A kind of preparation method of nanofiber-acupuncture PTFE base fabric filter materialTechnical field
The present invention relates to the preparation method of a kind of nanofiber-acupuncture PTFE base fabric filter material, belong to electrostatic spinning technique neckTerritory.
Background technology
Polytetrafluoroethylene (PTFE) synthetic fibers filter material is one of a kind of material the most high-end in filtering material, it is possible toThe continuous running temperature of 240 DEG C, under the moment temperature conditions of 260 DEG C, the soda acid being resistant in whole pH range corrodes.PolytetrafluoroEthylene synthase fiber self-lubricity is splendid, nonhygroscopic, can bear ultraviolet radiation.But the wearability of PTFE fiber filtrate is general, mistakeFilter effect still has much room for improvement.
Static Spinning is a kind of nanofiber technology of preparing utilizing high voltage to carry out spinning, is also a kind of nanofiber simultaneouslyA large amount of space charges can be injected in the middle of fiber during spinning by electret technology, space charge easily deep by fibrous insideTrap captures, and can polarize and produces polarization charge by induced dipole simultaneously, can pass through electrostatic during filtering particleAdsorption promotes filter efficiency.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of nanofiber-acupuncture PTFE base fabric filter materialPreparation method, concrete technical scheme is as follows:
The preparation method of a kind of nanofiber-acupuncture PTFE base fabric filter material, comprises the following steps: step one, locates before PTFE base fabricReason；Step 2, electrostatic spinning；Step 3, the preparation of superfine nano fiber dispersion；Step 4, composite filtering material immersion treatment；
In described step one,
(1) titanium dioxide nanofiber or nanometer activated carbon fiber are added in ethanol, and ultrasonic disperse, disperseed uniformlyLiquid A；
(2) take out after PTFE base fabric being soaked in dispersion liquid A and dry, it is thus achieved that surface deposition of titanium oxide nanofiber or nanometerThe PTFE base fabric base material A of activated carbon fiber；
In described step 2,
(1) inorganic nanoparticles is joined ultrasonic disperse in solvent, obtain uniform dispersion liquid B；
(2) adding polymer in dispersion liquid B, preparation obtains uniform spinning liquid B；
(3) spinning liquid B is carried out Multi needle electrostatic spinning, use PTFE base fabric base material A to be received, be obtain a homogeneously deposited quietThe composite filtering material B of electric spinning polymer nanofiber；
In described step 3, first prepare polyvinyl butyral solution, then by polyvinyl butyral solution and superfine nanoFiber adds in blender and disperses, and obtains uniform dispersion liquid C；
In described step 4, composite filtering material B step 2 obtained immerses in the dispersion liquid C that step 3 obtains, and takes out post-drying,Obtain electrostatic weaving composite filtering material: nanofiber-acupuncture PTFE base fabric filter material.
As the improvement of technique scheme, in (1) of described step one, the titanium dioxide nanofiber in dispersion liquid AOr the mass fraction of nanometer activated carbon fiber is 0.2%～4%, described titanium dioxide nanofiber or nanometer activated carbon fiber are straightFootpath is 30nm～80nm, a length of 300nm～600nm.
As the improvement of technique scheme, in (1) of described step 2, inorganic nanoparticles is silicon dioxide, dioxyChanging titanium, tantalum pentoxide, Barium metatitanate., tourmaline, boehmite or silsesquioxane nano granule, solvent is N, N-dimethyl formylAmine.
As the improvement of technique scheme, in (2) of described step 2, described polymer is Kynoar, polyoxyChange ethylene, polyvinylpyrrolidone, polyacrylonitrile, polycaprolactone, polyurethane, fluorinated polyurethane, polysulfones, polyether sulfone, poly-inclined fluorineIn ethylene-hexafluoropropene, Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether, Kynoar-CTFEThe mixture of one or more compositions.
As the improvement of technique scheme, in (3) of described step 2, between the syringe needle of Multi needle electrostatic spinning absolutelyEdge, and the surrounding of each syringe needle have insulant formed isolation groove, the degree of depth of groove is 2 times～4 times of needle length.
As the improvement of technique scheme, in (3) of described step 2, the process conditions of Multi needle electrostatic spinning are:Supply voltage 20KV～50KV, spinning environment condition is temperature 25 DEG C～35 DEG C, relative humidity 25%～80%；Multi needle spray webbingUnit syringe needle spacing 5cm～30cm, spray webbing unit syringe needle quantity is 20～90.
