CN109046040A - Gradient filtration membrane material based on nanofiber and preparation method thereof - Google Patents

Gradient filtration membrane material based on nanofiber and preparation method thereof Download PDF

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Publication number
CN109046040A
CN109046040A CN201810877291.0A CN201810877291A CN109046040A CN 109046040 A CN109046040 A CN 109046040A CN 201810877291 A CN201810877291 A CN 201810877291A CN 109046040 A CN109046040 A CN 109046040A
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layer
nanofiber
sub
thermoplastic polymer
fiber
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CN109046040B (en
Inventor
刘轲
王栋
程盼
王旭
郭启浩
赵青华
梅涛
李沐芳
刘琼珍
蒋海青
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Wuhan Weichen Technology Co ltd
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Wuhan Textile University
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    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • 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
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses gradient filtration membrane materials of a kind of nanofiber and preparation method thereof, belong to membrane material and textile material technical field.The present invention is using non-woven material as supporting layer, gradient sub-layer (having the function of gradient filtration) composition coated in support layer surface, gradient sub-layer is that thermoplastic polymer nanofiber fibrous layer is made of two layers or three layers of the thermoplastic polymer nanofiber fiber sub-layer with different pore size structure, it is acted on and being firmly combined by chemical crosslinking between each sub-layer, and there is slice gradient structure on the direction perpendicular to film surface.The gradient filtration membrane material of wanted different filtering functions can be made by the arrangement of the thermoplastic nanofibers fiber of flexible modulation different-diameter range using the thermoplastic nanofibers fiber of different-diameter range in each sub-layer.This material has greatly flexible controllability, and has water flux big, the high feature of filter efficiency.The present invention can be widely applied to ambient water filtering and other relevance filtering fields because of its unique regulatable gradient-structure.

Description

Gradient filtration membrane material based on nanofiber and preparation method thereof
Technical field
The present invention relates to a kind of filter membranes, belong to membrane material and textile material technical field, are based on more particularly to one kind Gradient filtration membrane material of nanofiber and preparation method thereof.
Background technique
With socio-economic development, water body environment pollution form is more serious, and the whole society is to water environment growing interest, especially Ground is also higher and higher with membrane material requirement to water process, designs excellent membrane material structure to efficient low-consume water process with important Meaning.
Micro-filtering flat plate membrane material development prospect is wide, and micro-filtering flat plate film in the market mainly uses phase inversion system Standby, the technological investment is at high cost, and structure is not easy to control, and especially the wide cut fenestra uniformity is not easy to control；A large amount of solvent is needed, It is seriously polluted；For filter layer thickness at 100 microns or more, porosity is low, is not easy to functionalization, realizes that final efficient low-consume is answered With.
On the other hand, fiber base micro-filtering flat plate film is with the obvious advantage, for example, porosity is high, is easy to functionalization, aperture size Fibre diameter is depended primarily on, the magnanimity technology of preparing shortcoming of nanofiber constrains the fiber base with 1 micron or less aperture The development of plate membrane.The yield of nanofiber can be effectively improved using melt blending phase separation method, while being prepared aperture and being existed 50nm to 1000nm is filter membrane material.
As Chinese invention patent application (application publication number: CN104014196A, data of publication of application: 2014-09-03) is open A kind of high absorption nanofiber composite filter material and preparation method thereof, specifically discloses composite filter material by non-woven base Material and nano fibrous membrane composition coated in its surface, the advantages of the application is the controlled diameter of nano fibrous membrane, and preparation is answered It closes filtering material to stablize with structural behaviour, the excellent feature of Adsorption Filtration Properties.
For another example Chinese invention patent application (application publication number: CN107137979A, data of publication of application: 2017-09-08) is public A kind of micrometer fibers three-dimensional framework/polymer nanofiber composite filter material and preparation method thereof has been opened, has specifically been disclosed logical It crosses melt-blending process and prepares polymer nanofiber, the polymer nanofiber and crosslinking agent dispersion are formed suspend in a solvent Then micrometer fibers non-woven fabrics skeleton is soaked in suspension by liquid, freeze-drying forms coagulated mass and removes solvent again, is obtained micro- Gradient distribution has the non-woven material of polymer nanofiber aeroge between rice fiber skeleton.The product of the application has good The air filtration performance of flexibility and efficient low-resistance.
