Benzimidazole based aerogel materials
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.
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—(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.
27. The method of claim 26 , 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.
28. The method of claim 21 , wherein the aldehyde compound is terephthalaldehyde.
29. The method of claim 21 , wherein the aryl amine is diaminobenzidene, and wherein the aldehyde compound is terephthalaldehyde.
30. The method of claim 15 , wherein the method for preparation of a benzimidazole-based aerogel more specifically comprises:
a. reacting at least one aryl amine having at least four amino groups and at least one aldehyde compound having at least two aldehyde groups 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;
d. replacing at least a portion the suitable solvent in the gel material with an alcohol solvent having 1 to 4 carbon atoms; and
e. drying the gel materials to remove at least a portion of the alcohol solvent to obtain a benzimidazole-based aerogel.
31. The method of claim 30 , wherein the aryl amine is diaminobenzidene, and wherein the aldehyde compound is terephthalaldehyde.
32. The method of claim 30 , wherein the aerogel is dried using carbon dioxide under supercritical carbon dioxide conditions.
33. The method of claim 30 , wherein the aerogel is dried using carbon dioxide under subcritical carbon dioxide conditions.