CN105200539A - Electrostatic spinning method and nanometer fiber/anti-sticking non-woven fabric composite filter material prepared through electrostatic spinning method - Google Patents
Electrostatic spinning method and nanometer fiber/anti-sticking non-woven fabric composite filter material prepared through electrostatic spinning method Download PDFInfo
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Abstract
The invention relates to an electrostatic spinning method and a nanometer fiber/anti-sticking non-woven fabric composite filter material prepared through the electrostatic spinning method. Multi-needle electrostatic spinning is adopted in the electrostatic spinning method, and needles of multi-needle electrostatic spinning are insulated from one another. The prepared nanometer fiber/anti-sticking non-woven fabric composite filter material is formed by overlapping and compositing materials for overlapping from bottom to top according to the low-to-high sequence of filtering efficiency of a filtering material, the face, with electrostatic spinning fiber, of each layer of material for overlapping faces upwards, the uppermost layer of material for overlapping is covered with anti-sticking non-woven fabric, and therefore it is ensured that the top layer and the bottommost layer are both anti-sticking non-woven fabric layers; of every two adjacent layers of materials for overlapping, the filtering efficiency value for particles with grain size of 0.02 micron to 10 microns of the upper layer is 1.03-1.3 times that of the lower layer, the number of overlapping layers of the materials for overlapping ranges from 2 to 6, the anti-sticking non-woven fabric and the interlayer structure with electret effect nanometer fibers arrayed at intervals are formed, and the nanometer fiber/anti-sticking non-woven fabric composite filter material is formed; the filtering efficiency of the nanometer fiber/anti-sticking non-woven fabric composite filter material for particles with grain size of 0.02 micron to 10 microns reaches 99.999% or higher, and the pressure resistance is kept between 10 Pa and 30 Pa.
Description
Technical field
The invention belongs to electrostatic spinning technique field, relate to the nanofiber/spun-bonded non-woven fabrics composite filter material of a kind of electrospinning process and preparation thereof.
Background technology
In Multi needle electrostatic spinning process, between syringe needle, can electric jamming be produced, make the electric-field intensity between syringe needle and syringe needle produce difference, thus cause jet unstable, finally affect the uniformity of the tunica fibrosa that spinning obtains.Electric-field intensity in spinning process is controlled, makes every root spinning head jet keep stable, effectively can improve the uniformity of tunica fibrosa, realize the stable of media performance.In existing document, the main metal auxiliary electrode that uses controls electric field between syringe needle, jet stability (ButtafocoL is made by adding the metal ring applying identical voltage with syringe needle at spinning head needle point place, KolkmanNG, Engbers-BuijtenhuijsP, etal.Electrospinningofcollagenandelastinfortissueenginee ringapplications [J] .Biomaterials, 2006, 27 (5): 724-34.), or use in syringe needle outside that metal is flexible carries out electric field controls (KimG, ChoY-S, KimWD.Stabilityanalysisformulti-jetselectrospinningproce ssmodifiedwithacylindricalelectrode [J] .EuropeanPolymerJournal, 2006, 42 (9): 2031-8.), patent CN203583021U discloses " a kind of plate electrode many shower nozzles electrostatic spinning device ", it, by adding a metallic plate before spinning head, metallic plate has the through hole coordinated with spinning head, and high voltage source is connected with spinning head and metallic plate simultaneously, make it have identical point position, thus make jet stability, (red legend is refined for the refined grade of red legend, history Jingjing, Yang Enlong. auxiliary electrode effect lower pair of nozzle electrospinning electric field and jet force analysis [J]. textile journal, 2012,06:6-9.) by installing conical metal auxiliary electrode additional at shower nozzle place, auxiliary electrode is connected to reduce electric jamming between needle adjacent with shower nozzle.These methods are by additional metal auxiliary electrode on spinning syringe needle, and auxiliary electrode and syringe needle apply the method for large small voltage of the same race, and spinning jet stability is improved.But when high voltage spinning, easily electric discharge phenomena occur between syringe needle and auxiliary electrode, the spark of generation very easily causes security incident.
Static Spinning is a kind of nanofiber technology of preparing utilizing high voltage to carry out spinning, also be a kind of nanofiber electret technology simultaneously, can a large amount of space charge be injected in the middle of fiber in the process of spinning, space charge is easily caught by the deep trap of fibrous inside, can polarize and produce polarization charge by induced dipole simultaneously, in the process that particle is filtered by electrostatic adsorption promote filter efficiency (Yao Cuie. fusion-jetting polypropylene filtrate electret Study on influencing factors [D]. Donghua University, 2014.).And electret filtering material is in use and storage process, because the moisture and particulate etc. that exist in air directly contact with electret material, surface charge loss in electret material is accelerated, thus the decay of electret effect is accelerated, finally cause media filtration efficiency instability (Tian Tao, Wu Jinhui, Hao Limei, Lin Song, Yang Jingquan. the accumulate performance [J] of polypropylene fibre electret filter. textile journal, 2010,31 (6): 25-28.).
Summary of the invention
Technical problem to be solved by this invention is to provide the nanofiber/spun-bonded non-woven fabrics composite filter material of a kind of electrospinning process and preparation thereof.For the problem of electric jamming in Multi needle electrostatic spinning process in prior art, insulating materials is used to carry out anti-tampering isolated process to each syringe needle.
A kind of electrospinning process of the present invention, is Multi needle electrostatic spinning, insulate between the syringe needle of described Multi needle electrostatic spinning.
As preferred technical scheme:
A kind of electrospinning process as above, the same insulating base of described Needle sharing.
A kind of electrospinning process as above, between described syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of described syringe needle and form isolated groove, the shape of isolated groove is square or circular, and the degree of depth of isolated groove is 1 ~ 5 times of described needle length.When spinning head place applies high voltage, insulating materials completely cuts off rooved face and produces polarization charge, the polarized electric field formed is contrary with former direction of an electric field, certain negative function can be produced to this direction electric-field intensity, electric field between making from needle adjacent interferes with each other reduction, thus make jet stability, and electric discharge phenomena can not be there are in high voltage electrostatic spinning process.
A kind of electrospinning process as above, described insulating materials is Acrylnitrile-Butadiene-Styrene, Merlon, polymethyl methacrylate, polypropylene, polyamide, polystyrene, polyvinyl chloride, polyethylene, polytetrafluoroethylene (PTFE), Kynoar or polyethylene terephthalate.
