CN105525441A - Foldable multilayer cross-linked composite fiber net film as well as preparation method and application thereof - Google Patents
Foldable multilayer cross-linked composite fiber net film as well as preparation method and application thereof Download PDFInfo
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- CN105525441A CN105525441A CN201610061220.4A CN201610061220A CN105525441A CN 105525441 A CN105525441 A CN 105525441A CN 201610061220 A CN201610061220 A CN 201610061220A CN 105525441 A CN105525441 A CN 105525441A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
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- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/005—Fluorescence in vivo characterised by the carrier molecule carrying the fluorescent agent
- A61K49/0054—Macromolecular compounds, i.e. oligomers, polymers, dendrimers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/222—Gelatin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/24—Collagen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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Abstract
The invention belongs to the field of high polymer materials and discloses a foldable multilayer cross-linked composite fiber net film as well as a preparation method and an application thereof. Superfine high-polymer fibers are prepared from a solution of a high polymer material or a solution of the high polymer material and a support through electrostatic spinning and subjected to solvent annealing treatment, and then the fiber net film is obtained; the composite fiber net film adopts a three-dimensional support structure, porous fiber gaps are kept inside, and the whole composite fiber net film can be folded and expanded; the superfine high-polymer fibers are placed on an expansible and/or contractible device when subjected to solvent annealing treatment. The preparation method is simple, feasible and good in repeatability; besides, the composite fiber net film adopts multilayer crosslinking, can be folded and expanded, has excellent performance and can be applied to fields of tissue engineering scaffolds, drug release carriers, protection materials, filter materials and battery separators.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of Foldable multi-layer and be cross-linked composite fibre nethike embrane and preparation method thereof and application.
Background technology
Electrostatic spinning (or claiming Static Spinning) is a kind of direct and easy superfine fibre (nanometer is to micron order) preparation method.Static Spinning applied widely, can prepare the fibrous materials such as single macromolecular fibre, macromolecule mixture fiber, organic polymer/inorganic molecules composite fibre by electrostatic spinning technique; And the driving force of electrostatic spinning is high-pressure electrostatic, electrostatic spinning technique has that energy consumption is low, device is simple, easily amplifies the advantage of large-scale production.Simultaneously, Static Spinning gained fibrous material has the features such as diameter is ultra-fine, specific area is large, pattern is various, fiber nethike embrane tool porous, therefore, electrostatic spinning technique and Static Spinning material are widely used in multiple fields, as chemical industry, energy environment protection, biological medicine etc.Particularly over nearly 20 years, electrostatic spinning is rapid at biomedical sector application development.Numerous degradable macromolecule and other composite by the standby superfine fibre of electro-spinning, and are applied in organizational project and regenerative medicine field, as the artificial organ support of skin, blood vessel, muscle, nerve, bone etc.But most electrostatic spinning fiber support shows as traditional bidimensional membrane-like, and cell permeability is poor, to exist between poor, the fiber of Inter-fiber voids cellule infiltration without problems such as crosslinked overall mechanics intensity differences, limit it and apply.
Summary of the invention
In order to overcome the shortcoming and defect of above Static Spinning macromolecular fibre tissue engineering bracket, the object of the present invention is to provide a kind of value that is widely used in tissue engineering bracket material, implantable material, drug release carrier material, protective materials, filtering material, battery diaphragm etc., the Foldable multi-layer that simple, the overall mechanical strength of processing technology is high is cross-linked composite fibre nethike embrane.
Another object of the present invention is to provide the preparation method being cross-linked composite fibre nethike embrane by above-mentioned Foldable multi-layer.
Another object of the present invention is to provide above-mentioned Foldable multi-layer to be cross-linked the application of composite fibre nethike embrane.
