CN103223302A - 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 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 67
- 238000001338 self-assembly Methods 0.000 title claims abstract description 34
- 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
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 15
- 230000009881 electrostatic interaction Effects 0.000 claims abstract description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- 210000004379 membrane Anatomy 0.000 claims description 117
- 239000000243 solution Substances 0.000 claims description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 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 48
- 239000002131 composite material Substances 0.000 claims description 43
- 239000003792 electrolyte Substances 0.000 claims description 40
- 239000008151 electrolyte solution Substances 0.000 claims description 29
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 24
- 229920000447 polyanionic polymer Polymers 0.000 claims description 24
- 238000012360 testing method Methods 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
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- 238000004132 cross linking Methods 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
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- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 230000003115 biocidal effect Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 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 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000011109 contamination Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 229940059939 kayexalate Drugs 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- -1 aldehyde radical Chemical class 0.000 claims description 3
- 238000012545 processing Methods 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
- 241000588724 Escherichia coli Species 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 230000008569 process Effects 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
- 239000002994 raw material Substances 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
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 3
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 abstract 2
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- 229960002504 capsaicin Drugs 0.000 abstract 1
- 235000017663 capsaicin Nutrition 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000003373 anti-fouling effect Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
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- 230000003993 interaction Effects 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
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- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 239000003242 anti bacterial agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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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 the diffusion barrier preparing technical field, relate to a kind of preparation method with self assembly covalent cross-linking NF membrane of biocidal property, with peppery plain derivative by being blended in the polyelectrolyte solution and form by self assembly is prepared into NF membrane, realize the immobilization of peppery plain derivative again by crosslinked action, 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, with holding back the corresponding membrane aperture of relative molecular mass is 1～3nm, be a kind of film between counter-infiltration and ultrafiltration, NF membrane can be held back low relative molecular mass organic matter such as carbohydrate and high price inorganic salts (as MgSO
4Deng), rejection to the unit price inorganic salts only is 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 handle with reuse and all be widely used at water treatment, medicine, dye field, food processing, black water.Research to the NF membrane technology of preparing, both at home and abroad with interfacial polymerization, phase inversion and surface graft modification method are main, along with the increase of separation system complexity and the raising that separating property is required, develop new, the NF membrane that has high flux and high selectivity simultaneously becomes the research focus 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, adopt the NF membrane of LBL method preparation that following advantage is arranged: the one, polyelectrolyte has a large amount of electric charges, can produce south, road effect with separated material, reach the purpose of selecting separation; The 2nd, by adjusting the substance classes and the sedimentary condition of polyelectrolyte, can control the structure and the performance of self-assembled film; The 3rd, every strata electrolyte molecule strengthens film strength by the ionic bond combination; The present 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 these stability based on the polymer multi-layer film of weak interaction are usually not enough, can not resist comparatively harsh external environment condition and destroyed, these external environment conditions comprise the dissolving of organic solvent, the erosion of soda acid salt and the decomposition of high temperature etc.At present, people are being developed some new package techniques that obtain stable multilayer film based on covalent bond, the intensity of covalent bond is bigger 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 more stable polymer ultrathin membrane of structure, this is because the group that intermolecular dependence can be reacted mutually combines, and forms highly cross-linked polymer network structure.Therefore, in case reaction is finished, just can not can not be destroyed by the soda acid of general concentration and salt by organic solvent dissolution, heat-resisting quantity improves, and still can keep the advantages such as facility of laminated assembling technology in the controlling diaphragm configuration aspects simultaneously.For improving self assembly nanofiltration film strength and stability, the material that has reactive group can be assembled in the film, carry out chemical