Present invention also offers a kind of nanofiber/spun-bonded non-woven fabrics composite filter material preparation method, concrete steps are:
(1) spun-bonded non-woven fabrics pre-treatment
Step is:
A) titanium dioxide nanofiber or nanometer activated carbon fiber are added in ethanol, and ultrasonic disperse, obtain uniform dispersion liquid;
B) take out after spun-bonded non-woven fabrics being soaked in the dispersion liquid of titanium dioxide nanofiber or nanometer activated carbon fiber, hang in baking oven, 50 ~ 60 DEG C of oven dry, obtain the spun-bonded non-woven fabrics base material of surface deposition titanium dioxide nanofiber or nanometer activated carbon fiber;
(2) electrostatic spinning
Step is:
A) inorganic nanoparticles is added in solvent, and ultrasonic disperse, obtain the homodisperse dispersion liquid of nano particle;
B) polymer is added in described dispersion liquid, be mixed with even and stable spinning solution;
C) spinning solution is carried out Multi needle electrostatic spinning, insulate between the syringe needle of described Multi needle electrostatic spinning; The spun-bonded non-woven fabrics base material obtained in the polymer nanofiber step (1) spun receives, obtain the composite filtering material of uniform deposition Static Spinning polymer nanofiber on spun-bonded non-woven fabrics, the deposition of polymer nanofiber can by regulating the spinning time to regulate and control;
(3) preparation of superfine nano fiber dispersion
First prepare polyvinyl butyral solution, then itself and superfine nano fiber are added in high speed beater and disperse, obtain uniform superfine nano fiber dispersion;
(4) composite filtering material immersion treatment
Take out after described composite filtering material is soaked in described superfine nano fiber dispersion, dry, obtain the filtrate of composite filtering material fiber surface deposition superfine nano fiber; Be lamination material;
The superfine nano fiber laydown thickness on the described composite filtering material surface after immersion treatment is 20 ~ 200nm;
Test obtains the filter efficiency value of this lamination material to the particle of 0.02 ~ 10 μm;
(5) step (1) ~ (4) are repeatedly repeated, obtain the lamination material of different filter efficiency, the filter efficiency of lamination material controls by the mass fraction of superfine nano fiber in dispersion liquid in Static Spinning polymer nanofiber deposition in regulation and control step (1) and step (4);
(6) by lamination material, superimposion is carried out successively from low to high from bottom to top by media filtration efficiency, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensures that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, the filter efficiency value of one deck to the particle of 0.02 ~ 10 μm is 1.03 ~ 1.3 times of one deck below above, form spun-bonded non-woven fabrics and there is electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material;
The lamination material superposition number of plies is 2 ~ 6 layers, forms spun-bonded non-woven fabrics and has electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics lamination composite filter material.
A kind of nanofiber as above/spun-bonded non-woven fabrics lamination composite filter material preparation method, in described step (1),
In described titanium dioxide nanofiber or nanometer activated carbon fiber dispersion liquid, fiber quality mark is 0.1 ~ 5%, and soak time is 5 ~ 10min; Described titanium dioxide nanofiber or nanometer activated carbon fiber diameter are 50 ~ 100nm, and length is 100 ~ 300nm;
Described spun-bonded non-woven fabrics, its composition fibre diameter is 1 ~ 50 μm, and nonwoven fabric aperture size is 5 ~ 120 μm, and grammes per square metre is 10 ~ 300g/m
2, exhibits initial filtration efficiency is 5% ~ 40%;
Described oven dry refers to and hangs in baking oven, and temperature is 50 ~ 60 DEG C;
Titanium dioxide nanofiber has photo-catalysis function, can carry out light degradation under illumination effect to adsorbed impurity, and nanometer activated carbon fiber, due to its higher specific area, has good adsorption function.On use spun-bonded non-woven fabrics, deposition of titanium oxide nanofiber or nanometer activated carbon fiber are as base material, and the product finally obtained in use, can play absorption and photodegradation to the peculiar smell in air.
A kind of nanofiber as above/spun-bonded non-woven fabrics composite filter material preparation method, in step (2) described spinning solution, the concentration of polymer is 5 ~ 40wt%, and the addition of inorganic nanoparticles is 0.1 ~ 10wt% of polymer and inorganic nanoparticles gross mass;
Described inorganic nanoparticles is silica, alundum (Al2O3), zinc oxide, barium monoxide, titanium dioxide, tantalum pentoxide, barium titanate, lead zirconate titanate, silicon nitride, tourmaline, boehmite or silsesquioxane nano particle;
The mechanism of action of described inorganic nanoparticles is: described inorganic nanoparticles has the injection of space charge and the generation of polarization charge under external electric field existent condition, very large humidification is had to electret effect, and inorganic nanoparticles mixes the interface produced can produce interfacial polarization with organic polymer under the existence of external electric field, produce polarization charge, same enhancing electret effect.
Described polymer is the one in Kynoar, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyvinyl acetate, nylon 6, polymethyl methacrylate, polyaniline, polyethylene glycol oxide, polyvinylpyrrolidone, polyacrylonitrile, polycaprolactone, polyurethane, fluorinated polyurethane, polysulfones, polyether sulfone, Kynoar-hexafluoropropene, Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether, Kynoar-CTFE, or is the mixture of above several polymer;
Wherein said solvent corresponds to respectively according to type of polymer:
Kynoar: DMF (DMF), 1-METHYLPYRROLIDONE (NMP), dimethylacetylamide (DMAc), triethyl phosphate and dimethyl sulfoxide (DMSO) (DMSO);
Polybutylene terephthalate: carrene, oxolane (THF), chloroform or acetone;
Polyethylene terephthalate: carrene, oxolane, chloroform or acetone;
Polyarylate: carrene, oxolane, chloroform or acetone;
Polyvinyl acetate: toluene, acetone, ethanol, acetic acid, ethyl acetate or chloroform;
Nylon 6: formic acid;
Polymethyl methacrylate: chloroform, acetic acid, ethyl acetate, acetone or toluene;
Polyaniline: DMF or 1-METHYLPYRROLIDONE;
Polyethylene glycol oxide: DMF, ethanol, water or chloroform;
Polyvinylpyrrolidone: water, ethanol, DMA or DMF;
Polyacrylonitrile: DMF or dimethyl sulfoxide (DMSO);
Polycaprolactone: DMF or acetone;
Polyurethane: DMF, acetone or 1-METHYLPYRROLIDONE;
Fluorinated polyurethane: DMF, acetone or 1-METHYLPYRROLIDONE;
Polysulfones and polyether sulfone: DMF, acetone, 1-METHYLPYRROLIDONE, dimethylacetylamide or oxolane;
Kynoar-hexafluoropropene: DMF, 1-METHYLPYRROLIDONE, dimethylacetylamide, triethyl phosphate or dimethyl sulfoxide (DMSO);
Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether: DMF, 1-METHYLPYRROLIDONE, dimethylacetylamide, triethyl phosphate or dimethyl sulfoxide (DMSO);
Kynoar-CTFE: DMF, 1-METHYLPYRROLIDONE, dimethylacetylamide, triethyl phosphate or dimethyl sulfoxide (DMSO);
Described step a) in, the ultrasonic disperse time is 20 ~ 70 minutes;
Described step b) in, polymer is added after in described dispersion liquid, magnetic agitation 8 ~ 10 hours;
Described step c) in, the process conditions of Multi needle electrostatic spinning are: supply voltage 10 ~ 60KV, and spinning environment condition is temperature 15 ~ 35 DEG C, relative humidity 25 ~ 90%; Multi needle spray silk unit syringe needle spacing 2 ~ 30cm, spray silk unit syringe needle quantity is 6 ~ 90; A kind of nanofiber as above/spun-bonded non-woven fabrics composite filter material preparation method, in step (3), in described polyvinyl butyral solution, Solute mass fraction is 0.1 ~ 5%; Described preparation polyvinyl butyral solution solvent for use is oxolane, N, the mixture of one or more in dinethylformamide, DMA, acetone, chloroform, cresols, dimethyl sulfoxide (DMSO), ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, DAA, methyl acetate, ethyl acetate, butyl acetate, toluene, 1-METHYLPYRROLIDONE, MEK, methyl ethyl ketone; The solubility parameter of described preparation polyvinyl butyral solution solvent for use at least differs 4 with electrostatic spinning fiber structure adaptability degree used parameter values, the structure that PVOH butyral still can not destroy the nanofiber that will disperse can be dissolved well, can not become loss to electrostatic spinning fiber inside electret effect, wherein the unit of solubility parameter is (J/cm
3)
1/2.
