CN101172164A - Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same - Google Patents
Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same Download PDFInfo
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Abstract
The invention relates to compound millimicron fibrous membrane material of cellulose and cellulose matrix which can perform the biological degradation and the biological absorption and a preparation method thereof and an industry and medical purpose, and belongs to the biological macro-molecule non woven fabric material field which can perform the biological degradation and the biological absorption. Electrostatic spinning equipment is used to obtain the fibrous membrane material which can perform the biological degradation and the biological absorption, the weight of the cellulose is taken as basic reference, the component of the material comprises cellulose more than 0 and less than or equal to 100 weight parts, other biomacromolecule more than and equal to 0 and less than 100 weight parts, 0 to 10 weight parts of curative drug or 0 to 50 weight parts of inorganic catalyzer and / or 0 to 50 weight parts of inorganic strengthening agent. The material of the invention has good biological compatibility, biological degradation property and degradation absorptivity, and can be used for haemostasia material, wound cladding material, organization engineering supporting rack material, the transportation and release of medicine, artificial skin and blood vessel, and postoperation anti blocking material, beauty material and catalyzer carrier, filtering membrane and radiation protection material and so on.
Description
Technical field
But the invention belongs to the biopolymer nonwoven cloth material field of biodegradable and bio-absorbable, but the cellulose of particularly biodegradable and bio-absorbable and cellulose based nano fiber film material and preparation method thereof and industry, medical application.
Background technology
Cellulose is a kind of Renewable resource cheap and easy to get, extensively be present in the various biologies of nature, the inorganic matter, timber, Cotton Gossypii, filter paper etc. all contain a large amount of celluloses, and cellulose also is the basis that constitutes plant cell, it is present in the middle of all plants, be the abundantest a kind of renewable organic resource in the plant kingdom, thereby it has excellent biological compatibility, but be a kind of resource of natural biodegradable and bio-absorbable.Unmodified cellulose is because intramolecularly and intermolecular powerful hydrogen bond action, and water insoluble, diluted acid or diluted alkaline also are insoluble to common organic solvents, thereby has the performance of excellent acid alkali, corrosion-resistant, organic solvent-resistant; Simultaneously, cellulose has more good calorifics and mechanical property compared with other natural polymer, thereby as Material Used stronger stability is arranged, and is convenient to machine-shaping and uses.The research of cellulose spinning is the history in existing more than 100 year so far.In most of the time in the past, cellulose spinning all utilizes viscose rayon to carry out, environmental problem had been wasted but also brought to this mode not only, so in recent decades, a large amount of work concentrates on and utilizes cellulosic pollution-free spining technology to make in the research of high-performance fiber.But be difficult to spin the cellulose fibre of diameter less than 500nm with traditional spinning process.
Method of electrostatic spinning is a kind of simply and effectively processing technique for preparing polymer superfine fibre, be found to the existing now history in 100 years nearly from it, the principle of this method be at first with on the polymer fluid band several thousand to volt high-pressure electrostatics up to ten thousand, the effect that charged polymer liquid drops in electric field force forms the Taylor awl down, and be accelerated at conical point, when electric field strength is enough big, the polymer drop overcomes surface tension and forms the injection thread, spraying instability that thread forms various ways aloft flows and finally drops on the receiving system of ground connection, can form the polymer fiber film of the superfine fibre composition of similar non-weaving cloth shape or ordered arrangement according to the difference of receiving system.At first by Zeleny (Phys.Rev.1914.3:69～91) invention, Formhals (US Patent, 1,975,504.1934) has applied for patent to it to electrospinning silk technology.People such as Taylor drive the work of being done on the sputter stream, the basis (Proc.Roy.Soc.Lond.A.1969,31:453～475.) of having established the electrospinning silk at electricity.Nanofiber shows better mechanical property, interfacial property than its conventional fibre of the same race, very strong absorption affinity and good filterability, barrier, cohesive and heat insulating ability etc. are arranged, (Polymer 2001,43 (3): 1025～1029 to can be used for a lot of special occasions; J.Polym.Sci., Part B:Polym.Phys.2001,39 (21): 2598～2606; AICHEJournal, 1999,45 (1): 190; J.Electrostatics, 1995.35:151～160; Polymer, 1999,40 (16): 4585～4592; Adv.Mater.2000,12 (9): 637～640; Nanotechnology, 1996,7 (3): 216～223; J.Coated Fabrics, 1998.28:63～72; J.Macromol.Sci.-Phys., 1997, B36 (2): 169～173), especially at biomedical sector: superfine fibre film can be used as tissue renovation material, as blood vessel etc.Also can be used as isolating membrane and hemostasis articles for use; The yardstick and the extracellular matrix of superfine fibre are suitable, can provide template preferably for breeding, migration and the growth of cell during therefore as support; Under the electric field force effect, the degradable polymer superfine fibre can directly stick on the wound of skin, and it not only promotes wound healing, helps the growth of normal skin, but also makes the skin preventing from scar; Because the superfine fibre film pore diameter range is usually at 500nm～1um, surface area is up to 5～100m
2/ g, thereby prevent the antibacterial intrusion as wound dressing, make receptor can carry out the exchange of matter and energy effectively with the external world simultaneously.
