CN109603563A - A kind of preparation method of zinc coordination organic nano particle hydridization PA membrane - Google Patents
A kind of preparation method of zinc coordination organic nano particle hydridization PA membrane Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of zinc coordination organic nano particle hydridization PA membrane, using polyamine as monomer molecule, zinc nitrate hexahydrate is metal ion compound, dopamine is bionical adhesive, it is configured to water phase mixed solution, by its dip-coating in open support film surface, then zinc is formed in situ through the aqueous solution impregnation containing 2-methylimidazole and is coordinated organic nano particle, is coordinated organic nano particle hydridization PA membrane containing zinc finally by the crosslinking preparation of polynary acyl chlorides monomer interface.The unique nanocrystailine microstructures of organic filler are coordinated using zinc, the nanochannel selectively retained conducive to water penetration and organic molecule is formed in PA membrane, high water permeability and stable separation selectivity can be obtained.Preparation method of the invention is simple and easy to do, and particle is formed in situ in film-forming process, and particle is evenly distributed stabilization in film, and preparation cost is cheap, has good industrial applications prospect.
Description
Technical field
The invention belongs to the preparations of UF membrane field more particularly to a kind of zinc coordination organic nano particle hydridization PA membrane
Method.
Background technique
Membrane separation technique generally includes micro-filtration, ultrafiltration, nanofiltration, reverse osmosis, positive infiltration and membrane bioreactor etc..UF membrane
As a kind of novel, energy-saving and environmental protection technologies, in the separation of sea water desalination, drink water purifying, wastewater treatment and industrial material, money
It is played an increasingly important role in the fields such as source recycling.Membrane material is the core of membrane separation technique development, is to determine its point
Key from performance.Since Cadotte in 1972 etc. is prepared for first PA membrane using interfacial polymerization, commercialization is received
Filter membrane, reverse osmosis membrane and forward osmosis membrane just (the US Patent 5,693,227 based on polyamide composite film；
J.Membr.Sci.,2013,446,164-170；J.Membr.Sci.,2018,555,318-326).As seperation film market needs
The expansion for the amount of asking, polyamide separation film kind are increasing, and domestic and international researcher has synthesized different types of organic phase/water phase
Monomer molecule, gained novel polyamide film have better anti-chlorine oxidation resistent susceptibility and antifouling property.Although China is in membrane material
The fields such as material and the preparation and application of special separation film achieve important research achievement, but there are also certain compared with international most advanced level
Gap cannot still fully meet the demand of complicated practical application system.
In recent years, with the rapid development of nanotechnology, some functional inorganic nano materials are introduced into PA membrane
The interior separating property for being used to be promoted film has evolved into an important research direction.Univ California-Los Angeles USA Hoek
NaA type zeolite molecular sieve is introduced into PA membrane by professor and professor Yan Yushan etc. in streamside branch school, is prepared for for the first time inorganic
Nano hybridization PA membrane, on the basis of not influencing inorganic salt rejection rate, the water flux of film is improved by about one time
(J.Membr.Sci.,2007,294,1-7).It there is now a large amount of reports using inorganic nano material as modifying agent, such as by zeolite point
Son sieve, SiO2、TiO2, CNT, GO and MOF etc. be introduced into PA membrane, improve the water penetration flux and stain resistance of PA membrane
Energy.(CN 1401417A；CN102989330A；ACS Appl.Mater.Interfaces 2016,8 6693-6700；
J.Am.Chem.Soc.,2013,135,15201-15208).But the synthesis of inorganic nano-particle and method of modifying are more complex,
Nano material itself dispersibility and its consistency problem between polyamide basement membrane limit its scale and repeat stable system
It is standby.Method the preparation chemical composition, structure-controllable for how passing through simplicity, being suitble to industrialization interfacial polymerization film forming, good dispersion, surely
Qualitative strong functional nanomaterials are to construct high-performance PA membrane major issue urgently to be resolved.