In described nanofiber dispersion liquid, shared by superfine nano fiber, mass fraction is 0.01% ~ 5%; Described nanofiber diameter is 10 ~ 150nm, and length is 100 ~ 150nm;
Described superfine nano fibrous material is the mixture of a kind of in polystyrene, polyester, polyvinyl acetate, nylon 6, nylon66 fiber, polyvinyl alcohol, polymethyl methacrylate, polyaniline, polyethylene glycol oxide, polyacrylonitrile, polycaprolactone, polyurethane, polysulfones, polyether sulfone or two kinds and above polymer;
The rotating speed of described high speed beater is 5000 revs/min ~ 8000 revs/min, the THE ADIABATIC SHEAR IN effect of cutter head of pulling an oar in this process, is conducive to the length reducing institute's dispersing ultrafine nanofiber, and obtains uniform superfine nano fiber dispersion.
A kind of nanofiber as above/spun-bonded non-woven fabrics composite filter material preparation method, in step (4), the time of described immersion is 5 ~ 30min; Described oven dry refers to and hangs in baking oven, 25 ~ 50 DEG C of oven dry; The deposition of nanofiber and the thickness of sedimentary deposit can control by controlling the mass ratio of nanofiber and the time of impregnation process in dispersion liquid.
A kind of nanofiber as above/spun-bonded non-woven fabrics composite filter material preparation method, in step (5), described repeatedly repetition refers to repetition 2 ~ 6 times, also namely obtains the lamination material of 2 ~ 6 layers.
By composition fiber surface deposition high-flexibility, superfine nano fiber at composite filtering material, form the lamination material containing " fractal secondary structure " on main fibre.Main body crude fibre has good filter effect for the particle that particle diameter is larger, form larger aperture structure simultaneously and be conducive to passing through smoothly of air-flow, and secondary fractal structure has excellent strainability for ultra-fine grain, its comparatively soft characteristic simultaneously, made high velocity air by time can not produce barrier effect to air-flow, thus the increase of resistance pressure drop can not be caused.The effect using polyvinyl butyral solution to prepare thin nanofiber dispersion liquid is: polyvinyl butyral solution can be used as adhesive, by the composition fiber surface of superfine nano fibres fasten at composite filtering material in composite filtering material immersion treatment step; In addition, PVOH butyral has hydrophobicity, can give composite filtering material certain hydrophobicity to being formed at composite filtering material composition fiber surface after composite filtering material immersion treatment.
Present invention also offers a kind of nanofiber/spun-bonded non-woven fabrics composite filter material, described nanofiber/spun-bonded non-woven fabrics composite filter material is the stacked composite filtering material of gradient, form for lamination material is carried out superimposion from low to high successively by media filtration efficiency from bottom to top, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensure that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, the filter efficiency value of one deck to the particle of 0.02 ~ 10 μm is 1.03 ~ 1.3 times of one deck below above, the lamination material superposition number of plies is 2 ~ 6 layers, form spun-bonded non-woven fabrics and there is electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material; Described nanofiber/spun-bonded non-woven fabrics composite filter material can reach more than 99.999% to the filter efficiency of the particle of 0.02 ~ 10 μm, and pressure drag remains on 10 ~ 30Pa.
For electret material in above-mentioned background technology when directly contacting with surrounding environment, be subject to the impact of moisture in air and other factors, the dissipation of electret material electric charge can be accelerated, make the problem that electret effect weakens, the stacked complex form of gradient is adopted to carry out interspersed superposition to obtained electrostatic spinning fiber and spun-bonded non-woven fabrics, the structure of structure electrostatic spinning fiber interlayer between spun-bonded non-woven fabrics.This structure forms classified filtering on the one hand, contributes to improving filtrate efficiency; On the other hand, electrostatic spinning fiber interlayer containing electret effect is between the spun-bonded non-woven fabrics through hydrophobic treatments, reduce and directly contact with external environment and the intensity that lotus affects is produced on electricity, the decay of electret effect can be slowed down, thus be conducive to the maintenance of media performance.
Beneficial effect
1. the present invention carries out anti-tampering isolated process by using insulating materials between Multi needle Static Spinning syringe needle, electric jamming between spinning syringe needle is weakened, be conducive to the stable of spinning jet, the nano fibrous membrane obtained by this kind of mode electrostatic spinning has good uniformity.Meanwhile, utilize during this mode high voltage electrostatic spinning and electric discharge phenomena can not occur, be conducive to safety in production.
2. the present invention is by the nano fibrous membrane that obtains at electrostatic spinning and spun-bonded non-woven fabrics deposit high-flexibility, superfine nano fiber, to form the composite filter material containing " fractal secondary structure " on main fibre.Main body crude fibre has good filter effect for the particle that particle diameter is larger, form larger aperture structure simultaneously and be conducive to passing through smoothly of air-flow, and secondary fractal structure has excellent strainability for ultra-fine grain, its comparatively soft characteristic simultaneously, made high velocity air by time can not produce barrier effect to air-flow, thus the increase of resistance pressure drop can not be caused.The filtering material using the manner to obtain has the filter of high filtration effect, the feature of low pressure drag.
3. the present invention is by carrying out interspersed superpose with hydrophilic spunbonded nonwoven cloth according to filter efficiency form from low to high by the electrostatic spinning nano fiber film of different filter capacity, make the nano fibrous membrane interlayer with electret effect between spun-bonded non-woven fabrics, hinder the electrostatic spinning fiber with electret effect directly to contact with external environment, the electrostatic spinning fiber obtained/spun-bonded non-woven fabrics composite filtering material has good Charge Storage Stability, thus filter effect maintenance is good.
Accompanying drawing explanation
Fig. 1 is Static Spinning syringe needle spacer assembly schematic diagram, and wherein, 1 is insulating materials dividing plate, and 2 is spinning head apparatus, and 3 is spray silk base.
Fig. 2 is nanofiber/spun-bonded non-woven fabrics composite filter material schematic diagram, and wherein, 4 is spun-bonded non-woven fabrics, and 5 is electrostatic spinning nano fiber.
Fig. 3 is that electrostatic spinning nano fiber/hydrophilic spunbonded nonwoven cloth composite filtering material and electrostatic spinning nano fiber/common spun-bonded non-woven fabrics composite filtering material are crossed performance and place number of days graph of a relation, wherein, environment temperature 23 DEG C, humidity 80%, this figure shows that nanofiber/spun-bonded non-woven fabrics composite filter material prepared by this patent has excellent charge storage stability, thus filter effect has good maintenance.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
A kind of electrospinning process of the present invention, is Multi needle electrostatic spinning, insulate between the syringe needle of Multi needle electrostatic spinning.Wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square or circular, and the degree of depth of isolated groove is 1 ~ 5 times of needle length; Insulating materials is Acrylnitrile-Butadiene-Styrene, Merlon, polymethyl methacrylate, polypropylene, polyamide, polystyrene, polyvinyl chloride, polyethylene, polytetrafluoroethylene (PTFE), Kynoar or polyethylene terephthalate.
Embodiment 1
A kind of electrospinning process, is Multi needle electrostatic spinning, insulate between the syringe needle of Multi needle electrostatic spinning.Fig. 1 is Static Spinning syringe needle spacer assembly schematic diagram, and wherein, 1 is insulating materials dividing plate, and 2 is spinning head apparatus, and 3 is spray silk base; The same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square, and the degree of depth of isolated groove is 1 times of needle length; Insulating materials is Acrylnitrile-Butadiene-Styrene.
Embodiment 2
A kind of electrospinning process, is Multi needle electrostatic spinning, insulate between the syringe needle of Multi needle electrostatic spinning.Wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove be circular, and the degree of depth completely cutting off groove is 3 times of needle length; Insulating materials is Merlon.
Embodiment 3
A kind of electrospinning process, is Multi needle electrostatic spinning, insulate between the syringe needle of Multi needle electrostatic spinning.
