CN103437071A - Electrostatic spinning nanofiber membrane as well as preparation method thereof - Google Patents
Electrostatic spinning nanofiber membrane as well as preparation method thereof Download PDFInfo
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Abstract
The invention provides an electrostatic spinning nanofiber membrane as well as a preparation method thereof. The electrostatic spinning nanofiber membrane provided by the invention comprises a fiber membrane obtained by electrostatically spinning a high-melting-point polymer and a fiber membrane obtained by electrostatically spinning a low-melting-point polymer, wherein the difference on the melting points of the high-melting-point polymer and the low-melting-point polymer is not less than 10 DEG C. The electrostatic spinning nanofiber membrane provided by the invention is multipurpose and can be applied to the fields such as biomedicines, energy and chemical industry, gas and liquid filtration, waterproofness and windproofness, windproofness and heat insulation, moisture permeability and ventilation, environmental management and semiconductor sensors. According to the electrostatic spinning nanofiber membrane provided by the invention, electrostatic spinning is respectively carried out on the high-melting-point polymer and the low-melting-point polymer, and the high-melting-point polymer fiber membrane and the low-melting-point polymer fiber membrane obtained are composited and hot-pressed to obtain the electrostatic spinning nanofiber membrane. The preparation method provided by the invention is high in production efficiency and low in energy consumption, and is suitable for industrial production.
Description
Technical field
The present invention relates to the Static Spinning technical field, relate in particular to a kind of applicable electrostatic spinning nano fiber film and preparation method thereof.
Background technology
Along with developing rapidly of industry, people have higher requirement for living environment, life comfort level, and environmental pollution, the energy reduce and become day by day serious problem, and meanwhile people's life production is also very high for the requirement of air, liquid.At present, prior art is accelerated research for environmental improvement, new forms of energy development, semi-conductor industry and biomedical development.
In order to meet the demand, such as: aspect the gas liquid filtration, many macromolecular materials are for making filter membrane material, be no lack of polytetrafluoroethylene (PTFE) arranged, polyphenylene sulfide, polyester fiber, acetate fiber etc. be all current business-like product, yet current these production complex process, porosity are low.And along with people to entering the raising of lung particle (PM2.5) attention rate, people have higher requirement for air-filtering membrane, and the made air filter bag of these common polymeric membranes sold does not in the market reach the requirement of people for air purity;
Aspect new forms of energy, the lithium ion battery separator material of selling in the market remains take the polyethylene, microporous polypropylene membrane of unidirectional or biaxial tension as main.It is upper that this series membranes mainly is used in small-sized lithium ion battery (as: mobile digital machinery equipment battery), the application on the lithium ion battery that is not suitable for using as new-energy automobile.Reason is described as Chinese invention patent CN102629679, the vehicle lithium ion battery has higher requirement for barrier film, stronger absorbent, high, the uniform porosity of heat endurance, uniform film thickness are arranged, higher mechanical strength etc., the disclosed above-mentioned membrane material of prior art can not meet the requirement of vehicle lithium ion battery for barrier film;
For another example, the whole world increases year by year to the demand of waterproof moisture permeating fabric, and the market demand is huge, and mainstream technology in the market is the ePTFE(expanded ptfe of U.S. Gore-Tex) laminar composite of microporous barrier and fabric.The lamination composite water-proof moisture permeable fabrics that the ePTFE perforated membrane of take is representative can, waterproof, warming, ventilative, saturating wet combining, can be realized ventilating fabric property truly.The United States Patent (USP) that is US4194041 as publication number discloses a kind of watertight composition rolled-up stock, comprises hydrophobicity skin and hydrophilic internal layer with microcellular structure; The Chinese patent that publication number is CN202005282U all discloses a kind of waterproof moisture-permeable composite fabric, comprises fabric skin, outer Waterproof Breathable layer, eyelet fabric, inner waterproofing soak layer and fabric internal layer.Although the waterproof moisture permeating fabric that the disclosed this PTFE perforated membrane of prior art is representative has waterproofing and moisture-penetration performances preferably, but need special unidirectional or biaxial tension equipment by its preparation, complex process, the product difficulty of processing is large, cost is high, percent defective is high, valuable product, has limited to a great extent it and has applied.
In prior art, do not have a fibrid film can meet the demand of multiple industry.
Summary of the invention
The object of the present invention is to provide a kind of electrostatic spinning nano fiber film and preparation method thereof, electrostatic spinning nano fiber film provided by the invention can meet the demand of multiple industry, and preparation method's production efficiency of electrostatic spinning nano fiber film is high.
The invention provides a kind of electrostatic spinning nano fiber film, comprise the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain;
The fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.
Preferably, described high-melting-point polymer and low melting point polymer are selected from polystyrene (PS), polysulfones (PSF), polyether sulfone (PES), Kynoar (PVDF), Kynoar-perfluoropropene (PVDF-HFP), Kynoar-CTFE (PVDF-CTFE), polyacrylonitrile (PAN), polyamide (PA), polyvinylcarbazole, acetyl cellulose (CA), cellulose family, shitosan (PAA), polyaniline, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polytrimethylene terephthalate (PTT), polyimides (PI), polyurethane (PU), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) Merlon (PC) polymine (PEI), , one or more in polyether-ether-ketone (PEEK), aliphatic amide, polyvinyl acetate (PVAc), polyformaldehyde (POM), polyvinyl chloride (PVC), nylon-6 (PA-6), nylon-66 (PA-66), poly-trifluoro-ethylene, polytrifluorochloroethylene, polyvinyl fluoride, PLA, poly(ethylene oxide) and polyvinylpyrrolidone.
Preferably, the thickness of electrostatic spinning nano fiber film is 2.0 μ m～5.0mm.
Preferably, the pore diameter of electrostatic spinning nano fiber film is 10nm～5000nm.
Preferably, in the electrostatic spinning nano fiber film, the diameter of fiber is 5nm～2000nm.
The invention provides a kind of preparation method of electrostatic spinning nano fiber film, comprise the following steps:
High-melting-point polymer is dissolved in the first spin solvent, obtains the high-melting-point polymer spinning solution;
Low melting point polymer is dissolved in the second spin solvent, obtains the low melting point polymer spinning solution, the fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃;
Described high-melting-point polymer spinning solution is carried out to the first electrostatic spinning, obtain the high-melting-point polymer tunica fibrosa;
Described low melting point polymer spinning solution is carried out to the second electrostatic spinning, obtain the low melting point polymer tunica fibrosa;
By described high-melting fibre film and the compound rear hot pressing of low-melting fiber film, obtain the electrostatic spinning nano fiber film, the temperature of described hot pressing is more than or equal to the fusing point of described low melting point polymer, and is less than the fusing point of high-melting-point polymer.
