CN103446899A - Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof - Google Patents
Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and a preparation method thereof. According to the filter membrane, sodium alginate is used as a membrane forming base material, micro-nanometer inorganic particles with carboxylic acid groups on the surfaces are used as an enhancer and a pore-enlarging agent and a waters-soluble compound is used as a pore-foaming agent so as to be crosslinked by virtue of an ionic crosslinking agent; after the pore-foaming agent is eluted, a polyelectrolyte layer with positive charges is deposited on the surface of a rear membrane, and then a hybrid hydrogel filter membrane is obtained through crosslinking by virtue of a chemical crosslinking agent and has better stability and mechanical properties and higher reject rate than a pure ionic crosslinked alginate hydrogel membrane. The mechanical strength of the membrane and the size of the whole membrane pores can be regulated by changing the types of the micro-nanometer inorganic particles and the ionic crosslinking agent, and controlling the size and amount of the inorganic particles as well as the concentration of the ionic crosslinking agent. The crosslinking degree and size of the surface membrane pores can be controlled by controlling the amount of the positive-charge polyelectrolyte as well as the amount and crosslinking time of the crosslinking agent.
Description
Technical field
The present invention relates to alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking and preparation method thereof, belong to environment functional material and film field.
Background technology
Membrane separation technique has the advantages such as separation process does not undergo phase transition, energy consumption is low, separator is simple, separative efficiency is high, mass transfer velocity is fast, be applicable to the separation of multiple special solution system, in aspect extensive uses such as the thickening-purification technology of desalinization, industrial wastewater treatment, macromolecular substances and classifications.Selection and research to membrane material are the important topics of film separation field.The conventional film filtering material, because the hydrophobicity of itself very easily causes large molecule, colloid, electrolyte etc. on the film surface or film inside irreversible deposition, causes film to pollute the flux of film is constantly descended, so that the film separation process can not normally be carried out.For the characteristics of the lyophobic dusts such as the easy adsorbed proteins of polymer film surface, effective ways that alleviate the film pollution are surface naturies of improving film, as chargedization on film surface or the hydrophiling of hydrophobic film etc.
Blending and modifying is a kind of short-cut method that improves film properties of learning from other's strong points to offset one's weaknesses on existing membrane material basis.By with the hydrophilic macromolecule blend, hydrophilic component is introduced in the casting solution system, thereby film properties is improved.It is constant that blend film not only can maintain original rejection, and pure water flux, resistance tocrocking and fungus resistance all reach significantly lifting.Be usually used in blend with improve membrane permeability can and the macromolecule of separating property mainly contain following several: polyethylene glycol (PEG), polymethyl methacrylate (PMMA), sulfonated polystyrene, polyvinyl alcohol (PVA), SPSF (SPS), polysulfones (PS), polyacrylonitrile (PAN), nylon 6, polyvinyl acetate (PVAc) and chloromethyl polysulphone (CMPS) etc., they respectively from hydrophobic polymer blended micro-filtration membrane and the milipore filter that is applicable to different separation systems that made.The people such as Su Yanlei can significantly improve resistance tocrocking and the permeance property [J.Membr.Sci., 2008,322 (1): 171-177] of film with the copolymer-modified poly (ether-sulfone) ultrafiltration membrane of Phosphorylcholine.
Surface coating modified is by the film surface, applying water soluble polymer or the surfactant that last layer contains functional group, can introduce on the surface of film the method for modifying of one deck functional polymer layer.Apply the layer of surface activating agent on the film surface, can improve equally the hydrophily of film, improve membrane flux, but the surfactant of the coating on film surface can come off gradually along with the prolongation of time, thereby cause the decline of membrane flux, until modified effect completely loses.The surface that the people such as Sun Xiuzhen are coated in polyether sulfone (PES) milipore filter, nylon-6 micro-filtration membrane and PVDF micro-filtration membrane by shitosan (CS) has prepared composite membrane, in this three classes composite membrane, the performance of PVDF-CS composite membrane is the best, under the operating condition of 0.25MPa, room temperature, rejection to PEG-20000 reaches the development of 98.4%[shitosan ultrafiltration composite membrane, ocean, the East Sea, 1999,17 (2): 21-25].