By the inspiration of mussel biomimetic chemistry, Messersmith etc. was reported in 2007 utilizes dopamine adhesion material pair
A variety of organic and inorganic materials are surface modified.Recent studies have found that under certain inductive condition, dopamine and its autopolymer
It can assemble to form melanin shape nanoparticle in aqueous solution, be introduced into polymer film, the structure of film can be improved
Stability, separation property and antifouling property (J.Membr.Sci.2014,457,73-81；J.Membr.Sci.2015,476,10-
19).Zinc nano material has good hydrophily, anti-pollution anti-microbial property (CN201420432075.2；CN
201710359570.3).In summary it analyzes, as can nanoparticle is formed in situ in interfacial polymerization film forming procedure, and nanometer
Contain dopamine and zinc nanometer component in particle, the unique nanocrystailine microstructures of zinc organic filler, strongly hydrophilic can be utilized simultaneously
With good antipollution stability, the nanometer selectively penetrated conducive to water penetration and organic molecule is formed in PA membrane
Channel, can obtain high water permeability and stable separation selectivity, and gained film can preferably meet the needs of practical application.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of zinc coordination organic nano particle hydridization polyamide
The preparation method of film.
A kind of preparation method of zinc coordination organic nano particle hydridization PA membrane includes the following steps:
1) using polyamine as monomer molecule, zinc nitrate hexahydrate is metal ion compound, and dopamine is bionical adhesive,
It is configured to water phase mixed solution, by its dip-coating in open support film surface, then through 2-methylimidazole aqueous solution impregnation, more
Hole support membrane surface in situ, which is formed, is coordinated organic nano particle nascent state film containing zinc；
2) in organic solvent by the dissolution of polynary acyl chlorides monomer, it is made into organic phase solution, by its dip-coating in above-mentioned zinc supported
The nascent state film surface for being coordinated organic nano particle carries out interface-cross-linked reaction, and heat cure processing is most washed through deionized water afterwards
Afterwards, it obtains being coordinated organic nano particle hydridization PA membrane containing zinc；
Polyamine monomer molecule described in step 1) be piperazine, N- aminoethyl piperazine, ethylenediamine, m-phenylene diamine (MPD), to benzene
Diamines or 1,3,5- triaminobenzene；Polynary acyl chlorides monomer described in step 2) is o-phthaloyl chloride, m-phthaloyl chloride, right
Phthalyl chloride, pyromellitic trimethylsilyl chloride or biphenyl tetracarboxylic acyl chlorides；Polynary amine monomers in water phase mixed solution described in step 1)
The mass percent concentration of molecule is 0.2~2%；The quality of zinc nitrate hexahydrate in water phase mixed solution described in step 1)
Percent concentration is 0.1~1%；The mass percent concentration of dopamine is 0.05 in water phase mixed solution described in step 1)
~0.5%；Porous support membrane described in step 1) is polysulfones, polyether sulfone, polyacrylonitrile or vinylidene difluoride planar ultrafiltration membrane；
The dip-coating conditions of water phase mixed solution described in step 1) are dip-coating 10~60 minutes at 15~25 DEG C；Described in step 1)
2-methylimidazole aqueous solution mass percent concentration be 0.5~5%；The leaching of 2-methylimidazole aqueous solution described in step 1)
Stain treatment conditions are impregnated 10~100 minutes at 15~25 DEG C；Polynary acyl chlorides list in organic phase solution described in step 2)
The mass percent concentration of body molecule is 0.1~1%；The solvent of organic phase solution described in step 2) is n-hexane, hexamethylene
Alkane or heptane；Organic phase solution dip-coating described in step 2), which carries out the condition of interface-cross-linked reaction, is reacted at 15~25 DEG C
2~10 minutes；Heat cure treatment conditions described in step 2) are solidified 10~40 minutes at 45~65 DEG C.
