CN106000116A - Preparation method of nanofiber membrane with hard magnetic property - Google Patents

Preparation method of nanofiber membrane with hard magnetic property Download PDF

Info

Publication number
CN106000116A
CN106000116A CN201610344244.0A CN201610344244A CN106000116A CN 106000116 A CN106000116 A CN 106000116A CN 201610344244 A CN201610344244 A CN 201610344244A CN 106000116 A CN106000116 A CN 106000116A
Authority
CN
China
Prior art keywords
composite
nano
preparation
fibrous membrane
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610344244.0A
Other languages
Chinese (zh)
Other versions
CN106000116B (en
Inventor
刘轲
王栋
易志兵
刘琼珍
李沐芳
鲁振坦
赵青华
蒋海青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KUNSHAN WISE-CHANNEL HYPER TECHNOLOGY Co Ltd
Wuhan Textile University
Original Assignee
KUNSHAN WISE-CHANNEL HYPER TECHNOLOGY Co Ltd
Wuhan Textile University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KUNSHAN WISE-CHANNEL HYPER TECHNOLOGY Co Ltd, Wuhan Textile University filed Critical KUNSHAN WISE-CHANNEL HYPER TECHNOLOGY Co Ltd
Priority to CN201610344244.0A priority Critical patent/CN106000116B/en
Publication of CN106000116A publication Critical patent/CN106000116A/en
Application granted granted Critical
Publication of CN106000116B publication Critical patent/CN106000116B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0095—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/50—Polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/46—Magnetic properties

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

The invention discloses a preparation method of a nanofiber membrane with a hard magnetic property, belonging to the technical field of nanometer materials. The preparation method comprises the following preparation steps: (1) demagnetizing magnetic nanoparticles to obtain demagnetized magnetic nanoparticles; (2) mixing the demagnetized magnetic nanoparticles with a vinyl-vinyl alcohol copolymer to obtain a composite material; (3) spinning the composite material particles, and extracting to obtain composite nanofibers; (4) dispersing the composite nanofibers, and coating to obtain a nanofiber membrane or a nanofiber composite membrane; (5) magnetizing. The nanofiber membrane prepared by the method has excellent adsorptive property, hydrophilia and stain resistance, and has high-efficient and low-consumption filtering performance for water and air; furthermore, the preparation method is simple in technology, environmentally-friendly, free from pollution and easy in industrial production.