Surface graft modification is the method that another large class can effectively be improved polymer film surface character, generally can pass through the initiation means such as plasma, light, irradiation, electron beam and form avtive spot on the film surface, this avtive spot further causes other function monomer again in the film surface grafting polymerization, gives the character of polymer film surface with grafted polymer.The characteristics of surface graft modification are within modification occurs over just several nanometers of film superficial layer, when giving the character of film surface with grafted polymer, do not affect the character of material body, and combine and make modified effect more firm with chemical bond between the macromolecular chain of grafting and film surface.The people such as Hsueh have prepared the AA-PVDF-DMAEA Bipolar Membrane by plasma graft, a side joint branch anionic monomer acrylic acid of pvdf membrane, and opposite side is grafted cation monomer acrylic acid-N, N-dimethyl amine ester.Owing to there being Ionomer to cover the surface of graft copolymer membrane, the pure water contact angle of graft copolymer membrane is significantly descended [J.Membr.Sci., 2003,219:1-13].
Nano inoganic particle is as Al
2o
3particle, TiO
2particle and SiO
2particles etc. can be used for improving the film hydrophily.The film made with the casting solution that contains this class particle, perfectly combine heat-resisting quantity, hydrophily and the high molecular pliability of inorganic material, is a kind of novel hydrophilic organic/inorganic substances compound membrane.Maria Arsuaga J passes through TiO
2, Al
2o
3and ZrO
2nano particle has carried out modification to the PES film.The more open and porous of the structure that the metal oxide of embedding makes film, the antifouling property of modification caudacoria and long-term flux stability be significantly improved [J.Membr.Sci., 2013,428:131-141].Daraei P etc. has prepared Fe by the phase method of converting
3o
4/ MWCNT/PES, PANI/Fe
3o
4/ PES and Fe
3o
4/ PES film.Detect the mixed matrix film properties by pure water flux and pollution parameters, at three kinds of film Fe of magnetic field casting
3o
4/ MWCNT/PES, PANI/Fe
3o
4/ PES and Fe
3o
4/ PES pure water flux has improved respectively 15%, 29% and 96%.Water contact angle is measured and is confirmed PANI/Fe
3o
4the hydrophily [Sep.Sci.Technol., 2013,109:111-121] that composite membrane is superior.
Mainly by blending and modifying, surface coating and surface graft modification, improve the hydrophily of film at present, thereby improve the antifouling property of film.But the blending and modifying complex process, surface applies and easily comes off, and surface graft modification is difficult to obtain uniform Modified Membrane.The exploitation of the improvement of film self-characteristic and new membrane material is the focus of studying both at home and abroad, mainly by following 3 aspects: the exploitation of (1) novel high flux membrane material (as metal film); (2) modification of organic film material, to improve flux and antifouling property; (3) manufacture the organic and inorganic composite membrane.
Hydrophilic film surface due to and hydrone between have interaction of hydrogen bond, make water be ordered structure in film near surface zone, Gu Shui preferentially adsorbs, if hydrophobic substance will approach the film surface, requires the expenditure of energy to destroy this ordered structure.Therefore, hydrophilic film more is difficult for contaminated.Hydrogel is the three-dimensional net structure formed with chemical bond or physical force between a kind of hydrophilic high molecular polymer chain, absorbs a certain amount of water and makes the macromolecule network swelling form the compound system that solvent and macromolecule network form.Occurred that in recent years some apply hydrogel on the film surface and alleviate the document that film pollutes.Young-Hye La etc. be take polyvinyl alcohol as pore-foaming agent under the existence of sensitising agent, utilize that ultraviolet irradiation is crosslinked goes out the hydrophilic gel layer at the polysulphone super-filter membrane surface construction, this hydrophilic gel layer reveals remarkable hydrophily and permeability, show good contamination resistance [J.Membr.Sci. for oil water mixture and bovine serum albumin, 2012,401:306-312].Chen Xiaolin etc. use sodium alginate as the surface-active layer material, with glutaraldehyde as cross linker, take polysulfones (PSF) and polyacrylonitrile (PAN) is supporting layer, has prepared a kind of novel nanofiltration membrane with negative electric charge [Chinese Marine University's journal, 2010,40 (10): 85-89].