Because electrostatic spinning technique using electric field power but not mechanical force is carried out the fiber manufacturing, so this technology has some special requirements to the character of solution, as carries electric charge ability, solvent volatility etc.And cellulose is because hydrogen bond action intermolecular and that intramolecularly is powerful, has the insoluble character of multiple organic and inorganic solvent, thereby, that more both at home and abroad at present is the high-voltage electrostatic spinning (J.Polym.Sci. of research modified cellulose, Part B:Polym.Phys.2004,42 (1): 5～11; Materials Letters2005,59:2998～3001; J.Polym.Sci, Part A:Polym.Chem.2004,42:4289～4299; Biomacromolecules 2004,5:197～201; Journal of Applied PolymerScience 2004,91:242～246), as the electrospinning of ethyl cellulose or cellulose acetate, the anti-solvent ability of the plain derivant of this fibrid weakens greatly.Can carry out the chemical after-treatment reason after the cellulose acetate spinning again, as be immersed in and destroy ester bond in the NaOH aqueous slkali and make it be reduced to the cellulose fibre film.But the cellulose electrostatic spinning by chemical modification has not only destroyed cellulosic natural character, and the loss of modifying process product is more, and form and performance to nanofiber in the reduction process are also influential, and suitability for industrialized production is seriously polluted, uses inconvenience.Existing electrostatic spinning experiment shows that by the exploration to new cellulose solution system the protofibre element can prepare superfine fibre by electrostatic spinning technique.Ethylene diamine/NH that U.S. Cornell university selects for use at first
4SCN class system (Polymer Preprints.2003,44 (2): 168～169) carry out cellulosic electrostatic spinning, its formulations prepared from solutions is comparatively complicated, and solvent toxicity is big, and spinning effect is not good, and cellosilk thickness inequality has pearl to exist; LiCl/DMAc system (J.Polym.Sci after it, Part B:Polym.Phys.2005,43:1673～1683) be used to carry out cellulosic electrostatic spinning solvent, because the adding of LiCl weakens or has destroyed in the cellulosic molecule and intermolecular hydrogen bonding, make cellulose can well be dissolved among the DMAc, but because the volatility of DMAc is bad, thereby collection condition is relatively harsher, needs about 100 degrees centigrade high temperature to make the DMAc volatilization or adopt filter membrane reception post-heating to make solvent evaporates.Piotr Kulpinski (the Journal of Applied PolymerScience.2005 of Poland, 98:1855～1859) select for use NMMO organic solvent dissolution cellulose to carry out electrostatic spinning, need receive in 80～100 degree water-baths, and because the problems such as cost height that the high toxicity of NMMO itself, side-product explosive, solvent recovery and recirculation use, also become the bottleneck problem of cellulose fibre film later stage application.People (Biomacromolecules.2006 such as Gunaranjan Viswanathan, 7 (2): 15～418) with cellulose dissolution at the 1-butyl, prepare cellulose fibre in the 3-methyl chloride imidazole salts ionic liquid, cellulose/heparin is dissolved in the 1-butyl, 3-methyl chloride imidazole salts/1-ethyl, prepare complex fiber material in the 3-benzoin methyl imidazole acid salt, receive micron-sized cellulose fibre by adopting ethanol bath to remove nonvolatile ionic liquid.But the fiber thickness of reporting in the literary composition is inhomogeneous, and mostly between 1～15 micron, and adhesion is serious between the fiber, becomes dendritic structure.
The electrostatic spinning process need is regulated and is controlled the many machined parameters (as the fluid rate of electric field intensity, electrode structure, spinnerette diameters and solution) and the physical parameter (as solution viscosity and surface tension) of solution.Protofibre is plain because intermolecular/powerful hydrogen bond network of intramolecularly own has the insoluble character of multiple solvent, and the physical parameter that dissolving back solution is still controlled in the dissolving of feasible cellulose itself all becomes difficult unusually.The present invention is by selecting suitable ion liquid dissolving protofibre element for use, physical parameter by adding the appropriate organic solvent regulator solution and by the suitable spinning technology parameter of design can be prepared controlled cellulose nano-fibrous of even thickness even fibre diameter continuously.In addition, orientation by dash receiver is regulated, make and be arranged in parallel or the nano fibrous membrane of non-woven fabrics form, and by two shower nozzles or multi-nozzle electrospinning device, make cellulose and other natural or high molecular nano-composite fiber film of synthetic, and further study its biology, physics, mechanical property, must enlarge the application of cellulose and cellulose based nano fibrous membrane.Cellulose and composite thereof with the electrostatic spinning technique preparation have excellent biological compatibility, biological degradability and bio-absorbable performance, can be used for hemostatic material, the wound clad material, tissue engineering bracket material, drug releasing membrane according, aspects such as artificial skin, artificial blood vessel, wound dressing, drug conveying, biomembrane, post-operation adhesion preventing material, beauty treatment material; The insoluble performance of multiple organic solvent that has based on cellulosic material itself can be applicable to catalyst carrier, filter membrane, aspects such as radioprotective, corrosion-resistant material again.
Summary of the invention
One of purpose of the present invention provides biopolymer micro/nano fibrous membrane material biodegradable and that absorb.
Two of purpose of the present invention provides the cellulose nano-fibrous membrane with good biological physical and mechanical property biodegradable and that absorb.
Three of purpose of the present invention provides the composite nano-fiber membrane material of the cellulose base with good biocompatibility of biodegradable and absorption.
Four of purpose of the present invention provides the preparation method of the cellulose nano-fibrous membrane with good biological physical and mechanical property of biodegradable and absorption.
Five of purpose of the present invention provides the preparation method of the cellulose base composite nano-fiber membrane with good biocompatibility of biodegradable and absorption.
Six of purpose of the present invention is the selections at ionic liquid, organic solvent, and the improvement by technological parameter, provides method of electrostatic spinning to prepare cellulose and cellulose base is biodegradable and the concrete technological parameter of the micro/nano fibrous membrane material that absorbs.
Seven of purpose of the present invention is by cellulose ionic liquid solution and one or more natural polymer aqueous solutions, utilize multi-nozzle electrospinning device, two kinds of totally different materials processings of performance are become composite nano fiber cloth, good anthemorrhagic performance and long characteristics of cellulose degradation in vivo time by selected natural polymer has prepare a kind of novel hemostatic material and wound clad material.
Eight of purpose of the present invention is by cellulose ionic liquid solution and one or more synthetic biocompatibility macromolecule solution, utilize multi-nozzle electrospinning device, the different cellulose based nano fibrous membrane of content is formed in preparation, and a kind of new material that can do the biodegradable absorption of extensive wound dressing and artificial skin is provided.
Nine of purpose of the present invention is natural polymer-cellulose high molecular nanometer composite fiber membrane materials that the different degrees of cross linking are provided by the method for chemical crosslinking, and by changing nano fibrous membrane microcosmic or macroscopic pattern with the compound novel tissue engineering bracket material of the plain base of the tencel of realizing the different cell adhesion speed of preparation.
Ten of purpose of the present invention provides the cellulose base biopolymer composite fiber membrane material that contains medicine and preparation method thereof and potential medical application.
11 of purpose of the present invention provides cellulose base biopolymer fiber membrane material that can be used as catalyst carrier and preparation method thereof.
Biodegradable and the biopolymer micro/nano fibrous membrane material that absorbs of the present invention, but comprise the cellulose membrane material of biodegradable and bio-absorbable and the composite nano-fiber membrane material of cellulose base, with the cellulose is benchmark, the composition of this material consists of 0＜cellulose≤100 weight portions, 0≤other biopolymer＜100 weight portions, curative drug 0～10 weight portion or organic catalyst 0～50 weight portion and/or inorganic strengthening agent 0～50 weight portion; The fibre diameter of described cellulose or other biopolymer is at 50nm～5000nm.
But the biodegradable fiber that reaches the biopolymer micro/nano fibrous membrane material of bio-absorbable of the present invention can be lack of alignment structure, unidirectional array structure, cross arrangement structure, curl disordered structure, the unidirectional array structure of curling or curling cross arrangement structure.