Description

A kind of preparation method of the nano fibrous membrane of hard magnetic properties
Technical field
The invention belongs to technical field of nano material, more particularly to the nanometer of a kind of hard magnetic properties The preparation method of fibrous membrane.
Background technology
Micro/nano fibrous membrane material has the feature such as high-specific surface area and high porosity, clean at environment The fields such as change, biological medicine and energy electronic show great performance advantage and application potential. By reducing the fibre diameter of micro/nano fibrous membrane material and increasing film thickness, can further improve and receive The rice fibrous membrane filter efficiency to particulate matter, but can cause reducing liquid and the output of air Rate.The absorption property of fibrous membrane itself can be improved by electromagnetism modification, thus pollute improving Liquid and the flux of air is ensured, it is thus achieved that the filtration of excellent performance separates while the rejection rate of thing Material.
Chinese invention patent (publication number: CN104014196A, publication date: 2014-9-3) is public Open a kind of high absorption nanofiber composite filter material and preparation method thereof.This preparation method is led to Cross addition functional particulate in nanofiber preparation process, make nanofiber composite filter material have There is higher absorbability, but be disadvantageous in that the addition of functional particulate improves nanofiber The effect of additional physical field, and the effect of additional physical field mostlys come from Electrostatic Absorption, easily The shortcoming that affected by environment, generation effect is unstable, electrostatic is easily cut down.
Comparatively speaking, Hard Magnetic effect is not easily susceptible to the impact of conventional environment, utilizes magnetic filter to go Depollution thing is a kind of more ripe method.As Chinese invention patent (publication number: CN102740981A, publication date: 2012-10-17) provide a kind of Magnetic filtration device equipment.Should Equipment list reveal filtering of excellence separate, especially removal ability to irony pollutant.This sets Standby shortcoming is, the cost of equipment is high, it is difficult to realizing need to be by little area flexibility at biologic medical etc. The extensive application of the filtration art of filter membrane.
For overcoming the shortcoming of above-mentioned magnetic apparatus, select to add hard magnetic in nanofiber Grain, the magnetic Nano fiber prepared can also solve the nano-fiber material filtration to pollutant Contradiction between efficiency and flux, turn avoid absorption property that Electrostatic Absorption material causes not simultaneously Stable problem.As Chinese invention patent (publication number: CN102978730A, publication date: 2013-3-20) provide the preparation method of a kind of inorganic/organic magnetic liposome nanofiber membrane. The method, with solubility trivalent iron salt, divalent iron salt as raw material, uses chemical coprecipitation to prepare Magnetic Fe2O3Nano-particle, more molten with the chloroform containing soybean lecithin PC and PVP Liquid is blended, and uses the method for electrostatic spinning to prepare the Nanowire that fibre diameter is 1000nm Dimension film.The shortcoming of the method is to rely on chemical reaction and electrostatic spinning technique, and reagent is complicated, difficult To realize industrialization；Although fiber size is uniform, but fibre diameter is relatively thick, and magnetic-particle exists Be easily generated agglomeration traits due to magnetic force during co-blended spinning, and in terms of not having filtration should With.
Therefore, although the technology of preparing of magnetic electrostatic spinning nano fibre is the most ripe, but still The problem that there is industrialization and application aspect.
Summary of the invention
For solving above-mentioned technical problem, the invention provides the nano fibrous membrane of a kind of hard magnetic properties Preparation method, this preparation method not only ensure that the structure of nanofiber and membrane material thereof is homogeneous Stable, and technique is simple, it is easy to industrialized production.
The invention provides the preparation method of the nano fibrous membrane of a kind of hard magnetic properties, this preparation side Method includes following preparation process:
1) magnetic nanoparticle is carried out demagnetization process, obtain the state magnetic nanoparticle that demagnetizes；
2) by step 1) the demagnetization state magnetic nanoparticle for preparing is placed in dimethylformamide In, dispersed with stirring, obtain the suspension of demagnetization state magnetic nanoparticle；By ethylene-vinyl alcohol altogether Polymers master batch is placed in dimethylformamide, and stirring, to dissolving, obtains ethylene-vinyl alcohol copolymer Solution；By suspension and the mixing of ethylene-vinyl alcohol copolymer solution of demagnetization state magnetic nanoparticle After, clipped, dispersion, it is cooled to room temperature, obtains emulsifying material；Emulsifying material is put into Deionized water precipitates, is dried, obtain composite, then composite is pulverized, answered Condensation material granule；
