CN105233568A - Static spinning method and nano fiber/glass fiber composite filter material prepared by same - Google Patents
Static spinning method and nano fiber/glass fiber composite filter material prepared by same Download PDFInfo
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- CN105233568A CN105233568A CN201510631903.4A CN201510631903A CN105233568A CN 105233568 A CN105233568 A CN 105233568A CN 201510631903 A CN201510631903 A CN 201510631903A CN 105233568 A CN105233568 A CN 105233568A
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- glass fiber
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- filter paper
- spinning
- filter
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- 239000000463 material Substances 0.000 title claims abstract description 180
- 239000002121 nanofiber Substances 0.000 title claims abstract description 156
- 239000003365 glass fiber Substances 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 119
- 238000009987 spinning Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000003068 static effect Effects 0.000 title claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 58
- 230000000694 effects Effects 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000010041 electrostatic spinning Methods 0.000 claims description 93
- 238000001914 filtration Methods 0.000 claims description 72
- 238000003475 lamination Methods 0.000 claims description 58
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 52
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000006185 dispersion Substances 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 47
- 230000008569 process Effects 0.000 claims description 45
- 238000002360 preparation method Methods 0.000 claims description 43
- 239000002105 nanoparticle Substances 0.000 claims description 39
- 239000011810 insulating material Substances 0.000 claims description 38
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 21
- -1 polypropylene Polymers 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- 238000007654 immersion Methods 0.000 claims description 18
- 239000007921 spray Substances 0.000 claims description 18
- 238000001523 electrospinning Methods 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
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- 229920002223 polystyrene Polymers 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
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- 238000013327 media filtration Methods 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 239000002648 laminated material Substances 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
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- 238000013019 agitation Methods 0.000 claims description 8
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 8
- 239000011118 polyvinyl acetate Substances 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001230 polyarylate Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 150000001896 cresols Chemical class 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052613 tourmaline Inorganic materials 0.000 claims description 2
- 229940070527 tourmaline Drugs 0.000 claims description 2
- 239000011032 tourmaline Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000010030 laminating Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 52
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
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- Filtering Materials (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention relates to a static spinning method and a nano fiber/glass fiber composite filter material prepared by the same. According to the static spinning method, multiple needles are used to carry out static spinning, and the needles are insulated to each other. The nano fiber/glass fiber composite filter material is prepared by laminating and combining different filter materials together from bottom to top, wherein the filter efficiency of filter materials increases from bottom to top; the side, which is provided with static spun fibers, of each filter material layer is upward, the surface of the top layer is covered by glass fiber filter paper to ensure that the top layer and bottom layer of the filter material are both made of glass fiber filter paper. For two neighbored filter material layers, the filter efficiency of the upper layer on particles with a size of 0.02 to 10 [mu]m is 1.03 to 1.3 times higher than that of the lower layer. The composite filter material comprises two to six filter material layers, and has an sandwich structure, wherein in the sandwich structure, glass fiber filter paper and nano fiber with an electret effect are arranged alternately. The nano fiber/glass fiber composite filter material has a filter efficiency of 99.999% or more on particles with a size of 0.02 to 10 [mu]m, and the pressure resistance is maintained at 10 to 30 Pa.
Description
Technical field
The invention belongs to electrostatic spinning technique field, relate to the nanofiber/glass fiber 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, 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/glass fiber 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 PET.
Present invention also offers a kind of nanofiber/glass fiber composite filter material preparation method, concrete steps are:
(1) 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 glass fiber filter paper spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber in glass fiber filter paper, and the deposition of polymer nanofiber can by regulating the spinning time to regulate and control;
(2) 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;
(3) 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;
(4) step (1) ~ (3) 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 (3);
(5) 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and there is electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material;
The lamination material superposition number of plies is 2 ~ 6 layers, forms glass fiber filter paper and has electret effect nanofiber sandwich alternately, making nanofiber/glass fibre lamination composite filter material.
A kind of nanofiber as above/glass fibre lamination composite filter material preparation method, step (1):
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;
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, PET, 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;
PET: 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; Described glass fiber filter paper, its composition fibre diameter is 1 ~ 50 μm, and filter paper aperture size is 5 ~ 120 μm, and grammes per square metre is 20 ~ 300g/m
2, exhibits initial filtration efficiency is 15% ~ 60%, and before receiving, described glass fiber filter paper EtOH Sonicate cleans, and uses at 20 ~ 50 DEG C after dry 0.5 ~ 3h.