Described cellulose is a medical absorbent cotton, and the degree of polymerization is in 1000～1500 scopes, or the non-solubility wood pulp cellulose, and the degree of polymerization is in 500～800 scopes.
The molecular weight of described other macromolecular material is 5～2,000,000.Be selected from: hyaluronic acid, gelatin, various alginate, fibroin, chitosan, chondroitin sulfate, heparin, collagen protein, nucleic acid, cellulose protein, fibronectin in serum, polypeptide, agar, the blend of one or more in various glucosans or the above-mentioned high molecular derivant; Or
Be selected from: the poly butyric valerate, the poly butyric alkyl caproate, polycaprolactone, poly-Acetic acid, hydroxy-, bimol. cyclic ester, polylactide, polylactic acid, the copolymer of polylactic acid and caprolactone or Acetic acid, hydroxy-, bimol. cyclic ester, poly-to two evil ketone, polyurethane, poly phosphate, the blend of one or more in the polyoxyethylene, and two or more the copolymer in the lactide, Acetic acid, hydroxy-, bimol. cyclic ester, butyrolactone, valerolactone, caprolactone, oxirane, expoxy propane; Or
Be selected from: polyvinylpyrrolidone or polyvinyl alcohol; Or
Be selected from: methylcellulose, ethyl cellulose, noncrystalline cellulose, hydroxy methocel, hydroxyethyl-cellulose, hydroxypropyl cellulose, the blend of one or more in the hydroxypropyl emthylcellulose; Or
Be selected from: the blend of one or more in starch, ethyl starch, the methyl starch.
Described curative drug is selected from: AgCl, TiO
2Nanometer silver, sulfadiazine, SMZ-SD-TMP, norfloxacin, ciprofloxacin, ofloxacin, calcitonin, insulin, nerve growth factor, ganglioside, hydrocortisone, the control growing factor, drive insect medicine, anticoagulation class medicine, mycobacteria, the antibiotic medicine, antibiotic, antiviral agents, anti-infective, antineoplastic agent, lonizing radiation class medicine, immunity class preparation, analgesic, antiallergic agent, anthelmintic, diuresis class preparation, muscle relaxant, gonadal hormone, antidepressants, antuepileptic, antihypertensive, anti-arrhythmic, antidiabetic drug, antithyroid drug, cough medicine, the steroid preparation, contrast agent, astringent, the blend of one or more in the resistance prostatitis class preparation medicine; Or be selected from from medical herbs, Tibetan medicine, mongolian medicine, Miao Ethnomedicine or other Chinese herbal medicine extract one or more the treatment various diseases effective ingredient.
The cellulose ionic liquid electrostatic spinning apparatus that is used to prepare biodegradable and the biopolymer micro/nano fibrous membrane material that absorbs can adopt single ejecting device as shown in Figure 1, or many ejecting devices as shown in Figure 2, or other can implement the inventive method, obtains any device of the biodegradable and biopolymer micro/nano fibrous membrane material that absorbs of the present invention.
Preparation method biodegradable and the biopolymer micro/nano fibrous membrane material that absorbs of the present invention is carried out according to the following steps:
(1). the preparation of cellulose electrostatic spinning stock solution: cellulose dissolution is obtained the cellulose solution of homogeneous transparent in ionic liquid, wherein the concentration of cellulose solution is 1wt%～15wt%; Add organic solvent afterwards in above-mentioned solution, the quality and the cellulose solution mass ratio that add organic solvent are 1: 1～8: 1; With the cellulose is benchmark, adds curative drug 0～10 weight portion or organic catalyst 0～50 weight portion and/or inorganic strengthening agent 0～50 weight portion therein;
Other macromolecule is mixed with the good solution of spinning effect separately respectively, concentration with suitable inorganic solvent (as water) and/or organic solvent (as formic acid, acetic acid, ethanol, acetone, dimethyl formamide or their any mixture etc.) preparation macromolecular solution is 0.5wt%～50wt%, with the cellulose is benchmark, adds curative drug 0～10 weight portion or organic catalyst 0～50 weight portion and/or inorganic strengthening agent 0～50 weight portion therein.
(2). electrostatic spinning process is: to be respectively charged into temperature be in 20～80 ℃ the charging gear of electrospinning device for contain cellulosic solution and other macromolecular solution that step (1) is obtained, the feeding rate of adjusting solution is 5～300ul/min, and preferred feeding rate is 10～150ul/min; Distance between the spinning head of charging gear and the catcher of ground connection is 5～25cm, is preferably 7～20cm; Ambient temperature is 20～70 ℃, is preferably 40～60 ℃; The air velocity of environment is 0～8.5m
3/ hr is preferably 0.5～5m
3/ hr; (electrostatic pressure is 1～60kV to open high voltage power supply, suitable value is 15～30kV), the charging gear pump that contains cellulose solution is equipped with in unlatching, and injection stream is ejected on the catcher (as cylinder), but obtains the cellulose high molecular nanometer membrane material of biodegradable and bio-absorbable; Or open the charging gear pump that cellulose solution and other macromolecular solution are housed simultaneously, but obtain the composite nano-fiber membrane material of the cellulose base of biodegradable and bio-absorbable; Wherein the temperature range of catcher is 30～80 ℃, and preference temperature is 40～60 ℃; The translational speed of catcher is 0～10m/nin, and the translational speed of spinning head is 0～5m/min;
(3). the high polymer nanometer fiber membrane material that step (2) is prepared soaks 2～24 hours to remove residual solvent in dehydrated alcohol, and with dehydrated alcohol repeatedly the drip washing fibrous membrane washed away fully until remaining spin solvent, with fibrous membrane vacuum drying after 0.5～50 hour in 20～60 ℃ of vacuum drying ovens, obtain biopolymer micro/nano fibrous membrane material biodegradable and that absorb, place exsiccator to preserve;
(4) but the biodegradable and bio-absorbable macromolecular fibre membrane material of the different degrees of cross linking is provided with the method for chemical crosslinking: with step (3) but the biodegradable and bio-absorbable macromolecular fibre membrane material that obtains places the mixed solution of ethanol/water, the cross-linking agent that adds metering, crosslinked 1～48 hour in 0～40 ℃, wash away fully with the cross-linking agent of a large amount of deionized water wash then, then vacuum drying about 2 days in 20～60 ℃ of vacuum drying ovens until remnants.But the weight and the volume ratio of the mixed solution of wherein biodegradable and bio-absorbable macromolecular fibre membrane material and ethanol/water are 1: 20～2000g/ml, the volume ratio of ethanol and water is 80～100: 0～20, and cross-linking agent concentration in mixed solution is 1～200mmol/L.