Preferably, described the first spin solvent and the second spin solvent independently are selected from water, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, hexafluoroisopropanol, trifluoroethanol, phenol, formic acid, acetic acid, trifluoroacetic acid, carrene, dichloroethanes, chloroform, acetone, N, one or more in dinethylformamide (DMF), DMA (DMAC), oxolane (THF), pyridine, toluene, cyclohexane, 1-METHYLPYRROLIDONE and carbon disulfide.
Preferably, also comprise inorganic nano-particle in described high-melting-point polymer spinning solution;
Also comprise inorganic nano-particle in described low melting point polymer spinning solution.
Preferably, the mass fraction of described high-melting-point polymer spinning solution is 3%～50%;
The mass fraction of described low melting point polymer spinning solution is 3%～50%.
Preferably, the voltage of described the first electrostatic spinning is 10kV～150kV, the humidity of described the first electrostatic spinning environment is 0%～60%, the pressure of described the first electrostatic spinning environment is 0.01MPa～0.5MPa, the temperature of described the first electrostatic spinning environment is 0 ℃～60 ℃, the receiving range of described the first electrostatic spinning is 5cm～50cm, and hello the liquid speed that forms a stable taylor cone in described the first electrostatic spinning is 0.05mL/h～20mL/h;
The voltage of described the second electrostatic spinning is 10kV～150kV, the humidity of described the second electrostatic spinning environment is 0%～60%, the pressure of described the second electrostatic spinning environment is 0.01MPa～0.5MPa, the temperature of described the second electrostatic spinning environment is 0 ℃～60 ℃, the receiving range of described the second electrostatic spinning is 5cm～50cm, and hello the liquid speed that forms a stable taylor cone in described the second electrostatic spinning is 0.05mL/h～20mL/h.
Preferably, the temperature of described hot pressing is 80 ℃～450 ℃;
The pressure of described hot pressing is 0.1MPa～10MPa;
The time of described hot pressing is 0.01h～1h.
The invention provides a kind of electrostatic spinning nano fiber film and preparation method thereof, electrostatic spinning nano fiber film provided by the invention comprises the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain; The fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.Electrostatic spinning nano fiber film provided by the invention serves many purposes, and can be used for the fields such as biomedicine, derived energy chemical, gas liquid filtration, water proof wind proof, wind-proof warming, moisture-penetrable ventilated, environmental improvement, semiconductor transducer.Experimental result shows, electrostatic spinning nano fiber film provided by the invention can be used as lithium ion battery separator, can also be used as air filting material, also can be used for preparing the Waterproof Breathable breathable fabric.
Method provided by the invention is carried out respectively electrostatic spinning by high-melting-point polymer and low melting point polymerization, and high-melting-point polymer tunica fibrosa and the compound rear hot pressing of low melting point polymer tunica fibrosa by obtaining, obtain the electrostatic spinning nano fiber film.Preparation method's production efficiency provided by the invention is high, energy consumption is low, is applicable to suitability for industrialized production.
The accompanying drawing explanation
Fig. 1 is the electrospinning device structural representation that the embodiment of the present invention adopts;
Fig. 2 is the spinning receiving equipment structural representation that the embodiment of the present invention adopts;
The SEM figure that Fig. 3 is the electrostatic spinning nano fiber film that obtains of the embodiment of the present invention 1;
Fig. 4 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 1 obtains;
The SEM figure that Fig. 5 is the electrostatic spinning nano fiber film that obtains of the embodiment of the present invention 2;
Fig. 6 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 2 obtains;
The SEM figure that Fig. 7 is the electrostatic spinning nano fiber film that obtains of the embodiment of the present invention 3;
Fig. 8 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 3 obtains;
The SEM figure that Fig. 9 is the electrostatic spinning nano fiber film that obtains of the embodiment of the present invention 4;
Figure 10 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 4 obtains.
The specific embodiment
The invention provides a kind of preparation method of electrostatic spinning nano fiber film of gaining in strength, comprise the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain;
The fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.
Electrostatic spinning nano fiber film provided by the invention can meet multiple industry requirement, is applicable to battery and electrode material, filtration, infiltration, biomedicine, clothes, shoes and hats, photoelectric material, sensor field.Especially aspect the thermal insulating and water-proof air-moisture-permeable, electrostatic spinning nano fiber film provided by the invention can meet the growth to comfortableness, functional clothing needs of outdoor sports apparel, fire-entry suit, special working suit and military clothes, can also meet the needs of shoes and hats gloves, tent, raincoat, warming wall.
Electrostatic spinning nano fiber film provided by the invention, comprise the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain.Those skilled in the art can select suitable polymer according to the applied technical field of required tunica fibrosa, and the present invention does not have special restriction to the kind of polymer, meet that the fusing point of low melting point polymer and high-melting-point polymer is poor to be not less than 10 ℃ and to get final product.In the present invention, described high-melting-point polymer and low melting point polymer are preferably selected from polystyrene (PS), polysulfones (PSF), polyether sulfone (PES), Kynoar (PVDF), Kynoar-perfluoropropene (PVDF-HFP), Kynoar-CTFE (PVDF-CTFE), polyacrylonitrile (PAN), polyamide (PA), polyvinylcarbazole, acetyl cellulose (CA), cellulose family, shitosan (PAA), polyaniline, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polytrimethylene terephthalate (PTT), polyimides (PI), polyurethane (PU), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) Merlon (PC) polymine (PEI), , one or more in polyether-ether-ketone (PEEK), aliphatic amide, polyvinyl acetate (PVAc), polyformaldehyde (POM), polyvinyl chloride (PVC), nylon-6 (PA-6), nylon-66 (PA-66), poly-trifluoro-ethylene, polytrifluorochloroethylene, polyvinyl fluoride, PLA, poly(ethylene oxide) and polyvinylpyrrolidone, more preferably be selected from one or more in PVDF, PVDF-HFP, PVDF-CTFE, PA-66, PET, PBT and PES.
In the present invention, the fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃, preferably is not less than 15 ℃, more preferably is not less than 20 ℃.
