CN1546754A - Twisted ultra-fine nanometer fiber film material and preparing method thereof - Google Patents

Twisted ultra-fine nanometer fiber film material and preparing method thereof Download PDF

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CN1546754A
CN1546754A CNA2003101065170A CN200310106517A CN1546754A CN 1546754 A CN1546754 A CN 1546754A CN A2003101065170 A CNA2003101065170 A CN A2003101065170A CN 200310106517 A CN200310106517 A CN 200310106517A CN 1546754 A CN1546754 A CN 1546754A
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fiber film
superfine nano
nano fiber
film material
distortion
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CN1226471C (en
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李新松
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Southeast University
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Southeast University
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Abstract

The invention is a kind of twisted superfine nano fiber film material which is manufactured with high molecular or compound of high molecular and additives, then carries on torsion and deformation to them. The torsion fiber diameter is between 20 nano and 6 micron meter. The method is: the high molecular or high molecular compound is dispersed or dissolved in the solvent into transparent liquid or mixer, gets the electric spinning compound. They are put into the storage pot, which is connected to the spraying head. The head is connected to high voltage electric field, the voltage is 3 KV-120 KV, and then carries on electrostatic spinning, gets the high molecular superfine fiber film material. The material is put into one ill solvent or compound of several ill solvents to be immersed, thus the superfine nano fiber are twisted, gets the twisted high molecular superfine nano fiber film material.

Description

Distortion superfine nano fiber film material and preparation method thereof
Technical field
The present invention is distortion superfine nano fiber film material and preparation method thereof, belongs to the technical field of twisted fibre material preparation.
Background technology
Dry method and wet spinning are linear pattern long fiber or staple fibre through what obtain after the drawing-off, and fibre diameter can make fiber bending by the twisting deformation technology about 10 microns, obtain elastomer, changes the mechanical property of fiber etc.What meltblowing method obtained also is the fiber of straight shape staple fibre or welding, and fibre diameter is about 10 microns.
Electrospinning is spinning under electric field with macromolecule melt or solution, stretches because electrostatic interaction produces, and through cooling or solvent evaporates, obtains the superfine nano fiber.Adopt this specific process can obtain diameter at the superfine nano fiber of tens nanometer to the number micrometer range, fiber can be piled into the superfine nano tunica fibrosa in the electrospinning process, and this is that other method institute is inaccessiable at present.This superfine nano fiber or nano fibrous membrane are on ten microns fiber type structures linearly usually in tens of micrometer ranges, or the linear pattern fibrous reticular structure.Because it has superfine diameter, this material has huge specific area, the well-regulated duct of the superfine fibre film of formation.
In the prior art, dry method and wet spinning, and by twisting the twisted fibre that deformation technology obtains, fibre diameter is thicker.Limited of the application of twisted fibre material at aspects such as biomedical material, filtering materials.
In the prior art, the linear pattern fibre structure superfine nano fiber that the electrospinning method obtains, or linear pattern fibrous reticular structure superfine nano tunica fibrosa, adjustable extents such as its mechanical property, biodegradability, bio-absorbable performance, strainability are narrower, limited the application of twisted fibre material at aspects such as biomedical material, filtering materials.
In the prior art, the linear pattern fibre structure superfine nano fiber that the electrospinning method obtains, or linear pattern fibrous reticular structure superfine nano tunica fibrosa, because polymer molecular chain stretches under the electric field force effect, strand is orientated along fiber axis, the modulus height of tunica fibrosa, percentage elongation is little, has limited the application of twisted fibre material at aspects such as biomedical material, filtering materials.
So it is little to be necessary to develop a fibrid diameter, be the superfine nano fiber of meander configuration fibre structure or the superfine nano tunica fibrosa of meander configuration fibrous reticular structure in tens of micrometer ranges in ten nanometers; Be necessary to develop the superfine nano fiber that is the meander configuration fibre structure of a class superfine fibre strand or segment disorientation, or the superfine nano tunica fibrosa of meander configuration fibrous reticular structure.They have wide practical use at aspects such as tissue engineering bracket material, implantable material, drug release carrier material, protective materials, filtering materials.
