Polymer aerogel with improved mechanical and thermal properties
Aerogel compositions that include polyamic amides, methods for preparing the aerogel compositions, and articles of manufacture that include or manufactured from the aerogel compositions are described.
1. A method of making an aerogel, the method comprising:
(a) providing at least one diamine compound to a polar aprotic solvent to form a solution;
(b) reacting the at least one diamine compound with at least one dianhydride compound to form a polyamic acid in the solution;
(c) adding a substituted imidazole to the solution from step (b) in an amount where the molar ratio of the substituted imidazole to the at least one dianhydride compound is 0.5:1 to 8:1;
(d) subsequently adding a dehydrating agent to the solution from step (c) in an amount where the molar ratio of the substituted imidazole to the dehydrating agent is 0.17:1 to 2.8:1 and reacting the solution at a temperature of 75° C. to 100° C. for 30 seconds to 30 minutes to produce a polymer matrix gel comprising a polyamic amide; and
(e) drying the polymer matrix gel to form an aerogel comprising an open-cell structured polymer matrix that includes 5 wt. % to 50 wt. % of the polyamic amide based on the total weight of the polymer aerogel,
wherein the substituted imidazole has the following structure:
where R 3 , R 4 , and R 5 are each individually a hydrogen (H) atom, an alkyl group, or a substituted alkyl group, with the proviso that at least one of R 3 , R 4 and R 5 is an alkyl group or a substituted alkyl group.
2. The method of claim 1 , wherein the polyamic amide polymer in the polymer matrix has a repeating structural unit of:
where has the following structure:
where R 3 , R 4 , and R 5 are each individually a hydrogen (H) atom, an alkyl group, or a substituted alkyl group, with the proviso that at least one of R 3 , R 4 and R 5 is an alkyl group, or a substituted alkyl group;
X is a first organic group derived from the at least one diamine selected from the group consisting of 4,4′-oxydianiline, 3,4′-oxydianiline, 3,3-oxydianiline, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, diaminobenzanilide, 3,5-diaminobenzoic acid, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfones, 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 2,2-Bis[4-(4-aminophenoxy)phenyl]-hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4′-isopropylidenedianiline, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-4-(3-aminophenoxy)benzene, bis-[4-(4-aminophenoxy)phenyl]sulfones, 2,2-bis[4-(3-aminophenoxy)phenyl]sulfones, bis-[4-(4-aminophenoxy]phenyl)ether, 2,2′-bis-(4-aminophenyl)-hexafluoropropane, (6F-diamine), 2,2′-bis-(4-phenoxyaniline)isopropylidene, meta-phenylenediamine, para-phenylenediamine, 1,2-diaminobenzene, 4,4′-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4′diaminodiphenylpropane, 4,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfone, 3,4′diaminodiphenylether, 4,4′-diaminodiphenylether, 2,6-diaminopyridine, bis(3-aminophenyl)diethyl silane, 4,4′-diaminodiphenyl diethyl silane, benzidine, dichlorobenzidine, 3,3′-dimethoxybenzidine, 4,4′-diaminobenzophenone, N,N-bis(4-aminophenyl)-n-butylamine, N,N-bis(4-aminophenyl)methylamine, 1,5-diaminonaphthalene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4-aminophenyl-3-aminobenzoate, N,N-bis(4-aminophenyl)aniline, bis(p-beta-amino-t-butylphenyl)ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,3-bis(4-aminophenoxy)benzene, m-xylenediamine, p-xylenediamine, 4,4′-diaminodiphenyletherphosphine oxide, 4,4′-diaminodiphenyl N-methylamine, 4,4′-diaminodiphenyl N-phenylamine, amino-terminal polydimethylsiloxanes, amino-terminal polypropyleneoxides, amino-terminal polybutyleneoxides, 4,4′-methylenebis(2-methylcyclohexylamine), 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 4,4′-methylenebisbenzeneamine, 2,2′-dimethylbenzidine, (also known as 4,4′-diamino-2,2′-dimethylbiphenyl (DMB), bisaniline-p-xylidene, 4,4′-bis(4-aminophenoxy)biphenyl, 3,3′-bis(4 aminophenoxy)biphenyl, 4,4′-(1,4-phenylenediisopropylidene)bisaniline, and 4,4′-(1,3-phenylenediisopropylidene)bisaniline, combinations thereof;
