CN115090134B - Membrane material with gradient pore structure and preparation method and application thereof - Google Patents

Membrane material with gradient pore structure and preparation method and application thereof Download PDF

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CN115090134B
CN115090134B CN202210756206.1A CN202210756206A CN115090134B CN 115090134 B CN115090134 B CN 115090134B CN 202210756206 A CN202210756206 A CN 202210756206A CN 115090134 B CN115090134 B CN 115090134B
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membrane
photoinitiator
gradient
film
base film
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CN115090134A (en
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张磊
张一琛
张玉香
李曼晴
李然
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Unicore Membrane Science And Technology Tianjin Co ltd
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Unicore Membrane Science And Technology Tianjin Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/10—Cellulose; Modified cellulose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/78—Graft polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/021—Pore shapes

Abstract

The invention provides a membrane material with a gradient pore structure, and a preparation method and application thereof, and belongs to the technical field of membrane materials. According to the invention, a polymer film with a gradient pore structure is used as a base film, hydrophilic polymers are grafted on the surface and the pores of a film skin layer through an ultraviolet light grafting method, the light intensity is attenuated along the thickness of the base film in the ultraviolet light irradiation process due to the self gradient pore structure of the polymer film, and meanwhile, the partial shielding effect of a photoinitiator on ultraviolet light is utilized to strengthen the gradient fixation of the photoinitiator in the base film, so that the gradient distribution of the hydrophilic polymers in the base film is realized, the prepared film material has the gradient pore structure with the pore size gradually increased from the light side to the backlight side, and the improvement of the film permeation and separation performance can be synchronously realized.

Description

Membrane material with gradient pore structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of membrane materials, in particular to a membrane material with a gradient pore structure, and a preparation method and application thereof.
Background
Currently, biotechnological products derived from cell lines may be at risk of contamination by viruses. The removal of viruses is a key step in reducing the iatrogenic transmission potential of pathogenic viruses, thereby reducing risk, and is critical to the safety of the product. The high price and the disposable property of the virus-removing filter make the virus-removing filter an important link for increasing the cost of biological products.
The membrane filtration technology has definite and stable high removal efficiency on lipid-coated viruses and non-lipid-coated viruses with various particle sizes, has no influence on product quality, and has been increasingly widely applied in the field of biological products in recent years due to the advantages of simple and mild operation, low chemical hazard and the like. However, membrane processing techniques also face a number of challenges in practical applications, such as non-adjustable pore size of membrane materials, and the "trade-off" effect of permeate flux and rejection performance. These disadvantages are more evident in the application to virus removal systems, because the solutions such as cell culture solutions and the like belong to complex biological systems, the components of the systems are complex, the molecular weights of the components are close, a large number of interactions exist, the viscosity of the solutions is high, a large number of components are enriched on the surface of the membrane to form membrane pollution, and membrane pores are easily blocked in the separation process, so that higher requirements are put forward on the membrane separation efficiency.
Disclosure of Invention
The invention aims to provide a membrane material with a gradient pore structure, a preparation method and application thereof, wherein the membrane material has a gradient structure with gradually increased pore diameter from a light side to a backlight side, virus particles can be separated through the gradient pore diameter in the membrane, the membrane blockage is avoided, and the membrane permeation and separation performance are synchronously improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a membrane material with a gradient pore structure, which comprises the following steps:
immersing a polymer base film into a photoinitiator solution for pre-coating, and carrying out first ultraviolet irradiation on the skin layer side of the obtained base film to obtain a polymer base film fixed with a photoinitiator; the polymer base film has an asymmetric gradient pore structure;
compounding the polymer base film fixed with the photoinitiator with a hydrophilic monomer, and carrying out second ultraviolet irradiation to obtain a film material with a gradient pore structure; the pore diameter of the membrane material is increased from the skin surface to the other surface in a gradient way.
Preferably, the material of the polymer-based film includes at least one of polyethersulfone, polysulfone, polymethyl methacrylate, polyacrylonitrile, regenerated cellulose, and ethylene-vinyl alcohol copolymer.
