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A crosslinked aromatic polyimide having shape memory properties and methods of making the same. The crosslinked aromatic polyimide comprises at least one aromatic diamine, at least one dianhydride monomer, and a tri(oxybenzene-amine) crosslinker. The crosslinked aromatic polyimide polymers and films

A crosslinked aromatic polyimide having shape memory properties and methods of making the same. The crosslinked aromatic polyimide comprises at least one aromatic diamine, at least one dianhydride monomer, and a tri(oxybenzene-amine) crosslinker. The crosslinked aromatic polyimide polymers and films possess superior shape memory properties at temperatures above 225° C.

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1. A crosslinked aromatic polyimide having shape memory properties, the crosslinked aromatic polyimide comprising: at least one aromatic diamine;at least one dianhydride monomer; anda tri(oxybenzene-amine) crosslinker having the general formula: wherein W is selected from a group consisting of N, P═

1. A crosslinked aromatic polyimide having shape memory properties, the crosslinked aromatic polyimide comprising: at least one aromatic diamine;at least one dianhydride monomer; anda tri(oxybenzene-amine) crosslinker having the general formula: wherein W is selected from a group consisting of N, P═O, or BO3; R is selected from a group consisting of H, F, Cl, CF3, or CH3; and the amine groups are located meta or para with respect to R, the crosslinked aromatic polyimide having the general formula: wherein Y is selected from the group consisting of —C(CF3)2—, —O—, —SO2—, >C═O—, -(Ph)C(CF3)—, —OPh-C(CH3)2-PhO—, —O(1,3-Ph)O— and —O(1,4-Ph)O—; and n, m, and 1 are degrees of polymerization of each branch of the crosslinked aromatic polyimide. 2. The crosslinked aromatic polyimide of claim 1 wherein the degrees of polymerization are the same with respect to one another. 3. The crosslinked aromatic polyimide of claim 1 wherein at least one of the degrees of polymerization is different. 4. The crosslinked aromatic polyimide of claim 1 wherein the degrees of polymerization comprise 10 to 110 units. 5. The crosslinked aromatic polyimide of claim 1 wherein the degrees of polymerization comprise 5 to 55 units. 6. The crosslinked aromatic polyimide of claim 1 wherein the tri(oxybenzene-amine) crosslinker comprises a concentration of 0.3-10 mol %. 7. The crosslinked aromatic polyimide of claim 1 wherein the tri(oxybenzene-amine) crosslinker comprises a concentration of 0.5-5.0 mol %. 8. The crosslinked aromatic polyimide of claim 1 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene; the dianhydride monomer is selected from the group consisting of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic anhydride, and 4,4′-(m-phenylenedioxy)diphthalic anhydride; andthe tri(oxybenzene-amine) crosslinker is selected from the group consisting of tris[(4-aminophenoxy)phenyl]amine, tris[(2-chloro-4-aminophenoxy)phenyl]-amine, tris[(2-fluoro-4-aminophenoxy)phenyl]amine, tris[(2-methyl-4-aminophenoxy)phenyl]amine, tris[(2-trifluoromethyl-4-aminophenoxy)phenyl]amine, tris[(2-chloro-5-aminophenoxy)phenyl]amine, tris[(2-chloro-5-aminophenoxy)phenyl]amine, tris[(2-chloro-5-aminophenoxy)phenyl]amine, tris[(2-fluoro-5-aminophenoxy)phenyl]amine, tris[(2-methyl-5-aminophenoxy)phenyl]amine, tris[(2-trifluoromethyl-5-aminophenoxy)phenyl]amine. 9. The crosslinked aromatic polyimide of claim 1 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene; the dianhydride monomer is selected from the group consisting of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic anhydride, and 4,4′-(m-phenylenedioxy)diphthalic anhydride; andthe tri(oxybenzene-amine) crosslinker is selected from the group consisting of tris[(4-aminophenoxy)phenyl]borate, tris[(2-chloro-4-aminophenoxy)phenyl]borate, tris[(2-chloro-4-aminophenoxy)phenyl]borate, tris[(2-fluoro-4-aminophenoxy)phenyl]borate, tris[(2-methyl-4-aminophenoxy)phenyl]borate, tris[(2-trifluoromethyl-4-aminophenoxy)phenyl]borate, tris[(2-chloro-5-aminophenoxy)phenyl]borate, tris[(2-fluoro-5-aminophenoxy)phenyl]borate, tris[(2-trifluoromethyl-5-aminophenoxy)phenyl]borate. 