Concrete steps are:
(1) inorganic nanoparticles titania nanoparticles is added in solvent DMF, and ultrasonic disperse 30 minutes, obtain the homodisperse dispersion liquid of nano particle;
(2) add in dispersion liquid by polymer polysulfones, magnetic agitation 8 hours, is mixed with even and stable spinning solution, and wherein, the mass fraction of polysulfones is 12%, and the addition of inorganic nanoparticles is 10% of polymer and inorganic nanoparticles gross mass;
(3) spinning solution is carried out Multi needle electrostatic spinning, the process conditions of Multi needle electrostatic spinning are: supply voltage 45KV, and spinning environment condition is temperature 35 DEG C, relative humidity 25%, spinning solution rate of flooding 4mL/h; Multi needle spray silk unit syringe needle spacing 3cm, spray silk unit syringe needle quantity is 60, and the spinning time is 40min; Insulate between the syringe needle of Multi needle electrostatic spinning, wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square, and the degree of depth of isolated groove is 2 times of needle length; Insulating materials is Acrylnitrile-Butadiene-Styrene; The polymer nanofiber spun-bonded non-woven fabrics base material spun receives, and obtains the composite filtering material of spun-bonded non-woven fabrics deposited on substrates Static Spinning polymer nanofiber, wherein, spun-bonded non-woven fabrics, its composition fibre diameter is 20 μm, and nonwoven fabric aperture size is 30 μm, and grammes per square metre is 10g/m
2, exhibits initial filtration efficiency is 5%;
(4) by the obtained spun-bonded non-woven fabrics in step (1) ~ (3) depositing the composite filtering material of Static Spinning polysulfones nanofiber, the composite filtering material obtained is divided into two parts, a part is for testing grammes per square metre, and a part is for testing strainability.
The composite filtering material being used for testing grammes per square metre is cut into 10 parts, tests the grammes per square metre of electrostatic spinning fiber layer in every part of composite filtering material respectively.Recording electrostatic spinning fiber layer grammes per square metre value is 30g/m
2, 34g/m
2, 33g/m
2, 33g/m
2, 32g/m
2, 33g/m
2, 33g/m
2, 34g/m
2, 32g/m
2, 33g/m
2, the grammes per square metre coefficient of variation is 3.36%;
Composite filtering material for testing strainability is got 10 test points at random, test its filter efficiency to the particle of 0.02 ~ 10 μm, obtaining filter efficiency value is 93.1225%, 93.1456%, 93.1458%, 93.1267%, 93.1258%, 93.0321%, 93.1467%, 93.1367%, 93.1457%, 93.1299%; Corresponding pressure drag is 19Pa, 20Pa, 19Pa, 19Pa, 20Pa, 18Pa, 19Pa, 19Pa, 20Pa, 19Pa.The coefficient of variation calculating composite filtering material filter efficiency is 0.035%, and the coefficient of variation of pressure drag is 3.13%;
Comparative example
This comparative example is the comparative example of embodiment 3
Concrete steps are:
Step (1) is identical with step (1) in embodiment 3;
Step (2) is identical with step (2) in embodiment 3;
In step (3) except spinning syringe needle does not carry out anti-tampering isolated process, all the other parameters are identical with step (3) in embodiment 3;
(4) by the obtained spun-bonded non-woven fabrics in step (1) ~ (3) depositing the composite filtering material of Static Spinning polyacrylonitrile nanofiber, the composite filtering material obtained is divided into two parts, a part is for testing grammes per square metre, and a part is for testing strainability.
The composite filtering material being used for testing grammes per square metre is cut into 10 parts, tests the grammes per square metre of electrostatic spinning fiber layer in every part of composite filtering material respectively.Recording electrostatic spinning fiber layer grammes per square metre value is 30g/m
2, 28g/m
2, 34g/m
2, 40g/m
2, 34g/m
2, 28g/m
2, 29g/m
2, 36g/m
2, 31g/m
2, 33g/m
2, the coefficient of variation of grammes per square metre is: 11.34%.
Composite filtering material for testing strainability is got 10 test points at random, test its filter efficiency to the particle of 0.02 ~ 10 μm, obtaining filter efficiency value is 90.1577%, 89.9892%, 92.0976%, 90.9104%, 90.2801%, 92.9726%, 92.0023%, 92.1078%, 93.1998%, 91.0947%; Corresponding pressure drag is 20Pa, 18Pa, 18Pa, 20Pa, 20Pa, 19Pa, 23Pa, 19Pa, 21Pa, 17Pa.The coefficient of variation calculating composite filtering material filter efficiency is 1.13%, and the coefficient of variation of pressure drag is 8.35%.
Comparative example 3 and all values for coefficient of variation in its comparative example, can find that the coefficient of variation of the coefficient of variation of the composite filtering material electrostatic spinning nano fiber layer grammes per square metre obtained in embodiment 3, composite filtering material filter efficiency and pressure drag is all little than value corresponding in its comparative example, illustrate that the composite filtering material obtained after using Static Spinning syringe needle spacer assembly is more even than the composite filtering material not using Static Spinning syringe needle spacer assembly to obtain.
Embodiment 4
A kind of nanofiber/spun-bonded non-woven fabrics composite filter material preparation method, concrete steps are:
(1) spun-bonded non-woven fabrics pre-treatment
Step is:
A) titanium dioxide nanofiber is added in ethanol, and ultrasonic disperse, obtain uniform dispersion liquid, wherein, in dispersion liquid, fiber quality mark is 0.1%, and soak time is 5min; Described titanium dioxide nanofiber diameter is 50nm, and length is 100nm;
B) take out after spun-bonded non-woven fabrics being soaked in the dispersion liquid of titanium dioxide nanofiber, hang in baking oven, 50 DEG C of oven dry, obtain the spun-bonded non-woven fabrics base material of surface deposition titanium dioxide nanofiber.Wherein, spun-bonded non-woven fabrics, its composition fibre diameter is 50 μm, and nonwoven fabric aperture size is 30 μm, and grammes per square metre is 68g/m
2, exhibits initial filtration efficiency is 15%;
(2) electrostatic spinning
Step is:
A) inorganic nanoparticles nano SiO 2 particle is added in solvent DMF, and ultrasonic disperse 30 minutes, obtain the homodisperse dispersion liquid of nano particle;
B) polymer polyvinylidene fluoride is added in dispersion liquid, magnetic agitation 8 hours, is mixed with even and stable spinning solution, wherein, the mass fraction of Kynoar is 20%, and the addition of inorganic nanoparticles is 9% of polymer and inorganic nanoparticles gross mass;
C) spinning solution is carried out Multi needle electrostatic spinning, the process conditions of Multi needle electrostatic spinning are: supply voltage 15KV, and spinning environment condition is temperature 35 DEG C, relative humidity 25%, spinning solution rate of flooding 6mL/h; Multi needle spray silk unit syringe needle spacing 2cm, spray silk unit syringe needle quantity is 90; Insulate between the syringe needle of Multi needle electrostatic spinning, wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square, and the degree of depth of isolated groove is 1 times of needle length; Insulating materials is Acrylnitrile-Butadiene-Styrene; The spun-bonded non-woven fabrics base material obtained in the polymer nanofiber step (1) spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber on base material;
(3) preparation of superfine nano fiber dispersion
First preparing Solute mass fraction is the polyvinyl butyral solution of 0.1%, and preparation polyvinyl butyral solution solvent for use is n-butanol; The solubility parameter of preparation polyvinyl butyral solution solvent for use differs 6 with electrostatic spinning fiber structure adaptability degree used parameter values, then itself and superfine nano fiber polystyrene are added in high speed beater and disperse, the rotating speed of high speed beater is 5000 revs/min, obtain uniform superfine nano fiber dispersion, in superfine nano fiber dispersion, mass fraction shared by nanofiber is 0.01%; Superfine nano fibre diameter is 10nm, and length is 100nm;
(4) composite filtering material immersion treatment
Take out after composite filtering material is soaked 5min in superfine nano fiber dispersion, hang in baking oven, 25 DEG C of oven dry, obtain the filtrate of composite filtering material fiber surface deposition superfine nano fiber; Be lamination material; The superfine nano fiber laydown thickness on the composite filtering material surface after immersion treatment is 20nm;
(5) repeat 4 step (1) ~ (4), also namely obtain 4 lamination materials, the filter efficiency of often opening lamination material was determined by the electrostatic spinning time in rate-determining steps (2).The spinning time is respectively 5min, 6min, 7min and 9min, and the corresponding filter efficiency value of lamination material to the particle of 0.02 ~ 10 μm of often opening is respectively 20.1442%, 22.6656%, 24.3764% and 26.5243%;
(6) by lamination material, superimposion is carried out successively from low to high from bottom to top by media filtration efficiency, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensures that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, one deck filter efficiency value is 1.1 times of one deck below above, the lamination material superposition number of plies is 4 layers, form spun-bonded non-woven fabrics and there is electret effect nanofiber sandwich alternately, make nanofiber/spun-bonded non-woven fabrics composite filter material, as shown in Figure 2, wherein, 4 is spun-bonded non-woven fabrics, and 5 is electrostatic spinning nano fiber; Nanofiber/the filter efficiency of spun-bonded non-woven fabrics composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 16Pa, and as shown in Figure 3, the electrostatic spinning fiber obtained/glass fibre composite filter paper has good Charge Storage Stability, and filter effect maintenance is good.
