Water co-catalyst for polyimide processes

Patent metadata

Field	Value
Publication number	US-11932745-B2
Application number	US-202117546529-A
Country	US
Kind code	B2
Filing date	Dec 9, 2021
Priority date	Dec 11, 2020
Publication date	Mar 19, 2024
Grant date	Mar 19, 2024

Abstract

The present disclosure is directed to methods of forming polyimide gels. The methods generally include forming a polyamic acid and dehydrating the polyamic acid with a dehydrating agent in the presence of water. The resulting polyimide gels may be converted to polyimide or carbon xerogels or aerogels. The methods are advantageous in providing rapid or even instantaneous gelation, which may be particularly useful in formation of beads comprising the polyimide gels. Polyimide or carbon gel materials prepared according to the disclosed method are suitable for use in environments containing electrochemical reactions, for example as an electrode material within a lithium-ion battery.

First claim

The invention claimed is:

1. A method of forming a polyimide gel, the method comprising:
a) providing a tetracarboxylic acid dianhydride and a multifunctional amine;
b) adding the tetracarboxylic acid dianhydride and the multifunctional amine to an organic solvent to form a solution;
c) allowing the tetracarboxylic acid dianhydride and the multifunctional amine to react in solution, forming a solution of a polyamic acid sol;
d) adding a dehydrating agent, a monoamine, and water to the solution of the polyamic acid sol, forming a gelation mixture and allowing the gelation mixture to gel to form the polyimide gel, wherein the water is added at a molar ratio of water to the tetracarboxylic acid dianhydride from about 5 to about 500.

2. The method of claim 1 , wherein the tetracarboxylic acid dianhydride is selected from the group consisting of pyromellitic anhydride (PMDA), biphthalic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), ethylenediaminetetraacetic dianhydride (EDDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride, and combinations thereof.

3. The method of claim 1 , wherein the multifunctional amine is 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), tris(4-aminophenyl)methane, melamine, or a combination thereof.

4. The method of claim 1 , wherein the multifunctional amine is an alkane diamine or an aryl diamine.

5. The method of claim 4 , wherein the alkane diamine is ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, or a combination thereof.

6. The method of claim 4 , wherein the aryl diamine is 1,4-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-methylenedianiline, or a combination thereof.

7. The method of claim 1 , wherein a molar ratio of the tetracarboxylic acid dianhydride to the multifunctional amine is from about 0.9 to about 3, or from about 0.9 to about 1.1.

8. The method of claim 1 , wherein a molar ratio of the monoamine to the polyamic acid sol is from about 0.1 to about 8.

9. The method of claim 1 , wherein a quantity of the monoamine required to be added to achieve formation of the polyimide gel with a gelation time under about 15 minutes is reduced by up to about 50-fold relative to a method of forming a polyimide gel in the absence of water.

10. The method of claim 1 , wherein the monoamine is a tertiary alkyl amine, a tertiary cycloalkyl amine, a heteroaromatic amine, a guanidine, or a quaternary ammonium hydroxide.

11. The method of claim 1 , wherein the monoamine is selected from the group consisting of trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, N-methylpyrrolidine, N-methylpiperidine, diisopropylethylamine, pyridine, quinoline, guanidine, and a tetraalkylammonium hydroxide.

12. The method of claim 1 , wherein the monoamine is pyridine.

13. The method of claim 1 , wherein a molar ratio of the dehydrating agent to the tetracarboxylic acid dianhydride is from about 2 to about 10, from about 3 to about 6, or from about 4 to about 5.

14. The method of claim 1 , wherein the dehydrating agent is a carboxylic acid anhydride.

15. The method of claim 14 , wherein the carboxylic acid anhydride is acetic anhydride.

16. The method of claim 1 , wherein the organic solvent is N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, or a combination thereof.

17. The method of claim 1 , wherein a range of concentration of the polyamic acid sol in the solution is from about 0.01 to about 0.3 g/cm 3 .

