Prepared by a kind of efficient low-resistance electrostatic spinning nano fiber air filting material and mass
Method
Technical field
The invention belongs to air filting material and preparation field thereof, particularly to a kind of efficient low-resistance electrostatic spinning nano fiber
Air filting material and mass preparation method.
Background technology
Along with China's process of industrialization is goed deep into and rapid economic development, air pollution problems inherent is the most serious, the most closely
The PM2.5 (particle diameter is less than the granule of 2.5 μm) that Nian Lai China various places persistently occur pollutes, and causes the healthy of people
Serious threat.Filter as a kind of safeguard procedures, can effectively resist and pollute the adverse effect brought.At present, China
Industry use the air filting material based on glass fibre or melt-blowing nonwoven in a large number, its to size more than micron order
Particulate matter there is preferable filter effect, but poor to submicron even nano-scale particle thing filter efficiency, and existed
The problems such as filtration resistance power is big, dust containing capacity is little, service life is short, therefore, are badly in need of a kind of high-efficient low-resistance air filting material of exploitation.
Electrostatic spinning nano fiber has that fibre diameter is little, aperture is little, specific surface area is big, porosity advantages of higher, by its with
Base material can prepare preferable air filting material after combining.But owing to electrostatic spinning fiber diameter is at submicron-scale, in reality
Now efficient the most generally with higher filtration resistance, existing document is mainly by adding inorganic nano in spinning liquid
Grain, prepare porous fibre, three kinds of modes of nano fibrous membrane electret are realized efficient low-resistance.(1) in spinning liquid, inorganic receiving is added
Rice grain, makes fibrous membrane have multistage surface roughness, increases specific surface area, and fibre section is non-circular simultaneously, efficiently
Reduce filtration resistance (N.Wang, Y.S.Si, N.Wang, et al.Multilevel structured simultaneously
polyacrylonitrile/silica nanofibrous membranes for high-performance air
filtration[J].Separation and Purification Technology,2014,126:44-51.).But it is inorganic
Nano-particle addition is limited, and too much nano-particle is reunited, and the filter efficiency of fibrous membrane reduces on the contrary, and is using
During inorganic nanoparticles can fall off, health of people is threatened.(2) porous fibre is prepared, patent
CN103952783A discloses " a kind of beading porous PLA nanofiber and preparation method thereof ", uses low boiling point solvent, in spinning
During, solvent quickly volatilizees, and induced jet surface solution is quickly separated and solidification, forms beading porous fibrous structure,
Realize efficient low-resistance.But porous fibrous material mechanical property is poor, in experimentation, a large amount of low boiling point solvents quickly volatilize simultaneously
People can be jeopardized healthy.(3) to nano fibrous membrane electret, patent CN104289042A discloses that " a kind of Static Spinning is received
Rice fiber electret filtering material and preparation thereof " by controlling inorganic nanoparticles content, polymer solution temperature and Nanowire
Dimension molding instantaneous cooling technique is prepared for nanofiber electret filtering material, but does not provide this material and place rear surface electricity
The related data of lotus whether loss.Electret material is during storing and using, and moisture and microgranule in air can accelerate electret
Material surface electric charge loss, makes electret effect gradually decay, and ultimately results in filtration of material efficiency and declines.Electrostatic spinning nano fiber material
Material yields poorly and always restricts the technological difficulties of its industrialized production, above method and the most unresolved electrostatic spinning nano fiber of patent
Filtering material can not the problem of mass production.
Summary of the invention
The technical problem to be solved is to provide a kind of efficient low-resistance electrostatic spinning nano fiber air filting material
And mass preparation method, the method technique is simple, controlled and reproducible, and the air filting material prepared has efficient low-resistance
Feature, thickness is uniform, and strainability is stable, can realize the mass production of nanofiber filtration material, in field of air filtration
There is extraordinary application prospect.
A kind of efficient low-resistance electrostatic spinning nano fiber air filting material of the present invention, described filtering material is spunbond non-knits
Making cloth and nanofiber sandwich alternately, nanofiber is electrostatic spinning nano fiber/microsphere composite membrane, wherein electrostatic
Spinning nano fibre/microsphere structure of composite membrane is: microsphere embeds the 3 D stereo cavity structure formed between electrostatic spinning nano fiber.
Described spun-bonded non-woven, fibre diameter is 1-10 μm, and grammes per square metre is 10-120g/m2, exhibits initial filtration efficiency is
0.1%-5%.