However, the aperture structure of the filtering material of above-mentioned two pieces application still not enough optimizes, flux still needs further It improves.
For another example Chinese invention patent application (application publication number: CN106730150A, data of publication of application: 2017-05-31) is public A kind of gradient aperture filter membrane and its preparation method and application is opened, disclosed gradient aperture filter membrane uses high molecular polymer Material electrostatic spinning is made, and including the three-decker fitted closely, the aperture of outside double-layer structure is 5~10 microns, with a thickness of 0.1~0.4mm；The aperture of interlayer structure is 0.5~5 micron, and with a thickness of 0.3~0.6mm, the filter membrane of this application can be real Now to the filtering of infusion apparatus particle；As Chinese utility model patent (Authorization Notice No.: CN207056133U, authorized announcement date: 2018-03-02) disclose gradient filtration complex nonwoven cloth material, the gradient filtration complex nonwoven cloth material by spun lacing without Woven fabric layer, spun-bonded non-woven fabrics layer and ultra-fine melt-blown non-woven fabric layer composition.Wherein, the fluffy softness of spunlace non-woven cloth layer, porosity are big, Spun-bonded non-woven fabrics layer strength is good, and melt spraying non-woven fabrics layer porosity is minimum, and filter efficiency is high, and three layers of fiber porosity reduce in gradient Trend arrangement, has excellent strainability, can reduce the frequency of replacement filtering material, reduce cost.However, above two The non-woven fabrics of structure does not have flexibility in structure design.
Therefore, it is very necessary to design and develop the micro/nano fibrous membrane material with superior filtration structure.
Summary of the invention
In view of the above technical problems, the purpose of the present invention is to provide one kind to have high absorption capacity, structure flexible design The gradient filtration membrane material based on nanofiber and preparation method thereof of property.
To achieve the above object, technical solution of the invention are as follows:
A kind of gradient filtration membrane material based on nanofiber, it is by supporting layer and the filter layer for being supported on support layer surface Composition, the filter layer is that the thermoplastic polymer nanofiber fiber sub-layer for having different pore size structure by two layers or three layers is constituted, It is combined by way of chemical crosslinking between each thermoplastic polymer nanofiber fiber sub-layer, the thermoplastic polymer nanofiber fiber The nanofiber diameter of sub-layer is divided into three ranks: 50~200nm rank, 200~600nm rank and 600~1000nm rank, Each thermoplastic polymer nanofiber fiber sub-layer with a thickness of 1~100 μm, the material of the supporting layer is non-woven material.
Preferably, it is combined between each thermoplastic polymer nanofiber fiber sub-layer by chemical cross-linking agent.
Further, the filter layer is by the sub-layer in supporting layer thermoplastic polymer nanofiber fiber from the near to the distant It is constituted with sub-layer outside thermoplastic polymer nanofiber fiber, the nanofiber diameter of sub-layer in the thermoplastic polymer nanofiber fiber Less than the nanofiber diameter of sub-layer outside thermoplastic polymer nanofiber fiber.
Preferably, the diameter of sub-layer is 50~200nm rank, the thermoplasticity in the thermoplastic polymer nanofiber fiber The diameter of the outer sub-layer of polymer nanofiber is 200~600nm rank.
Preferably, the diameter of sub-layer is 50~200nm rank, the thermoplasticity in the thermoplastic polymer nanofiber fiber The diameter of the outer sub-layer of polymer nanofiber is 600~1000nm rank.
Preferably, the diameter of sub-layer is 200~600nm rank, the thermoplastic in the thermoplastic polymer nanofiber fiber Property the outer sub-layer of polymer nanofiber diameter be 600~1000nm rank.
Further, the filter layer is by sub- in supporting layer thermoplastic polymer nanofiber fiber from the near to the distant Sub-layer and the outer sub-layer of thermoplastic polymer nanofiber fiber are constituted in layer, thermoplastic polymer nanofiber fiber, the thermoplasticity polymerization The nanofiber diameter of sub-layer is less than or equal to the nanofiber of the outer sub-layer of thermoplastic polymer nanofiber fiber in object nanofiber Diameter, it is outer sub- to be less than thermoplastic polymer nanofiber fiber for the nanofiber diameter of sub-layer in the thermoplastic polymer nanofiber fiber The nanofiber diameter of layer.