In the present invention, the tunica fibrosa that described high-melting-point polymer Static Spinning obtains can be one deck, it can be also multilayer, the present invention does not have special restriction to this, those skilled in the art can be according to the technical field difference of electrostatic spinning nano fiber film application, the number of plies of the tunica fibrosa of selecting suitable high-melting-point polymer Static Spinning to obtain.The tunica fibrosa that described low melting point polymer Static Spinning obtains can be one deck, it can be also multilayer, the present invention does not have special restriction to this, those skilled in the art can be according to the technical field difference of electrostatic spinning nano fiber film application, the number of plies of the nano fibrous membrane of selecting suitable low melting point polymer Static Spinning to obtain.The thickness of electrostatic spinning nano fiber film provided by the invention is preferably 2.0 μ m～5.0mm, and more preferably 3.0 μ m～4.5mm, most preferably be 5.0 μ m～4mm.The pore diameter of electrostatic spinning nano fiber film provided by the invention is preferably 10nm～5000nm, and more preferably 20nm～4900nm, most preferably be 50nm～4800nm, the most is preferably 100nm～4500nm.In electrostatic spinning nano fiber film provided by the invention, the diameter of nanofiber is preferably 5nm～2000nm, and more preferably 10nm～1900nm, most preferably be 30nm～1800nm, the most is preferably 100nm～1000nm.
The invention provides a kind of preparation method of electrostatic spinning nano fiber film, comprise the following steps:
High-melting-point polymer is dissolved in the first spin solvent, obtains the high-melting-point polymer spinning solution;
Low melting point polymer is dissolved in the second spin solvent, obtains the low melting point polymer spinning solution, the fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃;
Described high-melting-point polymer spinning solution is carried out to the first electrostatic spinning, obtain the high-melting-point polymer tunica fibrosa;
Described low melting point polymer spinning solution is carried out to the second electrostatic spinning, obtain the low melting point polymer tunica fibrosa;
By described high-melting fibre film and the compound rear hot pressing of low-melting fiber film, obtain the electrostatic spinning nano fiber film, the temperature of described hot pressing is more than or equal to the fusing point of described low melting point polymer, and is less than the fusing point of high-melting-point polymer.
The present invention carries out respectively electrostatic spinning by low melting point polymer and high-melting-point polymer, then, by the high-melting-point polymer tunica fibrosa and the compound rear hot pressing of low melting point polymer tunica fibrosa that obtain, obtains the electrostatic spinning nano fiber film.Method technique provided by the invention is simple, production efficiency is high, energy consumption is low, is suitable for suitability for industrialized production.
The present invention, by high-melting-point polymer solution the first spin solvent, obtains the high-melting-point polymer spinning solution.The present invention does not have special restriction to the kind of described the first spin solvent, and those skilled in the art can select the first suitable spin solvent according to the kind of high-melting-point polymer, and in the present invention, described the first spin solvent is preferably water, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, hexafluoroisopropanol, trifluoroethanol, phenol, formic acid, acetic acid, trifluoroacetic acid, carrene, dichloroethanes, chloroform, acetone, DMF (DMF), DMA (DMAC), oxolane (THF), pyridine, toluene, cyclohexane, one or more in 1-METHYLPYRROLIDONE and carbon disulfide, more preferably trifluoroacetic acid, carrene, DMF, trifluoroethanol, formic acid, isopropyl alcohol, dichloroethanes, DMA, oxolane, 1-METHYLPYRROLIDONE, a kind of and several in acetone and acetic acid, most preferably be trifluoroacetic acid, carrene, DMF, a kind of and several in acetone and acetic acid.
In the present invention, preferably also comprise inorganic nano-particle in described high-melting-point polymer spinning solution, the present invention is preferably dissolved high-melting-point polymer and inorganic nano-particle in the first spin solvent, obtains the high-melting-point polymer spinning solution.In the present invention, described inorganic nano-particle preferably includes titanium dioxide, silica, tin ash, zinc oxide, di-iron trioxide, lithium chloride, cupric oxide, indium sesquioxide, molybdenum trioxide, tungstic acid, zinc sulphide, silver sulfide, cadmium sulfide, material with carbon element, gold, silver, one or more in copper and inorganic macromolecule material, titanium dioxide more preferably, silica, tin ash, zinc oxide, di-iron trioxide, lithium chloride, cupric oxide, indium sesquioxide, molybdenum trioxide, tungstic acid, zinc sulphide, silver sulfide, cadmium sulfide, CNT, Graphene, gold, silver, one or more in copper and inorganic macromolecule material.The present invention does not have special restriction to source and the addition of described inorganic nano-particle, adopts in above-mentioned inorganic nano-particle well known to those skilled in the art and electrostatic spinning process inorganic nano-particle addition commonly used in spinning solution to get final product.
In the present invention, in described high-melting-point polymer spinning solution, the mass fraction of high-melting-point polymer is preferably 3%～50%, and more preferably 4%～45%, most preferably be 5%～40%, the most be preferably 5%～35%.
The present invention is dissolved in low melting point polymer in the second spin solvent, obtains the low melting point polymer spinning solution, and the fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.The present invention does not have special restriction to the kind of described the second spin solvent, and those skilled in the art can select the second suitable spin solvent according to the kind of low melting point polymer, and in the present invention, described the second spin solvent is preferably water, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, hexafluoroisopropanol, trifluoroethanol, phenol, formic acid, acetic acid, trifluoroacetic acid, carrene, dichloroethanes, chloroform, acetone, DMF (DMF), DMA (DMAC), oxolane (THF), pyridine, toluene, cyclohexane, one or more in 1-METHYLPYRROLIDONE and carbon disulfide, more preferably trifluoroacetic acid, carrene, DMF, trifluoroethanol, formic acid, isopropyl alcohol, dichloroethanes, DMA, oxolane, 1-METHYLPYRROLIDONE, a kind of and several in acetone and acetic acid, most preferably be trifluoroacetic acid, carrene, DMF, a kind of and several in acetone and acetic acid.
In the present invention, preferably also comprise inorganic nano-particle in described low melting point polymer spinning solution, the present invention is preferably dissolved low melting point polymer and inorganic nano-particle in the second spin solvent, obtains the low melting point polymer spinning solution.In the present invention, described inorganic nano-particle preferably includes titanium dioxide, silica, tin ash, zinc oxide, di-iron trioxide, lithium chloride, cupric oxide, indium sesquioxide, molybdenum trioxide, tungstic acid, zinc sulphide, silver sulfide, cadmium sulfide, material with carbon element, gold, silver, one or more in copper and inorganic macromolecule material, titanium dioxide more preferably, silica, tin ash, zinc oxide, di-iron trioxide, lithium chloride, cupric oxide, indium sesquioxide, molybdenum trioxide, tungstic acid, zinc sulphide, silver sulfide, cadmium sulfide, CNT, Graphene, gold, silver, one or more in copper and inorganic macromolecule material.The present invention does not have special restriction to source and the addition of described inorganic nano-particle, adopts in above-mentioned inorganic nano-particle well known to those skilled in the art and electrostatic spinning process inorganic nano-particle addition commonly used in spinning solution to get final product.
