CN113069938B - Anti-pollution antibacterial PTFE (polytetrafluoroethylene) oil-water separation membrane and preparation method thereof - Google Patents
Anti-pollution antibacterial PTFE (polytetrafluoroethylene) oil-water separation membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-pollution antibacterial PTFE (polytetrafluoroethylene) oil-water separation membrane and a preparation method thereof, wherein the preparation method comprises the following steps: 1) reacting DL-homocysteine thiolactone hydrochloride with acryloyl chloride to prepare thiolactone acrylamide; 2) preparing a random copolymer of dimethylaminoethyl methacrylate and sultone acrylamide, wherein the number average molecular weight of the copolymer is 20000-50000 Da; 3) immersing a clean polytetrafluoroethylene membrane into a catecholamine/tris (hydroxymethyl) aminomethane solution for deposition for 4-24 h, and then cleaning and drying to obtain a deposited membrane; 4) dissolving glucosamine and copolymer in tris solution, immersing the deposited film in the solution for 24h, and then washing and drying to obtain a modified film; the anti-pollution antibacterial PTFE oil-water separation membrane has excellent hydrophilic performance and antibacterial performance, expands the application range of the polytetrafluoroethylene membrane, provides a new idea for the surface functional modification of the polymer membrane, is simple and convenient in operation process, and does not need special equipment.
Description
Technical Field
The invention relates to the technical field of oil-water separation, and particularly relates to an anti-pollution antibacterial PTFE oil-water separation membrane and a preparation method thereof.
Background
With the increase of global energy demand, frequent occurrence of oil spill accidents and rapid increase of discharge of industrial oily sewage, and the vigorous development of industries such as petroleum, natural gas, pharmacy, metallurgy and food, a large amount of oily wastewater needs to be treated. On the other hand, the rapidly growing population leads to an increasing scarcity of water resources. Therefore, the method has important significance for further treating the oily wastewater to achieve the recycling of water resources. The membrane separation technology has the characteristics of high flux, good interception performance and wide application range, and has great application prospect in the field of oil-water separation.
However, common oil-water separation membrane materials are generally not hydrophilic enough, such as polyvinylidene fluoride (PVDF), Polysulfone (PSF), Polyacrylonitrile (PAN), Polytetrafluoroethylene (PTFE), etc., and are liable to cause membrane contamination, thereby reducing the use efficiency of the membrane. The PTFE membrane material is easy to generate organic pollution and biological pollution due to the inherent hydrophobicity and low surface tension, thereby causing serious pore blocking phenomenon, reducing the filtering performance and prolonging the service life of the membrane. Therefore, modification of the PTFE membrane is an ideal choice for improving its contamination resistance, oil-water separation performance, and expanding its application range.
At present, the modification strategy is single, multiple pollution including organic pollution and biological pollution is difficult to deal with, and a simple and convenient method needs to be developed to realize multifunctional modification of a membrane material. Various methods have been used for surface modification of PTFE films, such as low pressure plasma treatment, atmospheric pressure plasma sputtering, particle beam irradiation, synchrotron radiation irradiation (SR), surface graft polymerization, and "wet" chemical treatment. Although these treatment methods greatly improve the anti-adhesion property and water-immersion property of the membrane surface, the above methods cannot simultaneously impart the anti-organic contamination and anti-biological contamination (sterilization) properties to the membrane material on the one hand, and often require special equipment on the other hand. The method combines the coating technology and the grafting chemical technology, simultaneously endows the PTFE membrane with sterilization and pollution resistance, has simple and easy operation, and can be easily realized in large-scale industrial application.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-pollution antibacterial PTFE oil-water separation membrane.
The invention also aims to provide the anti-pollution antibacterial PTFE oil-water separation membrane prepared by the preparation method.
Therefore, the technical scheme of the invention is as follows:
a preparation method of an anti-pollution antibacterial PTFE oil-water separation membrane comprises the following preparation steps:
s1, reacting DL-homocysteine thiolactone hydrochloride with acryloyl chloride to prepare thiolactone acrylamide;
s2, preparing a copolymer of dimethylaminoethyl methacrylate and sultone acrylamide, wherein the number average molecular weight of the copolymer is 20000-50000 Da;
s3, immersing the clean polytetrafluoroethylene membrane into a catecholamine/tris (hydroxymethyl) aminomethane solution for deposition for 4-24 h, and then washing and drying the polytetrafluoroethylene membrane by using deionized water to obtain a deposited membrane;
wherein the catecholamine is dopamine hydrochloride, norepinephrine or epinephrine;
s4, dissolving glucosamine and the copolymer prepared in the step S2 in Tris solution, immersing the deposition film prepared in the step S3 for 24 hours, and then washing and drying the deposition film by using ethanol and deionized water in sequence to obtain the modified film.
