CN109046040B - Gradient filter membrane material based on nano-fibers and preparation method thereof - Google Patents

Gradient filter membrane material based on nano-fibers and preparation method thereof Download PDF

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CN109046040B
CN109046040B CN201810877291.0A CN201810877291A CN109046040B CN 109046040 B CN109046040 B CN 109046040B CN 201810877291 A CN201810877291 A CN 201810877291A CN 109046040 B CN109046040 B CN 109046040B
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thermoplastic polymer
nanofiber
layer
polymer nanofiber
gradient
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CN109046040A (en
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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 a gradient filtration membrane material of nano fibers and a preparation method thereof, belonging to the technical field of membrane materials and textile materials. The invention adopts non-woven material as a supporting layer, and consists of gradient sub-layers (with gradient filtering function) coated on the surface of the supporting layer, wherein the gradient sub-layers are thermoplastic polymer nanofiber layers consisting of two or three thermoplastic polymer nanofiber sub-layers with different pore structures, and the sub-layers are firmly combined through chemical crosslinking and have gradient layered structures in the direction vertical to the surface of the membrane. Each sublayer adopts thermoplastic nanofibers with different diameter ranges, and the arrangement of the thermoplastic nanofibers with different diameter ranges can be flexibly regulated to prepare the desired gradient filter membrane material with different filter functions. The material has the characteristics of great flexibility and controllability, large water flux and high filtering efficiency. The invention can be widely applied to the field of environmental water filtration and other related filtration due to the unique adjustable gradient structure.

Description

Gradient filter membrane material based on nano-fibers and preparation method thereof
Technical Field
The invention relates to a filtering membrane, belongs to the technical field of membrane materials and textile materials, and particularly relates to a gradient filtering membrane material based on nanofibers and a preparation method thereof.
Background
Along with the development of social economy, the form of water body environmental pollution is more serious, the whole society pays more and more attention to water environment, the requirements on membrane materials for water treatment are higher and higher, and the design of an excellent membrane material structure has important significance for high-efficiency low-consumption water treatment.
The micro-filtration flat membrane material has wide development prospect, the micro-filtration flat membrane on the market is mainly prepared by a phase inversion method, the technology has high investment cost, the structure is not easy to control, and especially the uniformity of wide membrane pores is not easy to control; a large amount of solvent is needed, and the pollution is serious; the thickness of the filter layer is more than 100 microns, the porosity is low, the functionalization is not easy, and the final high-efficiency and low-consumption application is realized.
On the other hand, the fiber-based micro-filtration flat membrane has obvious advantages, such as high porosity and easy functionalization, the pore size of the fiber-based micro-filtration flat membrane mainly depends on the diameter of the fiber, and the development of the fiber-based flat membrane with the pore size of less than 1 micron is restricted by the lack of the macro-preparation technology of the nanofiber. The melt blending phase separation method can effectively improve the yield of the nano fibers, and the filter membrane material with the aperture of 50nm to 1000nm is prepared.
For example, the Chinese invention patent application (application publication No. CN104014196A, application publication date: 2014-09-03) discloses a high-adsorption nanofiber composite filter material and a preparation method thereof, and particularly discloses that the composite filter material consists of a non-woven base material and a nanofiber membrane coated on the surface of the non-woven base material.
Also, for example, the chinese invention patent application (application publication No. CN107137979A, application publication date: 2017-09-08) discloses a microfiber three-dimensional skeleton/polymer nanofiber composite filter material and a preparation method thereof, and specifically discloses a method for preparing polymer nanofibers by a melt blending method, dispersing the polymer nanofibers and a cross-linking agent in a solvent to form a suspension, then soaking a microfiber non-woven fabric skeleton in the suspension, freeze-drying to form a solidified block, and removing the solvent to obtain a non-woven material in which polymer nanofiber aerogel is distributed in a gradient manner between microfiber skeletons. The product of the application has good flexibility and high-efficiency and low-resistance air filtration performance.
