula

wherein X is NO 2 , or a halogen.

21. A method of using the adhesive formulation of claim 15 , the method comprising heating the adhesive formulation according to a curing profile to form a poly(etherimide-phthalonitrile) thermoset polymer.

22. A poly(etherimide-phthalonitrile) thermoset polymer formed by curing the adhesive formulation of claim 15 .

23. The poly(etherimide-phthalonitrile) thermoset polymer of claim 22 having a degradation temperature of greater than 450° C., an average maximum load of from 300 psi to 6,000 psi, or both.

24. An adhesive article comprising a substrate and a layer of the adhesive formulation of claim 15 on a surface of the substrate, optionally, wherein the layer is cured to form a poly(etherimide-phthalonitrile) thermoset polymer.

25. The adhesive article of claim 24 , wherein the substrate is a metal, a metal alloy, a composite thereof, or combinations thereof.

26. An etherimide-phthalonitrile oligomer having formula

wherein n has a value of from 1 to 30.

Assignees

• Boeing Co

Inventors

• Drummey Kevin James
• Dustin Ashley Marie
• Nowak Andrew P
• Ventuleth Michael Jared
• Nowak Gregory Phillip

Classifications

• C09J179/08 Primary

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/127

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

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title

• C08K5/315

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