Summary of the invention
Technical problem: the purpose of this invention is to provide and a kind ofly have a wide range of applications at aspects such as tissue engineering bracket material, implantable material, drug release carrier material, protective materials, filtering materials, processing technology is simply twisted superfine nano fiber film material and preparation method thereof.
Technical scheme: distortion superfine nano fiber film material of the present invention and preparation method thereof.Distortion superfine nano fiber film material is that macromolecular material or polymer composite obtain the superfine nano tunica fibrosa after torsion of fibers distortion post processing obtains the distortion superfine nano fiber film material that fiber is distorted shape through electrospinning, and the diameter of twisted fibre is between 20 nanometers-6 micron.Wherein, macromolecular material is the Biodegradable high-molecular PLA, polyglycolic acid, polycaprolactone, poly--the 3-butyric ester, poly--the 3-hydroxyl valerate, poly-(3-hydroxybutyric acid-co-3-hydroxypentanoic acid), poly-acid anhydrides, poe, group of polyphosphazenes, polyphosphate, polyoxyethylene, poly--a-amino acid, shitosan, hyaluronic acid, chondroitin sulfate, collagen, carrageenan, alginates, gelatin, agar, glucan, fibrin, a kind of or their derivative in the silk-fibroin, or lactide, glycolide, caprolactone, valerolactone, butyrolactone, oxirane, the copolymer of two or more in the expoxy propane; Or the derivative of polyvinylpyrrolidone, polyvinyl alcohol, cellulose, carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, methylcellulose, ethyl cellulose, noncrystalline cellulose, phthalic acid cellulose ethanoate, starch, Hydroxyethyl Starch, carboxymethyl starch or starch; Or two or more blend wherein; Or a kind of or their derivative in the polyolefin, polyvinyl acetate, polysiloxanes, polyethers, polyamide, polyester, Merlon, polyurethane, polyacrylonitrile, polyacrylic acid family macromolecule or two or more blend wherein.Polymer composite is the compound of macromolecule and additive.Additive can be inorganic ultrafine particle, and the particle diameter of inorganic ultrafine particle is 10 nanometers-5 micron.Additive can be a kind of in bactericide, essence, medicine, enzyme, polypeptide or protein, Porcine HGF, surfactant, penetration enhancer, the Chinese medicine extract or two or more mixture wherein, and its content is less than 10% of nano-fiber material weight.Medicine is a pain-killer, antiphlogistic, anthelmintic, antiarrhymic, antibiotic, anticoagulant, antidepressants, antidiabetic, antiepileptic, antihistamine, antihypertensive, antineoplastic, immunodepressant, antithyroid drug, antiviral agent, astringent, contrast preparation, corticosteroid, antianxiety agent, anti-tussive agents, diuretics, immunizing agent, radiopharmaceutical, antihistamine, stimulant, muscle relaxant, dopaminergic, sympathomimetic drug, thyroid, sex hormone, antiallergic, vasodilator, prostaglandin, calcitonin, antimycobacterial drug, the fat conditioning agent, receptor blocking pharmacon; Or the mixture of said medicine.Surfactant is a polysorbas20,60 or 80; Or block copolymer, polyethylene glycol, monoglyceride or above-mentioned two or more surfactant mixtures of class of department 60,80, lauryl sodium sulfate, lecithin, sucrose fatty ester, oxirane and expoxy propane.
The preparation method of distortion superfine nano fiber film material is: macromolecular material or polymer composite are disperseed or be dissolved in and become clear solution or mixture in the solvent, obtain the electrospinning mixture, or macromolecular material or polymer composite fusion become melt, obtain the electrospinning mixture; Add in the storage tank then, be connected to injector head, injector head connects high voltage electric field, voltage is 3 kilovolts-120 kilovolts, carry out electrostatic spinning then, obtain the macromolecular ultrafine fibrous membrane material, with the macromolecular ultrafine fibrous membrane material it a kind of poor solvent or multiple poor solvent mixture in immersion treatment, make the superfine nano torsion of fibers, the temperature of handling the poor solvent system of macromolecule ultra-fine (nanometer) fiber film material can be more than the fusing point of solvent and the following temperature range of boiling point, obtains twisting macromolecule superfine nano fiber film material.Poor solvent is one or more the mixture in water, alcohol, ether, ketone, alkane, halogenated hydrocarbons, benzene or toluene, the acid amides.