The coordination organic nano particle hydridization PA membrane containing zinc can be used for the charged organic molecule of different molecular weight
Separation field.
A kind of separating property test method of zinc coordination organic nano particle hydridization PA membrane of the invention is as follows: by film
Piece is placed in the conventional panel pressure drive membrane test device of this field, tests cephacoria precompressed 1h under 0.5MPa operating pressure, so
Afterwards under 25 DEG C and 0.2MPa test condition, the rejection (R) of water penetration flux (J) and organic molecule to film is surveyed
It is fixed, its calculation formula is: J=V/ (A.t)；R=1-Cp/Cf；Wherein, V- feed liquid penetrates the volume of film, the effective area of A- film
For 22.4cm2, t- runing time, CpPenetrating fluid concentration, CfFeeding liquid concentration；Contained by total organic carbon in measurement solution
Amount, obtains organic solution concentration.
The separating layer of zinc coordination organic nano particle hydridization PA membrane is to be coordinated organic nano particle and polyamide by zinc
Macromolecule composition, zinc are coordinated organic filler in-situ preparation during film preparation, unique nanocrystailine microstructures, strong hydrophilicity
Property and good adhesion stability, can be formed in polyamide separating layer and selectively be cut conducive to water penetration and organic molecule
The nanochannel stayed.The present invention is coordinated organic nano particle particle size and content, gained in PA membrane by regulation zinc
The water penetration flux of film is generally greater than 80L.m-2.h-1.bar-1, 95% is higher than to the organic matter dye molecule rejection of bear electricity,
And 30% is generally below to the rejection of the organic matter dye molecule of lotus positive electricity.In addition, zinc coordination organic nano particle contains greatly
The reaction active groups and dopamine component of amount, particle and polyamide separating layer and its are capable of forming strong between porous support membrane
Covalent bond and non-covalent bond effect make film with Thief zone selectivity and good stability；In addition, the nanoparticle is in film
It is formed in situ, can largely be uniformly introduced in PA membrane in preparation process, membrane preparation method is easy, is easy to regulate and control, and has
Good industrialization large scale preparation and application prospect.
Specific embodiment
A kind of preparation method of zinc coordination organic nano particle hydridization PA membrane includes the following steps:
1) using polyamine as monomer molecule, zinc nitrate hexahydrate is metal ion compound, and dopamine is bionical adhesive,
It is configured to water phase mixed solution, by its dip-coating in open support film surface, then through 2-methylimidazole aqueous solution impregnation, more
Hole support membrane surface in situ, which is formed, is coordinated organic nano particle nascent state film containing zinc；
2) in organic solvent by the dissolution of polynary acyl chlorides monomer, it is made into organic phase solution, by its dip-coating in above-mentioned zinc supported
The nascent state film surface for being coordinated organic nano particle carries out interface-cross-linked reaction, and heat cure processing is most washed through deionized water afterwards
Afterwards, it obtains being coordinated organic nano particle hydridization PA membrane containing zinc；
Polyamine monomer molecule described in step 1) be piperazine, N- aminoethyl piperazine, ethylenediamine, m-phenylene diamine (MPD), to benzene
Diamines or 1,3,5- triaminobenzene；Polynary acyl chlorides monomer described in step 2) is o-phthaloyl chloride, m-phthaloyl chloride, right
Phthalyl chloride, pyromellitic trimethylsilyl chloride or biphenyl tetracarboxylic acyl chlorides；Polynary amine monomers in water phase mixed solution described in step 1)
The mass percent concentration of molecule is 0.2~2%；The quality of zinc nitrate hexahydrate in water phase mixed solution described in step 1)
Percent concentration is 0.1~1%；The mass percent concentration of dopamine is 0.05 in water phase mixed solution described in step 1)
~0.5%；Porous support membrane described in step 1) is polysulfones, polyether sulfone, polyacrylonitrile or vinylidene difluoride planar ultrafiltration membrane；
The dip-coating conditions of water phase mixed solution described in step 1) are dip-coating 10~60 minutes at 15~25 DEG C；Described in step 1)
2-methylimidazole aqueous solution mass percent concentration be 0.5~5%；The leaching of 2-methylimidazole aqueous solution described in step 1)
Stain treatment conditions are impregnated 10~100 minutes at 15~25 DEG C；Polynary acyl chlorides list in organic phase solution described in step 2)
The mass percent concentration of body molecule is 0.1~1%；The solvent of organic phase solution described in step 2) is n-hexane, hexamethylene
Alkane or heptane；Organic phase solution dip-coating described in step 2), which carries out the condition of interface-cross-linked reaction, is reacted at 15~25 DEG C
2~10 minutes；Heat cure treatment conditions described in step 2) are solidified 10~40 minutes at 45~65 DEG C.