The number of the spinning head of described charging gear is more than 1 or 1.
Described catcher can further be immersed in the corresponding poor solvent of macromolecule when collecting fiber, can more effectively remove residual ionic liquid.
In the electrostatic spinning process, the thickness of the stability of many parameter influence electrostatic spinning processes, seriality, fiber and the uniformity etc., for example cellulosic molecular weight, the translational speed of the speed air flow of other high molecular molecular weight, solution concentration, solvent, ambient temperature, environment, electrostatic pressure, shower nozzle, the rotating speed of catcher or translational speed etc.
The present invention is to be that spin solvent prepares fibrous material with ionic liquid and other organic solvent, can realize the electrostatic spinning of cellulose in the ionic liquid solution system by described electrical spinning method, and the electrostatic spinning of the blend solution of ionic liquid and other biopolymer, the composite nano fiber non-woven fabrics of preparation cellulose and cellulose base, can also by to the post processing of fiber after the spinning for the further extensive use of micro/nano fibrous membrane material provides may.
The electrostatic spinning course of processing device therefor of described cellulose or cellulose/other natural polymer solution comprises: formations such as high voltage power supply, charging pump, spinning head, gathering-device, ambient temperature control appliance; High voltage power supply generally can adopt positive negative dc high voltage out-put supply, and the maximum voltage of output is at 40～60kV; The way of output of charging pump can adopt the rear pump feed of multiple output frequency, and general maximum output area is below 300 mul/min; Good conductors such as spinning head material selection rustless steel, copper or iron-nickel alloy, spinnerette diameters is below 1mm, can also adopt the mode of single shower nozzle spinning or many shower nozzles distribution spinning according to the output needs, the parallel distribution of spinning head is generally selected in the spinning of many shower nozzles for use, can 1～5 row's spinning head, single spinning head quantity is generally below 20, and distance is 1～5cm between the adjacent spinning head; Gathering-device can be direct collection of aluminium foil or the netted collection that is arranged in parallel or hands over justice to arrange wiry of good conductors such as rustless steel, copper or iron-nickel alloy, gathering-device part can adopt various forms of catchers such as rotating circular disk, flat board, cylinder, also can adopt as required the poor solvent of the selected system liquid collecting mode as collection system; Electrospinning silk ambient temperature control device can adopt infrared lamp mode of heating, resistance wire mode of heating, recirculated hot air mode of heating, and general maximum heating temperature is not higher than 80 ℃, and system is PID control, and general control accuracy is in ± 3 ℃ of scopes.
Described ionic liquid is the 1-ethyl, 3-methylene diacetate imidazole salts ionic liquid, the 1-ethyl, 3-methyl chloride imidazole salts ionic liquid, the 1-ethyl, 3-methyl bromide imidazole salts ionic liquid, the 1-pi-allyl, 3-methyl chloride imidazole salts ionic liquid, the 1-pi-allyl, 3-methyl bromide imidazole salts ionic liquid, the 1-pi-allyl, 3-methyl thiocyanate imidazole salts ionic liquid, the 1-pi-allyl, 3-methylene diacetate imidazole salts ionic liquid, the 1-butyl, 3-methylene diacetate imidazole salts ionic liquid, the 1-butyl, 3-methyl chloride imidazole salts ionic liquid or 1-butyl, 3-methyl bromide imidazole salts ionic liquid.
Described organic solvent is sulfone, sulfoxide, dimethyl formamide or dimethyl acetylamide.
Described curative drug can suitably increase the interpolation content of medicines as requested, is as the criterion not influence spinning properties, also can be by preparing earlier the method for soaking behind the fiber to be written into more medicine in fiber.
Described inorganic strengthening agent is hydroxyapatite, beta-calcium phosphate, potassium titanate crystal whisker, chromic acid Potassium, calcium carbonate, calcium hydrogen phosphate or dalcium biphosphate etc.
Described catalyst is TiO
2, active carbon or metallic catalyst etc.
Described metallic catalyst is noble metal catalyst or metallocene catalysts such as Pt, Rh, Pd.
Described cross-linking agent is selected from carbodiimide, glutaraldehyde, formaldehyde, a kind of in diepoxides or the divinylsulfone etc.
The invention discloses a kind of based on ionic liquid, the spin solvent metric system that contains other organic solvent simultaneously is equipped with electrostatic spinning stock solution, control and the electrostatic spinning of regulating the realization cellulose solution by electrostatic spinning process, the preparation fibre diameter is at the fiber film material of tens nanometers to several microns, by with multiple biopolymer spinning blend, add novel cellulose or cellulose base composite nano fiber cloth that medicine or organic catalyst and/or inorganic strengthening agent prepare different components and function.Material of the present invention has excellent biological compatibility, biological degradability and bio-absorbable performance, can be used for catalyst carrier, filter membrane, industrial circles such as radiation proof material also can be used as medical tissue engineering scaffold material, drug releasing membrane according, artificial skin, artificial blood vessel, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), wound coated material, hemostatic material, wound clad material, post-operation adhesion preventing material and beauty treatment material etc.
Characteristics of the present invention:
1. provide a kind of and effectively prepared the method that cellulose and cellulose are main composite nano-fiber membrane material, captured the technical barrier that the cellulose solution system is difficult for spinning by electrostatic spinning;
2. pass through to realize the electrostatic spinning of cellulose ion solution, and, successfully prepare controlled cellulose of pattern and cellulose base composite nano-fiber membrane material by regulating technological parameter;
3. a kind of the have cellulose of nano-scale structures and the nano-composite fiber membrane material of cellulose base are provided, bigger performance the characteristics of cellulose base composite, especially as filter membrane, the application of catalyst carrier and biologic pharmacological science aspect.
4. the cellulose based nano fiber film material and preparation method and the medical application that contain medicine, inorganic strengthening agent, catalyst are provided.
Description of drawings
Fig. 1. the embodiment of the invention 1 single ejecting device sketch map.
Fig. 2. embodiment of the invention ejecting device more than 4 sketch map.
Fig. 3. the cellulose fibre SEM figure of the embodiment of the invention 1.
Fig. 4. the cellulose fibre SEM figure of the embodiment of the invention 2.
Fig. 5. the cellulose fibre SEM figure of the embodiment of the invention 3.
Fig. 6. the cellulose of the embodiment of the invention 5/ethyl cellulose composite fibre SEM figure.
Fig. 7. the cellulose/methyl starch of the embodiment of the invention 9/medicine composite fibre SEM figure.
