CN105964014B - A kind of preparation method of hydrophilic/oleophobic type water-oil separating stainless steel nethike embrane - Google Patents
A kind of preparation method of hydrophilic/oleophobic type water-oil separating stainless steel nethike embrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention relates to a kind of hydrophilic/oleophobic type water-oil separating stainless (steel) wire membrane preparation method, this method is using stainless (steel) wire as substrate, in one strata DA Mediated layer of stainless (steel) wire surface construction first by the way of dip-coating or spraying, then the stainless (steel) wire containing poly-dopamine mediation layer is immersed in the amphoteric ion polymer of the group containing active ester, or the amphoteric ion polymer of the group containing active ester is sprayed on to the stainless net surface and mesh of the mediation layer containing poly-dopamine, make it that amidatioon coupling reaction occur with poly-dopamine mediation layer and form one layer of stable hydrophilic polymer film on stainless (steel) wire surface and mesh.Hydrophilic/oleophobic type water-oil separating stainless steel the nethike embrane being prepared by the method for the present invention has Superhydrophilic, have the characteristics that water flux is big, structural behaviour is stable and contamination resistance is strong at the same time, oil slick recycling, crude oil water removal and oily waste water treatment etc. have broad application prospects in ocean.
Description
Technical field
The present invention relates to a kind of hydrophilic/oleophobic type water-oil separating stainless steel nethike embrane and preparation method thereof, and in particular to
Poly-dopamine is mediation layer, and the amphoteric ion polymer of the group containing active ester and poly-dopamine mediation layer generation amidatioon is anti-
Should, enable amphoteric ion polymer stably covalent bonding on stainless (steel) wire surface.
Background technology
Oil water separation process includes the separation of oily waste water and aqueous fluid.Oily waste water source is wide, content is big.In oil
The industries such as industry, process industry, communications and transportation, food food and drink all produce substantial amounts of oily waste water.The oily waste water of petroleum industry
Mainly there are exploration and development process, crude oil pipeline conveying transportational process, Oil Spills, discharge in source and the processes such as accident occurs；Sea
The processes such as spill and leakage and blowout of the base oil field in recovery process.Oil pollutant can to marine organisms, health, water resource,
Air etc. causes significant damage.Therefore, it is necessary to being separated containing pollutant, to reach recycling and qualified discharge
Purpose, for environmental protection, economizing on resources etc. has extremely important meaning.
The aqueous general moisture content of fluid has invented electricity below 30%, for this partially aqueous fluid U.S. in early 20th century
De- facture, moisture content can be less than 0.5% after processing.But with the continuous development of tertiary oil recovery technology and the exploitation of heavy crude reservoir,
It is strong that the emulsification situation of aqueous fluid becomes increasingly complex, stability, by this method it is difficult to handle, mainly have at present ultrasonic wave,
Heating, microwave, eddy flow, electric pulse, chemical method（Such as add demulsifier）, the technical method such as magnetic treatment.There is consumption for these means
Energy is big, easily causes secondary pollution problems.
The processing method of oily waste water mainly has Gravity separate, centrifugal separation, electrically separated, adsorbing separation, air supporting point
From, heating water-oil separating method etc..These separation methods there is low separation efficiency, consumed energy is big, can bring secondary pollution and
The problems such as processing cost is higher.
UF membrane is a kind of simple efficient oily water separation technique.At present, water-oil separating film base material has polymer, stainless
Steel, filter cloth etc., are mainly modified structure water-oil separationg film by carrying out hydrophobe in substrate surface.But it is smaller there is water flux and
The shortcomings of decay is very fast, treating capacity is small and contamination resistance is poor.Because the invention is a kind of with water flux is big, stability is strong, anti-pollution
The high film with cost the features such as relatively low of dye ability has great importance to carry out water-oil separating.
