Partially degradable fibers and microvascular materials formed from the fibers
A partially degradable polymeric fiber includes a thermally degradable polymeric core and a coating surrounding at least a portion of the core. The thermally degradable polymeric core includes a polymeric matrix including a poly(hydroxy-alkanoate), and a metal selected from the group consisting of an alkali earth metal and a transition metal, in the core polymeric matrix. The concentration of the metal in the polymeric matrix is at least 0.1 wt %. The partially degradable polymeric fiber may be used to form a microvascular system containing one or more microfluidic channels.
1. A partially degradable polymeric fiber comprising a thermally degradable polymeric core and a thermally stable coating surrounding substantially all of the thermally degradable polymeric core,
where the thermally stable coating comprises a thermally stable polymer having a higher degradation temperature than the degradation temperature of the thermally degradable polymeric core,
where the thermally degradable polymeric core comprises a polymeric matrix comprising a poly(hydroxyalkanoate) and 0.1-10 wt % of a metal selected from the group consisting of an alkaline earth metal and a transition metal, and
where the thermally stable coating forms a wall around a microfluidic channel when the thermally degradable polymeric core is degraded and the degradants are removed.
2. The fiber of claim 1 , where the degradation temperature of the thermally degradable polymeric core is at most 250° C., and the degradation temperature of the thermally stable polymer of the coating is at least 275° C.
3. The fiber of claim 2 , where the degradation temperature of the thermally degradable polymeric core is at most 220° C.
4. The fiber of claim 3 , where the degradation temperature of the thermally degradable polymeric core is at most 180° C.
5. The fiber of claim 1 , where the thermally stable polymer of the coating comprises a polysiloxane, polychloroprene, polysulfide, poly(hydroxyalkanoate), polyimide, polyester, polycarbonate, polyether, epoxy polymer, epoxy vinyl ester polymer, polyamide, phenol-formaldehyde polymer, amine-formaldehyde polymer, polysulfone, polyacrylonitrile-butadiene-styrene, polyurethane, polyolefin, polystyrene, polyacrylonitrile, polyvinyl chloride, poly(DCPD), polyacrylate, poly(alkylacrylate), polysilane, polyphospazene, or a combination thereof.
6. The fiber of claim 5 , where the thermally stable coating comprises:
(i) a polysiloxane;
(ii) a polyimide; or
(iii) a poly(hydroxyalkanoate) in combination with a polyimide or a polyester, where the poly(hydroxyalkanoate) of the thermally stable coating is different than or the same as the poly(hydroxyalkanoate) of the polymeric matrix of the thermally degradable polymeric core.
7. The fiber of claim 1 , where the poly(hydroxyalkanoate) of the polymeric matrix comprises poly(lactic acid), poly(3-hydroxybutyrate), poly(4-hydroxybutyrate), poly(3-hydroxy-valerate), polycaprolactone, poly(glycolic acid) and/or a copolymer of monomeric units of the preceding polymers.
8. The fiber of claim 7 , where the poly(hydroxyalkanoate) of the polymeric matrix of the thermally degradable polymeric core comprises poly(lactic acid).
9. The fiber of claim 1 , where the metal comprises MgO, CaO, BaO, SrO, tin(II) acetate, tin(II) oxalate, tin(II) octoate, or scandium triflate (Sc(OTf) 3 ).
10. The fiber of claim 1 , where the thermally stable coating further comprises a blend of the thermally stable polymer and a thermally unstable polymer having a degradation temperature that is the same as or less than the degradation temperature of the thermally degradable polymeric core.
11. A method of making a partially degradable polymeric fiber that comprises a thermally degradable polymeric core and a thermally stable coating surrounding substantially all of the thermally degradable polymeric core,
where the thermally stable coating comprises a thermally stable polymer having a higher degradation temperature than the degradation temperature of the thermally degradable polymeric core,
where the thermally degradable polymeric core comprises a polymeric matrix comprising a poly(hydroxyalkanoate) and 0.1-10 wt % of a metal selected from the group consisting of an alkaline earth metal and a transition metal, and
where the thermally stable coating forms a wall around a microfluidic channel when the thermally degradable polymeric core is degraded and the degradants are removed,
the method comprising:
(i) combining an initial fiber comprising the poly(hydroxyalkanoate) of the polymeric matrix, and a composition comprising a fluorinated fluid and the metal;
(ii) maintaining the initial fiber and the composition together at a temperature and for a time sufficient to provide a metal concentration of 0.1-10 wt % in the initial fiber and form the thermally degradable polymeric core;
(iii) separating the initial fiber from the fluorinated fluid; and
(iv) depositing the thermally stable coating on substantially all of the surface of the initial fiber to provide the partially degradable polymeric fiber.
12. The method of claim 11 , further comprising (v) applying a surface treatment to the thermally stable coating.
13. The method of claim 11 , where the poly(hydroxyalkanoate) of the polymeric matrix of the thermally degradable polymeric core comprises poly(lactic acid).
14. The method of claim 11 , where the metal comprises MgO, CaO, BaO, SrO, tin(II) acetate, tin(II) oxalate, tin(II) octoate, or scandium triflate (Sc(OTf) 3 ).
15. The method of claim 11 , where the depositing of step (iv) comprises contacting substantially all of the surface of the initial fiber with a liquified coating precursor, and solidifying the coating precursor to provide the thermally stable coating surrounding substantially all of the thermally degradable polymeric core.
16. A method of making a partially degradable polymeric fiber that comprises a thermally degradable polymeric core and a thermally stable coating surrounding substantially all of the thermally degradable polymeric core,
where the thermally stable coating comprises a thermally stable polymer having a higher degradation temperature than the degradation temperature of the thermally degradable polymeric core,
where the thermally degradable polymeric core comprises a polymeric matrix comprising a poly(hydroxyalkanoate) and 0.1-10 wt % of a metal selected from the group consisting of an alkaline earth metal and a transition metal, and
where the thermally stable coating forms a wall around a microfluidic channel when the thermally degradable polymeric core is degraded and the degradants are removed,
the method comprising:
(i) forming a spinning liquid comprising the poly(hydroxyalkanoate) of the polymeric matrix, a solvent, and the metal;
(ii) passing the spinning liquid through a spinneret to form a wet fiber comprising the poly(hydroxyalkanoate) of the polymeric matrix and the metal;
(iii) drying the wet fiber to provide a metal concentration of 0.1-10 wt % in the dried fiber and form the thermally degradable polymeric core; and
(iv) depositing the thermally stable polymeric coating on substantially all of the surface of the dried fiber to provide the partially degradable polymeric fiber.
17. The method of claim 16 , further comprising cold-drawing the dried fiber between steps (iii) and (iv).
18. The method of claim 16 , where the poly(hydroxyalkanoate) of the polymeric matrix of the thermally degradable polymeric core comprises poly(lactic acid).
19. The method of claim 16 , where the metal comprises MgO, CaO, BaO, SrO, tin(II) acetate, tin(II) oxalate, tin(II) octoate, or scandium triflate (Sc(OTf) 3 ).
20. The method of claim 16 , where the depositing of step (iv) comprises contacting substantially all of the surface of the dried fiber with a liquified coating precursor , and solidifying the coating precursor to provide the thermally stable coating surrounding substantially all of the thermally degradable polymeric core.