Embodiment 5
A kind of nanofiber/spun-bonded non-woven fabrics composite filter material preparation method, concrete steps are:
(1) spun-bonded non-woven fabrics pre-treatment
Step is:
A) nanometer activated carbon fiber is added in ethanol, and ultrasonic disperse, obtain uniform dispersion liquid, wherein, in dispersion liquid, fiber quality mark is 1%, and soak time is 8min; Described nanometer activated carbon fiber diameter is 100nm, and length is 300nm;
B) take out after spun-bonded non-woven fabrics being soaked in the dispersion liquid of nanometer activated carbon fiber, hang in baking oven, 60 DEG C of oven dry, obtain the spun-bonded non-woven fabrics base material of surface deposition titanium dioxide nanofiber or nanometer activated carbon fiber.Wherein, spun-bonded non-woven fabrics, its composition fibre diameter is 40 μm, and nonwoven fabric aperture size is 35 μm, and grammes per square metre is 40g/m
2, exhibits initial filtration efficiency is 20%;
(2) electrostatic spinning
Step is:
A) inorganic nanoparticles titanium dioxide is added in DMF, and ultrasonic disperse 60 minutes, obtain the homodisperse dispersion liquid of nano particle;
B) add in dispersion liquid by polymer polysulfones, magnetic agitation 10 hours, is mixed with even and stable spinning solution, and wherein, the mass fraction of polysulfones is 10%, and the addition of inorganic nanoparticles is 5% of polymer and inorganic nanoparticles gross mass;
C) spinning solution is carried out Multi needle electrostatic spinning, the process conditions of Multi needle electrostatic spinning are: supply voltage 20KV, and spinning environment condition is temperature 18 DEG C, relative humidity 35%, spinning solution rate of flooding 4mL/h; Multi needle spray silk unit syringe needle spacing 10cm, spray silk unit syringe needle quantity is 20; Insulate between the syringe needle of Multi needle electrostatic spinning, wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square, and the degree of depth of isolated groove is 2 times of needle length; Insulating materials is polyethylene terephthalate; The spun-bonded non-woven fabrics base material obtained in the polymer nanofiber step (1) spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber on spun-bonded non-woven fabrics;
(3) preparation of superfine nano fiber dispersion
First preparing Solute mass fraction is the polyvinyl butyral solution of 2.5%, and preparation polyvinyl butyral solution solvent for use is ethanol; The solubility parameter of preparation polyvinyl butyral solution solvent for use differs 5 with electrostatic spinning fiber structure adaptability degree used parameter values, then the mixture of itself and superfine nano fiber polystyrene and polyester is added in high speed beater and disperse, wherein the mass ratio of polystyrene and polyester is 1:1, the rotating speed of high speed beater is 5000 revs/min, obtain uniform superfine nano fiber dispersion, in superfine nano fiber dispersion, mass fraction shared by nanofiber is 2.5%; Superfine nano fibre diameter is 80nm, and length is 150nm;
(4) composite filtering material immersion treatment
Take out after composite filtering material is soaked 15min in superfine nano fiber dispersion, hang in baking oven, 35 DEG C of oven dry, obtain the filtrate of composite filtering material fiber surface deposition superfine nano fiber; Be lamination material; The superfine nano fiber laydown thickness on the composite filtering material surface after immersion treatment is 80nm;
(5) repeat 3 step (1) ~ (4), also namely obtain the lamination material of 3 layers, the filter efficiency of often opening lamination material was determined by the electrostatic spinning time in rate-determining steps (2).The spinning time is respectively 8min, 9.5min and 11min, and the corresponding filter efficiency value of lamination material to the particle of 0.02 ~ 10 μm of often opening is respectively 30.1248%, 31.6015% and 33.0743%;
(6) by lamination material, superimposion is carried out successively from low to high from bottom to top by media filtration efficiency, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensures that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, one deck filter efficiency value is 1.05 times of one deck below above, the lamination material superposition number of plies is 3 layers, forms spun-bonded non-woven fabrics and has electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material; Nanofiber/the filter efficiency of spun-bonded non-woven fabrics composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 23Pa, and as shown in Figure 3, the electrostatic spinning fiber obtained/glass fibre composite filter paper has good Charge Storage Stability, and filter effect maintenance is good.