Preferably, the diameter of sub-layer is 50~200nm rank, the thermoplasticity in the thermoplastic polymer nanofiber fiber The diameter of sub-layer is 50~200nm rank in polymer nanofiber, and sub-layer is straight outside the thermoplastic polymer nanofiber fiber Diameter is 200~600nm rank.
Preferably, the diameter of sub-layer is 200~600nm rank, the thermoplastic in the thermoplastic polymer nanofiber fiber Property polymer nanofiber in the diameter of sub-layer be 50~200nm rank, the outer sub-layer of the thermoplastic polymer nanofiber fiber Diameter is 200~600nm rank.
Preferably, the diameter of sub-layer is 200~600nm rank, the thermoplastic in the thermoplastic polymer nanofiber fiber Property polymer nanofiber in the diameter of sub-layer be 50~200nm rank, the outer sub-layer of the thermoplastic polymer nanofiber fiber Diameter is 600~1000nm rank.
Preferably, the diameter of sub-layer is 50~200nm rank, the thermoplasticity in the thermoplastic polymer nanofiber fiber The diameter of sub-layer is 50~200nm rank in polymer nanofiber, and sub-layer is straight outside the thermoplastic polymer nanofiber fiber Diameter is 600~1000nm rank.
Preferably, the diameter of sub-layer is 600~1000nm rank, the thermoplastic in the thermoplastic polymer nanofiber fiber Property polymer nanofiber in the diameter of sub-layer be 50~200nm rank, the outer sub-layer of the thermoplastic polymer nanofiber fiber Diameter is 600~1000nm rank.
Preferably, the diameter of sub-layer is 50~200nm rank, the thermoplasticity in the thermoplastic polymer nanofiber fiber The diameter of sub-layer is 200~600nm rank in polymer nanofiber, and sub-layer is straight outside the thermoplastic polymer nanofiber fiber Diameter is 600~1000nm rank.
Preferably, the diameter of sub-layer is 600~1000nm rank, the thermoplastic in the thermoplastic polymer nanofiber fiber Property polymer nanofiber in the diameter of sub-layer be 200~600nm rank, the outer sub-layer of the thermoplastic polymer nanofiber fiber Diameter is 600~1000nm rank.
Preferably, the diameter of sub-layer is 200~600nm rank, the thermoplastic in the thermoplastic polymer nanofiber fiber Property polymer nanofiber in the diameter of sub-layer be 200~600nm rank, the outer sub-layer of the thermoplastic polymer nanofiber fiber Diameter is 600~1000nm rank.
Further, the thickness of the thermoplastic polymer nanofiber fiber sub-layer is in 1~100 μm, i.e. thermoplastic polymer The thickness of sub-layer, middle sub-layer and outer sub-layer is at 1~100 μm in nanofiber, each thermoplastic polymer nanofiber fiber sub-layer Aperture structure is determined by the nanofiber diameter of each sub-layer and the thickness of each sub-layer.
Further, the non-woven material be spunlace non-woven cloth, needle punched non-woven fabrics, spun-bonded non-woven fabrics, melt spraying non-woven fabrics, One of heat seal non-woven fabrics, loop bonding non-woven fabrics, pulp air-lay process non-woven fabrics or wet nonwoven fabrics.
Further, it is greater than 1 μm that the non-woven material, which is diameter, and grammes per square metre is in 30~150g/m2, aperture is 5~20 μ Viscose rayon, cotton fiber, polyester fiber, Fypro, polyethylene fibre, polypropylene fibre, the polyurethane fiber, poly- third of m One of alkene nitrile fiber.
Preferably, the non-woven material is polyethylene spinning building.
Preferably, the non-woven material is PET spinning building.
Preferably, the non-woven material is viscose needle non-woven fabrics.
Preferably, the non-woven material is PP melt spraying non-woven fabrics.
Preferably, the non-woven material is PP spun-bonded non-woven fabrics.
