Covalently cross-linked malleable polymers and methods of use
View Patent ↗Disclosed herein are compositions and methods of making novel covalently cross-linked polyimines that non-malleable under standard conditions but yet may be rendered malleable.
1. A polyimine polymer comprising a backbone comprising monomers covalently linked through imine bonds, wherein said polymer is capable of repeating at least one cycle of transitioning between a non-malleable state and a malleable state, and between a malleable state and a non-malleable state, upon exposure to a temperature range comprising:
a low temperature range that is below a transitional temperature wherein said polymer exhibits rates of covalent bond exchange reactions that impart a non-malleable state to said polymer; and
a high temperature range above said transitional temperature wherein said polymer exhibits rates of covalent bond exchange reactions that impart a malleable state to said polymer,
wherein said transition temperature is from about 10° C. to about 250° C., and
wherein said polyimine polymer does not comprise a catalyst.
2. The polyimine polymer of claim 1 wherein said polymer is a vitrimer.
3. The polyimine polymer of claim 1 wherein said bond exchange reaction is selected from the group consisting essentially of an imine formation reaction, an imine exchange reaction, and an imine hydrolysis reaction.
4. The polyimine polymer of claim 1 wherein said transition temperature is from about 30° C. to about 250° C.
5. The polyimine polymer of claim 1 , wherein the stress relaxation of said polyimine polymer exhibits Arrhenius-like temperature dependence.
6. The polyimine polymer of claim 1 , wherein said polymer is elastomeric, and capable of strains in excess of 150% elongation.
7. The polyimine polymer of claim 1 wherein said polymer exhibits less than 10% weight increase when immersed in an aqueous solution for 24 hours.
8. The polyimine polymer of claim 1 , wherein said polymer is capable of self-healing.
9. The polyimine polymer of claim 1 , wherein said polymer is prepared by condensation of at least one dicarbonyl monomer, at least one diamine monomer, and at least one cross-linking agent.
10. The polyimine polymer of claim 9 , wherein said at least one dicarbonyl monomer, said at least one diamine monomer, and said at least one cross-linking agent are reacted in amounts such that the molar equivalent ratios for (i) carbonyl groups from the dicarbonyl monomer, (ii) amine groups from the diamine monomer, and (iii) amine groups or carbonyl groups from the cross-linking agent range from about 1:0.99:0.01 to about 1:0.01:0.99.
11. A polyimine polymer comprising a backbone comprising monomers covalently linked through imine bonds, wherein said polymer is capable of repeating at least one cycle of transitioning between a non-malleable state and a malleable state, and between a malleable state and a non-malleable state, upon exposure to a range of relative humidity comprising:
a low humidity range that is below a transitional relative humidity point wherein said polymer exhibits rates of covalent bond exchange reactions that impart a non-malleable state to said polymer; and
a high humidity range above said transitional relative humidity point wherein said polymer exhibits rates of covalent bond exchange reactions that impart a malleable state to said polymer.
12. The polyimine polymer of claim 11 wherein said bond exchange reaction is selected from the group consisting essentially of an imine formation reaction, an imine exchange reaction, and an imine hydrolysis reaction.
13. The polyimine polymer of claim 11 wherein said transitional relative humidity point is from about 50 to about 90 percent relative humidity.
14. The polyimine polymer of claim 11 , wherein said polyimine polymer does not comprise a catalyst.
15. A composite material comprising a polyimine polymer binder and a filler capable of repeating at least one cycle of transitioning between a non-malleable state and a malleable state and between a malleable state and a non-malleable state, upon exposure to a temperature range comprising:
a low temperature range that is below a transitional temperature wherein said polymer exhibits rates of covalent bond exchange reactions that impart a non-malleable state to said polymer; and
a high temperature range above said transition temperature wherein said polymer exhibits rates of covalent bond exchange reactions that impart a malleable state to said polymer.
16. The composite material of claim 15 wherein the ratio of said binder to said filler is from about 9:1 to about 1:9, and wherein said composite material comprises at least one selected from the group consisting of carbon fiber, fiberglass, kevlar, ultra-high molecular weight polyethylene, and carbon nanotubes.
17. A method of processing said composite material of claim 15 , said method comprising:
a.) contacting said composite material with a liquid comprising at least a molecule comprising a primary amine moiety; and
b.) allowing said composite material to substantially dissolve in said liquid of step a.); and
c.) separating a polymer solution from a fibrous or non-fibrous filler material.
18. A method for making said composite material of claim 15 , said method comprising:
a.) combining at least one polyimine polymer layer in between at least two plies of composite; and
b.) heating said combined layers and plies of step a.) to a temperature above said transitional temperature; and
c.) pressing said heated combined layers and plies of step b.) into a mold; and
d.) allowing the heated combined layers and plies of step c.) to cool to a temperature below said transitional temperature.
19. The composite material of claim 18 wherein said composite material is an orthotic.