3) by step 2) composite material granular for preparing and acetylbutyrylcellulose uniformly mix Close, through melt extruding, prepare composite fibre, composite fibre is placed in acetone backflow, Extract acetylbutyrylcellulose, the composite fibre after being extracted, then by being combined after extraction Fiber drying, obtains composite nano fiber, and composite nano fiber is with ethylene-vinyl alcohol copolymer For continuous phase, with the state magnetic nanoparticle that demagnetizes as dispersion phase；
4) by step 3) composite nano fiber for preparing is scattered in ethanol, forms Nanowire Dimension suspension, then nanofiber suspension is coated on the surface of nonwoven substrate, it is dried Obtain nano-fiber composite film；Or nanofiber suspension is coated in the table of plastic sheeting Face, is dried to obtain nano fibrous membrane；
5) step 4) nano-fiber composite film for preparing or nano fibrous membrane be placed in magnet charger Magnetize, prepare the nano fibrous membrane with hard magnetic properties.
Further, described step 1) in concrete processing procedure as follows:
Magnetic nanoparticle is placed in silica crucible, is warming up in inert atmosphere or vacuum drying oven 500～700 DEG C, then insulation 1～2h, then naturally cool to room temperature, obtain demagnetization state magnetic and receive Rice grain.
Yet further, described step 1) in magnetic nanoparticle be SrFe12O19、Fe3O4、 Nd2Fe14One or more in B, and the mean diameter of magnetic nanoparticle is 10～100nm.
Further, described step 2) in ethylene-vinyl alcohol copolymer master batch with demagnetization state magnetic The mass percent of property nano-particle is 80～99.5:0.5～20.
Further, described step 2) in concrete processing procedure as follows:
By step 1) the demagnetization state magnetic nanoparticle for preparing is placed in dimethylformamide, And the mass percent of demagnetization state magnetic nanoparticle and dimethylformamide is 1～5:95～99, Dispersed with stirring at 70～90 DEG C, obtains the suspension of demagnetization state magnetic nanoparticle；By ethylene- Ethenol copolymer master batch is placed in dimethylformamide, and ethylene-vinyl alcohol copolymer master batch with The mass percent of dimethylformamide is 1～25:75～99, and at 70～90 DEG C, stirring is to dissolving, Obtain ethylene-vinyl alcohol copolymer solution；By mixture and the ethylene of demagnetization state magnetic nanoparticle -ethenol copolymer solution mixes, and the demagnetization mixture of state magnetic nanoparticle and ethylene-second The volume ratio of enol copolymer solution is 1:1, more clipped, dispersion, is cooled to room temperature, Obtain emulsifying material；Emulsifying material is put in deionized water precipitate, be dried, obtain composite wood Material, meanwhile, emulsifying material is 1:5 with the volume ratio of deionized water；Again by composite powder Broken machine is pulverized, and obtains composite material granular.
Further, described step 2) middle employing mulser is sheared and disperses, and dispersion Time is 10～30min, and the rotating speed of mulser is 800～1500r/min.
Further, described step 3) in the matter of composite material granular and acetylbutyrylcellulose Amount percentage ratio is 5～40:60～95.
Further, described step 3) in concrete processing procedure as follows:
By step 2) composite material granular for preparing and acetylbutyrylcellulose mix homogeneously, Melt extrude through double screw extruder, prepare composite fibre, and the work of double screw extruder It it is 120～260 DEG C as temperature；Then composite fibre is placed in acetone backflow, the temperature of backflow Being 58～62 DEG C, the time of backflow is 70～75h, extracts acetylbutyrylcellulose, is extracted Composite fibre after taking, then the composite fibre after extraction is placed under room temperature dry, prepare Composite nano fiber, and composite nano fiber is with ethylene-vinyl alcohol copolymer as continuous phase, to move back Magnetic states magnetic nanoparticle is dispersion phase, and the average diameter of composite nano fiber is 50～500nm.
Further, described step 4) in, the composite nano fiber in nanofiber suspension Concentration is 1～10g/L, and coating thickness is 1～1000 μm.
Further, described step 4) in, described nonwoven substrate is polypropylene, poly-right One or more melt-blown or spunbonded nonwoven in PET or nylon Cloth, and drying condition is normal temperature drying.
In the present invention, ethylene-vinyl alcohol copolymer is abbreviated as EVOH, is to add polyvinyl The iris action of work and vinyl alcohol polymer combines, and therefore, ethylene-vinyl alcohol copolymer is not Only show fabulous processing characteristics, and gas, abnormal smells from the patient, spice, solvent etc. are presented Go out the blocking effect of excellence.
PP is abbreviated as by polypropylene, and polyethylene terephthalate is abbreviated as PET, and nylon is abridged For PA.
Dimethylformamide, is also called DMF, is the organic solvent that conventional polarity is stronger.
Magnetic nanoparticle SrFe12O19As a kind of important hard ferrite, stable performance, And moderate cost, therefore become the new high-tech industry important substance basis with social progress One.
Magnetic nanoparticle Fe3O4, also known as ferroso-ferric oxide, or it is commonly called as Magnet, magnet Or black ferrum, it is to have magnetic black crystals, is generally used for making pigment and polishing agent.