In the present invention, the fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃, preferably is not less than 15 ℃, more preferably is not less than 20 ℃.Those skilled in the art can select suitable polymer according to the applied technical field of required tunica fibrosa, and the present invention does not have special restriction to the kind of polymer, meet that the fusing point of low melting point polymer and high-melting-point polymer is poor to be not less than 10 ℃ and to get final product.In the present invention, described high-melting-point polymer and low melting point polymer are preferably selected from polystyrene (PS), polysulfones (PSF), polyether sulfone (PES), Kynoar (PVDF), Kynoar-perfluoropropene (PVDF-HFP), Kynoar-CTFE (PVDF-CTFE), polyacrylonitrile (PAN), polyamide (PA), polyvinylcarbazole, acetyl cellulose (CA), cellulose family, shitosan (PAA), polyaniline, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polytrimethylene terephthalate (PTT), polyimides (PI), polyurethane (PU), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) Merlon (PC) polymine (PEI), , one or more in polyether-ether-ketone (PEEK), aliphatic amide, polyvinyl acetate (PVAc), polyformaldehyde (POM), polyvinyl chloride (PVC), nylon-6 (PA-6), nylon-66 (PA-66), poly-trifluoro-ethylene, polytrifluorochloroethylene, polyvinyl fluoride, PLA, poly(ethylene oxide) and polyvinylpyrrolidone, more preferably be selected from one or more in PVDF, PVDF-HFP, PVDF-CTFE, PA-66, PET, PBT and PES.
After obtaining the high-melting-point polymer spinning solution, the present invention carries out the first electrostatic spinning by described high-melting-point polymer, obtains the high-melting-point polymer tunica fibrosa.The present invention is before carrying out the first electrostatic spinning, preferably measure the viscosity of the high-melting-point polymer spinning solution obtained, after viscosity preferably meets 0.2Pas～20Pas, then carry out the first electrostatic spinning, described viscosity is 0.3Pas～18Pas more preferably, most preferably is 0.3Pas～15Pas.The present invention does not have special restriction to the device of described the first electrostatic spinning, adopts the device of electrostatic spinning well known to those skilled in the art to get final product.As adopted the spinning head of single needle, also can adopt the spinning head of Multi needle, can also adopt the electrostatic spinning apparatus of needle-less, described spinning head can be standing, can be also perpetual motion; Receiving system wherein can be standing, can be also perpetual motion, and the present invention does not have special restriction to this.As an example, those skilled in the art can adopt the spinning receiving system shown in the electrospinning device shown in Fig. 1 of the present invention and Fig. 2, the structural representation of the electrospinning device that Fig. 1 is embodiment of the present invention employing, the structural representation of the spinning receiving equipment that Fig. 2 is embodiment of the present invention employing.
In the present invention, the voltage of described the first electrostatic spinning is preferably 10kV～150kV, and more preferably 10KV～140KV, most preferably be 12KV～130KV, the most is preferably 15KV～120KV; The humidity of described the first electrostatic spinning environment is preferably 0%～60%, and more preferably 5%～55%, most preferably be 10%～50%, the most be preferably 15%～45%; The pressure of described the first electrostatic spinning environment is preferably 0.01MPa～0.5MPa, and more preferably 0.02MPa～0.45MPa, most preferably be 0.03MPa～0.4MPa, the most is preferably 0.05MPa～0.35MPa; The temperature of described the first electrostatic spinning environment is preferably 0 ℃～60 ℃, and more preferably 5 ℃～55 ℃, most preferably be 10 ℃～50 ℃, the most be preferably 15 ℃～45 ℃; The receiving range of described the first electrostatic spinning is preferably 5cm～50cm, and more preferably 7cm～47cm, most preferably be 8cm～45cm, the most is preferably 10cm～40cm; In described the first electrostatic spinning process, preferably maintain certain liquid speed of feeding, make spinning solution form one or more stable taylor cones, to guarantee the stability of electrostatic spinning, obtain the nano fibrous membrane of even thickness and even thickness, the liquid speed of feeding that forms a stable taylor cone in described the first electrostatic spinning is preferably 0.05mL/h～20mL/h, more preferably 0.1mL/h～18mL/h, most preferably be 0.2mL/h～16mL/h, the most be preferably 0.3mL/h～15mL/h.The liquid speed of feeding that those skilled in the art are can be according to the purposes different choice of electrostatic spinning nano fiber film different, also can select the different liquid speed of feeding according to the kind of different high-melting-point polymers, can also select the different liquid speed of feeding according to different spinning head equipment, the present invention does not have special restriction to this.
In the present invention, the high-melting-point polymer spinning solution is in spinning process, and solvent evaporates is solidificated on receiving system, obtains the high-melting-point polymer tunica fibrosa.Release liners on described receiving system or base cloth are arranged between spinning head and minus plate, and described release liners or base cloth be close to minus plate, and described minus plate is preferably stainless steel material.
In the present invention, described spinning equipment or receiving equipment preferably have one or two relatively stable amplitude motion, and the amplitude of described amplitude motion is preferably 0.01m～2.0m, and more preferably 0.05m～1.9m, most preferably be 0.1m～1.8m; The direction of described the first electrostatic spinning is preferably from bottom to top or horizontal direction, and the spinning head in described electrospinning device can not be suspended from release liners or base cloth top, also can not be perpendicular to the direction from top to bottom on release liners or base cloth plane.
After obtaining the low melting point polymer spinning solution, the present invention carries out the second electrostatic spinning by described low melting point polymer, obtains the low melting point polymer tunica fibrosa.The present invention is before carrying out the second electrostatic spinning, preferably measure the viscosity of the low melting point polymer spinning solution obtained, after viscosity preferably meets 0.2Pas～20Pas, then carry out the second electrostatic spinning, described viscosity is 0.3Pas～18Pas more preferably, most preferably is 0.3Pas～15Pas.The present invention does not have special restriction to the device of described the second electrostatic spinning, adopts the device of electrostatic spinning well known to those skilled in the art to get final product.As adopted the spinning head of single needle, also can adopt the spinning head of Multi needle, can also adopt the electrostatic spinning apparatus of needle-less, described spinning head can be standing, can be also perpetual motion; Receiving system wherein can be standing, can be also perpetual motion, and the present invention does not have special restriction to this.As an example, those skilled in the art can adopt the spinning receiving system shown in the electrospinning device shown in Fig. 1 of the present invention and Fig. 2, the structural representation of the electrospinning device that Fig. 1 is embodiment of the present invention employing, the structural representation of the spinning receiving equipment that Fig. 2 is embodiment of the present invention employing.