However, the pore size structure of the filter material of the above two applications is still not sufficiently optimized, and the flux still needs to be further improved.
For another example, the Chinese invention patent application (application publication No. CN106730150A, application publication date: 2017-05-31) discloses a gradient aperture filter membrane and a preparation method and application thereof, the disclosed gradient aperture filter membrane is made of a high polymer material by electrostatic spinning and comprises a three-layer structure which is tightly attached, the aperture of the two-layer structure at the outer side is 5-10 microns, and the thickness is 0.1-0.4 mm; the aperture of the middle layer structure is 0.5-5 microns, the thickness of the middle layer structure is 0.3-0.6 mm, and the filtering membrane can filter particles of the infusion apparatus; for example, Chinese utility model patent (grant No. CN207056133U, grant No. 2018-03-02) discloses a gradient filtration composite nonwoven fabric material composed of a spunlace nonwoven fabric layer, a spunbond nonwoven fabric layer and an ultrafine meltblown nonwoven fabric layer. The spunlace nonwoven fabric layer is fluffy and soft, the porosity is high, the strength of the spunbonded nonwoven fabric layer is good, the porosity of the meltblown nonwoven fabric layer is minimum, the filtering efficiency is high, the porosity of the three layers of fibers is arranged in a gradient decreasing trend, the spunlace nonwoven fabric layer has excellent filtering performance, the frequency of replacing the filtering material can be reduced, and the cost is reduced. However, the nonwoven fabrics of the above two structures have no flexibility in structural design.
Therefore, it is necessary to design and develop a nanofiber membrane material having an excellent filter structure.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a gradient filtration membrane material based on nanofibers, which has high adsorption capacity and flexible structural design, and a preparation method thereof.
In order to achieve the purpose, the technical solution of the invention is as follows:
a gradient filter membrane material based on nano-fibers comprises a support layer and a filter layer loaded on the surface of the support layer, wherein the filter layer is composed of two or three thermoplastic polymer nano-fiber sub-layers with different pore structures, the thermoplastic polymer nano-fiber sub-layers are combined in a chemical crosslinking mode, and the diameters of the nano-fibers of the thermoplastic polymer nano-fiber sub-layers are divided into three grades: the thickness of each thermoplastic polymer nanofiber sublayer is 1-100 mu m, and the material of the supporting layer is a non-woven material.
Preferably, the thermoplastic polymer nanofiber sublayers are bonded to each other by a chemical crosslinking agent.
Further, the filtering layer is composed of a thermoplastic polymer nanofiber inner sub-layer and a thermoplastic polymer nanofiber outer sub-layer which are far away from the supporting layer, and the nanofiber diameter of the thermoplastic polymer nanofiber inner sub-layer is smaller than that of the thermoplastic polymer nanofiber outer sub-layer.
Preferably, the diameter of the thermoplastic polymer nanofiber inner sub-layer is in the order of 50-200 nm, and the diameter of the thermoplastic polymer nanofiber outer sub-layer is in the order of 200-600 nm.
Preferably, the diameter of the thermoplastic polymer nanofiber inner sub-layer is in the order of 50-200 nm, and the diameter of the thermoplastic polymer nanofiber outer sub-layer is in the order of 600-1000 nm.
Preferably, the diameter of the thermoplastic polymer nanofiber inner sub-layer is in the order of 200-600 nm, and the diameter of the thermoplastic polymer nanofiber outer sub-layer is in the order of 600-1000 nm.
Further, the filtering layer is composed of a thermoplastic polymer nanofiber inner sublayer, a thermoplastic polymer nanofiber middle sublayer and a thermoplastic polymer nanofiber outer sublayer which are far away from the supporting layer, the nanofiber diameter of the thermoplastic polymer nanofiber inner sublayer is smaller than or equal to the nanofiber diameter of the thermoplastic polymer nanofiber outer sublayer, and the nanofiber diameter of the thermoplastic polymer nanofiber middle sublayer is smaller than the nanofiber diameter of the thermoplastic polymer nanofiber outer sublayer.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 50-200 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm.