Magnetic nanoparticle Nd2Fe14B is neodymium-iron-boron iron permanent-magnet material, has high magnetic energy Long-pending and strong power, the advantage of high-energy-density makes Nd-Fe-B permanent magnet material at modern industry and electricity simultaneously Sub-technology is applied widely.
The operation principle of the preparation method of the present invention is:
This preparation method for avoid in blending and modifying and spinning process granule because of magnetic force the group of generation Poly-, first magnetic-particle is carried out high temperature demagnetization, through melt blending phase separation method, overlay film etc. After technique, then carry out operation of magnetizing, finally impart the excellent Hard Magnetic of micro/nano fibrous membrane material special Property.
Having the beneficial effects that of the preparation method of the present invention:
1, in the preparation method of the present invention, first magnetic nanoparticle is carried out high temperature demagnetization, keep away Exempt from granule in the blending and modifying in subsequent technique and spinning process and produce reunion because of magnetic force；Cause This fiber surface prepared is smooth, even thickness, it is ensured that nanofiber and the knot of membrane material thereof Structure stable homogeneous.
2, in preparation method of the present invention, the magnetic nanoparticle material of employing is that single shaft is respectively to different Property hexagonal structure compound, belong to the permanent-magnet ferrite of high residual induction, can high temperature demagnetization； After nanofiber film forming, carry out room temperature again magnetize, make scattered demagnetization state magnetic-particle again Obtain magnetic, finally impart micro/nano fibrous membrane material with excellent hard magnetic properties.
3, nano fibrous membrane prepared by preparation method of the present invention has the absorption property of excellence, carries Rise the rejection to pollutant；Due to adsorbing existence, the hole of film under identical rejection Footpath increases, thus improves the flux of water or air；Meanwhile, less surface contact angle shows Hydrophilic and the resistance to soiling of film are excellent so that it is have high product water or factor of created gase and regenerability； Additionally, the average pore size of film controllable precise in the range of tens to hundreds of nanometer, nanometer is described Fibrous membrane machinability is strong, Stability Analysis of Structures.
4, the technique such as the melt blending phase separation method in preparation method of the present invention, overlay film, demagnetization Being physical process, technique is simple, and environment friendly and pollution-free, it is easy to industrialized production.
Detailed description of the invention
In order to preferably explain the present invention, it is further elucidated with the present invention below in conjunction with specific embodiment Main contents, but present disclosure is not limited solely to following example.
Embodiment 1
1) by the SrFe of a size of 30nm12O19Nano-particle is placed in quartzy dry pot, at vacuum drying oven In be gradually heated to 500 DEG C and be incubated 60min, then naturally cool to room temperature, it is thus achieved that demagnetization State SrFe12O19Nano-particle.
2) by EVOH master batch and demagnetization state SrFe12O19Nano-particle is according to mass percent 95% And 5% weigh respectively, the EVOH master batch weighed is placed in DMF with the mass percent of 5% In, at 80 DEG C, stirring is to dissolving, and obtains EVOH solution；Demagnetization state SrFe that will weigh12O19 Nano-particle is placed in DMF with the mass percent of 5%, dispersed with stirring at 80 DEG C, obtains Demagnetization state SrFe12O19The suspension of nano-particle；By EVOH solution, demagnetization state SrFe12O19 The suspension of nano-particle is placed in mulser dispersion 15min, and emulsifying by the volume ratio of 1:1 The rotating speed of machine is 1000r/min, is cooled to room temperature, obtains emulsifying material；By emulsifying material Pour in deionized water by the volume ratio of 1:5 precipitate, be dried, obtain composite；Use again Pulverizer is pulverized composite and is obtained composite material granular.
3) by this composite material granular and acetylbutyrylcellulose by mass percentage 10% and 90% Uniformly mix, melt extrude in the double screw extruder of 180 DEG C, be combined Fiber；Composite fibre is refluxed 72 hours in the acetone of 60 DEG C and extracts acetate butyrate fiber Element, carries out normal temperature drying by the composite fibre after extraction, prepare with EVOH as continuous phase, Demagnetization state SrFe12O19Nano-particle is dispersion phase and average diameter is that the compound of 100nm is received Rice fiber.
4) this composite nano fiber is scattered in ethanol formation nanofiber suspension by 1g/L, Then nanofiber suspension is coated on the upper surface of PP melt-blowing nonwoven, coating thickness Degree is 1 μm, is dried under room temperature, prepares by PP melt-blowing nonwoven and is attached to its surface Composite nano fiber composition nano-fiber composite film.
5) this film is placed in magnet charger magnetizes, prepare hard magnetic properties EVOH@SrFe12O19/ PP nano fibrous membrane.