The embodiment of the present invention is given below, but the present invention should not be limited by the examples:
Embodiment 1:
0.2g piperazine is taken, 0.1g zinc nitrate hexahydrate and 0.05g dopamine, which are dissolved in 100g deionized water, is configured to water
Solution is mixed, dip-coating is dense with mass percent in polysulfone ultrafiltration membrane surface 60 minutes, and then at 15 DEG C at 15 DEG C by it
Degree is the impregnation of 2-methylimidazole aqueous solution 100 minutes of 0.5%, obtains being coordinated organic nano particle nascent state film containing zinc,
It is then impregnated into the pyromellitic trimethylsilyl chloride hexane solution that mass percent concentration is 0.1%, it is interface-cross-linked anti-at 15 DEG C
It answers 10 minutes, finally solidifies 40 minutes at 45 DEG C, after deionized water is washed, obtain being coordinated organic nano particle hydridization containing zinc
PA membrane.
The coordination organic nano particle hydridization PA membrane containing zinc is under 25 DEG C, 0.2MPa pressure, for 1g.L-1It is Congo red
With the separating resulting of alkali blue organic dye solution are as follows: water flux 87.5L.m-2.h-1.bar-1, it is to Congo red rejection
97.5%, the rejection of alkali blue is 25.3%.
Embodiment 2:
2g piperazine is taken, 1g zinc nitrate hexahydrate and 0.5g dopamine, which are dissolved in 100g deionized water, is configured to water phase mixing
Solution, by it, dip-coating in polysulfone ultrafiltration membrane surface 10 minutes, and then at 25 DEG C is 5% with mass percent concentration at 25 DEG C
The impregnation of 2-methylimidazole aqueous solution 10 minutes, obtain containing zinc be coordinated organic nano particle nascent state film, be then impregnated into
In the pyromellitic trimethylsilyl chloride hexane solution that mass percent concentration is 1%, interface cross-linking reaction 2 minutes at 25 DEG C, finally
Solidify 10 minutes at 65 DEG C, after deionized water is washed, obtains being coordinated organic nano particle hydridization PA membrane containing zinc.
The coordination organic nano particle hydridization PA membrane containing zinc is under 25 DEG C, 0.2MPa pressure, for 1g.L-1It is Congo red
With the separating resulting of alkali blue organic dye solution are as follows: water flux 98.5L.m-2.h-1.bar-1, it is to Congo red rejection
98.2%, the rejection of alkali blue is 27.5%.
Embodiment 3:
0.3g piperazine is taken, 0.3g zinc nitrate hexahydrate and 0.2g dopamine, which are dissolved in 100g deionized water, is configured to water phase
Mixed solution, by it, dip-coating and then uses mass percent concentration at 25 DEG C in polysulfone ultrafiltration membrane surface 30 minutes at 25 DEG C
For the impregnation of 2-methylimidazole aqueous solution 30 minutes of 0.4%, obtain being coordinated organic nano particle nascent state film containing zinc, then
It is impregnated into the pyromellitic trimethylsilyl chloride hexane solution that mass percent concentration is 0.2%, interface cross-linking reaction 5 is divided at 25 DEG C
Clock finally solidifies 20 minutes at 60 DEG C, after deionized water is washed, obtains being coordinated organic nano particle hydridization polyamide containing zinc
Film.