Embodiment 6
A kind of nanofiber/spun-bonded non-woven fabrics composite filter material preparation method, concrete steps are:
(1) spun-bonded non-woven fabrics pre-treatment
Step is:
A) titanium dioxide nanofiber is added in ethanol, and ultrasonic disperse, obtains uniform dispersion liquid, wherein, in dispersion liquid fiber altogether mass fraction be 1%, soak time is 8min; Described titanium dioxide nanofiber diameter is 80nm, and length is 200nm;
B) take out after spun-bonded non-woven fabrics being soaked in the dispersion liquid of titanium dioxide nanofiber, hang in baking oven, 55 DEG C of oven dry, obtain the spun-bonded non-woven fabrics base material of surface deposition titanium dioxide nanofiber.Wherein, spun-bonded non-woven fabrics, its composition fibre diameter is 32 μm, and nonwoven fabric aperture size is 20 μm, and grammes per square metre is 145g/m
2, exhibits initial filtration efficiency is 35%;
(2) electrostatic spinning
Step is:
A) inorganic nanoparticles titanium dioxide is added in DMF, and ultrasonic disperse 45 minutes, obtain the homodisperse dispersion liquid of nano particle;
B) polymer polyvinylidene fluoride-tetrafluoroethylene-perfluoro methyl vinyl ether is added in dispersion liquid, magnetic agitation 8 hours, be mixed with even and stable spinning solution, wherein, the mass fraction of Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether is 18%, and the addition of inorganic nanoparticles is 3% of polymer and inorganic nanoparticles gross mass;
C) spinning solution is carried out Multi needle electrostatic spinning, the process conditions of Multi needle electrostatic spinning are: supply voltage 55KV, and spinning environment condition is temperature 20 DEG C, relative humidity 30%, spinning solution rate of flooding 5mL/h; Multi needle spray silk unit syringe needle spacing 6cm, spray silk unit syringe needle quantity is 18; Insulate between the syringe needle of Multi needle electrostatic spinning, wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square, and the degree of depth of isolated groove is 2 times of needle length; Insulating materials is polyethylene terephthalate; The spun-bonded non-woven fabrics base material obtained in the polymer nanofiber step (1) spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber on spun-bonded non-woven fabrics;
(3) preparation of superfine nano fiber dispersion
First preparing Solute mass fraction is the polyvinyl butyral solution of 3%, and preparation polyvinyl butyral solution solvent for use is methyl ethyl ketone; The solubility parameter of preparation polyvinyl butyral solution solvent for use differs 5 with electrostatic spinning fiber structure adaptability degree used parameter values, then itself and superfine nano fiber polystyrene are added in high speed beater and disperse, the rotating speed of high speed beater is 5000 revs/min, obtain uniform superfine nano fiber dispersion, in superfine nano fiber dispersion, mass fraction shared by nanofiber is 3.5%; Superfine nano fibre diameter is 60nm, and length is 70nm;
(4) composite filtering material immersion treatment
Take out after composite filtering material is soaked 20min in superfine nano fiber dispersion, hang in baking oven, 40 DEG C of oven dry, obtain the filtrate of composite filtering material fiber surface deposition superfine nano fiber; Be lamination material; The superfine nano fiber laydown thickness on the composite filtering material surface after immersion treatment is 60nm;
(5) repeat 2 step (1) ~ (4), also namely obtain the lamination material of 2 layers, the filter efficiency of often opening lamination material was determined by the electrostatic spinning time in rate-determining steps (2).The spinning time is respectively 15min and 17min, and the corresponding filter efficiency value of lamination material to the particle of 0.02 ~ 10 μm of often opening is respectively 54.1062% and 63.9901%;
(6) by lamination material, superimposion is carried out successively from low to high from bottom to top by media filtration efficiency, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensures that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, one deck filter efficiency value is 1.2 times of one deck below above, the lamination material superposition number of plies is 2 layers, forms spun-bonded non-woven fabrics and has electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material; Nanofiber/the filter efficiency of spun-bonded non-woven fabrics composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 21Pa, and as shown in Figure 3, the electrostatic spinning fiber obtained/glass fibre composite filter paper has good Charge Storage Stability, and filter effect maintenance is good.
Embodiment 7
A kind of nanofiber/spun-bonded non-woven fabrics composite filter material preparation method, concrete steps are:
(1) spun-bonded non-woven fabrics pre-treatment
Step is:
A) titanium dioxide nanofiber is added in ethanol, and ultrasonic disperse, obtain uniform dispersion liquid, wherein, in dispersion liquid, fiber quality mark is 5%, and soak time is 10min; Described titanium dioxide nanofiber diameter is 70nm, and length is 150nm;
B) take out after spun-bonded non-woven fabrics being soaked in the dispersion liquid of titanium dioxide nanofiber, hang in baking oven, 50 DEG C of oven dry, obtain the spun-bonded non-woven fabrics base material of surface deposition titanium dioxide nanofiber.Wherein, spun-bonded non-woven fabrics, its composition fibre diameter is 30 μm, and nonwoven fabric aperture size is 43 μm, and grammes per square metre is 50g/m
2, exhibits initial filtration efficiency is 15%;
(2) electrostatic spinning
Step is:
A) inorganic nanoparticles titanium dioxide is added in solvent, and ultrasonic disperse 40 minutes, obtain the homodisperse dispersion liquid of nano particle;
B) mixture of polymer polyvinylidene fluoride and polybutylene terephthalate is added in dispersion liquid, wherein the mass ratio of Kynoar and polybutylene terephthalate is 1:1, magnetic agitation 8 hours, be mixed with even and stable spinning solution, wherein, the mass fraction of the mixture of Kynoar and polybutylene terephthalate two kinds of polymer is 25%, and the addition of inorganic nanoparticles is 2.5% of polymer and inorganic nanoparticles gross mass;
C) spinning solution is carried out Multi needle electrostatic spinning, the process conditions of Multi needle electrostatic spinning are: supply voltage 60KV, and spinning environment condition is temperature 25 DEG C, relative humidity 40%, spinning solution rate of flooding 2mL/h; Multi needle spray silk unit syringe needle spacing 4cm, spray silk unit syringe needle quantity is 50; Insulate between the syringe needle of Multi needle electrostatic spinning, wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square, and the degree of depth of isolated groove is 2 times of needle length; Insulating materials is polyethylene terephthalate; The spun-bonded non-woven fabrics base material obtained in the polymer nanofiber step (1) spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber on spun-bonded non-woven fabrics base material;
(3) preparation of superfine nano fiber dispersion
First preparing Solute mass fraction is the polyvinyl butyral solution of 3.2%, and preparation polyvinyl butyral solution solvent for use is the mixture of normal propyl alcohol, DAA and ethanol, and wherein the mass ratio of normal propyl alcohol, DAA and ethanol is 1:2:1; The solubility parameter of preparation polyvinyl butyral solution solvent for use differs 5 with electrostatic spinning fiber structure adaptability degree used parameter values, then itself and superfine nano filled nylon 6 are added in high speed beater and disperse, the rotating speed of high speed beater is 5500 revs/min, obtain uniform superfine nano fiber dispersion, in superfine nano fiber dispersion, mass fraction shared by nanofiber is 4%; Superfine nano fibre diameter is 90nm, and length is 100nm;
(4) composite filtering material immersion treatment
Take out after composite filtering material is soaked 16min in described superfine nano fiber dispersion, hang in baking oven, 25 DEG C of oven dry, obtain the filtrate of composite filtering material fiber surface deposition superfine nano fiber; Be lamination material; The superfine nano fiber laydown thickness on the described composite filtering material surface after immersion treatment is 28nm;
(5) repeat 5 step (1) ~ (4), also namely obtain the lamination material of 5 layers, the filter efficiency of often opening lamination material was determined by the electrostatic spinning time in rate-determining steps (2).The spinning time is respectively 6min, 7.5min, 10min, 12.5min and 15min, and the corresponding filter efficiency value of lamination material to the particle of 0.02 ~ 10 μm is respectively 22.52351%, 23.7671%, 25.5739%, 27.7328%, 29.9331%;
(6) by lamination material, superimposion is carried out successively from low to high from bottom to top by media filtration efficiency, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensures that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, one deck filter efficiency value is 1.08 times of one deck below above, the lamination material superposition number of plies is 5 layers, forms spun-bonded non-woven fabrics and has electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material; Nanofiber/the filter efficiency of spun-bonded non-woven fabrics composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 23Pa, and as shown in Figure 3, the electrostatic spinning fiber obtained/glass fibre composite filter paper has good Charge Storage Stability, and filter effect maintenance is good.