The content of the invention
For low separation efficiency, stability existing for current water-oil separating is poor, film surface and duct are easily contaminated and block
And the problems such as causing water flux to reduce, it is an object of the invention to provide the strong hydrophilic/oleophobic type oil of a kind of big flux, stability
Water separation stainless steel nethike embrane and preparation method thereof.
The present invention's realizes that process is as follows：
A kind of preparation method of hydrophilic/oleophobic type water-oil separating stainless steel nethike embrane, comprises the following steps：
（1）Clean stainless (steel) wire surface；
（2）Constitutionally stable poly-dopamine mediation layer is built using spraying and dip-coating on stainless (steel) wire surface；
（3）Use structural formula（I）The amphoteric ion polymer of the shown group containing active ester is by spraying or dip-coating in step
（2）Obtained stainless (steel) wire surface construction amphoteric ion polymer hydrophilic coating；
（I）
Wherein, m is 10 ~ 1000 integer, and n is 5 ~ 500 integer；The mole percent of m is moles the hundred of 60% ~ 95%, n
Fraction is 5% ~ 40%；R1、R2For-H or-CH3；
X is amphion group or hydrophilic radical containing 7 ~ 15 carbon atoms, and the amphion group is selected from phosphorus
Phatidylcholine group, carboxylic acid betaine group or sulphonic acid betaine group, hydrophilic radical are selected from quaternary ammonium group, pyridiniujm, sulfonate, sulphur
Acidic group, carboxylic acid group or phosphate；
Y is active ester group, and structural formula is：, b be 1 ~ 50 it is just whole
Number.
Above-mentioned steps（1）Described in stainless (steel) wire be 500 ~ 2500 mesh.
Above-mentioned steps（2）During using spraying method, the dopamine solution concentration is 2 ~ 5 mg/mL, pH value for 5.5 ~
7.5；Stainless (steel) wire after spraying dopamine solution is heated in aqueous and triethylamine air atmosphere, and heating-up temperature is
125 DEG C ~ 160 DEG C, heating time is the h of 5 min ~ 8.
Above-mentioned steps（2）During using dip coating manner, the dopamine concentration is 0.5mg/mL ~ 3mg/mL；Stainless (steel) wire exists
After the h of 1 min of dip-coating in dopamine solution ~ 2, stainless (steel) wire is taken out and is heated, heating-up temperature is 80 DEG C ~ 160 DEG C, during heating
Between for the h of 5 min ~ 8.
Above-mentioned steps（2）In, added in the dopamine solution in potassium peroxydisulfate, ammonium persulfate, copper sulphate and hydrogen peroxide
One or several kinds as oxidant.
Above-mentioned steps（3）In, the concentration of the amphoteric ion polymer solution of the group containing active ester for 2 mg/mL ~
10 mg/mL, amphoteric ion polymer molecular weight are 3500 ~ 280000.
Above-mentioned steps（3）In, the method that amidation process is carried out by spraying method contains active ester group to adjust
Amphoteric ion polymer pH value of solution to 6 ~ 8, the stainless (steel) wire surface containing poly-dopamine mediation layer and mesh spraying both sexes from
Sub- polymer solution 2 ~ 5 times, is spaced 10 more than min, and the h of 1 h ~ 24 is handled in 50 DEG C ~ 80 DEG C ethanol and vapor atmosphere.
Above-mentioned steps（3）In, the method that amidation process is carried out by dip coating manner mediates layer for that will contain poly-dopamine
Stainless (steel) wire be immersed in the amphoteric ion polymer solution containing active ester group, adjust pH value of solution to 6 ~ 8,40 DEG C ~
The h of 8 h ~ 24 is reacted at 80 DEG C.Solvent selected by amphoteric ion polymer solution containing active ester group is methanol, ethanol,
One or several kinds in acetone, isopropanol, deionized water；With one kind in sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethylamine or
Several solution ph that adjust are to 6 ~ 8.
