CN105833732B - The modified seperation film and preparation method thereof of hydrophilic anti-pollution gel coat - Google Patents
The modified seperation film and preparation method thereof of hydrophilic anti-pollution gel coat Download PDFInfo
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- CN105833732B CN105833732B CN201610173532.4A CN201610173532A CN105833732B CN 105833732 B CN105833732 B CN 105833732B CN 201610173532 A CN201610173532 A CN 201610173532A CN 105833732 B CN105833732 B CN 105833732B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
- B01D2323/385—Graft polymerization involving radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to a kind of modified seperation films and preparation method thereof of hydrophilic anti-pollution gel coat.The preparation method includes the following steps: that cross-linking monomer, crosslinking agent and photoinitiator dispersing and dissolving in solvent, are obtained monomer solution by (1), wherein the cross-linking monomer is polyethylene glycol methyl methacrylate, concentration 0.01-0.5g/mL；The crosslinking agent is ethyleneglycol dimethacrylate methyl esters, volumetric concentration 0.1-3%；The concentration of the photoinitiator is 0.1-2mg/mL；(2) seperation film is soaked in the monomer solution and is placed on progress cross-linking radiation reaction under ultraviolet light, take out the seperation film being modified after drying to get the hydrophilic anti-pollution gel coat.The modified seperation film of the hydrophilic anti-pollution gel coat has good hydrophily, and antifouling property is stable, it is thin and uniform and stable will not to be grafted thickness degree to the composite separating film that separate substance pollutes.
Description
Technical field
The present invention relates to seperation films, more particularly to a kind of hydrophilic anti-pollution gel coat modified seperation film and its system
Preparation Method.
Background technique
Membrane separation technique selects mixing liquid by membrane aperture size and surface compatibility using pressure as driving force
Property separation, compared with traditional separation method, UF membrane have that selectivity is high, low energy consumption, separative efficiency is high and be easy to implement from
The advantages that dynamicization.The effects of in UF membrane engineering due to concentration polarization and specific adsorption, is contaminated, and the pollution of seperation film is asked
Topic is to restrict the key factor that membrane separation technique is promoted and separative efficiency improves.
It, mainly can be by carrying out special designing, coupling air purge or rinsing unit to membrane module in seperation film engineering
The methods of carry out lessening membrane fouling, improve the separative efficiency in use process, this method can mitigate film caused by concentration polarization
Pollution.The basic reason of fouling membrane is that surface specific absorption occurs for solute in film surface property and filtrate, by carrying out to film
Hydrophilic modifying is only reducing this specific adsorption and the basic method of fouling membrane is effectively relieved, and common blending antipollution is modified
Substance is blended during the filtration process and is easy to be eluted pollution purifying substance for obtained hydrophily seperation film, is not able to satisfy biological medicine
Requirement in equal special dimensions separation process；Chemical grafting treated method also can unify layer hydrophily by covalently bonded in film surface
Substance, but chemical time is long, influences vulnerable to interior extraneous factor, reproducibility is bad, and grafting layer is uneven, and reaction may
Film properties are impacted, applicable reaction system is restricted.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of seperation film that hydrophilic anti-pollution gel coat is modified.
A kind of preparation method for the seperation film that hydrophilic anti-pollution gel coat is modified, includes the following steps:
(1) cross-linking monomer, crosslinking agent and photoinitiator dispersing and dissolving are obtained into monomer solution, wherein described in solvent
Cross-linking monomer is polyethylene glycol methyl methacrylate, concentration 0.01-0.5g/mL；The crosslinking agent is ethylene glycol dimethyl
Methyl acrylate, volumetric concentration 0.1-3%；The concentration of the photoinitiator is 0.1-2mg/mL；
(2) seperation film is soaked in the monomer solution and is placed on progress cross-linking radiation reaction under ultraviolet light, taken out dry
To get the seperation film that the hydrophilic anti-pollution gel coat is modified after dry.Water can be used in above-mentioned solvent.After immersion, preferably
To cover one layer of filter paper on the surface of seperation film, to guarantee that seperation film is smooth.