The preparation method of distortion superfine nano fiber film material can also be: macromolecular material or polymer composite are disperseed or be dissolved in and become clear solution or mixture in the solvent, obtain the electrospinning mixture, or macromolecular material or polymer composite fusion become melt, obtain the electrospinning mixture, add in the storage tank then, be connected to injector head, injector head connects high voltage electric field, voltage is 3 kilovolts-120 kilovolts, carry out electrostatic spinning then, obtain the macromolecular ultrafine fibrous membrane material, its electromicroscopic photograph is seen Fig. 1.The macromolecular ultrafine fibrous membrane material is handled in 40-200 ℃ air or inert gas atmosphere, made the superfine nano filament contraction become twisted fibre, obtain twisting macromolecule superfine nano fiber film material.Distortion superfine nano fiber film material is a tubulose, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, thread.
Beneficial effect: the present invention compared with prior art has following advantage:
(1) distortion superfine nano fiber film material provided by the invention is the material that high molecular superfine fiber is membranaceous or other shape of distorted shape structure, and fibre diameter is 20 nanometers-6 micron, and membrane material aperture minimum can reach several nanometers.
(2) distortion superfine nano fiber film material provided by the invention has the processing technology characteristic of simple, the superfine nano fiber film material is immersion treatment in a kind of poor solvent or multiple poor solvent mixture, perhaps heat treatment in 40-300 ℃ inert gas atmosphere, make the superfine nano torsion of fibers, obtain twisting macromolecule superfine nano fiber film material, this material is used for filtration, protection, antibacterial, sterilization, promotion organization healing material, can obtain good effect.
(3) distortion superfine nano fiber film material provided by the invention can be processed into tubulose, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, thread, is used for filtering material, tissue engineering bracket material, body embedded material, drug release carrier material etc., it is widely used at aspects such as tissue engineering bracket material, implantable material, drug release carrier material, protective materials, filtering materials.
Description of drawings
Fig. 1, PLA superfine fibrous membrane materials stereoscan photograph.
Fig. 2, PLA distortion superfine nano fiber film material stereoscan photograph.
Fig. 3, PLA distortion superfine nano fiber film material stereoscan photograph.
The specific embodiment
Distortion superfine nano fiber film material of the present invention is that macromolecular material or polymer composite obtain the superfine nano tunica fibrosa after torsion of fibers distortion post processing obtains the superfine nano fiber film material of torsion of fibers through electrospinning, and the diameter of twisted fibre is between 20 nanometers-6 micron.Macromolecular material is the Biodegradable high-molecular PLA, polyglycolic acid, polycaprolactone, poly--the 3-butyric ester, poly--the 3-hydroxyl valerate, poly-(3-hydroxybutyric acid-co-3-hydroxypentanoic acid), poly-acid anhydrides, poe, group of polyphosphazenes, polyphosphate, polyoxyethylene, poly--a-amino acid, shitosan, hyaluronic acid, chondroitin sulfate, collagen, carrageenan, alginates, gelatin, agar, glucan, fibrin, a kind of or their derivative in the silk-fibroin, or lactide, glycolide, caprolactone, valerolactone, butyrolactone, oxirane, the copolymer of two or more in the expoxy propane; Or the derivative of polyvinylpyrrolidone, polyvinyl alcohol, cellulose, carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, methylcellulose, ethyl cellulose, noncrystalline cellulose, phthalic acid cellulose ethanoate, starch, Hydroxyethyl Starch, carboxymethyl starch or starch; Or two or more blend wherein; Or a kind of or their derivative in the