CN103223302B - Preparation method of self-assembly covalent cross-linked sodium filter membrane - Google Patents
Preparation method of self-assembly covalent cross-linked sodium filter membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 238000001338 self-assembly Methods 0.000 title claims abstract description 31
- 239000011734 sodium Substances 0.000 title abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title abstract 4
- 229910052708 sodium Inorganic materials 0.000 title abstract 4
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 claims abstract description 45
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 15
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- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 210000004379 membrane Anatomy 0.000 claims description 111
- 239000000243 solution Substances 0.000 claims description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000008367 deionised water Substances 0.000 claims description 51
- 229910021641 deionized water Inorganic materials 0.000 claims description 51
- 210000002469 basement membrane Anatomy 0.000 claims description 46
- 239000002131 composite material Substances 0.000 claims description 43
- 239000003792 electrolyte Substances 0.000 claims description 41
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 13
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- 238000005516 engineering process Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
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- 230000003115 biocidal effect Effects 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940059939 kayexalate Drugs 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 3
- -1 aldehyde radical Chemical class 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 3
- IFQGISKNQARMMS-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)NCC1=C(C=CC(=C1)C)O Chemical compound C(C1=CC=CC=C1)(=O)NCC1=C(C=CC(=C1)C)O IFQGISKNQARMMS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
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- 229940015043 glyoxal Drugs 0.000 claims description 2
- 238000009396 hybridization Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 abstract description 2
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- 239000010408 film Substances 0.000 description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
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- 238000012360 testing method Methods 0.000 description 18
- 230000004907 flux Effects 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 230000003068 static effect Effects 0.000 description 15
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Abstract
The invention belongs to the technical field of preparation of separating membranes and relates to a preparation method of a self-assembly covalent cross-linked sodium filter membrane. The preparation method comprises the following steps of: pre-treating a base membrane, so that the surface of the base membrane has a functional group capable of generating electrostatic interaction with polyelectrolyte; dissolving capsaicin functional monomers in a polyelectrolyte solution; soaking the base membrane in the polyelectrolyte solution; getting out of the base membrane, washing the surface of the base membrane and soaking the washed base membrane in the polyelectrolyte solution with opposite charges; getting out the membrane, washing the surface of the membrane and soaking the washed membrane in a dialdehyde cross-linking agent to obtain the self-assembly covalent cross-linked sodium filter membrane with antibacterial activity. The self-assembly cross-linked sodium filter membrane with antibacterial activity is simple in preparation process, good in self-assembly effect, low in preparation cost and production environment-friendly.
Description
Technical field:
The invention belongs to diffusion barrier preparing technical field, relate to a kind of preparation method of the self assembly covalent cross-linking NF membrane with biocidal property, Capsaicin derivative is prepared into NF membrane by being blended in polyelectrolyte solution and by the form of self assembly, by crosslinked action, realize again the immobilization of Capsaicin derivative, strengthen the membrane stability of NF membrane.
Background technology:
The pore diameter range of NF membrane is at nanoscale, its molecular cut off is 200～1000, the membrane aperture corresponding with holding back relative molecular mass is 1～3nm, a kind of film between counter-infiltration and ultrafiltration, NF membrane can hold back the low relative molecular mass organic matters such as carbohydrate and high price inorganic salts (as MgSO