Comparative example 1
Referring to 3 step of embodiment, contain zinc coordination organic nano particle without being formed in situ, directly with piperazine and equal benzene front three
Acyl chlorides is that raw material (film forming condition is referring to embodiment 3) prepares PA membrane.
Comparative example 2
It is directly made referring to 3 step of embodiment without the processing of 2-methylimidazole aqueous solution (film forming condition is referring to embodiment 3)
Standby PA membrane containing zinc ion.
Comparative example 3
Referring to 3 step of embodiment, (film forming condition reference is added in PA membrane preparation process with dopamine nanoparticle
Embodiment 3), prepare the PA membrane of nanoparticle containing dopamine.
The separating property of 1 embodiment 3 of table, the PA membrane of comparative example 1-3 preparation compares
Table 1 the result shows that, 4 kinds of methods can be made PA membrane, but it is logical to the rejection and water of organic dye molecule
Caused by amount has biggish difference, reason to be that the chemical composition for being used to prepare PA membrane is different with microstructure.
In comparative example 1, be not added with other modified materials, PA membrane be crosslinked by semi-aromatic polyamide macromolecular chain and
At the finer and close flux of this film is low；In comparative example 2, without the processing of 2-methylimidazole aqueous solution, hydrophily is introduced in PA membrane
Zinc metal ion, on membrane structure influence less, the hydrophily of film increase water flux increase；In comparative example 3, dopamine is added
Nanoparticle is modified material, and such nano material directly adds the poor dispersion in PA membrane, and water flux is increased,
But the effective aquaporin structure of perforation can not be formed in film.
In embodiment 3, zinc coordination organic nano particle is formed in situ in film forming procedure, it is microcosmic using its unique nanometer
Structure and strongly hydrophilic can be formed with receiving conducive to water penetration and organic molecule Selective Separation in polyamide separating layer
Rice channel design, meanwhile, which contains a large amount of reaction active groups and dopamine component, and particle can be in polyamide
It is uniformly and stably distributed in separating layer, therefore, gained zinc, which is coordinated organic nano particle hydridization PA membrane, has high water penetration
Property, high organic molecule separation selectivity and good stability.
Embodiment 4:
0.2g N- aminoethyl piperazine is taken, 0.3g zinc nitrate hexahydrate and 0.15g dopamine are dissolved in 100g deionized water
It is configured to water phase mixed solution, dip-coating and then uses quality at 25 DEG C in polysulfone ultrafiltration membrane surface 40 minutes at 25 DEG C by it
Percent concentration is the impregnation of 2-methylimidazole aqueous solution 30 minutes of 0.3%, is obtained containing at the beginning of zinc coordination organic nano particle
Ecological film is then impregnated into the pyromellitic trimethylsilyl chloride cyclohexane solution that mass percent concentration is 0.5%, the interface at 25 DEG C
Cross-linking reaction 2 minutes, finally solidify 30 minutes at 50 DEG C, after deionized water is washed, obtains being coordinated organic nano grain containing zinc
Sub- hydridization PA membrane.
The coordination organic nano particle hydridization PA membrane containing zinc is under 25 DEG C, 0.2MPa pressure, for 1g.L-1It is Congo red
With the separating resulting of alkali blue organic dye solution are as follows: water flux 85.8L.m-2.h-1.bar-1, it is to Congo red rejection
96.5%, the rejection of alkali blue is 24.6%.