Object of the present invention is achieved through the following technical solutions:
A kind of Foldable multi-layer is cross-linked composite fibre nethike embrane, is that the solution of the solution of macromolecular material or macromolecular material and loaded article is prepared into ultra-fine macromolecular fibre by electrostatic spinning, then is obtained by solvent annealing in process by ultra-fine macromolecular fibre; Described composite fibre nethike embrane has three dimensional support structure, and its inside maintains porous fibre gap, and composite fibre nethike embrane entirety can folding retractable.Described ultra-fine macromolecular fibre is when carrying out solvent annealing in process, and ultra-fine macromolecular fibre is placed on the device that can expand and/or shrink.The described device that can expand and/or shrink is preferably balloon.
The ultra-fine macromolecular fibre diameter that described Foldable multi-layer is cross-linked composite fibre nethike embrane is 100nm ~ 30 μm.
Described macromolecular material is Biodegradable polymer material, a kind of or their derivative in PLA, polycaprolactone, PGA, polylactide, polyglycolic acid, poly-β-hydroxy butyl ester, condensing model (as aliphatic polymeric anhydride, aromatic series condensing model, Polyester anhydride), polyphosphate, transparent resin acid, fibrin (i.e. fibrinogen), silk-fibroin, polyethylene glycol, poly phosphazene class (as polyphenylene oxide phosphine nitrile), shitosan, collagen, carrageenan, gelatin;
Described macromolecular material is two or more the copolymer in caprolactone, valerolactone, butyrolactone, oxirane, expoxy propane, glycolide and lactide;
Described macromolecular material is polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivative (as cellulose diacetate, methylcellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethylcellulose, cyanethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methylcellulose), starch derivatives (as Hydroxyethyl Starch, carboxymethyl starch);
Described macromolecular material is poly-ethyl acetate, polyacrylonitrile, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-(ester-ammonia ester) urea (as poly-sub-nonyl urea), a kind of or their derivative in Merlon (PC), nylon (PA), polyformaldehyde (POM), polyacrylate (as polymethyl methacrylate) or wherein two or more blend;
Described macromolecular material is polyethylene glycol-polylactic acid block copolymer, PEG-PCL block copolymer, polyethylene glycol-vinylpyrrolidone block copolymer, styrene-butadiene block copolymer or SBS.
Described loaded article is medicine, antibody, albumen, genetic fragment, growth factor, fluorescence molecule or aggregation-induced emission molecule, but is not limited thereto.
Described medicine is one or more the composition of medicine in antineoplastic, digestive system drug, antibiosis anti-inflammatory drug, pain-killer, anthelmintic, antiarrhythmics, antibiotic, anticoagulant, antidepressants, antidiabetic, antihistamine, antihypertensive, immunosuppressive drug, antithyroid drug, antiviral agent, pectoral, antiallergic, radiopharmaceutical, cardiovascular drug, hormone.
The preferred antineoplastic of described medicine, digestive system drug, antibiosis anti-inflammatory drug, but be not limited thereto.Described antineoplastic is adriamycin (DOX), Farmorubine Hydrochloride, Pirarubicin, mitomycin, fluorouracil, actinomycin D, Letrozole, tamoxifen citrate, Flutamide, medroxyprogesterone acetate, aminoglutethimide, imuran, thioguanine or cyclosporine, but is not limited thereto.Described digestive system drug is hymecromone, atropine, domperidone, hyoscine, Dihydroxyaluminum Aminoacetate, Carbenoxolone, bismuth aluminate or ranitidine hydrochloride.Described antibiosis anti-inflammatory drug is Indomethacin, tetracycline, aspirin, erythromycin, ROX, Amoxicillin or rifampin, but is not limited thereto.
Described antibody is preferably Victibix (Vectibix), T-DM1 (Kadcyla) or antibody immunoglobulinG.Described albumen is preferably Bovine serum albumin (BSA), but is not limited thereto.
Described fluorescence molecule is rhodamine (Rhodamine), Nile red (Nilered), phycoerythrin (PE) or fluorescein isothiocynate (FITC), but is not limited thereto.
Described aggregation-induced emission molecule is that thiophene coughs up (silole) compounds, polyaryl replaces the rare compounds of second, tetraphernl pyrazine (TPP) compounds, tetraphenyl benzene (TPB) compounds or nitrile substituted diphenylamine ethylene compounds.