reaction then, make the assembling film interlayer form covalent bond, Chinese patent application numbers 201010249144.2 discloses a kind of method based on covalent effect assembling multilayer diffusion barrier, adopt self-assembling technique, the Multi-layered osmotic vaporization film by covalent effect forms is significantly improved the stability of film and resistance to acids and bases.The pollutants such as bacterium that NF membrane is held back in separation process can be attached in film surface even the fenestra, very easily form biomembrane on the film surface, and further growth breeding formation biofouling, organic solute discharged simultaneously, tunicle is held back the formation gel layer, forms the biological pollution that is difficult to remove.The biological pollution of film has reduced the 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.Peppery element has the broad-spectrum antibacterial effect, is a kind of natural antibacterial agent efficiently, now is applied in the marine antifouling coating.United States Patent (USP) 5226380,5397385,5925370 and Chinese patent 200510081683.9 all are relevant peppery plain derivative to be used in application in the antifouling paint, through patch test of paints on ship hull, gained is the result show: the peppery plain antifouling paint of this kind prescription can suppress adhering to of fouling organism preferably; Chinese patent application 201210056842.X discloses a kind of " hydrophily contains stable against biological contamination milipore filter of peppery plain functional group and preparation method thereof " has introduced peppery element in the casting solution of preparation polysulphone super-filter membrane, prepared novel antibacterial milipore filter by the immersion precipitation phase inversion, its bacteriostasis rate reaches about 85%, has increased the service life of film.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seeking to design provides a kind of combine with chemical crosslinking new method of preparation biocidal property NF membrane of self assembly layer by layer of utilizing on basement membrane, realization becomes NF membrane from the ultrafiltration basement membrane by one or more double-deck modifications, improve the stability and the biocidal property of composite membrane, obtain the high NF membrane of separating property, stability and biocidal property.
To achieve these goals, the present invention carries out preliminary treatment to basement membrane earlier, make its surface with on can with the functional group of polyelectrolyte generation electrostatic interaction, then peppery plain function monomer is dissolved in polyelectrolyte solution, and basement membrane is immersed in this polyelectrolyte solution, be immersed in the polyelectrolyte solution that has opposite charges with it after taking out basement membrane flushing surface again, be immersed in the crosslinking agent of twain-aldehyde compound after at last film being taken out the flushing surface, 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, and it is sp that two carbonyl carbonyl carbon are arranged in its molecule
2Hybridized orbit, carbonyl carbon has the part positive charge, ketonic oxygen has the part negative electrical charge, amino in the polycation electrolyte because the not share electron pair in its nitrogen-atoms also has nucleophilicity, amino is easy to the carbonyl carbon that has positive charge the Schiff alkali reaction take place, a dialdehyde molecule can be positioned at different big molecules as if these two amino with two amino reactions and then produce the intermolecular network structure that has been cross-linked to form, this just twain-aldehyde compound can carry out the principle place of crosslinking Treatment to self-assembled film as crosslinking agent, its concrete processing step is:
(1), polycation electrolyte and peppery plain functional structure monomer are dissolved in alcohols, the amine organic solvent, be mixed with the polycation electrolyte mass percent concentration and be 0.1%～1%, peppery plain function monomer mass percent is 0%～2% polycation electrolyte solution, standing and defoaming is standby;
(2), polycation electrolyte is mixed with mass percent concentration with alcohols, amine organic solvent or deionized water is 0.1%～1% polyanion electrolyte solution, standing and defoaming;
(3), polyanion electrolyte is mixed with mass percent concentration with alcohols, amine organic solvent or deionized water is 0.1%～1% polyanion electrolyte solution, standing and defoaming;
(4), the twain-aldehyde compound crosslinking agent is dissolved in deionized water or the 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 plasma treatment or Chemical Pretreatment, make the surperficial charge of basement membrane;
(6), the basement membrane of charge is immersed in the polyelectrolyte solution with its opposite charge, as 5～30min in the polycation electrolyte solution, polycation electrolyte is deposited on forms the polycation thin layer on the basement membrane; Then basement membrane is taken out, rinse out the unnecessary polyelectrolyte solution of membrane surface, obtain having the composite membrane of polycation thin layer with deionized water;
(7), the composite membrane that will have a polycation thin layer is immersed in 5～30min in the polyanion electrolyte solution, makes polycation electrolyte and polyanion electrolyte be assembled on the basement membrane by electrostatic interaction, forms the polyelectrolyte composite membrane of a bilayer;
(8), formed polyelectrolyte composite membrane is taken out, rinse out the unnecessary polyelectrolyte solution in composite membrane surface with deionized water;
(9), the polyelectrolyte composite membrane is immersed in 20min～2h in the 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, promptly obtain the cross linking membrane of a bilayer;
(11), repeat (6)～(10) step to required double-deck number, the polycation electrolyte solution of outermost bilayer changes the peppery cellulose solution of polycation electrolyte into, peppery element covers the surface of film and plays bacteriostasis.