As the improvement of technique scheme, in described step 3, superfine nano fiber is Kynoar, polyoxyethyleneAlkene, polyvinylpyrrolidone, polyacrylonitrile, polycaprolactone, polyurethane, fluorinated polyurethane, polysulfones, polyether sulfone, Kynoar-One in hexafluoropropene, Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether, Kynoar-CTFE orThe mixture of more than one compositions.
As the improvement of technique scheme, in described step 3, in dispersion liquid C, the content of superfine nano fiber is0.01wt%～4wt%, superfine nano fibre diameter is 10nm～150nm, a length of 100nm～200nm.
As the improvement of technique scheme, in described step 3, the rotating speed of blender is 6000r/min～8000r/min。
As the improvement of technique scheme, in (2) of described step one, PTFE base fabric uses PTFE fiber and PPS fineDimension mixes according to mass ratio 20～50:50～80, through shredding, combing, lapping and needling process, then carries out at immersionReason and surface deposition.
Technique scheme has a technique effect of following three aspects:
First, by depositing high-flexibility, superfine nano fiber on the nano fibrous membrane obtained at electrostatic spinning and PTFE base fabric,To form on main fibre the composite filter material containing " fractal secondary structure ", main body crude fibre is for the bigger granule of particle diameterThere is preferable filter effect, concurrently form passing through of larger aperture structure beneficially air-flow, and two grades of fractal structures pairThere is the strainability of excellence, simultaneously its more soft characteristic in ultra-fine grain so that will not be right when having high velocity air to pass throughAir-flow produces barrier effect, thus is not result in the increase of resistance pressure drop, and the filtering material using the manner to obtain has highFiltration efficiency；
Second, the present invention, by being attached between PTFE base fabric by the nano fibrous membrane with electret effect, hinders to have and staysThe electrostatic spinning fiber of pole effect directly contacts with external environment, and the electrostatic spinning fiber obtained/PTFE composite for base fabric filtrate has goodGood Charge Storage Stability, thus filter effect maintenance is good, after testing, this filter material to cement industry dust size isThe filter efficiency of the granule of 0.05 μm～15 μm reaches 99.999%；
3rd, PTFE base fabric uses PTFE fiber and PPS fiber to mix, and more traditional glass mat pliability is more preferable,Filter material spinnability, wearability are all greatly improved, and effects in 8 months of the glass fibre felt that service life is more common promoteBy 1 year～2 years, wide market.
Detailed description of the invention
The invention provides the preparation method of a kind of nanofiber-acupuncture PTFE base fabric filter material, comprise the following steps, stepOne, PTFE base fabric pre-treatment:
(1) titanium dioxide nanofiber or nanometer activated carbon fiber are added in ethanol, and ultrasonic disperse, disperseed uniformlyLiquid A, titanium dioxide nanofiber or the mass fraction of nanometer activated carbon fiber in dispersion liquid A are 0.2%～4%, described twoTiOx nano fiber or a diameter of 30nm～80nm of nanometer activated carbon fiber, a length of 300nm～600nm；
(2) take out after PTFE base fabric being soaked in dispersion liquid A and dry, it is thus achieved that surface deposition of titanium oxide nanofiber or nanometerThe PTFE base fabric base material A of activated carbon fiber；
Step 2, electrostatic spinning:
(1) inorganic nanoparticles is joined ultrasonic disperse in solvent, obtain uniform dispersion liquid B, wherein inorganic nanoparticlesFor silicon dioxide, titanium dioxide, tantalum pentoxide, Barium metatitanate., tourmaline, boehmite or silsesquioxane nano granule, solventFor N,N-dimethylformamide；
(2) adding polymer in dispersion liquid B, carry out magnetic agitation, preparation obtains uniform spinning liquid B, and wherein polymer isKynoar, polyethylene glycol oxide, polyvinylpyrrolidone, polyacrylonitrile, polycaprolactone, polyurethane, fluorinated polyurethane, poly-Sulfone, polyether sulfone, Kynoar-hexafluoropropene, Kynoar-tetrafluoroethylene-perfluoro methyl vinyl ether, polyvinylidene fluorideThe mixture of one or more compositions in alkene-CTFE；