4deng), to the rejection of unit price inorganic salts, be only 10%～80%, under identical flux condition, the desired driving pressure of NF membrane is lower than reverse osmosis membrane, general nanofiltration operating pressure is 0.5～1.5MPa, and the separating property of NF membrane uniqueness makes NF membrane all be widely used at water treatment, medicine, dye field, food processing, black water treatment and reuse.To the research of NF membrane technology of preparing, both at home and abroad with interfacial polymerization, phase inversion and surface graft modification method are main, the raising requiring along with the increase of separation system complexity with to separating property, develop new, the NF membrane simultaneously with high flux and high selectivity becomes the study hotspot of film separation field, layer-by-layer (LBL) is shown great attention in recent years, its method is simple, it is the alternating deposit of polyelectrolyte molecules or the charge species electrostatic interaction on liquid/liquid/solid interface, and be not limited to the kind of substrate, size and surface configuration, the NF membrane that adopts LBL method to prepare has following advantage: the one, and polyelectrolyte is with a large amount of electric charges, can produce south, road effect with separated material, reach the object of selecting separation, the 2nd, by adjusting substance classes and the sedimentary condition of polyelectrolyte, can control the structure of self-assembled film and performance, the 3rd, every strata electrolyte molecule, by ionic bond combination, strengthens film strength, the current over-borrowing of self assembly layer by layer helps electrostatic force, hydrogen bond, electric charge transferance, coordination, subjective and objective interaction and the soda acid peer interaction of layer and interlayer, and the stability of these polymer multilayer films based on weak interaction is usually not enough, can not resist comparatively harsh external environment condition and destroyed, these external environment conditions comprise dissolving, the erosion of acid-alkali salt and the decomposition of high temperature etc. of organic solvent.At present, people are being developed some and are obtaining based on covalent bond the new package technique of stable multilayer film, the intensity of covalent bond is larger than weak interaction forces such as static and hydrogen bonds, if prepare the multilayer film of polymer by the method for covalent bond, can obtain the polymer ultra-thin film that structure is more stable, this is because the group that intermolecular dependence can be reacted mutually combines, the polymer network structure that height of formation is crosslinked.Therefore, once reacted, just can not be by organic solvent dissolution, can not be destroyed by soda acid and the salt of general concentration, heat-resisting quantity improves, and still can keep laminated assembling technology in advantages such as the facilities of controlling diaphragm structure aspects simultaneously.For improving the strength and stability of self assembly NF membrane, can will be assembled in film with the material of reactive group, then carry out chemical reaction, make assembling film interlayer form covalent bond, Chinese Patent Application No. 201010249144.2 discloses a kind of method based on covalent effect assembling multilayer diffusion barrier, adopt self-assembling technique, the Multi-layered osmotic forming by covalent effect vaporization film, is significantly improved the stability of film and resistance to acids and bases.The pollutants such as the bacterium that NF membrane is held back in separation process can be attached to film surface even in fenestra, very easily on film surface, form biomembrane, and further growth breeding formation biofouling, organic solute discharged simultaneously, tunicle is held back formation gel layer, forms the biological pollution that is difficult to remove.The biological pollution of film has reduced filter efficiency and the film aquifer yield of film, has increased the cleaning frequency of film simultaneously, has shortened the service life of film, has increased the number of times that film is changed, thereby the use cost of membrane module and operating cost are increased.The NF membrane that preparation has bacteriostasis is the direction of Future Development.Capsaicin has broad-spectrum antibacterial effect, is a kind of natural antibacterial agent efficiently, has now been applied in marine antifouling coating.United States Patent (USP) 5226380,5397385,5925370 and Chinese patent 200510081683.9 are all about Capsaicin derivative is used in to the application in antifouling paint, through patch test of paints on ship hull, acquired results shows: the Capsaicin antifouling paint of this kind of formula can suppress adhering to of fouling organism preferably; Chinese Patent Application No. 201210056842.X discloses one " hydrophily contains anti-biological-contamination ultrafiltration membrane of Capsaicin functional group and preparation method thereof " and Capsaicin has been introduced in the casting solution of preparing polysulphone super-filter membrane, by immersion precipitation phase inversion, prepared Novel antibacterial milipore filter, its bacteriostasis rate reaches 85% left and right, has increased the service life of film.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seeking design provides a kind of and on basement membrane, utilizes self assembly layer by layer to combine with chemical crosslinking to prepare the new method of biocidal property NF membrane, realization becomes NF membrane from ultrafiltration membranes by one or more double-deck modifications, the stability and the biocidal property that improve composite membrane, obtain the NF membrane that separating property, stability and biocidal property are high.