In the present invention, the voltage of described the second electrostatic spinning is preferably 10kV～150kV, and more preferably 10KV～140KV, most preferably be 12KV～130KV, the most is preferably 15KV～120KV; The humidity of described the second electrostatic spinning environment is preferably 0%～60%, and more preferably 5%～55%, most preferably be 10%～50%, the most be preferably 15%～45%; The pressure of described the second electrostatic spinning environment is preferably 0.01MPa～0.5MPa, and more preferably 0.02MPa～0.45MPa, most preferably be 0.03MPa～0.4MPa, the most is preferably 0.05MPa～0.35MPa; The temperature of described the second electrostatic spinning environment is preferably 0 ℃～60 ℃, and more preferably 5 ℃～55 ℃, most preferably be 10 ℃～50 ℃, the most be preferably 15 ℃～45 ℃; The receiving range of described the second electrostatic spinning is preferably 5cm～50cm, and more preferably 7cm～47cm, most preferably be 8cm～45cm, the most is preferably 10cm～40cm; In described the second electrostatic spinning process, preferably maintain certain liquid speed of feeding, make spinning solution form one or more stable taylor cones, to guarantee the stability of electrostatic spinning, obtain the nano fibrous membrane of even thickness and even thickness, the liquid speed of feeding that forms a stable taylor cone in described the second electrostatic spinning is preferably 0.05mL/h～20mL/h, more preferably 0.1mL/h～18mL/h, most preferably be 0.2mL/h～16mL/h, the most be preferably 0.3mL/h～15mL/h.The liquid speed of feeding that those skilled in the art are can be according to the purposes different choice of electrostatic spinning nano fiber film different, also can select the different liquid speed of feeding according to the kind of different low melting point polymers, can also select the different liquid speed of feeding according to different spinning head equipment, the present invention does not have special restriction to this.
In the present invention, the low melting point polymer spinning solution is in spinning process, and solvent evaporates is solidificated on receiving system, obtains the low melting point polymer tunica fibrosa.Release liners on described receiving system or base cloth are arranged between spinning head and minus plate, and described release liners or base cloth be close to minus plate, and described minus plate is preferably stainless steel material.
In the present invention, described spinning equipment or receiving equipment preferably have one or two relatively stable amplitude motion, and the amplitude of described amplitude motion is preferably 0.01m～2.0m, and more preferably 0.05m～1.9m, most preferably be 0.1m～1.8m; The direction of described the second electrostatic spinning is preferably from bottom to top or horizontal direction, and the spinning head in described electrospinning device can not be suspended from release liners or base cloth top, also can not be perpendicular to the direction from top to bottom on release liners or base cloth plane.
After obtaining high-melting-point polymer tunica fibrosa and low melting point polymer tunica fibrosa, the present invention is by described high-melting-point polymer tunica fibrosa and the compound rear hot pressing of low melting point polymer tunica fibrosa, obtain the electrostatic spinning nano fiber film, the temperature of described hot pressing is more than or equal to the fusing point of described low melting point polymer, and is less than the fusing point of high-melting-point polymer.The present invention being not less than the low melting point polymer fusing point, the temperature that is less than the high-melting-point polymer fusing point carries out hot pressing to high-melting-point polymer tunica fibrosa and low melting point polymer tunica fibrosa, bonding with the high-melting-point polymer tunica fibrosa after the micro-thawing of low melting point polymer, obtain the electrostatic spinning nano fiber film of excellent performance after cooling, be applicable to the demand in battery and electrode material, filtration, infiltration, biomedicine, clothes, shoes and hats, photoelectric material, sensor field.Method technique provided by the invention is simple, production efficiency is high.
The present invention does not have special restriction to the method for described hot pressing, adopts the equipment of hot pressing well known to those skilled in the art to get final product.The present invention preferably is placed in low melting point polymer tunica fibrosa and high-melting-point polymer tunica fibrosa between hot pressing die and soft mould, carries out hot pressing, obtains the electrostatic spinning nano fiber film.The present invention does not have special restriction to the kind of described hot pressing die, adopts hot pressing die well known to those skilled in the art to get final product, as be flat board or hot-rolling; In the present invention, the steel rider that described soft mould is a heating or the unit equipment of heating plate and rubber rollers or rubber slab.In the present invention, the temperature of described hot pressing is preferably 80 ℃～450 ℃, and more preferably 85 ℃～445 ℃, most preferably be 90 ℃～440 ℃, the most be preferably 100 ℃～420 ℃; The pressure of described hot pressing is preferably 0.1MPa～10MPa, and more preferably 0.2MPa～9MPa, most preferably be 0.3MPa～8MPa; The time of described hot pressing is preferably 0.01h～1h, and more preferably 0.05h～0.9h, most preferably be 0.1h～0.8h.
After completing described hot-pressing processing, the present invention carries out drying after preferably the composite membrane constant voltage cooling obtained being cooled to room temperature, obtains the electrostatic spinning nano fiber film.The present invention can constant voltage lower the temperature or remove the cooling of mould constant voltage in mould, and the present invention does not have special restriction to the mode of described constant voltage cooling.The present invention does not have special restriction to the method for described drying, adopts the technical scheme of drying well known to those skilled in the art to get final product.In the present invention, described drying is preferably vacuumize, and the temperature of described drying is preferably 50 ℃～200 ℃, and more preferably 55 ℃～190 ℃, most preferably be 60 ℃～180 ℃, the most be preferably 65 ℃～150 ℃; The time of described drying is preferably 1h～20h, and more preferably 2h～19h, most preferably be 3h～18h.
The invention provides a kind of electrostatic spinning nano fiber film and preparation method thereof, electrostatic spinning nano fiber film provided by the invention comprises the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain; The fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.Electrostatic spinning nano fiber film provided by the invention serves many purposes, and can be used in different technical fields.Electrostatic spinning nano fiber film provided by the invention can be used as lithium ion battery separator, can also be used as air filting material, also can be used for preparing the Waterproof Breathable breathable fabric.