The concentration of the cross-linking monomer is 0.05-0.15g/mL, the volume of the crosslinking agent in one of the embodiments,
Concentration is 0.2-0.6%, and the concentration of the photoinitiator is 0.3-0.7mg/mL.
The weight average molecular weight of the polyethylene glycol methyl methacrylate is 200-2000 in one of the embodiments,.
The weight average molecular weight of the polyethylene glycol methyl methacrylate is 200-400 in one of the embodiments,.
The condition of the cross-linking radiation reaction in one of the embodiments, are as follows: ultraviolet lighting power is 10-50mW/
cm2, reaction time 0.5-10min.
The condition of the cross-linking radiation reaction in one of the embodiments, are as follows: ultraviolet lighting power is 10-15mW/
cm2, reaction time 4-6min.
First the seperation film is pre-processed before impregnating in one of the embodiments: the seperation film is placed at
1-3h is impregnated in the ethanol water that volumetric concentration is 45-55%, is then dried in 35-45 DEG C.
The seperation film is plate membrane, hollow-fibre membrane or tubular membrane in one of the embodiments, and material is polyamides
Amine, Kynoar, polysulfones, polyether sulfone, polyvinyl chloride or polyacrylonitrile.
The photoinitiator is potassium peroxydisulfate, ammonium persulfate or dibenzoyl peroxide in one of the embodiments,.
The present invention also provides the preparation methods of the modified seperation film of the hydrophilic anti-pollution gel coat to be prepared
The modified seperation film of hydrophilic anti-pollution gel coat.
The principle of the present invention and advantage are as follows:
There are blend corrosions to pollute separate substance, antifouling property not for the modification of existing polymer separation film by the present invention
Stable problem proposes the side that a kind of ultraviolet light cross-linking grafting prepares the modified seperation film of hydrophilic anti-pollution gel coat
Method.
By systematic research, the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat of the present invention,
Using hydrophilic cross-linking monomer polyethylene glycol methyl methacrylate cooperation ethyleneglycol dimethacrylate methyl esters as crosslinking
Agent triggers graft reaction by ultraviolet light, can generate between film surface and polyethylene glycol methyl methacrylate monomer steady
The covalent bond of fixed free radical coupling, while monomer is crosslinked mutually under the action of crosslinking agent ethyleneglycol dimethacrylate methyl esters
The firm gel structure of three-dimensional space network structure is formed, is thus formed on the surface of seperation film and is grafted stable compound painting
Layer, thus be prepared good hydrophilic property, antifouling property it is stable, will not be to the seperation film that separate substance pollutes.
The concentration of each raw material and the ultraviolet irradiation condition of cross-linking reaction in reaction system are further rationally controlled, can protected
While demonstrate,proving seperation film hydrophily and antipollution effect, keep the carry out of graft reaction more stable, improves reaction reproducibility, and make
The grafting thickness degree of acquisition is moderate and uniform and stable, and porosity is big, membrane flux and the salt retention of the seperation film after graft modification pair
Rate does not reduce significantly.
Compared with prior art, the invention has the following advantages:
1, the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat of the present invention is by using specific
Cross-linking monomer and crosslinking agent carry out cross-linking reaction under ultraviolet irradiation condition, the hydrophilic anti-pollution gel coat being prepared
Modified seperation film has good hydrophily, and antifouling property is stable, will not pollute to separate substance compound point
From film, it is thin and uniform and stable to be grafted thickness degree.In addition, composite coating thickness moderate (30-100nm) that grafting is formed and uniformly steady
It is fixed, while guaranteeing seperation film hydrophily and antipollution effect, also have biggish porosity, membrane flux and salt rejection rate do not have
There is apparent reduction.
2, the preparation method reacts controllable using ultraviolet radioactive as the excitaton source of graft polymerization reaction, applied widely, connects
Branch process is simple to operation, and reaction period is high-efficient, and uniformity is good, has expanded seperation film in biological medicine, food and drink etc.