polyolefin, polyvinyl acetate, polysiloxanes, polyethers, polyamide, polyester, Merlon, polyurethane, polyacrylonitrile, polyacrylic acid family macromolecule or two or more blend wherein.Additive is a kind of in bactericide, essence, medicine, enzyme, polypeptide or protein, Porcine HGF, surfactant, penetration enhancer, the Chinese medicine extract or two or more mixture wherein, and its content is less than 10% of nano-fiber material weight.Medicine is a pain-killer, antiphlogistic, anthelmintic, antiarrhymic, antibiotic, anticoagulant, antidepressants, antidiabetic, antiepileptic, antihistamine, antihypertensive, antineoplastic, immunodepressant, antithyroid drug, antiviral agent, astringent, contrast preparation, corticosteroid, antianxiety agent, anti-tussive agents, diuretics, immunizing agent, radiopharmaceutical, antihistamine, stimulant, muscle relaxant, dopaminergic, sympathomimetic drug, thyroid, sex hormone, antiallergic, vasodilator, prostaglandin, calcitonin, antimycobacterial drug, the fat conditioning agent, receptor blocking pharmacon; Or the mixture of said medicine.Surfactant is a polysorbas20,60 or 80; Or block copolymer, polyethylene glycol, monoglyceride or above-mentioned two or more surfactant mixtures of class of department 60,80, lauryl sodium sulfate, lecithin, sucrose fatty ester, oxirane and expoxy propane.
The preparation method of distortion superfine nano fiber film material is: macromolecular material or polymer composite are disperseed or be dissolved in and become clear solution or mixture in the solvent, obtain the electrospinning mixture, or macromolecular material or polymer composite fusion become melt, obtain the electrospinning mixture, add in the storage tank then, be connected to injector head, injector head connects high voltage electric field, voltage is 3 kilovolts-120 kilovolts, carry out electrostatic spinning then, obtain the macromolecular ultrafine fibrous membrane material, with the macromolecular ultrafine fibrous membrane material it a kind of poor solvent or multiple poor solvent mixture in immersion treatment, make the superfine nano torsion of fibers, the temperature of handling the poor solvent system of macromolecule ultra-fine (nanometer) fiber film material can be more than the fusing point of solvent and the following temperature range of boiling point, obtains twisting macromolecule superfine nano fiber film material.Poor solvent is one or more the mixture in water, alcohol, ether, ketone, alkane, halogenated hydrocarbons, benzene or toluene, the acid amides.
The preparation method of distortion superfine nano fiber film material can also be: macromolecular material or polymer composite are disperseed or be dissolved in and become clear solution or mixture in the solvent, obtain the electrospinning mixture, or macromolecular material or polymer composite fusion become melt, obtain the electrospinning mixture, add in the storage tank then, be connected to injector head, injector head connects high voltage electric field, voltage is 3 kilovolts-120 kilovolts, carry out electrostatic spinning then, obtain the macromolecular ultrafine fibrous membrane material, its electromicroscopic photograph is seen Fig. 1.The macromolecular ultrafine fibrous membrane material is handled in 40-200 ℃ air or inert gas atmosphere, made the superfine nano filament contraction become twisted fibre, obtain twisting macromolecule superfine nano fiber film material.The stereoscan photograph of distortion macromolecule superfine nano fiber film material is seen Fig. 2,3.
Distortion superfine nano fiber film material of the present invention can be processed into tubulose, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, thread, is used for embedded material, tissue engineering bracket, drug release carrier of filtering material, protective materials, promotion organization healing etc.
Embodiment 1
The preparation of distortion superfine nano fiber film material: macromolecule can be the binary or the multiple copolymer of monomers such as PLA, lactide and glycolide, caprolactone.