Reference numeral
1. syringe 2. high voltage power supplies 3. cylinders 4. syringe pumps 5. spinning heads
The specific embodiment
Embodiment 1
See also Fig. 1.High voltage power supply 2 adopts the negative dc high voltage out-put supply, and the maximum voltage of output is 40kV, and high voltage power supply is wired to the ejection end of the spinning head 5 of syringe 1; The way of output of syringe pump 4 adopts the rear pump injector-actuated feed of multiple output frequency, and maximum output area is 300 mul/min, and syringe pump is connected to the spinning head material feeding end of syringe 1 by conduit; Spinning head material selection rustless steel, spinnerette diameters are 0.8mm; Gathering-device is the swing roller 3 that copper wire is arranged in parallel, and the diameter of cylinder 3 is 80mm, and the copper wire spacing is 7.5mm; Electrostatic spinning ambient temperature control device adopts the infrared lamp mode of heating, and system is PID control, and control accuracy is in ± 3 ℃ of scopes.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-ethyl of 5wt%, 3-methylene diacetate imidazole salts solution 5ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of dimethyl sulfoxide and cellulose solution is 2/1, stir, place syringe;
(2) adjust electrostatic spinning apparatus: select single spinning head apparatus for use, swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 12cm; The ambient temperature of spinning is 25 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 22KV, the delivery rate of solution is 100ul/min, drum rotation speed is 300r/min, carries out spinning, and the cellulose fibre film on the cylinder is soaked in the 10ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 10ml dehydrated alcohol in addition, 20 degree vacuum dryings 1 day, obtaining cellulose nano-fibrous membrane material biodegradable and that absorb is the unidirectional array structure, average fibre diameter is the 800nm (see figure 3);
(4) prepared fibrous membrane can be used for filter membrane, catalyst carrier, radiation proof material, wound clad material, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material etc.
Equipment is identical with embodiment 1.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 10wt%, 3-methylene diacetate imidazole salts solution 10ml, wherein cellulose is that the degree of polymerization is 800 wood pulp cellulose, in above-mentioned solution, add the organic solvent dimethyl formamide, wherein the mass ratio of the quality/cellulose solution of dimethyl formamide is 2/1, stir, place syringe;
(2) adjust electrostatic spinning apparatus: select single spinning head apparatus for use, swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 15cm; The ambient temperature of spinning is 45 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 18KV, the delivery rate of solution is 60ul/min, drum rotation speed is 200r/min, the spinning head translational speed is 2m/min, cylinder rotates through dehydrated alcohol and bathes, carry out spinning, cellulose fibre film on the cylinder is soaked in the 20ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 20ml dehydrated alcohol in addition, in 20 degree vacuum dryings 1 day, obtaining cellulose nano-fibrous membrane material biodegradable and that absorb is the unidirectional array structure afterwards, and average fibre diameter is the 500nm (see figure 4);
(4) prepared fibrous membrane can be used for filter membrane, catalyst carrier, radiation proof material, wound clad material, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material etc.
Equipment is identical with embodiment 1, and gathering-device changes the swing roller of copper wire cross arrangement into.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 10wt%, 3-methyl chloride imidazole salts solution 5ml, wherein cellulose is that the degree of polymerization is 800 wood pulp cellulose, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, stir, place syringe;
(2) adjust electrostatic spinning apparatus: select single spinning head apparatus for use, swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 15cm; The ambient temperature of spinning is 25 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 22KV, the delivery rate of solution is 30ul/min, drum rotation speed is 300r/min, cylinder is immersed in the dehydrated alcohol bath and rotates, carry out spinning, cellulose fibre film on the cylinder is collected, be soaked in the 10ml dehydrated alcohol behind the 12h, divide the drip washing fibrous membrane 5 times with the 10ml dehydrated alcohol, in 20 degree vacuum dryings 1 day, obtain cellulose nano-fibrous membrane material biodegradable and that absorb and be the cross arrangement structure of curling, average fibre diameter is the 200nm (see figure 5);
(4) prepared fibrous membrane can be used for filter membrane, catalyst carrier, radiation proof material, wound clad material, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material etc.
Embodiment 4
See also Fig. 2.High voltage power supply 2 adopts the negative dc high voltage out-put supply, and the maximum voltage of output is 40kV, and high voltage power supply is wired to the ejection end of the spinning head 5 of syringe 1; The way of output of syringe pump 4 adopts the rear pump injector-actuated feed of multiple output frequency, and maximum output area is 300 mul/min, and syringe pump is connected to the spinning head material feeding end of syringe 1 by conduit; Spinning head material selection rustless steel, spinnerette diameters are 0.8mm; The parallel distribution of 1～5 row's spinning head, every row's spinning head quantity is 1～20, distance is 1～5cm between the adjacent spinning head; Gathering-device is the swing roller 3 that copper wire is arranged in parallel, and the diameter of cylinder 3 is 120mm, and the copper wire spacing is 7.5mm, and electrostatic spinning ambient temperature control device adopts the infrared lamp mode of heating, and system is PID control, and control accuracy is in ± 3 ℃ of scopes.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 5wt%, 3 methyl chloride imidazole salts solution 20ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, stirs; In addition, compound concentration is hyaluronic water/dimethyl formamide solution 20ml of 1.3wt%, and wherein hyaluronic acid is that molecular weight is 2,000,000 pharmaceutical grade hyaluronic acid, and the volume ratio of water/dimethyl formamide is 50: 150; To contain cellulosic solution and contain in two groups of syringes that hyaluronic macromolecular solution is respectively charged into electrospinning device;
(2) adjust electrostatic spinning apparatus: select the double-spinneret device for use, two spinning heads are adjacent, between distance be 2cm, swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 15cm; The ambient temperature of spinning is 45 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 20KV, and the delivery rate of solution is 50ul/min, and drum rotation speed is 100r/min, and roller shifting speed is 3m/min, carries out spinning.Fibrous membrane on the cylinder collected be soaked in the 40ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 40ml dehydrated alcohol in addition, spend vacuum dryings 1 day in 20 afterwards, obtaining cellulose and the compound nano-fiber composite film material of hyaluronic acid biodegradable and that absorb is the unidirectional array structure, and average fibre diameter is the 900nm (see figure 6);
(4) composite cellulosic membrane being immersed in molar concentration is in 50% the glutaraldehyde water solution (500ml), add mass concentration and be 1% aqueous hydrochloric acid solution 1ml and carry out cross-linking reaction, crosslinking time is 1h, temperature is 30 degree, take out with a large amount of deionized water rinsings the crosslinked back that finishes, 30 degree vacuum dryings 1 day.Prepared fibrous membrane can be used for post-operation adhesion preventing material, hemostatic material, the wound clad material, tissue engineering bracket material, drug releasing membrane according, artificial skin, artificial blood vessel, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), beauty treatment material etc.