Preferably, the non-woven material is PBT spun-bonded non-woven fabrics.
Further, the thermoplastic polymer nanofiber fiber sub-layer be PVA-co-PE or PP or PA or PET or PBT or Nanofiber of the diameter that one of PTT is prepared by melt blending phase separation method in 50~1000nm.
Preferably, the thermoplastic polymer nanofiber fiber sub-layer is PVA-co-PE nanofiber.
Preferably, the thermoplastic polymer nanofiber fiber sub-layer is PA6 nanofiber.
Preferably, the thermoplastic polymer nanofiber fiber sub-layer is PP nanofiber.
In order to preferably realize technical purpose of the invention, the invention also discloses a kind of technical solutions:
A kind of preparation method of the gradient filtration membrane material based on nanofiber, including following preparation step:
1) the thermoplastic polymer nanofiber fiber that diameter is divided into three ranks is prepared using melt blending phase separation method respectively；
2) it disperses the thermoplastic polymer nanofiber fiber for having different-diameter rank in step 1) in ethyl alcohol and goes respectively The in the mixed solvent of ionized water is added crosslinking agent, stirs to get thermoplastic polymer nanofiber fibrous suspension；
3) the thermoplastic polymer nanofiber fibrous suspension of step 2) is pressed and is coated in non-woven material surface, every layer of painting It covers with a thickness of 1~100 μm, it is dry after coating, that is, the heat for having different pore size structure comprising two layers or three layers is prepared The gradient filtration membrane material of thermoplastic polymer nanofiber sub-layer.
Preferably, the diameter of nanofiber is respectively 50~200nm rank, 200~600nm rank and 600 in step 1) ~1000nm rank.
Further, in step 2), by the thermoplastic polymer nanofiber fiber for having different-diameter rank in step 1) point It is not scattered in the in the mixed solvent that mass ratio between ethyl alcohol and deionized water is 1:1 according to the ratio of 5~50g/L, adds matter Amount is 0.1~10% crosslinking agent of thermoplastic polymer nanofiber fiber quality, and stirring, sufficiently reaction obtain solid content (quality Percentage) be 0.5~5.0% thermoplastic polymer nanofiber fibrous suspension, be sealed.
Preferably, solid content 1.0%, 1.2%, 1.5%, 1.8%, 2.2%, 2.5%, 3.0%, 3.3%, 3.5%, Any one in 4.0%.
Further, the crosslinking agent is esters of acrylic acid, organic silicon, polyalcohols, styrene, Alpha-Methyl benzene second One of alkene, acrylonitrile, acrylic acid, methacrylic acid, glyoxal, aziridine.
Further, in the step 3), coating grammes per square metre is 3~20g/m2。
Preferably, coating grammes per square metre is 5g/m2、7g/m2、10g/m2、15g/m2、18g/m2One of for.
The beneficial effects are mainly reflected as follows following several respects:
(1) present invention carries out the coating of multiple pressurized layers using the nanofiber of different-diameter range, prepares with gradient The filter membrane of structure, the sub-layer in the structure with small-bore can ensure efficient filter efficiency, and the coating with large aperture can Ensure the smooth transmission of the liquid mediums such as water, and then that realizes filter efficiency and water flux cooperates with promotion；Realize efficient low-consume mistake Filter.
(2) present invention uses nanofiber gradient layer for filter layer, with spunlace non-woven cloth, needle punched non-woven fabrics, spunbond nonwoven The non-woven materials such as cloth, melt spraying non-woven fabrics, heat seal non-woven fabrics, loop bonding non-woven fabrics, pulp air-lay process non-woven fabrics or wet nonwoven fabrics Material be used as supporting layer, carry out therebetween it is compound, it is sturdy and durable；In addition, the nano fibrous membrane with gradient-structure of the invention Material interacts between multiple sub-layers, mutually protects, and is conducive to the intensity for improving coating, has ensured making for entire membrane material Use the service life.
(3) nanofiber gradient filtration membrane material large specific surface area of the invention, medium transmission performance is excellent, after being conducive to Phase functionalization realizes the efficient preparation of multi-functional micro-filtering flat plate film.