The a diameter of 100-300nm of described electrostatic spinning nano fiber;The particle diameter of microsphere is 500-800nm.
A kind of efficient low-resistance electrostatic spinning nano fiber air filting material of the present invention and mass preparation method, including:
(1) polymer is added in solvent, stirring, obtain the electrostatic spinning polymer solution of high concentration;Wherein Static Spinning
The mass percentage concentration of silk polymer solution is 10-40%;
(2) polymer is added in solvent, stirring, obtain the electrostatic spray polymer solution of low concentration;Wherein electrostatic
The mass percentage concentration of mist polymer solution is 3-30%;
(3) needle-free electrostatic spinning nozzle is used, then by electrostatic spinning and electrostatic spray locking phase combination technology, system
Obtain nanofiber/microsphere composite membrane, be reception base material to rotate cylinder as reception device, spun-bonded non-woven, obtain nanometer
Fiber/non-weaving cloth composite material, can regulate and control the grammes per square metre of electrostatic spinning nano fiber/microsphere composite membrane by adjusting the spinning time
For 0.1-10g/m2;
(4) by above-mentioned nanofiber/non-weaving cloth composite material surface cover one layer spun-bonded non-woven, spunbond non-knit is formed
Make cloth and nanofiber sandwich alternately, then adhesion process, obtain electrostatic spinning nano fiber air filting material.
In described step (1), (2), polymer is polyacrylonitrile, polyurethane, polysulfones, polyvinylpyrrolidone, poly-inclined fluorine
One in ethylene, polyethylene glycol oxide, polystyrene, polymethyl methacrylate, polycaprolactone, polycaprolactam, chitosan
Or it is several;Solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetone, oxolane, two
One or more in chloromethanes, chloroform, hexafluoroisopropanol, formic acid, acetic acid, ethanol.
In described step (1), (2), stirring is magnetic agitation 10-12h.
Step (3) uses insulant, needle-free electrostatic spinning nozzle surface is divided into from center there is identical faces
Amass or the 2-8 part of length, respectively electrostatic spinning polymer solution and electrostatic spray polymer solution be injected into different piece,
Spinning is carried out by electrostatic spinning and electrostatic spray locking phase combination technology.
Described insulant be politef, Kynoar, polymethyl methacrylate, Merlon, polyethylene,
One in polypropylene, polystyrene.
In described step (3), electrostatic spinning with the concrete technology parameter of electrostatic spray locking phase combination technology is: spinning electricity
Pressure 40-75KV, drum rotation speed 10-400r/min, shower nozzle and roller pitch are from 10-25cm, shower nozzle transverse moving speed 10-300cm/
Min, liquid supply speed 20-500mL/h, ambient temperature 20-35 DEG C, ambient humidity 20-80%.
Whole spinning-drawing machine is airtight, is provided with temperature and humidity measure and device for automatically regulating in confined space, and spinning nozzle is with horizontal
Moving mechanism is connected, and spinning nozzle is connected with tube for transfusion, and the tube for transfusion other end connects liquid feed device, in whole spinning process, feed flow
Device is sustainedly and stably to shower nozzle feed flow, it is ensured that spinning is carried out continuously, it is achieved electrostatic spinning nano fiber material mass production.
In described step (4), adhesion process is ultrasonic bonds, and this bonding mode is little to the destruction of nanofiber, after process
Composite remain to keep efficient low-resistance feature, the strength of filter material is greatly improved simultaneously.
The present invention uses needle-free electrostatic spinning nozzle, by electrostatic spinning and electrostatic spray locking phase combination technology, wound
New property be prepared for electrostatic spinning nano fiber/microsphere composite membrane, one-step shaping obtains high-efficiency low-resistance nano fiber filter material
The filtering material that the present invention prepares has 3 D stereo cavity structure and good structure Modulatory character, filter material
Expecting a length of 1.6m, fabric width is 0.6m, and the time used by a filter material that produces is 20-30min, and this filtering material is straight to quantity intermediate value
Footpath be the particle filtration efficiency of 75nm up to 99.99%, filtration resistance is 50-150Pa, and the method provided by the present invention is to receiving
After rice fiber membrane structure is optimized, compared with common nanofiber filtration material, under identical filter efficiency, filtration resistance drops
Low by 35%.