The application of field separate engineering.
Detailed description of the invention
Fig. 1 is that Fourier infrared spectrograph tests embodiment 1-4 and the surface infrared spectrum of comparative example under the emission mode that is all-trans
Figure；
Fig. 2 changes over time relational graph for the contact angle on embodiment 1 and comparative example surface；
Fig. 3 is contact angle schematic diagram after the contact angle on embodiment 1 and comparative example surface is stable at any time.
Specific embodiment
Below in conjunction with the specific embodiment seperation film and its preparation modified to hydrophilic anti-pollution gel coat of the invention
Method is described in further detail.
Two brown reagent bottles are taken, 2.0054 grams of cross-linking monomers of one of addition, 10 milligrams of photoinitiators and 4 milliliters
Water is labeled as A liquid；188 microlitres of crosslinking agents and 4 milliliters of water are added in another, and concussion shakes up for 20 minutes, are labeled as B liquid.
Embodiment 1
A kind of preparation method of the modified seperation film of hydrophilic anti-pollution gel coat of the present embodiment, includes the following steps:
(1) taking one piece of seperation film reverse osmosis membrane to be modified, (Tao Shi BW30 reverse osmosis (plate membrane), material are multiple for polyamide
Close film), it is cut into uniform circular film, while cutting size filter paper identical with the diaphragm；
(2) diaphragm is placed to concussion in the ethanol water of volume fraction 50% and impregnates 2h, is then dried in 40 DEG C of vacuum
It is dried for standby in case；
(3) size and the comparable clean glass culture dish of diaphragm are taken, NO2 is labeled as, the diaphragm that distilled water soaks is placed on
In culture dish, and one layer of filter paper is covered, then inject 0.5 milliliter of A liquid with liquid-transfering gun, 0.25 milliliter of B liquid adds water 3.25
Milliliter, wherein the concentration of cross-linking monomer polyethylene glycol methyl methacrylate (Mw=300) is 0.0625g/mL；Crosslinking agent second
The volumetric concentration of glycol methyl methacrylate is 0.29%；The concentration of photoinitiator ammonium persulfate is 0.31mg/mL, gently
Concussion stands 15 minutes after shaking up；
(4) intensity of illumination that ultraviolet irradiation case is arranged is 10mW/cm2, while culture dish is transferred in ultraviolet irradiation case and shines
It penetrates to take out after five minutes and rinse well, the seperation film modified to get hydrophilic anti-pollution gel coat is dried in vacuum drying oven.
Embodiment 2
A kind of preparation method of the modified seperation film of hydrophilic anti-pollution gel coat of the present embodiment, includes the following steps:
(1) one piece of seperation film reverse osmosis membrane to be modified (GEM series (plate membrane), material is polyacrylonitrile) is taken, is cut into
Uniform circular film, while cutting size filter paper identical with the diaphragm；
(2) diaphragm is placed to concussion in the ethanol water of volume fraction 45% and impregnates 3h, is then dried in 35 DEG C of vacuum
It is dried for standby in case；
(3) size and the comparable clean glass culture dish of diaphragm are taken, NO3 is labeled as, the diaphragm that distilled water soaks is placed on
In culture dish, and one layer of filter paper is covered, then inject 1 milliliter of A liquid with liquid-transfering gun, 0.5 milliliter of B liquid adds 2.5 milli of water
It rises, wherein the concentration of cross-linking monomer polyethylene glycol methyl methacrylate (Mw=400) is 0.125g/mL；Crosslinking agent ethylene glycol
The volumetric concentration of methyl methacrylate is 0.59%；The concentration of photoinitiator potassium peroxydisulfate is 0.625mg/mL, is gently shaken
It swings and stands 15 minutes after shaking up；
(4) intensity of illumination that ultraviolet irradiation case is arranged is 15mW/cm2, while culture dish is transferred in ultraviolet irradiation case and shines
It penetrates to take out after five minutes and rinse well, the seperation film modified to get hydrophilic anti-pollution gel coat is dried in vacuum drying oven.