Further, the preparation method of sultone acrylamide of step S1 is:
s101, dissolving DL-homocysteine thiolactone hydrochloride in a mixed solvent obtained by mixing ethyl acetate and water, placing the mixed solvent in an ice water bath, stirring for 10min, then adding sodium bicarbonate, and stirring for 30min to obtain a mixed reaction solution;
s102, under the ice-water bath condition, dropwise adding acryloyl chloride into the mixed reaction solution, stirring for 30min, then removing the ice-water bath, and reacting for 12h at room temperature;
s103, washing the product obtained in the step S102 with brine, extracting with ethyl acetate for three times, and taking an organic layer;
s104, drying the obtained organic layer liquid by using anhydrous sodium sulfate, carrying out rotary evaporation, and crystallizing and purifying the obtained crude product in dichloromethane to obtain the white solid acrylamide sultone.
Preferably, in step S101, the volume ratio of ethyl acetate to water is 1: 1. The volume of the mixed solvent is 25-30 times of the weight of the DL-homocysteine thiolactone hydrochloride.
Preferably, the addition amount of the sodium bicarbonate is 4-5 times of the weight of the DL-homocysteine thiolactone hydrochloride.
Preferably, in step S101 and step S102, the mass ratio of DL-homocysteine thiolactone hydrochloride to acryloyl chloride is 1: 2.2.
Preferably, in step S103, the brine is a 1mol/L aqueous solution of sodium chloride.
Preferably, in step S103, the amount of brine used is the same as the amount of the mixed solvent used in step S101; the amount of ethyl acetate used is the same as the amount of the mixed solvent used in step S101.
Preferably, the preparation method of the copolymer of step S2 is:
s201, dissolving dimethylaminoethyl methacrylate, acrylamide thiolactone, azodiisobutyronitrile and cyanomethyl dodecyl trithiocarbonate in dioxane, dehydrating and degassing for 4-5 freeze-thaw cycles, and reacting at 65 ℃ for 12 hours in a nitrogen environment;
s202, transferring the reaction product liquid into an ice-water bath, and exposing the reaction product liquid to air to stop polymerization to obtain oily liquid;
s203, dissolving the oily liquid by using tetrahydrofuran, dropwise adding the oily liquid into n-hexane to obtain a precipitate product, and drying the precipitate product in vacuum to obtain the copolymer of dimethylaminoethyl methacrylate and sultone acrylamide.
Preferably, in step S201, the mass ratio of dimethylaminoethyl methacrylate, thiolactone acrylamide, azobisisobutyronitrile, cyanomethyl dodecyl trithiocarbonate is 43.9:10.9:0.07: 0.174.
Preferably, the specific implementation steps of step S3 are:
s301, respectively ultrasonically cleaning a polytetrafluoroethylene membrane for 15min by using ethanol and acetone in sequence to obtain a clean polytetrafluoroethylene membrane;
s302, immersing a clean polytetrafluoroethylene membrane into a catecholamine/tris (hydroxymethyl) aminomethane solution with the concentration of 2g/L, and placing the polytetrafluoroethylene membrane on a shaker to shake at a constant speed for 4 hours at room temperature;
wherein, the 2g/L catecholamine/tris solution is prepared by dissolving 2g catecholamine in 50mM tris solution with pH 8.5 per liter;
s303, repeatedly washing the membrane processed in the step S302 for three times by using deionized water, and placing the membrane on a shaking table to shake and clean the membrane in a pure water medium for 10 min; then taking out and placing in vacuum at 40 ℃ for drying to constant weight to prepare the deposition film.
Preferably, the specific implementation steps of step S4 are:
s401, dissolving glucosamine and the copolymer prepared in the step S2 in a tris solution to prepare a mixed solution with the glucosamine concentration of 2.4mmol/L and the copolymer concentration of 1.2 mmol/L;
s402, immersing the deposition film prepared in the step S3 into the solution prepared in the step S401, and shaking the deposition film on a shaking table for 24 hours at room temperature;
and S403, washing the membrane treated in the step S402 by using ethanol and deionized water for three times in sequence, and placing the membrane at 40 ℃ for vacuum drying until the weight is constant to obtain the modified membrane.
