CN108404684B - Preparation method of super-hydrophilic modified anti-pollution PVDF separation membrane - Google Patents
Preparation method of super-hydrophilic modified anti-pollution PVDF separation membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
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Abstract
The invention relates to a preparation method of a super-hydrophilic modified anti-pollution PVDF separation membrane, which comprises the steps of treating the surface of PVDF with an alkaline solution to generate double bonds, and crosslinking hyperbranched polyethyleneimine on the surface of the PVDF through chemical bonds through amino-alkene addition reaction and amino-epoxy ring-opening reaction; and (3) carrying out amino-epoxy ring-opening reaction on the hyperbranched polyethyleneimine on the surface of the membrane and an epoxy propanol solution to obtain the PVDF membrane with the anti-pollution performance. The modified PVDF membrane has a large number of active groups such as amino groups, hydroxyl groups and the like, so that the hydrophilicity of the surface of the membrane is greatly improved. The invention solves the problem of stronger hydrophobicity of the PVDF separation membrane, prevents pollutants from being easily adsorbed and deposited on the surface or in the pores of the membrane in the application process, improves the anti-pollution capacity of the membrane and prolongs the service life of the membrane. The invention adopts a chemical method for modification, has mild conditions, simple and convenient operation, no need of expensive instruments, easy popularization, firm obtained product, good pollution resistance and potential wide application value in the field of water treatment.
Description
Technical Field
The invention relates to a preparation method of a super-hydrophilic modified anti-pollution PVDF separation membrane, belonging to the field of water treatment science and technology.
Background
The membrane separation technology has the advantages of accurate separation, high-efficiency purification, environmental protection and the like, and is widely applied to the field of membrane sewage treatment. Polyvinylidene fluoride (PVDF) is a membrane material with excellent performance, and has the characteristics of high strength, high temperature resistance, chemical corrosion resistance and the like. However, in the application process of the PVDF membrane separation technology, the PVDF membrane has low surface energy and extremely strong hydrophobicity, so that the PVDF membrane has low flux and is easy to pollute, and the application of the PVDF membrane in the field of membrane sewage treatment is severely limited. Therefore, hydrophilic modification of the PVDF separation membrane to improve the anti-pollution performance of the membrane and prolong the service life of the membrane has become a hotspot in the membrane preparation field.
At present, a great number of reports on pollution resistance modification of PVDF separation membranes exist. The surface grafting modification method for realizing pollution control of the PVDF membrane by constructing an anti-pollution functional layer interface on the membrane surface is widely concerned by researchers in the field of PVDF membrane preparation due to the advantages of rich modification method, high modification efficiency and the like. For example, in patent CN107096398A, potassium persulfate is used as a catalyst, 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) reacts with Methyl Methacrylate (MMA) to generate an amphiphilic copolymer, a PVDF membrane is dehydrofluorinated, and the amphiphilic copolymer is used as a grafting monomer to improve the hydrophilicity of the PVDF membrane and improve the anti-pollution performance of the membrane. The invention patent CN104043351A adopts an ultraviolet radiation grafting method, takes ceric sulfate as an initiator and maleic anhydride as a grafting monomer, and grafts the ceric sulfate and the maleic anhydride on the surface of a PVDF ultrafiltration membrane to achieve the aim of pollution resistance. In patent CN103736407A, after the PVDF microfiltration membrane is pretreated by removing hydrogen fluoride, dibenzoyl peroxide is used as an initiator, naphthenic acid diamond or zernic acid diamond is used as an accelerator, and maleic anhydride is used as a grafting monomer, so that the hydrophilic anti-pollution membrane is obtained. However, the modification method is mostly to graft a linear polymer modifier such as a nonionic polymer and a polyethylene glycol polymer on the surface of the PVDF membrane material, and the modification is influenced by the structure of a linear molecular chain (steric effect), and the modification quantity of hydrophilic groups is small, so that the coverage rate of the membrane surface of the modifier is low, and the improvement of the anti-pollution efficiency is limited; in addition, the above modification method is complex and has harsh reaction conditions, which are difficult to meet the requirements of commercial production.
The hyperbranched polyethyleneimine is used as a polymer which is highly branched and has a large number of amino active groups at the branched end, and has higher anti-pollution efficiency than a linear analogue of the hyperbranched polyethyleneimine under the same grafting concentration. The method utilizes hyperbranched polyethyleneimine as a carrier, introduces a large number of amino active groups onto the surface of the membrane to increase the hydrophilicity of the membrane, and introduces hydroxyl with negative charge at the tail end of the hyperbranched polyethyleneimine through a ring-opening reaction to further improve the hydrophilicity of the surface of the membrane and simultaneously improve the electronegativity of the surface of the membrane, thereby realizing the super-hydrophilic modification of the surface of the membrane and forming the PVDF separation membrane with an anti-pollution effect. The method is simple to operate and easy to control, the prepared anti-pollution layer is firm and efficient, the problem of membrane pollution in the use process of a membrane separation technology can be effectively solved, and technical support is provided for the application of the membrane material in the fields of water treatment and the like.