Polycation electrolyte of the present invention is the polyelectrolyte that has with twain-aldehyde compound crosslinking agent generation covalent effect functional group, comprises polymine (PEI), polyallylamine hydrochloride (PAH), PDDA (PDDA) and contains amino protein macromolecule; Polyanion electrolyte is and the polyanion electrolyte of polycation electrolyte generation electrostatic interaction, comprises polyacrylic acid (PAA) and kayexalate (PSS); Peppery plain function monomer comprises N-(5-methyl-2 hydroxybenzyl) benzamide, N-(6-methyl-5-hydroxyl-1,3-benzo two oxa-s penta ring) benzamide, N-(5-benzamide methyl-2-hydroxyl-3-methoxy-benzyl) benzamide, the N-(5-methyl-3-tert-butyl group-2-hydroxybenzyl) benzamide and N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl) acrylamide; The twain-aldehyde compound crosslinking agent comprises glyoxal and glutaraldehyde; Basement membrane is a milipore filter, and the material of basement membrane is inoranic membrane or organic film, or the organic inorganic hybridization film, and the kit form of basement membrane is tubular membrane, hollow-fibre membrane, flat sheet membrane or rolled film.
Preparation of the present invention is the self-assembled film process layer by layer, and wherein the mass percent of the contained peppery plain function monomer of each double-deck polycation electrolyte solution that uses can be different.
When the NF membrane of the inventive method preparation is carried out the separating property test, select the Na of 2g/L for use
2SO
4The NaCl aqueous solution of the aqueous solution and 2g/L is that 1.0MPa and temperature are to test separating property under 25 ℃ the condition at operating pressure, and salt rejection rate (R) and water flux (J) are calculated as follows respectively:
C wherein
FBe concentration of raw material, C
PFor seeing through liquid concentration, Δ V is long-pending for seeing through liquid, and A is the effective film area, and t is the testing time.
When the NF membrane of the inventive method preparation is carried out the performance test of stable against biological contamination, adopting dilution spread plate method, is indicator bacteria with Escherichia coli, judges the NF membrane bacteriostasis property according to bacteriostasis rate, and 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 the modification.
The present invention compared with prior art, only need bilayer of assembling and with regard to realizing the milipore filter modification is become NF membrane by cross-linking reaction, self assembly and chemical crosslinking are combined, the film solvent resistance of preparation and stability are high, the cortex construction of peppery plain function monomer introducing film, strengthen the stable against biological contamination ability of film by blend; 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.
Description of drawings:
Fig. 1 is the structural formula schematic diagram of the peppery plain function monomer that the present invention relates to.
The 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 are 28.26cm
2Used polyanion electrolyte is Sodium Polyacrylate (PAA, molecular weight are 100,000); Used polycation electrolyte is polymine (PEI, molecular weight are 60,000), and the molecular weight of glutaraldehyde (GA) is 100; Function monomer N-(5-methyl-2 hydroxybenzyl of peppery element) benzamide (HMBB) laboratory self-control, its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation electrolyte solution, wherein the mass percent concentration of PEI is 0.4%, the mass percent concentration 0.25% of HMBB;
(2), with deionized water preparation mass percent concentration be 0.25% PAA solution;
(3), with deionized water preparation mass percent concentration be 0.5% GA solution;
(4), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed 1h in the 2N NaOH solution, be bear with the polyacrylonitrile-radical membrane surface modification;
(5), rinse out the NaOH solution on film surface, be neutral until the pH value with deionized water;
(6), with the PAN basement membrane static immersing after the modification in polycation electrolyte solution, take out the unnecessary polycation electrolyte solution that rinses out the film surface with deionized water behind the 15min;
(7), be in the 0.25%PAA solution with PAN/ polycation composite membrane static immersing at mass percent concentration, take out the unnecessary polyelectrolyte solution that rinses out the composite membrane surface with deionized water behind the 15min;
(8), the polyelectrolyte composite membrane is immersed in mass percent concentration is 30min in 0.5% the GA solution, makes it that chemical crosslink reaction take place;
(9), the film after crosslinked is taken out, be immersed in the deionized water, rinsing composite membrane surface, can form the compound number of plies is the self assembly NF membrane based on covalent effect of 1 bilayer.