To achieve these goals, the present invention first carries out pretreatment to basement membrane, make on its surface band can with the functional group of polyelectrolyte generation electrostatic interaction, then Capsaicin function monomer is dissolved in to polyelectrolyte solution, and basement membrane is immersed in this polyelectrolyte solution, taking out basement membrane rinses and is immersed in behind surface with it in the polyelectrolyte solution with opposite charges again, after finally film being taken out to flushing surface, be immersed in the crosslinking agent of twain-aldehyde compound, obtain having the self assembly covalent cross-linking NF membrane of biocidal property, twain-aldehyde compound is because its special chemical constitution is widely used as crosslinking agent, in its molecule, having two carbonyl carbonyl carbon is sp
2hybridized orbit, carbonyl carbon is with part positive charge, ketonic oxygen is with part negative electrical charge, amino because the not share electron pair in its nitrogen-atoms also has nucleophilicity in polycation electrolyte, amino is easy to, with the carbonyl carbon with positive charge, Schiff alkali reaction occurs, if a dialdehyde molecule can be positioned at different large molecules from two amino these two amino of reaction and produce the intermolecular network structure that has been cross-linked to form, this just twain-aldehyde compound can to self-assembled film, carry out as crosslinking agent the principle place of crosslinking Treatment, its concrete technology step is:
(1), polycation electrolyte and Capsaicin functional structure monomer are dissolved in alcohols, amine organic solvent, the polycation electrolyte solution that be mixed with polycation electrolyte mass percent concentration and be 0.1%～1%, Capsaicin function monomer mass percent is 0%～2%, standing and defoaming is standby;
(2), alcohols, amine organic solvent or deionized water for polycation electrolyte are mixed with to mass percent concentration is 0.1%～1% polyanion electrolyte solution, standing and defoaming;
(3), alcohols, amine organic solvent or deionized water for polyanion electrolyte are mixed with to mass percent concentration is 0.1%～1% polyanion electrolyte solution, standing and defoaming;
(4), twain-aldehyde compound crosslinking agent is dissolved in deionized water or alcohols solvent, be mixed with mass percent concentration and be 0.1%～2% cross-linking agent solution, standing and defoaming;
(5), basement membrane is carried out to plasma treatment or Chemical Pretreatment, make the surface electric charge of basement membrane;
(6), the basement membrane of charge is immersed in the polyelectrolyte solution with its opposite charge,, as 5～30min in polycation electrolyte solution, polycation electrolyte is deposited on and on basement membrane, forms polycation thin layer; Then basement membrane is taken out, by deionized water, rinse out the unnecessary polyelectrolyte solution of membrane surface, obtain having the composite membrane of polycation thin layer;
(7), the composite membrane with polycation thin layer is immersed in to 5～30min in polyanion electrolyte solution, polycation electrolyte and polyanion electrolyte are assembled on basement membrane by electrostatic interaction, form double-deck polyelectrolyte composite membrane;
(8), formed polyelectrolyte composite membrane is taken out, by deionized water, rinse out the unnecessary polyelectrolyte solution in composite membrane surface;
(9), polyelectrolyte composite membrane is immersed in to 20min～2h in cross-linking agent solution, make the aldehyde radical functional group of crosslinking agent and the amido functional group generation covalent effect of polycation, aldehyde radical becomes carbon-to-nitrogen double bon with amino dehydrating condensation, form the covalent bond ultrathin membrane of three-dimensional compact texture, cross-linking reaction makes polymer become three-dimensional-structure by linear structure, and resistance to water, solvent resistance and the intensity of basement membrane are improved;
(10), with the clean composite membrane of rinsed with deionized water surface, obtain double-deck cross linking membrane;
(11), repeat (6)～(10) steps to required double-deck number, the polycation electrolyte solution of outermost bilayer changes polycation electrolyte Capsaicin solution into, Capsaicin covers the surface of film and plays bacteriostasis.
Polycation electrolyte of the present invention be with the polyelectrolyte of twain-aldehyde compound crosslinking agent generation covalent effect functional group, comprise polymine (PEI), polyallylamine hydrochloride (PAH), PDDA (PDDA) and containing amino protein macromolecule; Polyanion electrolyte is and the polyanion electrolyte of polycation electrolyte generation electrostatic interaction, comprises polyacrylic acid (PAA) and kayexalate (PSS); Capsaicin function monomer comprises N-(5-methyl-2 hydroxybenzyl) benzamide, N-(6-methyl-5-hydroxyl-1,3-benzo dioxa penta encircles) benzamide, N-(5-benzamide methyl-2-hydroxyl-3-methoxybenzy) benzamide, the N-(5-methyl-3-tert-butyl group-2-hydroxybenzyl) benzamide and N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl) acrylamide; Twain-aldehyde compound crosslinking agent comprises glyoxal and glutaraldehyde; Basement membrane is milipore filter, and the material of basement membrane is inoranic membrane or organic film, or organic inorganic hybridization film, and the kit form of basement membrane is tubular membrane, hollow-fibre membrane, Flat Membrane or rolled film.
Preparation of the present invention is self-assembled film process layer by layer, and wherein the mass percent of the contained Capsaicin function monomer of each double-deck polycation electrolyte solution using can be different.