Method provided by the invention is carried out respectively electrostatic spinning by high-melting-point polymer and low melting point polymerization, and high-melting-point polymer tunica fibrosa and the compound rear hot pressing of low melting point polymer tunica fibrosa by obtaining, obtain the electrostatic spinning nano fiber film.Preparation method's production efficiency provided by the invention is high, energy consumption is low, is applicable to suitability for industrialized production.
The invention provides a kind of electrostatic spinning nano fiber film and preparation method thereof, electrostatic spinning nano fiber film provided by the invention comprises the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain; The fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.Electrostatic spinning nano fiber film provided by the invention serves many purposes, and can be used for the fields such as biomedicine, derived energy chemical, gas liquid filtration, water proof wind proof, wind-proof warming, moisture-penetrable ventilated, environmental improvement, semiconductor transducer.Experimental result shows, electrostatic spinning nano fiber film provided by the invention can be used as lithium ion battery separator, can also be used as air filting material, also can be used for preparing the Waterproof Breathable breathable fabric.
Method provided by the invention is carried out respectively electrostatic spinning by high-melting-point polymer and low melting point polymerization, and high-melting-point polymer tunica fibrosa and the compound rear hot pressing of low melting point polymer tunica fibrosa by obtaining, obtain the electrostatic spinning nano fiber film.Preparation method's production efficiency provided by the invention is high, energy consumption is low, is applicable to suitability for industrialized production.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of electrostatic spinning nano fiber film provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as to limiting the scope of the present invention.
In the following embodiments, Kynoar (PVDF) and Kynoar-perfluoropropene (PVDF-HFP) are French Su Wei production, and polyamide (PA-66), poly terephthalic acid diethylester (PET) and polybutylene terephthalate (PBT) are Dupont production; Polyether sulfone (PES) is purchased from German BASF; Solvent is AR, purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Nano silicon is purchased from Shanghai Aladdin reagent Co., Ltd; Tension tester Instron5900 twin columns electronic universal material puller system, Japanese KEYENCE VE-8800 type scanning electronic microscope; Rich the strangling of U.S. Brookfield(flies) DV-III Ultra flow graph;
Embodiment 1
By PET powder, PVDF powder 110 ℃ of dryings after 12 hours in vacuum drying chamber, be cooled to room temperature, take the PET powder dissolution of 100g drying in the mixed solvent of 700g trifluoroacetic acid and carrene, at room temperature stir 12h, obtain transparent PET organic solution; Add the 1g nano-silicon dioxide particle in the PET organic solution obtained, by after the ultrasonic dispersion of the mixed solution obtained 6h, obtain the PET spinning solution, standby;
The PVDF powder that takes the 100g drying is dissolved in 400g DMF and acetone mixed solvent, at room temperature stirs 12h, obtains the PVDF spinning solution, standby;
The viscosity of the spinning solution that mensuration obtains is 5.1Pas, then by PET spinning solution and PVDF spinning solution 25 ℃ of room temperatures, relative air humidity approximately 30% time, respectively by the spinning of high-voltage electrostatic spinning machine.In the electrostatic spinning process of PET spinning solution, each taylor cone (adding) liquid speed of feeding is 1.2mL/h, and spinning voltage is 35kV, and receiving range is 25cm, relative air humidity approximately 30%, 25 ℃ of room temperatures; In the spinning process of PVDF spinning solution, each taylor cone (adding) liquid speed of feeding is 2.0mL/h, and spinning voltage is 50kV, and receiving range is 30cm, relative air humidity approximately 30%, 25 ℃ of room temperatures;
Spinning finishes, by the PET tunica fibrosa that obtains and PVDF tunica fibrosa, in temperature, be under 140 ℃, the pressure condition that is 1MPa after hot pressing 0.5h, after being cooled to room temperature, the Static Spinning film obtained is put into to vacuum drying chamber, at 110 ℃ of dry 4h, obtaining thickness is the electrostatic spinning nano fiber film of 20 ± 1 μ m.
The present invention carries out scanning electron microscope analysis by the electrostatic spinning nano fiber film obtained, result as shown in Figure 3, the SEM figure that Fig. 3 is the nano fibrous membrane that obtains of the embodiment of the present invention 1, as seen from Figure 3, the fibre diameter homogeneous in the electrostatic spinning nano fiber film that the present invention obtains.The present invention's test obtains, and the average fibre diameter of the electrostatic spinning nano fiber film that the present embodiment obtains is that 300nm～500nm, pore diameter are 0.1 μ m～1.0 μ m, and porosity is 70%～80%.Electrolytical adsorption rate is 600%～700%;
The present invention carries out Mechanics Performance Testing by the electrostatic spinning nano fiber film obtained, result as shown in Figure 4, Fig. 4 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 1 obtains, and result shows, the TENSILE STRENGTH of the electrostatic spinning nano fiber film that the present embodiment obtains is 25MPa～32MPa.
The electrostatic spinning nano fiber film that the present embodiment provides can be used for producing lithium ion battery separator, and the nano fiber diaphragm that obtains lithium ion battery is cut apart nano fibrous membrane in the present invention.
Embodiment 2
To be dissolved in 126gN through the 80g of super-dry Kynoar (PVDF), the mixed solvent of dinethylformamide (DMF) and 294g acetone, after the solution obtained is at room temperature stirred to 12h, obtain the PVDF spinning solution of transparent homogeneous, standby;
The 80g polyether sulfone (PES) of vacuumize is dissolved in 420g DMF solvent, by the mixture stirring and dissolving 12h in oil bath obtained, obtains the PES spinning solution of transparent homogeneous;
After measuring the viscosity of spinning solution, by the PVDF spinning solution that obtains and PES spinning solution, 25 ℃ of room temperatures, relative air humidity approximately 35% time, mixes the intersection spinning by the high-voltage electrostatic spinning machine respectively.In the electrostatic spinning process of PVDF spinning solution, it is 2.0mL/h that each taylor cone is fed (adding) liquid speed, and spinning voltage is 45kV, and receiving range is 25cm.In the electrostatic spinning process of PES spinning solution, it is 1.5mL/h that each taylor cone is fed (adding) liquid speed, and spinning voltage is 35kV, and receiving range is 20cm.
After spinning finishes, by the PVDF tunica fibrosa that obtains and PES tunica fibrosa, in temperature, be under 130 ℃, the pressure condition that is 5MPa after hot-pressing processing 0.3h, the composite membrane obtained is cooled to room temperature, then the Static Spinning film obtained is put into to vacuum drying chamber, at 110 ℃ of dry 4h, obtain the nano fibrous membrane that thickness is 25.0 ± 1.5 μ m.