The anti-pollution antibacterial PTFE oil-water separation membrane prepared by the preparation method.
Compared with the prior art, the anti-pollution antibacterial PTFE oil-water separation membrane realizes the simultaneous introduction of the sugar-containing group and the tertiary amine group by introducing the thiolactone group on the membrane surface and subsequently carrying out the ring-opening reaction on thiolactone, so that the original membrane surface has excellent hydrophilic performance and antibacterial performance, the application range of the polytetrafluoroethylene membrane is expanded, a new thought is provided for the surface functional modification of the polymer membrane, the operation process is simple and convenient, and no special equipment is needed.
Drawings
FIG. 1 is a graph showing the results of the flux of PTFE-PDA24-PTla membrane prepared in example 4 of the present invention in the oil-water contamination test as a function of time;
FIG. 2 is a graph showing the results of the test of the bacteriostatic ratio of the PTFE-PDA24-PTla membrane prepared in example 4 of the present invention against different bacteria.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
Example 1
(1) Synthesis of acrylamide thiolactone:
adding a mixed solution of DL-homocysteine thiolactone hydrochloride (7.68g, 50mmol), 200mL of ethyl acetate and water (volume ratio is 1:1) into a three-neck flask, and placing the flask in an ice water bath to stir for 10 min; sodium bicarbonate (18.9g, 225mmol) was then added and stirred for 30 min; acryloyl chloride (10.1g, 110mmol) was then added dropwise thereto and stirred for 30 min; the ice-water bath was removed, the reaction was carried out at room temperature for 12 hours, and the resulting product was washed with 200mL of 1mol/L sodium chloride solution and extracted three times with ethyl acetate (200 mL/time), taking the organic layer each time; finally, drying the organic layer liquid obtained by extraction with anhydrous sodium sulfate, carrying out rotary evaporation, and crystallizing and purifying the obtained crude product in dichloromethane to obtain white solid acrylamide sultone (TlaAm);
(2) synthesis of P (DMAEMA-co-TlaAm) copolymer:
adding dimethylaminoethyl methacrylate (DMAEMA) (6.90g, 43.9mmol), acrylamide thiolactone (1.74g, 10.9mmol), azobisisobutyronitrile (11.8mg, 0.07mmol) and cyanomethyl dodecyl trithiocarbonate (176mg, 0.74mmol) into the same test tube, dissolving in 20mL dioxane, dehydrating and degassing through 4-5 freeze-thaw cycles, and subjecting to N2Reacting for 12 hours at 65 ℃ in the atmosphere; stopping reaction, immersing the test tube into an ice-water bath, and exposing the test tube to air to stop polymerization to obtain orange oily liquid; dissolving the oily liquid product with tetrahydrofuran, dropwise adding into n-hexane to obtain a precipitate product, and vacuum drying the precipitate product to obtain yellow powdery copolymer P (DMAEMA-co-TlaAm).
The number average molecular weight of copolymer P (DMAEMA-co-TlaAm) was 24100Da as determined by Gel Permeation Chromatography (GPC).
Comparative example 1
Different from the embodiment 1, in the step (2), the reactants are dehydrated and degassed through 4-5 freeze-thaw cycles, and then are placed at the temperature of 65 ℃ for reaction for 4 hours, namely, the reaction is stopped.
The number average molecular weight of copolymer P (DMAEMA-co-TlaAm) prepared by the preparation method of comparative example 1 was 1280Da as measured by Gel Permeation Chromatography (GPC).
Comparative example 2
Different from the embodiment 1, in the step (2), the reactants are dehydrated and degassed through 4-5 freeze-thaw cycles, and then are placed at the temperature of 65 ℃ for reaction for 24 hours, namely, the reaction is stopped.
The number average molecular weight of copolymer P (DMAEMA-co-TlaAm) prepared by the preparation method of comparative example 2 was 16651Da as measured by Gel Permeation Chromatography (GPC).
Example 2
An antifouling and antibacterial oil-water separation membrane is prepared based on the copolymer P (DMAEMA-co-TlaAm) prepared in example 1, and the preparation steps are as follows:
step one, sequentially and respectively ultrasonically cleaning a polytetrafluoroethylene membrane for 15min by using ethanol and acetone; then immersed in a 2g/L dopamine hydrochloride/Tris (pH 8.5, 50mM) solution and placed on a shaker at room temperature with constant shaking for 4 h; then repeatedly washing with deionized water for three times, placing on a shaking table, and washing in pure water for 10min in a shaking way; taking out, placing in vacuum at 40 ℃, and drying to constant weight to obtain a deposited film PTFE-PDA-4;
step two, dissolving glucosamine (0.0216g and 0.12mmol) and copolymer P (DMAEMA-co-TlaAm) (1.446g and 0.06mmol) in 50mL of Tris solution, then immersing the deposition membrane prepared in the step one into the solution, and placing the solution on a shaking table to shake for 24 hours at room temperature; then, the mixture is respectively washed 3 times by ethanol and deionized water, and is placed at 40 ℃ for vacuum drying until the weight is constant, and the modified film PTFE-PDA4-PTla is prepared.