It is that hexaphenyl thiophene is coughed up or tetraphenyl thiophene is coughed up that described thiophene coughs up compounds, but is not limited thereto; It is tetraphenylethylene, talan anthracene (DSA), diphenylfluorene ethene, tetraphenyl-Isosorbide-5-Nitrae-butadiene (TPBD) or triphenylethylene that described polyaryl replaces the rare compounds of second, but is not limited thereto.
Foldable multi-layer is cross-linked a preparation method for composite fibre nethike embrane, and concrete steps are:
1) method of electrostatic spinning prepares ultra-fine macromolecular fibre:
Macromolecular material or macromolecular material and loaded article are dissolved in solvent, obtain Polymer Solution; Polymer Solution is loaded with in the reservoir vessel of injector head, carries out electrostatic spinning by high-pressure electrostatic, adopt gathering-device to collect, obtain ultra-fine macromolecular fibre;
The concentration of described Polymer Solution is 1 ~ 40wt%, and in described Polymer Solution, the mass ratio of macromolecular material and loaded article is 1: (0.01 ~ 1); Described high-pressure electrostatic voltage is 5 ~ 40kV, and described Polymer Solution is 0.1 ~ 15mL/h from the rate of outflow of spinning head, and ambient temperature is 15 ~ 50 DEG C, and relative air humidity is 30 ~ 90%;
The distance of described injector head and gathering-device is 5 ~ 50cm;
When gathering-device is aerating ballon, the distance of injector head and aerating ballon is preferably 5 ~ 30cm, and the distance of aerating ballon and ground connection syringe needle is 2 ~ 6cm, and aerating ballon diameter is 6-15cm, and the rotating speed that described aerating ballon rotates is 50 ~ 2000r/min;
Described gathering-device be dull and stereotyped or cylinder (diameter of cylinder 8-15cm, rotating speed is 100 ~ 2000r/min) time, ultra-fine macromolecular fibre need be positioned on the device that can expand and/or shrink, then carry out next step solvent annealing in process;
2) the ultra-fine macromolecular fibre nethike embrane be placed on the device that can expand and/or shrink is put in solvent atmosphere and carries out solvent annealing in process, obtain multilayer and be cross-linked composite fibre nethike embrane; The temperature of described solvent annealing in process is 20 ~ 50 DEG C, and the time of solvent annealing in process is 5 ~ 30min;
In the device that described solvent annealing in process adopts, 12000cm
3device in the solvent of 30-50mL is housed, after ultra-fine macromolecular fibre nethike embrane is put into the device of annealing in process, obturator carries out solvent annealing in process; The described device that can expand and/or shrink is preferably balloon;
3) step 2 is taken out) multilayer is cross-linked composite fibre nethike embrane, and after the residual solvent volatilization on fiber nethike embrane, constriction device takes off fiber nethike embrane, obtains Foldable multi-layer and is cross-linked composite fibre nethike embrane.
Step 1) and 2) described in solvent be oxolane, N, more than one in dinethylformamide, DMA, carrene, chloroform, chloroform, methyl acetate, methyl cyanide, ethanol, water, methylisobutylketone, hexafluoroisopropanol, trifluoroacetic acid, trifluoroethanol, acetone, isopropyl alcohol or N-methylmorpholine-N-oxide (NMMO).
Above-mentioned Foldable multi-layer is cross-linked the application of composite fibre nethike embrane at tissue engineering bracket, preferably in the application of artificial urinary bladder tissue engineering bracket;
Above-mentioned Foldable multi-layer is cross-linked the application of composite fibre nethike embrane at drug release carrier;
Above-mentioned Foldable multi-layer is cross-linked the application of composite fibre nethike embrane at protective materials;
Above-mentioned Foldable multi-layer is cross-linked the application of composite fibre nethike embrane at filtering material;
Above-mentioned Foldable multi-layer is cross-linked the application of composite fibre nethike embrane at battery diaphragm.