Prepared by the present embodiment has the EVOH@SrFe of hard magnetic properties12O19/ PP nanofiber The structural behaviour index of film is as follows: average pore size is 700nm, and contact angle is 46.2 °, and empty Gas filter efficiency is as shown in table 1 with the performance indications of resistance pressure drop.
The air filter efficiency of the nano fibrous membrane of table 1 embodiment 1 preparation and resistance pressure drop performance
Understand in conjunction with table 1, on the one hand, bigger aperture ensure that film has low resistance pressure drop, On the other hand, the magneticaction of equally distributed magnetic-particle ensure that film has high filtration effect Rate；And low contact angle shows that film has excellent hydrophilic, can wash, it is achieved repeat Use, and the air filtration performance after washing is improved.Therefore, the nanometer of the present embodiment Fibrous membrane has air filtration performance and the repeat performance of excellence.
Embodiment 2
1) by the Fe of a size of 60nm3O4Nano-particle is placed in quartzy dry pot, in a vacuum furnace It is gradually heated to 600 DEG C and is incubated 80min, then naturally cooling to room temperature, it is thus achieved that demagnetization state Fe3O4Nano-particle.
2) by EVOH master batch and demagnetization state Fe3O4Nano-particle according to mass percent 80% and 20% weighs respectively, and with the mass percent of 25%, the EVOH master batch weighed is placed in DMF In, at 70 DEG C, stirring is to dissolving, and obtains EVOH solution；Demagnetization state Fe that will weigh3O4 Nano-particle is placed in DMF with the mass percent of 1%, dispersed with stirring at 70 DEG C, obtains Demagnetization state Fe3O4The suspension of nano-particle；By EVOH solution, demagnetization state Fe3O4Nanometer The suspension of granule is placed in mulser by the volume ratio of 1:1 and disperses 10min, and mulser Rotating speed is 800r/min, is cooled to room temperature, obtains emulsifying material；Emulsifying material is pressed 1:5 Volume ratio pour in deionized water precipitate, be dried, obtain composite；Use pulverizer again Pulverize composite and obtain composite material granular.
3) by this composite material granular and acetylbutyrylcellulose by mass percentage 5% and 95% Uniformly mix, melt extrude in the double screw extruder of 120 DEG C, be combined Fiber；Composite fibre is refluxed 70 hours in the acetone of 58 DEG C and extracts acetate butyrate fiber Element, carries out normal temperature drying by the composite fibre after extraction, prepare with EVOH as continuous phase, Demagnetization state Fe3O4Nano-particle be dispersion phase and composite Nano that average diameter is 200nm fine Dimension.
4) this composite nano fiber is scattered in ethanol formation nanofiber suspension by 2g/L, Then nanofiber suspension is coated on the upper surface of PET spun-bonded non-woven, coating thickness Degree is 5 μm, is dried under room temperature, prepares by PET spun-bonded non-woven and is attached to its table The nano-fiber composite film of the composite nano fiber composition in face.
5) this film is placed in magnet charger magnetizes, prepare hard magnetic properties EVOH@Fe3O4/ PET nano fibrous membrane.
Prepared by the present embodiment has the EVOH@Fe of hard magnetic properties3O4/ PET nano fibrous membrane Structural behaviour index as follows: average pore size 150nm, contact angle 62.4 °, and water filtration effect Rate is as shown in table 2 with flux performance.
The water filtration efficiency of the nano fibrous membrane of table 2 embodiment 2 preparation and flux performance
Embodiment 2 Water filtration efficiency (0.1 μm TiO2, 0.2MPa) Flux L/ (m2h)
Do not rinse 99.9% 12000
Backwash 1 time 100.0% 11800
Backwash 2 times 100.0% 11700
Understanding in conjunction with table 2, repeatedly wash, water filtration efficiency keeps constant, can realize repeating to make With.
Embodiment 3
1) by the Nd of a size of 20nm2Fe14B nano-particle is placed in quartzy dry pot, at vacuum drying oven In be gradually heated to 700 DEG C and be incubated 120min, then naturally cool to room temperature, it is thus achieved that demagnetization State Nd2Fe14B nano-particle.
2) by EVOH master batch and demagnetization state Nd2Fe14B nano-particle is according to mass percent 90% And 10% weigh respectively, the EVOH master batch weighed is placed in DMF with the mass percent of 1% In, at 90 DEG C, stirring is to dissolving, and obtains EVOH solution；Demagnetization state Nd that will weigh2Fe14B Nano-particle is placed in DMF with the mass percent of 3%, dispersed with stirring at 90 DEG C, obtains Demagnetization state Nd2Fe14The suspension of B nano-particle；By EVOH solution, demagnetization state Nd2Fe14B The suspension of nano-particle is placed in mulser dispersion 30min, and emulsifying by the volume ratio of 1:1 The rotating speed of machine is 1500r/min, is cooled to room temperature, obtains emulsifying material；By emulsifying material Pour in deionized water by the volume ratio of 1:5 precipitate, be dried, obtain composite；Use again Pulverizer is pulverized composite and is obtained composite material granular.