We are list of references [Nature in work before, 2012,489 (7414): 133-136] prepared a kind of water filtration hybridized hydrogel flat sheet membrane, this flat sheet membrane be take sodium alginate as macromolecular scaffold, take acrylamide and derivative thereof as polymerization single polymerization monomer, add chemical cross-linking agent and ion crosslinking agent, take water soluble compound as pore-foaming agent, initiated polymerization forms two cross-linked network hydrogels of high-intensity high-tenacity, wash away the flat sheet membrane that obtains after pore-foaming agent for water filtration, there is high hydrophily and good resistance tocrocking [201310112790.8].But, after the polymerisation of monomer, pore-foaming agent, by partially grafted, is difficult to wash-out, the membrane flux therefore obtained is very little, and unreacted monomer has affected the water quality after the membrane filtration.We attempted take sodium alginate as matrix, take calcium chloride as crosslinking agent, the water soluble polymer of take prepares calcium alginate hydrogel flat sheet membrane as pore-foaming agent, find that pore-foaming agent can be by abundant wash-out, flux obviously improves, but pure ionomer hydrogel filter membrane poor stability, the easy swelling of film, mechanical strength is low, thereby film makes Pore Blocking being depressed attenuation, and therefore under the pressure more than 0.16MPa, flux almost no longer increases with pressure.In addition, the fenestra of pure alginate hydrogel film is larger, is difficult to hold back low-molecular-weight material.We have attempted using ion crosslinking agent and the crosslinked alginate hydrogel film of chemical cross-linking agent simultaneously, although little molecule rejection has been improved, the membrane flux obtained becomes less, and also there is the problem that attenuation makes Pore Blocking of being depressed in film.We attempted adding nano inoganic particle to improve film strength simultaneously, really obtained good effect, and the flux of film also improves a lot, but such film swelling of electrolyte-resistant solution is not improved not obvious to micromolecular rejection.If utilize the simultaneously characteristics of the micro-nano inorganic particulate of crosslinked sodium alginate and surface band hydroxy-acid group of ion crosslinking agent, micro-nano inorganic particulate and alginate hydrogel are arrived to nano level compound and doping, can greatly improve mechanical performance, hot property and the potential resistance to electrolyte contamination solution swellability of alginate hydrogel, thereby alginic acid alkali organic inorganic hybridization hydrogel is used as filter membrane is stable.Utilize between inorganic particulate and inorganic particulate and alginate hydrogel between space play the reaming effect, thereby can significantly improve the flux of film.By the micro-nano inorganic particulate of change surface band hydroxy-acid group and the kind of ion crosslinking agent, the concentration of controlling particle size, consumption and the ion crosslinking agent of inorganic particulate can be regulated mechanical strength and the integral membrane hole size of film.Wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electrical polyelectrolyte; hydroxy-acid group by alginate and micro-nano surface of inorganic particles and the polyelectrolyte generation self assembly of lotus positive electricity are also crosslinked through chemical cross-linking agent; form finer and close protective layer and the filter course of one deck on the film surface; by controlling the consumption of lotus positive electrical polyelectrolyte, the factors such as the consumption of crosslinking agent and crosslinking time can be controlled crosslinking degree and skin covering of the surface hole size.Such film inside has micro-nano inorganic particulate to strengthen and reaming, has improved its mechanical performance and flux simultaneously, and the film skin is crosslinked through chemical bond, forms compacted zone, has improved the anti-swelling of film, and has improved the rejection to small-molecule substance.
Poor for normal film material hydrophily, pure ionomer aquagel membrane mechanical strength is low, poor stability, and flux is low, is difficult to hold back the problems such as little molecule, and the present invention designs the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking.This filter membrane with sodium alginate for becoming film base material, the micro-nano inorganic particulate of surface band hydroxy-acid group of take is reinforcing agent and expanding agent, take water soluble compound as pore-foaming agent, crosslinked through ion crosslinking agent, the polyelectrolyte of wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electricity is also crosslinked through chemical cross-linking agent, the hybridized hydrogel filter membrane obtained has than the better stability of pure ionomer alginate hydrogel film and mechanical performance, little molecule is had to higher rejection, can reach the nanofiltration effect.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that normal film material hydrophily is poor, and pure ionomer aquagel membrane mechanical strength is low, poor stability, and flux is low, is difficult to hold back the problems such as little molecule.
It is poor that the present invention solves described normal film material hydrophily, pure ionomer aquagel membrane mechanical strength is low, poor stability, flux is low, and the technical scheme that is difficult to hold back the problems such as little molecule is the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of design a kind of top layer chemical crosslinking.