For example, with 0.5 grammes per square metre average molecular weight is that the polyoxyethylene of 130,000 PLAs and 0.5 gram-molecular weight 100,000 is dissolved in the 10ml dimethyl formamide, be made into Polymer Solution, join in the storage tank, be connected to injector head, injector head connects high voltage electric field, distance is controlled at about 5cm between injector head and reception thing, solution flow rate 6ml/h, voltage is about 6kv, carry out electrospinning, obtain PLA superfine nano fiber film material, membrane material was soaked 30 minutes in the mixing material of ethanol and water, the filament contraction distortion, obtain twisting the superfine nano fiber film material, can obtain tubulose by processing such as folding, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, thread distortion superfine nano fiber film material.
Embodiment 2
2 gram nylon 6 are dissolved in the 20ml formic acid, be made into Polymer Solution, be connected to injector head by conduit, carry out electrospinning, obtain the nylon 6/nanometer tunica fibrosa, obtain antibacterial nano fiber material, membrane material was handled 30 minutes in 80 ℃ of baking ovens, filament contraction distortion obtains twisting the superfine nano fiber film material, by processing such as folding can obtain tubulose, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, thread distortion superfine nano fiber film material.
Embodiment 3
The preparation of distortion superfine nano fiber film material: 5 gram polystyrene are dissolved in 50 milliliters of carrene, be connected to 6 injector heads by conduit, injector head connects high voltage electric field, distance is controlled at about 6cm between injector head and reception thing, and voltage is about 10kv, carries out electrospinning, obtain the pipe/polyhenylethylene nano fiber film material, membrane material was handled 30 minutes in 80 ℃ of baking ovens, and the filament contraction distortion obtains twisting the superfine nano fiber film material.
Embodiment 4
The preparation of distortion superfine nano fiber film material: 100 gram polyoxyethylene heating and meltings become melt, be connected to injector head by conduit, injector head connects high voltage electric field, and receiving thing is copper mesh, and distance is controlled at about 10cm between injector head and reception thing, voltage is about 15kv, carry out electrospinning, obtain the polyoxyethylene micro/nano fibrous membrane material, membrane material was handled 30 minutes in 60 ℃ of baking ovens, the filament contraction distortion obtains twisting the superfine nano fiber film material.
Embodiment 5
The preparation of distortion superfine nano fiber film material: with 0.5 grammes per square metre average molecular weight is that the polyoxyethylene of 130,000 poly (l-lactic acid)s and 0.5 gram-molecular weight 100,000 is dissolved in the 10ml dimethyl formamide, be made into the Polymer Solution of 10% (mass fraction), add 0.3 gram chitin ultrafine particle, particle size is about 1 micron, be uniformly dispersed, mixture joins in the storage tank, be connected to injector head, injector head connects high voltage electric field, distance is controlled at about 5cm between injector head and reception thing, fibroreticulate below is a copper mesh, solution flow rate 6ml/h, voltage is about 10kv, carries out electrospinning, obtains poly (l-lactic acid) and polyoxyethylene blend micro/nano fibrous membrane material, membrane material was soaked 30 minutes in the mixing material of ethanol and water, filament contraction distortion obtains twisting the superfine nano fiber film material, can obtain tubulose by processing such as folding, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, thread distortion superfine nano fiber film material.
Embodiment 6
The preparation of distortion superfine nano fiber film material: 2 gram nylon 6 are dissolved in the 20ml formic acid, be made into the Polymer Solution of 10% (mass fraction), the zeolite ultrafine particle and the 0.3 gram zinc sulfate ultrafine particle that add 0.3 gram argentiferous, particle size is about 1 micron, be uniformly dispersed, be connected to injector head by conduit, injector head connects the high pressure positive electric field, carry out electrospinning, obtain containing the nylon 6/nanometer fiber film material of antiseptic ultrafine particle, membrane material was handled 30 minutes in 80 ℃ of baking ovens, the filament contraction distortion, obtain twisting the superfine nano fiber film material, can obtain tubulose by processing such as folding, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, thread distortion superfine nano fiber film material.
