Benzimidazole based aerogel materials

Patent metadata

Field	Value
Publication number	US-9434831-B2
Application number	US-201414450942-A
Country	US
Kind code	B2
Filing date	Aug 4, 2014
Priority date	Nov 4, 2013
Publication date	Sep 6, 2016
Grant date	Sep 6, 2016

Abstract

The present invention provides aerogel materials based on imidazoles and polyimidazoles. The polyimidazole based aerogel materials can be thermally stable up to 500° C. or more, and can be carbonized to produce a carbon aerogel having a char yield of 60% or more, specifically 70% or more. The present invention also provides methods of producing polyimidazole based aerogel materials by reacting at least one monomer in a suitable solvent to form a polybenzimidazole gel precursor solution, casting the polybenzimidazole gel precursor solution into a fiber reinforcement phase, allowing the at least one gel precursor in the precursor solution to transition into a gel material, and drying the gel materials to remove at least a portion of the solvent, to obtain an polybenzimidazole-based aerogel material.

First claim

What is claimed is:

1. A benzimidazole-based aerogel.

2. A fiber-reinforced aerogel material comprising the benzimidazole-based aerogel of claim 1 .

3. The aerogel of claim 1 , wherein the benzimidazole-based aerogel has a char yield of 57% or more.

4. The aerogel of claim 3 , wherein the benzimidazole-based aerogel has a char yield of 60% or more.

5. The aerogel of claim 1 , wherein the benzimidazole-based aerogel has a thermal stability of 400° C. of more.

6. The aerogel of claim 5 , wherein the benzimidazole-based aerogel has a thermal stability of 500° C. of more.

7. The aerogel of claim 1 , wherein the benzimidazole-based aerogel is comprised of a benzimidazole polymer in an aerogel framework, said benzimidazole polymer is the product of a reaction between an aryl amine having at least four amino groups and an aldehyde compound having at least two aldehyde groups.

8. The aerogel of claim 7 , wherein the aryl amine is represented by the general formula: (H 2 N) 2 —(Ar) m -L-(Ar) n —(NH 2 ) 2 ; where Ar is an aryl group; m is an integer; n is an integer; and L is independently a bond, a single bonded O, CO, S, SO 2 , a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 alkylarylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, or a substituted or unsubstituted C2 to C30 alkenylene group.

9. The aerogel of claim 8 , wherein the aryl amine is a compound of Formula 1 or Formula 2:

where L is independently a bond, a single bonded O, CO, S, SO 2 , a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 alkylarylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, or a substituted or unsubstituted C2 to C30 alkenylene group.

10. The aerogel of claim 7 , wherein the aryl amine is diaminobenzidene.

11. The aerogel of claim 7 , wherein the aldehyde compound is represented by the general formula: OCH—(Ar) p -L-(Ar) q —CHO; where Ar is an aryl group; p is an integer; q is an integer; and L is independently a bond, a single bonded O, CO, S, SO 2 , a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 alkylarylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, or a substituted or unsubstituted C2 to C30 alkenylene group.

12. The aerogel of claim 11 , wherein the aldehyde compound is a compound of Formula 3, Formula 4, Formula 5, or Formula 6:

where L is independently a bond, a single bonded O, CO, S, SO 2 , a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 alkylarylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, or a substituted or unsubstituted C2 to C30 alkenylene group.

13. The aerogel of claim 7 , wherein the aldehyde compound is terephthalaldehyde.

14. The aerogel of claim 7 , wherein the aryl amine is diaminobenzidene, and wherein the aldehyde compound is terephthalaldehyde.

15. A method for preparing a benzimidazole-based aerogel, comprising:
a. reacting at least one suitable monomer in a suitable solvent to form a polybenzimidazole gel precursor solution;
b. allowing the at least one gel precursor in the precursor solution to transition into a gel material; and
c. drying the gel materials to remove at least a portion of the solvent to obtain a benzimidazole-based aerogel.

16. The method of claim 15 , wherein the aerogel is dried using carbon dioxide under supercritical carbon dioxide conditions.

17. The method of claim 15 , wherein the aerogel is dried using carbon dioxide under subcritical carbon dioxide conditions.

18. The method of claim 15 , wherein the method for preparation of a benzimidazole-based aerogel more specifically comprises:
a. reacting at least one monomer in a suitable solvent to form a polybenzimidazole gel precursor solution;
b. casting the polybenzimidazole gel precursor solution into a fiber reinforcement phase;
c. allowing the at least one gel precursor in the precursor solution to transition into a gel material; and
d. drying the gel materials to remove at least a portion of the solvent to obtain a benzimidazole-based aerogel.

19. The method of claim 18 , wherein the aerogel is dried using carbon dioxide under supercritical carbon dioxide conditions.

20. The method of claim 18 , wherein the aerogel is dried using carbon dioxide under subcritical carbon dioxide conditions.

21. The method of claim 15 , wherein the benzimidazole polymers in the aerogel framework are the product of a reaction between an aryl amine having at least four amino groups and an aldehyde compound having at least two aldehyde groups.

22. The method of claim 18 , wherein the benzimidazole polymers in the aerogel framework are the product of a reaction between an aryl amine having at least four amino groups and an aldehyde compound having at least two aldehyde groups.

23. The method of claim 21 , wherein the aryl amine is represented by the general formula: (H 2 N) 2 —(Ar) m -L-(Ar) n —(NH 2 ) 2 ; where Ar is an aryl group; m is an integer; n is an integer; and L is independently a bond, a single bonded O, CO, S, SO 2 , a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 alkylarylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, or a substituted or unsubstituted C2 to C30 alkenylene group.

24. The method of claim 23 , wherein the aryl amine is a compound of Formula 1 or Formula 2:

where L is independently a bond, a single bonded O, CO, S, SO 2 , a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 alkylarylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, or a substituted or unsubstituted C2 to C30 alkenylene group.

25. The method of claim 21 , wherein the aryl amine is diaminobenzidene.

26. The method of claim 21 , wherein the aldehyde compound is represented by the general formula: OCH

Assignees

• Aspen Aerogels Inc

Inventors

• Rhine Wendell E
• Mihalcik David

Classifications

• C08J9/0066 Primary

  Use of inorganic compounding ingredients · CPC title

• C08J2201/0502

  the liquid phase being organic · CPC title

• C08J2205/026

  Aerogel, i.e. a supercritically dried gel · CPC title

• C08J9/28 Primary

  by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum · CPC title

• C08J2379/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title