The invention provides alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking and preparation method thereof, it is characterized in that comprising the following steps:
A) take the 1-5g sodium alginate, the pore-foaming agent of sodium alginate mass percent 1%-100%, the micro-nano inorganic particulate of the surface band hydroxy-acid group of sodium alginate mass percent 0.01-100%, pour into together in the 100ml deionized water, stirring and dissolving, ultrasonic being uniformly dispersed, be positioned in the closed container of 4 ℃-30 ℃ and obtain casting solution after standing froth breaking;
B) aqueous metal salt that preparing metal mass of ion percentage is 0.1%-10%, as ion crosslinking agent; The preparation mass percent lotus positive electrical polyelectrolyte aqueous solution that is 0.05%-10%, wherein containing the pore-foaming agent of lotus positive electrical polyelectrolyte mass percent 1%-100%; The chemical cross-linking agent aqueous solution of preparation mass percent 0.1%-5%;
C) casting solution step a) obtained is poured on the sheet glass of dry cleansing, scrape with the knifing rod the uniform film that thickness is 20-2000 μ m, the vacuum outgas bubble, be dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtain the organic inorganic hybridization aquagel membrane containing the ionomer of pore-foaming agent;
D) by step c) the organic inorganic hybridization aquagel membrane containing the ionomer of pore-foaming agent that obtains under 4 ℃-90 ℃ with deionized water concussion wash-out 8-48h, remove pore-foaming agent and unreacted ion crosslinking agent, obtain alginic acid alkali organic inorganic hybridization hydrogel filter membrane;
E) by steps d) the alginic acid alkali organic inorganic hybridization hydrogel filter membrane that obtains is dipped into step b) 1min-24h in the lotus positive electrical polyelectrolyte aqueous solution of preparation, wash away pore-foaming agent by deionized water after taking-up, use step b) preparation the crosslinked 0.5-24h of the chemical cross-linking agent aqueous solution, wash away unreacted chemical cross-linking agent by deionized water again, finally obtain the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of top layer chemical crosslinking.
The preparation method of the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking of the present invention, it is characterized in that described aqueous metal salt is any one or the two or more mixture in zinc chloride, barium chloride, iron chloride, frerrous chloride, aluminium chloride, calcium chloride, copper sulphate, calcium nitrate aqueous solution, the SiO that the micro-nano inorganic particulate of described hydroxy-acid group is the carboxyl grafting
2, the carboxyl grafting TiO
2, the carboxyl grafting Fe
3o
4, one or more mixtures in carboxylation CNT, carboxylation Graphene, the particle diameter of inorganic particulate is at 5nm-150 μ m.
Pore-foaming agent of the present invention is any one or the two or more mixture in polyacrylamide, PVP, polyethylene glycol, urea, polyvinyl alcohol, APEO, gelatin, water soluble starch, its molecular weight is at 200-50000, and chemical cross-linking agent is one or more mixtures in epoxychloropropane, glutaraldehyde, Geniposide, carbodiimide, succinyl oxide, hexamethylene diisocyanate.
Lotus positive electrical polyelectrolyte of the present invention is one or more mixtures in shitosan, polymine, polyvinylamine, polyvinyl pyridine, poly-trimethylallylammonium chloride, polymethyl acyl-oxygen ethyl-trimethyl salmiac, PDDA.
Preparation technology is simple for this composite aquogel filter membrane, and cost is low, does not have organic liquid waste to produce, and the pressure that the hydrogel flat sheet membrane obtained can anti-0.1-1MPa can be realized the effect of low pressure nanofiltration.
The specific embodiment
Below introduce specific embodiments of the invention, but the present invention is not subject to the restriction of embodiment.