Preferably, the photoinitiator in the photoinitiator solution comprises a benzophenone photoinitiator; the solvent used for the photoinitiator solution comprises at least one of acetone, diethyl ether, methylene dichloride, chloroform and tetrahydrofuran.
Preferably, the benzophenone photoinitiator comprises at least one of 2,2', 4' -tetrahydroxybenzophenone, 2' -dihydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone.
Preferably, the concentration of the photoinitiator solution is 10-80 g/L.
Preferably, the pre-coating time is 2-8 hours.
Preferably, the hydrophilic monomer includes at least one of dimethylaminoethyl methacrylate, maleic anhydride, sodium styrenesulfonate, glycidyl methacrylate, methacryloyloxyethyl phosphorylcholine, and methacrylate sulfobetaine.
The invention provides the membrane material with the gradient pore structure prepared by the preparation method, and the pore diameter of the skin layer surface of the membrane material is 0.001-0.09 mu m; the other side of the membrane material is of a macroporous structure, and the pore diameter is 0.1-5.0 mu m.
The invention provides application of the membrane material with the gradient pore structure in virus removal as an ultrafiltration membrane.
Preferably, the skin surface of the ultrafiltration membrane faces the light side, the macroporous structure surface is a backlight side, the backlight side is used as a water inlet side, and the light side is a water outlet side.
The invention provides a preparation method of a membrane material with a gradient pore structure, which takes a polymer membrane with a gradient pore structure as a base membrane, and grafts hydrophilic polymers on the surface and in holes of a membrane cortex by an ultraviolet light grafting method, because of the self gradient pore structure of the polymer membrane, the light intensity is attenuated along the thickness of the base membrane in the ultraviolet light irradiation process, and meanwhile, the partial shielding effect of a photoinitiator on ultraviolet light is utilized to strengthen the gradient fixation of the photoinitiator in the base membrane, so as to realize the gradient distribution of the hydrophilic polymers in the base membrane, and the prepared membrane material has the gradient pore structure with the pore size gradually increased from the light side to the backlight side. The pore space inside the membrane is obviously higher than the surface of the membrane, and the pore sizes are distributed in a gradient manner, so that the gradual separation of components in the system is facilitated, and the separation efficiency is improved. In addition, the surface and the internal pore diameter of the grafted polymer base membrane are reduced, so that the grafted polymer base membrane has the capacity of separating nano-scale virus; meanwhile, the hydrophilicity of the graft has the function of reducing membrane pollution, and is beneficial to obtaining high permeability.
The hydrophilic graft layer is prepared by an ultraviolet grafting method, and the film surface and the inner pore diameter can be regulated and controlled by regulating the concentration of the photoinitiator and the grafting time, so that the film material with different gradient structures is obtained.
When the membrane material prepared by the invention is used for virus removal filtration, a backlight side (macroporous structure) is adopted as a water inlet side, a light side (cortex surface) is adopted as a water outlet side, raw material liquid enters from the macroporous side, and gradient holes are beneficial to step-by-step separation of components with molecular weights close to each other, so that the separation efficiency is improved, virus particles in the solution can be step-by-step separated through the gradient pore diameter in the membrane, the membrane blockage is avoided, and the improvement of the membrane permeation and separation performance is synchronously realized.
The invention adopts ultraviolet grafting technology to modify the hydrophilic polymer of the base film, and has the advantages of low energy consumption, short reaction time, mild condition, easy industrial amplification and the like.
Drawings
FIG. 1 is a cross-sectional field emission electron micrograph of the film material prepared in example 1;
FIG. 2 is a photograph of a light-side field emission electron microscope of the film material prepared in example 1;
FIG. 3 is a photograph of a film material prepared in example 1 as a back-lit side-view field emission electron micrograph.
