CN109224884B - Polymer film and preparation method and application thereof - Google Patents

Polymer film and preparation method and application thereof Download PDF

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CN109224884B
CN109224884B CN201811203740.XA CN201811203740A CN109224884B CN 109224884 B CN109224884 B CN 109224884B CN 201811203740 A CN201811203740 A CN 201811203740A CN 109224884 B CN109224884 B CN 109224884B
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polyvinylidene fluoride
film
dimethyl
substrate
aminopropanesulfonic acid
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CN109224884A (en
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李义涛
张魁
程堂剑
张凌飞
肖文武
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Dongguan HEC Tech R&D 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • 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
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/14—Membrane materials having negatively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

Abstract

The invention provides a temperature-sensitive easy-to-clean polymer film, which takes a polyvinylidene fluoride film as a basic film, and one surface of the polyvinylidene fluoride film is grafted with a temperature-sensitive material poly (N, N-dimethyl (acrylamide propyl) amino propanesulfonic acid); the preparation method of the film comprises the steps of carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid under the initiation of an initiator, grafting poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid on one surface of the polyvinylidene fluoride film, and then removing the substrate to obtain the film. The film has high backwashing efficiency and repeated utilization rate, can form a firm and stable hydration layer with water molecules, and can reduce the pollution of protein to the surface of the film.

Description

Polymer film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials and films, relates to a polymer film and a preparation method and application thereof, and particularly relates to a temperature-sensitive easy-to-clean polymer film and a preparation method and application thereof.
Background
The membrane separation technology is widely applied to food, medicine, biology and water treatment because of having the functions of separation, purification, concentration, refining and the like, and has the advantages of simple operation, safe working environment, energy consumption saving and the like compared with the traditional process. The separation process belongs to a physical process and does not involve any chemical change, and under the action of a driving force, a penetrating substance is firstly dissolved and enters the upstream side of the membrane, and due to the selectivity of the membrane, small molecules are diffused to the downstream side of the membrane, and large molecules are intercepted, so that the separation process is realized, and the membrane separation technology is considered to be one of the most promising separation technologies.
As a common separation membrane material, polyvinylidene fluoride has excellent mechanical properties, thermal stability and chemical stability, is not easy to be corroded by acid, alkali, strong oxidants and halogens, and has the characteristics of good tensile strength, ultraviolet resistance, weather aging resistance and the like. The hydrophobic material has strong hydrophobicity, so the hydrophobic material is an ideal material for non-aqueous system separation processes such as gas purification, membrane distillation, organic solvent refining and the like, but has a serious problem of membrane pollution when being applied to water phase separation such as biochemistry, food and water purification, dirt and impurities are easily adsorbed in the use process, and the service life is shortened. Taking seawater desalination as an example, various marine microorganisms are easy to adhere to the membrane surface, and further grow, reproduce and secrete proteins and polysaccharides, finally form a stubborn biological membrane on the membrane surface, so that the membrane flux is reduced sharply, and even though pretreatment measures can be adopted for relieving, the membrane is difficult to radically cure.
In order to solve the problems, polyvinylidene fluoride membranes need to be modified, and at present, the modification method of the polyvinylidene fluoride membranes can be mainly divided into surface modification and bulk modification. The surface modification is carried out on the surface of the prepared membrane, and the method has the advantages that the bulk property and the structure of the membrane are not changed, and the surface of the membrane is provided with a hydrophilic layer only by the methods of surface coating, surface grafting and the like, so that the hydrophilicity and the anti-pollution performance of the surface of the membrane are improved. The bulk modification is to introduce a substance with hydrophilic property into the material by methods of chemical grafting, physical blending and the like, so as to improve the hydrophobic property of the material.
CN108310984A discloses a pollution-resistant hydrophilic polyvinylidene fluoride modified membrane and a preparation method thereof, wherein the modified membrane is a composite membrane consisting of polyvinylidene fluoride and graft copolymer; the thickness is 50-250 μm, the contact angle is 53-71 °, and the pure water flux is 52-328L/m2H, the retention rate of 0.5g/L bovine serum albumin is 91-98.7%, the retention molecular weight of glucan is 5000-; the graft copolymer is polyvinylidene fluoride-g-polydimethyl amino propyl methacrylamide or polyvinylidene fluoride-g-polydimethyl amino propyl acrylamide. The preparation method comprises the following specific steps: performing alkali treatment on PVDF powder; preparation of graft copolymer: carrying out grafting reaction on the powder subjected to alkali treatment and an acrylamide monomer to synthesize a graft copolymer; preparing a membrane casting solution; modified PVDF membranes were prepared by a non-solvent induced phase separation method. The polyvinylidene fluoride modified membrane can improve the hydrophilicity, greatly increase the flux and increase the anti-pollution performanceSo as to prolong the service life of the cable.
CN102728241B discloses an anti-pollution separation membrane and a preparation method thereof, firstly, a random copolymer with a zwitterionic structure of MMA, DMC and AMPS is synthesized through free radical polymerization, the copolymer and a pore-forming agent polyethylene glycol are added into polyvinylidene fluoride, N-dimethylformamide is used as a solvent, water is used as a coagulant, and the anti-pollution separation membrane is prepared through a phase inversion method. Because the copolymer structure simultaneously contains the quaternary amine group with positive electricity and the sulfonic group with negative electricity, the binding capacity to water molecules is stronger than that of the traditional polyethylene glycol and the derivative thereof, and the formed hydration layer is more stable, so that the prepared novel polyvinylidene fluoride membrane has lasting anti-pollution performance.
CN1279093C discloses a preparation method of a temperature-sensitive polyvinylidene fluoride hollow fiber intelligent membrane and a product thereof, wherein the temperature-sensitive polyvinylidene fluoride hollow fiber intelligent membrane is obtained by chemically grafting and copolymerizing N-isopropyl acrylamide on the surface of a polyvinylidene fluoride membrane, and the intelligent membrane has the advantages of large flux, low filtration pressure, easy cleaning and the like.