(4) present invention prepares nanofiber using melt blending phase disengagement method green magnanimity, using green coating bulk Multiple coatings are prepared, production process cost of investment is low, and energy conservation and environmental protection is easy to industrialization promotion.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
Using melt spinning phase separation method, PVA-co-PE and acetylbutyrylcellulose (CAB) blending are spun out into 100nm With the PVA-co-PE nanofiber of 450nm, the PVA-co-PE nanofiber of the 100nm and 450nm of 12g are taken respectively.It weighs The polyacrylate emulsion of 0.9g, the ratio for being dissolved in 1L water and ethyl alcohol be in the mixed liquor of 1:1, then by the 100nm and 450nm of 12g PVA-co-PE nanofiber be distributed to the suspension that 12g/L is configured in mixed liquor respectively.It is 50g/m in grammes per square metre2PP spin On sticky cloth, 3g/m is uniformly coated2100nm PVA-co-PE nanofiber, uniformly applied after drying at room temperature, then on its surface Cover 3g/m2450nm PVA-co-PE nanofiber.Drying at room temperature, then be placed in 80 DEG C of insulating box and be heat-treated 2min, i.e., Obtaining gradient filtration layer is 6g/m2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 1:
The membrane material characteristic parameter of 1 embodiment 1 of table
Embodiment 2
Using melt spinning phase separation method, PVA-co-PE and acetylbutyrylcellulose (CAB) blending are spun out into 100nm With the PVA-co-PE nanofiber of 450nm, the PVA-co-PE nanofiber of the 100nm and 450nm of 12g are taken respectively.It weighs The methacrylic acid of 0.8g, the ratio for being dissolved in 1L water and ethyl alcohol be in the mixed liquor of 1:1, then by the 100nm's of 12g and 450nm PVA-co-PE nanofiber is distributed to the suspension that 12g/L is configured in mixed liquor respectively.It is 50g/m in grammes per square metre2PET spin On sticky cloth, 4g/m is uniformly coated2100nm PVA-co-PE nanofiber, uniformly applied after drying at room temperature, then on its surface Cover 3g/m2450nm PVA-co-PE nanofiber.Drying at room temperature, then be placed in 80 DEG C of insulating box and be heat-treated 2min, i.e., Obtaining gradient filtration layer is 6g/m2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 2:
The membrane material characteristic parameter of 2 embodiment 2 of table
Embodiment 3
Using melt spinning phase separation method, PA6 and acetylbutyrylcellulose (CAB) blending are spun out into 100nm and 450nm PA6 nanofiber, take the PA6 nanofiber of the 100nm and 450nm of 12g respectively.The glyoxal for weighing 0.9g is dissolved in 1L water In the mixed liquor for being 1:1 with the ratio of ethyl alcohol, then the PA6 nanofiber of the 100nm of 12g and 450nm is distributed to mixing respectively The suspension of 12g/L is configured in liquid.It is 100g/m in grammes per square metre2Viscose needle non-woven fabrics on, uniformly coat 2g/m2100nm PA6 nanofiber, uniformly coat 4g/m after drying at room temperature, then on its surface2450nm PA6 nanofiber.Room temperature is dry It is dry, then be placed in 80 DEG C of insulating box and be heat-treated 2min to get being 6g/m to gradient filtration layer2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 3:
The membrane material characteristic parameter of 3 embodiment 3 of table
Embodiment 4
Using melt spinning phase separation method, PA6 and acetylbutyrylcellulose (CAB) blending are spun out into 100nm and 800nm PA6 nanofiber, take the PA6 nanofiber of the 100nm and 800nm of 12g respectively.The glyoxal for weighing 0.9g is dissolved in 1L water In the mixed liquor for being 1:1 with the ratio of ethyl alcohol, then the PA6 nanofiber of the 100nm of 12g and 800nm is distributed to mixing respectively The suspension of 12g/L is configured in liquid.It is 100g/m in grammes per square metre2PP melt spraying non-woven fabrics on, uniformly coat 3g/m2100nm PA6 nanofiber uniformly coats 3g/m after drying at room temperature, then on its surface2800nm PA6 nanofiber.Room temperature is dry It is dry, then be placed in 80 DEG C of insulating box and be heat-treated 2min to get being 6g/m to gradient filtration layer2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 4:
The membrane material characteristic parameter of 4 embodiment 4 of table
Embodiment 5