Barium alginate/the SiO of 1. 1 kinds of top layer glutaraldehyde cross-linkings of embodiment
2hybridized hydrogel filter membrane and preparation method thereof
A) take the 1g sodium alginate, the polyacrylamide of sodium alginate mass percent 1%, the SiO of the carboxyl grafting of sodium alginate mass percent 100%
2, pour into together in the 100ml deionized water, stirring and dissolving, ultrasonic being uniformly dispersed, be positioned in the closed container of 4 ℃ and obtain casting solution after standing froth breaking;
B) barium chloride solution that preparation barium ions mass percent is 0.1%, as ion crosslinking agent; The preparation mass percent polyvinyl pyridine aqueous solution that is 0.05%, wherein containing the polyacrylamide of polyvinyl pyridine mass percent 100%; The glutaraldehyde water solution of preparation mass percent 0.1%;
C) casting solution step a) obtained is poured on the sheet glass of dry cleansing, scrape with the knifing rod the uniform film that thickness is 20 μ m, the vacuum outgas bubble, be dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 24h, obtain barium alginate containing the ionomer of polyacrylamide/SiO2 hybridized hydrogel film;
D) by step c) barium alginate/SiO containing the ionomer of polyacrylamide that obtains
2the hybridized hydrogel film with deionized water concussion wash-out 8h, is removed polyacrylamide and unreacted glutaraldehyde under 90 ℃, obtains barium alginate/SiO
2the hybridized hydrogel filter membrane;
E) by steps d) barium alginate/SiO of obtaining
2the hybridized hydrogel filter membrane is dipped into step b) preparation the polyvinyl pyridine aqueous solution in 12h, wash away polyacrylamide by deionized water after taking-up, use step b) preparation the crosslinked 0.5h of glutaraldehyde water solution, wash away unreacted glutaraldehyde by deionized water again, finally obtain the barium alginate/SiO of top layer glutaraldehyde cross-linking
2the hybridized hydrogel filter membrane.
The calcium alginate of 2. 1 kinds of top layer glutaraldehyde cross-linkings of embodiment/carboxylation carbon nano-tube hybridization hydrogel filter membrane and preparation method thereof
A) take the 5g sodium alginate, sodium alginate mass percent 100% polyvinylpyrrolidone, the carboxylation CNT of sodium alginate mass percent 0.01%, pour into together in the 100ml deionized water, stirring and dissolving, ultrasonic being uniformly dispersed, be positioned in the closed container of 30 ℃ and obtain casting solution after standing froth breaking;
B) calcium chloride water that preparation calcium ion mass percent is 10%, as ion crosslinking agent; The polyvinylamine aqueous solution that the preparation mass percent is 10%, the wherein polyvinylpyrrolidone of polyvinylamine mass percent 100%; The glutaraldehyde water solution of preparation mass percent 5%;
C) casting solution step a) obtained is poured on the sheet glass of dry cleansing, scrape with the knifing rod the uniform film that thickness is 2000 μ m, the vacuum outgas bubble, be dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 24h, obtain containing the calcium alginate of pore-foaming agent/carboxylation carbon nano-tube hybridization hydrogel;
D) by step c) obtain containing the calcium alginate of pore-foaming agent/carboxylation carbon nano-tube hybridization hydrogel under 90 ℃ with deionized water concussion wash-out 48h, remove polyvinylpyrrolidone and unreacted glutaraldehyde, obtain calcium alginate/carboxylation carbon nano-tube hybridization hydrogel filter membrane;
E) by steps d) calcium alginate that obtains/carboxylation carbon nano-tube hybridization hydrogel filter membrane is dipped into step b) 12h in the polyvinylamine aqueous solution of preparation, wash away polyvinylpyrrolidone by deionized water after taking-up, use step b) preparation the crosslinked 24h of the chemical cross-linking agent aqueous solution, wash away unreacted glutaraldehyde by deionized water again, finally obtain the calcium alginate of top layer glutaraldehyde cross-linking/carboxylation carbon nano-tube hybridization hydrogel filter membrane.