The test result that the self assembly NF membrane of present embodiment preparation 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 are 80.5%.
Embodiment 2:
The used basement membrane of present embodiment, 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 0.4%, the mass percent concentration 0.25% of HMBB;
(2), with deionized water preparation mass percent concentration be 0.25% PAA solution;
(3), with deionized water preparation mass percent concentration be: 0.5% GA solution;
(4), for making polyacrylonitrile basement membrane surface charged, adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed 1h in the 2N NaOH solution, it is modified as the polyanion basement membrane;
(5), rinse out the NaOH solution on film surface, be neutral until the pH value with deionized water;
(6), with the PAN basement membrane static immersing after the modification in said polycation solution, take out the unnecessary electrolyte solution that rinses out the film surface with deionized water behind the 15min;
(7), be in the 0.25%PAA solution with PAN/ polycation composite membrane static immersing at mass percent concentration, take out the unnecessary polyelectrolyte solution that rinses out the composite membrane surface with deionized water behind the 15min;
(8), the polyelectrolyte composite membrane is immersed in mass percent concentration is 1h in 0.5% the GA solution, makes it that chemical crosslink reaction take place;
(9), the film after crosslinked is taken out, be immersed in the deionized water, rinsing composite membrane surface, can form the compound number of plies is the self assembly NF membrane based on covalent effect of 1 bilayer.
The test result that the self assembly NF membrane of the present invention's preparation 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 are 81%.
Embodiment 3:
The used basement membrane of present embodiment, 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 0.4%, the mass percent concentration 0.25% of HMBB;
(2), with absolute ethyl alcohol preparation mass percent concentration be 0.25% PAA solution;
(3), with deionized water preparation mass percent concentration be 1% GA solution;
(4), for making polyacrylonitrile basement membrane surface charged, adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed 1h in the 2N NaOH solution, it is modified as the polyanion basement membrane;
(5), rinse out the NaOH solution on film surface, be neutral until the pH value with deionized water;
(6), with the PAN film static immersing after the modification in said polycation solution, take out the unnecessary electrolyte solution that rinses out the film surface with deionized water behind the 15min;
(7), be in the 0.25%PAA solution with PAN/ polycation composite membrane static immersing at mass percent concentration, take out behind the 15min, rinse out the unnecessary polyelectrolyte solution on composite membrane surface with deionized water;
(8), the polyelectrolyte composite membrane is immersed in mass percent concentration is 1h in 1% the GA solution, makes it that chemical crosslink reaction take place;
(9), the film after crosslinked is taken out, be immersed in the deionized water, rinsing composite membrane surface, can form the compound number of plies is the self assembly NF membrane based on covalent effect of 1 bilayer.
The test result that the self assembly NF membrane of present embodiment preparation 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 are 82%.
Embodiment 4:
The used basement membrane of present embodiment, 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 0.4%, the mass percent concentration 0.4% of HMBB;
(2), with absolute ethyl alcohol preparation mass percent concentration be 0.25% PAA solution;
(3), with deionized water preparation mass percent concentration be 1% GA solution;
(4), for making polyacrylonitrile basement membrane surface charged, adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed 1h in the 2N NaOH solution, it is modified as the polyanion basement membrane;
(5), rinse out the NaOH solution on film surface, be neutral until the pH value with deionized water;
(6), with the PAN film static immersing after the modification in said polycation solution, take out behind the 15min, rinse out the unnecessary electrolyte solution on film surface with deionized water;
(7), with PAN/ polycation composite membrane static immersing in mass percent concentration is 0.25% PAA solution, take out behind the 15min, rinse out the unnecessary polyelectrolyte solution on composite membrane surface with deionized water;
(8), the polyelectrolyte composite membrane is immersed in mass percent concentration is 1h in 1% the GA solution, makes it that chemical crosslink reaction take place;
(9), the film after crosslinked is taken out, be immersed in the deionized water, rinsing composite membrane surface, can form the compound number of plies is the self assembly NF membrane based on covalent effect of 1 bilayer.