Detailed Description
The invention provides a preparation method of a membrane material with a gradient pore structure, which comprises the following steps:
immersing a polymer base film into a photoinitiator solution for pre-coating, and carrying out first ultraviolet irradiation on the skin layer side of the obtained base film to obtain a polymer base film fixed with a photoinitiator; the polymer base film has an asymmetric gradient pore structure;
compounding the polymer base film fixed with the photoinitiator with a hydrophilic monomer, and carrying out second ultraviolet irradiation to obtain a film material with a gradient pore structure; the pore diameter of the membrane material is increased from the skin surface to the other surface in a gradient way.
In the present invention, the preparation materials are commercially available as known to those skilled in the art unless otherwise specified.
The method comprises the steps of immersing a polymer base film into a photoinitiator solution for pre-coating, and carrying out first ultraviolet irradiation on the skin layer side of the obtained base film to obtain the polymer base film fixed with the photoinitiator. In the present invention, the preparation material of the polymer-based film preferably includes at least one of polyethersulfone, polysulfone, polymethyl methacrylate, polyacrylonitrile, regenerated cellulose, and ethylene-vinyl alcohol copolymer; when the preparation materials of the polymer base film are more than two of the above, the proportion of different materials is not particularly limited, and any proportion can be used.
In the present invention, the polymer base film is preferably prepared by an immersion precipitation phase inversion method; the preparation method of the polymer base film preferably comprises the following steps: dispersing the polymer in an organic solvent, and performing ultrasonic defoaming at room temperature to obtain a casting solution; and scraping the casting film liquid to prepare a film, solidifying and forming, and sequentially soaking and drying to obtain the polymer base film. In the present invention, the organic solvent is preferably dimethyl sulfoxide, dimethylformamide or dimethylacetamide; the content of the polymer in the casting solution is preferably 12 to 25wt.%. The dispersing process is not particularly limited, and the dispersing process is ensured to be fully dissolved according to the process known in the art; the time of ultrasonic defoaming is preferably 2-3 hours; the curing and forming temperature is preferably 20-30 ℃, more preferably 25 ℃; the soaking is preferably performed in purified water, and the soaking time is preferably 2 days; the drying mode is preferably freeze drying; the specific conditions for the freeze-drying are not particularly limited in the present invention, and may be carried out according to a process well known in the art.
In the present invention, the process of scraping the film is preferably performed on a glass plate; the form and thickness of the polymer-based film are not particularly limited in the present invention, and film forms well known in the art and film thickness may be adjusted according to actual demands, and in the examples of the present invention, flat plate films having thicknesses of 0.1mm, 0.15mm and 0.2mm are particularly used.
In the present invention, the polymer-based film has an asymmetric gradient pore structure; preferably a monocortical asymmetric gradient pore structure, the pore diameter of the membrane increases from the surface of the cortex to the other surface in a gradient way, and the gradient pore diameter of the surface of the cortex is 0.001-0.45 mu m, preferably 0.01-0.09 mu m; the other surface is a macroporous structure, and the gradient pore diameter is 0.1-5.0 mu m, preferably 0.5-4 mu m. In the invention, the skin surface of the polymer base film is a separating layer, and the other surface of the polymer base film is a porous loose structure, and the ultraviolet light which is incident into the interior of the polymer base film and initiates the reaction is reduced along with the increase of the incidence depth in the ultraviolet grafting modification process, so that the gradient structure film material is obtained.
In the invention, the polymer base membrane is prepared by a phase inversion method, the pore diameter of the membrane surface is slightly larger than that of the membrane, and the virus separation performance is not enough to be obtained.
In the present invention, the photoinitiator in the photoinitiator solution preferably comprises a benzophenone-type photoinitiator; the diphenyl ketone photoinitiator preferably comprises at least one of 2,2', 4' -tetrahydroxydiphenyl ketone, 2' -dihydroxyl-4-methoxyl diphenyl ketone, 2, 4-dihydroxyl diphenyl ketone, 2' -dihydroxyl-4, 4' -dimethoxyl diphenyl ketone, 2-hydroxy-4-methoxyl diphenyl ketone and 2-hydroxy-4-n-octoxydiphenyl ketone; when the number of the photoinitiators is two or more, the ratio of the different types of photoinitiators is not particularly limited, and any ratio can be used.