When NF membrane prepared by the inventive method is carried out separating property test, select the Na of 2g/L
2sO
4the NaCl aqueous solution of the aqueous solution and 2g/L, is that 1.0MPa and temperature are to test separating property under the condition of 25 ℃ at operating pressure, and salt rejection rate (R) and water flux (J) are calculated as follows respectively:
Wherein C
ffor concentration of raw material, C
pfor seeing through liquid concentration, Δ V is long-pending for seeing through liquid, and A is effective film area, and t is the testing time.
When NF membrane prepared by the inventive method is carried out the performance test of stable against biological contamination, adopt dilution spread flat band method, take Escherichia coli as indicator bacteria, according to bacteriostasis rate, judge NF membrane bacteriostasis property, bacteriostasis rate (Q) is calculated as follows
Q=(1-C/B)×100%，
Wherein B is the clump count of basement membrane sample, and C is the clump count of the membrane sample after modification.
The present invention compared with prior art, only need bilayer of assembling and just realize milipore filter modification is become to NF membrane by cross-linking reaction, self assembly and chemical crosslinking are combined, film solvent resistance and the stability of preparation are high, by blend, Capsaicin function monomer is introduced to the cortex construction of film, strengthened the stable against biological contamination ability of film; The THICKNESS CONTROL of polyelectrolyte diffusion barrier is at nanoscale; Its preparation process is simple, and self assembly is respond well, and preparation cost is low, production environment close friend.
Accompanying drawing explanation:
Fig. 1 is the structural formula schematic diagram of the Capsaicin function monomer that the present invention relates to.
Instantiation mode:
Below in conjunction with specific embodiment, the inventive method is described further.
Embodiment 1:
The basement membrane that the present invention adopts is polyacrylonitrile (PAN) film, molecular cut off 50000Da(dalton), flat milipore filter, membrane area is 28.26cm
2; Polyanion electrolyte used is Sodium Polyacrylate (PAA, molecular weight is 100,000); Polycation electrolyte used is polymine (PEI, molecular weight is 60,000), and the molecular weight of glutaraldehyde (GA) is 100; Function monomer N-(5-methyl-2 hydroxybenzyl of Capsaicin) self-control of benzamide (HMBB) laboratory, its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation electrolyte solution, wherein the mass percent concentration of PEI is the mass percent concentration 0.25% of 0.4%, HMBB;
(2) the PAA solution that is, 0.25% with deionized water preparation mass percent concentration;
(3) the GA solution that is, 0.5% with deionized water preparation mass percent concentration;
(4), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed to 1h in 2N NaOH solution, by polyacrylonitrile-radical membrane surface modification, be bear electricity;
(5), by deionized water, rinse out the NaOH solution on film surface, until pH value is neutral;
(6), by the PAN basement membrane static immersing after modification in polycation electrolyte solution, after 15min, take out and rinse out the unnecessary polycation electrolyte solution on film surface by deionized water;
(7), by PAN/ polycation composite membrane static immersing, at mass percent concentration, be in 0.25%PAA solution, after 15min, take out and rinse out the unnecessary polyelectrolyte solution on composite membrane surface by deionized water;
(8), polyelectrolyte composite membrane is immersed in to mass percent concentration is 30min in 0.5% GA solution, makes it that chemical crosslink reaction occur;
(9), the film after crosslinked is taken out, be immersed in deionized water, rinsing composite membrane surface, can form the compound number of plies is 1 double-deck self assembly NF membrane based on covalent effect.
The test result that self assembly NF membrane prepared by the present embodiment is carried out separating property and antifouling property test is: to Na
2sO
4rejection be 81%, solution flux is 60L/m
2h, is 48% to the rejection of NaCl, and solution flux is 80L/m
2h, bacteriostasis rate is 80.5%.