The test result that the self assembly NF membrane of present embodiment preparation 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 are 90.7%.
Embodiment 5:
The basement membrane that present embodiment adopts is polyacrylonitrile (PAN) film, molecular cut off 50000Da(dalton), flat milipore filter, membrane area are 28.26cm
2Used polyanion electrolyte is kayexalate (PSS, molecular weight are 70,000); Used polycation electrolyte is polymine (PEI, molecular weight are 60,000), glutaraldehyde (GA, molecular weight 100); Peppery plain structure function monomer N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl) acrylamide (NHMBA) laboratory self-control, its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation electrolyte solution, wherein the mass percent concentration of PEI is 0.4%, the mass percent concentration of NHMBA is 0.25%;
(2), with absolute ethyl alcohol preparation mass percent concentration be 0.25% PAA solution;
(3), with deionized water preparation mass percent concentration be 1% GA solution;
(4), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed 1h in the 2N NaOH solution, be bear with the polyacrylonitrile-radical membrane surface modification;
(5), rinse out the NaOH solution on film surface, be neutral until the pH value with deionized water;
(6), with the PAN basement membrane static immersing 15min in said polycation solution after the modification; Rinse out the unnecessary electrolyte solution on film surface with deionized water;
(7), be in the 0.25%PAA solution with PAN/ polycation composite membrane static immersing at mass percent concentration, take out behind the 15min, rinse out the unnecessary polyelectrolyte solution on composite membrane surface with deionized water;
(8), the polyelectrolyte composite membrane is immersed in mass percent concentration is 1h in 1% the GA solution, makes it that chemical crosslink reaction take place;
(9), the film after crosslinked is taken out, be immersed in the deionized water, rinsing composite membrane surface, can form the compound number of plies is the self assembly NF membrane based on covalent effect of 1 bilayer.
The test result that the self assembly NF membrane of present embodiment preparation 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 are 84.5%.
Embodiment 6:
The basement membrane that present embodiment adopts is polyacrylonitrile (PAN) film, molecular cut off 50000Da(dalton), flat milipore filter, membrane area are 28.26cm
2Used polyanion electrolyte is kayexalate (PSS, molecular weight are 70,000); Used polycation electrolyte is PAH hydrochloride (PAH, molecular weight are 5.6 ten thousand), glutaraldehyde (GA, molecular weight 100); The function monomer N-(5-acetyl group of peppery element-4-hydroxyl-2-methoxy-benzyl) acrylamide (NHMBA) laboratory self-control.Its preparation process is as follows:
(1), with absolute ethyl alcohol preparation polycation electrolyte solution, wherein the mass percent concentration of PEI is 0.4%, the mass percent concentration 0.25% of NHMBA;
(2), with absolute ethyl alcohol preparation mass percent concentration be 0.25% PAA solution;
(3), with deionized water preparation mass percent concentration be 1% GA solution;
(4), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed 1h in the 2N NaOH solution, be bear with the polyacrylonitrile-radical membrane surface modification;
(5), rinse out the NaOH solution on film surface, be neutral until the pH value with deionized water;
(6), with the PAN basement membrane static immersing after the modification in polycation electrolyte solution, take out behind the 15min, rinse out the unnecessary electrolyte solution on film surface with deionized water;
(7), be in the 0.25%PAH solution with PAN/ polycation composite membrane static immersing at mass percent concentration, take out behind the 15min, rinse out the unnecessary polyelectrolyte solution on composite membrane surface with deionized water;
(8), the polyelectrolyte composite membrane is immersed in mass percent concentration is 1h in 1% the GA solution, makes it that chemical crosslink reaction take place;
(9), the film after crosslinked is taken out, be immersed in the deionized water, rinsing composite membrane surface, can form the compound number of plies is the self assembly NF membrane based on covalent effect of 1 bilayer.