(3) spinning liquid B is carried out Multi needle electrostatic spinning, use PTFE base fabric base material A to be received, be obtain a homogeneously deposited quietThe composite filtering material B of electric spinning polymer nanofiber；Wherein insulate between the syringe needle of Multi needle electrostatic spinning, and the four of each syringe needleHaving insulant to form isolation groove in week, the degree of depth of groove is 2 times～4 times of needle length, the technique of this Multi needle electrostatic spinningCondition is: supply voltage 20KV～50KV, and spinning environment condition is temperature 25 DEG C～35 DEG C, relative humidity 25%～80%；ManySyringe needle spray webbing unit syringe needle spacing 5cm～30cm, spray webbing unit syringe needle quantity is 20～90；
Step 3, the preparation of superfine nano fiber dispersion: first prepare polyvinyl butyral solution, then polyvinyl alcohol is contractedButyraldehyde solution adds in blender with superfine nano fiber and disperses, and the rotating speed of blender is 6000r/min～8000r/Min, obtains uniform dispersion liquid C, wherein superfine nano fiber be Kynoar, polyethylene glycol oxide, polyvinylpyrrolidone,Polyacrylonitrile, polycaprolactone, polyurethane, fluorinated polyurethane, polysulfones, polyether sulfone, Kynoar-hexafluoropropene, polyvinylidene fluorideMixing of one or more compositions in alkene-tetrafluoroethylene-perfluoro methyl vinyl ether, Kynoar-CTFECompound, in dispersion liquid C, the content of superfine nano fiber is 0.01wt%～4wt%, superfine nano fibre diameter be 10nm～150nm, a length of 100nm～200nm；
Step 4, composite filtering material immersion treatment: composite filtering material B step 2 obtained immerses in the dispersion liquid C that step 3 obtains,Take out post-drying, obtain electrostatic weaving composite filtering material: nanofiber-acupuncture PTFE base fabric filter material.
In such scheme, in (2) of step one, PTFE base fabric uses PTFE fiber and PPS fiber according to mass ratio 20～50:50～80 mixes, through shredding, combing, lapping and needling process, then carry out immersion treatment and surface deposition.
It is described in detail below in conjunction with specific embodiment.
Embodiment one
Carry out the preparation of nanofiber-acupuncture PTFE base fabric filter material in accordance with the following methods:
Step one, PTFE base fabric pre-treatment:
(1) first 2.6g titanium dioxide nanofiber is added ultrasonic disperse in 130ml ethanol, obtain uniform dispersion liquid A；
(2) PTFE fiber and PPS fiber are mixed according to mass ratio 5:8, through shredding, combing, lapping and needling process,Then in dispersion liquid A, soak 6min, then take out 72 DEG C of drying, it is thus achieved that the PTFE of surface deposition of titanium oxide nanofiberBase fabric base material A；
Step 2, electrostatic spinning:
(1) inorganic nanoparticles joining ultrasonic disperse in solvent, the ultrasonic disperse time is 30min, is disperseed uniformlyLiquid B, wherein inorganic nanoparticles is silicon dioxide, and solvent is DMF；
(2) adding polymer in dispersion liquid B, carry out magnetic agitation, mixing time 2h, preparation obtains uniform spinning liquid B, itsMiddle polymer is Kynoar；
(3) spinning liquid B is carried out Multi needle electrostatic spinning, use PTFE base fabric base material A to be received, be obtain a homogeneously deposited quietThe composite filtering material B of electric spinning polymer nanofiber, wherein insulate between the syringe needle of Multi needle electrostatic spinning, and the four of each syringe needleHaving insulant to form isolation groove in week, the degree of depth of groove is 3 times of needle length, the process conditions of this Multi needle electrostatic spinningFor: supply voltage 50KV, spinning environment condition is temperature 30 DEG C, relative humidity 40%；Multi needle spray webbing unit syringe needle spacing20cm, spray webbing unit syringe needle quantity is 90；
Step 3, the preparation of superfine nano fiber dispersion: first prepare polyvinyl butyral solution, then polyvinyl alcohol is contractedButyraldehyde solution adds in blender with superfine nano fiber and disperses, and the rotating speed of blender is 6000r/min, obtains uniformDispersion liquid C, wherein superfine nano fiber is polycaprolactone；
Step 4, composite filtering material immersion treatment: composite filtering material B step 2 obtained immerses in the dispersion liquid C that step 3 obtains,Soak time be 30min, 25 DEG C of drying after taking-up, obtain electrostatic weave composite filtering material: nanofiber-acupuncture PTFE base fabricFilter material.
