CN103446899B - 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
Alginic acid alkali organic inorganic hybridization hydrogel filter membrane that the present invention relates to the chemical crosslinking of a kind of top layer and preparation method thereof, belongs 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, extensive use in the thickening-purification technology and classification etc. of desalinization, industrial wastewater treatment, macromolecular substances.It is the important topic in UF membrane field to the selection of membrane material and research.Conventional film filtering material very easily causes large molecule, colloid, electrolyte etc. in film surface or film inside irreversible deposition due to the hydrophobicity of itself, causes fouling membrane that the flux of film is constantly declined, so that membrane separating process can not normally carry out.For the feature of the lyophobic dusts such as the easy adsorbed proteins of polymer film surface, the effective ways alleviating fouling membrane are the surface naturies improving film, as chargedization on film surface or the hydrophiling etc. of hydrophobic film.
Blending and modifying is a kind of short-cut method of improvement film properties of learning from other's strong points to offset one's weaknesses on existing membrane material basis.By blended with hydrophilic macromolecule, hydrophilic component is introduced in casting solution system, thus 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 and significantly promote.Be usually used in blended 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 are blended from hydrophobic polymeric has respectively obtained the microfiltration membranes and milipore filter that are applicable to different separation system.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 the water soluble polymer or the surfactant that contain functional group by applying last layer on film surface, can introduce the method for modifying of one deck functional polymer layer on the surface of film.At film surface coating layer of surface activating agent, the hydrophily of film can be improved equally, improve membrane flux, but the surfactant of the coating on film surface can come off gradually along with the prolongation of time, thus cause the decline of membrane flux, until modified effect completely loses.Composite membrane has been prepared in the surface that shitosan (CS) is coated in polyether sulfone (PES) milipore filter, nylon-6 microfiltration membranes and PVDF microfiltration membranes by the people such as Sun Xiuzhen, in this three classes composite membrane, the performance of PVDF-CS composite membrane is the most excellent, under the operating condition of 0.25MPa, room temperature, the development of 98.4%[shitosan ultrafiltration composite membrane is reached to the rejection of PEG-20000, ocean, the East Sea, 1999,17 (2): 21-25].
Surface graft modification is the method that another large class effectively can improve polymer film surface character, generally cause means by plasma, light, irradiation, electron beam etc. and form avtive spot on film surface, this avtive spot causes other function monomer to be more further polymerized at film surface grafting, gives polymer film surface with the character of grafted polymer.The feature of surface graft modification is that modification occurs over just within several nanometers of film superficial layer, while imparting film surface is with the character of grafted polymer, do not affect the character of material body, and combine with chemical bond between the macromolecular chain of grafting with film surface and make modified effect more firm.The people such as Hsueh have prepared AA-PVDF-DMAEA Bipolar Membrane by plasma graft, the side grafting anionic monomer acrylic acid of pvdf membrane, and opposite side is grafted cation monomeric acrylic-N then, N-dimethyl amine ester.Due to the surface having Ionomer to cover graft copolymer membrane, the pure water contact angle of graft copolymer membrane is made significantly to decline [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 film hydrophily.With the film that the casting solution containing this kind of particle is obtained, perfectly combining the heat-resisting quantity of inorganic material, hydrophily and high molecular pliability, 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 PES film.The metal oxide of embedding makes the structure of film more open and porous, and antifouling property and the long-term flux stability of modification caudacoria are significantly improved [J.Membr.Sci., 2013,428:131-141].Daraei P etc. has prepared Fe by phase in version method
3o
4/ MWCNT/PES, PANI/Fe
3o
4/ PES and Fe
3o
4/ PES film.Mixed matrix film properties is detected, at three kinds of film Fe of magnetic field casting by pure water flux and pollution parameters
3o
4/ MWCNT/PES, PANI/Fe
3o
4/ PES and Fe
3o
4/ PES pure water flux improves 15%, 29% and 96% respectively.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.
Improve the hydrophily of film at present mainly through blending and modifying, surface coating and surface graft modification, thus improve the antifouling property of film.But blending and modifying complex process, surface coating easily comes off, and surface graft modification is difficult to obtain uniform Modified Membrane.The improvement of film self-characteristic and the exploitation of new membrane material are the focuses of research both at home and abroad, mainly through 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) Organic inorganic film is manufactured.