In the present invention, the solvent used for the photoinitiator solution preferably includes at least one of acetone, diethyl ether, methylene chloride, chloroform and tetrahydrofuran; when the solvent used in the photoinitiator solution is more than two of the above solvents, the invention has no special limitation on the ratio of different solvents, and any ratio can be used; the concentration of the photoinitiator solution is preferably 10 to 80g/L, more preferably 20 to 60g/L, and even more preferably 40g/L. The invention controls the concentration of the photoinitiator solution in the range, can realize the fixation of the photoinitiator on the surface and the inside of the film and realize a gradient structure, avoids lower grafting rate caused by the concentration of the photoinitiator lower than 10g/L, reduces the ultraviolet shielding effect of the film on the near light side, and is difficult to obtain an obvious gradient structure in the film; meanwhile, when the concentration of the photoinitiator is higher than 80g/L, the grafting reaction tends to occur only on the surface of the membrane, and the grafting amount in the membrane is reduced.
The process of immersing the polymer-based film in the photoinitiator solution is not particularly limited in the present invention, and may be completely immersed according to a process well known in the art. The invention has no special limitation on the dosage of the photoinitiator solution, and ensures that the polymer base film is fully immersed.
In the present invention, the time for the pre-coating is preferably 2 to 8 hours, more preferably 4 to 6 hours; the pre-coating is preferably performed under shaking conditions, the specific conditions of the shaking are not particularly limited in the present invention, and the shaking ensures that the photoinitiator solution is sufficiently immersed in the polymer base film according to a process well known in the art.
After the pre-coating is completed, the obtained polymer base film is taken out and subjected to first ultraviolet light irradiation.
In the present invention, the time of the first ultraviolet light irradiation is preferably 10 to 20 minutes, more preferably 15 to 18 minutes; the invention realizes the fixation of the photoinitiator on the surface and the inside of the base film by carrying out first ultraviolet irradiation on the skin layer side of the base film.
After the polymer base film fixed with the photoinitiator is obtained, the polymer base film fixed with the photoinitiator is compounded with the hydrophilic monomer, and the second ultraviolet light irradiation is carried out, so that the film material with the gradient pore structure is obtained. In the present invention, the hydrophilic monomer preferably includes at least one of dimethylaminoethyl methacrylate, maleic anhydride, sodium styrenesulfonate, glycidyl methacrylate, oxyethyl phosphorylcholine methacrylate, and sulfobetaine methacrylate; when the hydrophilic monomers are two or more of the above, the invention has no special limitation on the ratio of different types of hydrophilic monomers, and any ratio can be used. The amount of the hydrophilic monomer is not particularly limited, and the polymer base film with the photoinitiator fixed therein can be completely infiltrated.
In the present invention, the compounding means is preferably coating, more preferably coating a hydrophilic monomer on the skin surface of the polymer base film to which the photoinitiator is immobilized.
In the present invention, the time of the second ultraviolet light irradiation is preferably 10 to 20 minutes, more preferably 12 to 15 minutes. In the second ultraviolet irradiation process, the polymer base film has a shading effect on ultraviolet light, and simultaneously combines the light absorption of the photoinitiator to attenuate the ultraviolet light along the film thickness direction so as to form the gradient fixation of the hydrophilic polymer on the polymer base film.
Under the ultraviolet irradiation process, the initiator pre-coated on the polymer base film deprives hydrogen on the film to form semipinacol free radical and film surface free radical, and the semipinacol free radical and the film surface free radical are combined to form surface initiator; after hydrophilic monomer is added, the film surface photoinitiator is decomposed into semipinacol free radical and film surface free radical by ultraviolet excitation and initiates graft polymerization of the monomer on the film surface to form the film material with hydrophilic graft layer.