Disclosure of Invention
The invention aims to solve the problem of strong hydrophobicity of the existing PVDF membrane and provides a preparation method of a super-hydrophilic modified anti-pollution PVDF separation membrane.
According to the preparation method of the super-hydrophilic modified PVDF separation membrane, the surface of the modified separation membrane can obviously improve the surface hydrophilicity of the membrane, reduce the adhesion and deposition of protein and polysaccharide on the surface of the membrane, and has obvious pollution resistance effect.
In order to achieve the purpose, the invention provides a preparation method of a super-hydrophilic modified anti-pollution PVDF separation membrane, which is prepared by crosslinking hyperbranched polyethyleneimine by using chemical bonds, crosslinking epoxypropanol by ring-opening action and performing surface modification, and comprises the following specific steps:
(1) adding diamine into sodium carbonate buffer solution with pH of 11.0; the mass concentration of the diamine solution is 8.0-24.0%;
(2) soaking a PVDF separation membrane serving as a base membrane into the solution obtained in the step (1), reacting for 10-12 hours at the temperature of 20-30 ℃ at 200-300 rpm, performing amino-alkene addition reaction to form an ammonia salt compound layer on the surface of the PVDF separation membrane to obtain an activated PVDF separation membrane, and washing the activated PVDF separation membrane for later use;
(3) soaking the PVDF separation membrane obtained in the step (2) in an ethanol solution of epoxy chloropropane, adding a catalyst under the protection of nitrogen, reacting for 5-7 h at 55-65 ℃ at 100-200 rpm, then dropwise adding a sodium hydroxide solution, continuing to react for 3-5 h at 40-50 ℃ at 100-200 rpm, forming an epoxy compound layer on the surface of the PVDF separation membrane by a phase transfer catalysis method, and washing with ethanol and deionized water for later use; the mass concentration of the epichlorohydrin solution is 1.0-3.0%; the mass concentration of the catalyst is 0.01-0.03; the catalyst is a quaternary ammonium chloride catalyst; the concentration of the sodium hydroxide solution is 0.01-0.03%;
(4) reacting the hyperbranched polyethyleneimine ethanol solution with the PVDF separation membrane obtained in the step (3) at 70-90 ℃ for 24-36 h, crosslinking hyperbranched polyethyleneimine to the surface of the PVDF separation membrane obtained in the step (3) through a chemical bond, and washing with ethanol and deionized water for later use; the mass fraction of the hyperbranched polyethyleneimine is 2.5-7.5%;
(5) immersing the PVDF separation membrane obtained in the step (4) in a methanol solution, dropwise adding epoxy propanol, reacting for 10-12 h at 20-30 ℃ at 200-300 rpm, and carrying out an amino-epoxy ring opening reaction to cover the terminal amino group of the hyperbranched polyethyleneimine layer on the surface of the PVDF separation membrane by a hydroxyl group to form a super-hydrophilic anti-pollution PVDF separation membrane material; the mass fraction of the epoxypropanol is 0.1-5 percent;
(6) and after the reaction is finished, taking out the super-hydrophilic anti-pollution PVDF separation membrane material, washing the membrane material with ethanol and deionized water, and drying the membrane material to obtain the PVDF separation membrane with the anti-pollution performance.
In the invention, the diamine in the step (1) is one or more of propane diamine, butane diamine or pentane diamine.
In the invention, the chlorinated quaternary ammonium salt catalyst in the step (3) is any one of benzyltriethylammonium chloride, hexadecyltrimethylammonium chloride or tetrabutylammonium chloride.
In the invention, the PVDF separation membrane in the step (3) is soaked in the solution completely, and the surface to be modified is upward.