10. The crosslinked aromatic polyimide of claim 1 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene; the dianhydride monomer is selected from the group consisting of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic anhydride, and 4,4′-(m-phenylenedioxy)diphthalic anhydride; andthe tri(oxybenzene-amine) crosslinker is tris[(4-aminophenoxy)phenyl]phosphine oxide, tris[(4-aminophenoxy)phenyl]phosphine oxide, tris[(2-fluoro-4-aminophenoxy)phenyl]phosphine oxide, tris[(2-methyl-4-aminophenoxy)phenyl]phosphine oxide, tris[(2-trifluoromethyl-4-aminophenoxy)phenyl]phosphine oxide, tris[(2-chloro-5-aminophenoxy)phenyl]phosphine oxide, tris[(2-trifluoromethyl-5-aminophenoxy)phenyl]phosphine oxide, tris[(2-methyl-5-aminophenoxy)phenyl]phosphine oxide, tris[(2-fluoro-5-aminophenoxy)phenyl]phosphine oxide. 11. The crosslinked aromatic polyimide of claim 10 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene, the dianhydride monomer is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, and the tri(oxybenzene-amine) crosslinker is tris[(4-aminophenoxy)phenyl]phosphine oxide. 12. A method for preparation of a film comprising the crosslinked aromatic polyimide of claim 1 comprising the steps of: mixing at least one aromatic diamine and at least one dianhydride monomer in a polar solvent to form poly(amic acid) oligomers;adding a solid tri(oxybenzene-amine) crosslinker to the poly(amic acid) oligomers to form a soluble sol-gel precursor;pouring the soluble sol-gel precursor onto glass plates or petri dishes; andcuring and crosslinking by simultaneously heating and removing the polar solvent from the soluble sol-gel precursor to form the crosslinked aromatic polyimide having shape memory properties. 13. The method of claim 12 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene; the dianhydride monomer is selected from the group consisting of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic anhydride, and 4,4′-(m-phenylenedioxy)diphthalic anhydride;the polar solvent is selected from the group consisting of N,N-dimethylacetamide and N,N-dimethylformamide; andthe tri(oxybenzene-amine) crosslinker is selected from the group consisting of tris[(4-aminophenoxy)phenyl]amine, tris[(2-chloro-4-aminophenoxy)phenyl]amine, tris[(2-fluoro-4-aminophenoxy)phenyl]amine, tris[(2-methyl-4-aminophenoxy)phenyl]amine, tris[(2-trifluoromethyl-4-aminophenoxy)phenyl]amine, tris[(2-chloro-5-aminophenoxy)phenyl]amine, tris[(2-chloro-5-aminophenoxy)phenyl]amine, tris[(2-chloro-5-aminophenoxy)phenyl]amine, tris[(2-fluoro-5-aminophenoxy)phenyl]amine, tris[(2-methyl-5-aminophenoxy)phenyl]amine, tris[(2-trifluoromethyl-5-aminophenoxy)phenyl]amine. 14. The method of claim 12 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene; the dianhydride monomer is selected from the group consisting of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic anhydride, and 4,4′-(m-phenylenedioxy)diphthalic anhydride;the polar solvent is selected from the group consisting of N,N-dimethylacetamide and N,N-dimethylformamide; andthe tri(oxybenzene-amine) crosslinker is selected from the group consisting of tris[(4-aminophenoxy)phenyl]borate, tris[(2-chloro-4-aminophenoxy)phenyl]borate, tris[(2-chloro-4-aminophenoxy)phenyl]borate, tris[(2-fluoro-4-aminophenoxy)phenyl]borate, tris[(2-methyl-4-aminophenoxy)phenyl]borate, tris[(2-trifluoromethyl-4-aminophenoxy)phenyl]borate, tris[(2-chloro-5-aminophenoxy)phenyl]borate, tris[(2-fluoro-5-aminophenoxy)phenyl]borate, tris[(2-trifluoromethyl-5-aminophenoxy)phenyl]borate. 15. The method of claim 12 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene; the dianhydride monomer is selected from the group consisting of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic anhydride, and 4,4′-(m-phenylenedioxy)diphthalic anhydride;the polar solvent is selected from the group consisting of N,N-dimethylacetamide and N,N-dimethylformamide; andthe tri(oxybenzene-amine) crosslinker is selected from the group consisting of tris[(4-aminophenoxy)phenyl]phosphine oxide, tris[(4-aminophenoxy)phenyl]phosphine oxide, tris[(2-fluoro-4-aminophenoxy)phenyl]phosphine oxide, tris[(2-methyl-4-aminophenoxy)phenyl]phosphine oxide, tris[(2-trifluoromethyl-4-aminophenoxy)phenyl]phosphine oxide, tris[(2-chloro-5-aminophenoxy)phenyl]phosphine oxide, tris[(2-trifluoromethyl-5-aminophenoxy)phenyl]phosphine oxide, tris[(2-methyl-5-aminophenoxy)phenyl]phosphine oxide, tris[(2-fluoro-5-aminophenoxy)phenyl]phosphine oxide. 16. The method of claim 15 wherein the aromatic diamine is 1,3-bis(3-aminophenoxy)benzene, the dianhydride monomer is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, the polar solvent is N,N-dimethylacetamide, and the tri(oxybenzene-amine) crosslinker is tris[(4-aminophenoxy)phenyl]phosphine oxide.