The test result that the self assembly NF membrane of present embodiment preparation 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 are 81.5%.
Embodiment 7:
The basement membrane that present embodiment adopts is polyacrylonitrile (PAN) film, molecular cut off 50000Da(dalton), flat milipore filter, membrane area are 28.26cm
2Used polyanion electrolyte is Sodium Polyacrylate (PAA, molecular weight are 100,000); Used polycation electrolyte is polymine (PEI, molecular weight are 60,000), and the molecular weight of glutaraldehyde (GA) is 100; The function monomer N-(5-acetyl group of peppery element-4-hydroxyl-2-methoxy-benzyl) acrylamide (NHMBA) laboratory self-control.In its preparation process, wherein the PEI polycation electrolyte solution of the 8th step use when first bilayer of preparation does not contain peppery plain function monomer NHMBA, and second the double-deck PEI polycation electrolyte solution that uses contains peppery plain 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 0.4%, the mass percent concentration 0.25% of NHMBA;
(2), with the mass percent concentration of absolute ethyl alcohol preparation PEI be 0.4% polycation electrolyte solution;
(3), with deionized water preparation mass percent concentration be 0.4% PEI solution;
(4), with deionized water preparation mass percent concentration be 0.25% PAA solution;
(5), with deionized water preparation mass percent concentration be 1% GA solution;
(6), adopt hydrolyzed modified technology, under 65 ℃ of constant temperatures, polyacrylonitrile ultrafiltration film is immersed 1h in the 2N NaOH solution, be bear with the polyacrylonitrile-radical membrane surface modification;
(7), rinse out the NaOH solution on film surface, be neutral until the pH value with deionized water;
(8), be 15min in 0.4% the solution with the PAN basement membrane static immersing after the modification at the PEI mass percent concentration, rinse out the unnecessary polyelectrolyte solution on film surface with deionized water;
(9), be in the 0.25%PAH solution with PAN/ polycation composite membrane static immersing at mass percent concentration, take out behind the 15min, rinse out the unnecessary polyelectrolyte solution on composite membrane surface with deionized water;
(10), repeat (8)～(9) step, can form the compound number of plies is the NF membrane that contains peppery element of two bilayers.
(11), the polyelectrolyte composite membrane is immersed in mass percent concentration is 1h in 1% the GA solution, makes it that chemical crosslink reaction take place;
(12), the film after crosslinked is taken out, be immersed in the deionized water, rinsing composite membrane surface, can form the compound number of plies is the self assembly NF membrane based on covalent effect of two bilayers.
The test result that the self assembly NF membrane of present embodiment preparation 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 are 90%.