Embodiment 2:
The present embodiment basement membrane used, polycation electrolyte, polyanion electrolyte are with embodiment 1, and its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation preparation liquid, wherein the mass percent concentration of PEI is the mass percent concentration 0.25% of 0.4%, HMBB;
(2) the PAA solution that is, 0.25% with deionized water preparation mass percent concentration;
(3) with deionized water preparation mass percent concentration, be: 0.5% GA solution;
(4), for making polyacrylonitrile basement membrane surface charge, adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed to 1h in 2N NaOH solution, be modified as polyanion basement membrane;
(5), by deionized water, rinse out the NaOH solution on film surface, until pH value is neutral;
(6), by the PAN basement membrane static immersing after modification in said polycation solution, after 15min, take out and rinse out the unnecessary electrolyte solution on film surface by deionized water;
(7), by PAN/ polycation composite membrane static immersing, at mass percent concentration, be in 0.25%PAA solution, after 15min, take out and rinse out the unnecessary polyelectrolyte solution on composite membrane surface by deionized water;
(8), polyelectrolyte composite membrane is immersed in to mass percent concentration is 1h in 0.5% GA solution, makes it that chemical crosslink reaction occur;
(9), the film after crosslinked is taken out, be immersed in deionized water, rinsing composite membrane surface, can form the compound number of plies is 1 double-deck self assembly NF membrane based on covalent effect.
The test result that self assembly NF membrane prepared by the present invention is carried out separating property and antifouling property test is: to Na
2sO
4rejection be 85%, solution flux is 40L/m
2h, is 52% to the rejection of NaCl, and solution flux is 60L/m
2h, bacteriostasis rate is 81%.
Embodiment 3:
The present embodiment basement membrane used, polycation electrolyte, polyanion electrolyte are with embodiment 1, and its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation preparation liquid, wherein the mass percent concentration of PEI is the mass percent concentration 0.25% of 0.4%, HMBB;
(2) the PAA solution that is, 0.25% with absolute ethyl alcohol preparation mass percent concentration;
(3) the GA solution that is, 1% with deionized water preparation mass percent concentration;
(4), for making polyacrylonitrile basement membrane surface charge, adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed to 1h in 2N NaOH solution, be modified as polyanion basement membrane;
(5), by deionized water, rinse out the NaOH solution on film surface, until pH value is neutral;
(6), by the PAN film static immersing after modification in said polycation solution, after 15min, take out and rinse out the unnecessary electrolyte solution on film surface by deionized water;
(7), by PAN/ polycation composite membrane static immersing, at mass percent concentration, be in 0.25%PAA solution, after 15min, take out, by deionized water, rinse out the unnecessary polyelectrolyte solution on composite membrane surface;
(8), polyelectrolyte composite membrane is immersed in to mass percent concentration is 1h in 1% GA solution, makes it that chemical crosslink reaction occur;
(9), the film after crosslinked is taken out, be immersed in deionized water, rinsing composite membrane surface, can form the compound number of plies is 1 double-deck self assembly NF membrane based on covalent effect.
The test result that self assembly NF membrane prepared by the present embodiment is carried out separating property and antifouling property test is: to Na
2sO
4rejection be 88%, solution flux is 38L/m
2h, is 62% to the rejection of NaCl, and solution flux is 45L/m
2h, bacteriostasis rate is 82%.
Embodiment 4:
The present embodiment basement membrane used, polycation electrolyte, polyanion electrolyte are with embodiment 1, and its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation preparation liquid, wherein the mass percent concentration of PEI is the mass percent concentration 0.4% of 0.4%, HMBB;
(2) the PAA solution that is, 0.25% with absolute ethyl alcohol preparation mass percent concentration;
(3) the GA solution that is, 1% with deionized water preparation mass percent concentration;
(4), for making polyacrylonitrile basement membrane surface charge, adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed to 1h in 2N NaOH solution, be modified as polyanion basement membrane;
(5), by deionized water, rinse out the NaOH solution on film surface, until pH value is neutral;
(6), by the PAN film static immersing after modification in said polycation solution, after 15min, take out, by deionized water, rinse out the unnecessary electrolyte solution on film surface;
(7), in the PAA solution that is 0.25% by PAN/ polycation composite membrane static immersing at mass percent concentration, after 15min, take out, by deionized water, rinse out the unnecessary polyelectrolyte solution on composite membrane surface;
(8), polyelectrolyte composite membrane is immersed in to mass percent concentration is 1h in 1% GA solution, makes it that chemical crosslink reaction occur;
(9), the film after crosslinked is taken out, be immersed in deionized water, rinsing composite membrane surface, can form the compound number of plies is 1 double-deck self assembly NF membrane based on covalent effect.