Preferably, the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is in the order of 200-600 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is in the order of 600-1000 nm.
Further, the thickness of the thermoplastic polymer nanofiber sub-layer is 1-100 μm, namely the thickness of the thermoplastic polymer nanofiber inner sub-layer, the thickness of the thermoplastic polymer nanofiber middle sub-layer and the thickness of the thermoplastic polymer nanofiber outer sub-layer are 1-100 μm, and the pore size structure of each thermoplastic polymer nanofiber sub-layer is determined by the nanofiber diameter of each sub-layer and the thickness of each sub-layer.
Further, the nonwoven material is one of spunlace nonwoven fabric, needle-punched nonwoven fabric, spun-bonded nonwoven fabric, melt-blown nonwoven fabric, heat-sealed nonwoven fabric, stitch-bonded nonwoven fabric, pulp air-laid nonwoven fabric or wet-laid nonwoven fabric.
Further, the non-woven material has a diameter of more than 1 mu m and a gram weight of 30-150 g/m2And the pore diameter is 5-20 mu m, and the fiber is one of viscose fiber, cotton fiber, polyester fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, polyurethane fiber and polyacrylonitrile fiber.
Preferably, the nonwoven material is a polyethylene spunbonded fabric.
Preferably, the nonwoven material is PET spunbonded.
Preferably, the nonwoven material is a viscose needle-punched nonwoven fabric.
Preferably, the nonwoven material is a PP meltblown nonwoven.
Preferably, the nonwoven material is a PP spunbond nonwoven.
Preferably, the nonwoven material is a PBT spunbond nonwoven fabric.
Further, the thermoplastic polymer nanofiber sub-layer is a nanofiber with the diameter of 50-1000 nm, which is prepared from one of PVA-co-PE, PP, PA, PET, PBT and PTT through a melt blending phase separation method.
Preferably, the thermoplastic polymer nanofiber sub-layer is PVA-co-PE nanofibers.
Preferably, the thermoplastic polymer nanofiber sub-layer is PA6 nanofibers.
Preferably, the thermoplastic polymer nanofiber sub-layer is a PP nanofiber.
In order to better realize the technical purpose of the invention, the invention also discloses a technical scheme that:
a preparation method of a gradient filtration membrane material based on nanofibers comprises the following preparation steps:
1) respectively preparing thermoplastic polymer nanofibers with the diameters of three levels by adopting a melt blending phase separation method;
2) respectively dispersing the thermoplastic polymer nanofibers with different diameter grades in the step 1) in a mixed solvent of ethanol and deionized water, adding a cross-linking agent, and stirring to obtain a thermoplastic polymer nanofiber suspension;
3) coating the thermoplastic polymer nanofiber suspension obtained in the step 2) on the surface of a non-woven material, wherein the coating thickness of each layer is 1-100 mu m, and drying after coating to obtain the gradient filter membrane material comprising two or three thermoplastic polymer nanofiber sub-layers with different pore diameter structures.
Preferably, the diameters of the nanofibers in step 1) are respectively 50-200 nm, 200-600 nm and 600-1000 nm.
Further, in the step 2), the thermoplastic polymer nanofibers with different diameter grades in the step 1) are respectively dispersed in a mixed solvent with the mass ratio of 1:1 between ethanol and deionized water according to the proportion of 5-50 g/L, then a cross-linking agent with the mass of 0.1-10% of that of the thermoplastic polymer nanofibers is added, the mixture is stirred and fully reacted to obtain a thermoplastic polymer nanofiber suspension with the solid content (mass percentage) of 0.5-5.0%, and the suspension is sealed and stored.
Preferably, the solid content is any one of 1.0%, 1.2%, 1.5%, 1.8%, 2.2%, 2.5%, 3.0%, 3.3%, 3.5%, and 4.0%.