Embodiment 7
The preparation of distortion superfine nano fiber film material: 1 grammes per square metre average molecular weight is about 130,000 PLA and is dissolved in the 10ml acetone, be made into the Polymer Solution of 10% (mass fraction), add the big enzyme element of 0.01 gram celebrating, mixing adds in the storage tank then.Storage tank is connected to injector head by conduit, injector head connects high voltage electric field, carry out electrospinning, obtain containing the PLA superfine nano fiber film material of celebrating big enzyme element, membrane material was handled 15 minutes in 60 ℃ of baking ovens, the filament contraction distortion, obtain twisting the superfine nano fiber film material, by processing such as folding can obtain tubulose, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, filamentary material, can be used for repair tissue implanted in the body or surrounding tissue engineering rack, or be used for the reparation of body surface organization.
Embodiment 8
1 grammes per square metre average molecular weight being about 130,000 polycaprolactone is dissolved in the 10ml acetone, be made into the Polymer Solution of 10% (mass fraction), add 0.01 gram adriamycin, mixing, add in the storage tank then, storage tank is received injector head, injector head connects high voltage electric field, carry out electrospinning, obtain containing the PLA superfine nano fiber film material of celebrating big enzyme element, the superfine nano fiber film material was handled 15 minutes in 50 ℃ of baking ovens, obtain twisting the superfine nano fiber film material, can obtain tubulose by processing such as folding, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, filamentary material can be used for release chemotherapeutics implanted in the body.
Embodiment 9
20 grammes per square metre average molecular weights are about 150,000 PLA to add in the storage tank, heating and melting, storage tank is received injector head, injector head connects high voltage electric field, carries out electrospinning, obtains PLA superfine nano fiber film material, the superfine nano fiber film material was handled 15 minutes in 50 ℃ of baking ovens, obtain twisting the superfine nano fiber film material, can be used for repair tissue implanted in the body or surrounding tissue engineering rack, or be used for the damaged reparation of body surface organization.
Embodiment 10
For example, with 1 grammes per square metre average molecular weight is that 300,000 PLAs are dissolved in the 10ml dimethyl formamide, be made into Polymer Solution, join in the storage tank, and be connected to injector head, injector head connects high voltage electric field, distance is controlled at about 7cm between injector head and reception thing, and solution flow rate 6ml/h, voltage are about 6kv, carry out electrospinning, obtain PLA superfine nano fiber film material.1 grammes per square metre average molecular weight being about 130,000 polycaprolactone is dissolved in the 10ml acetone, be made into the Polymer Solution of 10% (mass fraction), add 0.01 gram adriamycin, carry out electrospinning, there is the acceptor of PLA superfine nano fiber film material to accept to contain the polycaprolactone superfine nano tunica fibrosa of celebrating big enzyme element with above-mentioned surface, obtains the composite superfine micro/nano fibrous membrane material.The composite superfine micro/nano fibrous membrane material was handled 15 minutes in 50 ℃ of baking ovens, obtained twisting the composite superfine micro/nano fibrous membrane material.
Embodiment 11
1 grammes per square metre average molecular weight is about poly--D of 130,000, L-lactic acid is dissolved in the 10ml acetone, be made into the Polymer Solution of 10% (mass fraction), add 0.01 gram insulin, carry out electrospinning, obtain the superfine nano fiber film material, the superfine nano fiber film material was handled 15 minutes in 40 ℃ of baking ovens, obtain twisting the composite superfine micro/nano fibrous membrane material.
Embodiment 12
1 grammes per square metre average molecular weight being about 130,000 polycaprolactone is dissolved in the 10ml acetone, be made into the Polymer Solution of 10% (mass fraction), the adding particle diameter is the shitosan powder about 1 micron, mixing, add in the storage tank then, storage tank is received injector head, injector head connects high voltage electric field, carry out electrospinning, obtain the PLA superfine nano fiber film material of chitosan-containing, the superfine nano fiber film material was handled 4 hours in 45 ℃ of baking ovens, obtained twisting the superfine nano fiber film material, can obtain tubulose by processing such as folding, individual layer is membranaceous, multilayer is membranaceous, block, graininess, strip, filamentary material.