According to the invention, a polymer porous membrane obtained by a polymer immersed precipitation phase inversion method is taken as a base membrane, ultraviolet light irradiation is carried out on the skin layer side of the base membrane, the gradient fixation of the photoinitiator in the base membrane is realized by utilizing the attenuation of ultraviolet light in the polymer base membrane and the optical characteristics of the photoinitiator, then hydrophilic monomers are coated on the skin layer side of the base membrane fixed with the photoinitiator, and the grafting of the water-based polymer on the membrane skin layer side and Kong Naqin is realized by an ultraviolet light grafting technology, so that the membrane material with a gradient pore structure is obtained.
The invention provides the membrane material with the gradient pore structure prepared by the preparation method, wherein the pore diameter of the skin layer surface of the membrane material is 0.001-0.09 mu m, preferably 0.01-0.05 mu m; the other side of the membrane material is of a macroporous structure, and the pore diameter is 0.1-5.0 mu m, preferably 0.5-3 mu m; the membrane pore size decreases stepwise from the light side to the backlight side.
The invention provides application of the membrane material with the gradient pore structure in virus removal as an ultrafiltration membrane. In the invention, the skin surface of the ultrafiltration membrane is a light-facing side, the macroporous structure surface is a backlight side, and the backlight side is used as a water inlet side and the light-facing side is a water outlet side.
In the present invention, the ultrafiltration membrane is preferably a flat plate membrane or a hollow fiber membrane; the cortical face of the membrane material with the gradient pore structure is a separating layer.
In the invention, when the membrane material with the gradient pore structure is adopted for virus removal and filtration, the back light side of the membrane is adopted as the water inlet side, the light side is adopted as the water outlet side, the space of pore channels in the membrane is obviously higher than the surface of the membrane, the pore channel sizes are in gradient distribution, the gradual separation of components in a system is facilitated, the separation efficiency is improved, virus particles in the solution are separated through the gradient pore diameter in the membrane, the membrane blockage is avoided, and the simultaneous improvement of the membrane permeation and separation performance can be realized. The existing virus-removing ultrafiltration membrane adopts a membrane pore side to treat feed liquid, a large amount of components in the system are enriched on the surface of the membrane, interaction among the components is enhanced, a pollution layer is extremely easy to form, and the membrane separation performance is rapidly reduced.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Dissolving an ethylene-vinyl alcohol copolymer in dimethyl sulfoxide, and performing ultrasonic deaeration for 3 hours at normal temperature to prepare a casting solution with the ethylene-vinyl alcohol copolymer content of 15 wt.%; scraping the casting solution on a glass plate to form a flat film with the thickness of 0.15mm, solidifying and forming the flat film at 25 ℃, soaking the flat film in purified water for 2 days, and freeze-drying the flat film to obtain a polymer base film-EVAL film;
immersing the EVAL membrane into an acetone solution with the concentration of 2,2', 4' -tetrahydroxybenzophenone of 60g/L, irradiating for 20min under ultraviolet light by taking the membrane cortex side as the light side after oscillating for 2h, coating methacrylic acid monomer on the surface of the membrane, and irradiating for 20min under ultraviolet light to obtain the MEVAL membrane with a gradient pore structure, wherein the pore diameter of the membrane cortex side is 0.01 mu m, and the pore diameter of the macroporous structure side is 0.5-3.0 mu m.
Example 2
Dissolving polyethersulfone in dimethylformamide, and carrying out ultrasonic defoaming for 2 hours at normal temperature to prepare a casting solution with the polyethersulfone content of 14 wt%; scraping the casting solution on a glass plate to form a flat membrane with the thickness of 0.10mm, solidifying and forming the flat membrane at 20 ℃, soaking the flat membrane in purified water for 2 days, and freeze-drying to obtain a polymer base membrane-PES membrane;
immersing the PES film serving as a base film in an diethyl ether solution with the concentration of 2,2' -dihydroxy-4-methoxybenzophenone of 40g/L, oscillating for 4 hours, irradiating for 15 minutes under ultraviolet light by taking the film cortex side as the light side, uniformly coating an acrylic acid monomer on the surface of the film, and irradiating for 10 minutes under ultraviolet light to obtain the MPES film with a gradient pore structure, wherein the pore diameter of the film cortex side is 0.015 mu m, and the pore diameter of the macroporous structure side is 0.2-2.0 mu m.