Embodiment 3
A kind of preparation method of the modified seperation film of hydrophilic anti-pollution gel coat of the present embodiment, includes the following steps:
(1) one piece of ultrafiltration of separating film film to be modified (Hydranautics PW is serial (plate membrane), and material is polyether sulfone) is taken, is cut into
Uniform circular film, while cutting size filter paper identical with the diaphragm；
(2) diaphragm is placed to concussion in the ethanol water of volume fraction 55% and impregnates 1h, is then dried in 45 DEG C of vacuum
It is dried for standby in case；
(3) size and the comparable clean glass culture dish of diaphragm are taken, NO4 is labeled as, the diaphragm that distilled water soaks is placed on
In culture dish, and one layer of filter paper is covered, then inject 1.5 milliliters of A liquid with liquid-transfering gun, 1 milliliter of B liquid adds 1.5 milli of water
It rises, wherein the concentration of cross-linking monomer polyethylene glycol methyl methacrylate (Mw=1000) is 0.19g/mL；Crosslinking agent ethylene glycol
The volumetric concentration of methyl methacrylate is 1.17%；The concentration of photoinitiator potassium peroxydisulfate is 0.94mg/mL, is gently shaken
15 minutes are stood after shaking up；
(4) intensity of illumination that ultraviolet irradiation case is arranged is 30mW/cm2Left and right, while culture dish is transferred to ultraviolet irradiation case
Middle irradiation is taken out after ten minutes rinses well, and point modified to get hydrophilic anti-pollution gel coat is dried in vacuum drying oven
From film.
Embodiment 4
A kind of preparation method of the modified seperation film of hydrophilic anti-pollution gel coat of the present embodiment, includes the following steps:
(1) one piece of nanofiltration membrane to be modified (Hydranautics ESNA1-K1 (plate membrane), material are composite polyamide) is taken, is cut into
Uniform circular film, while cutting size filter paper identical with the diaphragm；
(2) diaphragm is placed to concussion in the ethanol water of volume fraction 50% and impregnates 2h, is then dried in 40 DEG C of vacuum
It is dried for standby in case；
(3) size and the comparable clean glass culture dish of diaphragm are taken, NO5 is labeled as, the diaphragm that distilled water soaks is placed on
In culture dish, and one layer of filter paper is covered, then inject 2 milliliters of A liquid with liquid-transfering gun, 1.5 milliliters of B liquid add 0.5 milli of water
It rises, wherein the concentration of cross-linking monomer polyethylene glycol methyl methacrylate (Mw=2000) is 0.25g/mL；Crosslinking agent ethylene glycol
The volumetric concentration of methyl methacrylate is 1.76%；The concentration of photoinitiator dibenzoyl peroxide is 1.25mg/mL, gently
Light concussion stands 15 minutes after shaking up；
(4) intensity of illumination that ultraviolet irradiation case is arranged is 50mW/cm2Left and right, while culture dish is transferred to ultraviolet irradiation case
Middle irradiation is taken out after 1 minute and is rinsed well, and the separation modified to get hydrophilic anti-pollution gel coat is dried in vacuum drying oven
Film.
Comparative example
The modified seperation film of a kind of hydrophilic anti-pollution gel coat of this comparative example (being labeled as NO1), raw material and preparation side
With embodiment 1, difference is method: being added without B liquid, is only added 4 milliliters of A liquid.
Embodiment 1-4 and the surface infrared spectrum of comparative example under the emission mode that is all-trans, knot are tested with Fourier infrared spectrograph
Fruit is as shown in Figure 1；Compared with comparative example, embodiment 1-4 is in 1487cm-1And 1584cm-1There is the absorption peak of basement membrane polysulfones,
1720cm-1There is the vibration absorption peak of grafted monomers amide in place.