Embodiment 8
A kind of nanofiber/spun-bonded non-woven fabrics composite filter material preparation method, concrete steps are:
(1) spun-bonded non-woven fabrics pre-treatment
Step is:
A) nanometer activated carbon fiber is added in ethanol, and ultrasonic disperse, obtain uniform dispersion liquid, wherein, in dispersion liquid, fiber quality mark is 3%, and soak time is 8min; Described nanometer activated carbon fiber diameter is 90nm, and length is 250nm;
B) take out after spun-bonded non-woven fabrics being soaked in the dispersion liquid of nanometer activated carbon fiber, hang in baking oven, 54 DEG C of oven dry, obtain the spun-bonded non-woven fabrics base material of surface deposition nanometer activated carbon fiber.Wherein, its composition fibre diameter is 30 μm, and nonwoven fabric aperture size is 100 μm, and grammes per square metre is 140g/m
2, exhibits initial filtration efficiency is 15%;
(2) electrostatic spinning
Step is:
A) inorganic nanoparticles titanium dioxide is added in solvent, and ultrasonic disperse 45 minutes, obtain the homodisperse dispersion liquid of nano particle;
B) mixture of polymer polyurethane, fluorinated polyurethane and polysulfones is added in dispersion liquid, the mass ratio of polyurethane, fluorinated polyurethane and polysulfones is 1:2:1, magnetic agitation 8 hours, be mixed with even and stable spinning solution, wherein, the mass fraction of the mixture of polyurethane, fluorinated polyurethane and polysulfones is 30%, and the addition of inorganic nanoparticles is 6.5% of polymer and inorganic nanoparticles gross mass;
C) spinning solution is carried out Multi needle electrostatic spinning, the process conditions of Multi needle electrostatic spinning are: supply voltage 50KV, and spinning environment condition is temperature 10 DEG C, relative humidity 40%, spinning solution rate of flooding 3mL/h; Multi needle spray silk unit syringe needle spacing 10cm, spray silk unit syringe needle quantity is 25; Insulate between the syringe needle of Multi needle electrostatic spinning, wherein, the same insulating base of Needle sharing; Between syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of syringe needle and form isolated groove, the shape of isolated groove is square, and the degree of depth of isolated groove is 2 times of needle length; Insulating materials is polyethylene terephthalate; The spun-bonded non-woven fabrics base material obtained in the polymer nanofiber step (1) spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber on spun-bonded non-woven fabrics base material;
(3) preparation of superfine nano fiber dispersion
First preparing Solute mass fraction is the polyvinyl butyral solution of 0.1%, and preparation polyvinyl butyral solution solvent for use is the mixture of ethanol and normal propyl alcohol, and wherein the mass ratio of ethanol and normal propyl alcohol is 2:1; The solubility parameter of preparation polyvinyl butyral solution solvent for use differs 5 with electrostatic spinning fiber structure adaptability degree used parameter values, then the mixture of itself and superfine nano fiber polystyrene, polyester and polyvinyl acetate is added in high speed beater and disperse, wherein, the mass ratio of polystyrene, polyester and polyvinyl acetate is 2:1:1, the rotating speed of high speed beater is 5500 revs/min, obtain uniform superfine nano fiber dispersion, in superfine nano fiber dispersion, mass fraction shared by nanofiber is 4.0%; Superfine nano fibre diameter is 70nm, and length is 105nm;
(4) composite filtering material immersion treatment
Take out after composite filtering material is soaked 12min in superfine nano fiber dispersion, hang in baking oven, 45 DEG C of oven dry, obtain the filtrate of composite filtering material fiber surface deposition superfine nano fiber; Be lamination material; The superfine nano fiber laydown thickness on the composite filtering material surface after immersion treatment is 60nm;
(5) repeat 6 step (1) ~ (3), also namely obtain the lamination material of 6 layers, the filter efficiency of often opening lamination material was determined by the electrostatic spinning time in rate-determining steps (2).The spinning time is respectively 5min, 5.5min, 6min, 8.5min, 10min and 11min, and the corresponding filter efficiency value of lamination material to the particle of the mistake 0.02 ~ 10 μm of grain is respectively 20.2158%, 20.9103%, 21.7903%, 22.8130%, 23.7562% and 24.7810%;
(6) by lamination material, superimposion is carried out successively from low to high from bottom to top by media filtration efficiency, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensures that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, one deck filter efficiency value is 1.03 times of one deck below above, the lamination material superposition number of plies is 6 layers, forms spun-bonded non-woven fabrics and has electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material; Nanofiber/the filter efficiency of spun-bonded non-woven fabrics composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 28Pa, and as shown in Figure 3, the electrostatic spinning fiber obtained/glass fibre composite filter paper has good Charge Storage Stability, and filter effect maintenance is good.
Embodiment 9-56 preparation process is with embodiment 4, and wherein solution parameter, technological parameter and composite filter material performance parameter are as shown in table 1-6:
Table 1:
Table 2:
Table 3:
Table 4:
Table 5:
Table 6:
Embodiment 56-69 preparation process is with embodiment 5, and wherein solution parameter, technological parameter and composite filter material performance parameter are as shown in table 7-8:
Table 7:
Table 8:
Embodiment 70-78 preparation process is with embodiment 6, and wherein solution parameter, technological parameter and composite filter material performance parameter are as shown in table 9-10:
Table 9
Table 10:
Claims (10)
1. an electrospinning process, is Multi needle electrostatic spinning, it is characterized in that: insulate between the syringe needle of described Multi needle electrostatic spinning.
2. a kind of electrospinning process according to claim 1, is characterized in that, the same insulating base of described Needle sharing.
3. a kind of electrospinning process according to claim 1, is characterized in that, between described syringe needle, insulation refers to and uses insulating materials to carry out anti-tampering isolated process to each syringe needle; Be specially and be with insulating materials in the surrounding of described syringe needle and form isolated groove, the shape of isolated groove is square or circular, and the degree of depth of isolated groove is 1 ~ 5 times of described needle length.
4. a kind of electrospinning process according to claim 3, it is characterized in that, described insulating materials is Acrylnitrile-Butadiene-Styrene, Merlon, polymethyl methacrylate, polypropylene, polyamide, polystyrene, polyvinyl chloride, polyethylene, polytetrafluoroethylene (PTFE), Kynoar or polyethylene terephthalate.
5. nanofiber/spun-bonded non-woven fabrics composite filter material preparation method, is characterized in that concrete steps are:
(1) spun-bonded non-woven fabrics pre-treatment
Step is:
A) titanium dioxide nanofiber or nanometer activated carbon fiber are added in ethanol, and ultrasonic disperse, obtain uniform dispersion liquid;
B) take out oven dry after being soaked in the dispersion liquid of titanium dioxide nanofiber or nanometer activated carbon fiber by spun-bonded non-woven fabrics, obtain the spun-bonded non-woven fabrics base material of surface deposition titanium dioxide nanofiber or nanometer activated carbon fiber;
(2) electrostatic spinning
Step is:
A) inorganic nanoparticles is added in solvent, and ultrasonic disperse, obtain the homodisperse dispersion liquid of nano particle;
B) polymer is added in described dispersion liquid, be mixed with even and stable spinning solution;
C) spinning solution is carried out Multi needle electrostatic spinning, insulate between the syringe needle of described Multi needle electrostatic spinning; The polymer nanofiber spun-bonded non-woven fabrics base material spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber on spun-bonded non-woven fabrics base material;
(3) preparation of superfine nano fiber dispersion
First prepare polyvinyl butyral solution, then itself and superfine nano fiber are added in high speed beater and disperse, obtain uniform superfine nano fiber dispersion;
(4) composite filtering material immersion treatment
Take out after described composite filtering material is soaked in described superfine nano fiber dispersion, dry, obtain the filtrate of composite filtering material fiber surface deposition superfine nano fiber; Be lamination material;
The superfine nano fiber laydown thickness on the described composite filtering material surface after immersion treatment is 20 ~ 200nm;
Test obtains the filter efficiency value of this lamination material to 0.02 ~ 10 μm of particle;
(5) repeatedly repeat step (1) ~ (4), obtain the lamination material of different filter efficiency;
(6) by lamination material, superimposion is carried out successively from low to high from bottom to top by media filtration efficiency, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensures that top layer and the bottom are all spun-bonded non-woven fabrics layer; Adjacent two layers lamination material, the filter efficiency value of one deck to the particle of 0.02 ~ 10 μm is 1.03 ~ 1.3 times of one deck below above, form spun-bonded non-woven fabrics and there is electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material.