At present, no report of modifying polyvinylidene fluoride membrane by poly-N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is available, so that it is very meaningful to develop a poly-N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid modified polyvinylidene fluoride membrane which is easy to clean.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polymer film and a preparation method and application thereof, and particularly relates to a temperature-sensitive easy-to-clean polymer film and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a polymer film, wherein the polymer film is a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted on one side of the polyvinylidene fluoride film.
The poly-N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid is a sulfobetaine polymer, has higher critical solution temperature when the molecular weight is higher, and has the critical temperature of more than 30 ℃ and higher than normal temperature when the molecular weight of the poly-N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid exceeds 6 ten thousand. The polymer is grafted on one surface of the polyvinylidene fluoride membrane, at normal temperature, the polymer is in a colloidal particle structure and is attached to the periphery and in the membrane hole, and after the membrane is used for a period of time at normal temperature, the membrane hole can be blocked by pollutants with similar diameters. When hot water with the temperature higher than the critical solution temperature is used for backwashing the non-grafted surface of the membrane, the polymer is changed into a coil-shaped structure from a colloidal particle shape, and pollutants can be easily backwashed from membrane holes, so that the backwashing efficiency and the repeated utilization rate of the membrane are greatly improved, and the secondary damage to the membrane is greatly reduced.
In addition, the poly-N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid contains positive charges and negative charges simultaneously, can form a hydration layer with water molecules, is firmer and more stable compared with a hydration layer formed by a hydrophilic material by utilizing hydrogen bonding, and can reduce the adsorption of protein on the surface of the membrane and reduce the pollution of the membrane.
In the invention, the molecular structure of the polyvinylidene fluoride membrane grafted with poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid is shown as formula I:
Figure BDA0001830679280000041
wherein n is 9000-14000 (e.g., 9000, 9500, 9800, 10000, 11000, 12000, 13000 or 14000), and m is 200-2200 (e.g., 200, 400, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000 or 2200).
In the invention, polyvinylidene fluoride with proper molecular weight is selected, so that the obtained polymer film has excellent mechanical property, and the polymer film has proper phase transition temperature by controlling the molecular weight of poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid chain segment.
In the present invention, the grafting ratio of poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid on one side of the polyvinylidene fluoride membrane is 3-15%, for example 3%, 5%, 7%, 9%, 11%, 13% or 15%.
The polyvinylidene fluoride membrane has a pore diameter of 10-100nm, such as 10nm, 15nm, 20nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, or 100 nm.
In another aspect, the present invention provides a method for preparing a polymer film as described above, comprising the steps of:
under the initiation of an initiator, carrying out polymerization reaction on the polyvinylidene fluoride base film coated on the substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid, grafting the poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid on one surface of the polyvinylidene fluoride film, and then removing the substrate to obtain the polymer film.
In the invention, the preparation method of the polyvinylidene fluoride base film coated on the substrate comprises the following steps:
and coating the casting solution containing the polyvinylidene fluoride on the substrate, then carrying out phase separation and cleaning to obtain the polyvinylidene fluoride base film coated on the substrate.
Preferably, the casting solution further comprises a pore-forming agent, a hydrophilic modifier and a silane coupling agent.
Preferably, the porogen is at least one of PVP K30, PVP K64, or PVP K90.
Preferably, the hydrophilic modifier is PEG400 or PEG 600.
Preferably, the silane coupling agent is KH550 or KH 560.
Preferably, the solvent in the casting solution is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Preferably, the weight percentage of the polyvinylidene fluoride membrane in the casting solution is 10-20%, such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or the like.
Preferably, the weight percentage of the pore former in the casting solution is 5-15%, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or the like.
Preferably, the weight percentage of the hydrophilic modifier in the casting solution is 5-10%, such as 5%, 6%, 7%, 8%, 9%, 10%, or the like.
Preferably, the weight percentage of the silane coupling agent in the casting solution is 1-5%, such as 1%, 2%, 3%, 4%, 5%, or the like.
Preferably, the solvent is present in the casting solution in an amount of 60-70% by weight, such as 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%, etc.
Preferably, the substrate is a glass substrate or a PET substrate.
Preferably, the phase separation is performed in a coagulation bath at a concentration of 20-40% (e.g., 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, or 40%, etc.).
Preferably, the temperature of the phase separation is 30-40 ℃, such as 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃ and the like.
Preferably, the cleaning is done using deionized water.
Preferably, the preparation method of the casting solution comprises the following steps: dissolving polyvinylidene fluoride, a pore-forming agent, a hydrophilic modifier and a silane coupling agent in a solvent at 60-90 ℃ (for example, 60 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 85 ℃, 88 ℃ or 90 ℃), stirring for 12-24h (for example, 12h, 14h, 16h, 18h, 20h, 22h or 24h), and then standing and defoaming for 12-24h (for example, 12h, 14h, 16h, 18h, 20h, 22h or 24h) at 40-60 ℃ (for example, 40 ℃, 43 ℃, 45 ℃, 48 ℃, 50 ℃, 55 ℃, 58 ℃ or 60 ℃) to obtain a casting solution.
In the preparation method of the casting solution, the solvent is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.
In the invention, the N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid is prepared by reacting 1, 3-propyl sultone with N- [3- (dimethylamino) propyl ] acrylamide.
Preferably, the molar ratio of the 1, 3-propylsultone to the N- [3- (dimethylamino) propyl ] acrylamide is 1: 1.
Preferably, the reaction temperature is 30-60 ℃, such as 30 ℃, 33 ℃, 35 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 53 ℃, 55 ℃ or 60 ℃.
Preferably, the reaction time is 10-24h, such as 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, etc.
Preferably, the solvent of the reaction is at least one of acetonitrile, ethanol or acetone.
The N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid prepared by the above reaction was post-treated as follows: n, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid was allowed to stand at 5 ℃ for 40h, washed with acetonitrile and acetone, and then vacuum-dried in a hollow drying oven for 10 h.
Before the polyvinylidene fluoride base film coated on the substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid are subjected to polymerization reaction, placing the polyvinylidene fluoride base film coated on the substrate in a strong base solution containing potassium permanganate, and reacting for 1-3h at 40-60 ℃ to generate double bonds on the polyvinylidene fluoride base film; the reaction temperature is 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃ or 60 ℃ and the like; the reaction time is 1h, 1.5h, 2h, 2.5h or 3h and the like.
In the invention, potassium permanganate plays an oxidizing role and can promote polyvinylidene fluoride molecules to remove HF.
Preferably, the mass fraction of the strong base solution is 20-40%, such as 20%, 23%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, or the like.
Preferably, the strong base is sodium hydroxide and/or potassium hydroxide.
Preferably, the mass ratio of the base contained in the strong alkaline solution to the potassium permanganate is 7:1 to 9:1, such as 7:1, 7.3:1, 7.5:1, 7.8:1, 8:1, 8.3:1, 8.5:1, 8.8:1 or 9: 1.
Preferably, the initiator is one of potassium peroxodisulfate, sodium peroxodisulfate or ammonium peroxodisulfate.
Preferably, the concentration of the N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid in the polymerization reaction system is 10-100 g/L;
preferably, the polymerization is carried out in a NaCl solution or a KCl solution.
Preferably, the mass fraction of the NaCl solution or KCl solution is 0.01-0.1%, such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1%, etc.
Preferably, the polymerization temperature is 50-80 ℃, such as 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
Preferably, the polymerization reaction time is 12-24h, e.g., 12h, 14h, 16h, 18h, 20h, 22h, 24h, or the like.
Preferably, the polymerization is carried out under the protection of a protective gas, preferably nitrogen.
Preferably, after the substrate is removed, the obtained film is soaked in glycerol for 10-20h, for example, 10h, 12h, 14h, 16h, 18h or 20h, and dried to obtain the polymer film.
Preferably, the mass fraction of glycerol is 25-45%, e.g., 25%, 28%, 30%, 33%, 35%, 38%, 40%, 42%, or 45%, etc.
As a preferred technical solution of the present invention, the method for preparing the polymer film specifically comprises the following steps:
(1) preparing a polyvinylidene fluoride base film coated on a substrate: coating a film casting solution containing polyvinylidene fluoride, a pore-forming agent, a hydrophilic modifier, a silane coupling agent and a solvent on a glass substrate or a PET substrate, then carrying out phase separation in a coagulating bath with the concentration of 20-40% of the solvent at the temperature of 30-40 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film coated on the glass substrate or the PET substrate; the polyvinylidene fluoride, the pore-forming agent, the hydrophilic modifier, the silane coupling agent and the solvent respectively account for 10-20%, 5-15%, 5-10%, 1-5% and 60-70% of the weight percentage in the casting solution; the pore-forming agent is at least one of PVP K30, PVP K64 and PVP K90, the hydrophilic modifier is PEG400 or PEG600, the silane coupling agent is KH550 or KH560, and the solvent is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
(2) preparation of N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid: respectively dissolving 1, 3-propylsultone and N- [3- (dimethylamino) propyl ] acrylamide in a solvent, mixing and stirring the mixture according to the molar ratio of 1:1 of the 1, 3-propylsultone and the N- [3- (dimethylamino) propyl ] acrylamide, and continuously reacting for 10-24h at 30-60 ℃ to obtain N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid; the solvent is at least one of acetonitrile, ethanol or acetone;
(3) preparation of polymer film: placing the polyvinylidene fluoride base film coated on the glass substrate or the PET substrate in a sodium hydroxide and/or potassium hydroxide solution containing potassium permanganate with the mass fraction of 20-40%, wherein the mass ratio of the sodium hydroxide and/or potassium hydroxide to the potassium permanganate is 7:1-9:1, and reacting for 1-3h at 40-60 ℃ to generate double bonds on the polyvinylidene fluoride base film; in a nitrogen atmosphere, under the initiation of an initiator with the concentration of 0.23g/L, carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid with the concentration of 10-100g/L in a NaCl or KCl solution with the mass fraction of 0.01-0.1%, wherein the reaction temperature is 50-80 ℃, and the reaction lasts for 12-24h, so that one surface of the polyvinylidene fluoride film is grafted with the poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid; then removing the substrate, soaking the obtained film for 10-20h by using 25-45% of glycerol by mass fraction, and airing to obtain the polymer film; the initiator is one of potassium peroxodisulfate, potassium peroxodisulfate and ammonium peroxodisulfate.
In a further aspect, the present invention provides the use of a polymeric film as described above in a filter material.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares a temperature-sensitive easily-cleaned film by modifying poly-N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid with high critical solution temperature on the surface of a polyvinylidene fluoride film, wherein after the film is polluted for a period of time at normal temperature, when the film is back flushed by hot water with temperature higher than the critical solution temperature, the poly-N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid is changed into a coil structure from colloidal particle shape, the film hole is enlarged, so that pollutants can be back flushed from the film hole easily, the back flushing efficiency and the repeated utilization rate of the film are greatly improved, the recovery rate of tertiary flux is improved to more than 90%, and the secondary damage to the film is greatly reduced.
In addition, poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid contains positive charges and negative charges, a hydration layer formed by the poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid and water molecules is firmer and more stable than a hydration layer formed by a hydrophilic material by utilizing hydrogen bonding, and the pollution of protein to the surface of the membrane can be reduced.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This embodiment provides a polymer film, which uses a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted on one side of the polyvinylidene fluoride film, and the preparation method thereof includes the following steps:
(1) mixing polyvinylidene fluoride, PVP K30, PEG400, KH550 and N, N-dimethylacetamide, stirring and dissolving at 80 ℃ for 12h, and standing and defoaming at 50 ℃ for 12h to obtain the casting solution. Coating the film casting solution on a glass substrate at normal temperature, standing for 10s, performing phase separation in a coagulating bath of a solvent with the concentration of 30% at 35 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film (the aperture of the polyvinylidene fluoride film is 10-50nm) coated on the glass substrate; the weight percentages of polyvinylidene fluoride, PVPK30, PEG400, KH550 and N, N-dimethylacetamide in the casting solution are respectively 15%, 10%, 7%, 1% and 67%;
(2) respectively dissolving 1, 3-propylsultone and N- [3- (dimethylamino) propyl ] acrylamide in an acetonitrile solution, mixing and stirring the 1, 3-propylsultone and the N- [3- (dimethylamino) propyl ] acrylamide according to a molar ratio of 1:1, continuously stirring the mixture for reaction for 20 hours at 30 ℃, standing the mixture for 40 hours at 5 ℃, washing the obtained white precipitate with acetonitrile and acetone, and then drying the white precipitate in a hollow drying box for 10 hours in vacuum to obtain N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid;
(3) placing the polyvinylidene fluoride base film coated on the glass substrate into a sodium hydroxide aqueous solution containing potassium permanganate with the mass fraction of 36%, wherein the mass ratio of sodium hydroxide to potassium permanganate is 8:1, and reacting for 1.5h at 50 ℃ to generate double bonds on the polyvinylidene fluoride base film; then washing with deionized water to remove residual solution; in a nitrogen atmosphere, under the initiation of potassium peroxodisulfate with the concentration of 0.23g/L, carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid with the concentration of 10g/L in a NaCl solution with the mass fraction of 0.01%, wherein the reaction temperature is 50 ℃, and the reaction is carried out for 12 hours under a closed condition, so that one surface of a polyvinylidene fluoride film is grafted with poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid; and then removing the glass substrate, soaking the obtained film in 35% by mass of glycerol for 12 hours, and airing to obtain the polymer film.
The grafting rate is tested by adopting a method for measuring the grafting rate of the fluorine-containing graft polymer disclosed in CN 200910196785; the molecular weight was measured using the test method of GB/T21864-2008.
The calculation method of the polymerization degree n comprises the following steps:
Figure BDA0001830679280000101
the calculation method of the polymerization degree m comprises the following steps:
Figure BDA0001830679280000111
wherein Mw (PVDF) is the molecular weight of polyvinylidene fluoride (PVDF), M (VDF) is the molecular weight of PVDF monomer unit, Mw (PVDF-g-PA3) is the molecular weight of PVDF grafted with poly-N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid, DG is the grafting ratio, M (F) is the molecular weight of fluorine atom, M (A3) is poly-N, N-dimethylMolecular weight of (acrylamidopropyl) aminopropanesulfonic acid monomer units.
The grafting rate of poly-N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid on one side of the polyvinylidene fluoride membrane in the obtained film was 3.2%, N was 9471, and m was 267.
Example 2
This example provides a polymer film, which is a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted to one side of the polyvinylidene fluoride film, and the preparation method of the polymer film is different from that of example 1 only in that the concentration of N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid in step (3) is 60g/L, and the other steps are the same, so that the polymer film is obtained.
The same procedure as in example 1 was repeated to obtain a film in which the degree of grafting of poly (N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid to one side of the polyvinylidene fluoride film was 6.6%, N was 9471, and m was 708.
Example 3
This example provides a polymer film, which is a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted to one side of the polyvinylidene fluoride film, and the preparation method thereof is different from example 1 only in that the concentration of N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid in step (3) is 100g/L, and the other steps are the same, so as to obtain the polymer film.
The same procedure as in example 1 was repeated to obtain a film in which the degree of grafting of poly (N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid to one side of the polyvinylidene fluoride film was 7.3%, N was 9471, and m was 869.
Example 4
This example provides a polymer film, which uses a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted on one side of the polyvinylidene fluoride film, and the preparation method of the polymer film is different from that of example 1 only in that the reaction time of the polyvinylidene fluoride base film in step (3) and N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is 18h, and the other steps are the same, so as to obtain the polymer film.
The same procedure as in example 1 was repeated to obtain a film in which the degree of grafting of poly (N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid to one surface of a polyvinylidene fluoride film was 9.5%, N was 9471, and m was 599.
Example 5
This example provides a polymer film, which uses a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted on one side of the polyvinylidene fluoride film, and the preparation method of the polymer film is different from that of example 1 only in that the reaction time of the polyvinylidene fluoride base film in step (3) and N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is 24 hours, and the other steps are the same, so as to obtain the polymer film.
The same procedure as in example 1 was repeated to obtain a film in which the degree of grafting of poly (N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid to one surface of a polyvinylidene fluoride film was 10.1%, N was 9471, and m was 722.
Example 6
This embodiment provides a polymer film, which uses a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted on one side of the polyvinylidene fluoride film, and the preparation method thereof includes the following steps:
(1) mixing polyvinylidene fluoride, PVP K64, PEG400, KH550 and N, N-dimethylacetamide, stirring and dissolving for 24h at 60 ℃, and standing and defoaming for 24h at 40 ℃ to obtain the casting solution. Coating the film casting solution on a PET substrate, standing for 10s, performing phase separation in a coagulating bath with a solvent with the concentration of 20% at 40 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film (the aperture of the polyvinylidene fluoride film is 10-80nm) coated on the PET substrate; the weight percentages of polyvinylidene fluoride, PVP K64, PEG400, KH550 and N, N-dimethylacetamide in the membrane casting solution are respectively 10%, 15%, 10%, 1% and 64%;
(2) respectively dissolving 1, 3-propylsultone and N- [3- (dimethylamino) propyl ] acrylamide in an acetonitrile solution, mixing and stirring the 1, 3-propylsultone and the N- [3- (dimethylamino) propyl ] acrylamide according to a molar ratio of 1:1, continuously stirring and reacting for 10 hours at 60 ℃, standing for 40 hours at 5 ℃, washing the obtained white precipitate with acetonitrile and acetone, and then drying in a hollow drying oven for 10 hours in vacuum to obtain N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid;
(3) placing the polyvinylidene fluoride base film coated on the PET substrate into a sodium hydroxide aqueous solution containing potassium permanganate with the mass fraction of 20%, wherein the mass ratio of sodium hydroxide to potassium permanganate is 7:1, and reacting for 1h at 60 ℃ to generate double bonds on the polyvinylidene fluoride base film; then washing with deionized water to remove residual solution; in a nitrogen atmosphere, under the initiation of potassium peroxodisulfate with the concentration of 0.23g/L, carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid with the concentration of 10g/L in a NaCl solution with the mass fraction of 0.01%, wherein the reaction temperature is 80 ℃, and the reaction is carried out for 12 hours under a closed condition, so that one surface of a polyvinylidene fluoride film is grafted with poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid; and then removing the glass substrate, soaking the obtained film for 10 hours by using glycerol with the mass fraction of 45%, and airing to obtain the polymer film.
The grafting rate is tested by adopting a method for measuring the grafting rate of the fluorine-containing graft polymer of CN 200910196785; the molecular weight was measured using the test method of GB/T21864-2008.
The calculation method of the polymerization degree n comprises the following steps:
Figure BDA0001830679280000131
the calculation method of the polymerization degree m comprises the following steps:
Figure BDA0001830679280000132
where, Mw (PVDF) is the molecular weight of PVDF, M (vdf) is the molecular weight of PVDF monomer unit, Mw (PVDF-g-PA3) is the molecular weight of PVDF grafted with poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid, DG is the grafting ratio, M (f) is the molecular weight of fluorine atoms, and M (A3) is the molecular weight of poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid monomer unit.
The grafting ratio of poly N, N-dimethyl (acrylamide propyl) amino propane sulfonic acid on one surface of the polyvinylidene fluoride membrane in the obtained membrane is 6.3 percent, N is 9471, and m is 502.
Example 7
This embodiment provides a polymer film, which uses a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted on one side of the polyvinylidene fluoride film, and the preparation method thereof includes the following steps:
(1) mixing polyvinylidene fluoride, PVP K90, PEG400, KH550 and N, N-dimethylacetamide, stirring and dissolving at 90 ℃ for 12h, and standing and defoaming at 50 ℃ for 12h to obtain the casting solution. Coating the film casting solution on a glass substrate, standing for 10s, performing phase separation in a coagulating bath of a solvent with the concentration of 30% at 35 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film (the aperture of the polyvinylidene fluoride film is 20-80nm) coated on the glass substrate; the weight percentages of polyvinylidene fluoride, PVP K90, PEG400, KH550 and N, N-dimethylacetamide in the membrane casting solution are respectively 15%, 5%, 9%, 1% and 70%;
(2) 1, 3-propylsultone and N- [3- (dimethylamino) propyl ] acrylamide were dissolved in acetonitrile solutions, respectively, and then the ratio of 1, 3-propylsultone: mixing and stirring N- [3- (dimethylamino) propyl ] acrylamide at a molar ratio of 1:1, continuously stirring and reacting at 45 ℃ for 18h, standing at 5 ℃ for 40h, washing the obtained white precipitate with acetonitrile and acetone, and then drying in a hollow drying oven under vacuum for 10h to obtain N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid;
(3) placing the polyvinylidene fluoride base film coated on the glass substrate into a sodium hydroxide aqueous solution containing potassium permanganate with the mass fraction of 40%, wherein the mass ratio of sodium hydroxide to potassium permanganate is 9:1, and reacting for 2 hours at 50 ℃ to generate double bonds on the polyvinylidene fluoride base film; then washing with deionized water to remove residual solution; in a nitrogen atmosphere, under the initiation of potassium peroxodisulfate with the concentration of 0.23g/L, carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid with the concentration of 10g/L in a NaCl solution with the mass fraction of 0.05%, wherein the reaction temperature is 40 ℃, and the reaction is carried out for 24 hours under a closed condition, so that one surface of a polyvinylidene fluoride film is grafted with poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid; and then removing the glass substrate, soaking the obtained film for 15 hours by using glycerol with the mass fraction of 30%, and airing to obtain the polymer film.
The grafting rate is tested by adopting a method for measuring the grafting rate of the fluorine-containing graft polymer disclosed in CN 200910196785; the molecular weight was measured using the test method of GB/T21864-2008.
The calculation method of the polymerization degree n comprises the following steps:
Figure BDA0001830679280000151
the calculation method of the polymerization degree m comprises the following steps:
Figure BDA0001830679280000152
where, Mw (PVDF) is the molecular weight of PVDF, M (vdf) is the molecular weight of PVDF monomer unit, Mw (PVDF-g-PA3) is the molecular weight of PVDF grafted with poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid, DG is the grafting ratio, M (f) is the molecular weight of fluorine atoms, and M (A3) is the molecular weight of poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid monomer unit.
The grafting rate of poly N, N-dimethyl (acrylamide propyl) amino propane sulfonic acid on one surface of the polyvinylidene fluoride membrane in the obtained film is 6.9%, N is 9471, and m is 460.
Example 8
This embodiment provides a polymer film, which uses a polyvinylidene fluoride film as a base film, and poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is grafted on one side of the polyvinylidene fluoride film, and the preparation method thereof includes the following steps:
(1) mixing polyvinylidene fluoride, PVP K30, PEG600, KH560 and N, N-dimethylacetamide, stirring and dissolving at 80 ℃ for 12h, and standing and defoaming at 60 ℃ for 12h to obtain the casting solution. Coating the film casting solution on a glass substrate, standing for 10s, performing phase separation in a coagulating bath of a solvent with the concentration of 40% at 30 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film (the aperture of the polyvinylidene fluoride film is 20-100nm) coated on the glass substrate; the weight percentages of polyvinylidene fluoride, PVP K30, PEG600, KH560 and N, N-dimethylacetamide in the membrane casting solution are respectively 20%, 10%, 5% and 60%;
(2) 1, 3-propylsultone and N- [3- (dimethylamino) propyl ] acrylamide were dissolved in acetonitrile solutions, respectively, and then the ratio of 1, 3-propylsultone: mixing and stirring N- [3- (dimethylamino) propyl ] acrylamide at a molar ratio of 1:1, continuously stirring and reacting at 30 ℃ for 24 hours, standing at 5 ℃ for 40 hours, washing the obtained white precipitate with acetonitrile and acetone, and then drying in a hollow drying oven in vacuum for 10 hours to obtain N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid;
(3) placing the polyvinylidene fluoride base film coated on the glass substrate into a sodium hydroxide aqueous solution containing potassium permanganate with the mass fraction of 30%, wherein the mass ratio of sodium hydroxide to potassium permanganate is 8:1, and reacting for 3 hours at 40 ℃ to generate double bonds on the polyvinylidene fluoride base film; then washing with deionized water to remove residual solution; in a nitrogen atmosphere, under the initiation of potassium peroxodisulfate with the concentration of 0.23g/L, carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid with the concentration of 10g/L in a NaCl solution with the mass fraction of 0.1%, wherein the reaction temperature is 60 ℃, and the reaction is carried out for 18 hours under a closed condition, so that one surface of a polyvinylidene fluoride film is grafted with poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid; and then removing the glass substrate, soaking the obtained film in 25% glycerol for 20h, and airing to obtain the polymer film.
The grafting rate is tested by adopting a method for measuring the grafting rate of the fluorine-containing graft polymer disclosed in CN 200910196785; the molecular weight was measured using the test method of GB/T21864-2008.
The calculation method of the polymerization degree n comprises the following steps:
Figure BDA0001830679280000171
the calculation method of the polymerization degree m comprises the following steps:
Figure BDA0001830679280000172
where, Mw (PVDF) is the molecular weight of PVDF, M (vdf) is the molecular weight of PVDF monomer unit, Mw (PVDF-g-PA3) is the molecular weight of PVDF grafted with poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid, DG is the grafting ratio, M (f) is the molecular weight of fluorine atoms, and M (A3) is the molecular weight of poly N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid monomer unit.
The grafting ratio of poly N, N-dimethyl (acrylamide propyl) amino propane sulfonic acid on one surface of the polyvinylidene fluoride membrane in the obtained film is 9.1 percent, N is 9471, and m is 759.
Comparative example 1
The comparative example provides a polyvinylidene fluoride base film, the preparation method of which comprises the following steps:
mixing polyvinylidene fluoride, PVP K30, PEG400, KH550 and N, N-dimethylacetamide, stirring and dissolving at 80 ℃ for 12h, and standing and defoaming at 50 ℃ for 12h to obtain the casting solution. And coating the film casting solution on a glass substrate, standing for 10s, performing phase separation in a coagulating bath of a solvent with the concentration of 30% at 35 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film coated on the glass substrate (the aperture of the polyvinylidene fluoride film is 10-50 nm). The weight percentages of polyvinylidene fluoride, PVP K30, PEG400, KH550 and N, N-dimethylacetamide in the membrane casting solution are respectively 15%, 10%, 7%, 1% and 67%.
Comparative example 2
This comparative example provides a polymer film based on a polyvinylidene fluoride film having poly (N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid) grafted to both sides of the polyvinylidene fluoride film, which was prepared by a process comprising the steps of:
(1) mixing polyvinylidene fluoride, PVP K30, PEG400, KH550 and N, N-dimethylacetamide, stirring and dissolving at 80 ℃ for 12h, and standing and defoaming at 50 ℃ for 12h to obtain the casting solution. Coating the film casting solution on a glass substrate, standing for 10s, performing phase separation in a coagulating bath of a solvent with the concentration of 30% at 35 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film (the aperture of the polyvinylidene fluoride film is 10-50nm) coated on the glass substrate; the weight percentages of polyvinylidene fluoride, PVP K30, PEG400, KH550 and N, N-dimethylacetamide in the membrane casting solution are respectively 15%, 10%, 7%, 1% and 67%; removing the obtained polyvinylidene fluoride base film from the glass plate;
(2) 1, 3-propylsultone and N- [3- (dimethylamino) propyl ] acrylamide were dissolved in acetonitrile solutions, respectively, and then the ratio of 1, 3-propylsultone: dissolving and stirring N- [3- (dimethylamino) propyl ] acrylamide at a molar ratio of 1:1, continuously stirring and reacting at 30 ℃ for 20h, standing at 5 ℃ for 40h, washing the obtained white precipitate with acetonitrile and acetone, and then drying in a hollow drying oven under vacuum for 10h to obtain N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid;
(3) placing the removed polyvinylidene fluoride base film into a sodium hydroxide aqueous solution containing potassium permanganate with the mass fraction of 36%, wherein the mass ratio of sodium hydroxide to potassium permanganate is 8:1, and reacting for 1.5h at 50 ℃ to generate double bonds on the polyvinylidene fluoride base film; then washing with deionized water to remove residual solution; in a nitrogen atmosphere, under the initiation of potassium peroxodisulfate with the concentration of 0.23g/L, carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid with the concentration of 10g/L in a NaCl solution with the mass fraction of 0.1%, wherein the reaction temperature is 50 ℃, and the reaction is carried out for 12 hours under a closed condition, so that the poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid is grafted on both surfaces of the polyvinylidene fluoride film; and soaking the obtained film in 35% by mass of glycerol for 12 hours, and airing to obtain the polymer film.
The grafting rate is tested by adopting a method for measuring the grafting rate of the fluorine-containing graft polymer disclosed in CN 200910196785; the molecular weight was measured using the test method of GB/T21864-2008. The calculation method of the polymerization degree n comprises the following steps:
Figure BDA0001830679280000191
meter of polymerization degree mThe calculation method comprises the following steps:
Figure BDA0001830679280000192
where, Mw (PVDF) is the molecular weight of PVDF, M (vdf) is the molecular weight of PVDF monomer unit, Mw (PVDF-g-PA3) is the molecular weight of PVDF grafted with PA3, DG is the grafting ratio, M (f) is the molecular weight of fluorine atom, and M (A3) is the molecular weight of poly-N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid monomer unit.
The total graft of poly-N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid in the resulting film was 7.8%, N was 9471, and m was 329.
Example 9
Filtration performance measurement test:
in this example, the polymer films prepared in examples 1 to 8 and comparative examples 1 to 2 were subjected to a filtration performance measurement test using bovine serum albumin as a membrane contaminant, a phosphate buffer solution of bovine serum albumin having a pH of 7.0 and a concentration of 1g/L was filtered through the membrane for a filtration time of 10min, the water flux of the membrane was measured, the membrane was back-washed with hot water at 65 ℃ for a washing time of 10min, and the water flux and the flux recovery rate of the membrane were measured. The test was carried out for 3 cycles in total, the water flux was measured by a stopwatch and a measuring cylinder, and the recovery rate of the membrane flux was calculated as follows:
Jr＝(Jii/Ji)×100％
wherein, JrFor membrane flux recovery, JiiFor the water flux of the membrane after backwashing, JiIs the initial water flux.
The test results are shown in table 1.
TABLE 1
Figure BDA0001830679280000193
Figure BDA0001830679280000201
The water flux in the contaminated state described in Table 1 means the water flux in the contaminated state after filtering the bovine serum albumin solution.
From the results shown in table 1, it is known that although the initial flux of the polymer membrane prepared by the method is reduced due to the fact that poly-N, N-dimethyl (acrylamido propyl) aminopropanesulfonic acid is grafted on the surface of the membrane pores and the membrane pores are reduced, the bovine serum albumin pollution is obviously reduced, the recovery rate of the tertiary flux is improved from 37.6% (comparative example 1) to 95.6% (example 4), and the use efficiency of the membrane is greatly improved. And compared with the comparative example 2, the water flux recovery rate of 3 times of the examples 1 to 8 is higher, which is caused by that the membrane pores of the membrane grafted with poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid on the two sides are blocked by graft during back flushing, and pollutants are not thoroughly flushed.
The applicant states that the present invention is illustrated by the above examples of the polymer film of the present invention and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims (40)

1. A polymer film is characterized in that the polymer film takes a polyvinylidene fluoride film as a base film, and poly (N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid) is grafted on one surface of the polyvinylidene fluoride film;
the grafting rate of the poly-N, N-dimethyl (acrylamide propyl) amino propane sulfonic acid on one surface of the polyvinylidene fluoride membrane is 3-15%;
the molecular structure of the polyvinylidene fluoride membrane grafted with poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid is shown as formula I:
Figure FDA0003128244150000011
wherein n is 9000-14000 and m is 200-2200.
2. The polymer film according to claim 1, wherein the polyvinylidene fluoride membrane has an average pore diameter of 10 to 100 nm.
3. The method for producing a polymer film according to claim 1 or 2, characterized by comprising the steps of:
under the initiation of an initiator, carrying out polymerization reaction on the polyvinylidene fluoride base film coated on the substrate and N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid, grafting the poly N, N-dimethyl (acrylamide propyl) aminopropanesulfonic acid on one surface of the polyvinylidene fluoride film, and then removing the substrate to obtain the polymer film.
4. The method according to claim 3, wherein the polyvinylidene fluoride base film coated on the substrate is prepared by:
and coating the casting solution containing the polyvinylidene fluoride on the substrate, then carrying out phase separation and cleaning to obtain the polyvinylidene fluoride base film coated on the substrate.
5. The production method according to claim 4, characterized in that the casting solution further comprises a pore-forming agent, a hydrophilic modifier and a silane coupling agent.
6. The method according to claim 4, wherein the casting solution is prepared by: dissolving polyvinylidene fluoride, a pore-forming agent, a hydrophilic modifier and a silane coupling agent in a solvent at 60-90 ℃, stirring for 12-24h, and then standing and defoaming at 40-60 ℃ for 12-24h to obtain the casting solution.
7. The method of claim 6, wherein the pore former is at least one of PVP K30, PVP K64, or PVP K90.
8. The method according to claim 6, wherein the hydrophilic modifier is PEG400 or PEG 600.
9. The method according to claim 6, wherein the silane coupling agent is KH550 or KH 560.
10. The production method according to claim 6, characterized in that the solvent in the casting solution is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, or dimethylsulfoxide.
11. The production method according to claim 6, wherein the weight percentage of the polyvinylidene fluoride membrane in the casting solution is 10 to 20%.
12. The production method according to claim 6, wherein the weight percentage of the pore-forming agent in the casting solution is 5 to 15%.
13. The method according to claim 6, wherein the hydrophilic modifier is present in the casting solution in an amount of 5 to 10% by weight.
14. The production method according to claim 6, wherein the weight percentage of the silane coupling agent in the casting solution is 1 to 5%.
15. The production method according to claim 6, wherein the weight percentage of the solvent in the dope solution is 60 to 70%.
16. The production method according to claim 4, wherein the substrate is a glass substrate or a PET substrate.
17. The method of claim 4, wherein the phase separation is performed in a coagulation bath having a solvent concentration of 20-40%.
18. The method according to claim 4, wherein the temperature of the phase separation is 30 to 40 ℃.
19. The method of claim 4, wherein the cleaning is performed using deionized water.
20. The method of claim 3, wherein the N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid is prepared by reacting 1, 3-propylsultone with N- [3- (dimethylamino) propyl ] acrylamide.
21. The method of claim 20, wherein the molar ratio of 1, 3-propylsultone to N- [3- (dimethylamino) propyl ] acrylamide is 1: 1.
22. The method of claim 20, wherein the reaction temperature is 30-60 ℃.
23. The method of claim 20, wherein the reaction time is 10-24 hours.
24. The method of claim 20, wherein the solvent for the reaction is at least one of acetonitrile, ethanol, or acetone.
25. The method according to claim 4, wherein the polyvinylidene fluoride base film coated on the substrate is placed in a strong alkaline solution containing potassium permanganate and reacted at 40-60 ℃ for 1-3 hours before the polyvinylidene fluoride base film coated on the substrate is polymerized with N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid, so that double bonds are generated on the polyvinylidene fluoride base film.
26. The method of claim 25, wherein the alkali solution is present in an amount of 20 to 40 wt.%.
27. The method of claim 25, wherein the strong base is sodium hydroxide and/or potassium hydroxide.
28. The method according to claim 25, wherein the alkali and potassium permanganate are present in the strong alkaline solution in a mass ratio of 7:1 to 9: 1.
29. The method according to claim 25, wherein the polymerization initiator is one of potassium peroxodisulfate, sodium peroxodisulfate, or ammonium peroxodisulfate.
30. The method according to claim 25, wherein the concentration of N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid in the polymerization system is from 10 to 100 g/L.
31. The method of claim 25, wherein the polymerization is performed in a NaCl solution or a KCl solution.
32. The method according to claim 31, wherein the mass fraction of the NaCl solution or the KCl solution is 0.01-0.1%.
33. The method of claim 25, wherein the polymerization reaction temperature is 50-80 ℃.
34. The method of claim 25, wherein the polymerization time is 12 to 24 hours.
35. The method of claim 25, wherein the polymerization is carried out under a protective gas.
36. The method of claim 35, wherein the protective gas is nitrogen.
37. The preparation method according to claim 3, wherein after the substrate is removed, the obtained film is soaked in glycerol for 10-20h and dried to obtain the polymer film.
38. The method according to claim 37, wherein the glycerol is present in an amount of 25 to 45% by mass.
39. The method of manufacturing according to claim 3, comprising the steps of:
(1) preparing a polyvinylidene fluoride base film coated on a substrate: coating a film casting solution containing polyvinylidene fluoride, a pore-forming agent, a hydrophilic modifier, a silane coupling agent and a solvent on a glass substrate or a PET substrate, then carrying out phase separation in a coagulating bath with the concentration of 20-40% of the solvent at the temperature of 30-40 ℃, and washing with deionized water to obtain a polyvinylidene fluoride base film coated on the glass substrate or the PET substrate; the polyvinylidene fluoride, the pore-forming agent, the hydrophilic modifier, the silane coupling agent and the solvent respectively account for 10-20%, 5-15%, 5-10%, 1-5% and 60-70% of the weight percentage in the casting solution; the pore-forming agent is at least one of PVP K30, PVP K64 or PVP K90, and the hydrophilic modifier is PEG400 or PEG 600; the silane coupling agent is KH550 or KH560, and the solvent is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide;
(2) preparation of N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid: respectively dissolving 1, 3-propylsultone and N- [3- (dimethylamino) propyl ] acrylamide in a solvent, mixing and stirring the mixture according to the molar ratio of 1:1 of the 1, 3-propylsultone and the N- [3- (dimethylamino) propyl ] acrylamide, and continuously reacting for 10-24h at 30-60 ℃ to obtain N, N-dimethyl (acrylamidopropyl) aminopropanesulfonic acid; the solvent is at least one of acetonitrile, ethanol or acetone;
(3) preparation of polymer film: placing the polyvinylidene fluoride base film coated on the glass substrate or the PET substrate in a sodium hydroxide and/or potassium hydroxide solution containing potassium permanganate with the mass fraction of 20-40%, wherein the mass ratio of the sodium hydroxide and/or potassium hydroxide to the potassium permanganate is 7:1-9:1, and reacting for 1-3h at 40-60 ℃ to generate double bonds on the polyvinylidene fluoride base film; in a nitrogen atmosphere, under the initiation of an initiator, carrying out polymerization reaction on a polyvinylidene fluoride base film coated on a substrate and N, N-dimethyl (acrylamido propyl) aminopropanesulfonic acid with the concentration of 10-100g/L in a NaCl solution or a KCl solution with the mass fraction of 0.01-0.1%, wherein the reaction temperature is 50-80 ℃, and the reaction lasts for 12-24h, so that one surface of the polyvinylidene fluoride film is grafted with the poly N, N-dimethyl (acrylamido propyl) aminopropanesulfonic acid; then removing the substrate, soaking the obtained film for 10-20h by using 25-45% of glycerol by mass fraction, and airing to obtain the polymer film; the initiator is one of potassium peroxodisulfate, sodium persulfate or ammonium persulfate.
40. Use of a polymer film according to claim 1 or 2 in a filter material.
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