Equipment is identical with embodiment 4.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 5wt%, 3-methyl chloride imidazole salts solution 50ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, in stirring; In addition, compound concentration is the acetone soln 50ml of the ethyl cellulose of 15wt%, wherein the molecular weight of ethyl cellulose is 200,000, and the macromolecular solution that will contain the high molecular solution of cellulose and contain ethyl cellulose is respectively charged in two groups of syringes of electrospinning device;
(2) adjust electrostatic spinning apparatus: select four spinning head apparatus for use, be divided into two rows, two spinning heads of every row, distance is 2cm between adjacent two spinning heads, first row's spinning head connects cellulose solution, and second row's spinning head connects ethyl cellulose solution, and swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 18cm; The ambient temperature of spinning is 45 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 25KV, the delivery rate of solution is 10ul/min, drum rotation speed is 300r/min, roller shifting speed is 5m/min, carry out spinning, fibrous membrane on the cylinder collected be soaked in the 40ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 40ml dehydrated alcohol in addition, spend vacuum dryings 1 day in 20 afterwards, obtaining cellulose and the compound nano-fiber composite film material of ethyl cellulose biodegradable and that absorb is the lack of alignment structure, and average fibre diameter is 50nm;
(4) prepared composite cellulosic membrane can be used for wound dressing, drug conveying, post-operation adhesion preventing material, hemostatic material, the wound clad material, tissue engineering bracket material, drug releasing membrane according, artificial skin, artificial blood vessel, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), beauty treatment material etc.
Embodiment 6
Equipment is identical with embodiment 4.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 5wt%, 3-methyl chloride imidazole salts solution 50ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, stirs; In addition, compound concentration is the water/alcoholic solution 50ml of gelatin/sodium alginate of 15wt%, and wherein the molecular weight of gelatin is 80,000, and the molecular weight of sodium alginate is 50,000, and gelatin/sodium alginate weight is divided into 100/20, and water/alcoholic acid volume ratio is 90: 10; The macromolecular solution that will contain the high molecular solution of cellulose and contain gelatin/sodium alginate is respectively charged in two groups of syringes of electrospinning device;
(2) adjust electrostatic spinning apparatus: select six spinning head apparatus for use, be divided into two rows, three spinning heads of every row, distance is 3cm between the adjacent spinning head, and every row's odd number spinning head connects cellulose solution, and the even numbers spinning head connects gelatin solution, and swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 10cm; The ambient temperature of spinning is 60 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 17KV, the delivery rate of solution is 50ul/min, drum rotation speed is 300r/min, the spinning head translational speed is 3m/min, carry out spinning, fibrous membrane on the cylinder collected be soaked in the 100ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 100ml dehydrated alcohol in addition, spend vacuum dryings 1 day in 20 afterwards, obtaining cellulose and the compound nano-fiber composite film material of gelatin/sodium alginate biodegradable and that absorb is the lack of alignment structure, and average diameter is 1000nm;
(4) composite cellulosic membrane being immersed in molar concentration is to carry out cross-linking reaction in the 50mmol/L carbodiimide alcoholic solution (100ml), and crosslinking time is 24 hours, and temperature is 30 degree, and take out with a large amount of deionized water rinsings the crosslinked back that finishes, 30 degree vacuum dryings 1 day.The composite cellulosic membrane of preparation can be used for hemostatic material, the wound clad material, tissue engineering bracket material, drug releasing membrane according, artificial skin, artificial blood vessel, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material etc.Composite fiber membrane material has sodium alginate and good biocompatibility and the haemostatic effect of gelatin simultaneously, possesses the characteristics of the high-specific surface area of general electrospinning squeeze again; Cellulose degradation time in human body is long simultaneously; and has certain corrosion-resistant effect; make the hemostasis of composite and the ability of absorption wound transudate further strengthen; be expected to make a kind of have certain adhesiveness and high oxygen permeability; simultaneously antibacterial there are barrier action and cheap novel wound clad material; be specially adapted to burn; the nursing of wound surface such as wound; can alleviate patient's misery; reducing cicatrix and wound shrinks; accelerate healing rate, especially the patient to extensive wound is protecting wound; protect from infection; aspects such as quickening blood coagulation have good effect.
Embodiment 7
Equipment is identical with embodiment 4.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 5wt%, 3-methyl chloride imidazole salts solution 100ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, stirs; In addition, compound concentration is the dimethyl formamide solution 100ml of the polylactic acid of 20wt%, and wherein the molecular weight of polylactic acid is 500,000; The macromolecular solution that will contain the high molecular solution of cellulose and contain polylactic acid is respectively charged in two groups of syringes of electrospinning device;
(2) adjust electrostatic spinning apparatus: select 20 spinning head apparatus for use, be divided into two rows, ten spinning heads of every row, distance is 1cm between the adjacent spinning head, and first row's spinning head connects cellulose solution, and second row's spinning head connects polylactic acid solution, and swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 15cm; The ambient temperature of spinning is 45 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 22KV, the delivery rate of solution is 60ul/min, drum rotation speed is 300r/min, roller shifting speed is 3m/min, carry out spinning, fibrous membrane on the cylinder collected be soaked in the 200ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 200ml dehydrated alcohol in addition, spend vacuum dryings 1 day in 20 afterwards, obtaining cellulose and the compound nano-fiber composite film material of polylactic acid biodegradable and that absorb is the unidirectional array structure, and average fibre diameter is 800nm;
(4) prepared composite cellulosic membrane can be used for filter membrane, catalyst carrier, radiation proof material, wound clad material, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material, antibacterial material etc.
Embodiment 8
Equipment is identical with embodiment 1.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 5wt%, 3-methyl chloride imidazole salts solution 10ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, and add the amorphous active carbon of 1mg, and stir, place syringe;
(2) adjust electrostatic spinning apparatus: select single spinning head apparatus for use, swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 8cm; The ambient temperature of spinning is 25 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 15KV, the delivery rate of solution is 150ul/min, drum rotation speed is 100r/min, carry out spinning, fibrous membrane on the cylinder collected be soaked in the 20ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 20ml dehydrated alcohol in addition, spend vacuum dryings 1 day in 20 afterwards, obtaining the cellulose nano-fibrous membrane material that contains amorphous active carbon biodegradable and that absorb is the unidirectional array structure, and average fibre diameter is 2500nm;
(4) prepared fibrous membrane can be used for filter membrane, catalyst carrier, radiation proof material, wound clad material, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material, antibacterial material etc.