Beneficial effect
(1) present invention is by electrostatic spinning and electrostatic spray locking phase combination technology, and polymer highly concentrated solution is through quiet
The diameter fiber at 100-300nm is formed after Electrospun, can be as fibrous membrane supporting construction.Polymer low concentration solution is through quiet
Forming diameter after electron spray at the microsphere of 500-800nm, microsphere embeds between nanofiber, increased fiber with interfibrous away from
From, forming 3 D stereo cavity structure, reduce filtration resistance, polymer low concentration solution can be formed straight while forming microsphere
Filter efficiency, at the superfine nano fiber of about 80nm, is improved while reducing filtration resistance in footpath, and one-step shaping obtains the lowest
Resistance nanofiber filtration material;
(2) present invention uses needle-free electrostatic spinning nozzle, it is to avoid multiple single needle electrostatic spinning syringe needles and syringe needle it
Between electric field interfere, the problem causing the fibrous membrane lack of homogeneity prepared;The preparation method that the present invention provides, prepared nanometer
Fibrous membrane thickness is uniform, and strainability is stable, and production efficiency is high, prepares an a length of 1.6m, and fabric width is the nanometer mistake of 0.6m
Filtering material required time is only 20-30min, can realize the mass production of electrostatic spinning nano fiber air filting material;
(3) present invention process parameter is the most controlled, and the nanofiber filtration material of preparation has good structure controllable
Property, can be realized fibrous material packing density, hole by the jet-flow proportioning of regulation electrostatic spinning with electrostatic spray polymer solution
Footpath and the accuracy controlling of porosity;
(4) the nanofiber filtration material aperture that prepared by the present invention is little, porosity big, and the existence of microsphere makes this material have
Having 3 D stereo cavity structure, this structure makes it have bigger dust containing capacity in actual use, extends filtering material
Service life, there is good actual application prospect.
Accompanying drawing explanation
Fig. 1 is efficient low-resistance electrostatic spinning nano fiber air filting material preparation flow figure of the present invention;
Fig. 2 is the SEM Electronic Speculum of the efficient low-resistance electrostatic spinning nano fiber/microsphere composite membrane of preparation in the embodiment of the present invention 1
Figure.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Embodiment 1
Filtering material is spun-bonded non-woven and nanofiber sandwich alternately, and nanofiber is that Static Spinning is received
Rice fiber/microsphere composite membrane, wherein electrostatic spinning nano fiber/microsphere structure of composite membrane is: microsphere embeds electrostatic spinning nano fiber
Between formed 3 D stereo cavity structure;Wherein nanofiber diameter is 139nm;The particle diameter of microsphere is 658nm;Static Spinning is received
The grammes per square metre of rice fiber/microsphere composite membrane is 1.08g/m2.Spun-bonded non-woven used, its composition fibre diameter is 5 μm, and grammes per square metre is
25g/m2, spun-bonded non-woven exhibits initial filtration efficiency is 0.2%.
A kind of efficient low-resistance electrostatic spinning nano fiber air filting material and mass preparation method, concretely comprise the following steps:
The first step: be placed in vacuum drying oven by polyacrylonitrile powder, is vacuum dried 8 hours at 70 DEG C;
Second step: dried polyacrylonitrile powder is dissolved in DMF solvent, at magnetic stirring apparatus
Upper stirring 12 hours, is made into the polyacrylonitrile highly concentrated solution that mass fraction is 10wt%;
Dried polyacrylonitrile powder is dissolved in DMF solvent, magnetic stirring apparatus stirs 12
Hour, it is made into the polyacrylonitrile low concentration solution that mass fraction is 5wt%;
3rd step: use umbrella spinning nozzle (CN103088443A), uses tenon sheet by nozzle surface certainly
Center is divided into the two parts with same circumference length, uses liquid feed device, makes nozzle surface left-half fill 10wt%
Polyacrylonitrile highly concentrated solution, nozzle surface right half part fills the polyacrylonitrile low concentration solution of 5wt%, passes through Static Spinning
Silk and electrostatic spray locking phase combination technology, prepare nanofiber/microsphere composite membrane.With spun-bonded non-woven for receiving base
Material, whole spinning process is carried out in airtight space, spinning voltage 65KV, drum rotation speed 70r/min, shower nozzle and roller pitch
From 20cm, shower nozzle transverse moving speed 120cm/min, liquid supply speed 50mL/h, ambient temperature 23 DEG C, ambient humidity 25%, during spinning
Between 20min;
4th step: the nanofiber/spun-bonded non-woven material upper surface obtained in the 3rd step covers one layer of non-weaving cloth again,
Form spun-bonded non-woven and nanofiber sandwich alternately, eventually pass after ultrasonic bonds processes and obtain electrostatic
Spinning nano fibre air filting material.