The crosslinked aluminium alginate of 3. 1 kinds of top layer hexamethylene diisocyanates of embodiment/carboxylation Graphene hybridized hydrogel filter membrane and preparation method thereof
A) take the 3.5g sodium alginate, sodium alginate mass percent 50% polyethylene glycol, the surface band carboxylation Graphene of sodium alginate mass percent 60%, pour into together in the 100ml deionized water, stirring and dissolving, ultrasonic being uniformly dispersed, be positioned in the closed container of 30 ℃ and obtain casting solution after standing froth breaking;
B) aluminum chloride aqueous solution that preparation aluminium ion mass percent is 5%, as ion crosslinking agent; The poly-trimethylallylammonium chloride aqueous solution that the preparation mass percent is 6%, wherein containing the polyethylene glycol that gathers trimethylallylammonium chloride mass percent 60%; The hexamethylene diisocyanate aqueous solution of preparation mass percent 4%;
C) casting solution step a) obtained is poured on the sheet glass of dry cleansing, scrape with the knifing rod the uniform film that thickness is 500 μ m, the vacuum outgas bubble, be dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtain containing the aluminium alginate of pore-foaming agent/carboxylation Graphene hybridized hydrogel filter membrane;
D) by step c) obtain containing the aluminium alginate of pore-foaming agent/carboxylation Graphene hybridized hydrogel filter membrane under 60 ℃ with deionized water concussion wash-out 24h, remove polyethylene glycol and unreacted hexamethylene diisocyanate, obtain alginic acid alkali aluminium alginate/carboxylation Graphene hybridized hydrogel filter membrane;
E) by steps d) aluminium alginate that obtains/carboxylation Graphene hybridized hydrogel filter membrane is dipped into step b) 8h in the poly-trimethylallylammonium chloride aqueous solution of preparation, wash away polyethylene glycol by deionized water after taking-up, use step b) preparation the crosslinked 15h of hexamethylene diisocyanate, wash away unreacted hexamethylene diisocyanate by deionized water again, finally obtain the crosslinked aluminium alginate of top layer hexamethylene diisocyanate/carboxylation Graphene hybridized hydrogel filter membrane.
The crosslinked ferric alginate of 4. 1 kinds of top layer carbodiimides of embodiment/carboxylation Graphene hybridized hydrogel filter membrane and preparation method thereof
A) take the 4g sodium alginate, the polyvinyl alcohol of sodium alginate mass percent 75%, the Fe of the carboxyl grafting of sodium alginate mass percent 35%
3o
4, pour into together in the 100ml deionized water, stirring and dissolving, ultrasonic being uniformly dispersed, be positioned in the closed container of 25 ℃ and obtain casting solution after standing froth breaking;
B) ferric chloride in aqueous solution that preparation iron ion mass percent is 0.1%-10%, as ion crosslinking agent; The preparation mass percent PDDA aqueous solution that is 0.05%-10%, wherein containing the polyvinyl alcohol of PDDA mass percent 60%; The carbodiimide aqueous solution of preparation mass percent 2.5%;
C) casting solution step a) obtained is poured on the sheet glass of dry cleansing, scrape with the knifing rod the uniform film that thickness is 600 μ m, the vacuum outgas bubble, be dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtain containing the ferric alginate of polyvinyl alcohol/carboxylation Graphene hybridized hydrogel film;
D) by step c) obtain containing the ferric alginate of polyvinyl alcohol/carboxylation Graphene hybridized hydrogel film under 75 ℃ with deionized water concussion wash-out 8-48h, remove polyvinyl alcohol and unreacted carbodiimide, obtain ferric alginate/carboxylation Graphene hybridized hydrogel filter membrane;
E) by steps d) ferric alginate that obtains/carboxylation Graphene hybridized hydrogel filter membrane is dipped into step b) 6h in the carbodiimide aqueous solution of preparation, wash away polyvinyl alcohol by deionized water after taking-up, use step b) preparation the crosslinked 10h of the chemical cross-linking agent aqueous solution, wash away unreacted carbodiimide by deionized water again, finally obtain the crosslinked ferric alginate of top layer carbodiimide/carboxylation Graphene hybridized hydrogel filter membrane.
Claims (10)
1. the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a top layer chemical crosslinking, it is characterized in that this filter membrane with sodium alginate for becoming film base material, the micro-nano inorganic particulate of surface band hydroxy-acid group of take is reinforcing agent and expanding agent, take water soluble compound as pore-foaming agent, crosslinked through ion crosslinking agent, the polyelectrolyte of wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electricity is also crosslinked through chemical cross-linking agent, the hybridized hydrogel filter membrane obtained has than the better stability of pure ionomer alginate hydrogel film and mechanical performance, little molecule is had to higher rejection, can reach the nanofiltration effect.
2. the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a top layer chemical crosslinking, it is characterized in that utilizing the ion crosslinking agent characteristics of the micro-nano inorganic particulate of crosslinked sodium alginate and surface band hydroxy-acid group simultaneously, micro-nano inorganic particulate and alginate hydrogel are arrived to nano level compound and doping, greatly improve mechanical performance, hot property and the potential resistance to electrolyte contamination solution swellability of alginate hydrogel, thereby alginic acid alkali organic inorganic hybridization hydrogel is used as filter membrane is stable.