Embodiment 5:
1g m-phenylene diamine (MPD) is taken, 0.5g zinc nitrate hexahydrate and 0.2g dopamine, which are dissolved in 100g deionized water, is configured to water
Solution is mixed, dip-coating and then uses mass percent at 25 DEG C in poly (ether-sulfone) ultrafiltration membrane surface 30 minutes at 25 DEG C by it
Concentration is the impregnation of 2-methylimidazole aqueous solution 60 minutes of 0.5%, obtains being coordinated organic nano particle nascent state film containing zinc,
It is then impregnated into the pyromellitic trimethylsilyl chloride cyclohexane solution that mass percent concentration is 1%, the interface cross-linking reaction 2 at 25 DEG C
Minute, finally solidify 15 minutes at 50 DEG C, after deionized water is washed, obtains being coordinated organic nano particle hydridization polyamides containing zinc
Amine film.
The coordination organic nano particle hydridization PA membrane containing zinc is under 25 DEG C, 0.2MPa pressure, for 1g.L-1It is Congo red
With the separating resulting of alkali blue organic dye solution are as follows: water flux 82.5L.m-2.h-1.bar-1, it is to Congo red rejection
98.5%, the rejection of alkali blue is 28.5%.
Embodiment 6:
1g ethylenediamine is taken, 0.6g zinc nitrate hexahydrate and 0.1g dopamine, which are dissolved in 100g deionized water, is configured to water phase
Mixed solution, by it, dip-coating is dense with mass percent in poly (ether-sulfone) ultrafiltration membrane surface 30 minutes, and then at 25 DEG C at 25 DEG C
Degree is the impregnation of 2-methylimidazole aqueous solution 30 minutes of 4%, obtains being coordinated organic nano particle nascent state film containing zinc, then
It is impregnated into the m-phthaloyl chloride hexane solution that mass percent concentration is 0.5%, interface cross-linking reaction 5 is divided at 25 DEG C
Clock finally solidifies 30 minutes at 50 DEG C, after deionized water is washed, obtains being coordinated organic nano particle hydridization polyamide containing zinc
Film.
The coordination organic nano particle hydridization PA membrane containing zinc is under 25 DEG C, 0.2MPa pressure, for 1g.L-1It is Congo red
With the separating resulting of alkali blue organic dye solution are as follows: water flux 90.7L.m-2.h-1.bar-1, it is to Congo red rejection
95.5%, the rejection of alkali blue is 19.6%.
Embodiment 7:
1.5g1,3,5- triaminobenzenes are taken, 0.5g zinc nitrate hexahydrate and 0.2g dopamine are dissolved in 100g deionized water
It is configured to water phase mixed solution, dip-coating and then is used in polyacrylonitrile ultrafiltration film surface 10 minutes at 25 DEG C at 25 DEG C by it
Mass percent concentration is the impregnation of 2-methylimidazole aqueous solution 40 minutes of 5%, obtains being coordinated organic nano particle containing zinc
Nascent state film is then impregnated into the biphenyl tetracarboxylic acyl chlorides n-heptane solution that mass percent concentration is 0.2%, the interface at 25 DEG C
Cross-linking reaction 5 minutes, finally solidify 30 minutes at 60 DEG C, after deionized water is washed, obtains being coordinated organic nano grain containing zinc
Sub- hydridization PA membrane.
The coordination organic nano particle hydridization PA membrane containing zinc is under 25 DEG C, 0.2MPa pressure, for 1g.L-1It is Congo red
With the separating resulting of alkali blue organic dye solution are as follows: water flux 106.2L.m-2.h-1.bar-1, to Congo red rejection
It is 97.8%, the rejection of alkali blue is 26.5%.