Example 3
Dissolving polyacrylonitrile in dimethylformamide, and carrying out ultrasonic defoaming for 2 hours at normal temperature to prepare a casting solution with the polyacrylonitrile content of 12 wt.%; scraping the casting solution on a glass plate to form a flat membrane with the thickness of 0.20mm, solidifying and forming the flat membrane at 25 ℃, soaking the flat membrane in purified water for 2 days, and freeze-drying the flat membrane to obtain a polyacrylonitrile membrane;
immersing the polyacrylonitrile membrane into tetrahydrofuran solution with the concentration of 2,2 '-dihydroxyl-4, 4' -dimethoxybenzophenone of 20g/L, oscillating for 6 hours, taking the membrane cortex side as the light side, irradiating for 18 minutes under ultraviolet light, uniformly coating a vinyl pyrrolidone monomer on the surface of the membrane, and irradiating for 12 minutes under ultraviolet light to obtain the polyacrylonitrile MPAN membrane with a gradient pore structure, wherein the pore diameter of the membrane cortex side is 0.03 mu m, and the pore diameter of the macroporous structure side is 1.0-3.0 mu m.
Example 4
Dissolving Polysulfone (PSU) in dimethylacetamide, and performing ultrasonic defoaming for 3 hours at normal temperature to prepare a casting solution with polysulfone content of 12 wt.%; scraping the casting solution on a glass plate to form a flat film with the thickness of 0.15mm, solidifying and forming the flat film at the temperature of 30 ℃, soaking the flat film in purified water for 2 days, and freeze-drying to obtain a polymer base film-PSU film;
immersing the PSU membrane into an acetone solution with the concentration of 2-hydroxy-4-methoxybenzophenone of 10g/L, oscillating for 8 hours, irradiating for 10 minutes under ultraviolet light by taking the membrane cortex side as the light side, uniformly coating the ethyl methacrylate triethylammonium monomer on the surface of the membrane, and irradiating for 20 minutes under ultraviolet light to obtain the MPSS membrane with a gradient pore structure, wherein the pore diameter of the membrane cortex side is 0.05 mu m, and the pore diameter of the macroporous structure side is 1.5-3.0 mu m.
Characterization and performance testing
1) The film material prepared in example 1 was observed by electron microscopy using a Japanese Hitachi S-4800 type field emission scanning electron microscope (FETS) with an acceleration voltage of 10kV, and subjected to metal spraying treatment to improve the conductivity before sample detection, and the obtained results are shown in FIGS. 1-3; the cross-sectional structure of the film gradually increases from the near light-to-light portion to the backlight side aperture (fig. 1), and the light-to-light side aperture is small (fig. 2), about 10nm; the backlight side aperture is large (fig. 3), about 2.0 μm, and the aperture of the film increases stepwise from the light side to the backlight side.
2) The membrane materials prepared in examples 1 to 4 were subjected to permeation and separation performance tests using a cross-flow membrane filtration device:
according to a conventional cross-flow membrane filtration method, the membrane materials prepared in examples 1 to 4 are subjected to separation performance test based on the entrapment rate of colloidal gold particle solutions with different sizes, absorbance of the colloidal gold 519nm of the solution before and after filtration is measured by an ultraviolet-visible light spectrophotometer, the entrapment rate is calculated, and the entrapment rate is calculated as shown in the following formula: the retention% = (1-absorbance of permeate/absorbance of crude colloidal gold) ×100%, and the results are shown in table 1.