18. The method of claim 1 , wherein the multifunctional amine and the tetracarboxylic acid dianhydride are allowed to react for a period of time from about 0.5 hour to about 17 hours.

19. The method of claim 1 , wherein the multifunctional amine and the tetracarboxylic acid dianhydride are allowed to react at a temperature from about 10 to about 100° C., from about 15 to about 60° C., from about 15 to about 50° C., or from about 15 to about 25° C.

20. The method of claim 1 , wherein a length of time from addition of the monoamine and water until gelation of the polyimide is less than about 1 minute, or less than about 30 seconds, or less than about 15 seconds.

21. The method of claim 1 , further comprising:
prior to complete gelation of the gelation mixture, casting the gelation mixture in a mold to form a polyimide wet-gel monolith;
demolding the polyimide wet-gel monolith;
washing or solvent exchanging the polyimide wet-gel monolith; and
drying the polyimide wet-gel monolith to form a monolithic polyimide aerogel or xerogel.

22. The method of claim 21 , wherein the monolith has a thickness from about 5 to about 25 mm.

23. The method of claim 21 , wherein the monolith is a film having a thickness from about 50 microns to about 1 mm.

24. The method of claim 21 , wherein the washing or solvent exchanging is performed with water, a C1 to C3 alcohol, acetone, acetonitrile, ether, tetrahydrofuran, toluene, liquid carbon dioxide, or a combination thereof.

25. The method of claim 21 , wherein drying comprises lyophilizing the polyimide wet-gel, or contacting the polyimide wet-gel with supercritical fluid CO 2 .

26. The method of claim 21 , further comprising carbonizing the monolithic polyimide aerogel or xerogel to form a carbon aerogel or xerogel.

27. The method of claim 26 , wherein the carbon aerogel has substantially the same properties as a carbon aerogel prepared by carbonizing a corresponding polyimide wet-gel that has been prepared by an imidization method which does not include water.

28. The method of claim 1 , wherein the polyimide gel is in the form of beads, the method further comprising:
e) prior to complete gelation of the gelation mixture, adding the gelation mixture to mineral oil, silicone oil, a C5-C12 hydrocarbon, or mineral spirits to form an emulsion; and
f) stirring the emulsion under high-shear conditions to form polyimide beads having a diameter from about 5 microns to about 200 microns.

29. The method of claim 28 , further comprising adding one or more surfactants to the gelation mixture or the emulsion.

30. The method of claim 28 , further comprising drying the polyimide beads under elevated temperature conditions or with supercritical fluid CO 2 .

31. The method of claim 1 , wherein the polyimide gel is in the form of beads, the method further comprising:
e) prior to complete gelation, spraying the gelation mixture into air or into mineral oil, silicone oil, a C5-C12 hydrocarbon, or mineral spirits, to form polyimide beads having a diameter from about 5 microns to about 250 microns.

32. The method of claim 31 , wherein the method is carried out as a continuous process, the continuous process further comprising conveying the polyimide beads through one or more of:
filtering;
aging;
solvent exchanging;
drying;
carbonizing.

33. The method of claim 1 , further comprising adding silicon to the polyamic acid prior to dehydration or prior to gelation.

34. A method of forming a polyimide gel, the method comprising:
a) providing a tetracarboxylic acid dianhydride and a multifunctional amine;
b) adding the tetracarboxylic acid dianhydride and the multifunctional amine to an organic solvent to form a solution;
c) allowing the tetraca

Assignees

• Aspen Aerogels Inc

Inventors

• Begag Redouane
• Trifu Roxana
• Zafiropoulos Nicholas A
• Miller Harris R
• Gould George L
• Leventis Nicholas

Classifications

• C08J9/286 Primary

  the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers · CPC title

• C08G73/1007

  from tetracarboxylic acids or derivatives and diamines · CPC title

• C08G73/1067

  Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound · CPC title

• C08G73/1085

  Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties · CPC title

• C08J9/36

  After-treatment (C08J9/22 takes precedence) · CPC title