Embodiment 9
Equipment is identical with embodiment 4.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 5wt%, 3 methyl chloride imidazole salts solution 100ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, stirs; In addition, compound concentration is the water/alcoholic solution 50ml of the methyl starch of 15wt%, and wherein the molecular weight of starch is 100,000, and water/alcoholic acid volume ratio is 80: 20, adds norfloxacin 1 gram in macromolecular solution, stirs; The macromolecular solution that will contain the high molecular solution of cellulose and contain methyl starch is respectively charged in two groups of syringes of electrospinning device;
(2) adjust electrostatic spinning apparatus: select 12 spinning head apparatus for use, be divided into three rows, four spinning heads of every row, distance between the adjacent spinning head is 2cm, single odd number, double even numbers spinning head connect cellulose solution, single even numbers, double odd number spinning head connect methyl starch solution, and swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 15cm; The ambient temperature of spinning is 45 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 22KV, the delivery rate of solution is 60ul/min, drum rotation speed is 300r/min, carry out spinning, fibrous membrane on the cylinder collected be soaked in the 100ml dehydrated alcohol behind the 24h, divide the drip washing fibrous membrane 5 times with the 100ml dehydrated alcohol in addition, spend vacuum dryings 1 day in 20 afterwards, obtaining cellulose that contains norfloxacin and the compound nano-fiber composite film material of methyl starch biodegradable and that absorb is the lack of alignment structure, and average fibre diameter is the 800nm (see figure 7);
(4) composite cellulosic membrane being immersed in molar concentration is to carry out cross-linking reaction in the 50mmol/L carbodiimide alcoholic solution (500ml), and crosslinking time is 24 hours, and temperature is 30 degree, and take out with a large amount of deionized water rinsings the crosslinked back that finishes, 30 degree vacuum dryings 1 day.The composite cellulosic membrane of preparation can be used for hemostatic material, the wound clad material, tissue engineering bracket material, drug releasing membrane according, artificial skin, artificial blood vessel, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material etc.
Embodiment 10
Equipment is identical with embodiment 4.
(1) preparation of solution: compound concentration is the cellulosic ionic liquid 1-pi-allyl of 5wt%, 3-methyl chloride imidazole salts solution 10ml, wherein cellulose is that the degree of polymerization is 1500 medical absorbent cotton, in above-mentioned solution, add the organic solvent dimethyl sulfoxide, wherein the mass ratio of the quality/cellulose solution of dimethyl sulfoxide is 2/1, stirs; In addition, compound concentration is the aqueous solution 20ml of the polyvinyl alcohol of 5wt%, and wherein the molecular weight of polyvinyl alcohol is 200,000, adds sulfadiazine 200mg in macromolecular solution, and adds dalcium biphosphate 5mg, stirs; The macromolecular solution that will contain the high molecular solution of cellulose and contain polyvinyl alcohol is respectively charged in two groups of syringes of electrospinning device;
(2) adjust electrostatic spinning apparatus: select the double-spinneret device for use, spinning head is adjacent, between distance be 3cm, swing roller is as catcher; The distance of regulating between spinning head and the gathering-device is 15cm; The ambient temperature of spinning is 45 degree, and the air velocity in the environment is controlled at 0.5～0.8m
3/ hr;
(3) spinning technology parameter is set: open high voltage power supply, regulation voltage is to 17KV, the delivery rate of solution is 30ul/min, drum rotation speed is 300r/min, roller shifting speed is 2m/min, carry out spinning, obtaining cellulose that contains sulfadiazine and dalcium biphosphate and the compound nanofiber compound bio of polyvinyl alcohol high polymer nanometer fiber membrane material biodegradable and that absorb is the lack of alignment structure, and average fibre diameter is 500nm;
(4) composite cellulosic membrane being immersed in molar concentration is in 50% glutaraldehyde water solution (100ml), add mass concentration and be 1% aqueous hydrochloric acid solution 1ml and carry out cross-linking reaction, crosslinking time is 1h, and temperature is 30 degree, take out with a large amount of deionized water rinsings the crosslinked back that finishes, 30 degree vacuum dryings 1 day.The composite cellulosic membrane of preparation can be used for hemostatic material, the wound clad material, tissue engineering bracket material, drug releasing membrane according, artificial skin, artificial blood vessel, wound dressing, drug conveying, biomembrane (substrate of immobilized enzyme and catalyst system and catalyzing), post-operation adhesion preventing material, beauty treatment material etc.
Claims (10)
1. biodegradable and absorb biopolymer micro/nano fibrous membrane material, it is characterized in that: described biopolymer micro/nano fibrous membrane material is to be benchmark with the cellulose, the composition of this material consists of 0＜cellulose≤100 weight portions, 0≤other biopolymer＜100 weight portions, curative drug 0～10 weight portion or organic catalyst 0～50 weight portion and/or inorganic strengthening agent 0～50 weight portion; The fibre diameter of described cellulose or other biopolymer is at 50nm～5000nm.
2. biopolymer micro/nano fibrous membrane material according to claim 1 is characterized in that: but the described biodegradable fiber that reaches the biopolymer micro/nano fibrous membrane material of bio-absorbable is lack of alignment structure, unidirectional array structure, cross arrangement structure, curl disordered structure, the unidirectional array structure of curling or curling cross arrangement structure.
3. biopolymer micro/nano fibrous membrane material according to claim 1 and 2 is characterized in that: described cellulose is a medical absorbent cotton, and the degree of polymerization is in 1000～1500 scopes, or the non-solubility wood pulp cellulose, and the degree of polymerization is in 500～800 scopes.
4. biopolymer micro/nano fibrous membrane material according to claim 1 and 2 is characterized in that: the molecular weight of described other macromolecular material is 5～2,000,000; Be selected from: hyaluronic acid, gelatin, alginate, fibroin, chitosan, chondroitin sulfate, heparin, collagen protein, nucleic acid, cellulose protein, fibronectin in serum, polypeptide, agar, the blend of one or more in glucosan or the above-mentioned high molecular derivant; Or
Be selected from: the poly butyric valerate, the poly butyric alkyl caproate, polycaprolactone, poly-Acetic acid, hydroxy-, bimol. cyclic ester, polylactide, polylactic acid, the copolymer of polylactic acid and caprolactone or Acetic acid, hydroxy-, bimol. cyclic ester, poly-to two evil ketone, polyurethane, poly phosphate, the blend of one or more in the polyoxyethylene, and two or more the copolymer in the lactide, Acetic acid, hydroxy-, bimol. cyclic ester, butyrolactone, valerolactone, caprolactone, oxirane, expoxy propane; Or
Be selected from: polyvinylpyrrolidone or polyvinyl alcohol; Or
Be selected from: methylcellulose, ethyl cellulose, noncrystalline cellulose, hydroxy methocel, hydroxyethyl-cellulose, hydroxypropyl cellulose, the blend of one or more in the hydroxypropyl emthylcellulose; Or
Be selected from: the blend of one or more in starch, ethyl starch, the methyl starch.