Using melt spinning phase separation method, PVA-co-PE and acetylbutyrylcellulose (CAB) blending are spun out into 100nm With the PVA-co-PE nanofiber of 800nm, the PVA-co-PE nanofiber of the 100nm and 800nm of 12g are taken respectively.It weighs The glyoxal of 0.9g, the ratio for being dissolved in 1L water and ethyl alcohol be in the mixed liquor of 1:1, then by the PVA- of the 100nm of 12g and 800nm Co-PE nanofiber is distributed to the suspension that 12g/L is configured in mixed liquor respectively.It is 100g/m in grammes per square metre2PP be meltblown nothing In woven fabric, 2g/m is uniformly coated2100nm PVA-co-PE nanofiber, uniformly applied after drying at room temperature, then on its surface Cover 5g/m2800nm PVA-co-PE nanofiber.Drying at room temperature, then be placed in 80 DEG C of insulating box and be heat-treated 2min, i.e., Obtaining gradient filtration layer is 7g/m2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 5:
The membrane material characteristic parameter of 5 embodiment 5 of table
Embodiment 6
Using melt spinning phase separation method, PA6 and acetylbutyrylcellulose (CAB) blending are spun out into 450nm and 800nm PA6 nanofiber, take the PA6 nanofiber of the 450nm and 800nm of 12g respectively.The glyoxal for weighing 0.9g is dissolved in 1L water In the mixed liquor for being 1:1 with the ratio of ethyl alcohol, then the PA6 nanofiber of the 450nm of 12g and 800nm is distributed to mixing respectively The suspension of 12g/L is configured in liquid.It is 100g/m in grammes per square metre2Viscose needle non-woven fabrics on, uniformly coat 2g/m2450nm PA6 nanofiber, uniformly coat 4g/m after drying at room temperature, then on its surface2800nm PA6 nanofiber.Room temperature is dry It is dry, then be placed in 80 DEG C of insulating box and be heat-treated 2min to get being 6g/m to gradient filtration layer2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 6:
The membrane material characteristic parameter of 6 embodiment 6 of table
Embodiment 7
Using melt spinning phase separation method, PVA-co-PE and acetylbutyrylcellulose (CAB) blending are spun out into 100nm With the PVA-co-PE nanofiber of 800nm, the PVA-co-PE nanofiber of 100nm, 450nm and the 800nm of 12g is taken respectively. The glyoxal for weighing 0.9g, the ratio for being dissolved in 1L water and ethyl alcohol be in the mixed liquor of 1:1, then by the 100nm of 12g, 450nm and The PVA-co-PE nanofiber of 800nm is distributed to the suspension that 12g/L is configured in mixed liquor respectively.It is 100g/m in grammes per square metre2 PP spun-bonded non-woven fabrics on, uniformly coat 2g/m2100nm PVA-co-PE nanofiber, after drying at room temperature, then at it Surface uniformly coats 2g/m2450nm PVA-co-PE nanofiber, uniformly coated after drying at room temperature, then on its surface 2g/m2800nm PVA-co-PE nanofiber.Drying at room temperature, then be placed in 80 DEG C of insulating box be heat-treated 2min to get It is 6g/m to gradient filtration layer2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 7:
The membrane material characteristic parameter of 7 embodiment 7 of table
Embodiment 8
Using melt spinning phase separation method, PVA-co-PE and acetylbutyrylcellulose (CAB) blending are spun out into 100nm With the PVA-co-PE nanofiber of 800nm, the PVA-co-PE nanofiber of 100nm, 450nm and the 800nm of 12g is taken respectively. The acrylic emulsion for weighing 0.9g, the ratio for being dissolved in 1L water and ethyl alcohol be in the mixed liquor of 1:1, then by the 100nm of 12g, 450nm It is distributed to the suspension that 12g/L is configured in mixed liquor respectively with the PVA-co-PE nanofiber of 800nm.It is 100g/ in grammes per square metre m2PBT spun-bonded non-woven fabrics on, uniformly coat 2g/m2450nm PVA-co-PE nanofiber, after drying at room temperature, then Its surface uniformly coats 2g/m2100nm PVA-co-PE nanofiber, uniformly coated after drying at room temperature, then on its surface 2g/m2800nm PVA-co-PE nanofiber.Drying at room temperature, then be placed in 80 DEG C of insulating box be heat-treated 2min to get It is 6g/m to gradient filtration layer2Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 8:
The membrane material characteristic parameter of 8 embodiment 8 of table
Embodiment 9