Contact angle after the contact angle on testing example 1 and comparative example surface changes over time relationship and stablizes, as a result such as Fig. 2
Shown in 3, specifically, the contact angle of embodiment 1-4 is respectively 38 °, and 41 °, 48 °, 50 °, and comparative example is more than 80 degree, it is of the invention
The separation membrane surface contact angle being prepared substantially reduces.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (8)
1. a kind of preparation method of the modified seperation film of hydrophilic anti-pollution gel coat, which comprises the steps of:
(1) cross-linking monomer, crosslinking agent and photoinitiator dispersing and dissolving are obtained into monomer solution in solvent, wherein the crosslinking
Monomer is polyethylene glycol methyl methacrylate, weight average molecular weight 200-2000, concentration 0.01-0.5g/mL；The crosslinking
Agent is ethyleneglycol dimethacrylate methyl esters, volumetric concentration 0.1-3%；The concentration of the photoinitiator is 0.1-2mg/mL；
(2) seperation film is soaked in the monomer solution and is placed on progress cross-linking radiation reaction, ultraviolet lighting function under ultraviolet light
Rate is 10-50mW/cm2, reaction time 0.5-10min then takes out dry to get the hydrophilic anti-pollution gel coat
Modified seperation film.
2. the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat according to claim 1, feature exist
In the concentration of the cross-linking monomer is 0.05-0.15g/mL, and the volumetric concentration of the crosslinking agent is 0.2-0.6%, and the light draws
The concentration for sending out agent is 0.3-0.7mg/mL.
3. the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat according to claim 1, feature exist
In the weight average molecular weight of the polyethylene glycol methyl methacrylate is 200-400.
4. the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat according to claim 1, feature exist
In the condition of the cross-linking radiation reaction are as follows: ultraviolet lighting power is 10-15mW/cm2, reaction time 4-6min.
5. the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat according to claim 1, feature exist
In immersion is preceding first to pre-process the seperation film: the seperation film is placed at the ethanol water that volumetric concentration is 45-55%
1-3h is impregnated in solution, is then dried in 35-45 DEG C.
6. the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat according to claim 1-5,
It is characterized in that, the seperation film is plate membrane, hollow-fibre membrane or tubular membrane, material is polyamide, Kynoar, gathers
Sulfone, polyether sulfone, polyvinyl chloride or polyacrylonitrile.
7. the preparation method of the modified seperation film of hydrophilic anti-pollution gel coat according to claim 1-5,
It is characterized in that, the photoinitiator is potassium peroxydisulfate, ammonium persulfate or dibenzoyl peroxide.
8. the preparation method of the modified seperation film of the described in any item hydrophilic anti-pollution gel coats of claim 1-7 is prepared into
The modified seperation film of the hydrophilic anti-pollution gel coat arrived.
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| CN109046028B (en) * | 2018-09-30 | 2020-05-15 | 浙江云度新材料科技有限公司 | Preparation method of modified PVDF ultrafiltration membrane |
| CN109908776B (en) * | 2019-04-04 | 2021-07-16 | 苏州科技大学 | Anti-pollution composite distillation membrane based on amphiphilic network and preparation method thereof |
| CN112044280B (en) * | 2019-06-05 | 2022-08-16 | 广州中国科学院先进技术研究所 | Anti-membrane biological pollution coating and preparation method thereof |
| CN110652890B (en) * | 2019-10-14 | 2021-08-31 | 曲靖师范学院 | Surface hydrophilic modification method for polyacrylonitrile separation membrane |
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| CN102029117A (en) * | 2009-09-29 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for modifying surface of ultrafiltration membrane |
| CN104707486A (en) * | 2015-03-03 | 2015-06-17 | 浙江大学 | Preparation method for high-strength hydrogel filtering membrane |
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| CN102029117A (en) * | 2009-09-29 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for modifying surface of ultrafiltration membrane |
| CN104707486A (en) * | 2015-03-03 | 2015-06-17 | 浙江大学 | Preparation method for high-strength hydrogel filtering membrane |
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