5. biopolymer micro/nano fibrous membrane material according to claim 1 and 2 is characterized in that: described curative drug is selected from: AgCl, TiO
2Nanometer silver, sulfadiazine, SMZ-SD-TMP, norfloxacin, ciprofloxacin, ofloxacin, calcitonin, insulin, nerve growth factor, ganglioside, hydrocortisone, the control growing factor, drive insect medicine, anticoagulation class medicine, mycobacteria, the antibiotic medicine, antibiotic, antiviral agents, anti-infective, antineoplastic agent, lonizing radiation class medicine, immunity class preparation, analgesic, antiallergic agent, anthelmintic, diuresis class preparation, muscle relaxant, gonadal hormone, antidepressants, antuepileptic, antihypertensive, anti-arrhythmic, antidiabetic drug, antithyroid drug, cough medicine, the steroid preparation, contrast agent, astringent, the blend of one or more in the resistance prostatitis class preparation medicine; Or be selected from from medical herbs, Tibetan medicine, mongolian medicine, Miao Ethnomedicine or other Chinese herbal medicine extract one or more the treatment various diseases effective ingredient.
6. biopolymer micro/nano fibrous membrane material according to claim 1 and 2 is characterized in that: described inorganic strengthening agent is hydroxyapatite, beta-calcium phosphate, potassium titanate crystal whisker, Neutral potassium chromate, calcium carbonate, calcium hydrogen phosphate or dalcium biphosphate; Described catalyst is TiO
2, active carbon, Pt, Rh, Pd or metallocene catalyst.
7. the preparation method according to each described biopolymer micro/nano fibrous membrane material of claim 1～6 is characterized in that, this method is carried out according to the following steps:
(1). the preparation of cellulose electrostatic spinning stock solution: cellulose dissolution is obtained the cellulose solution of homogeneous transparent in ionic liquid, wherein the concentration of cellulose solution is 1wt%～15wt%; Add organic solvent afterwards in above-mentioned solution, the quality and the cellulose solution mass ratio that add organic solvent are 1: 1～8: 1; With the cellulose is benchmark, adds curative drug 0～10 weight portion or organic catalyst 0～50 weight portion and/or inorganic strengthening agent 0～50 weight portion therein;
The concentration of preparing other macromolecular solution with inorganic solvent and/or organic solvent is 0.5wt%～50wt%, with the cellulose is benchmark, adds curative drug 0～10 weight portion or organic catalyst 0～50 weight portion and/or inorganic strengthening agent 0～50 weight portion therein;
(2). electrostatic spinning process is: to be respectively charged into temperature be that the feeding rate of solution is 5～300ul/min in 20～80 ℃ the charging gear of electrospinning device for contain cellulosic solution and other macromolecular solution that step (1) is obtained; Distance between the spinning head of charging gear and the catcher of ground connection is 5～25cm; Ambient temperature is 20～70 ℃; The air velocity of environment is 0～8.5m
3/ hr; Open high voltage power supply, open the charging gear pump that contains cellulose solution is housed, injection stream is ejected on the catcher, but obtains the cellulose high molecular nanometer membrane material of biodegradable and bio-absorbable; Or open the charging gear pump that cellulose solution and other macromolecular solution are housed simultaneously, but obtain the composite nano-fiber membrane material of the fiber rope base of biodegradable and bio-absorbable; Wherein the temperature range of catcher is 30～80 ℃; The translational speed of catcher is 0～10m/nin, and the translational speed of spinning head is 0～5m/min;
(3). the high polymer nanometer fiber membrane material that step (2) is prepared soaks to remove residual solvent in dehydrated alcohol, and with dehydrated alcohol repeatedly the drip washing fibrous membrane washed away fully until remaining spin solvent, with fibrous membrane vacuum drying in vacuum drying oven, obtain biopolymer micro/nano fibrous membrane material biodegradable and that absorb.
8. method according to claim 7, it is characterized in that: the biopolymer micro/nano fibrous membrane material biodegradable and that absorb that will obtain places the mixed solution of ethanol/water, the cross-linking agent that adds metering carries out crosslinked, wash away fully with the cross-linking agent of a large amount of deionized water wash then until remnants, vacuum drying in vacuum drying oven then, the biopolymer micro/nano fibrous membrane material that obtains the biodegradable of the different degrees of cross linking and absorb; But the weight and the volume ratio of the mixed solution of wherein biodegradable and bio-absorbable macromolecular fibre membrane material and ethanol/water are 1: 20～2000g/ml, the volume ratio of ethanol and water is 80～100: 0～20, and cross-linking agent concentration in mixed solution is 1～200mmol/L;
Described cross-linking agent is selected from carbodiimide, glutaraldehyde, formaldehyde, a kind of in diepoxides or the divinylsulfone.
9. method according to claim 7, it is characterized in that: described ionic liquid is the 1-ethyl, 3-methylene diacetate imidazole salts ionic liquid, the 1-ethyl, 3-methyl chloride imidazole salts ionic liquid, the 1-ethyl, 3-methyl bromide imidazole salts ionic liquid, the 1-pi-allyl, 3-methyl chloride imidazole salts ionic liquid, the 1-pi-allyl, 3-methyl bromide imidazole salts ionic liquid, the 1-pi-allyl, 3-methyl thiocyanate imidazole salts ionic liquid, the 1-pi-allyl, 3-methylene diacetate imidazole salts ionic liquid, the 1-butyl, 3-methylene diacetate imidazole salts ionic liquid, the 1-butyl, 3-methyl chloride imidazole salts ionic liquid or 1-butyl, 3-methyl bromide imidazole salts ionic liquid;
Described organic solvent is sulfone, sulfoxide, dimethyl formamide or dimethyl acetylamide.
10. purposes according to each described biopolymer micro/nano fibrous membrane material of claim 1～6, it is characterized in that: described biopolymer micro/nano fibrous membrane material biodegradable and that absorb is used for catalyst carrier, filter membrane, radiation proof material, or as medical tissue engineering scaffold material, drug releasing membrane according, artificial skin, artificial blood vessel, wound dressing, drug conveying, biomembrane, wound coated material, hemostatic material, wound clad material, post-operation adhesion preventing material or beauty treatment material.
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-
2006
- 2006-11-03 CN CNA2006101143120A patent/CN101172164A/en active Pending
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