Through tests, the modified membrane (PTFE-PDA4-PTla) prepared by the method has the pure water flux of 3670 L.m < -2 > h < -1 > bar < -1 > under 0.1MPa, the flux recovery rate of 100 percent, the oil-water separation efficiency of 97.5 percent and the bacteriostasis rate of 99 percent on staphylococcus aureus.
Example 3
An antifouling and antibacterial oil-water separation membrane is prepared based on the copolymer P (DMAEMA-co-TlaAm) prepared in example 1, and the preparation steps are as follows:
step one, sequentially and respectively ultrasonically cleaning a polytetrafluoroethylene membrane for 15min by using ethanol and acetone; then immersed in a 2g/L dopamine hydrochloride/Tris (pH 8.5, 50mM) solution and placed on a shaker at room temperature with constant shaking for 12 h; then repeatedly washing with deionized water for three times, placing on a shaking table, and washing in pure water for 10min in a shaking way; taking out, placing in vacuum at 40 ℃, drying to constant weight, and preparing a deposition film which is PTFE-PDA-12;
step two, dissolving glucosamine (0.0216g and 0.12mmol) and copolymer P (DMAEMA-co-TlaAm) (1.446g and 0.06mmol) in 50mL of Tris solution, then immersing the deposition membrane prepared in the step one into the solution, and placing the solution on a shaking table to shake for 24 hours at room temperature; then, the mixture is respectively washed 3 times by ethanol and deionized water, and is placed at 40 ℃ for vacuum drying until the weight is constant, and the modified film PTFE-PDA12-PTla is prepared.
Through tests, the pure water flux of the modified membrane (PTFE-PDA12-PTla) prepared by the method is 2490 L.m < -2 > h < -1 > bar < -1 > under 0.1MPa, the flux recovery rate is 100%, the oil-water separation efficiency is 97.5%, and the bacteriostasis rate to staphylococcus aureus is 99%.
Example 4
An antifouling and antibacterial oil-water separation membrane is prepared based on the copolymer P (DMAEMA-co-TlaAm) prepared in example 1, and the preparation steps are as follows:
step one, sequentially and respectively ultrasonically cleaning a polytetrafluoroethylene membrane for 15min by using ethanol and acetone; then immersed in a 2g/L dopamine hydrochloride/Tris (pH 8.5, 50mM) solution and placed on a shaker at room temperature with constant shaking for 24 h; then repeatedly washing with deionized water for three times, placing on a shaking table, and washing in pure water for 10min in a shaking way; taking out, placing in vacuum at 40 ℃, drying to constant weight, and preparing a deposition film which is PTFE-PDA-24;
step two, dissolving glucosamine (0.0216g and 0.12mmol) and copolymer P (DMAEMA-co-TlaAm) (1.446g and 0.06mmol) in 50mL of Tris solution, then immersing the deposition membrane prepared in the step one into the solution, and placing the solution on a shaking table to shake for 24 hours at room temperature; then, the mixture is respectively washed 3 times by ethanol and deionized water, and is placed at 40 ℃ for vacuum drying until the weight is constant, and the modified film PTFE-PDA24-PTla is prepared.
Tests show that the modified membrane (PTFE-PDA24-PTla) prepared by the method has the pure water flux of 1080 L.m < -2 > h < -1 > bar < -1 > under 0.1MPa, the flux recovery rate of 100 percent, the oil-water separation efficiency of 97.4 percent and the bacteriostasis rate of 99 percent on staphylococcus aureus.
And (3) performance testing:
the modified films prepared in examples 2 to 4 were subjected to an antifouling property test, an oil-water separation efficiency test, and an antibacterial property test in this order.