Hydrophilic film surface, owing to there is interaction of hydrogen bond between hydrone, makes water be ordered structure in film near-surface region, therefore water Preferential adsorption, hydrophobic substance destroys this ordered structure to then require the expenditure of energy close to film surface.Therefore, hydrophilic film is more not easily contaminated.Hydrogel is the three-dimensional net structure with chemical bond or physical force formation between a kind of hydrophilic high molecular polymer chain, absorbs a certain amount of water and makes the compound system that the swelling formation solvent of macromolecule network and macromolecule network form.Some are there are in recent years at film surface coating hydrogel to alleviate the document of fouling membrane.Young-Hye La etc. is pore-foaming agent with polyvinyl alcohol under the existence of sensitising agent, utilize ultraviolet irradiation to be cross-linked and go out hydrophilic gel layer at polysulphone super-filter membrane surface construction, this hydrophilic gel layer reveals remarkable hydrophily and permeability, excellent contamination resistance [J.Membr.Sci. is shown for oil water mixture and bovine serum albumin, 2012,401:306-312].Chen Xiaolin etc. use sodium alginate as surface-active layer material, with glutaraldehyde as cross linker, with polysulfones (PSF) and polyacrylonitrile (PAN) for supporting layer, prepare a kind of novel nanofiltration membrane with negative electric charge [Chinese Marine University's journal, 2010,40 (10): 85-89].
We are bibliography [Nature in work before, 2012, 489 (7414): 133-136] a kind of Hybridization hydrogel flat membrane for water filtration has been prepared, this Flat Membrane take sodium alginate as macromolecular scaffold, with acrylamide and derivative thereof for 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, the Flat Membrane obtained after washing away pore-foaming agent is for water filtration, there is high hydrophily and excellent resistance tocrocking [201310112790.8].But after being through the polymerisation of monomer, pore-foaming agent is partially grafted, is difficult to wash-out, the membrane flux therefore obtained is very little, and unreacted monomer have impact on the water quality after membrane filtration.We attempted taking sodium alginate as matrix, take calcium chloride as crosslinking agent, be that pore-foaming agent prepares calcium alginate hydrogel Flat Membrane with water soluble polymer, find that pore-foaming agent can by abundant wash-out, flux significantly improves, but pure ionomer hydrogel filter membrane poor stability, film is easily swelling, mechanical strength is low, and film is being subject to pressure thinning thus is making Pore Blocking, and therefore under the pressure of more than 0.16MPa, flux almost no longer increases with pressure and increases.In addition, the fenestra of pure alginate hydrogel film is comparatively large, is difficult to retain low-molecular-weight material.We have attempted using ion crosslinking agent and chemical cross-linking agent cross-linked alginate aquagel membrane simultaneously, although improve Small molecular rejection, the membrane flux obtained becomes less, and film also exists by the thinning problem making Pore Blocking of pressure.We attempted adding nano inoganic particle simultaneously and improved film strength, and really obtain good effect, the flux of film also improves a lot, but such film not electrolyte-resistant solution is swelling, improved not obvious to micromolecular rejection.If utilize ion crosslinking agent can the feature of the simultaneously micro-nano inorganic particulate of crossslinked sodium alginate and surface band hydroxy-acid group, micro-nano inorganic particulate and alginate hydrogel are arrived nano level compound and doping, greatly can improve the mechanical performance of alginate hydrogel, hot property and potential resistance to electrolyte contamination solution swellability, thus alginic acid alkali organic inorganic hybridization hydrogel is used as filter membrane is stable.Utilize the space between inorganic particulate and between inorganic particulate and alginate hydrogel to play reaming effect, thus the flux of film can be significantly improved.By the micro-nano inorganic particulate of change surface band hydroxy-acid group and the kind of ion crosslinking agent, control mechanical strength and the integral membrane hole size of the adjustable film of concentration of the particle size of inorganic particulate, consumption and ion crosslinking agent.Wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electrical polyelectrolyte; to be cross-linked through chemical cross-linking agent by alginate and the hydroxy-acid group of micro-nano surface of inorganic particles and the polyelectrolyte generation self assembly of lotus positive electricity; the finer and close protective layer of one deck and filter course is formed on film surface; by controlling the consumption of lotus positive electrical polyelectrolyte, the factors such as the consumption of crosslinking agent and crosslinking time can control crosslinking degree and skin covering of the surface hole size.Such film inside has micro-nano inorganic particulate to strengthen and reaming, improves its mechanical performance and flux simultaneously, and film is outer to be cross-linked through chemical bond, forms compacted zone, improves the anti-swelling of film, and improve the rejection to small-molecule substance.