TABLE 1 separation Performance data for the Membrane materials prepared in examples 1 to 4
As can be seen from Table 1, the MEVAL film prepared in example 1 has a 20nm colloid Jin Jieliu ratio of 99.99% as measured on the backlight side of the film as water inlet; the MPES film prepared in example 2, with the backlight side of the film as the water inlet side, had a Jin Jieliu rate of 99.99% for 20nm colloid and a Jin Jieliu rate of 40% for 10nm colloid; the MPAN film prepared in example 3, measured on the backlight side of the film as water inlet, had a Jin Jieliu rate of 95% for 30nm colloid and a Jin Jieliu rate of 90% for 20nm colloid; the MPSA film prepared in example 4, measured on the backlight side of the film as water inlet, had a rate of 98% for 50nm colloid Jin Jieliu and 35% for 35nm colloid Jin Jieliu.
3) The membrane materials prepared in examples 1 to 4 were subjected to permeability test by using a cross-flow membrane filtration device, and the results show that the membrane pure water flux of the MEVAL membrane prepared in example 1 is 150L/m by taking the back light side of the membrane as the water inlet 2 h, performing H; MPES film prepared in example 2 with a membrane pure water flux of 800L/m 2 h, performing H; MPAN membrane prepared in example 3 with membrane pure water flux of 200L/m 2 h, performing H; MPSS U membrane prepared in example 4 has pure water flux of 550L/m 2 h。
4) The model viral load of the membrane materials prepared in examples 1 to 4 is detected by adopting a real-time fluorescent probe RT-PCR method described in national standard GB/T22287-2008, and the viral removal rate is calculated, and is shown in the following formula: the% removal = (1-permeate viral load/stock model viral load) ×100% and the results are shown in table 2.
TABLE 2 Virus removal data for Membrane materials prepared in examples 1-4
As can be seen from Table 2, the membrane material prepared by the present invention is capable of effectively removing viruses.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The preparation method of the membrane material with the gradient pore structure is characterized by comprising the following steps of:
immersing a polymer base film into a photoinitiator solution for pre-coating, and carrying out first ultraviolet irradiation on the skin layer side of the obtained base film to obtain a polymer base film fixed with a photoinitiator; the polymer base film has an asymmetric gradient pore structure;
compounding the polymer base film fixed with the photoinitiator with a hydrophilic monomer, and carrying out second ultraviolet irradiation to obtain a film material with a gradient pore structure; the pore diameter of the membrane material is increased from the skin surface to the other surface in a gradient manner; the hydrophilic monomer is at least one of sodium styrene sulfonate, methacryloxyethyl phosphorylcholine and methacrylate sulfobetaine;
the polymer-based membrane has an asymmetric gradient pore structure with a single skin layer, the pore diameter of the membrane is increased in a gradient way from the skin layer surface to the other surface, and the pore diameter of the skin layer surface is 0.001-0.09 mu m; the skin surface of the polymer base film is a separating layer, and the other surface of the polymer base film is a porous loose structure;
the concentration of the photoinitiator solution was 10g/L.
2. The method of claim 1, wherein the polymer-based film material comprises at least one of polyethersulfone, polysulfone, polymethyl methacrylate, polyacrylonitrile, regenerated cellulose, and ethylene-vinyl alcohol copolymer.
3. The method of claim 1, wherein the photoinitiator in the photoinitiator solution comprises a benzophenone-type photoinitiator; the solvent used for the photoinitiator solution comprises at least one of acetone, diethyl ether, methylene dichloride, chloroform and tetrahydrofuran.
4. The method of preparing according to claim 3, wherein the benzophenone photoinitiator comprises at least one of 2,2', 4' -tetrahydroxybenzophenone, 2' -dihydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone.
5. The method according to claim 1, wherein the pre-coating time is 2 to 8 hours.
6. The membrane material with a gradient pore structure prepared by the preparation method of any one of claims 1 to 5, which is characterized in that the pore diameter of the skin surface of the membrane material is 0.001 to 0.09 μm; the other side of the membrane material is of a macroporous structure, and the pore diameter is 0.1-5.0 mu m.
7. The use of the membrane material with a gradient pore structure as claimed in claim 6 as an ultrafiltration membrane in virus removal, wherein the skin layer surface of the ultrafiltration membrane is a light-facing side, the macroporous structure surface is a backlight side, the backlight side is used as a water inlet side, and the light-facing side is used as a water outlet side.
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