and Y is a second organic group derived from the at least one dianhydride selected from the group consisting of hydroquinone dianhydride; 3,3′,4,4′-biphenyltetracarboxylic dianhydride; pyromellitic dianhydride; 3,3′,4,4′-benzophenone-tetracarboxylic dianhydride; 4,4′-oxydiphthalic anhydride; 3,3′,4,4′-diphenylsulfone-tetracarboxylic dianhydride; 4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride); 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride; 4,4′-(hexafluoroisopropylidene)diphthalic anhydride; bis(3,4-dicarboxyphenyl)sulfoxide dianhydride; polysiloxane-containing dianhydride; 2,2′,3,3′-biphenyltetracarboxylic dianhydride; 2,3,2′,3′-benzophenonetetraearboxylic dianhydride; 3,3′,4,4′-benzophenonetetraearboxylic dianhydride; naphthalene-2,3,6,7-tetracarboxylic dianhydride; naphtholene-1,4,5,8-tetracarboxylic dianhydride; 4,4′-oxydiphthalic dianhydride; 3,3′,4,4′-biphenylsulfone tetracarboxylic dianhydride; 3,4,9,10-peryene tetracarboxylic dianhydride; bis(3,4-dicarboxyphenyl)sulfide dianhydride; bis(3,4-dicarboxypheny)methane dianhydride; 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride; 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropene; 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride; 2,7-dichloronapthalene-1,4,5,8-tetracarboxylic dianhydride; 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride; phenanthrene-8,9,10-tetracarboxylic dianhydride; pyrazine-2,3,5,6-tetracarboxylic dianhydride; benzene-1,2,3,4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic dianhydride; and combinations thereof.
3. The method of claim 2 , wherein the alkyl group or the substituted alkyl group has 1 to 12 carbon atoms.
4. The method of claim 2 , wherein R 3 is a methyl group or an ethyl group and R 4 and R 5 are H atoms, an alkyl group, or a substituted alkyl group.
5. The method of claim 4 , wherein R 3 is a methyl group, and R 4 and R 5 are H atoms.
6. The method of claim 4 , wherein R 3 is an ethyl group and R 4 and R 5 are each individually a H atom, an alkyl group, or a substituted alkyl.
7. The method of claim 2 , wherein the polymer matrix further comprises a polyimide polymer.
8. The method of claim 7 , wherein the polyimide polymer has a repeating structural unit of:
wherein X and Y are the same as defined above.
9. The method of claim 2 , wherein the polyamic amide comprises a copolymer comprising two repeating structural units of:
where m and n are average number of repeat units per chain ranging from 1 to 2000, and the Z group has the following structure:
where R 3 , R 4 , and R 5 are each individually a hydrogen (H) atom, an alkyl group, or a substituted alkyl group, with the proviso that at least one of R 3 , R 4 and R 5 is an alkyl group, or a substituted alkyl group;
and wherein X and Y are the same as defined above.
10. The method of claim 9 , wherein the copolymer is a branched copolymer.
11. The method of claim 1 , wherein the aerogel includes 5 wt. % to 25 wt. %, of the polyamic amide polymer based on the total weight of the polymer aerogel.
12. The method of claim 1 , wherein the polymer matrix has an average pore size of greater than 50 nanometers (nm) to 5000 nm in diameter.
13. The method of claim 12 , wherein the polymer matrix has an average pore size of 1000 nm to 1400 nm in diameter.
14. The method of claim 13 , wherein the polymer matrix has an average pore size of 1100 nm to 1300 nm.
15. The method of claim 1 , further comprising including the aerogel in a substrate for a radiofrequency antenna or a radome.
16. The method of claim 1 , wherein the substituted imidazole is 2-methyl imidazole or 2-ethyl-4-methyl imidazole.
17. The method of claim 16 , wherein the substituted imidazole is 2-methyl imidazole.
18. The method of claim 1 , wherein the polymer matrix gel further comprises the solvent and the drying of the polymer matrix gel removes the solvent, and wherein the drying comprises supercritical drying, subcritical drying, thermal drying, evaporative air drying, vacuum drying, or any combination thereof.
19. The method of claim 18 , wherein the drying comprises evaporative air drying.
20. The method of claim 1 , further comprising subjecting the step (d) polymer matrix gel to at least one solvent exchange with a different solvent.