3) by this composite material granular and acetylbutyrylcellulose by mass percentage 40% and 60% Uniformly mix, melt extrude in the double screw extruder of 200 DEG C, be combined Fiber；Composite fibre is refluxed 75 hours in the acetone of 60 DEG C and extracts acetate butyrate fiber Element, carries out normal temperature drying by the composite fibre after extraction, prepare with EVOH as continuous phase, Demagnetization state Nd2Fe14B nano-particle is dispersion phase and average diameter is the composite Nano of 60nm Fiber.
4) this composite nano fiber is scattered in ethanol formation nanofiber suspension by 5g/L, Then nanofiber suspension is coated on the upper surface of PET spun-bonded non-woven, coating thickness Degree is 10 μm, is dried under room temperature, prepares by PET spun-bonded non-woven and is attached to its table The nano-fiber composite film of the composite nano fiber composition in face.
5) this film is placed in magnet charger magnetizes, prepare hard magnetic properties EVOH@Nd2Fe14B/PET nano fibrous membrane.
Prepared by the present embodiment has the EVOH@Nd of hard magnetic properties2Fe14B/PET nanofiber The structural behaviour index of film is as follows: average pore size is 80nm, and contact angle is 66.4 °.Water filtration Efficiency and flux performance are as shown in table 3.
The water filtration efficiency of the nano fibrous membrane of table 3 embodiment 3 preparation and flux performance
Embodiment 3 Water filtration efficiency (0.1 μm TiO2, 0.2MPa) Flux L/ (m2h)
Do not rinse 100.0% 9000
Backwash 1 time 100.0% 8990
Backwash 2 times 100.0% 8850
Understanding in conjunction with table 3, owing to magnetic-particle is evenly distributed on inside nanofiber, it is excellent Magneticaction ensure that film have excellence rejection.
Embodiment 4
1) by the Nd of a size of 20nm2Fe14B nano-particle is placed in quartzy dry pot, at vacuum drying oven In be gradually heated to 500 DEG C and be incubated 60min, then naturally cool to room temperature, it is thus achieved that demagnetization State Nd2Fe14B nano-particle.
2) by EVOH master batch and demagnetization state Nd2Fe14B nano-particle is according to mass percent 80% And 20% weigh respectively, the EVOH master batch weighed is placed in DMF with the mass percent of 25% In, at 80 DEG C, stirring is to dissolving, and obtains EVOH solution；Demagnetization state Nd that will weigh2Fe14B Nano-particle is placed in DMF with the mass percent of 2.5%, dispersed with stirring at 80 DEG C, To demagnetization state Nd2Fe14The suspension of B nano-particle；By EVOH solution, demagnetization state Nd2Fe14The suspension of B nano-particle is placed in mulser dispersion 15min by the volume ratio of 1:1, And the rotating speed of mulser is 1000r/min, it is cooled to room temperature, obtains emulsifying material；By breast Compound material pour in deionized water by the volume ratio of 1:5 precipitate, be dried, obtain composite； Use pulverizer to pulverize composite again and obtain composite material granular.
3) by this composite material granular and acetylbutyrylcellulose by mass percentage 5% and 95% Uniformly mix, melt extrude in the double screw extruder of 260 DEG C, be combined Fiber；Composite fibre is refluxed 72 hours in the acetone of 60 DEG C and extracts acetate butyrate fiber Element, carries out normal temperature drying by the composite fibre after extraction, prepare with EVOH as continuous phase, Demagnetization state Nd2Fe14B nano-particle is dispersion phase and average diameter is the composite Nano of 60nm Fiber.
4) this composite nano fiber is scattered in ethanol formation nanofiber suspension by 3g/L, Then nanofiber suspension is coated on the upper surface of PA6 spun-bonded non-woven, coating thickness Degree is 10 μm, is dried under room temperature, prepares by PA6 spun-bonded non-woven and is attached to its table The nano-fiber composite film of the composite nano fiber composition in face.
5) above-mentioned nano-fiber composite film is placed in magnet charger magnetizes, prepare Hard Magnetic The EVOH@Nd of characteristic2Fe14B/PA6 nano fibrous membrane.
Prepared by the present embodiment has the EVOH@Nd of hard magnetic properties2Fe14B/PA6 nanofiber The structural behaviour index of film is as follows: average pore size 70nm, contact angle 40.1 °, and water filtration effect Rate is as shown in table 4 with flux.
The water filtration efficiency of the nano fibrous membrane of table 4 embodiment 4 preparation and flux performance
Embodiment 4 Water filtration efficiency (0.06 μm TiO2, 0.2MPa) Flux L/ (m2h)
Do not rinse 100.0% 5000
Backwash 1 time 100.0% 4992
Backwash 2 times 100.0% 4860
Understanding in conjunction with table 4, owing to magnetic-particle is evenly distributed on inside nanofiber, it is excellent Magneticaction ensure that film have excellence rejection；Meanwhile, less contact angle shows film There is hydrophilic and the anti-pollution characteristic of excellence, thus ensure that film has high producing water ratio and regeneration Performance；Additionally, the average pore size of film is the least, illustrate that the nano fibrous membrane of the present embodiment can be processed Property strong, and Stability Analysis of Structures.
Above example is only optimal citing, and is not the restriction to embodiments of the present invention. In addition to the implementation, the present invention also has other embodiments.All employing equivalents or equivalence The technical scheme that conversion is formed, all falls within the protection domain of application claims.