The test result that self assembly NF membrane prepared by the present embodiment is carried out separating property and antifouling property test is: to Na
2sO
4rejection be 90%, solution flux is 35L/m
2h, is 67% to the rejection of NaCl, and solution flux is 42L/m
2h, bacteriostasis rate is 90.7%.
Embodiment 5:
The basement membrane that the present embodiment adopts is polyacrylonitrile (PAN) film, molecular cut off 50000Da(dalton), flat milipore filter, membrane area is 28.26cm
2; Polyanion electrolyte used is kayexalate (PSS, molecular weight is 70,000); Polycation electrolyte used is polymine (PEI, molecular weight is 60,000), glutaraldehyde (GA, molecular weight 100); Capsaicin structure function monomer N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl) self-control of acrylamide (NHMBA) laboratory, its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation electrolyte solution, wherein the mass percent concentration of PEI is that the mass percent concentration of 0.4%, NHMBA is 0.25%;
(2) the PAA solution that is, 0.25% with absolute ethyl alcohol preparation mass percent concentration;
(3) the GA solution that is, 1% with deionized water preparation mass percent concentration;
(4), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed to 1h in 2N NaOH solution, by polyacrylonitrile-radical membrane surface modification, be bear electricity;
(5), by deionized water, rinse out the NaOH solution on film surface, until pH value is neutral;
(6), by the PAN basement membrane static immersing 15min in said polycation solution after modification; By deionized water, rinse out the unnecessary electrolyte solution on film surface;
(7), by PAN/ polycation composite membrane static immersing, at mass percent concentration, be in 0.25%PAA solution, after 15min, take out, by deionized water, rinse out the unnecessary polyelectrolyte solution on composite membrane surface;
(8), polyelectrolyte composite membrane is immersed in to mass percent concentration is 1h in 1% GA solution, makes it that chemical crosslink reaction occur;
(9), the film after crosslinked is taken out, be immersed in deionized water, rinsing composite membrane surface, can form the compound number of plies is 1 double-deck self assembly NF membrane based on covalent effect.
The test result that self assembly NF membrane prepared by the present embodiment is carried out separating property and antifouling property test is: to Na
2sO
4rejection be 85.7%, solution flux is 41L/m
2h, is 56% to the rejection of NaCl, and solution flux is 53L/m
2h, bacteriostasis rate is 84.5%.
Embodiment 6:
The basement membrane that the present embodiment adopts is polyacrylonitrile (PAN) film, molecular cut off 50000Da(dalton), flat milipore filter, membrane area is 28.26cm
2; Polyanion electrolyte used is kayexalate (PSS, molecular weight is 70,000); Polycation electrolyte used is PAH (PAH, molecular weight is 5.6 ten thousand), glutaraldehyde (GA, molecular weight 100); Function monomer N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl of Capsaicin) self-control of acrylamide (NHMBA) laboratory.Its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation electrolyte solution, wherein the mass percent concentration of PEI is the mass percent concentration 0.25% of 0.4%, NHMBA;
(2) the PAA solution that is, 0.25% with absolute ethyl alcohol preparation mass percent concentration;
(3) the GA solution that is, 1% with deionized water preparation mass percent concentration;
(4), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed to 1h in 2N NaOH solution, by polyacrylonitrile-radical membrane surface modification, be bear electricity;
(5), by deionized water, rinse out the NaOH solution on film surface, until pH value is neutral;
(6), by the PAN basement membrane static immersing after modification in polycation electrolyte solution, after 15min, take out, by deionized water, rinse out the unnecessary electrolyte solution on film surface;
(7), by PAN/ polycation composite membrane static immersing, at mass percent concentration, be in 0.25%PAH solution, after 15min, take out, by deionized water, rinse out the unnecessary polyelectrolyte solution on composite membrane surface;
(8), polyelectrolyte composite membrane is immersed in to mass percent concentration is 1h in 1% GA solution, makes it that chemical crosslink reaction occur;
(9), the film after crosslinked is taken out, be immersed in deionized water, rinsing composite membrane surface, can form the compound number of plies is 1 double-deck self assembly NF membrane based on covalent effect.
The test result that self assembly NF membrane prepared by the present embodiment is carried out separating property and antifouling property test is: to Na
2sO
4rejection be 83.5%, solution flux is 46L/m
2h, is 50.4% to the rejection of NaCl, and solution flux is 57L/m
2h, bacteriostasis rate is 81.5%.