Embodiment 8:
1g p-phenylenediamine is taken, 0.6g zinc nitrate hexahydrate and 0.2g dopamine, which are dissolved in 100g deionized water, is configured to water
Solution is mixed, dip-coating is dense with mass percent in polysulfone ultrafiltration membrane surface 60 minutes, and then at 25 DEG C at 25 DEG C by it
Degree is the impregnation of 2-methylimidazole aqueous solution 30 minutes of 2%, obtains being coordinated organic nano particle nascent state film containing zinc, then
It is impregnated into the o-phthaloyl chloride hexane solution that mass percent concentration is 0.5%, interface cross-linking reaction 5 is divided at 25 DEG C
Clock finally solidifies 40 minutes at 50 DEG C, after deionized water is washed, obtains being coordinated organic nano particle hydridization polyamide containing zinc
Film.
The coordination organic nano particle hydridization PA membrane containing zinc is under 25 DEG C, 0.2MPa pressure, for 1g.L-1It is Congo red
With the separating resulting of alkali blue organic dye solution are as follows: water flux 96.8L.m-2.h-1.bar-1, it is to Congo red rejection
94.8%, the rejection of alkali blue is 20.5%.
Claims (10)
1. a kind of preparation method of zinc coordination organic nano particle hydridization PA membrane, characterized by the following steps:
1) using polyamine as monomer molecule, zinc nitrate hexahydrate is metal ion compound, and dopamine is bionical adhesive, configuration
At water phase mixed solution, by its dip-coating in open support film surface, then through 2-methylimidazole aqueous solution impregnation, in porous branch
Support film surface, which is formed in situ, is coordinated organic nano particle nascent state film containing zinc；
2) in organic solvent by the dissolution of polynary acyl chlorides monomer, it is made into organic phase solution, its dip-coating is coordinated in above-mentioned zinc supported
The nascent state film surface of organic nano particle carries out interface-cross-linked reaction, and heat cure processing most afterwards after deionized water is washed, obtains
Organic nano particle hydridization PA membrane is coordinated to containing zinc；
Polyamine monomer molecule described in step 1) is piperazine, N- aminoethyl piperazine, ethylenediamine, m-phenylene diamine (MPD), p-phenylenediamine
Or 1,3,5- triaminobenzene；Polynary acyl chlorides monomer described in step 2) is o-phthaloyl chloride, m-phthaloyl chloride, to benzene two
Formyl chloride, pyromellitic trimethylsilyl chloride or biphenyl tetracarboxylic acyl chlorides.
2. preparation method as described in claim 1, it is characterised in that: polyamine in water phase mixed solution described in step 1)
The mass percent concentration of monomer molecule is 0.2~2%.
3. preparation method as described in claim 1, it is characterised in that: six hydration in water phase mixed solution described in step 1)
The mass percent concentration of zinc nitrate is 0.1~1%.
4. preparation method as described in claim 1, it is characterised in that: dopamine in water phase mixed solution described in step 1)
Mass percent concentration be 0.05~0.5%.
5. preparation method as described in claim 1, it is characterised in that: porous support membrane described in step 1) is polysulfones, is gathered
Ether sulfone, polyacrylonitrile or vinylidene difluoride planar ultrafiltration membrane.
6. preparation method as described in claim 1, it is characterised in that: the dip-coating item of water phase mixed solution described in step 1)
Part is dip-coating 10~60 minutes at 15~25 DEG C.
7. preparation method as described in claim 1, it is characterised in that: the matter of 2-methylimidazole aqueous solution described in step 1)
Measuring percent concentration is 0.5~5%；Impregnation condition is impregnated 10~100 minutes at 15~25 DEG C.
8. preparation method as described in claim 1, it is characterised in that: polynary acyl chlorides in organic phase solution described in step 2)
The mass percent concentration of monomer molecule is 0.1~1%.
9. preparation method as described in claim 1, it is characterised in that: the solvent of organic phase solution described in step 2) is just
Hexane, hexamethylene or heptane.
10. preparation method as described in claim 1, it is characterised in that: organic phase solution dip-coating described in step 2) carries out
The condition of interface-cross-linked reaction is reacted 2~10 minutes at 15~25 DEG C；Heat cure treatment conditions are solid at 45~65 DEG C
Change 10~40 minutes.
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