Further, the cross-linking agent is one of acrylate, silicone, polyol, styrene, alpha-methyl styrene, acrylonitrile, acrylic acid, methacrylic acid, glyoxal and aziridine.
Further, in the step 3)The coating weight is 3-20 g/m2。
Preferably, the coating grammage is 5g/m2、7g/m2、10g/m2、15g/m2、18g/m2Is one of the above.
The beneficial effects of the invention are mainly embodied in the following aspects:
(1) according to the invention, the nano fibers with different diameter ranges are adopted to carry out coating of a plurality of pressing layers, so that the filtering membrane with a gradient structure is prepared, the sub-layer with small pore size in the structure can ensure high-efficiency filtering efficiency, and the coating with large pore size can ensure smooth transmission of liquid media such as water and the like, thereby realizing the cooperative improvement of the filtering efficiency and the water flux; realizing high-efficiency and low-consumption filtration.
(2) The nano-fiber gradient layer is used as a filter layer, and is combined with non-woven materials such as spunlace non-woven fabrics, needle-punched non-woven fabrics, spun-bonded non-woven fabrics, melt-blown non-woven fabrics, heat-seal non-woven fabrics, stitch-bonded non-woven fabrics, pulp air-laid non-woven fabrics or wet non-woven fabrics and the like as a support layer, so that the filter layer is firm and durable; in addition, the nanofiber membrane material with the gradient structure provided by the invention has the advantages that a plurality of sub-layers interact with each other and are mutually protected, the strength of the coating is favorably improved, and the service life of the whole membrane material is ensured.
(3) The nanofiber gradient filtration membrane material disclosed by the invention is large in specific surface area and excellent in medium transmission performance, is beneficial to later-stage functionalization, and realizes efficient preparation of a multifunctional microfiltration flat membrane.
(4) The invention adopts a melt blending phase separation method to prepare the nano-fiber in a green and macroscopic manner, adopts green coating to prepare a plurality of coatings in batch, has low investment cost in the production process, is energy-saving and environment-friendly, and is easy for industrialized popularization.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A melt spinning phase separation method is adopted to blend PVA-co-PE and Cellulose Acetate Butyrate (CAB) to spin PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 450nm, and 12g of PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 450nm are respectively taken. 0.9g of polyacrylic acid emulsion is weighed and dissolved in 1L of mixed solution of water and ethanol in a ratio of 1:1, and 12g of PVA-co-PE nano fibers with the particle size of 100nm and 450nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 50g/m2The PP spunbonded fabric is evenly coated with 3g/m2After drying at room temperature, uniformly coating the PVA-co-PE nano fiber with the particle size of 3g/m on the surface2450nm PVA-co-PE nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 1:
table 1 film material performance parameters for example 1
Figure BDA0001753590580000081
Example 2
A melt spinning phase separation method is adopted to blend PVA-co-PE and Cellulose Acetate Butyrate (CAB) to spin PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 450nm, and 12g of PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 450nm are respectively taken. 0.8g of methacrylic acid is weighed and dissolved in 1L of mixed solution of water and ethanol with the ratio of 1:1, and 12g of PVA-co-PE nano-fibers with the particle size of 100nm and 450nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 50g/m2The PET spunbonded fabric is evenly coated with 4g/m2After drying at room temperature, uniformly coating the PVA-co-PE nano fiber with the particle size of 3g/m on the surface2450nm PVA-co-PE nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 2:
table 2 film material performance parameters for example 2
Figure BDA0001753590580000082
Figure BDA0001753590580000091
Example 3