The present invention carries out scanning electron microscope analysis by the electrostatic spinning nano fiber film obtained, result as shown in Figure 5, the SEM figure that Fig. 5 is the nano fibrous membrane that obtains of the embodiment of the present invention 2, as seen from Figure 5, the fibre diameter homogeneous in the electrostatic spinning nano fiber film that the present invention obtains.The present invention's test obtains, and the bore dia of the electrostatic spinning nano fiber film that the present embodiment obtains is below 1 μ m, and the average diameter of electrostatic spinning nano fiber is that 500nm～600nm, pore diameter are 0.1 μ m～0.8 μ m;
The present invention carries out Mechanics Performance Testing by the electrostatic spinning nano fiber film obtained, result as shown in Figure 6, Fig. 6 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 2 obtains, and result shows, the TENSILE STRENGTH of the electrostatic spinning nano fiber film that the present embodiment obtains is 25MPa～32MPa;
The present invention carries out the air filtration test by the electrostatic spinning nano fiber film obtained, and result shows, this electrostatic spinning nano fiber film can effectively filter the PM2.5 particle.The electrostatic spinning nano fiber film that the present embodiment obtains can be used for the preparation of the electrostatic spinning nano fiber film of air filting material.
Embodiment 3
The 100g PA-66 powder of vacuumize is dissolved in 400g acetic acid, obtains the PA-66 spinning solution, standby;
The 80g PVDF powder of vacuumize is dissolved in 400g DMF and acetone mixed solvent, forms the solution of transparent and homogeneous, obtain the PVDF spinning solution, standby;
After measuring the viscosity of spinning solution, the PVDF spinning solution that obtains and PA-66 spinning solution, 25 ℃ of room temperatures, relative air humidity approximately 40% time, are mixed to the intersection spinning by the high-voltage electrostatic spinning machine respectively.In the electrostatic spinning process of PVDF spinning solution, the single needle injection speed of plastic injection pump is that 5mL/h, voltage are 30kV, and receiving range is 18cm.In the electrostatic spinning process of PA-66 spinning solution, the single needle injection speed of plastic injection pump is 2.0mL/h, and voltage is 35kV, and receiving range is 20cm;
After spinning, by the PVDF tunica fibrosa that obtains and PA-66 tunica fibrosa, in temperature, be hot-pressing processing 0.2h under 150 ℃, the pressure condition that is 6MPa, the complexes membrane obtained is cooled to room temperature, then the Static Spinning film obtained is put into to vacuum drying chamber, dry 4h under 110 ℃, obtaining thickness is the electrostatic spinning nano fiber film of 20 ± 2 μ m.
The present invention carries out scanning electron microscope analysis by the electrostatic spinning nano fiber film obtained, result as shown in Figure 7, the SEM figure that Fig. 7 is the nano fibrous membrane that obtains of the embodiment of the present invention 3, as seen from Figure 7, the fibre diameter homogeneous in the electrostatic spinning nano fiber film that the present invention obtains.The present invention's test obtains, and in the electrostatic spinning fiber film that the present embodiment obtains, the average diameter of fiber is that 400nm～500nm, pore diameter are 0.2 μ m～1.0 μ m;
The present invention carries out Mechanics Performance Testing by the electrostatic spinning nano fiber film obtained, result as shown in Figure 8, Fig. 8 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 3 obtains, and result shows, the TENSILE STRENGTH of the electrostatic spinning nano fiber film that the present embodiment obtains is 30MPa～35MPa.
Embodiment 4
The 100g PBT powder of vacuumize is dissolved in to the trifluoroacetic acid of 700g and the mixed solvent of carrene, forms the solution of transparent and homogeneous, obtain the PBT spinning solution, standby;
80g Kynoar (PVDF) powder of vacuumize is dissolved in the mixed solvent of 126g DMF and 294g acetone, in stirring at room, dissolves 12h, form the solution of transparent and homogeneous, obtain the PVDF spinning solution, standby;
80g Kynoar-perfluoropropene copolymer (PVDF-HFP) powder is dissolved in the mixed solvent of 126g DMF and 294g acetone, after stirring at room is dissolved 12h, forms the solution of transparent and homogeneous, obtain the PVDF-HFP spinning solution, standby;
After the viscosity of the spinning solution that mensuration obtains, by PBT spinning solution, PVDF spinning solution and PVDF-HFP spinning solution, 25 ℃ of room temperatures, relative air humidity approximately 40% time, respectively by the spinning of high-voltage electrostatic spinning machine.In the electrostatic spinning process of PBT spinning solution, the speed that plastic injection pump injection speed is assigned to single needle is that 5mL/h, voltage are 30kV, and receiving range is 18cm.In the electrostatic spinning process of PVDF spinning solution, the speed that plastic injection pump injection speed is assigned to single needle is that 2.0mL/h, voltage are that 35kV, receiving range are 20cm.In the electrostatic spinning process of PVDF-HFP spinning solution, the speed that plastic injection pump injection speed is assigned to single needle is that 2.0mL/h, voltage are that 45kV, receiving range are 25cm;
After spinning completes, the PVDF tunica fibrosa obtained is arranged on the PVDF-HEP tunica fibrosa, the PBT tunica fibrosa is set on the PVDF-HEP tunica fibrosa, by the composite membrane that obtains, in temperature, be under 135 ℃, the pressure condition that is 10MPa after hot-pressing processing 0.5h, be cooled to room temperature, again the Static Spinning film obtained is put into to vacuum drying chamber, dry 4h under 110 ℃, obtaining thickness is the electrostatic spinning nano fiber film of 35 ± 3 μ m.
The present invention carries out scanning electron microscope analysis by the electrostatic spinning nano fiber film obtained, result as shown in Figure 9, the SEM figure that Fig. 9 is the nano fibrous membrane that obtains of the embodiment of the present invention 10, as seen from Figure 9, the fibre diameter homogeneous in the electrostatic spinning nano fiber film that the present invention obtains.The present invention's test obtains, and in the electrostatic spinning fiber film that the present embodiment obtains, the average diameter of fiber is that 300nm～500nm, pore diameter are 0.1 μ m～1.0 μ m.
The present invention carries out Mechanics Performance Testing by the electrostatic spinning nano fiber film obtained, result as shown in figure 10, Figure 10 is the electrostatic spinning nano fiber film strength resolution chart that the embodiment of the present invention 4 obtains, result shows, the TENSILE STRENGTH of the electrostatic spinning nano fiber film that the present embodiment obtains is 28MPa～35MPa.
