Post polymerization cure shape memory polymers
This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.
1. A polymer composition comprising a polymer: (a) having shape memory properties and crosslinkable sites substantially regularly spaced from each other, (b) which comprises at least one of a hack bone and a side chain having an electron withdrawing group with alpha and beta positions, a methyne carbon in the alpha position, and an unsaturated carbon-carbon double bond in the beta position, and (c) which may be formed into a shape and then crosslinked to form a thermoset polymer having shape memory properties, wherein the polymer is a polyurethane.
2. The polymer composition of claim 1 , wherein the polymer composition is formed into the shape and crosslinked to form a thermoset polymer composition and the crosslinkable sites are double bonds.
3. The polymer composition of claim 1 wherein the polymer composition is formed into the shape and crosslinked to form a thermoset polymer composition and the crosslinking is accomplished by at least one of heat and electron beam radiation.
4. The polymer composition of claim 1 wherein the polymer has the side chain comprising the electron withdrawing group, the methyne carbon in the alpha position, and the unsaturated carbon-carbon double bond in the beta position.
5. The polymer composition of claim 1 wherein the polymer composition is fabricated into a porous structure or foam by one or a combination of processes from the group comprising freeze drying, high inverse phase emulsion foaming, physical blowing, pore templating utilizing a solid or liquid pore former, solution spinning, stereolithographic patterning, micro-extrusion or ink pen printing, 3D microdot based printing, or laser machining.
6. The polymer composition of claim 1 wherein the polymer composition is formed into the shape and crosslinked to form a thermoset polymer composition.
7. The polymer composition of claim 1 wherein the polymer composition is formed into the shape and crosslinked to for a thermoset polymer composition and the crosslinking includes a curing mechanism selected from the group consisting of, thermally or radiatively initiated radical crosslinking of vinyl groups, peroxide or sulfur based crosslinking of vinyl groups, thiol addition to vinyl, reaction of isocyanate containing curing agents with hydroxyl, carboxylic acid, amine, or other functionality on the polymer chains; condensation of ester linkages, epoxy chemistry, silane and siloxane coupling reactions.
8. The polymer composition of claim 1 wherein the polymer composition is derived from alkene diol monomers, formed into the shape, and crosslinked by e-beam radiation to form a thermoset polymer composition.
9. The polymer composition of claim 1 comprising at least one radiation sensitizer.
10. The polymer composition of claim 9 wherein the radiation sensitizer comprises at least one tris[2-(acryloyloxy)ethyl]isocyanurate (TAcIc) and pentaerithol triacrylate (PETA).