Claims (10)

1. the preparation method of the nano fibrous membrane of a hard magnetic properties, it is characterised in that: include Following preparation process:
1) magnetic nanoparticle is carried out demagnetization process, obtain the state magnetic nanoparticle that demagnetizes；
2) by step 1) the demagnetization state magnetic nanoparticle for preparing is placed in dimethylformamide In, dispersed with stirring, obtain the suspension of demagnetization state magnetic nanoparticle；By ethylene-vinyl alcohol altogether Polymers master batch is placed in dimethylformamide, and stirring, to dissolving, obtains ethylene-vinyl alcohol copolymer Solution；By suspension and the mixing of ethylene-vinyl alcohol copolymer solution of demagnetization state magnetic nanoparticle After, clipped, dispersion, it is cooled to room temperature, obtains emulsifying material；Emulsifying material is put into Deionized water precipitates, is dried, obtain composite, then composite is pulverized, answered Condensation material granule；
3) by step 2) composite material granular for preparing and acetylbutyrylcellulose uniformly mix Close, through melt extruding, prepare composite fibre；Composite fibre is placed in acetone backflow, Extract acetylbutyrylcellulose, the composite fibre after being extracted, then by being combined after extraction Fiber drying, obtains composite nano fiber, and composite nano fiber is with ethylene-vinyl alcohol copolymer For continuous phase, with the state magnetic nanoparticle that demagnetizes as dispersion phase；
4) by step 3) composite nano fiber for preparing is scattered in ethanol, forms Nanowire Dimension suspension, then nanofiber suspension is coated on the surface of nonwoven substrate, it is dried After obtain nano-fiber composite film；Or nanofiber suspension is coated in the table of plastic sheeting Face, obtains nano fibrous membrane after drying；
5) step 4) nano-fiber composite film for preparing or nano fibrous membrane be placed in magnet charger Magnetize, prepare the nano fibrous membrane with hard magnetic properties.
The preparation method of the nano fibrous membrane of hard magnetic properties the most according to claim 1, It is characterized in that: described step 1) in concrete processing procedure as follows:
Magnetic nanoparticle is placed in silica crucible, is warming up in inert atmosphere or vacuum drying oven 500～700 DEG C, then insulation 1～2h, then naturally cool to room temperature, obtain demagnetization state magnetic and receive Rice grain.
The preparation side of the nano fibrous membrane of hard magnetic properties the most according to claim 1 and 2 Method, it is characterised in that: described step 1) in magnetic nanoparticle be SrFe12O19、Fe3O4、 Nd2Fe14One or more in B, and the mean diameter of magnetic nanoparticle is 10～100nm.
The preparation method of the nano fibrous membrane of hard magnetic properties the most according to claim 1, It is characterized in that: described step 2) in ethylene-vinyl alcohol copolymer master batch with demagnetization state magnetic receive The mass percent of rice grain is 80～99.5:0.5～20.
5. according to the preparation side of the nano fibrous membrane of the hard magnetic properties described in claim 1 or 4 Method, it is characterised in that: described step 2) in concrete processing procedure as follows:
By step 1) the demagnetization state magnetic nanoparticle for preparing is placed in dimethylformamide, And the mass percent of demagnetization state magnetic nanoparticle and dimethylformamide is 1～5:95～99, Dispersed with stirring at 70～90 DEG C, obtains the suspension of demagnetization state magnetic nanoparticle；By ethylene- Ethenol copolymer master batch is placed in dimethylformamide, and ethylene-vinyl alcohol copolymer master batch with The mass percent of dimethylformamide is 1～25:75～99, and at 70～90 DEG C, stirring is to dissolving, Obtain ethylene-vinyl alcohol copolymer solution；By mixture and the ethylene of demagnetization state magnetic nanoparticle -ethenol copolymer solution mixes, and the demagnetization suspension of state magnetic nanoparticle and ethylene-second The volume ratio of enol copolymer solution is 1:1, more clipped, dispersion, is cooled to room temperature, Obtain emulsifying material；Emulsifying material is put in deionized water precipitate, be dried, obtain composite wood Material, meanwhile, emulsifying material is 1:5 with the volume ratio of deionized water；Again by composite powder Broken machine is pulverized, and obtains composite material granular.
The preparation method of the nano fibrous membrane of hard magnetic properties the most according to claim 5, It is characterized in that: described step 2) middle employing mulser is sheared and disperses, and jitter time Being 10～30min, the rotating speed of mulser is 800～1500r/min.
The preparation method of the nano fibrous membrane of hard magnetic properties the most according to claim 1, It is characterized in that: described step 3) in the quality hundred of composite material granular and acetylbutyrylcellulose Proportion by subtraction is 5～40:60～95.
8. according to the preparation side of the nano fibrous membrane of the hard magnetic properties described in claim 1 or 7 Method, it is characterised in that: described step 3) in concrete processing procedure as follows:
By step 2) composite material granular for preparing and acetylbutyrylcellulose mix homogeneously, Melt extrude through double screw extruder, prepare composite fibre, and the work of double screw extruder It it is 120～260 DEG C as temperature；Then composite fibre is placed in acetone backflow, the temperature of backflow Being 58～62 DEG C, the time of backflow is 70～75h, extracts acetylbutyrylcellulose, is extracted Composite fibre after taking, then the composite fibre after extraction is placed under room temperature dry, prepare Composite nano fiber, and composite nano fiber is with ethylene-vinyl alcohol copolymer as continuous phase, to move back Magnetic states magnetic nanoparticle is dispersion phase, and the average diameter of composite nano fiber is 50～500nm.
The preparation method of the nano fibrous membrane of hard magnetic properties the most according to claim 1, It is characterized in that: described step 4) in, the composite nano fiber concentration in nanofiber suspension It is 1～10g/L, and coating thickness is 1～1000 μm.
10. according to the preparation side of the nano fibrous membrane of the hard magnetic properties described in claim 1 or 9 Method, it is characterised in that: described step 4) in, nonwoven substrate is polypropylene, gathers benzene two One or more melt-blown or spun-bonded non-woven in formic acid glycol ester or nylon, and Drying condition is normal temperature drying.
CN201610344244.0A 2016-05-23 2016-05-23 A kind of preparation method of the nano fibrous membrane of hard magnetic properties Active CN106000116B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610344244.0A CN106000116B (en) 2016-05-23 2016-05-23 A kind of preparation method of the nano fibrous membrane of hard magnetic properties