The electrostatic spinning nano fiber film that the present embodiment obtains can be used as the Waterproof Breathable ventilated membrane, the present invention adopts ASTM E96BW2000 version standard to be detected the vapor transfer rate of waterproof humidity-permeant film, adopt the AATCC127 standard to be detected the resistance to hydrostatic pressure of waterproof humidity-permeant film, result shows, the resistance to hydrostatic pressure of the waterproof moisture permeating fabric that the present embodiment obtains can be up to 10080mmH
2o, vapor transfer rate can be up to 11000g/m
224h.
As seen from the above embodiment, the invention provides a kind of electrostatic spinning nano fiber film and preparation method thereof, electrostatic spinning nano fiber film provided by the invention comprises the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain; The fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.Electrostatic spinning nano fiber film provided by the invention serves many purposes, and can be used for the fields such as biomedicine, derived energy chemical, gas liquid filtration, water proof wind proof, wind-proof warming, moisture-penetrable ventilated, environmental improvement, semiconductor transducer.Experimental result shows, electrostatic spinning nano fiber film provided by the invention can be used as lithium ion battery separator, can also be used as air filting material, also can be used for preparing the Waterproof Breathable breathable fabric.
Method provided by the invention is carried out respectively electrostatic spinning by high-melting-point polymer and low melting point polymerization, and high-melting-point polymer tunica fibrosa and the compound rear hot pressing of low melting point polymer tunica fibrosa by obtaining, obtain the electrostatic spinning nano fiber film.Preparation method's production efficiency provided by the invention is high, energy consumption is low, is applicable to suitability for industrialized production.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (11)
1. an electrostatic spinning nano fiber film, comprise the tunica fibrosa that tunica fibrosa that the high-melting-point polymer Static Spinning obtains and low melting point polymer Static Spinning obtain;
The fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃.
2. electrostatic spinning nano fiber film according to claim 1, is characterized in that, described high-melting-point polymer and low melting point polymer are selected from polystyrene (PS), polysulfones (PSF), polyether sulfone (PES), Kynoar (PVDF), Kynoar-perfluoropropene (PVDF-HFP), Kynoar-CTFE (PVDF-CTFE), polyacrylonitrile (PAN), polyamide (PA), polyvinylcarbazole, acetyl cellulose (CA), cellulose family, shitosan (PAA), polyaniline, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polytrimethylene terephthalate (PTT), polyimides (PI), polyurethane (PU), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) Merlon (PC) polymine (PEI), polyether-ether-ketone (PEEK), aliphatic amide, polyvinyl acetate (PVAc), polyformaldehyde (POM), polyvinyl chloride (PVC), nylon-6 (PA-6), nylon-66 (PA-66), poly-trifluoro-ethylene, polytrifluorochloroethylene, polyvinyl fluoride, PLA, one or more in poly(ethylene oxide) and polyvinylpyrrolidone.
3. electrostatic spinning nano fiber film according to claim 1, is characterized in that, the thickness of electrostatic spinning nano fiber film is 2.0 μ m～5.0mm.
4. electrostatic spinning nano fiber film according to claim 1, is characterized in that, the pore diameter of electrostatic spinning nano fiber film is 10nm～5000nm.
5. electrostatic spinning nano fiber film according to claim 1, is characterized in that, in the electrostatic spinning nano fiber film, the diameter of fiber is 5nm～2000nm.
6. the preparation method of an electrostatic spinning nano fiber film comprises the following steps:
High-melting-point polymer is dissolved in the first spin solvent, obtains the high-melting-point polymer spinning solution;
Low melting point polymer is dissolved in the second spin solvent, obtains the low melting point polymer spinning solution, the fusing point of described high-melting-point polymer and low melting point polymer is poor is not less than 10 ℃;
Described high-melting-point polymer spinning solution is carried out to the first electrostatic spinning, obtain the high-melting-point polymer tunica fibrosa;
Described low melting point polymer spinning solution is carried out to the second electrostatic spinning, obtain the low melting point polymer tunica fibrosa;
By described compound rear high-melting fibre film and the hot pressing of low-melting fiber film, obtain high strength electrostatic spinning nano fiber film, the temperature of described hot pressing is more than or equal to the fusing point of described low melting point polymer, and is less than the fusing point of high-melting-point polymer.
7. preparation method according to claim 6, it is characterized in that, described the first spin solvent and the second spin solvent independently are selected from water, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, hexafluoroisopropanol, trifluoroethanol, phenol, formic acid, acetic acid, trifluoroacetic acid, carrene, dichloroethanes, chloroform, acetone, N, one or more in dinethylformamide (DMF), DMA (DMAC), oxolane (THF), pyridine, toluene, cyclohexane, 1-METHYLPYRROLIDONE and carbon disulfide.
8. preparation method according to claim 6, is characterized in that, in described high-melting-point polymer spinning solution, also comprises inorganic nano-particle;
Also comprise inorganic nano-particle in described low melting point polymer spinning solution.
9. preparation method according to claim 6, is characterized in that, the mass fraction of described high-melting-point polymer spinning solution is 3%～50%;
The mass fraction of described low melting point polymer spinning solution is 3%～50%.
10. preparation method according to claim 6, it is characterized in that, the voltage of described the first electrostatic spinning is 10kV～150kV, the humidity of described the first electrostatic spinning environment is 0%～60%, the pressure of described the first electrostatic spinning environment is 0.01MPa～0.5MPa, the temperature of described the first electrostatic spinning environment is 0 ℃～60 ℃, the receiving range of described the first electrostatic spinning is 5cm～50cm, and hello the liquid speed that forms a stable taylor cone in described the first electrostatic spinning is 0.05mL/h～20mL/h;
The voltage of described the second electrostatic spinning is 10kV～150kV, the humidity of described the second electrostatic spinning environment is 0%～60%, the pressure of described the second electrostatic spinning environment is 0.01MPa～0.5MPa, the temperature of described the second electrostatic spinning environment is 0 ℃～60 ℃, the receiving range of described the second electrostatic spinning is 5cm～50cm, and hello the liquid speed that forms a stable taylor cone in described the second electrostatic spinning is 0.05mL/h～20mL/h.
11. preparation method according to claim 6, is characterized in that, the temperature of described hot pressing is 80 ℃～450 ℃;
The pressure of described hot pressing is 0.1MPa～10MPa;
The time of described hot pressing is 0.01h～1h.
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Application publication date: 20131211 |