Advantages of the present invention and good effect：Stainless (steel) wire has the features such as intensity is big, corrosion-resistant, and mesh aperture is adjustable,
The present invention is using stainless (steel) wire as base material, from the angle of mussel bionical " omnipotent adhesion ", first in stainless (steel) wire surface construction
One strata DA Mediated layer, then occurs amidatioon by the amphoteric ion polymer of the group containing active ester and poly-dopamine coating
Reaction, enables amphoteric ion polymer to be firmly bonded in the surface of stainless (steel) wire.The stainless steel netting gear prepared according to the present invention
There are Superhydrophilic, wherein advancing angle in dynamic contact angle<20 °, 10 ° of receding angle ＜；Static contact angle is less than 5 °, under normal pressure only
Flux may be up to 5 × 10 when carrying out water-oil separating by gravity4 L m-2More than h.Obtained using the preparation method stainless
The advantages that steel mesh can be used for water-oil separating, which has the function of " automatically cleaning ", and separating effect is high, and water flux is big, have
Wide application prospect.
Brief description of the drawings
Fig. 1 is PMEN91's1H-NMR spectrum (CDCl3)；
Fig. 2 builds schematic diagram for hydrophilic/hydrophobic type water-oil separating stainless steel nethike embrane；
Fig. 3 separates experimentation figure for gasoline/water；
Fig. 4 is crude oil/water, comparison diagram before and after gasoline/water separation.
Embodiment
The present invention is described in further detail with reference to specific embodiment, but it is not as a limitation of the invention.
The structure of hydrophilic/oleophobic type water-oil separationg film mainly includes 3 steps：
（1）Poly-dopamine mediates the structure of layer；
（2）The preparation of amphoteric ion polymer containing active ester；
（3）Using stainless (steel) wire as substrate, poly-dopamine is mediation layer, makes the active ester group of amphoteric ion polymer with gathering
The amino of dopamine occurs amidation process and builds hydrophilic/oleophobic type water-oil separationg film.
The present invention is described in further detail with reference to specific embodiment, but it is not as a limitation of the invention.
Embodiment 1 builds poly-dopamine by spraying process and mediates layer
（1）By 1000 mesh to be modified（13 μm of aperture）Stainless (steel) wire acetone and absolute ethyl alcohol surpass in instrument is cleaned by ultrasonic
Sound cleans 15 minutes, is then cleaned by ultrasonic 15 minutes with 5% sodium hydroxide solution of mass fraction again, afterwards with deionized water rinsing,
Dried up with nitrogen stand-by；
（2）Under conditions of pH=6.8, prepare the dopamine solution containing ammonium persulfate, ammonium persulfate concentrations 2
Mg/mL, dopamine concentration are 4 mg/mL；
（3）Above-mentioned prepared dopamine solution is equably sprayed on to the surface of stainless (steel) wire to be modified；
（4）The stainless (steel) wire sprayed is placed in vapor atmosphere, heating-up temperature is 120 DEG C, 4 h of heating time,
Accelerate the structure of poly-dopamine mediation layer；
（5）Unstable poly-dopamine is combined with distilled water flushing stainless (steel) wire surface and mesh.
Embodiment 2 builds poly-dopamine by dip coating and mediates layer
（1）By 1000 mesh to be modified（13 μm of aperture）Stainless (steel) wire acetone and absolute ethyl alcohol are in instrument is cleaned by ultrasonic
It is cleaned by ultrasonic 15 minutes, is then cleaned by ultrasonic 15 minutes with 5% sodium hydroxide solution of mass fraction again, is rushed afterwards with deionized water
Wash, dried up with nitrogen stand-by；
（2）Under conditions of pH=7.8, prepare the dopamine solution containing ammonium persulfate, ammonium persulfate concentrations 1
Mg/mL, dopamine concentration are 2 mg/mL；
（3）Stainless (steel) wire is immersed in above-mentioned prepared dopamine solution, time of immersion is 4 h；
（4）After 4 h, stainless (steel) wire is taken out from dopamine solution, 1 h is heated at a temperature of being placed into 140 DEG C；
（5）Unstable poly-dopamine is combined with distilled water flushing stainless (steel) wire surface and mesh.