(1) Antifouling performance test the antifouling performance test was carried out as follows: adopting a self-made device, utilizing a cross flow mode, and judging the anti-fouling performance of the membrane material by analyzing the change of the water flux of the membrane and the recovery rate of the water flux under certain pressureAnd (5) dyeing the fabric. The specific test steps are as follows: preparing an oil-water emulsion, adding 10mL of isoparaffin isoparM into 990mL of deionized water, adding 30mg of Tween-80 as an emulsifier, and stirring at 2000rpm for 5h to obtain the required emulsion; cutting the original membrane and the modified membrane into a circle with the diameter of 2.8cm, placing the circle in a membrane test pool, connecting pure water, stably pre-pressing for 30min under 0.2MPa, reducing the pressure to 0.1MPa after the pressure is stable, testing the volume of the pure water passing through every 3min, and testing the volume of the pure water passing through every 3min according to a formula JwThe pure water flux was calculated as V/(S · T · P).
Then, pure water is replaced by prepared oil-water emulsion, the pressure is kept at 0.1MPa, and the change of water flux is tested once every 3 min; after five tests, the membrane was rinsed with deionized water and after about 25min, changed to an oil-water emulsion, the water flux was tested as before, and this was repeated three times. The change of the oil-water pollution resistance before and after the membrane modification is estimated according to the change of the water flux of the membrane and the change of the recovery rate of the water flux, and the formula FRR is Jw2/Jw1X 100% the flux recovery was calculated.
(2) Testing oil-water separation efficiency:
the experiment adopts a self-made oil-water separation device in a laboratory and tests in a cross flow mode. The experimental conditions were as follows: the testing pressure is 0.1MPa, and the effective area of the membrane sample is 5.85cm2The separation efficiency R of the membrane in oil-water separation is represented by testing the TOC values of the stock solution and the separated solution.
Wherein, C2Represents the TOC concentration value, C, in the solution after oil-water separation1Represents the TOC concentration value of the solution before oil-water separation.
(3) And (3) testing antibacterial performance: the test is carried out by adopting an oscillation method suitable for the contact type antibacterial material, escherichia coli and staphylococcus aureus are used as antibacterial objects, and the antibacterial effect of the membrane is compared according to the bacterial colony number of the contact culture of the original membrane and the modified membrane.
The test results are shown in table 1.
Table 1:
from the test results in the table 1, the modified membranes prepared in the embodiments 2 to 4 have high flux, good antifouling performance and antibacterial performance, the flux recovery rate is about 100%, the bacteriostatic rate of staphylococcus aureus is more than or equal to 99%, and the range of the functionalized modification of the surfaces of the polymer membranes is widened.
FIG. 1 is a graph showing the results of the flux of the PTFE-PDA24-PTla membrane prepared in example 4 in the oil-water contamination test as a function of time. From the test results of fig. 1, it can be seen that the water flux of the modified membrane prepared by the present application is significantly higher than that of the Polytetrafluoroethylene (PTFE) raw membrane, and after washing, the modified membrane can always maintain high antifouling performance for a long time (100 min).
FIG. 2 is a graph showing the results of the test of the bacteriostatic rate of the PTFE-PDA24-PTla membrane prepared in example 4 against Staphylococcus aureus and Escherichia coli. As can be seen from the test results of FIG. 2, the modified membrane prepared by the method has an obvious bacteriostatic effect on Staphylococcus aureus, and the bacteriostatic rate is greater than or equal to 99%; the antibacterial agent has a high antibacterial effect on escherichia coli, and the antibacterial rate can reach 60%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of an anti-pollution antibacterial PTFE oil-water separation membrane is characterized by comprising the following steps:
s1, reacting DL-homocysteine thiolactone hydrochloride with acryloyl chloride to prepare thiolactone acrylamide;
s2, preparing a random copolymer of dimethylaminoethyl methacrylate and thiolactone acrylamide, wherein the number average molecular weight of the copolymer is 20000-50000 Da;
s3, immersing the clean polytetrafluoroethylene membrane into a catecholamine/tris (hydroxymethyl) aminomethane solution for deposition for 4-24 h, and then washing and drying the polytetrafluoroethylene membrane by using deionized water to obtain a deposited membrane;
wherein the catecholamine is dopamine hydrochloride, norepinephrine or epinephrine;
s4, dissolving glucosamine and the copolymer prepared in the step S2 in a tris solution, immersing the deposited film prepared in the step S3 for 24 hours, and then washing and drying the film by using ethanol and deionized water in sequence to obtain the modified film.