Using melt spinning phase separation method, by PVA-co-PE and acetylbutyrylcellulose (CAB) blending spin out 450nm, The PVA-co-PE nanofiber of 800nm takes the PVA-co-PE nanofiber of the 450nm and 800nm of 12g respectively.Weigh 0.9g Glyoxal, the ratio for being dissolved in 1L water and ethyl alcohol is in the mixed liquor of 1:1, then by the PVA-co-PE of the 450nm of 12g and 800nm Nanofiber is distributed to the suspension that 12g/L is configured in mixed liquor respectively.It is 100g/m in grammes per square metre2PP spun-bonded non-woven fabrics On, uniformly coat 2g/m2800nm PVA-co-PE nanofiber, uniformly coat 2g/ after drying at room temperature, then on its surface m2450nm PVA-co-PE nanofiber, uniformly coat 2g/m after drying at room temperature, then on its surface2800nm PVA- Co-PE nanofiber.Drying at room temperature, then be placed in 80 DEG C of insulating box and be heat-treated 2min to get being 6g/m to gradient filtration layer2 Gradient Film filtering material.
Through laboratory testing, which has both the synthesis excellent properties of big flux and filtration efficiency, see the table below 9:
The membrane material characteristic parameter of 9 embodiment 9 of table
By above-described embodiment 1~6 it is found that filter layer of the invention includes the thermoplasticity polymerization apart from supporting layer from the near to the distant Sub-layer and the outer sub-layer of thermoplastic polymer nanofiber fiber in object nanofiber, and sub-layer in the thermoplastic polymer nanofiber fiber Diameter be less than the diameter of the outer sub-layer of thermoplastic polymer nanofiber fiber.The gradient filtration membrane material being prepared is compared with by interior sub-layer The filter membrane material of the identical grammes per square metre of nanofiber composition has higher flux and similar filter efficiency；Compared to by outer sub-layer The filter membrane material of the identical grammes per square metre of nanofiber composition has higher filter efficiency and similar flux；It shows more excellent Different synthetic filter separating property.
By above-described embodiment 7~9 it is found that filter layer of the invention includes the thermoplasticity polymerization apart from supporting layer from the near to the distant Sub-layer in object nanofiber, sub-layer and the outer sub-layer of thermoplastic polymer nanofiber fiber in thermoplastic polymer nanofiber fiber, and institute The diameter for stating sub-layer in thermoplastic polymer nanofiber fiber is less than or equal to the diameter of the outer sub-layer of thermoplastic polymer nanofiber fiber, institute The diameter for stating sub-layer in thermoplastic polymer nanofiber fiber is less than the diameter of the outer sub-layer of thermoplastic polymer nanofiber fiber.It is prepared into To filter membrane material compare the identical grammes per square metre being made of interior sub-layer or outer sub-layer nanofiber filter membrane material have it is higher Flux and similar filter efficiency；Have compared with the filter membrane material for the identical grammes per square metre being made of middle sub-layer nanofiber higher Filter efficiency and similar flux；There is bigger flux and similar filtering effect compared with gradient filtration membrane material in Examples 1 to 6 Rate；Show more excellent synthetic filter separating property.
Above embodiments are only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment Outside, there are also other embodiments by the present invention.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention It is required that protection scope.

Claims (10)

1. a kind of gradient filtration membrane material based on nanofiber, it is characterised in that: it is by supporting layer and is supported on supporting layer table The filter layer in face forms, and the filter layer has the thermoplastic polymer nanofiber fibre of different pore size structure by two layers or three layers respectively It ties up sub-layer to constitute, be combined by way of chemical crosslinking between each thermoplastic polymer nanofiber fiber sub-layer, the thermoplastic poly The fibre diameter for closing object nanofiber sub-layer is divided into three ranks: 50~200nm rank, 200~600nm rank and 600~ 1000nm rank, each thermoplastic polymer nanofiber fiber sub-layer with a thickness of 1~100 μm, the material of the supporting layer is non-knits Producing material material.