Embodiment 3
Group containing active ester and Phosphorylcholine group amphoteric ion polymer syntheti c route are as follows：
Reference literature method（Macromol. Biosci. 2012, 12, 979-985.）, synthesized by " starvation method "
Free radical triggers randomcopolymer p (MPC-co-NPEM）, abbreviation PMEN.Detailed process is as follows：In 250 mL three-necked bottles, add
10 mL ethanol and 0.005 g azodiisobutyronitriles（AIBN), condenser pipe is filled, is heated to 65 °C and logical N230 min remove body
Oxygen in system.Weigh 4 g 2- methacryloxyethyl Phosphorylcholines（MPC）, 1.1 g p-nitrophenyl oxygen formyl methyls third
Olefin(e) acid ethyl ester（NPCEMA）With 0.04g initiator As IBN in 500 mL round-bottomed flasks, the ethanol and 6 that 180 mL have been removed water is added
ML tetrahydrofurans, make it be transferred to after fully dissolving in constant pressure funnel.Electromagnetic agitation, N2Under protection, by monomer and initiator
Mixed solution be added drop-wise in three-necked bottle, drip, be changed to enclosed system.React 24 h stoppings.React and loaded reaction solution
Molecular cut off is in 3500 bag filter, and dialysis 2 days is carried out with the buffer solution of pH 4.01.White is obtained after freeze-drying
Solid.1H NMR test results show that the molar content of MPC and NPCEMA is respectively 91% and 9%, and GPC measures the molecule of polymer
Measure (Mw) it is about 6000 g/mol.The copolymer of the proportion of composing is referred to as PMEN91（Fig. 1）.
Embodiment 4 builds amphoteric ion polymer coating by spraying process（Fig. 2）
（1）The amphoteric ion polymer prepared in embodiment 3 is dissolved in absolute ethyl alcohol, amphoteric ion polymer solution
Concentration is 5 mg/mL；
（2）Polymer solution pH to 7 is adjusted with triethylamine aqueous solution, polymer solution spraying obtains in embodiment 1
The stainless (steel) wire surface of the mediation layer containing poly-dopamine and mesh；
（3）By step（2）Stainless (steel) wire after middle spraying is placed in ethanol atmosphere, heats 12 h, 60 DEG C of heating-up temperature, makes
Poly-dopamine mediates the amphoteric ion polymer of layer and the group containing active ester that amidation process occurs；
（4）After reaction, unstable zwitterion polymerization is combined with distilled water flushing stainless (steel) wire surface and mesh
Thing.
Embodiment 5 builds amphoteric ion polymer coating by dip coating
（1）The amphoteric ion polymer prepared in embodiment 3 is dissolved in deionized water, amphoteric ion polymer solution
Concentration is 2 mg/mL；
（2）The solution for adjusting amphoteric ion polymer with sodium hydroxide solution will be obtained containing poly- to 7.0 in embodiment 1
The stainless (steel) wire of DA Mediated layer immerses in a polymer solution, and reaction temperature is 60 DEG C, and the reaction time is 24 h；
（3）After reaction, unstable zwitterion polymerization is combined with distilled water flushing stainless (steel) wire surface and mesh
Thing.
Embodiment 6
The stainless (steel) wire prepared to above-described embodiment is tested for the property and water-oil separating experiment, wherein poly-dopamine mediate
Layer and amphoteric ion polymer coating use spraying process.
（1）Performance test
Hydrophilic/oleophobic type water-oil separating stainless steel the nethike embrane being prepared by the method for the present invention, has Superhydrophilic, wherein dynamic
Advancing angle is 8.2 ° in state contact angle, and receding angle is 0 °；Static contact angle is 0 °.