Embodiment 7:
The basement membrane that the present embodiment adopts is polyacrylonitrile (PAN) film, molecular cut off 50000Da(dalton), flat milipore filter, membrane area is 28.26cm
2; Polyanion electrolyte used is Sodium Polyacrylate (PAA, molecular weight is 100,000); Polycation electrolyte used is polymine (PEI, molecular weight is 60,000), and the molecular weight of glutaraldehyde (GA) is 100; Function monomer N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl of Capsaicin) self-control of acrylamide (NHMBA) laboratory.In its preparation process, the PEI polycation electrolyte solution that wherein the 8th step is used when first bilayer of preparation is containing Capsaicin function monomer NHMBA, and second the double-deck PEI polycation electrolyte solution using contains Capsaicin function monomer NHMBA.Concrete preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation electrolyte solution, wherein the mass percent concentration of PEI is the mass percent concentration 0.25% of 0.4%, NHMBA;
(2) the polycation electrolyte solution that is, 0.4% with the mass percent concentration of absolute ethyl alcohol preparation PEI;
(3) the PEI solution that is, 0.4% with deionized water preparation mass percent concentration;
(4) the PAA solution that is, 0.25% with deionized water preparation mass percent concentration;
(5) the GA solution that is, 1% with deionized water preparation mass percent concentration;
(6), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed to 1h in 2N NaOH solution, by polyacrylonitrile-radical membrane surface modification, be bear electricity;
(7), by deionized water, rinse out the NaOH solution on film surface, until pH value is neutral;
(8), 15min in the solution that is 0.4% by the PAN basement membrane static immersing after modification at PEI mass percent concentration, by deionized water, rinse out the unnecessary polyelectrolyte solution on film surface;
(9), by PAN/ polycation composite membrane static immersing, at mass percent concentration, be in 0.25%PAH solution, after 15min, take out, by deionized water, rinse out the unnecessary polyelectrolyte solution on composite membrane surface;
(10), repeat (8)～(9) steps, can form the compound number of plies is two double-deck NF membrane containing Capsaicin.
(11), polyelectrolyte composite membrane is immersed in to mass percent concentration is 1h in 1% GA solution, makes it that chemical crosslink reaction occur;
(12), the film after crosslinked is taken out, be immersed in deionized water, rinsing composite membrane surface, can form the compound number of plies is two double-deck self assembly NF membrane based on covalent effect.
The test result that self assembly NF membrane prepared by the present embodiment is carried out separating property and antifouling property test is: to Na
2sO
4rejection be 98.73%, solution flux 17.64L/m
2h, is 82.89% to the rejection of NaCl, and solution flux is 20.78L/m
2h, bacteriostasis rate is 90%.
Claims (2)
1. the preparation method of a self assembly covalent cross-linking NF membrane, it is characterized in that first basement membrane being carried out to pretreatment, make on its surface band can with the functional group of polyelectrolyte generation electrostatic interaction, then Capsaicin function monomer is dissolved in to polyelectrolyte solution, and basement membrane is immersed in this polyelectrolyte solution, taking out basement membrane rinses and is immersed in behind surface with it in the polyelectrolyte solution with opposite charges again, after finally film being taken out to flushing surface, be immersed in the crosslinking agent of twain-aldehyde compound, the self assembly covalent cross-linking NF membrane that obtains having biocidal property, its concrete technology step is:
(1), polycation electrolyte and Capsaicin function monomer are dissolved in alcohols or amine organic solvent, the polycation electrolyte Capsaicin solution that be mixed with polycation electrolyte mass percent concentration and be 0.1%～1%, Capsaicin function monomer mass percent is 0%～2%, standing and defoaming is standby;
(2), polycation electrolyte is mixed with to mass percent concentration by alcohols or amine organic solvent or deionized water is 0.1%～1% polycation electrolyte solution, standing and defoaming;
(3), polyanion electrolyte is mixed with to mass percent concentration by alcohols or amine organic solvent or deionized water is 0.1%～1% polyanion electrolyte solution, standing and defoaming;
(4), twain-aldehyde compound crosslinking agent is dissolved in deionized water or alcohols solvent, be mixed with mass percent concentration and be 0.1%～2% cross-linking agent solution, standing and defoaming;