Employing solvent annealing ratio juris is, by its steam after solvent evaporates at macromolecular fibre surface enrichment, the macromolecular chain on each macromolecular fibre surface in the region that macromolecular fibre contacts with each other in the short time is dissolved again form solution microcell and mutually tangle, after solvent evaporates, these macromolecular fibres form three-dimensional cross-linked composite fibre nethike embrane and maintain interfibrous gap structure because of the physical crosslinking of contact point.The overall mechanical property of this crosslinked compound nethike embrane has huge raising because interfibrous cross-linked structure has jointly born stress.And macromolecular fibre nethike embrane carry out on balloon crosslinked after, then by the contraction of cooling down of balloon, crosslinked nethike embrane is folded equably; Therefore can again carry out stretching and can not stress be produced when tensile elongation does not exceed former length (balloon inflation state).This so be applicable to very much the application of some artificial bladder body supports.
Compared with current material technology of preparing, tool of the present invention has the following advantages and beneficial effect:
1, most electrostatic spinning fiber support shows as traditional bidimensional membrane-like, cell permeability is poor, exist between poor, the fiber of Inter-fiber voids cellule infiltration without being cross-linked the problems such as overall mechanics intensity difference, but Foldable multi-layer of the present invention is cross-linked composite fibre nethike embrane and overcomes these problems, and there is three dimensional support structure, simultaneously inside maintains porous fibre gap, and composite fibre nethike embrane entirety can folding retractable;
2, preparation method's technique simple possible of the present invention, reproducible, and the multilayer that can be suitable for preparing variety classes polymer fiber material is cross-linked, the composite fibre nethike embrane of foldable telescopic;
3, multilayer of the present invention is cross-linked composite fibre nethike embrane and has the premium properties such as good overall mechanical property, and can be applicable to implantable material, drug release carrier material, protective materials, filtering material, battery diaphragm etc., economic efficient latent is huge.
Accompanying drawing explanation
Fig. 1 is the electrostatic spinning apparatus schematic diagram that the present invention utilizes balloon to be receiving system; 1 is high voltage source, and 2 is the holder (syringe) with injector head (spinning head), and 3 is Polymer Solution, and 4 is the syringe needle of ground connection, and 5 is balloon, and 6 is Polymer Solution liquid stream;
Fig. 2 is that multilayer prepared by embodiment 2 is cross-linked the shape appearance figure of composite fibre nethike embrane;
Fig. 3 is that multilayer prepared by embodiment 3 is cross-linked the stereoscan photograph of composite fibre nethike embrane;
Fig. 4 is that multilayer prepared by embodiment 4 is cross-linked the stereoscan photograph of composite fibre nethike embrane.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiment does not limit in any form the present invention.
Embodiment 1
(1) be dissolved in carrene by PLA, obtain the dichloromethane solution of Polymer Solution and PLA, its concentration is 8wt%;
(2) dichloromethane solution of PLA is carried out electrostatic spinning by the device shown in Fig. 1, Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (on syringe syringe needle), a balloon inflated is put between spinning head and ground connection syringe needle, spinning head is 12cm to balloon distance, the distance of aerating ballon and ground connection syringe needle is 3cm, balloon diameter is 10cm, and balloon is with 1000r/min rotating speed rotating collection fiber; After adding voltage, Polymer Solution can be pulled out syringe needle by electric field force and form Polymer Solution liquid stream, along with the continuous volatilization of solvent and the drawing-off effect of electric field force, finally on balloon, collects ultra-fine macromolecular fibre; Spinning condition is: spinning voltage is 15kV, and during spinning, ambient temperature is 22 DEG C, and relative humidity is 60%, and described Polymer Solution is 5mL/h from the rate of outflow of spinning head;
(3) after spinning completes, at 25 DEG C, the balloon of ultra-fine macromolecular fibre is had to put into glass box (30cm is long, 20cm is wide, 20cm high) collection, put into the beaker that is equipped with 50mL carrene again, closed glass case, annealing in process is after 20 minutes, balloon is taken out, after solvent remaining on fiber volatilizees completely, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane.The multilayer of gained is cross-linked composite fibre nethike embrane to be rich in gauffer and can repeatedly to stretch and fold; This Foldable multi-layer is cross-linked composite fibre nethike embrane and is applied to artificial urinary bladder organization bracket.