Described nano-fiber air filter material to the filter efficiency that quantity median diameter is 75nm granule up to
99.99%, filtration resistance is 130.7Pa.
Embodiment 2
Filtering material is spun-bonded non-woven and nanofiber sandwich alternately, and nanofiber is that Static Spinning is received
Rice fiber/microsphere composite membrane, wherein electrostatic spinning nano fiber/microsphere structure of composite membrane is: microsphere embeds electrostatic spinning nano fiber
Between formed 3 D stereo cavity structure;Wherein nanofiber diameter is 204nm;The particle diameter of microsphere is 569nm;Static Spinning is received
The grammes per square metre of rice fiber/microsphere composite membrane is 1.25g/m2.Spun-bonded non-woven used, its composition fibre diameter is 5 μm, and grammes per square metre is
30g/m2, spun-bonded non-woven exhibits initial filtration efficiency is 0.2%.
A kind of efficient low-resistance electrostatic spinning nano fiber air filting material and mass preparation method, concretely comprise the following steps:
The first step: be placed in vacuum drying oven by polyacrylonitrile powder, is vacuum dried 8 hours at 70 DEG C;
Second step: be dissolved in dimethyl sulfoxide solvent by dried polyacrylonitrile powder, stirs on magnetic stirring apparatus
12 hours, it is made into the polyacrylonitrile highly concentrated solution that mass fraction is 12wt%;
Dried polyacrylonitrile powder is dissolved in dimethyl sulfoxide solvent, magnetic stirring apparatus stirs 12 hours,
It is made into the polyacrylonitrile low concentration solution that mass fraction is 6wt%;
3rd step: use umbrella spinning nozzle (CN103088443A), uses tenon sheet by nozzle surface certainly
Center is divided into four parts with same circumference length, uses liquid feed device, makes shower nozzle a portion fill 12wt%'s
Polyacrylonitrile highly concentrated solution, other three are partially filled with the polyacrylonitrile low concentration solution of 6wt%, by electrostatic spinning and electrostatic
Spraying locking phase combination technology, prepares nanofiber/microsphere composite membrane.With spun-bonded non-woven for receiving base material, whole
Spinning process is carried out in airtight space, spinning voltage 60KV, drum rotation speed 100r/min, shower nozzle and the spacing of cylinder
15cm, shower nozzle transverse moving speed 80cm/min, liquid supply speed 40mL/h, ambient temperature 25 DEG C, ambient humidity 30%, the spinning time
30min;
4th step: the nanofiber/spun-bonded non-woven material upper surface obtained in the 3rd step covers one layer of non-weaving cloth again,
Form spun-bonded non-woven and nanofiber sandwich alternately, eventually pass after ultrasonic bonds processes and obtain electrostatic
Spinning nano fibre air filting material.
Described nano-fiber air filter material to the filter efficiency that quantity median diameter is 75nm granule up to
99.91%, filtration resistance is 102.8Pa.
Embodiment 3
Filtering material is spun-bonded non-woven and nanofiber sandwich alternately, and nanofiber is that Static Spinning is received
Rice fiber/microsphere composite membrane, wherein electrostatic spinning nano fiber/microsphere structure of composite membrane is: microsphere embeds electrostatic spinning nano fiber
Between formed 3 D stereo cavity structure;Wherein nanofiber diameter is 236nm;The particle diameter of microsphere is 631nm;Static Spinning is received
The grammes per square metre of rice fiber/microsphere composite membrane is 1.96g/m2.Spun-bonded non-woven used, its composition fibre diameter is 10 μm, grammes per square metre
For 30g/m2, spun-bonded non-woven exhibits initial filtration efficiency is 0.1%.