The invention has the beneficial effects that: compared with the prior art, the membrane preparation method provided by the invention has the advantages that the hyperbranched polymer with amino active groups is fixed on the surface of the membrane through surface modification, and the epoxypropanol is crosslinked through a chemical bond under the action of ring opening, so that the surface of the membrane contains a large number of hydrophilic groups such as hydroxyl, amino and the like, super-hydrophilic modification is successfully carried out, and the anti-pollution performance of the membrane is improved. The antibacterial and anti-pollution modified PVDF separation membrane prepared by the method has the following advantages:
(1) the method takes hyperbranched polyethyleneimine as a carrier layer, improves the anti-pollution performance of the surface of the membrane by crosslinking epoxypropanol through chemical bonds, and has stable and durable hydrophilic performance and obviously increased anti-pollution performance;
(2) the surface of the hydrophilic modified PVDF separation membrane has a large number of hydroxyl groups, the binding capacity to water molecules is stronger than that of the traditional linear polyethylene glycol derivative, the hydrophilic modified PVDF separation membrane has obvious anti-adhesion effect on pollutants such as protein, polysaccharide and the like, and the anti-pollution performance is durable;
(3) the hyperbranched polyethyleneimine is cheap and easy to obtain, has a large number of active amino groups on the surface, and is a good carrier for various modifications;
(4) the preparation method has the advantages of mild film preparation conditions, easy operation, low equipment cost, good controllability and easy industrial implementation.
Drawings
FIG. 1 shows the films P0, P-NH obtained in example 12P-EPI, P-HPEI and P-HPEI-GLY.
FIG. 2 is a graph of the clear water flux of the films P0 and P-HPEI-GLY obtained in example 1.
FIG. 3 is a CLSM image of protein and polysaccharide after 3h of contact with the membrane P0 and P-HPEI-GLY prepared in example 1, the stained part being protein/polysaccharide. Panel (A) is a CLSM profile of a protein after 3h of contact with the membrane P0 obtained in example 1, panel (B) is a CLSM profile of a protein after 3h of contact with the membrane P-HPEI-GLY obtained in example 1, panel (C) is a CLSM profile of a polysaccharide after 3h of contact with the membrane P obtained in example 1, and panel (D) is a CLSM profile of a polysaccharide after 3h of contact with the membrane P-HPEI-GLY obtained in example 1.
FIG. 4 is a graph showing the statistics of the dynamic resistance of the P0 and P-HPEI-GLY films prepared in example 1 to protein and polysaccharide contamination. FIG. A is a graph showing comparison of FRR, IFR, and RFR values of the membrane P0 and P-HPEI-GLY obtained in example 1 after dead-end filtration for 190min, with protein as a contaminant, and FIG. B is a graph showing comparison of FRR, IFR, and RFR values of the membrane P0 and P-HPEI-GLY obtained in example 1 after dead-end filtration for 190min, with polysaccharide as a contaminant.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
and (3) soaking the PVDF separation membrane in clear water for 24 hours to remove impurities (marked as P0) on the surface of the PVDF separation membrane. The pretreated isolate membrane was placed in a teflon closed box (single-sided reaction box), 1M 1, 4-butanediamine was dissolved in sodium carbonate buffer (pH 11.0) and reacted at 25 ℃ for 12h at 200rpm until a light yellow ammonium salt compound layer appeared on the membrane. Then alternately cleaning the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the PVDF separation membrane (marked as P-NH) modified by the first step2). The obtained membrane P-NH2The mixture is immersed in 150mL of absolute ethyl alcohol with the front side facing upwards, 3mL of epoxy chloropropane is dripped into the absolute ethyl alcohol, the device is protected by nitrogen filling, 40mg of benzyltriethylammonium chloride is slowly added, the mixture reacts for 5 hours at the temperature of 65 ℃ at the rpm of 100, 5mL of 0.06M sodium hydroxide solution is dripped into the mixture, and the reaction continues for 3 hours at the temperature of 40 ℃ at the rpm of 100. And then alternately washing the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the PVDF separation membrane (marked as P-EPI) crosslinked by epoxy compounds. The obtained membrane P-EPI is soaked in 30g/L ethanol solution of hyperbranched polyethyleneimine (weight average molecular weight is 10,000g/mol), and the reaction is carried out for 24h at 100rpm and 85 ℃, so that the hyperbranched polyethyleneimine is crosslinked to the surface of the PVDF separation membrane through chemical bonds. And then alternately cleaning the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the hyperbranched polyethyleneimine crosslinked PVDF (marked as P-HPEI). Immersing a single surface of the hyperbranched polyethyleneimine crosslinked PVDF separation membrane into a methanol solution, dropwise adding 0.5mL of epoxy propanol, reacting for 10h at the temperature of 25 ℃ and at the rpm of 250, and fixing the epoxy propanol on the surface of the hyperbranched polyethyleneimine through a chemical bond. And then alternately cleaning the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the super-hydrophilic anti-pollution PVDF separation membrane (marked as P-HPEI-GLY).