Embodiment 2
(1) be dissolved in chloroform by polycaprolactone, obtain Polymer Solution, its concentration is 10wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (syringe needle on syringe), spinning head is 15cm to collection cylinder (gathering-device) distance of ground connection, collection cylinder diameter is 10cm, with 1000r/min rotating speed rotating collection fiber, carry out spinning by method of electrostatic spinning, obtain ultra-fine macromolecular fibre; Spinning condition is: spinning voltage is 15kV, and when spinning, ambient temperature is 25 DEG C, and relative humidity is 60%, and described Polymer Solution is 8mL/h from the rate of outflow of spinning head;
(3) ultra-fine macromolecular fibre (polycaprolactone fiber) is taken off from cylinder, and transfer sticking is on the aerating ballon of diameter 8cm, at room temperature 25 DEG C, the balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into the beaker that 50mL chloroform is housed again, closed glass case, solvent annealing in process 20 minutes, balloon is taken out, after solvent remaining on fiber volatilizees completely, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane (shown in Fig. 2).As seen from Figure 2, originally level and smooth fiber nethike embrane becomes is rich in gauffer, folding fiber nethike embrane, and can repeatedly stretch and fold.
Embodiment 3
(1) be dissolved in oxolane by PLA-polycaprolactone co-polymer, obtain Polymer Solution, its concentration is 9wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (syringe needle on syringe), spinning head is 12cm to collection cylinder (gathering-device) distance of ground connection, collection cylinder diameter is 10cm, with 500r/min rotating speed rotating collection fiber, carry out spinning by method of electrostatic spinning, obtain ultra-fine macromolecular fibre; Spinning condition is: spinning voltage is 13kV, and when spinning, ambient temperature is 25 DEG C, and relative humidity is 60%, and described Polymer Solution is 10mL/h from the rate of outflow of spinning head;
(3) ultra-fine macromolecular fibre (PLA-polycaprolactone co-polymer fiber) is taken off from gathering-device, and transfer sticking is on the aerating ballon of diameter 10cm; At 30 DEG C, the balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into the beaker that 50mL oxolane is housed again, solvent annealing in process is after 10 minutes, balloon is taken out, after solvent remaining on fiber volatilizees completely, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane (shown in Fig. 3).Visible under scanning electron microscopic observation, macromolecular fibre has all been cross-linked to form the three-dimensional net structure of porous.This Foldable multi-layer is cross-linked composite fibre nethike embrane and is applied to tissue engineering bracket afterwards.
Embodiment 4
(1) by shitosan/silk protein mixtures (shitosan and silk-fibroin weight ratio are 1: 3) Fibrinolysis in hexafluoroisopropanol/trifluoroacetic acid (hexafluoroisopropanol and trifluoroacetic acid weight ratio are 9: 1) solution, obtain Polymer Solution, its concentration is 16wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (on syringe syringe needle), a balloon inflated is put between spinning head and ground connection syringe needle, spinning head is 12cm to balloon distance, the distance of aerating ballon and ground connection syringe needle is 3cm, aerating ballon diameter is 12cm and with 1000r/min rotating speed rotating collection fiber, carry out spinning by method of electrostatic spinning, obtain ultra-fine macromolecular fibre; Spinning condition is: spinning voltage is 15kV, and during spinning, ambient temperature is 25 DEG C, and relative humidity is 60%, and described Polymer Solution is 8mL/h from the rate of outflow of spinning head;
(3) after spinning completes, at 25 DEG C, the balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into the beaker that 50mL hexafluoroisopropanol/trifluoroacetic acid (weight ratio is 9: 1) is housed again, seal glass case, solvent annealing in process is after 15 minutes, balloon is taken out, after solvent volatilizees completely, by balloon remaining on fiber venting, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane (shown in Fig. 4).