A kind of nanofiber/glass fiber composite filter material preparation method as above, in step (2), 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/glass fiber composite filter material preparation method as above, in step (3), 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/glass fiber composite filter material preparation method as above, in step (4), 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/glass fiber composite filter material, described nanofiber/glass fiber 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and there is electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material; Described nanofiber/glass fiber 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 glass fiber filter paper, the structure of structure electrostatic spinning fiber interlayer between glass fiber filter paper.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 glass fiber filter paper through hydrophobic treatment, 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 glass fiber filter paper 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 hydrophobized glass fibers filter paper 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 glass fiber filter paper, hinder the electrostatic spinning fiber with electret effect directly to contact with external environment, the electrostatic spinning fiber obtained/glass fibre composite filter paper 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/glass fiber composite filter material schematic diagram, and wherein, 4 is glass fiber filter paper, and 5 is electrostatic spinning nano fiber.
Fig. 3 is that electrostatic spinning nano fiber/glass fibre composite filter material and electrostatic spinning nano fiber/simple glass fiber composite filtrate 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/glass fiber composite filter material prepared by this patent has excellent charge storage stability, and 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 PET.
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 nano SiO 2 particle is added in solvent DMF, and ultrasonic disperse 30 minutes, obtain the homodisperse dispersion liquid of nano particle;
(2) polymer poly acrylonitrile is added in dispersion liquid, magnetic agitation 8 hours, is mixed with even and stable spinning solution, wherein, the mass fraction of polyacrylonitrile is 9%, 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 50KV, 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 3cm, spray silk unit syringe needle quantity is 60, and the spinning time is 30min; 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 glass fiber filter paper spun receives, and obtains composite filtering material glass fiber filter paper depositing Static Spinning polymer nanofiber, wherein, glass fiber filter paper, its composition fibre diameter is 50 μm, and filter paper aperture size is 40 μm, and grammes per square metre is 68g/m
2, exhibits initial filtration efficiency is 15%, receives front glass fiber filter paper EtOH Sonicate and cleans, use at 40 DEG C after dry 2.5h;
(4) by the obtained glass fiber filter paper 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 32g/m
2, 34g/m
2, 33g/m
2, 33g/m
2, 32g/m
2, 35g/m
2, 33g/m
2, 34g/m
2, 32g/m
2, 33g/m
2, the grammes per square metre coefficient of variation is 2.85%;
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 90.1325%, 90.1456%, 90.1458%, 90.1277%, 90.1298%, 90.0321%, 90.1457%, 90.1367%, 90.1457%, 90.1299%; Corresponding pressure drag is 20Pa, 21Pa, 20Pa, 21Pa, 21Pa, 19Pa, 20Pa, 20Pa, 20Pa, 20Pa.The coefficient of variation calculating composite filtering material filter efficiency is 0.036%, and the coefficient of variation of pressure drag is 2.97%;
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 glass fiber filter paper 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, 27g/m
2, 29g/m
2, 36g/m
2, 31g/m
2, 33g/m
2, the coefficient of variation of grammes per square metre is: 11.76%.
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 90.1587%, 89.9992%, 90.0976%, 88.9104%, 90.2801%, 89.9726%, 91.0023%, 90.1078%, 90.1998%, 89.0947%; Corresponding pressure drag is 20Pa, 18Pa, 18Pa, 20Pa, 21Pa, 19Pa, 23Pa, 19Pa, 21Pa, 17Pa.The coefficient of variation calculating composite filtering material filter efficiency is 0.63%, and the coefficient of variation of pressure drag is 8.59%.