2. the gradient filtration membrane material according to claims 1 based on nanofiber, it is characterised in that: the filter layer by The sub-layer structure outside sub-layer in the thermoplastic polymer nanofiber fiber of supporting layer from the near to the distant and thermoplastic polymer nanofiber fiber At the fibre diameter of sub-layer is less than the fibre of the outer sub-layer of thermoplastic polymer nanofiber fiber in the thermoplastic polymer nanofiber fiber Tie up diameter.
3. the gradient filtration membrane material according to claims 1 based on nanofiber, it is characterised in that: the filter layer by Sub-layer and heat in sub-layer in the thermoplastic polymer nanofiber fiber of supporting layer from the near to the distant, thermoplastic polymer nanofiber fiber The outer sub-layer of thermoplastic polymer nanofiber is constituted, and the fibre diameter of sub-layer is less than or waits in the thermoplastic polymer nanofiber fiber The fiber of sub-layer is straight in the fibre diameter of sub-layer outside thermoplastic polymer nanofiber fiber, the thermoplastic polymer nanofiber fiber Diameter is less than the fibre diameter of the outer sub-layer of thermoplastic polymer nanofiber fiber.
4. the gradient filtration membrane material according to claims 1 or 2 or 3 based on nanofiber, it is characterised in that: described non- Weaving material be spunlace non-woven cloth, needle punched non-woven fabrics, spun-bonded non-woven fabrics, melt spraying non-woven fabrics, heat seal non-woven fabrics, loop bonding non-woven fabrics, One of pulp air-lay process non-woven fabrics or wet nonwoven fabrics.
5. the gradient filtration membrane material according to claims 4 based on nanofiber, it is characterised in that: the non-woven material Material is that diameter is greater than 1 μm, and grammes per square metre is in 30~150g/m2, aperture is 5~20 μm of viscose rayon, cotton fiber, polyester fiber, gathers One of nylon, polyethylene fibre, polypropylene fibre, polyurethane fiber, polyacrylonitrile fibre.
6. the gradient filtration membrane material according to claims 1 based on nanofiber, it is characterised in that: the thermoplastic poly Closing object nanofiber sub-layer is that PVA-co-PE or PP or PA or PET or one of PBT or PTT are mutually separated by melt blending Nanofiber of the diameter that method is prepared between 50~1000nm.
7. a kind of preparation method of the gradient filtration membrane material described in claim 1 based on nanofiber, it is characterised in that: including Following preparation step:
1) thermoplastic polymer nanofiber that nanofiber diameter is divided into three ranks is prepared using melt blending phase separation method respectively Fiber；
2) it disperses ethyl alcohol and deionized water respectively by the thermoplastic polymer nanofiber fiber for having different stage in step 1) In the mixed solvent is added crosslinking agent, stirs to get thermoplastic polymer nanofiber fibrous suspension；
3) the thermoplastic polymer nanofiber fibrous suspension of step 2) is coated in non-woven material surface, every layer of coating thickness It is 1~100 μm, it is dry after coating, that is, the thermoplastic poly for having different pore size structure comprising two layers or three layers is prepared Close the gradient filtration membrane material of object nanofiber sub-layer.
8. the preparation method of the gradient filtration membrane material based on nanofiber according to claim 7, it is characterised in that: described In step 3), coating grammes per square metre is 3~20g/m2。
9. the preparation method of the gradient filtration membrane material based on nanofiber according to claim 7, it is characterised in that: described In step 2), the quality of crosslinking agent is the 0.1~10% of thermoplastic polymer nanofiber fiber quality, and the thermoplastic polymer is received The solid content of rice fibrous suspension is 0.5~5.0%.
10. the preparation method of the gradient filtration membrane material according to any one of claim 7~9 based on nanofiber, It is characterized by: the crosslinking agent is esters of acrylic acid, organic silicon, polyalcohols, styrene, α-first in the step 2) One of base styrene, acrylonitrile, acrylic acid, methacrylic acid, glyoxal, aziridine.
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