The PA6 nano-fibers with the wavelength of 100nm and the PA6 nano-fibers with the wavelength of 450nm are respectively obtained by blending PA6 and Cellulose Acetate Butyrate (CAB) by adopting a melt spinning phase separation method, and 12g of the PA6 nano-fibers with the wavelength of 100nm and 450nm are respectively obtained. 0.9g of glyoxal is weighed and dissolved in 1L of mixed solution of water and ethanol in a ratio of 1:1, and 12g of PA6 nano-fibers with the particle size of 100nm and 450nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 100g/m2Uniformly coating the viscose needle-punched non-woven fabric with 2g/m2After drying at room temperature, the 100nm PA6 nano-fiber is evenly coated on the surface of the fiber by 4g/m2450nm PA6 nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 3:
table 3 film material performance parameters for example 3
Figure BDA0001753590580000092
Figure BDA0001753590580000101
Example 4
By melt spinningThe silk phase separation method comprises blending PA6 and Cellulose Acetate Butyrate (CAB) to spin PA6 nanofiber with the length of 100nm and the length of 800nm, and respectively taking 12g of PA6 nanofiber with the length of 100nm and the length of 800 nm. 0.9g of glyoxal is weighed and dissolved in 1L of mixed solution of water and ethanol in a ratio of 1:1, and 12g of PA6 nano-fibers with the particle size of 100nm and 800nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 100g/m2The PP melt-blown non-woven fabric is evenly coated with 3g/m2After drying at room temperature, the 100nm PA6 nano-fiber is evenly coated on the surface of the fiber by 3g/m2800nm PA6 nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 4:
table 4 film material performance parameters for example 4
Figure BDA0001753590580000102
Example 5
A melt spinning phase separation method is adopted to blend PVA-co-PE and Cellulose Acetate Butyrate (CAB) to spin PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 800nm, and 12g of PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 800nm are respectively taken. 0.9g of glyoxal is weighed and dissolved in 1L of mixed solution of water and ethanol in a ratio of 1:1, and 12g of PVA-co-PE nano fibers with the particle size of 100nm and 800nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 100g/m2The PP melt-blown non-woven fabric is evenly coated with 2g/m2After drying at room temperature, uniformly coating 5g/m of PVA-co-PE nano fiber with the particle size of 100nm on the surface2800nm PVA-co-PE nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 7g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 5:
table 5 film material performance parameters for example 5
Figure BDA0001753590580000111
Example 6
The PA6 nano-fibers with the wavelength of 450nm and the PA6 nano-fibers with the wavelength of 800nm are respectively obtained by blending PA6 and Cellulose Acetate Butyrate (CAB) by adopting a melt spinning phase separation method, and 12g of the PA6 nano-fibers with the wavelength of 450nm and the PA6 nano-fibers with the wavelength of 800nm are respectively obtained. 0.9g of glyoxal is weighed and dissolved in 1L of mixed solution of water and ethanol in a ratio of 1:1, and 12g of 450nm and 800nm of PA6 nanofibers are respectively dispersed in the mixed solution to prepare 12g/L of suspension. The gram weight is 100g/m2Uniformly coating the viscose needle-punched non-woven fabric with 2g/m2450nm of PA6 nano-fiber, after drying at room temperature, uniformly coating 4g/m on the surface of the nano-fiber2800nm PA6 nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 6:
table 6 film material performance parameters for example 6
Figure BDA0001753590580000121
Example 7
A melt spinning phase separation method is adopted to blend PVA-co-PE and Cellulose Acetate Butyrate (CAB) to spin PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 800nm, and 12g of PVA-co-PE nano fibers with the particle size of 100nm, 450nm and 800nm are respectively taken. 0.9g of glyoxal is weighed and dissolved in 1L of mixed solution of water and ethanol in a ratio of 1:1, and 12g of PVA-co-PE nano fibers with the particle size of 100nm, 450nm and 800nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 100g/m2Uniformly coating the PP spun-bonded non-woven fabric with 2g/m2After drying at room temperature, uniformly coating 2g/m of PVA-co-PE nano fiber with the particle size of 100nm on the surface2The 450nm PVA-co-PE nano-fiber is evenly coated with 2g/m of the PVA-co-PE nano-fiber on the surface after being dried at room temperature2800nm PVA-co-PE nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 7:
table 7 film material performance parameters for example 7
Figure BDA0001753590580000131
Example 8