Claims (10)

1, a kind of distortion superfine nano fiber film material, it is characterized in that the superfine nano fiber film material is that macromolecular material or polymer composite obtain the superfine nano tunica fibrosa after torsion of fibers distortion post processing obtains the distortion superfine nano fiber film material that fiber is distorted shape through electrospinning, the diameter of twisted fibre is between 20 nanometers-6 micron.
2, distortion superfine nano fiber film material according to claim 1 is characterized in that polymer composite is the compound of macromolecular material and inorganic ultrafine particle or additive.
3, distortion superfine nano fiber film material according to claim 2, the particle diameter that it is characterized in that inorganic ultrafine particle are 10 nanometers-5 micron.
4, distortion superfine nano fiber film material according to claim 1 and 2, it is characterized in that macromolecular material is the Biodegradable high-molecular PLA, polyglycolic acid, polycaprolactone, poly--the 3-butyric ester, poly--the 3-hydroxyl valerate, poly-(3-hydroxybutyric acid-co-3-hydroxypentanoic acid), poly-acid anhydrides, poe, group of polyphosphazenes, polyphosphate, polyoxyethylene, poly--a-amino acid, shitosan, hyaluronic acid, chondroitin sulfate, collagen, carrageenan, alginates, gelatin, agar, glucan, fibrin, a kind of or their derivative in the silk-fibroin, or lactide, glycolide, caprolactone, valerolactone, butyrolactone, oxirane, the copolymer of two or more in the expoxy propane; Or the derivative of polyvinylpyrrolidone, polyvinyl alcohol, cellulose, carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, methylcellulose, ethyl cellulose, noncrystalline cellulose, phthalic acid cellulose ethanoate, starch, Hydroxyethyl Starch, carboxymethyl starch or starch; Or two or more blend wherein; Or a kind of or their derivative in the polyolefin, polyvinyl acetate, polysiloxanes, polyethers, polyamide, polyester, Merlon, polyurethane, polyacrylonitrile, polyacrylic acid family macromolecule or two or more blend wherein.
5, according to claim the 2 distortion superfine nano fiber film materials of stating, it is characterized in that additive in the superfine nano fiber film material is a kind of in bactericide, essence, medicine, enzyme, polypeptide or protein, Porcine HGF, surfactant, penetration enhancer, the Chinese medicine extract or two or more mixture wherein, its content is less than 10% of nano-fiber material weight.
6, according to claim the 5 distortion superfine nano fiber film materials of stating, it is characterized in that the medicated premix in the superfine nano fiber film material is a pain-killer, antiphlogistic, anthelmintic, antiarrhymic, antibiotic, anticoagulant, antidepressants, antidiabetic, antiepileptic, antihistamine, antihypertensive, antineoplastic, immunodepressant, antithyroid drug, antiviral agent, astringent, contrast preparation, corticosteroid, antianxiety agent, anti-tussive agents, diuretics, immunizing agent, radiopharmaceutical, antihistamine, stimulant, muscle relaxant, dopaminergic, sympathomimetic drug, thyroid, sex hormone, antiallergic, vasodilator, prostaglandin, calcitonin, antimycobacterial drug, the fat conditioning agent, receptor blocking pharmacon; Or the mixture of said medicine.
7, according to claim the 5 distortion superfine nano fiber film materials of stating, it is characterized in that the surfactant in the superfine nano fiber film material is a polysorbas20,60 or 80; Or the block copolymer of department class 60,80, lauryl sodium sulfate, lecithin, sucrose fatty ester, oxirane and expoxy propane, polyethylene glycol, monoglyceride or above-mentioned two or more mixture.
8, a kind of preparation method who is applicable to the distortion superfine nano fiber film material of claim 1, its
Be characterised in that the preparation method is: macromolecular material or polymer composite are disperseed or be dissolved in and become clear solution or mixture in the solvent, obtain the electrospinning mixture, or with macromolecular material
Or the polymer composite fusion becomes melt, obtains the electrospinning mixture, adds storage tank then
In, being connected to injector head, injector head connects high voltage electric field, and voltage is 3 kilovolts-120 kilovolts,
Carry out electrostatic spinning then, obtain the macromolecular ultrafine fibrous membrane material, with the ultra-fine fibre of macromolecule
The dimension membrane material it a kind of poor solvent or multiple poor solvent mixture in immersion treatment,
Make the superfine nano torsion of fibers, obtain twisting macromolecule superfine nano fiber film material.