Poor for normal film material hydrophilic, pure ionomer aquagel membrane mechanical strength is low, poor stability, and flux is low, is difficult to retain the problems such as Small molecular, 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 take into sodium alginate as film base material, with the micro-nano inorganic particulate of surface band hydroxy-acid group for reinforcing agent and expanding agent, take water soluble compound as pore-foaming agent, be cross-linked through ion crosslinking agent, the polyelectrolyte of wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electricity is also cross-linked 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, to Small molecular, there is higher rejection, nanofiltration effect can be reached.
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 hydrophilic is poor, and pure ionomer aquagel membrane mechanical strength is low, and poor stability, flux is low, is difficult to retain the problems such as Small molecular.
It is poor that the present invention solves described normal film material hydrophilic, pure ionomer aquagel membrane mechanical strength is low, poor stability, flux is low, and the technical scheme being difficult to retain the problems such as Small molecular is the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of design a kind of top layer chemical crosslinking.
Alginic acid alkali organic inorganic hybridization hydrogel filter membrane that the invention provides the chemical crosslinking of a kind of top layer and preparation method thereof, is characterized in that comprising the following steps:
A) 1-5g sodium alginate is taken, 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 in 100ml deionized water together, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 4 DEG C-30 DEG C and obtains casting solution;
B) preparing metal mass of ion percentage is the aqueous metal salt of 0.1%-10%, as ion crosslinking agent; Preparation mass percent is the lotus positive electrical polyelectrolyte aqueous solution of 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 that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 20-2000 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtains the organic inorganic hybridization aquagel membrane of the ionomer containing pore-foaming agent;
D) by step c) the organic inorganic hybridization aquagel membrane of ionomer containing pore-foaming agent that obtains at 4 DEG C-90 DEG C with deionized water concussion wash-out 8-48h, removing 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 prepared, pore-foaming agent is washed away by deionized water after taking-up, use step b) the chemical cross-linking agent aqueous solution prepared is cross-linked 0.5-24h, 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 two or more mixture in zinc chloride, barium chloride, iron chloride, frerrous chloride, aluminium chloride, calcium chloride, copper sulphate, calcium nitrate aqueous solution, the micro-nano inorganic particulate of described hydroxy-acid group is the SiO of carboxyl grafting
2, carboxyl grafting TiO
2, carboxyl grafting Fe
3o
4, carboxylation CNT, one or more mixtures in carboxylation Graphene, the particle diameter of inorganic particulate is at 5nm-150 μm.
Pore-foaming agent of the present invention is any one or 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 acyloxyethyl trimethyl ammonium chloride, PDDA.
This composite aquogel filter membrane preparation technology is simple, and cost is low, does not have organic liquid waste to produce, and the hydrogel Flat Membrane obtained can the pressure of resistance to 0.1-1MPa, can realize the effect of low pressure nanofiltration.
Detailed description of the invention
Introduce specific embodiments of the invention below, but the present invention is not by the restriction of embodiment.
Barium alginate/the SiO of embodiment 1. 1 kinds of top layer glutaraldehyde cross-linkings
2hybridized hydrogel filter membrane and preparation method thereof
A) 1g sodium alginate is taken, the polyacrylamide of sodium alginate mass percent 1%, the SiO of the carboxyl grafting of sodium alginate mass percent 100%
2, pour in 100ml deionized water together, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 4 DEG C and obtains casting solution;
B) preparing barium ions mass percent is the barium chloride solution of 0.1%, as ion crosslinking agent; Preparation mass percent is the polyvinyl pyridine aqueous solution of 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 that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 20 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 24h, obtains the barium alginate/SiO2 hybridized hydrogel film of the ionomer containing polyacrylamide;
D) by step c) barium alginate/SiO of ionomer containing polyacrylamide that obtains
2hybridized hydrogel film is with deionized water concussion wash-out 8h at 90 DEG C, and removing polyacrylamide and unreacted glutaraldehyde, obtain barium alginate/SiO
2hybridized hydrogel filter membrane;
E) by steps d) barium alginate/SiO of obtaining
2hybridized hydrogel filter membrane is dipped into step b) 12h in the polyvinyl pyridine aqueous solution prepared, polyacrylamide is washed away by deionized water after taking-up, use step b) glutaraldehyde water solution prepared is cross-linked 0.5h, wash away unreacted glutaraldehyde by deionized water again, finally obtain the barium alginate/SiO of top layer glutaraldehyde cross-linking
2hybridized hydrogel filter membrane.