（2）Water-oil separating is tested
Utilize the hydrophilic/oleophobic type stainless steel nethike embrane prepared in above-described embodiment（1000 mesh, 13 μm of aperture）Carry out grease
Separating experiment.Before water-oil separating experiment, oil and water high-speed stirred are mixed（The volume ratio of oil/water is 50/50）, rotating speed 3000
Rpm/s, mixing time 30min.Experimental provision is as shown in figure 3, wherein a diameter of 35mm of separator.Red is to be contaminated with oil red
The gasoline of color.
1）Flux measures
Experiment is mixed with 175mL oil and 175mL water, then carries out water-oil separating experiment, water can run through stainless
Steel mesh.When wherein separating crude oil and aqueous mixtures, completely by complete in 13s when separating gasoline and aqueous mixtures in water phase 15s
Full by.According to formula（1）Calculate fluxf。
It is respectively 4.37 × 10 by the water flux for calculating crude oil/water, gasoline/aqueous mixtures separating experiment4 L m-2H and
5.04×104 L m-2H, much larger than other water-oil separationg films built using stainless steel as base material.And after separating 30 times, flux is protected
Holdup is more than 98%（Fig. 4）.
2）Oil content and separative efficiency measure
The oil content in water phase after separation is measured using Infrared Oil Determination Instrument, assay method is as follows：By certain volume
Water sample be all poured into separatory funnel, add hydrochloric acid to be acidified to pH≤2, liquid separation moved into after washing sampling bottle with 20ml carbon tetrachloride
In funnel, add about 20g sodium chloride, fully vibrate 2min, and be vented through normally open piston.After stratification, by extract through
The glass sand core funnel for placing about 10mm thickness anhydrous sodium sulfates is flowed into volumetric flask.Extraction one is repeated with 20ml carbon tetrachloride
It is secondary.Suitable carbon tetrachloride cleaning glass sand core funnel is taken, cleaning solution flows into volumetric flask in the lump.Carbon tetrachloride is added to be diluted to graticule
Constant volume, and shake up.Use Infrared Oil Determination Instrument（Oil 460, Beijing ChinaInvent Instrument Technology Co., Ltd.）It is measured oil content.
At the same time according to formula（2）Separative efficiency measure is carried out
Crude oil/water, the separative efficiency of vapour oil/water are respectively 99.99% and 99.98%.
Claims (10)
1. a kind of preparation method of hydrophilic/oleophobic type water-oil separating stainless steel nethike embrane, it is characterised in that comprise the following steps：
（1）Clean stainless (steel) wire surface；
（2）Constitutionally stable poly-dopamine mediation layer is built using spraying and dip-coating on stainless (steel) wire surface；
（3）Use structural formula（I）The amphoteric ion polymer of the shown group containing active ester is by spraying or dip-coating in step（2）
The stainless (steel) wire surface construction amphoteric ion polymer hydrophilic coating arrived；
（I）
Wherein, m is 10 ~ 1000 integer, and n is 5 ~ 500 integer；The mole percent of m is the mole percent of 60% ~ 95%, n
For 5% ~ 40%；R1、R2For-H or-CH3；
X is amphion group or hydrophilic radical containing 7 ~ 15 carbon atoms, and the amphion group is selected from phosphinylidyne courage
Base groups, carboxylic acid betaine group or sulphonic acid betaine group, hydrophilic radical are selected from quaternary ammonium group, pyridiniujm, sulfonate, sulfuric acid
Base, carboxylic acid group or phosphate；
Y is active ester group, and structural formula is：, b is 1 ~ 50 positive integer.
2. preparation method according to claim 1, it is characterised in that：The mesh size of the stainless (steel) wire for 500 ~
2500 mesh.