3. the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a top layer chemical crosslinking, is characterized in that utilizing between inorganic particulate and the reaming effect is played in the space between inorganic particulate and alginate hydrogel, thereby significantly improve the flux of film; By the micro-nano inorganic particulate of change surface band hydroxy-acid group and the kind of ion crosslinking agent, mechanical strength and the integral membrane hole size of the concentration adjustment film of particle size, consumption and the ion crosslinking agent of control inorganic particulate.
4. the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a top layer chemical crosslinking; it is characterized in that wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electrical polyelectrolyte; hydroxy-acid group by alginate and micro-nano surface of inorganic particles and the polyelectrolyte generation self assembly of lotus positive electricity are also crosslinked through chemical cross-linking agent; form finer and close protective layer and the filter course of one deck on the film surface; by controlling the consumption of lotus positive electrical polyelectrolyte, factor controlling crosslinking degree and the skin covering of the surface hole sizes such as the consumption of crosslinking agent and crosslinking time.
5. the preparation method of the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a top layer chemical crosslinking is characterized in that comprising the following steps:
A) take the 1-5g sodium alginate, the pore-foaming agent of sodium alginate mass percent 1%-100%, the micro-nano inorganic particulate of the surface band hydroxy-acid group of sodium alginate mass percent 0.01-100%, pour into together in the 100ml deionized water, stirring and dissolving, ultrasonic being uniformly dispersed, be positioned in the closed container of 4 ℃-30 ℃ and obtain casting solution after standing froth breaking;
B) aqueous metal salt that preparing metal mass of ion percentage is 0.1%-10%, as ion crosslinking agent; The preparation mass percent lotus positive electrical polyelectrolyte aqueous solution that is 0.05%-10%, wherein containing the pore-foaming agent of lotus positive electrical polyelectrolyte mass percent 1%-100%; The chemical cross-linking agent aqueous solution of preparation mass percent 0.1%-5%;
C) casting solution step a) obtained is poured on the sheet glass of dry cleansing, scrape with the knifing rod the uniform film that thickness is 20-2000 μ m, the vacuum outgas bubble, be dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtain the organic inorganic hybridization aquagel membrane containing the ionomer of pore-foaming agent;
D) by step c) the organic inorganic hybridization aquagel membrane containing the ionomer of pore-foaming agent that obtains under 4 ℃-90 ℃ with deionized water concussion wash-out 8-48h, remove pore-foaming agent and unreacted ion crosslinking agent, obtain alginic acid alkali organic inorganic hybridization hydrogel filter membrane;
E) by steps d) the alginic acid alkali organic inorganic hybridization hydrogel filter membrane that obtains is dipped into step b) 1min-24h in the lotus positive electrical polyelectrolyte aqueous solution of preparation, wash away pore-foaming agent by deionized water after taking-up, use step b) preparation the crosslinked 0.5-24h of the chemical cross-linking agent aqueous solution, wash away unreacted chemical cross-linking agent by deionized water again, finally obtain the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of top layer chemical crosslinking.
6. the preparation method of the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 5, is characterized in that described aqueous metal salt is any one or the two or more mixture in zinc chloride, barium chloride, iron chloride, frerrous chloride, aluminium chloride, calcium chloride, copper sulphate, calcium nitrate aqueous solution.
7. the preparation method of the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 5, the SiO that the micro-nano inorganic particulate that it is characterized in that described hydroxy-acid group is the carboxyl grafting
2, the carboxyl grafting TiO
2, the carboxyl grafting Fe
3o
4, one or more mixtures in carboxylation CNT, carboxylation Graphene, the particle diameter of inorganic particulate is at 5nm-150 μ m.
8. the preparation method of the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 5, it is characterized in that described pore-foaming agent is any one or the two or more mixture in polyacrylamide, PVP, polyethylene glycol, urea, polyvinyl alcohol, APEO, gelatin, water soluble starch, its molecular weight is at 200-50000.
9. the preparation method of the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 5, is characterized in that described chemical cross-linking agent is one or more mixtures in epoxychloropropane, glutaraldehyde, Geniposide, carbodiimide, succinyl oxide, hexamethylene diisocyanate.
10. the preparation method of the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 5, is characterized in that described lotus positive electrical polyelectrolyte is one or more mixtures in shitosan, polymine, polyvinylamine, polyvinyl pyridine, poly-trimethylallylammonium chloride, polymethyl acyl-oxygen ethyl-trimethyl salmiac, PDDA.
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