A kind of efficient low-resistance electrostatic spinning nano fiber air filting material and mass preparation method, concretely comprise the following steps:
The first step: be placed in vacuum drying oven by polyurethane particles, is vacuum dried 8 hours at 110 DEG C;
Second step: dried polyurethane particles is dissolved in DMF solvent, on magnetic stirring apparatus
Stir 12 hours, be made into the polyurethane highly concentrated solution that mass fraction is 35wt%;
Dried polyurethane particles is dissolved in DMF solvent, magnetic stirring apparatus stirs 12 little
Time, it is made into the polyurethane low concentration solution that mass fraction is 20wt%;
3rd step: use the electrostatic spinning apparatus (CN104593880A) of a kind of polymer fiber mass production, uses
Many one metal wires, as electrostatic spinning nozzle, use tenon sheet to be divided into from center by reservoir and have equal length
Two parts, use liquid feed device, make reservoir left-half fill the polyurethane highly concentrated solution of 35wt%, reservoir right half
It is partially filled with the polyurethane low concentration solution of 20wt%, by electrostatic spinning and electrostatic spray locking phase combination technology, is prepared into
To nanofiber/microsphere composite membrane.With spun-bonded non-woven for receiving base material, whole spinning process is entered in airtight space
OK, spinning voltage 70KV, drum rotation speed 120r/min, shower nozzle and roller pitch from 25cm, shower nozzle transverse moving speed 100cm/min,
Liquid supply speed 80mL/h, ambient temperature 27 DEG C, ambient humidity 35%, spinning time 25min;
4th step: the nanofiber/spun-bonded non-woven material upper surface obtained in the 3rd step covers one layer of non-weaving cloth again,
Form spun-bonded non-woven and nanofiber sandwich alternately, eventually pass after ultrasonic bonds processes and obtain electrostatic
Spinning nano fibre air filting material.
Described nano-fiber air filter material to the filter efficiency that quantity median diameter is 75nm granule up to
99.26%, filtration resistance is 76.3Pa.
Embodiment 4
Filtering material is spun-bonded non-woven and nanofiber sandwich alternately, and nanofiber is that Static Spinning is received
Rice fiber/microsphere composite membrane, wherein electrostatic spinning nano fiber/microsphere structure of composite membrane is: microsphere embeds electrostatic spinning nano fiber
Between formed 3 D stereo cavity structure;Wherein nanofiber diameter is 152nm;The particle diameter of microsphere is 670nm;Static Spinning is received
The grammes per square metre of rice fiber/microsphere composite membrane is 1.68g/m2.Spun-bonded non-woven used, its composition fibre diameter is 10 μm, grammes per square metre
For 35g/m2, spun-bonded non-woven exhibits initial filtration efficiency is 0.2%.
A kind of efficient low-resistance electrostatic spinning nano fiber air filting material and mass preparation method, concretely comprise the following steps:
The first step: be placed in vacuum drying oven by polyacrylonitrile powder, is vacuum dried 8 hours at 70 DEG C;Will poly-inclined fluorine
Ethylene powder is placed in vacuum drying oven, is vacuum dried 8 hours at 130 DEG C;
Second step: be dissolved in dimethyl sulfoxide solvent by dried polyacrylonitrile powder, stirs on magnetic stirring apparatus
12 hours, it is made into the polyacrylonitrile highly concentrated solution that mass fraction is 10wt%;
Dried Kynoar powder is dissolved in DMF solvent, magnetic stirring apparatus stirs
12 hours, it is made into the Kynoar low concentration solution that mass fraction is 6wt%;
3rd step: use the electrostatic spinning apparatus (CN104593880A) of a kind of polymer fiber mass production, uses
Many one metal wires as electrostatic spinning nozzle, use tenon sheet to be divided into by reservoir and have four of equal length
Point, use liquid feed device, make reservoir a portion fill the polyacrylonitrile highly concentrated solution of 10wt%, other three part notes
The Kynoar low concentration solution of full 6wt%, by electrostatic spinning and electrostatic spray locking phase combination technology, prepares and receives
Rice fiber/microsphere composite membrane.With spun-bonded non-woven for receiving base material, whole spinning process carries out in airtight space, spins
Spacing 20cm of filament voltage 55KV, drum rotation speed 140r/min, shower nozzle and cylinder, shower nozzle transverse moving speed 60cm/min, feed flow
Speed 30mL/h, ambient temperature 25 DEG C, ambient humidity 40%, spinning time 30min;
4th step: the nanofiber/spun-bonded non-woven material upper surface obtained in the 3rd step covers one layer of non-weaving cloth again,
Form spun-bonded non-woven and nanofiber sandwich alternately, eventually pass after ultrasonic bonds processes and obtain electrostatic
Spinning nano fibre air filting material.
Described nano-fiber air filter material to the filter efficiency that quantity median diameter is 75nm granule up to
99.82%, filtration resistance is 95.1Pa.