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610344244.0A CN106000116B (en) 2016-05-23 2016-05-23 A kind of preparation method of the nano fibrous membrane of hard magnetic properties

Publications (2)

Publication Number Publication Date
CN106000116A true CN106000116A (en) 2016-10-12
CN106000116B CN106000116B (en) 2018-12-28

Family

ID=57096824

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610344244.0A Active CN106000116B (en) 2016-05-23 2016-05-23 A kind of preparation method of the nano fibrous membrane of hard magnetic properties

Country Status (1)

Country Link
CN (1) CN106000116B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109319872A (en) * 2018-10-29 2019-02-12 浙江海洋大学 A kind of industrial sewage treating agent and preparation method thereof
CN111501149A (en) * 2020-04-17 2020-08-07 华中科技大学 Magnetic yarn, magnetic fabric, magnetic control robot and preparation method thereof
CN112680999A (en) * 2020-12-21 2021-04-20 宁波日新恒力科技有限公司 Preparation method of semi-permeable membrane support body with uniform pores
CN113244697A (en) * 2021-05-19 2021-08-13 武汉纺织大学 Melt-blown high-efficiency air filter material with multiple physical field effects and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102978730A (en) * 2012-11-23 2013-03-20 东华大学 Preparation method of inorganic/organic magnetic liposome nanofiber membrane
CN104689724A (en) * 2015-03-18 2015-06-10 武汉纺织大学 Organic and inorganic composite nanofiber membrane filtering material and preparation method thereof
CN105536052A (en) * 2015-12-28 2016-05-04 北京航空航天大学 Preparing method of magnetic-electro dual function nanofiber membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102978730A (en) * 2012-11-23 2013-03-20 东华大学 Preparation method of inorganic/organic magnetic liposome nanofiber membrane
CN104689724A (en) * 2015-03-18 2015-06-10 武汉纺织大学 Organic and inorganic composite nanofiber membrane filtering material and preparation method thereof
CN105536052A (en) * 2015-12-28 2016-05-04 北京航空航天大学 Preparing method of magnetic-electro dual function nanofiber membrane

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109319872A (en) * 2018-10-29 2019-02-12 浙江海洋大学 A kind of industrial sewage treating agent and preparation method thereof
CN111501149A (en) * 2020-04-17 2020-08-07 华中科技大学 Magnetic yarn, magnetic fabric, magnetic control robot and preparation method thereof
CN112680999A (en) * 2020-12-21 2021-04-20 宁波日新恒力科技有限公司 Preparation method of semi-permeable membrane support body with uniform pores
CN113244697A (en) * 2021-05-19 2021-08-13 武汉纺织大学 Melt-blown high-efficiency air filter material with multiple physical field effects and preparation method thereof

Also Published As

Publication number Publication date
CN106000116B (en) 2018-12-28

Similar Documents

Publication Publication Date Title
CN104689724B (en) A kind of organic and inorganic composite nanofiber membrane filtration material and preparation method thereof
Zhang et al. Structural design and environmental applications of electrospun nanofibers
Cui et al. High performance, environmentally friendly and sustainable nanofiber membrane filter for removal of particulate matter 1.0
CN106000116A (en) Preparation method of nanofiber membrane with hard magnetic property
CN104014196B (en) A kind of high absorption nanofiber composite filter material and preparation method thereof
KR101118473B1 (en) Nanoporous films and method of manufacturing nanoporous films
CN102302875B (en) Method for preparing antibacterial air-filtering membrane
Zhou et al. Electrospinning ultrathin continuous cellulose acetate fibers for high-flux water filtration
CN106039839B (en) A kind of Ke Xunhuanliyong, efficient low-resistance, antibacterial antifogging haze air filting material
CN106807250B (en) A kind of preparation method of graphene oxide/silica/high molecular polymer composite nanometer filtering film
CN106311165B (en) Chitosan nano fiber composite membrane and its preparation method and application for adsorbing separation heavy metal ion
CN106299213B (en) A kind of bacteria cellulose-base microporous compound film and its preparation method and application
CN103894077A (en) Composite filter membrane with multidimensional pore structure and preparation method thereof
CN106245232A (en) Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application
CN107456879B (en) Nano silica/nanofiber water-oil separating composite membrane and preparation method thereof
CN107441848B (en) Silk fibroin nanofiltration membrane with micro-nano structure on surface, preparation method and application thereof
CN109137131A (en) The modified antibacterial degradable nanofiber of solution gunite and its application in air filtration
CN106334538B (en) A kind of preparation method with hard magnetic nanofiber aerogel material
CN112522856A (en) Metal organic framework and electrospun nanofiber composite protective cover film and preparation
CN109046040A (en) Gradient filtration membrane material based on nanofiber and preparation method thereof
CN113368712B (en) Efficient air filtration composite nanofiber membrane and preparation method thereof
CN111303539A (en) Melt-blown polypropylene electret master batch and preparation method thereof
CN105780299B (en) Preparation method of supermolecule adsorption filter screen
CN104587981A (en) Nanofiber membrane with heavy metal adsorbing function and preparation method of nanofiber membrane
Pang et al. Ultralight ethyl cellulose-based electret fiber membrane for low-resistance and high-efficient capture of PM2. 5

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant