CN111286068B - Method for preparing hydrophilic-hydrophobic composite membrane by grafting zwitterion on surface - Google Patents
Method for preparing hydrophilic-hydrophobic composite membrane by grafting zwitterion on surface Download PDFInfo
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
Abstract
The invention discloses a method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface, which comprises the steps of hydroxylating the surface of a PVDF membrane, preparing a grafting solution and preparing the hydrophilic-hydrophobic composite membrane. In addition, after hydrophilic modification is carried out on the permeation side of the hydrophilic-hydrophobic composite membrane, the membrane can be promoted to adsorb water molecules, so that the flux of the membrane distillation process is improved, a hydrophilic layer is formed on the feeding side of the membrane surface, so that wetting caused by dirt or dirt can be effectively prevented, and the pollution resistance is higher.
Description
Technical Field
The invention relates to the field of a method for preparing a hydrophilic-hydrophobic composite membrane, in particular to a method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface.
Background
Currently, the growing population and the process of industrialization put increasing pressure on the world's fresh water resources. Statistically, one-sixth of the world's population has no access to potable water sources. Effective treatment of salt-containing water (seawater, brackish water and high salinity industrial wastewater) is of great significance to ensure sufficient and safe supply of water resources and sustainable development of economy and environment. Membrane Distillation (MD) is a membrane-based thermally driven desalination technology, has the advantages of small floor area, high separation efficiency, mild operation conditions and the like, and has wide application prospects in the fields of seawater desalination and high-salinity industrial wastewater treatment. However, the membrane distillation technology has not been applied to large-scale industrialization so far, and the main factors restricting the industrialization development are the problem of membrane pollution and the problem of low membrane flux, so that the preparation of a novel membrane for membrane distillation with high flux and pollution resistance is a key problem to be solved urgently in the field at present.
At present, novel pollution-resistant membranes for membrane distillation mainly comprise super-hydrophobic membranes, all-hydrophobic membranes and hydrophilic-hydrophobic composite membranes. Among them, the superhydrophobic film essentially enhances moisture resistance, but fouling due to forces acting between the film and contaminants is inevitable, which in the long run reduces MD performance. Due to the special structure of the all-hydrophobic membrane, the all-hydrophobic membrane has strong resistance to wetting induced by a surfactant, but still has the problem of oil pollution, and the flux is obviously reduced after long-time operation. After hydrophilic modification is carried out on the permeation side of the hydrophilic-hydrophobic composite membrane, the membrane can be promoted to adsorb water molecules, so that the flux of the membrane distillation process is improved. While the formation of a hydrophilic modification layer on the feed side of the membrane surface is more effective in preventing wetting by dirt or soil. Mouth piece
There are two main classes of hydrophilic materials in the past: (i) conventional hydrophilic materials such as PEG, chitosan, titanium dioxide, silica, and the like, and (ii) zwitterionic molecules, wherein the zwitterionic molecules, due to the same number of evenly distributed anionic and cationic moieties, result in the formation of a denser, more compact hydrated layer than other hydrophilic materials, and thus the zwitterionic polymers are super hydrophilic. The preparation method of the hydrophilic-hydrophobic composite membrane commonly used at present comprises the following steps: surface coating methods, plasma techniques, electrospinning methods, and the like. However, these manufacturing techniques are performed under severe operating conditions and complicated operating techniques, which limit their practical applications. In addition, the durability and long-term stability of hydrophilic surfaces are issues that need to be addressed.
Disclosure of Invention
The invention provides a method for preparing a hydrophilic-hydrophobic composite membrane by surface grafting aiming at the problems in the prior art, a compact super-hydrophilic surface is formed on a polyvinylidene fluoride (PVDF) base membrane to prepare the hydrophilic-hydrophobic composite membrane, and the grafted hydrophilic layer has no damage to the base membrane and excellent pollution resistance.
The invention is realized by the following technical scheme:
a method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
putting the dried PVDF basal membrane and the Fenton solution into a reactor, carrying out Fenton reaction in a water bath at 45-55 ℃ for 0.5-2.5h, taking out the membrane after the reaction is finished, cleaning the membrane by using dilute sulfuric acid and deionized water, and finally drying the membrane in an oven to obtain a modified membrane PVDF-OH;
due to the chemical inertness of the PVDF base membrane, enough active sites are difficult to introduce into the PVDF base membrane, so that the PVDF base membrane needs to be activated in advance, reaction groups are introduced into the surface of the PVDF base membrane, hydroxyl groups are formed on the surface of the PVDF base membrane by utilizing the strong oxidizing property of a Fenton solution, and active sites are provided for grafting polyampholytes.
(2) Preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1-1.3: 11-12: 3-3.5;
the method takes ammonium ceric nitrate as an initiator and N, N-methylene bisacrylamide as a cross-linking agent, and grafts the zwitterionic monomer methacrylic acid sulfobetaine to the surface of the membrane through free radical polymerization reaction.
The zwitterion monomer contains positive and negative charge units, except hydrogen bonds, a hydration layer can be formed near the surface through electrostatic interaction, and a large number of water molecules are combined, so that the zwitterion monomer has high hydration capability and electric neutrality. Among a plurality of zwitterionic monomers, the sulfobetaine methacrylate is particularly selected, so that the sulfobetaine methacrylate has higher stability and better antifouling performance, can be quickly, simply and conveniently synthesized and applied, promotes better grafting of PVDF-OH of a modified membrane, and improves the durability and long-term stability of the hydrophilic surface of the membrane.
(3) Preparing a hydrophilic-hydrophobic composite membrane:
and (2) putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30-40min, sealing, reacting for 1-5h at 40-60 ℃, taking out the membrane after the reaction is finished, washing the membrane with ethanol and deionized water, and drying for 20-25h by air blast after the membrane is washed, thus obtaining the hydrophilic-hydrophobic composite membrane PVDF-T.
In some embodiments, in step (1), the Fenton solution is prepared from FeSO 4 ·7H 2 O、H 2 O 2 Anhydrous ethanol and deionized water, the FeSO 4 ·7H 2 O、H 2 O 2 The mass ratio of the absolute ethyl alcohol to the deionized water is FeSO 4 ·7H 2 O∶H 2 O 2 Absolute ethyl alcohol and deionized water in the weight ratio of 1 to (1-1.6) to (38-43) to (47-53).
The Fenton solution is prepared from H 2 O 2 With catalyst Fe 2+ The oxidation system has very high oxidation capability because of Fe 2+ Catalysis of ions with H 2 O 2 The decomposition activation energy of (2) is low, and the hydroxyl radical can be generated by decomposition. The Fenton solution adopts absolute ethyl alcohol and deionized water as solvents, and FeSO 4 ·7H 2 Fe provided by O 2+ As catalyst, catalyze H 2 O 2 Decomposing to generate hydroxyl free radicals, and providing active sites for grafting polyzwitterions on the PVDF base membrane.
In some of these embodiments, the FeSO 4 ·7H 2 O、H 2 O 2 The mass ratio of the absolute ethyl alcohol to the deionized water is FeSO 4 ·7H 2 O∶H 2 O 2 The ratio of absolute ethyl alcohol to deionized water is 1: 1.47: 40: 50.
In some of these embodiments, the H 2 O 2 Is 30 percent.
In some embodiments, the cleaning in step (1) is specifically dilute sulfuric acid and deionized water alternate cleaning, and more specifically cleaning with dilute sulfuric acid first and then deionized water, and circulating cleaning for 2-3 times.
In some embodiments, the temperature of the oven in step (1) is 70-80 ℃.
In some embodiments, the molar ratio of cerium ammonium nitrate, N-nitro, N-methylene bisacrylamide, sulfobetaine methacrylate, and nitric acid in step (2) is 1: 1.16: 11.6: 3.33 cerium ammonium nitrate to N, N-methylene bisacrylamide to sulfobetaine methacrylate to nitric acid.
In some embodiments, the washing in the step (3) is specifically washing with ethanol for 20-25h, then washing with deionized water for 46-50h, and circulating washing for 2-3 times.
In some embodiments, the temperature of the forced air drying in step (3) is 40-50 ℃.
In some of these embodiments, the PVDF-based membrane has a pore size of 0.45 μm.
Compared with the prior art, the method for preparing the hydrophilic-hydrophobic composite membrane by grafting the zwitterion on the surface has the following beneficial effects:
the invention can form a layer of nano-scale super-hydrophilic surface on the PVDF base film, the hydrophilic coating does not damage the base film, the static contact angle of the surface of the coating is reduced from 98 degrees to 46 degrees on the base film, and the grafted hydrophilic layer still stably exists after ultrasonic treatment for 180min by an ultrasonic cleaner at 70 ℃. In addition, after hydrophilic modification is carried out on the permeation side of the hydrophilic-hydrophobic composite membrane, the membrane can be promoted to adsorb water molecules, so that the flux in the membrane distillation process is improved, a hydrophilic layer is formed on the feeding side of the membrane surface, so that wetting caused by dirt or dirt can be effectively prevented, and the pollution resistance is higher;
the method for preparing the hydrophilic-hydrophobic composite membrane by grafting the zwitterion on the surface is uncomplicated in process, easily available in raw materials and low in cost, only needs to prepare a grafting solution for grafting in the process of preparing the coating, does not need a complex and precise instrument, is superior to other treatment modes, is suitable for large-area preparation, and improves the application of the hydrophilic-hydrophobic composite membrane.
Drawings
FIG. 1 is a graph showing the results of measuring the static contact angle of a hydrophilic-hydrophobic composite film at different hydroxylation treatment times in the present invention;
FIG. 2 is a graph showing the measurement results of the static contact angle of the hydrophilic-hydrophobic composite membrane at different grafting times in the present invention;
FIG. 3 shows the result of the measurement and calculation of the grafting density of the hydrophilic-hydrophobic composite membrane at different grafting times.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific embodiments, which are described herein for purposes of illustration only and are not intended to be limiting.
In the present invention, it should be noted that: PVDF is named as polyvinylidene fluoride in Chinese, Fenton is named as Fenton in Chinese, and FeSO is named as 4 ·7H 2 O Chinese name is ferrous sulfate, H 2 O 2 The Chinese name is hydrogen peroxide;
the composition of the ammonium ceric nitrate is H s CeN 8 O 1s Molecular weight 548.22; the composition of N, N-methylene bisacrylamide is C 7 H 10 N 2 O 2 Molecular weight 154.17; sulfobetaine methacrylate composition C 11 H 21 NO 5 S molecular weight 279.35.
Example 1
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H2O∶H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 is placed in a reactor, Fenton reaction is carried out for 0.5h in water bath at 50 ℃, after the reaction is finished, a membrane is taken out, is washed by dilute sulfuric acid and then by deionized water, and is circularly washed for 2 times, and finally the membrane is dried in a 70 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
adding ammonium ceric nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ammonium ceric nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is ceric ammonium nitrate: n, N-methylene bisacrylamide, methacrylic acid sulfobetaine and nitric acid are 1: 1.16: 11.6: 3.33, and the addition amount of pure water is 15% of the total amount of ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine and nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 3h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane for 24h with ethanol, then cleaning the membrane for 48h with deionized water, circularly cleaning for 2 times, and then drying the membrane for 24h by blowing at 40 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 2
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O：H 2 O 2 (30%): putting a mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 into a reactor, carrying out Fenton reaction for 1.0h in a water bath at 50 ℃, taking out a membrane after the reaction is finished, cleaning the membrane by using dilute sulfuric acid, cleaning the membrane by using deionized water, circularly cleaning the membrane for 2 times, and finally drying the membrane in a drying oven at 70 ℃ to generate hydroxyl active sites on the surface of the membrane, thereby obtaining the modified membrane PVDF-OH;
(2) preparation of the grafting solution:
adding ammonium ceric nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ammonium ceric nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is ceric ammonium nitrate: n, N-methylene bisacrylamide, methacrylic acid sulfobetaine and nitric acid are 1: 1.16: 11.6: 3.33, and the addition amount of pure water is 15% of the total amount of ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine and nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 3h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane for 24h with ethanol, then cleaning the membrane for 48h with deionized water, circularly cleaning for 2 times, and then drying the membrane for 24h by blowing at 40 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 3
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O：H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 is placed in a reactor, Fenton reaction is carried out for 1.5h in water bath at 50 ℃, after the reaction is finished, a membrane is taken out, is washed by dilute sulfuric acid and then by deionized water, and is circularly washed for 2 times, and finally the membrane is dried in a 70 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
adding ammonium ceric nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ammonium ceric nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is ceric ammonium nitrate: n, N-methylene bisacrylamide, methacrylic acid sulfobetaine and nitric acid are 1: 1.16: 11.6: 3.33, and the addition amount of pure water is 15% of the total amount of ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine and nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 3h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane for 24h with ethanol, then cleaning the membrane for 48h with deionized water, circularly cleaning for 2 times, and then drying the membrane for 24h by blowing at 40 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 4
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O：H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 is placed in a reactor, Fenton reaction is carried out for 2.0h in water bath at 50 ℃, after the reaction is finished, the membrane is taken out, washed by dilute sulfuric acid and then by deionized water, and is circularly washed for 2 times, and finally the membrane is dried in a 70 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is ceric ammonium nitrate to N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine: nitric acid is 1: 1.16: 11.6: 3.33, and the addition amount of pure water is 15% of the total amount of ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine and nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 3h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane for 24h with ethanol, then cleaning the membrane for 48h with deionized water, circularly cleaning for 2 times, and then drying the membrane for 24h by blowing at 40 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 5
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
dried PVDF-based membrane having a pore size of 0.45 μm and massRatio of FeSO 4 ·7H 2 O：H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 is placed in a reactor, Fenton reaction is carried out for 2.5h in water bath at 50 ℃, after the reaction is finished, the membrane is taken out, washed by dilute sulfuric acid and then by deionized water, and is circularly washed for 2 times, and finally the membrane is dried in a 70 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1.16: 11.6: 3.33, and the addition amount of the pure water is 15% of the sum of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the methacrylic acid sulfobetaine and the nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 3h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane for 24h with ethanol, then cleaning the membrane for 48h with deionized water, circularly cleaning for 2 times, and then drying the membrane for 24h by blowing at 40 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 6
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O：H 2 O 2 (30 percent) mixed solution of absolute ethyl alcohol and deionized water of 1: 1.47: 40: 50 is put into a reactor, Fenton reaction is carried out for 2.0h in water bath at 50 ℃, after the reaction is finished, the membrane is taken out, washed by dilute sulphuric acid and then by deionized water, circularly washed for 2 times, and finally dried in an oven at 70 DEG CDrying to generate hydroxyl active sites on the surface of the membrane, thus obtaining modified membrane PVDF-OH;
(2) preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1.16: 11.6: 3.33, and the addition amount of the pure water is 15% of the sum of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the methacrylic acid sulfobetaine and the nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 1h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane with ethanol for 24h, then cleaning with deionized water for 48h, circularly cleaning for 2 times, and then drying by blowing at 40 ℃ for 24h to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 7
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O∶H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 is placed in a reactor, Fenton reaction is carried out for 2.0h in water bath at 50 ℃, after the reaction is finished, the membrane is taken out, washed by dilute sulfuric acid and then by deionized water, and is circularly washed for 2 times, and finally the membrane is dried in a 70 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
sequentially adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1.16: 11.6: 3.33, and the addition amount of the pure water is 15% of the total amount of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the methacrylic acid sulfobetaine and the nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 2h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane for 24h with ethanol, then cleaning the membrane for 48h with deionized water, circularly cleaning for 2 times, and then drying the membrane for 24h by blowing at 40 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 8
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O∶H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 is placed in a reactor, Fenton reaction is carried out for 2.0h in water bath at 50 ℃, after the reaction is finished, the membrane is taken out, washed by dilute sulfuric acid and then by deionized water, and is circularly washed for 2 times, and finally the membrane is dried in a 70 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1.16: 11.6: 3.33, and the addition amount of the pure water is 15% of the sum of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the methacrylic acid sulfobetaine and the nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 4h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane for 24h by using ethanol, then cleaning the membrane for 48h by using deionized water, circularly cleaning for 2 times, and then drying the membrane for 24h by blowing at 40 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 9
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O∶H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.47: 40: 50 is placed in a reactor, Fenton reaction is carried out for 2.0h in water bath at 50 ℃, after the reaction is finished, the membrane is taken out, washed by dilute sulfuric acid and then by deionized water, and is circularly washed for 2 times, and finally the membrane is dried in a 70 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
sequentially adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1.16: 11.6: 3.33, and the addition amount of the pure water is 15% of the total amount of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the methacrylic acid sulfobetaine and the nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
and (2) putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 5h at 40 ℃, taking out the membrane after the reaction, cleaning the membrane for 24h by using ethanol, cleaning the membrane for 48h by using deionized water, circularly cleaning for 2 times, and drying the membrane for 24h by blowing at 40 ℃ after the cleaning is finished to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 10
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
the mass ratio of the dried PVDF basal membrane with the aperture of 0.45 mu m to the FeSO 4 ·7H 2 O：H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 43: 47 is placed in a reactor, Fenton reaction is carried out for 2.0h in water bath at 45 ℃, after the reaction is finished, the membrane is taken out, is washed by dilute sulfuric acid and then by deionized water, is circularly washed for 3 times, and is dried in a 75 ℃ oven, so that hydroxyl active sites are generated on the surface of the membrane, and the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1.3: 11: 3.5, and the addition amount of the pure water is 15% of the sum of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the methacrylic acid sulfobetaine and the nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 2h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane with ethanol for 20h, then cleaning with deionized water for 50h, circularly cleaning for 3 times, and after the cleaning is finished, blowing and drying for 24h at 50 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Example 11
A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface comprises the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
will holeThe mass ratio of the dried PVDF-based film with the diameter of 0.45 mu m to the FeSO film 4 ·7H 2 O∶H 2 O 2 (30%) mixed solution of absolute ethyl alcohol and deionized water in a ratio of 1: 1.6: 38: 53 is placed in a reactor, Fenton reaction is carried out for 2.0h in water bath at 55 ℃, after the reaction is finished, a membrane is taken out, is washed by dilute sulfuric acid and then by deionized water, is circularly washed for 3 times, and is dried in an oven at 80 ℃ to generate hydroxyl active sites on the surface of the membrane, so that the modified membrane PVDF-OH is obtained;
(2) preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1.3: 12: 3, and the addition amount of the pure water is 15% of the sum of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the methacrylic acid sulfobetaine and the nitric acid;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30min, sealing, reacting for 2h at 40 ℃, taking out the membrane after the reaction is finished, firstly cleaning the membrane with ethanol for 25h, then cleaning with deionized water for 46h, circularly cleaning for 3 times, and after the cleaning is finished, blowing and drying for 24h at 45 ℃ to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
Comparative example 1
The difference from example 4 is that in comparative example 1, the hydroxylation treatment time was 3 hours.
Comparative example 2
The difference from example 4 is that in comparative example 2 the grafting time was 6 h.
Comparative example 3
The difference from example 4 is that in comparative example 3, sulfobetaine methacrylate was replaced with methacryloyloxyethyl-N, N' -dimethyl-N-propanesulfonic acid amine salt.
The hydrophilic-hydrophobic composite membranes prepared in examples 1 to 9 and comparative examples 1 to 2 were subjected to the following evaluation of technical indexes.
Film surface contact angle test: the film was placed flat on a glass slide, on a platform of a contact angle measuring instrument (model OCA40Micro), 3 microliters of pure water was dropped onto the film surface each time by means of a syringe in the apparatus, and the angle of the water drop on the film surface was calculated by means of contact angle imaging software. Each sample was measured 5 times and the average was calculated.
The measurement results of the static contact angle of the hydrophilic-hydrophobic composite membranes of examples 1 to 5 with different hydroxylation treatment time are shown in fig. 1, and it can be seen from fig. 1 that the contact angle is 83 ° when the hydroxylation treatment time is 0.5h, 75 ° when the hydroxylation treatment time is 1h, 66 ° when the hydroxylation treatment time is 1.5h, 56 ° when the hydroxylation treatment time is 2h, 57 ° when the hydroxylation treatment time is 2.5h, which indicates that the contact angle is the smallest when the hydroxylation treatment time is 2h, and the hydrophilic effect is the best.
The static contact angle measurements of the hydrophilic-hydrophobic composite membranes of example 4, example 6 to example 9 at different grafting times are shown in fig. 2, and it can be seen from fig. 2 that the contact angle is 98 ° when grafting is not started, 75 ° when grafting time is 1h, 62 ° when grafting time is 2h, 56 ° when grafting time is 3h, 49 ° when grafting time is 4h, 46 ° when grafting time is 5h, indicating that the contact angle is the smallest when grafting time is 5h and the hydrophilic effect is the best.
The results of the measurement of the graft density of the hydrophilic-hydrophobic composite membranes of examples 4, 6 and 9 at different grafting times are shown in FIG. 3. As can be seen from FIG. 3, the graft density is 165.2. mu.g/cm when the grafting time is 1h -2 When the grafting time is 2 hours, the grafting density is 183.6 mu g/cm -2 When the grafting time is 3 hours, the grafting density is 208.8 mu g/cm -2 When the grafting time was 4 hours, the graft density was 229.4. mu.g/cm -2 When the grafting time is 5When h is used, the grafting density is 234.1 mu g/cm -2 It is stated that the grafting density is the greatest and the hydrophilic effect is the best at a grafting time of 5 hours.
Note: the grafting density formula is as follows:
GD＝(W-WO)/A
GD is the grafting density, W is the weight of the membrane after grafting, WO is the weight of the membrane before grafting, and A is the membrane area.
Static contact angle measurement and graft density measurement were performed on the hydrophilic-hydrophobic composite membranes prepared in comparative example 1 and comparative example 2, in which comparative example 1 had a contact angle of 87 °, higher than 83 ° of example 1, which is the maximum contact angle of the present invention, comparative example 2 had a contact angle of 85 °, higher than 75 ° of example 6, which is the minimum graft time, and comparative example 2 had a graft density of 147.9 μ g/cm -2 Less than 165.2. mu.g/cm for example 6 with minimum grafting time -2 。
The grafted hydrophilic layer is still stable after ultrasonic treatment of the ultrasonic cleaner for 180min at 70 ℃ in examples 1 to 11, which shows that the grafted hydrophilic surface of the hydrophilic-hydrophobic composite membrane has durability and long-term stability.
The antifouling property test was carried out for examples 1 to 11 and comparative examples 1 to 3:
water flux test method of the membrane: the membrane with the area of 12 cm is placed in a self-made flux testing device, after prepressing for 30min under 0.15MPa, the membrane flux tends to be stable, the pressure is reduced to 0.1MPa, and the pure water flux is the volume of water permeating in unit time. The flux value is the volume of water per membrane area per unit time, and the flux J ═ V/(a × t), where V is the volume of water 22 permeated (L), a is the membrane area (m), t is the permeation time, and J is units L/mh.
Static contamination test: the membrane is placed in a 1g/L BSA (bovine serum albumin) solution (pH 7.4), the adsorption balance is achieved after oscillation for 12 hours, the membrane is taken out, the concentration change before and after adsorption of the BSA solution is detected through an ultraviolet-visible spectrum, the BSA quality adsorbed on the surface of the membrane is calculated through the concentration change, the amount of BSA adsorbed in the unit area of the membrane is further calculated, the less the adsorption amount is, and the better the anti-fouling performance is.
And (3) testing the recovery rate of the secondary water flux of the membrane: and (3) placing the membrane in a filtering device, filtering pure water for 2 hours in sequence to obtain stable water flux J1, then replacing the feed liquid with 1g/L BSA solution, filtering for 2 hours until the flux is stable, taking out the membrane, washing with pure water, placing the membrane back into a testing mold, and measuring the stable flux of the pure water for 2 hours to obtain stable water flux J2. The ratio of the second water flux to the first water flux is the recovery rate of the second water flux (FRR value), and the higher the FRR value is, the better the anti-fouling performance is.