3. preparation method according to claim 1, it is characterised in that：Above-mentioned steps（2）It is described during using spraying method
Dopamine solution concentration is 2 ~ 5 mg/mL, and pH value is 5.5 ~ 7.5；The stainless (steel) wire after dopamine solution is sprayed aqueous and three
Heated in the air atmosphere of ethamine, heating-up temperature is 125 DEG C ~ 160 DEG C, and heating time is the h of 5 min ~ 8.
4. preparation method according to claim 1, it is characterised in that：Above-mentioned steps（2）It is described more during using dip coating manner
Bar amine concentration is 0.5mg/mL ~ 3mg/mL；Stainless (steel) wire is in dopamine solution after the h of 1 min of dip-coating ~ 2, by stainless (steel) wire
Heating is taken out, heating-up temperature is 80 DEG C ~ 160 DEG C, and heating time is the h of 5 min ~ 8.
5. preparation method according to claim 1, it is characterised in that：Above-mentioned steps（2）In, add in the dopamine solution
Enter the one or several kinds in potassium peroxydisulfate, ammonium persulfate, copper sulphate or hydrogen peroxide as oxidant.
6. preparation method according to claim 1, it is characterised in that：Above-mentioned steps（3）In, the group containing active ester
The concentration of amphoteric ion polymer solution be the mg/mL of 2 mg/mL ~ 10, amphoteric ion polymer molecular weight for 3500 ~
280000。
7. preparation method according to claim 1, it is characterised in that：Above-mentioned steps（3）In, acyl is carried out by spraying method
The method of aminating reaction is containing poly-dopamine to adjust the amphoteric ion polymer pH value of solution containing active ester group to 6 ~ 8
Mediate stainless (steel) wire surface and the mesh spraying amphoteric ion polymer solution 2 ~ 5 times of layer, be spaced 10 more than min, 50 DEG C ~
The h of 1 h ~ 24 is handled in 80 DEG C of ethanol and vapor atmosphere.
8. preparation method according to claim 1, it is characterised in that：Above-mentioned steps（3）In, acyl is carried out by dip coating manner
The method of aminating reaction is that containing poly-dopamine the stainless (steel) wire of layer will be mediated to be immersed in the amphion containing active ester group
In polymer solution, pH value of solution is adjusted to 6 ~ 8, and the h of 8 h ~ 24 is reacted at 40 DEG C ~ 80 DEG C.
9. preparation method according to claim 8, it is characterised in that：Amphoteric ion polymer containing active ester group is molten
Solvent selected by liquid is methanol, the one or several kinds in ethanol, acetone, isopropanol, deionized water.
10. preparation method according to claim 8, it is characterised in that：With sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethylamine
In one or several kinds of solution ph that adjust to 6 ~ 8.
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| CN109385173A (en) * | 2017-08-10 | 2019-02-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Oleophobic coating material, oil-water separating function material, preparation method and the usage |
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| WO2014118382A1 (en) * | 2013-02-04 | 2014-08-07 | W. L. Gore & Associates, Inc. | Coating for substrate |
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| WO2014118382A1 (en) * | 2013-02-04 | 2014-08-07 | W. L. Gore & Associates, Inc. | Coating for substrate |
| CN103601826A (en) * | 2013-10-17 | 2014-02-26 | 华南理工大学 | Hydrophilic oleophobic polymer and preparation method thereof, and application thereof in humidity response oil and water separating membrane |
| CN103893999A (en) * | 2014-03-31 | 2014-07-02 | 华南理工大学 | Super-hydrophilic and underwater super-oleophobic oil-water separation mesh film and preparation method thereof |
| CN105062360A (en) * | 2015-08-19 | 2015-11-18 | 中国科学院兰州化学物理研究所 | Transparent super-hydrophobic paint and application thereof |
| CN105413236A (en) * | 2015-12-18 | 2016-03-23 | 华南理工大学 | Super-hydrophilic oil water separation net film with antifouling and antibacterial functions and preparation as well as application thereof |
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