Embodiment 5
(1) be dissolved in trifluoroethanol by gelatin/hyaluronic acid mixtures (gelatin and hyaluronic acid weight ratio are 1: 4), obtain Polymer Solution, its concentration is 10wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (syringe needle on syringe), spinning head is 20cm to collection cylinder (gathering-device) distance of ground connection, collection cylinder diameter is 10cm and with 800r/min rotating speed rotating collection fiber, carry out spinning by method of electrostatic spinning, obtain ultra-fine macromolecular fibre; Spinning condition is: spinning voltage is 15kV, and when spinning, ambient temperature is 25 DEG C, and relative humidity is 50%, and described Polymer Solution is 8mL/h from the rate of outflow of spinning head;
(3) ultra-fine macromolecular fibre (gelatin/hyaluronic acid mixtures fiber) is taken off from gathering-device, and transfer sticking is on the aerating ballon of diameter 12cm, the balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into the beaker that 50mL trifluoroethanol is housed again, seal glass case, solvent annealing in process is after 15 minutes, balloon is taken out, after solvent remaining on fiber volatilizees completely, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane.
Embodiment 6
(1) cellulose diacetate/polyethylene glycol mixture (cellulose diacetate and polyethylene glycol weight ratio are 1: 1) is dissolved in 50mLN, in dinethylformamide, obtain Polymer Solution, its concentration is 15wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (syringe needle on syringe), spinning head is 15cm to collection cylinder (gathering-device) distance of ground connection, collection cylinder diameter is 10cm and with 800r/min rotating speed rotating collection fiber, carry out spinning by method of electrostatic spinning, obtain ultra-fine macromolecular fibre; Spinning condition is: spinning voltage is 15kV, and when spinning, ambient temperature is 25 DEG C, and relative humidity is 40%, and described Polymer Solution is 9mL/h from the rate of outflow of spinning head;
(3) ultra-fine macromolecular fibre (cellulose diacetate/polyethylene glycol mixture of fibers) is taken off from gathering-device, and transfer sticking is on the aerating ballon of diameter 9cm; The balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into again and 40mLN is housed, the beaker of dinethylformamide, closed glass case, balloon, after 15 minutes, takes out, after solvent volatilizees completely by solvent annealing in process, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane.
Embodiment 7
(1) cellulose diacetate is dissolved in N, dinethylformamide and acetone (N, dinethylformamide and acetone weight ratio are 2: 1) in mixed solvent, add tetracycline powder (cellulose diacetate and tetracycline mass ratio are 1: 0.5), mix, obtain Polymer Solution, its concentration is 22wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (syringe needle on syringe), spinning head is 10cm to collecting board (gathering-device) distance of ground connection, carry out spinning by method of electrostatic spinning, obtain ultra-fine macromolecular fibre; Spinning condition is: when spinning, ambient temperature is 25 DEG C, and relative humidity is 70%, and the voltage of electrospinning is 12KV, and described Polymer Solution is 8mL/h from the rate of outflow of spinning head;
(3) ultra-fine macromolecular fibre (cellulose diacetate/tetracycline mixture of fibers) is taken off from collecting board, and transfer sticking is on the aerating ballon of diameter 15cm; The balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into again and 50mLN is housed, the beaker of dinethylformamide, closed glass case, balloon, after 15 minutes, takes out, after solvent volatilizees completely by solvent annealing in process, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane.
Embodiment 8
(1) be dissolved in oxolane by SBS, obtain Polymer Solution, its concentration is 14wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (syringe needle on syringe), spinning head is 40cm to collection cylinder (gathering-device) distance of ground connection, collection cylinder diameter is 10cm and with 1000r/min rotating speed rotating collection fiber, carry out spinning by method of electrostatic spinning, obtain ultra-fine macromolecular fibre; Spinning condition is: spinning voltage is 30kV, and when spinning, ambient temperature is 25 DEG C, and relative humidity is 60%, and described Polymer Solution is 8mL/h from the rate of outflow of spinning head;
(3) ultra-fine macromolecular fibre (SBS fiber) is taken off from gathering-device, and transfer sticking is on the aerating ballon of diameter 10cm; At 25 DEG C, the balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into the beaker that 50mL oxolane is housed, closed glass case, balloon, after 15 minutes, takes out by solvent annealing in process, after solvent remaining on fiber volatilizees completely, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane.
Embodiment 9
(1) polyethylene terephthalate (PET) be dissolved in carrene/trifluoroacetic acid (v/v=2: 1 of carrene/trifluoroacetic acid) mixed solvent, obtain Polymer Solution, its concentration is 15wt%;
(2) electrostatic spinning: Polymer Solution to be loaded in syringe and to connect high voltage source by spinning head (syringe needle on syringe), spinning head is 40cm to collection cylinder (gathering-device) distance of ground connection, collection cylinder diameter is 10cm and with 2000r/min rotating speed rotating collection fiber, spinning voltage is 15kV, when spinning, ambient temperature is 25 DEG C, relative humidity is 65%, and described Polymer Solution is 10mL/h from the rate of outflow of spinning head;
(3) ultra-fine macromolecular fibre (PET) is taken off from gathering-device, and transfer sticking is on the aerating ballon of diameter 10cm; At 25 DEG C, the balloon being loaded with ultra-fine macromolecular fibre is put into glass box (30cm is long, 20cm is wide, 20cm high), put into the beaker that 40mL carrene/trifluoroacetic acid (v/v=2: 1) mixed solvent is housed again, closed glass case, balloon, after 20 minutes, takes out by solvent annealing in process, after solvent remaining on fiber volatilizees completely, exitted by balloon, the multilayer obtaining foldable telescopic is cross-linked composite fibre nethike embrane.
Claims (10)
1. a Foldable multi-layer is cross-linked composite fibre nethike embrane, it is characterized in that: be that the solution of the solution of macromolecular material or macromolecular material and loaded article is prepared into ultra-fine macromolecular fibre by electrostatic spinning, more ultra-fine macromolecular fibre is obtained by solvent annealing in process; Described composite fibre nethike embrane has three dimensional support structure, and its inside maintains porous fibre gap, and composite fibre nethike embrane entirety can folding retractable; Described ultra-fine macromolecular fibre is when carrying out solvent annealing in process, and ultra-fine macromolecular fibre is placed on the device that can expand and/or shrink.
2. Foldable multi-layer is cross-linked composite fibre nethike embrane according to claim 1, it is characterized in that: the described device that can expand and/or shrink is balloon.
3. Foldable multi-layer is cross-linked composite fibre nethike embrane according to claim 1, it is characterized in that: described macromolecular material is a kind of in PLA, polycaprolactone, PGA, polylactide, polyglycolic acid, poly-β-hydroxy butyl ester, condensing model, polyphosphate, transparent resin acid, fibrin, silk-fibroin, polyethylene glycol, poly phosphazene class, shitosan, collagen, carrageenan or gelatin or their derivative;
Or described macromolecular material is two or more the copolymer in caprolactone, valerolactone, butyrolactone, oxirane, expoxy propane, glycolide and lactide;
Or described macromolecular material is polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivative or starch derivatives;
Or described macromolecular material is poly-ethyl acetate, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, poly-(ester-ammonia ester) urea, Merlon, nylon, polyformaldehyde, more than one or they in polyacrylate derivative;
Or described macromolecular material is polyethylene glycol-polylactic acid block copolymer, PEG-PCL block copolymer, polyethylene glycol-vinylpyrrolidone block copolymer, styrene-butadiene block copolymer or SBS.
4. Foldable multi-layer is cross-linked composite fibre nethike embrane according to claim 1, it is characterized in that: described loaded article is medicine, antibody, albumen, genetic fragment, growth factor, fluorescence molecule or aggregation-induced emission molecule.