6. a kind of nanofiber according to claim 5/spun-bonded non-woven fabrics composite filter material preparation method, it is characterized in that, in described step (1), in described titanium dioxide nanofiber or nanometer activated carbon fiber dispersion liquid, fiber quality mark is 0.1 ~ 5%, and soak time is 5 ~ 10min; Described titanium dioxide nanofiber or nanometer activated carbon fiber diameter are 50 ~ 100nm, and length is 100 ~ 300nm; Described spun-bonded non-woven fabrics, its composition fibre diameter is 1 ~ 50 μm, and nonwoven fabric aperture size is 5 ~ 120 μm, and grammes per square metre is 10 ~ 300g/m
2, exhibits initial filtration efficiency is 5% ~ 40%; Described oven dry refers to and hangs in baking oven, and temperature is 50 ~ 60 DEG C;
In step (2), in described spinning solution, the concentration of polymer is 5 ~ 40wt%, and the addition of inorganic nanoparticles is 0.1 ~ 10wt% of polymer and inorganic nanoparticles gross mass;
Described inorganic nanoparticles is silica, alundum (Al2O3), zinc oxide, barium monoxide, titanium dioxide, tantalum pentoxide, barium titanate, lead zirconate titanate, silicon nitride, tourmaline, boehmite or silsesquioxane nano particle;
Described polymer is the one in Kynoar, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyvinyl acetate, nylon 6, polymethyl methacrylate, polyaniline, polyethylene glycol oxide, polyvinylpyrrolidone, polyacrylonitrile, polycaprolactone, polyurethane, fluorinated polyurethane, polysulfones, polyether sulfone, Kynoar-hexafluoropropene, Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether, Kynoar-CTFE, or is the mixture of above several polymer;
Wherein said solvent corresponds to respectively according to type of polymer:
Kynoar: DMF, 1-METHYLPYRROLIDONE, dimethylacetylamide, triethyl phosphate and dimethyl sulfoxide (DMSO);
Polybutylene terephthalate: carrene, oxolane, chloroform or acetone;
Polyethylene terephthalate: carrene, oxolane, chloroform or acetone;
Polyarylate: carrene, oxolane, chloroform or acetone;
Polyvinyl acetate: toluene, acetone, ethanol, acetic acid, ethyl acetate or chloroform;
Nylon 6: formic acid;
Polymethyl methacrylate: chloroform, acetic acid, ethyl acetate, acetone or toluene;
Polyaniline: DMF or 1-METHYLPYRROLIDONE;
Polyethylene glycol oxide: DMF, ethanol, water or chloroform;
Polyvinylpyrrolidone: water, ethanol, DMA or DMF;
Polyacrylonitrile: DMF or dimethyl sulfoxide (DMSO);
Polycaprolactone: DMF or acetone;
Polyurethane: DMF, acetone or 1-METHYLPYRROLIDONE;
Fluorinated polyurethane: DMF, acetone or 1-METHYLPYRROLIDONE;
Polysulfones and polyether sulfone: DMF, acetone, 1-METHYLPYRROLIDONE, dimethylacetylamide or oxolane;
Kynoar-hexafluoropropene: DMF, 1-METHYLPYRROLIDONE, dimethylacetylamide, triethyl phosphate or dimethyl sulfoxide (DMSO);
Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether: DMF, 1-METHYLPYRROLIDONE, dimethylacetylamide, triethyl phosphate or dimethyl sulfoxide (DMSO);
Kynoar-CTFE: DMF, 1-METHYLPYRROLIDONE, dimethylacetylamide, triethyl phosphate or dimethyl sulfoxide (DMSO);
Described step a) in, the ultrasonic disperse time is 20 ~ 70 minutes;
Described step b) in, polymer is added after in described dispersion liquid, magnetic agitation 8 ~ 10 hours;
Described step c) in, the process conditions of Multi needle electrostatic spinning are: supply voltage 10 ~ 60KV, and spinning environment condition is temperature 15 ~ 35 DEG C, relative humidity 25 ~ 90%; Multi needle spray silk unit syringe needle spacing 2 ~ 30cm, spray silk unit syringe needle quantity is 6 ~ 90.
7. a kind of nanofiber according to claim 5/spun-bonded non-woven fabrics composite filter material preparation method, is characterized in that, in step (3), in described polyvinyl butyral solution, Solute mass fraction is 0.1 ~ 5%; Described preparation polyvinyl butyral solution solvent for use is oxolane, N, the mixture of one or more in dinethylformamide, DMA, acetone, chloroform, cresols, dimethyl sulfoxide (DMSO), ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, DAA, methyl acetate, ethyl acetate, butyl acetate, toluene, 1-METHYLPYRROLIDONE, MEK, methyl ethyl ketone; The solubility parameter of described preparation polyvinyl butyral solution solvent for use at least differs 4 with electrostatic spinning fiber structure adaptability degree used parameter values, and wherein the unit of solubility parameter is (J/cm
3)
1/2;
In described superfine nano fiber dispersion, shared by nanofiber, mass fraction is 0.01% ~ 5%; Described superfine nano fibre diameter is 10 ~ 150nm, and length is 100 ~ 150nm;
Described superfine nano fibrous material is the mixture of a kind of in polystyrene, polyester, polyvinyl acetate, nylon 6, nylon66 fiber, polymethyl methacrylate, polyaniline, polyethylene glycol oxide, polyacrylonitrile, polycaprolactone, polyurethane, polysulfones, polyether sulfone or two kinds and above polymer;
The rotating speed of described high speed beater is 5000 revs/min ~ 8000 revs/min.
8. a kind of nanofiber according to claim 5/spun-bonded non-woven fabrics composite filter material preparation method, is characterized in that, in step (4), the time of described immersion is 5 ~ 30min; Described oven dry refers to and hangs in baking oven, 25 ~ 50 DEG C of oven dry.
9. a kind of nanofiber according to claim 5/spun-bonded non-woven fabrics composite filter material preparation method, is characterized in that, in step (5), described repeatedly repetition refers to repetition 2 ~ 6 times, also namely obtains 2 ~ 6 lamination materials.
10. nanofiber/spun-bonded non-woven fabrics the composite filter material obtained by a kind of nanofiber according to any one of claim 5 ~ 9/spun-bonded non-woven fabrics composite filter material preparation method, it is characterized in that: described nanofiber/spun-bonded non-woven fabrics composite filter material is the stacked composite filtering material of gradient, form for lamination material is carried out superimposion from low to high successively by media filtration efficiency from bottom to top, every layer laminate material all makes the one side of electrostatic spinning fiber upwards, and in most last layer surface coverage one spun-bonded non-woven fabrics, ensure that top layer and the bottom are all spun-bonded non-woven fabrics layer, adjacent two layers lamination material, the filter efficiency value of one deck to the particle of 0.02 ~ 10 μm is 1.03 ~ 1.3 times of one deck below above, the lamination material superposition number of plies is 2 ~ 6 layers, form spun-bonded non-woven fabrics and there is electret effect nanofiber sandwich alternately, making nanofiber/spun-bonded non-woven fabrics composite filter material, described nanofiber/the filter efficiency of spun-bonded non-woven fabrics composite filter material to the particle of 0.02 ~ 10 μm reach 99.999% and more than, pressure drag remains on 10 ~ 30Pa.
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