2. The preparation method of the anti-pollution antibacterial PTFE oil-water separation membrane according to claim 1, wherein the preparation method of the sultone acrylamide of the step S1 comprises the following steps:
s101, dissolving DL-homocysteine thiolactone hydrochloride in a mixed solvent obtained by mixing ethyl acetate and water, placing the mixed solvent in an ice water bath, stirring for 10min, then adding sodium bicarbonate, and stirring for 30min to obtain a mixed reaction solution;
s102, under the ice-water bath condition, dropwise adding acryloyl chloride into the mixed reaction solution, stirring for 30min, then removing the ice-water bath, and reacting for 12h at room temperature;
s103, washing the product obtained in the step S102 with brine, extracting with ethyl acetate for three times, and taking an organic layer;
s104, drying the obtained organic layer liquid by using anhydrous sodium sulfate, carrying out rotary evaporation, and crystallizing and purifying the obtained crude product in dichloromethane to obtain the white solid acrylamide sultone.
3. The method for preparing an anti-pollution antibacterial PTFE oil-water separation membrane according to claim 2, wherein in step S101, the volume ratio of ethyl acetate to water is 1: 1.
4. The method for preparing an anti-pollution antibacterial PTFE oil-water separation membrane according to claim 1, wherein in the steps S101 and S102, the mass ratio of DL-homocysteine thiolactone hydrochloride to acryloyl chloride is 1: 2.2.
5. The method for preparing an anti-pollution antibacterial PTFE oil-water separation membrane according to claim 1, wherein in step S103, the brine is 1mol/L sodium chloride aqueous solution.
6. The method for preparing an anti-pollution antibacterial PTFE oil-water separation membrane according to claim 1, wherein the copolymer obtained in step S2 is prepared by the following steps:
s201, dissolving dimethylaminoethyl methacrylate, acrylamide thiolactone, azodiisobutyronitrile and cyanomethyl dodecyl trithiocarbonate in dioxane, dehydrating and degassing for 4-5 freeze-thaw cycles, and reacting at 65 ℃ for 12 hours in a nitrogen environment;
s202, transferring the reaction product liquid into an ice-water bath, and exposing the reaction product liquid to air to stop polymerization to obtain oily liquid;
s203, dissolving the oily liquid by using tetrahydrofuran, dropwise adding the oily liquid into n-hexane to obtain a precipitate product, and drying the precipitate product in vacuum to obtain the random copolymer of dimethylaminoethyl methacrylate and sultone acrylamide.
7. The method of claim 6, wherein in step S201, the weight ratio of dimethylaminoethyl methacrylate, sultone acrylamide, azobisisobutyronitrile, cyanomethyl dodecyl trithiocarbonate is 43.9:10.9:0.07: 0.174.
8. The preparation method of the anti-pollution antibacterial PTFE oil-water separation membrane according to claim 1, wherein the step S3 is implemented by the following steps:
s301, respectively ultrasonically cleaning a polytetrafluoroethylene membrane for 15min by using ethanol and acetone in sequence to obtain a clean polytetrafluoroethylene membrane;
s302, immersing a clean polytetrafluoroethylene membrane into a catecholamine/tris (hydroxymethyl) aminomethane solution with the concentration of 2g/L, and placing the polytetrafluoroethylene membrane on a shaker to shake at a constant speed for 4 hours at room temperature;
wherein, the 2g/L catecholamine/tris solution is prepared by dissolving 2g catecholamine in 50mM tris solution with pH 8.5 per liter;
s303, repeatedly washing the membrane processed in the step S302 for three times by using deionized water, and placing the membrane on a shaking table to shake and clean the membrane in a pure water medium for 10 min; then taking out and placing in vacuum at 40 ℃ for drying to constant weight to prepare the deposition film.
9. The preparation method of the anti-pollution antibacterial PTFE oil-water separation membrane according to claim 1, wherein the step S4 is implemented by the following steps:
s401, dissolving glucosamine and the copolymer prepared in the step S2 in a tris solution to prepare a mixed solution with the glucosamine concentration of 2.4mmol/L and the copolymer concentration of 1.2 mmol/L;
s402, immersing the deposition film prepared in the step S3 into the solution prepared in the step S401, and shaking the deposition film on a shaking table for 24 hours at room temperature;
and S403, washing the membrane treated in the step S402 with ethanol and deionized water for three times, and placing the membrane at 40 ℃ for vacuum drying until the weight is constant to obtain the modified membrane.
10. An anti-pollution antibacterial PTFE oil-water separation membrane prepared by the preparation method of any one of claims 1-9.
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| CN108404684A (en) * | 2018-03-14 | 2018-08-17 | 同济大学 | A kind of preparation method of the anti-pollution PVDF seperation film of super hydrophilic modification |
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