Calcium alginate/carboxylation carbon nano-tube hybridization hydrogel filter membrane of embodiment 2. 1 kinds of top layer glutaraldehyde cross-linkings and preparation method thereof
A) 5g sodium alginate is taken, sodium alginate mass percent 100% polyvinylpyrrolidone, the carboxylation CNT of sodium alginate mass percent 0.01%, pour in 100ml deionized water together, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 30 DEG C and obtains casting solution;
B) preparing calcium ion mass percent is the calcium chloride water of 10%, as ion crosslinking agent; Preparation mass percent is the Aqueous polyvinylamine solutions of 10%, the wherein polyvinylpyrrolidone of polyvinylamine mass percent 100%; The glutaraldehyde water solution of preparation mass percent 5%;
C) casting solution that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 2000 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 24h, obtains the calcium alginate/carboxylation carbon nano-tube hybridization hydrogel containing pore-foaming agent;
D) by step c) obtain containing the calcium alginate/carboxylation carbon nano-tube hybridization hydrogel of pore-foaming agent at 90 DEG C with deionized water concussion wash-out 48h, removing polyvinylpyrrolidone and unreacted glutaraldehyde, obtain calcium alginate/carboxylation carbon nano-tube hybridization hydrogel filter membrane;
E) by steps d) calcium alginate/carboxylation carbon nano-tube hybridization hydrogel filter membrane of obtaining is dipped into step b) 12h in the Aqueous polyvinylamine solutions prepared, polyvinylpyrrolidone is washed away by deionized water after taking-up, use step b) the chemical cross-linking agent aqueous solution prepared is cross-linked 24h, wash away unreacted glutaraldehyde by deionized water again, finally obtain the calcium alginate/carboxylation carbon nano-tube hybridization hydrogel filter membrane of top layer glutaraldehyde cross-linking.
Aluminium alginate/carboxylation Graphene hybridized hydrogel filter membrane that embodiment 3. 1 kinds of top layer hexamethylene diisocyanates are crosslinked and preparation method thereof
A) 3.5g sodium alginate is taken, sodium alginate mass percent 50% polyethylene glycol, the surface band carboxylation Graphene of sodium alginate mass percent 60%, pour in 100ml deionized water together, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 30 DEG C and obtains casting solution;
B) preparing aluminium ion mass percent is the aluminum chloride aqueous solution of 5%, as ion crosslinking agent; Preparation mass percent is the poly-trimethylallylammonium chloride aqueous solution of 6%, wherein containing the polyethylene glycol of poly-trimethylallylammonium chloride mass percent 60%; The hexamethylene diisocyanate aqueous solution of preparation mass percent 4%;
C) casting solution that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 500 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtains the aluminium alginate/carboxylation Graphene hybridized hydrogel filter membrane containing pore-foaming agent;
D) by step c) obtain containing the aluminium alginate/carboxylation Graphene hybridized hydrogel filter membrane of pore-foaming agent at 60 DEG C with deionized water concussion wash-out 24h, removing polyethylene glycol and unreacted hexamethylene diisocyanate, obtain alginic acid alkali aluminium alginate/carboxylation Graphene hybridized hydrogel filter membrane;
E) by steps d) aluminium alginate/carboxylation Graphene hybridized hydrogel filter membrane of obtaining is dipped into step b) 8h in the poly-trimethylallylammonium chloride aqueous solution prepared, polyethylene glycol is washed away by deionized water after taking-up, use step b) hexamethylene diisocyanate prepared is cross-linked 15h, wash away unreacted hexamethylene diisocyanate by deionized water again, finally obtain aluminium alginate/carboxylation Graphene hybridized hydrogel filter membrane that top layer hexamethylene diisocyanate is crosslinked.