(5), basement membrane is carried out to plasma treatment or Chemical Pretreatment, make the surface electric charge of basement membrane;
(6), the basement membrane of charge is immersed in to 5～30min in polycation electrolyte solution, polycation electrolyte is deposited on and on basement membrane, forms polycation thin layer; Then basement membrane is taken out, by deionized water, rinse out the unnecessary polyelectrolyte solution of membrane surface, obtain having the composite membrane of polycation thin layer;
(7), the composite membrane with polycation thin layer is immersed in to 5～30min in polyanion electrolyte solution, polycation electrolyte and polyanion electrolyte are assembled on basement membrane by electrostatic interaction, form double-deck polyelectrolyte composite membrane;
(8), formed polyelectrolyte composite membrane is taken out, by deionized water, rinse out the unnecessary polyelectrolyte solution in composite membrane surface;
(9), polyelectrolyte composite membrane is immersed in to 20min～2h in cross-linking agent solution, make the aldehyde radical functional group of crosslinking agent and the amido functional group generation covalent effect of polycation, aldehyde radical becomes carbon-to-nitrogen double bon with amino dehydrating condensation, form the covalent bond ultrathin membrane of three-dimensional compact texture, cross-linking reaction makes polymer become three-dimensional-structure by linear structure, and resistance to water, solvent resistance and the intensity of basement membrane are improved;
(10), with the clean composite membrane of rinsed with deionized water surface, obtain double-deck cross linking membrane;
(11), repeat (6)～(10) steps to required double-deck number, the polycation electrolyte solution of outermost bilayer changes polycation electrolyte Capsaicin solution into, Capsaicin covers the surface of film and plays bacteriostasis.
2. the preparation method of self assembly covalent cross-linking NF membrane according to claim 1, it is characterized in that described polycation electrolyte be with the polyelectrolyte of twain-aldehyde compound crosslinking agent generation covalent effect functional group, comprise polymine, polyallylamine hydrochloride, PDDA and containing amino protein macromolecule; Polyanion electrolyte is and the polyanion electrolyte of polycation electrolyte generation electrostatic interaction, comprises polyacrylic acid and kayexalate; Capsaicin function monomer comprises N-(5-methyl-2 hydroxybenzyl) benzamide, N-(6-methyl-5-hydroxyl-1,3-benzo dioxa penta encircles) benzamide, N-(5-benzamide methyl-2-hydroxyl-3-methoxybenzy) benzamide, the N-(5-methyl-3-tert-butyl group-2-hydroxybenzyl) benzamide and N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl) acrylamide; Twain-aldehyde compound crosslinking agent comprises glyoxal and glutaraldehyde; Basement membrane is milipore filter, and the material of basement membrane is inoranic membrane or organic film, or organic inorganic hybridization film, and the kit form of basement membrane is tubular membrane, hollow-fibre membrane, Flat Membrane or rolled film.
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| CN105498559B (en) * | 2015-12-29 | 2018-10-16 | 中国科学院烟台海岸带研究所 | Composite membrane based on functional protein |
| DE102016102782A1 (en) * | 2016-02-17 | 2017-09-14 | B. Braun Avitum Ag | Dialysis membrane and process for its preparation |
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| CN111659268A (en) * | 2020-06-17 | 2020-09-15 | 埃隆水处理技术(上海)有限公司 | Preparation method of low-pressure multi-electrolyte-layer hollow fiber nanofiltration membrane |
| CN111992040B (en) * | 2020-09-10 | 2022-05-10 | 德州学院 | Preparation method of polyelectrolyte nanofiltration membrane |
| CN112221353B (en) * | 2020-09-30 | 2022-09-20 | 武汉工程大学 | Polyelectrolyte compound nanofiltration membrane and preparation method and application thereof |
| CN112516822B (en) * | 2020-10-29 | 2022-08-23 | 南京工业大学 | Nanofiltration membrane and membrane performance regulation and control method based on nanocapsules |
| CN113075271B (en) * | 2021-03-31 | 2022-04-22 | 华中科技大学 | 4D printing chemical sensor and preparation method thereof |
| CN113441013A (en) * | 2021-06-28 | 2021-09-28 | 哈尔滨工业大学 | Preparation method of conductive nanofiltration membrane for water treatment |
| CN114832642B (en) * | 2022-04-11 | 2022-11-01 | 贵州省材料产业技术研究院 | PVDF (polyvinylidene fluoride) antibacterial nanofiltration membrane capable of realizing layer-by-layer self-assembly host-guest recognition and preparation method |
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