A melt spinning phase separation method is adopted to blend PVA-co-PE and Cellulose Acetate Butyrate (CAB) to spin PVA-co-PE nano fibers with the particle size of 100nm and the particle size of 800nm, and 12g of PVA-co-PE nano fibers with the particle size of 100nm, 450nm and 800nm are respectively taken. 0.9g of acrylic emulsion is weighed and dissolved in 1L of mixed solution of water and ethanol with the ratio of 1:1, and then 12g of PVA-co-PE nano-fibers with the particle sizes of 100nm, 450nm and 800nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 100g/m2Evenly coating 2g/m on the PBT spun-bonded non-woven fabric2The 450nm PVA-co-PE nano-fiber is evenly coated with 2g/m of the PVA-co-PE nano-fiber on the surface after being dried at room temperature2After drying at room temperature, uniformly coating 2g/m of PVA-co-PE nano fiber with the particle size of 100nm on the surface2800nm PVA-co-PE nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 8:
table 8 film material performance parameters for example 8
Figure BDA0001753590580000141
Example 9
A melt spinning phase separation method is adopted to blend PVA-co-PE and Cellulose Acetate Butyrate (CAB) to spin PVA-co-PE nano fibers with the wavelength of 450nm and 800nm, and 12g of PVA-co-PE nano fibers with the wavelength of 450nm and 800nm are respectively taken. 0.9g of glyoxal is weighed and dissolved in 1L of mixed solution of water and ethanol in a ratio of 1:1, and 12g of PVA-co-PE nano-fibers with the wavelength of 450nm and 800nm are respectively dispersed in the mixed solution to prepare 12g/L suspension. The gram weight is 100g/m2Uniformly coating the PP spun-bonded non-woven fabric with 2g/m2The PVA-co-PE nano-fiber with the particle size of 800nm is evenly coated with 2g/m on the surface after being dried at room temperature2The 450nm PVA-co-PE nano-fiber is evenly coated with 2g/m of the PVA-co-PE nano-fiber on the surface after being dried at room temperature2800nm PVA-co-PE nanofibers. Drying at room temperature, and heat treating in a constant temperature box at 80 deg.C for 2min to obtain gradient filter layer of 6g/m2The gradient membrane filter material of (1).
Through laboratory detection, the gradient membrane material has comprehensive excellent performances of large flux and high filtration efficiency, and is shown in the following table 9:
table 9 film material performance parameters for example 9
Figure BDA0001753590580000151
As can be seen from examples 1 to 6, the filtration layer of the present invention includes an inner thermoplastic polymer nanofiber sublayer and an outer thermoplastic polymer nanofiber sublayer, which are located from the near side to the far side of the support layer, and the diameter of the inner thermoplastic polymer nanofiber sublayer is smaller than that of the outer thermoplastic polymer nanofiber sublayer. The prepared gradient filter membrane material has higher flux and similar filter efficiency than a filter membrane material with the same gram weight consisting of the inner sublayer nano fibers; higher filtration efficiency and similar flux than a filter membrane material of the same grammage consisting of the outer sublayer nanofibers; shows more excellent comprehensive filtration and separation performance.
In the embodiments 7 to 9, the filter layer of the present invention includes the inner thermoplastic polymer nanofiber sublayer, the middle thermoplastic polymer nanofiber sublayer, and the outer thermoplastic polymer nanofiber sublayer, which are located from the near side to the far side of the support layer, wherein the diameter of the inner thermoplastic polymer nanofiber sublayer is equal to or less than the diameter of the outer thermoplastic polymer nanofiber sublayer, and the diameter of the middle thermoplastic polymer nanofiber sublayer is smaller than the diameter of the outer thermoplastic polymer nanofiber sublayer. The prepared filtering membrane material has higher flux and similar filtering efficiency compared with a filtering membrane material with the same gram weight consisting of the inner sublayer or the outer sublayer nano fibers; the filter membrane material has higher filtration efficiency and similar flux compared with the filter membrane material with the same gram weight consisting of the middle-sublayer nano fibers; compared with the gradient filter membrane materials in the embodiments 1-6, the gradient filter membrane material has larger flux and similar filtering efficiency; shows more excellent comprehensive filtration and separation performance.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.