Example 2:
and (3) soaking the PVDF separation membrane in clear water for 24 hours to remove impurities (marked as P0) on the surface of the PVDF separation membrane. Placing the pretreated isolate membrane in a polytetrafluoroethylene closed box (single-sided reaction box), dissolving 1M 1, 4-pentanediamine in sodium carbonate buffer solution (adjusting pH to 11.0), placing in a shaking table, reacting at 25 deg.C for 12h at 200rpm until the membrane is completely removedA yellowish ammonium salt compound layer appeared. Then alternately cleaning the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the PVDF separation membrane (marked as P-NH) modified by the first step2). The obtained membrane P-NH2The mixture is immersed in 150mL of absolute ethyl alcohol with the front side facing upwards, 3mL of epoxy chloropropane is dripped into the absolute ethyl alcohol, the device is protected by nitrogen filling, 40mg of benzyltriethylammonium chloride is slowly added, the mixture reacts for 5 hours at the temperature of 65 ℃ at the rpm of 100, 5mL of 0.06M sodium hydroxide solution is dripped into the mixture, and the reaction continues for 3 hours at the temperature of 40 ℃ at the rpm of 100. And then alternately washing the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the PVDF separation membrane (marked as P-EPI) crosslinked by epoxy compounds. The obtained membrane P-EPI is soaked in 30g/L ethanol solution of hyperbranched polyethyleneimine (with the weight-average molecular weight of 60,000g/mol), and the reaction is carried out for 24h at 100rpm and 85 ℃, so that the hyperbranched polyethyleneimine is crosslinked to the surface of the PVDF separation membrane through chemical bonds. And then alternately cleaning the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the hyperbranched polyethyleneimine crosslinked PVDF (marked as P-HPEI). Immersing a single surface of the hyperbranched polyethyleneimine crosslinked PVDF separation membrane into a methanol solution, dropwise adding 0.5mL of epoxy propanol, reacting for 10h at the temperature of 25 ℃ and at the rpm of 250, and fixing the epoxy propanol on the surface of the hyperbranched polyethyleneimine through a chemical bond. And then alternately cleaning the membrane by using water and ethanol for 24 hours, and drying the membrane in vacuum at the temperature of 40 ℃ to obtain the super-hydrophilic anti-pollution PVDF separation membrane (marked as P-HPEI-GLY).
Example 3:
contact angle test: and testing the contact angle of water on the surface of the PVDF film by using a contact angle tester.
The contact angle of the film P0 obtained in example 1 was 85-95 degrees, and the contact angles of the modified films P-HPEI and P-HPEI-GLY were significantly reduced to 30-40 degrees compared with the contact angle of the film P0 and reduced to 0 degree within 15s, which proves that the modified film had good hydrophilicity.
Example 4:
and (3) clear water flux test: the membranes P0 and P-HPEI-GLY prepared in example 1 were selected for dead-end filtration under 20kPa, the inlet water was deionized water, and the clear water flux was recorded and calculated.
Tests prove that the clear water flux of the membrane P0 obtained in example 1 is significantly smaller than that of the modified membrane P-HPEI-GLY, and the modified membrane has good hydrophilicity and is consistent with a contact angle test.
Example 5:
static anti-protein/polysaccharide adsorption test: the protein/polysaccharide resisting experiment of the membrane of the invention uses bovine serum albumin PBS solution and sodium alginate water solution, the concentration is 50 mg/L. The PVDF raw film P0 and the anti-contamination PVDF film P-HPEI-GLY in example 1 were cut into 1X 1cm2The membrane was sized and immersed in 5mL of protein/polysaccharide solution, shaken in the dark at 37 ℃ for 3h, removed and washed 2 times with PBS/DI water. The patches were placed on a glass slide and stained with Fluorescein Isothiocyanate (FITC)/concanavalin A (Con A) and incubated at 37 ℃ for 0.5h in the dark. The stained patches were washed 2 times with PBS/DI water and mounted for observation using a Confocal Laser Scanning Microscope (CLSM).
It can be seen from CLSM analysis that the content of protein and polysaccharide contaminants on the anti-fouling PVDF membrane P-HPEI-GLY is significantly less than that of the original membrane P0, indicating that the membrane P-HPEI-GLY has a significant anti-adhesion effect.
Example 6:
dynamic anti-protein/polysaccharide assay: the membranes P0 and P-HPEI-GLY prepared in example 1 were each selected for dead-end filtration at 20kPa, and the water inlet procedure was 20min pure water-60 min protein/polysaccharide solution-30 min pure water for backwash, for 2 cycles in total. The decay of the flux of both was recorded over time. The anti-fouling performance of the membrane was measured by the water Flux Recovery Ratio (FRR), the irreversible water flux reduction ratio (IFR), and the Relative Fouling Ratio (RFR). The calculation formula of the three is as follows:
wherein, JrRepresents the flux recovered after the membrane was back-washed, J0Denotes the initial flux of the membrane, JpIndicating a stable water flux after 60min of membrane fouling.