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/glass fiber composite filter material preparation method, concrete steps are:
(1) 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 polymer nanofiber glass fiber filter paper spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber in glass fiber filter paper, wherein, glass fiber filter paper, its composition fibre diameter is 50 μm, and filter paper aperture size is 40 μm, and grammes per square metre is 68g/m
2, exhibits initial filtration efficiency is 15%, receives front glass fiber filter paper EtOH Sonicate and cleans, use at 40 DEG C after dry 2.5h;
(2) 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;
(3) 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;
(4) repeat 4 step (1) ~ (3), 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 (1).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 20.1342%, 22.7656%, 24.2764% and 26.6243%;
(5) 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and there is electret effect nanofiber sandwich alternately, make nanofiber/glass fiber composite filter material, as shown in Figure 2, wherein, 4 is glass fiber filter paper, and 5 is electrostatic spinning nano fiber; The filter efficiency of nanofiber/glass fiber composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 15Pa, 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/glass fiber composite filter material preparation method, concrete steps are:
(1) 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 PET; The polymer nanofiber glass fiber filter paper spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber in glass fiber filter paper, wherein, glass fiber filter paper, its composition fibre diameter is 42 μm, and filter paper aperture size is 30 μm, and grammes per square metre is 120g/m
2, exhibits initial filtration efficiency is 20%, receives front glass fiber filter paper EtOH Sonicate and cleans, use at 30 DEG C after dry 2.5h;
(2) 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;
(3) 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;
(4) repeat 3 step (1) ~ (3), 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 (1).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 30.0241%, 31.5001% and 33.0753%;
(5) 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and has electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material; The filter efficiency of nanofiber/glass fiber composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 25Pa, 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/glass fiber composite filter material preparation method, concrete steps are:
(1) 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 PET; The polymer nanofiber glass fiber filter paper spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber in glass fiber filter paper, wherein, glass fiber filter paper, its composition fibre diameter is 30 μm, and filter paper aperture size is 20 μm, and grammes per square metre is 150g/m
2, exhibits initial filtration efficiency is 35%, receives front glass fiber filter paper EtOH Sonicate and cleans, use at 40 DEG C after dry 2h;
(2) 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;
(3) 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;
(4) repeat 2 step (1) ~ (3), 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 (1).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 53.1362% and 63.6901%;
(5) 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and has electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material; The filter efficiency of nanofiber/glass fiber composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 20Pa, 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/glass fiber composite filter material preparation method, concrete steps are:
(1) 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 PET; The polymer nanofiber glass fiber filter paper spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber in glass fiber filter paper, wherein, glass fiber filter paper, its composition fibre diameter is 40 μm, and filter paper aperture size is 53 μm, and grammes per square metre is 100g/m
2, exhibits initial filtration efficiency is 15%, receives front glass fiber filter paper EtOH Sonicate and cleans, use at 40 DEG C after dry 2.5h;
(2) 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;
(3) 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;
(4) repeat 5 step (1) ~ (3), 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 (1).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 22.5001%, 23.7610%, 25.6603%, 27.7101%, 29.9321%;
(5) 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and has electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material; The filter efficiency of nanofiber/glass fiber composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 24Pa, 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/glass fiber composite filter material preparation method, concrete steps are:
(1) 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 PET; The polymer nanofiber glass fiber filter paper spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber in glass fiber filter paper, wherein, glass fiber filter paper, its composition fibre diameter is 30 μm, and filter paper aperture size is 50 μm, and grammes per square metre is 150g/m
2, exhibits initial filtration efficiency is 15%, receives front glass fiber filter paper EtOH Sonicate and cleans, use at 40 DEG C after dry 2.5h;
(2) 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;
(3) 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;
(4) 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 (1).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 20.1021%, 20.9010%, 21.8341%, 22.7809%, 23.762% and 24.7701%;
(5) 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and has electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material; The filter efficiency of nanofiber/glass fiber composite filter material to the particle of 0.02 ~ 10 μm reaches 99.999%, pressure drag remains on 29Pa, 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 PET.
5. nanofiber/glass fiber composite filter material preparation method, is characterized in that concrete steps are:
(1) 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 glass fiber filter paper spun receives, and obtains the composite filtering material of uniform deposition Static Spinning polymer nanofiber in glass fiber filter paper;
(2) 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;
(3) 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;
(4) repeatedly repeat step (1) ~ (3), obtain the lamination material of different filter efficiency;
(5) 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and there is electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material.
6. a kind of nanofiber/glass fiber composite filter material preparation method according to claim 5, is characterized in that, described step (1):
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, PET, 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;
PET: 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; Described glass fiber filter paper, its composition fibre diameter is 1 ~ 50 μm, and filter paper aperture size is 5 ~ 120 μm, and grammes per square metre is 20 ~ 300g/m
2, exhibits initial filtration efficiency is 15% ~ 60%, and before receiving, described glass fiber filter paper EtOH Sonicate cleans, and uses at 20 ~ 50 DEG C after dry 0.5 ~ 3h.
7. a kind of nanofiber/glass fiber composite filter material preparation method according to claim 5, is characterized in that, in step (2), 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/glass fiber composite filter material preparation method according to claim 5, is characterized in that, in step (3), 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/glass fiber composite filter material preparation method according to claim 5, is characterized in that, in step (4), described repeatedly repetition refers to repetition 2 ~ 6 times, also namely obtains 2 ~ 6 lamination materials.
10. nanofiber/the glass fiber composite filter material obtained by a kind of nanofiber/glass fiber composite filter material preparation method according to any one of claim 5 ~ 9, it is characterized in that: described nanofiber/glass fiber 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 glass fiber filter paper, ensure that top layer and the bottom are all glass fiber filter paper 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 glass fiber filter paper and there is electret effect nanofiber sandwich alternately, making nanofiber/glass fiber composite filter material, the filter efficiency of described nanofiber/glass fiber 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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