Claims (5)
1. the preparation method of a self assembly covalent cross-linking NF membrane, it is characterized in that earlier basement membrane being carried out preliminary treatment, make its surface with on can with the functional group of polyelectrolyte generation electrostatic interaction, then peppery plain function monomer is dissolved in polyelectrolyte solution, and basement membrane is immersed in this polyelectrolyte solution, be immersed in the polyelectrolyte solution that has opposite charges with it after taking out basement membrane flushing surface again, be immersed in the crosslinking agent of twain-aldehyde compound after at last film being taken out the flushing surface, obtain having the self assembly covalent cross-linking NF membrane of biocidal property, its concrete processing step is:
(1), polycation electrolyte and peppery plain functional structure monomer are dissolved in alcohols, the amine organic solvent, be mixed with the polycation electrolyte mass percent concentration and be 0.1%～1%, peppery plain function monomer mass percent is 0%～2% polycation electrolyte solution, standing and defoaming is standby;
(2), polycation electrolyte is mixed with mass percent concentration with alcohols, amine organic solvent or deionized water is 0.1%～1% polyanion electrolyte solution, standing and defoaming;
(3), polyanion electrolyte is mixed with mass percent concentration with alcohols, amine organic solvent or deionized water is 0.1%～1% polyanion electrolyte solution, standing and defoaming;
(4), the twain-aldehyde compound crosslinking agent is dissolved in deionized water or the 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 plasma treatment or Chemical Pretreatment, make the surperficial charge of basement membrane;
(6), the basement membrane of charge is immersed in the polyelectrolyte solution with its opposite charge, as 5～30min in the polycation electrolyte solution, polycation electrolyte is deposited on forms the polycation thin layer on the basement membrane; Then basement membrane is taken out, rinse out the unnecessary polyelectrolyte solution of membrane surface, obtain having the composite membrane of polycation thin layer with deionized water;
(7), the composite membrane that will have a polycation thin layer is immersed in 5～30min in the polyanion electrolyte solution, makes polycation electrolyte and polyanion electrolyte be assembled on the basement membrane by electrostatic interaction, forms the polyelectrolyte composite membrane of a bilayer;
(8), formed polyelectrolyte composite membrane is taken out, rinse out the unnecessary polyelectrolyte solution in composite membrane surface with deionized water;
(9), the polyelectrolyte composite membrane is immersed in 20min～2h in the 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, promptly obtain the cross linking membrane of a bilayer;
(11), repeat (6)～(10) step to required double-deck number, the polycation electrolyte solution of outermost bilayer changes the peppery cellulose solution of polycation electrolyte into, peppery element 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 is the polyelectrolyte that has with twain-aldehyde compound crosslinking agent generation covalent effect functional group, comprise polymine (PEI), polyallylamine hydrochloride (PAH), PDDA (PDDA) and contain amino protein macromolecule; Polyanion electrolyte is and the polyanion electrolyte of polycation electrolyte generation electrostatic interaction, comprises polyacrylic acid (PAA) and kayexalate (PSS); Peppery plain function monomer comprises N-(5-methyl-2 hydroxybenzyl) benzamide, N-(6-methyl-5-hydroxyl-1,3-benzo two oxa-s penta ring) benzamide, N-(5-benzamide methyl-2-hydroxyl-3-methoxy-benzyl) benzamide, the N-(5-methyl-3-tert-butyl group-2-hydroxybenzyl) benzamide and N-(5-acetyl group-4-hydroxyl-2-methoxy-benzyl) acrylamide; The twain-aldehyde compound crosslinking agent comprises glyoxal and glutaraldehyde; Basement membrane is a milipore filter, and the material of basement membrane is inoranic membrane or organic film, or the organic inorganic hybridization film, and the kit form of basement membrane is tubular membrane, hollow-fibre membrane, flat sheet membrane or rolled film.
3. the preparation method of self assembly covalent cross-linking NF membrane according to claim 1, it is characterized in that described preparation self-assembled film process layer by layer, wherein the mass percent of the contained peppery plain function monomer of each double-deck polycation electrolyte solution that uses can be different.
4. the preparation method of self assembly covalent cross-linking NF membrane according to claim 1 when it is characterized in that the NF membrane for preparing is carried out the separating property test, selects the Na of 2g/L for use
2SO
4The NaCl aqueous solution of the aqueous solution and 2g/L is that 1.0MPa and temperature are to test separating property under 25 ℃ the condition at operating pressure, and salt rejection rate R and water flux J are calculated as follows respectively:
C wherein
FBe concentration of raw material, C
PFor seeing through liquid concentration, Δ V is long-pending for seeing through liquid, and A is the effective film area, and t is the testing time.
5. the preparation method of self assembly covalent cross-linking NF membrane according to claim 1, when it is characterized in that the NF membrane for preparing is carried out the performance test of stable against biological contamination, adopt dilution spread plate method, with Escherichia coli is indicator bacteria, judge the NF membrane bacteriostasis property according to bacteriostasis rate, 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 the modification.
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| CN114832642A (en) * | 2022-04-11 | 2022-08-02 | 贵州省材料产业技术研究院 | PVDF (polyvinylidene fluoride) antibacterial nanofiltration membrane for layer-by-layer self-assembly subject-object recognition and preparation method thereof |
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