5. Foldable multi-layer is cross-linked composite fibre nethike embrane according to claim 4, it is characterized in that: described medicine is more than one in antineoplastic, digestive system drug, antibiosis anti-inflammatory drug, pain-killer, anthelmintic, antiarrhythmics, antibiotic, anticoagulant, antidepressants, antidiabetic, antihistamine, antihypertensive, immunosuppressive drug, antithyroid drug, antiviral agent, pectoral, antiallergic, radiopharmaceutical, cardiovascular drug or hormone;
Described antibody is Victibix, T-DM1, antibody immunoglobulinG; Described albumen is Bovine serum albumin;
Described fluorescence molecule is rhodamine, Nile red, phycoerythrin or fluorescein isothiocynate;
Described aggregation-induced emission molecule is that thiophene coughs up compounds, polyaryl replaces the rare compounds of second, tetraphernl pyrazine compounds, tetraphenyl benzene-like compounds or nitrile substituted diphenylamine ethylene compounds.
6. according to any one of Claims 1 to 5, Foldable multi-layer is cross-linked the preparation method of composite fibre nethike embrane, it is characterized in that: concrete steps are:
1) method of electrostatic spinning prepares ultra-fine macromolecular fibre:
Macromolecular material or macromolecular material and loaded article are dissolved in solvent, obtain Polymer Solution; Polymer Solution is loaded with in the reservoir vessel of injector head, carries out electrostatic spinning by high-pressure electrostatic, adopt gathering-device to collect, obtain ultra-fine macromolecular fibre;
2) the ultra-fine macromolecular fibre be placed on the device that can expand and/or shrink is put in solvent atmosphere and carries out solvent annealing in process, obtain multilayer and be cross-linked composite fibre nethike embrane;
3) step 2 is taken out) multilayer is cross-linked composite fibre nethike embrane, and after the residual solvent volatilization on fiber nethike embrane, constriction device takes off fiber nethike embrane, obtains Foldable multi-layer and is cross-linked composite fibre nethike embrane.
7. Foldable multi-layer is cross-linked the preparation method of composite fibre nethike embrane according to claim 6, it is characterized in that: step 1) and 2) described in solvent be oxolane, N, more than one in dinethylformamide, DMA, carrene, chloroform, chloroform, methyl acetate, methyl cyanide, ethanol, water, methylisobutylketone, hexafluoroisopropanol, trifluoroacetic acid, trifluoroethanol, acetone, isopropyl alcohol or N-methylmorpholine-N-oxide;
Step 2) temperature of described solvent annealing in process is 20 ~ 50 DEG C, the time of solvent annealing in process is 5 ~ 30min; Step 2) the described device that can expand and/or shrink is balloon;
Step 1) concentration of described Polymer Solution is 1 ~ 40wt%, in described Polymer Solution, the mass ratio of macromolecular material and loaded article is 1: (0.01 ~ 1); Described high-pressure electrostatic voltage is 5 ~ 40kV, and described Polymer Solution is 0.1 ~ 15mL/h from the rate of outflow of spinning head, and ambient temperature is 15 ~ 50 DEG C, and relative air humidity is 30 ~ 90%; The distance of described injector head and gathering-device is 5 ~ 50cm.
8. according to claim 6 or 7, Foldable multi-layer is cross-linked the preparation method of composite fibre nethike embrane, it is characterized in that: when described gathering-device is aerating ballon, the distance of injector head and aerating ballon is 5 ~ 30cm, the distance of aerating ballon and ground connection syringe needle is 2 ~ 6cm, aerating ballon diameter is 6 ~ 15cm, and the rotating speed that described aerating ballon rotates is 50 ~ 2000r/min;
Described gathering-device be dull and stereotyped or cylinder time, ultra-fine macromolecular fibre need be positioned on the device that can expand and/or shrink, then carry out next step solvent annealing in process.
9. according to any one of Claims 1 to 5, Foldable multi-layer is cross-linked the application of composite fibre nethike embrane, it is characterized in that: described Foldable multi-layer is cross-linked the application of composite fibre nethike embrane in tissue engineering bracket, drug release carrier, protective materials, filtering material and battery diaphragm.
10. Foldable multi-layer is cross-linked the application of composite fibre nethike embrane according to claim 9, it is characterized in that: described Foldable multi-layer is cross-linked the application of composite fibre nethike embrane in artificial urinary bladder tissue engineering bracket.
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