Ferric alginate/carboxylation Graphene hybridized hydrogel filter membrane that embodiment 4. 1 kinds of top layer carbodiimides are crosslinked and preparation method thereof
A) 4g sodium alginate is taken, the polyvinyl alcohol of sodium alginate mass percent 75%, the Fe of the carboxyl grafting of sodium alginate mass percent 35%
3o
4, pour in 100ml deionized water together, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 25 DEG C and obtains casting solution;
B) preparing iron ion mass percent is the ferric chloride in aqueous solution of 0.1%-10%, as ion crosslinking agent; Preparation mass percent is the PDDA aqueous solution of 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 that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 600 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtains the ferric alginate/carboxylation Graphene hybridized hydrogel film containing polyvinyl alcohol;
D) by step c) obtain containing the ferric alginate/carboxylation Graphene hybridized hydrogel film of polyvinyl alcohol at 75 DEG C with deionized water concussion wash-out 8-48h, removing polyvinyl alcohol and unreacted carbodiimide, obtain ferric alginate/carboxylation Graphene hybridized hydrogel filter membrane;
E) by steps d) ferric alginate/carboxylation Graphene hybridized hydrogel filter membrane of obtaining is dipped into step b) 6h in the carbodiimide aqueous solution prepared, polyvinyl alcohol is washed away by deionized water after taking-up, use step b) the chemical cross-linking agent aqueous solution prepared is cross-linked 10h, wash away unreacted carbodiimide by deionized water again, finally obtain ferric alginate/carboxylation Graphene hybridized hydrogel filter membrane that top layer carbodiimide is crosslinked.
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 take into sodium alginate as film base material, with the micro-nano inorganic particulate of surface band hydroxy-acid group for reinforcing agent and expanding agent, take water soluble compound as pore-foaming agent, be cross-linked through ion crosslinking agent, the polyelectrolyte of wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electricity is also cross-linked through chemical cross-linking agent, obtains hybridized hydrogel filter membrane.
2. the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 1, it is characterized in that utilizing ion crosslinking agent can the feature of the micro-nano inorganic particulate of crossslinked sodium alginate and surface band hydroxy-acid group simultaneously, micro-nano inorganic particulate and alginate hydrogel are arrived nano level compound and doping.
3. the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 1, it is characterized in that utilizing the space between inorganic particulate and between inorganic particulate and alginate hydrogel to play reaming effect, thus 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, control mechanical strength and the integral membrane hole size of the concentration adjustment film of the particle size of inorganic particulate, consumption and ion crosslinking agent.
4. the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of a kind of top layer chemical crosslinking as claimed in claim 1; it is characterized in that wash-out pore-foaming agent caudacoria surface deposition one deck lotus positive electrical polyelectrolyte; to be cross-linked through chemical cross-linking agent by alginate and the hydroxy-acid group of micro-nano surface of inorganic particles and the polyelectrolyte generation self assembly of lotus positive electricity; the finer and close protective layer of one deck and filter course is formed on film surface; by controlling the consumption of lotus positive electrical polyelectrolyte, the consumption of crosslinking agent and crosslinking time factor controlling crosslinking degree and skin covering of the surface hole size.
5. a preparation method for the alginic acid alkali organic inorganic hybridization hydrogel filter membrane of top layer chemical crosslinking, is characterized in that comprising the following steps:
A) 1-5g sodium alginate is taken, 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 in 100ml deionized water together, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 4 DEG C-30 DEG C and obtains casting solution;
B) preparing metal mass of ion percentage is the aqueous metal salt of 0.1%-10%, as ion crosslinking agent; Preparation mass percent is the lotus positive electrical polyelectrolyte aqueous solution of 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 that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 20-2000 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtains the organic inorganic hybridization aquagel membrane of the ionomer containing pore-foaming agent;
D) by step c) the organic inorganic hybridization aquagel membrane of ionomer containing pore-foaming agent that obtains at 4 DEG C-90 DEG C with deionized water concussion wash-out 8-48h, removing 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 prepared, pore-foaming agent is washed away by deionized water after taking-up, use step b) the chemical cross-linking agent aqueous solution prepared is cross-linked 0.5-24h, 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 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, is characterized in that the micro-nano inorganic particulate of described hydroxy-acid group is the SiO of carboxyl grafting
2, carboxyl grafting TiO
2, carboxyl grafting Fe
3o
4, carboxylation CNT, one or more mixtures in carboxylation Graphene, the particle diameter of inorganic particulate is at 5nm-150 μm.
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 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 acyloxyethyl trimethyl ammonium chloride, PDDA.
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| Publication Number | Publication Date |
|---|---|
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