9, according to claim the preparation method of the 8 distortion superfine nano fiber film materials of stating, it is characterized in that described poor solvent is one or more the mixture in water, alcohol, ether, ketone, alkane, halogenated hydrocarbons, benzene or toluene, the acid amides.
10, a kind of preparation method who is applicable to the distortion superfine nano fiber film material of claim 1, it is characterized in that the preparation method is: macromolecular material or polymer composite are disperseed or be dissolved in and become clear solution or mixture in the solvent, obtain the electrospinning mixture, or macromolecular material or polymer composite fusion become melt, obtain the electrospinning mixture, add in the storage tank then, be connected to injector head, injector head connects high voltage electric field, voltage is 3 kilovolts-120 kilovolts, carry out electrostatic spinning then, obtain the macromolecular ultrafine fibrous membrane material, the macromolecular ultrafine fibrous membrane material is handled in 40-200 ℃ air or inert gas atmosphere, made the superfine nano filament contraction become twisted fibre, obtain twisting macromolecule superfine nano fiber film material.
CN 200310106517 2003-12-04 2003-12-04 Twisted ultra-fine nanometer fiber film material and preparing method thereof Expired - Fee Related CN1226471C (en)

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CN100577720C (en) * 2005-03-21 2010-01-06 中国科学院化学研究所 Biodegradable and absorb polymer nano fibrous membrane materials and method for making and purposes
CN100404126C (en) * 2005-12-23 2008-07-23 北京纳诺天地科技有限公司 Fibrous nanometer catalyst material excited with natural light and its prepn process
CN100362079C (en) * 2006-01-13 2008-01-16 四川世纪双虹显示器件有限公司 Spheroidal structure fluorophor preparation method
CN101586258B (en) * 2009-05-23 2010-11-03 青岛大学 Method for preparing micro-nano fibers with twisted spiral structure
CN102517687A (en) * 2011-11-17 2012-06-27 北京航空航天大学 Elastic fiber with multi-level micro-nano structure and bionic preparation method thereof
CN103572508B (en) * 2012-07-26 2016-06-08 中国科学院理化技术研究所 Preparation of biodegradable polymer nanofiber membrane by emulsion electrospinning method
CN103572508A (en) * 2012-07-26 2014-02-12 中国科学院理化技术研究所 Preparation of biodegradable polymer nanofiber membrane by emulsion electrospinning method
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CN105327357A (en) * 2015-10-14 2016-02-17 北京科技大学 Catechol modified hyaluronic acid drug carrier system and preparation method thereof
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CN108210994A (en) * 2018-03-06 2018-06-29 福建工程学院 A kind of preparation method for homogenizing poly-dopamine coating modified biological stent
CN108642714A (en) * 2018-07-13 2018-10-12 合肥洁诺医疗用品有限公司 A kind of disposable medical sheet non-woven fabrics
CN109260514A (en) * 2018-08-31 2019-01-25 湖南大学 A kind of texifolin modified fibre bracket and its preparation method and application
TWI680140B (en) * 2018-11-29 2019-12-21 高苑科技大學 Manufacturing method of hermetia illucens shell polyester composite fiber
CN109705730A (en) * 2018-12-28 2019-05-03 东南大学苏州医疗器械研究院 Durable type super-amphiphobic coating and preparation method thereof
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CN111013256A (en) * 2020-01-15 2020-04-17 中原工学院 High-efficiency low-resistance multi-component air filtering material with three-dimensional cavity structure and preparation method thereof
CN113183594A (en) * 2021-04-07 2021-07-30 广东工业大学 Preparation method of electrostatic spinning functional nanofiber film for epidermis repair
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