The results are shown in table 1:
TABLE 1
| Secondary water flux recovery of 1g/L BSA solution | |
| Example 1 | 91％ |
| Example 2 | 92％ |
| Example 3 | 94％ |
| Example 4 | 96％ |
| Example 5 | 95％ |
| Example 6 | 90％ |
| Example 7 | 93％ |
| Example 8 | 95％ |
| Example 9 | 97％ |
| Example 10 | 95％ |
| Example 11 | 94％ |
| Comparative example 1 | 83％ |
| Comparative example 2 | 85％ |
| Comparative example 3 | 76％ |
As can be seen from Table 1, examples 1 to 11 according to the present invention all showed better anti-fouling performance than comparative examples 1 to 3, wherein comparative example 3 showed the worst anti-fouling performance, indicating that the anti-fouling capability of other zwitterionic monomers was much smaller than that of sulfobetaine methacrylate.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A method for preparing a hydrophilic-hydrophobic composite membrane by grafting zwitterions on the surface is characterized by comprising the following steps:
(1) surface hydroxylation of PVDF (polyvinylidene fluoride) membrane:
putting the dried PVDF basal membrane and the Fenton solution into a reactor, carrying out Fenton reaction in a water bath at 45-55 ℃ for 0.5-2.5h, taking out the membrane after the reaction is finished, cleaning the membrane by using dilute sulfuric acid and deionized water, and finally drying the membrane in an oven to obtain a modified membrane PVDF-OH; the aperture of the PVDF basal membrane is 0.45 μm; the Fenton solution is prepared from FeSO 4 ·7H 2 O、H 2 O 2 Anhydrous ethanol and deionized water, the FeSO 4 ·7H 2 O、H 2 O 2 The mass ratio of the absolute ethyl alcohol to the deionized water is FeSO 4 ·7H 2 O∶H 2 O 2 Absolute ethyl alcohol and deionized water in the weight ratio of 1 to (1-1.6) to (38-43) to (47-53);
(2) preparation of the grafting solution:
adding ceric ammonium nitrate, N-methylene bisacrylamide, methacrylic acid sulfobetaine, nitric acid and pure water into a reactor in sequence, and uniformly mixing to prepare a grafting solution, wherein the molar ratio of the ceric ammonium nitrate to the N, N-methylene bisacrylamide to the methacrylic acid sulfobetaine to the nitric acid is 1: 1-1.3: 11-12: 3-3.5;
(3) preparing a hydrophilic-hydrophobic composite membrane:
putting the PVDF-OH membrane into the grafting solution, introducing nitrogen to deoxidize for 30-40min, sealing, reacting for 1-5h at 40-60 ℃, taking out the membrane after the reaction, washing the membrane with ethanol and deionized water, wherein the washing is specifically to wash the membrane with ethanol for 20-25h, then wash the membrane with deionized water for 46-50h, circularly wash the membrane for 2-3 times, and dry the membrane with blast air for 20-25h after the washing is finished, so as to obtain the hydrophilic-hydrophobic composite membrane PVDF-T.
2. The method for preparing the hydrophilic-hydrophobic composite membrane by grafting zwitterion on the surface according to claim 1, wherein the FeSO 4 ·7H 2 O、H 2 O 2 Anhydrous ethanol andthe mass ratio of the deionized water is FeSO 4 ·7H 2 O∶H 2 O 2 The ratio of absolute ethyl alcohol to deionized water is 1: 1.47: 40: 50.
3. The method for preparing a hydrophilic-hydrophobic composite membrane by surface grafting zwitterions according to claim 2, wherein the H is 2 O 2 Is 30 percent.
4. The method for preparing the hydrophilic-hydrophobic composite membrane by grafting the zwitterion on the surface according to claim 1, wherein the cleaning in the step (1) is specifically dilute sulfuric acid and deionized water alternate cleaning, more specifically, the dilute sulfuric acid is firstly cleaned, then the deionized water is cleaned, and the cleaning is circulated for 2-3 times.
5. The method for preparing the hydrophilic-hydrophobic composite membrane by grafting the zwitterion on the surface according to claim 1, wherein the temperature of the oven in the step (1) is 70-80 ℃.
6. The method for preparing a hydrophilic-hydrophobic composite membrane by surface grafting zwitterion according to claim 1, wherein the molar ratio of the ceric ammonium nitrate, the N, N-methylene bisacrylamide, the sulfobetaine methacrylate and the nitric acid in the step (2) is 1: 1.16: 11.6: 3.33.
7. The method for preparing a hydrophilic-hydrophobic composite membrane by surface grafting zwitterions according to claim 1, wherein the temperature of forced air drying in the step (3) is 40-50 ℃.
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