Nanomodified backbones for polyimides with difunctional and mixed-functionality endcaps

Patent metadata

Field	Value
Publication number	US-9505864-B2
Application number	US-201414473232-A
Country	US
Kind code	B2
Filing date	Aug 29, 2014
Priority date	Aug 29, 2014
Publication date	Nov 29, 2016
Grant date	Nov 29, 2016

Abstract

Polyimides containing a backbone with at least one nanoparticle component and made from oligomers having endcaps that are difunctional or a mix of di- and monofunctionality are provided. The endcaps may be nadic or phenylethynyl. The backbone may be wholly inorganic or made from a mixture of inorganic and organic groups. The oligomers may be created in-situ using standard polymerization of monomeric reactants chemistry using a solvent or may be provided as a pre-imidized compound that may be either a solid or liquid. It is believed that the nanoparticle component of the polymer backbone provides superior thermo-oxidative stability verses unmodified organic backbones. It is further believed that providing difunctional or a mixture of di- and monofunctional endcaps allows for increased crosslinking to provide improved strength and stiffness verses wholly monofunctional endcapped oligomers for polyimides. The nanoparticle is part of the backbone of the polymer and not solely a pendant group.

First claim

What is claimed is:

1. A resin system, comprising:
a first capped oligomer having the formula:
Y i -A-Y i ,

 wherein:
i=1 or 2;
Y is a phenylethynyl or a diphenylethynyl functional endcap; and
A is a chemical backbone, wherein the chemical backbone comprises one or more nanoparticles; and

a second capped oligomer having the formula:
D i -Q-D i ,

 wherein:
i=1 or 2;
D is a phenylethynyl or a diphenylethynyl functional endcap; and
Q is a hydrocarbon backbone without nanoparticles.

2. The resin system of claim 1 , wherein:
from about 1% to about 25% of the chemical backbones and hydrocarbon backbones have phenylethynyl endcaps; and
from about 75% to about 99% of the chemical backbones and hydrocarbon backbones have diphenylethynyl endcaps.

3. The resin system of claim 1 , wherein the one or more nanoparticles are inorganic nanoparticles.

4. The resin system of claim 1 , wherein the one or more nanoparticles are organic nanoparticles.

5. The resin system of claim 1 , wherein the one or more nanoparticles have inorganic portions and organic portions.

6. The resin system of claim 1 , wherein the one or more nanoparticles are selected from the group consisting of: functionalized silsesquioxanes, functionalized carbon black, functionalized silicates, functionalized graphene, functionalized nanographite, functionalized carbon nanotubes, functionalized halloysite nanotubes, functionalized boron nitride nanotubes and combinations thereof.

7. The resin system of claim 1 , wherein the chemical backbone further comprises one or more moieties selected from the group consisting of: imidesulfone, ether, ethersulfone, amide, imide, ester, estersulfone, etherimide, amideimide, oxazolyl, oxazolyl sulfone, thiazolyl, thiazolyl sulfone, imidazolyl, imidazolyl sulfone, heterocyclyl sulfone, and combinations thereof.

8. The resin system of claim 7 , wherein the hydrocarbon backbone includes one or more moieties selected from the group consisting of: imidesulfone, ether, ethersulfone, amide, imide, ester, estersulfone, etherimide, amideimide, oxazolyl, oxazolyl sulfone, thiazolyl, thiazolyl sulfone, imidazolyl, imidazolyl sulfone, and combinations thereof.

9. The resin system of claim 1 , wherein at least one of Y or D is the diphenylethynyl functional endcap and is selected from the group consisting of:

wherein:
Ph=phenyl;
G=—SO 2 —, —S—, —O—, —CH 2 —, —CO—, —SO—, —CHR—, —CR 2 —, C 3 F 6 , or NHCO; and
R 1 =amine, hydroxyl, acid chloride, or anhydride, where R 1 is the point of attachment to the oligomeric backbone.

10. The resin system of claim 1 , wherein at least one of Y or D is the phenylethynyl functional endcap and is selected from the group consisting of:

wherein R=hydrogen, lower alkyl, or phenyl, and
wherein R 1 =amine, hydroxyl, acid chloride, or anhydride, where R 1 is the point of attachment to the oligomeric backbone.

11. The resin system of claim 1 , wherein at least part of the first capped oligomer is reacted with at least part of the second capped oligomer to form a reaction product.

12. The resin system of claim 6 , wherein the nanoparticles are functionalized with one or more functional groups selected from the group consisting of: carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, and combinations thereof.

13. The resin system of claim 1 , wherein the one or more nanoparticles are directly attached to Y.

14. The resin system of claim 1 , wherein the one or more nanoparticles are selected from the group consisting of: functionalized carbon black, functionalized silicates, functionalized graphene, functionalized nanographite, functionalized carbon nanotubes, functionalized halloysite nanotubes, functionalized boron nitride nanotubes and combinations thereof.

15. The resin system of claim 1 , comprising:
from about 50% to about 99% of the chemical backbones comprising one or more nanoparticles; and
from about 1% to about 50% of the hydrocarbon backbones without nanoparticles.

16. The resin system of claim 15 , comprising:
from about 75% to about 99% of the chemical backbones comprising one or more nanoparticles; and
from about 1% to about 25% of the hydrocarbon backbones without nanoparticles.

17. The resin system of claim 1 , further comprising:
a third capped oligomer having the formula:
Z i —B—Z i ,

 wherein:
i=1 or 2;
Z is a phenylethynyl or a diphenylethynyl functional endcap; and
B is a nanoparticle.

18. The resin system of claim 17 , wherein the one or more nanoparticles are selected from the group consisting of: functionalized silsesquioxanes, functionalized carbon black, functionalized silicates, functionalized graphene, functionalized nanographite, functionalized carbon nanotubes, functionalized halloysite nanotubes, functionalized boron nitride nanotubes and combinations thereof.

19. The resin system of claim 1 , wherein the first capped oligomer and the second capped oligomer are polyimide oligomers.

Assignees

• Boeing Co

Inventors

• Tsotsis Thomas K

Classifications

• C08L79/08

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

• C08F226/06

  by a heterocyclic ring containing nitrogen · CPC title

• C08F238/00 Primary

  Copolymers of compounds having one or more carbon-to-carbon triple bonds · CPC title

• C08G73/101

  containing chain terminating or branching agents · CPC title