Embodiment two
Carry out the preparation of nanofiber-acupuncture PTFE base fabric filter material in accordance with the following methods:
Step one, PTFE base fabric pre-treatment:
(1) first 1.1g nanometer activated carbon fiber is added ultrasonic disperse in 70ml ethanol, obtain uniform dispersion liquid A；
(2) PTFE fiber and PPS fiber are mixed according to mass ratio 5:16, through shredding, combing, lapping and acupuncture workSkill, then soaks 4min in dispersion liquid A, then takes out 80 DEG C of drying, it is thus achieved that surface deposition nanometer activated carbon fiberPTFE base fabric base material A；
Step 2, electrostatic spinning:
(1) inorganic nanoparticles joining ultrasonic disperse in solvent, the ultrasonic disperse time is 40min, is disperseed uniformlyLiquid B, wherein inorganic nanoparticles is silicon dioxide, and solvent is DMF；
(2) adding polymer in dispersion liquid B, carry out magnetic agitation, mixing time 2h, preparation obtains uniform spinning liquid B, itsMiddle polymer is Kynoar；
(3) spinning liquid B is carried out Multi needle electrostatic spinning, use PTFE base fabric base material A to be received, be obtain a homogeneously deposited quietThe composite filtering material B of electric spinning polymer nanofiber, wherein insulate between the syringe needle of Multi needle electrostatic spinning, and the four of each syringe needleHaving insulant to form isolation groove in week, the degree of depth of groove is 3 times of needle length, the process conditions of this Multi needle electrostatic spinningFor: supply voltage 20KV, spinning environment condition is temperature 35 DEG C, relative humidity 40%；Multi needle spray webbing unit syringe needle spacing10cm, spray webbing unit syringe needle quantity is 90；
Step 3, the preparation of superfine nano fiber dispersion: first prepare polyvinyl butyral solution, then polyvinyl alcohol is contractedButyraldehyde solution adds in blender with superfine nano fiber and disperses, and obtains uniform dispersion liquid C, wherein superfine nano fiberFor polyethylene glycol oxide；
Step 4, composite filtering material immersion treatment: composite filtering material B step 2 obtained immerses in the dispersion liquid C that step 3 obtains,Soak time be 5min, 50 DEG C of drying after taking-up, obtain electrostatic weave composite filtering material: nanofiber-acupuncture PTFE base fabricFilter material.
Embodiment three
Carry out the preparation of nanofiber-acupuncture PTFE base fabric filter material in accordance with the following methods:
Step one, PTFE base fabric pre-treatment:
(1) first 1.9g titanium dioxide nanofiber is added ultrasonic disperse in 90ml ethanol, obtain uniform dispersion liquid A；
(2) PTFE fiber and PPS fiber are mixed according to mass ratio 1:1, through shredding, combing, lapping and needling process,Then in dispersion liquid A, soak 4min, then take out 80 DEG C of drying, it is thus achieved that the PTFE of surface deposition of titanium oxide nanofiberBase fabric base material A；
Step 2, electrostatic spinning:
(1) inorganic nanoparticles joining ultrasonic disperse in solvent, the ultrasonic disperse time is 40min, is disperseed uniformlyLiquid B, wherein inorganic nanoparticles is silicon dioxide, and solvent is DMF；
(2) adding polymer in dispersion liquid B, carry out magnetic agitation, mixing time 3h, preparation obtains uniform spinning liquid B, itsMiddle polymer is Kynoar；
(3) spinning liquid B is carried out Multi needle electrostatic spinning, use PTFE base fabric base material A to be received, be obtain a homogeneously deposited quietThe composite filtering material B of electric spinning polymer nanofiber, wherein insulate between the syringe needle of Multi needle electrostatic spinning, and the four of each syringe needleHaving insulant to form isolation groove in week, the degree of depth of groove is 3 times of needle length, the process conditions of this Multi needle electrostatic spinningFor: supply voltage 50KV, spinning environment condition is temperature 30 DEG C, relative humidity 40%；Multi needle spray webbing unit syringe needle spacing10cm, spray webbing unit syringe needle quantity is 90；
Step 3, the preparation of superfine nano fiber dispersion: first prepare polyvinyl butyral solution, then polyvinyl alcohol is contractedButyraldehyde solution adds in blender with superfine nano fiber and disperses, and obtains uniform dispersion liquid C, wherein superfine nano fiberFor polyethylene glycol oxide；
Step 4, composite filtering material immersion treatment: composite filtering material B step 2 obtained immerses in the dispersion liquid C that step 3 obtains,Soak time be 5min, 50 DEG C of drying after taking-up, obtain electrostatic weave composite filtering material: nanofiber-acupuncture PTFE base fabricFilter material.
After testing, this filter material reaches to the filter efficiency of the granule that cement industry dust size is 0.05 μm～15 μm99.999%, filter effect is excellent.