High-output solvent-based electrospinning
View Patent ↗The present invention generally relates to solution electrospinning processes for fabricating fibers, to the fibers prepared thereby, and to non-woven webs, fabrics, porous composite filter media, and articles comprising the fibers.
1. A process comprising:
providing a solution of a self-assembling material and a solvent;
feeding the solution into an electrospinning device; and
applying a voltage to the device such that the solution of the self-assembling material and the solvent is drawn and a jet is formed from which the solvent dissipates to provide fibers of the self-assembling material, wherein the self-assembling material of the fibers comprises oligomers or polymers comprising a supramolecular structure, the oligomers and polymers having repeat units that contain functional groups having directional interactions that are (a) electrostatic interactions (ion-ion, ion-dipole or dipole-dipole) or coordinative bonding (metal-ligand), (b) hydrogen bonding, (c) π-π stacking interactions, or (d) van der Waals forces, or a combination thereof, the supramolecular structure being formed upon a triggering event; and the number average molecular weight (M n ) of the self assembling material is between 5,000 grams per mole (g/mol) and 18,000 g/mol as measured by proton nuclear magnetic resonance spectroscopy ( 1 H-NMR); wherein the self-assembling material comprises one or more x units and one or more y units:
wherein:
and wherein
R at each occurrence is independently a C 2 -C 12 alkylene, a heteroalkylene of 2 to 12 backbone atoms, C 3 -C 7 cycloalkyl, -alkylene-cycloalkyl-, -alkylene-cycloalkyl-alkylene-, -heteroalkylene-cycloalkyl-, -heteroalkylene-cycloalkyl-heteroalkylene-, a polyether chain [(CH 2 ) n —O-] m where m and n are independently integers;
R′ and R″ at each occurrence are independently a covalent bond, an aliphatic group having 2-6 carbon atoms, C 3 -C 7 cycloalkyl, -alkylene-cycloalkyl-, or -alkylene-cycloalkyl-alkylene-;
R 2 at each occurrence is H;
Ra is an alkylene group of 2-6 carbon atoms, C 3 -C 7 cycloalkyl, -alkylene-cycloalkyl-, or -alkylene-cycloalkyl-alkylene, or the —N(R 2 )—Ra—N(R 2 )— moiety is piperazinyl; and
x represents the number of ester units and y represents the number of amide units in the copolymer, provided that neither x nor y is zero.
2. A process according to claim 1 , wherein the self assembling material comprises self assembling units comprising multiple hydrogen bonding arrays.
3. A process according to claim 1 , wherein the copolymer is of formula (I-1):
4. A process according to claim 1 , wherein the polymer or oligomer is of the formula:
wherein
p, q, and r are independently 2, 3, 4, 5, 6 or 8;
n is 2-6 and
the number average molecular weight of the polymer or oligomer is between about 1000 g/mol and 30,000 g/mol.
5. A process according to claim 1 , wherein the self-assembling material is present in the solution at a concentration that is below an entanglement concentration (c e ) of the self-assembling material.
6. A process according to claim 1 , wherein the self-assembling material is present in the solution at a concentration that is from about at an entanglement concentration (c e ) of the self-assembling material up to 20% above the c e .
7. A process according to claim 1 , wherein the self-assembling material is present in the solution at a concentration that is about at critical chain overlap concentration (c*) of the self-assembling material.
8. A process according to claim 1 , wherein the fibers being characterized as having an average diameter of from about 10 nanometers to about 1500 nanometers.
9. A process according to claim 1 , wherein the fibers have an average diameter of about 1500 nanometers or less and the process being characterized by having a product of a Helgeson-Wagner dimensionless number Π 1 times a fiber Ohnesorge dimensionless number Oh of between about 8 times 10 −7 (8×10 −7 ) and about 1×10 −4 .
10. A porous composite filter media comprising a porous non-woven web comprising fibers made according to claim 1 and a porous filter substrate, wherein the porous filter substrate is in supporting operative contact with the porous non-woven web.
11. A porous composite filter media of claim 10 , wherein the porous filter substrate comprises wood, glass, metal, paper, ceramic, polymer that is not a self-assembling material, or a combination thereof.
12. A porous composite filter media of claim 10 , the porous filter substrate having a structure comprising a web, foil, film, paper, fabric, woven structure, non-woven structure, or a combination thereof.
13. A process of making the porous composite filter media of claim 10 , the process comprising contacting the porous non-woven web to the porous filter substrate to produce the porous composite filter media, wherein the porous filter substrate is in supporting operative contact with the porous non-woven web.
14. A process of claim 13 , wherein the electrospinning device further comprises a collector and the collector yields the porous filter substrate.
15. Fibers prepared according to the process of claim 1 , the fibers being characterized as having beading.
16. The fibers of claim 15 , the fibers having an average diameter of from about 10 nm to about 1500 nm.
17. An article comprising the fibers of claim 15 .