Tests show that after the membrane P-HPEI-GLY is polluted by protein or polysaccharide, the water flux recovery ratio is obviously higher than that of the original membrane P0, and the irreversible water flux ratio and the relative pollution ratio are obviously lower than those of the original membrane P0, which shows that the modified membrane is not easy to be polluted, easy to clean and good in anti-pollution performance.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. A preparation method of a super-hydrophilic modified anti-pollution PVDF separation membrane is characterized by comprising the following specific steps:
(1) adding diamine into sodium carbonate buffer solution with pH of 11.0; the mass concentration of the diamine solution is 8.0-24.0%;
(2) soaking a PVDF separation membrane serving as a base membrane into the solution obtained in the step (1), reacting for 10-12 hours at the speed of 200-300 rpm and the temperature of 20-30 ℃, forming an ammonia salt compound layer on the surface of the PVDF separation membrane through amino-alkene addition reaction to obtain an activated PVDF separation membrane, and washing the activated PVDF separation membrane for later use;
(3) soaking the PVDF separation membrane obtained in the step (2) in an ethanol solution of epoxy chloropropane, adding a catalyst under the protection of nitrogen, reacting for 5-7 h at 55-65 ℃ at 100-200 rpm, then dropwise adding a sodium hydroxide solution, continuously reacting for 3-5 h at 40-50 ℃ at 100-200 rpm, forming an epoxy compound layer on the surface of the PVDF separation membrane by a phase transfer catalysis method, and washing with ethanol and deionized water for later use; the mass concentration of the epichlorohydrin solution is 1.0-3.0%; the mass concentration of the catalyst is 0.01-0.03, and the catalyst is a chlorinated quaternary ammonium salt catalyst; the concentration of the sodium hydroxide solution is 0.01-0.03%;
(4) reacting the hyperbranched polyethyleneimine ethanol solution with the PVDF separation membrane obtained in the step (3) at 70-90 ℃ for 24-36 h, crosslinking hyperbranched polyethyleneimine to the surface of the PVDF separation membrane obtained in the step (3) through a chemical bond, and washing with ethanol and deionized water for later use; the mass fraction of the hyperbranched polyethyleneimine is 2.5-7.5%;
(5) immersing the PVDF separation membrane obtained in the step (4) in a methanol solution, dropwise adding epoxy propanol, reacting for 10-12 h at 20-30 ℃ at 200-300 rpm, and carrying out an amino-epoxy ring opening reaction to cover the terminal amino group of the hyperbranched polyethyleneimine layer on the surface of the PVDF separation membrane by a hydroxyl group to form a super-hydrophilic anti-pollution PVDF separation membrane material; the mass fraction of the epoxypropanol is 0.1-5 percent;
(6) and after the reaction is finished, taking out the super-hydrophilic anti-pollution PVDF separation membrane material, washing the membrane material with ethanol and deionized water, and drying the membrane material to obtain the PVDF separation membrane with the anti-pollution performance.
2. The method for preparing an anti-pollution PVDF separation membrane as defined in claim 1, wherein the diamine in step (1) is one or more of propane diamine, butane diamine or pentane diamine.
3. The method for preparing an anti-pollution PVDF separation membrane as defined in claim 1, wherein the quaternary ammonium chloride catalyst in step (3) is any one of benzyltriethylammonium chloride, cetyltrimethylammonium chloride or tetrabutylammonium chloride.
4. The method for preparing an anti-pollution PVDF separation membrane as defined in claim 1, wherein the PVDF separation membrane in step (3) is soaked in the solution with the modified surface facing upwards.
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| CN114288878B (en) * | 2021-12-07 | 2023-02-07 | 武汉工程大学 | Hydrophilic modified PVDF membrane and green in-situ covalent hydrophilic modification method thereof |
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| CN101596422B (en) * | 2009-07-07 | 2011-08-10 | 浙江大学 | Method for preparing polyvinylidene fluoride affinity membrane using amino acid as ligand |
| CN104524986A (en) * | 2014-12-08 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of hydrophilic antimicrobial film of which surface is coated with dopamine and polyethyleneimine cations |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115569536A (en) * | 2022-09-28 | 2023-01-06 | 浙江大学 | Anti-pollution ultrafiltration membrane and preparation method and application thereof |
| CN115569536B (en) * | 2022-09-28 | 2023-04-28 | 浙江大学 | Anti-pollution ultrafiltration membrane and preparation method and application thereof |
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