Claims (8)

1. A gradient filtration membrane material based on nanofibers is characterized in that: the filter layer consists of a thermoplastic polymer nanofiber inner sublayer, a thermoplastic polymer nanofiber middle sublayer and a thermoplastic polymer nanofiber outer sublayer which are far away from the support layer, and the thermoplastic polymer nanofiber sublayers are combined in a chemical crosslinking mode; the diameter of the inner sub-layer of the thermoplastic polymer nanofiber is 200-600 nm, the diameter of the middle sub-layer of the thermoplastic polymer nanofiber is 50-200 nm, and the diameter of the outer sub-layer of the thermoplastic polymer nanofiber is 600-1000 nm; the thickness of each thermoplastic polymer nanofiber sub-layer is 1-100 mu m, and the supporting layer is made of a non-woven material;
the gradient filter membrane material is prepared by respectively dispersing thermoplastic polymer nanofibers of different grades in a mixed solvent of ethanol and deionized water, adding a cross-linking agent, and stirring to obtain a thermoplastic polymer nanofiber suspension; and then sequentially coating the mixture on the surface of the non-woven material, and drying the non-woven material after coating.
2. The nanofiber-based gradient filtration membrane material of claim 1, wherein: the non-woven material is one of spunlace non-woven fabrics, needle-punched non-woven fabrics, spun-bonded non-woven fabrics, melt-blown non-woven fabrics, heat-seal non-woven fabrics, stitch-bonded non-woven fabrics, pulp air-laid non-woven fabrics or wet non-woven fabrics.
3. The nanofiber-based gradient filtration membrane material of claim 2, wherein: the non-woven material is one of viscose fiber, cotton fiber, polyester fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, polyurethane fiber and polyacrylonitrile fiber with the diameter of more than 1 mu m, the gram weight of 30-150 g/m and the pore diameter of 5-20 mu m.
4. The nanofiber-based gradient filtration membrane material of claim 1, wherein: the thermoplastic polymer nanofiber sub-layer is a nanofiber with the diameter of 50-1000 nm, which is prepared from one of PVA-co-PE, PP, PA, PET, PBT and PTT through a melt blending phase separation method.
5. A method of preparing a nanofiber-based gradient filtration membrane material of claim 1, wherein: the preparation method comprises the following preparation steps: 1) Respectively preparing thermoplastic polymer nanofibers with the diameters of the nanofibers divided into three levels by adopting a melt blending phase separation method;
2) respectively dispersing the thermoplastic polymer nanofibers with different grades in the step 1) in a mixed solvent of ethanol and deionized water, adding a cross-linking agent, and stirring to obtain a thermoplastic polymer nanofiber suspension;
3) coating the thermoplastic polymer nanofiber suspension obtained in the step 2) on the surface of a non-woven material, wherein the coating thickness of each layer is 1-100 mu m, and drying after coating to obtain the gradient filter membrane material comprising three thermoplastic polymer nanofiber sublayers with different pore diameter structures.
6. The method of claim 5, wherein the nanofiber-based gradient filtration membrane material is prepared by: in the step 3), the coating gram weight is 3-20 g/m.
7. The method of claim 5, wherein the nanofiber-based gradient filtration membrane material is prepared by: in the step 2), the mass of the cross-linking agent is 0.1-10% of that of the thermoplastic polymer nanofiber, and the solid content of the thermoplastic polymer nanofiber suspension is 0.5-5.0%.
8. The method for preparing a gradient filtration membrane material based on nanofibers according to any one of claims 5 to 7, wherein: in the step 2), the cross-linking agent is one of acrylates, silicones, polyols, styrene, alpha-methylstyrene, acrylonitrile, acrylic acid, methacrylic acid, glyoxal and aziridine.
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