CN103446897B - Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof - Google Patents
Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a chemical and ionic cross-linked alginate hydrogel flat membrane for filtration, which is designed and prepared aiming at the problems of poor stability, low mechanical strength, overlarge pores and the like of a pure ionic cross-linked hydrogel filtering membrane. According to the flat membrane, sodium alginate is used as a membrane forming substrate, a water-soluble compound is used as a pore-forming agent, and a chemical cross-linking agent and an ionic cross-linking agent are added, so that the sodium alginate is subjected to covalent bonding and ionic cross-linking to improve the stability of the membrane. The mechanical strength and the pore size of the membrane and the stability in an electrolyte solution are adjusted by changing the types and the proportions of the chemical cross-linking agent and the ionic cross-linking agent. The hydrogel flat membrane is prepared through a simple preparation process and is low in cost; no organic waste liquid is produced; the obtained hydrogel membrane can resist the pressure of 0.2-1 MPa and has a good application prospect in the separation field in which membrane pollution is easy to produce, such as oil-water separation, protein separation and biological sample filtration. The hydrogel flat membrane is directly discarded and can be fully degraded by microorganisms after being used, so that no environmental harm is caused.
Description
Technical field
The present invention relates to a kind of filtration chemistry and ionomer alginate hydrogel Flat Membrane and preparation method thereof, belong to environment functional material and film field.
Background technology
Membrane filtration material very easily causes large molecule, colloid, electrolyte and particle etc. in film surface or film inside irreversible deposition due to itself hydrophobicity, and the fouling membrane caused thus causes the flux of film constantly to decline, so that membrane separating process can not normally carry out.Have employed a lot of method at present, as pretreatment feed water, the exploitation of pollution-resistant membrane, the novel designs of membrane module, optimization of operating condition and membrane process is combined with other technologies.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.
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 the film of blended system 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, sulfonated polyether sulphone (SPES-C), 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.Except hydrophilic macromolecule, Small molecular inorganic particulate also can be used for improving film hydrophily, such as Al
2o
3particle, α aluminum particulate, TiO
2particle and SiO
2particle etc.With the film that the casting solution containing this kind of particle is obtained, perfectly combine the heat-resisting quantity of inorganic material, hydrophily and high molecular pliability, a kind of novel hydrophilic organic/inorganic compound film [study on the modification of milipore filter and application, membrane science and technology, 2003,23 (4): 97-102].
Surface coating modified is the water soluble polymer or the surfactant that contain functional group by applying last layer on film surface, can introduce one deck functional polymer layer method of modifying on the surface of film.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, 98.4%[shitosan ultrafiltration composite membrane development [J] 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 [Bipolar membrane prepared bygrafting and plasma polymerization.Membr. Sci., 2003,219:1-13].
Also greatly can improve flux to the hydrophilic modifying of former film and improve the antifouling property of film, therefore domestic and international many scholars are to the hydrophilic modification of hydrophobic film and select hydrophilic material masking etc. to carry out research work, and development of new membrane material rarely has report these years.Blending and modifying complex process, surface coating easily comes off, and surface graft modification is difficult to obtain uniform Modified Membrane, the more important thing is that these methods fundamentally can not solve the hydrophily problem of film, also just fundamentally can not solve the pollution of film.
The multicomponent system that macromolecule hydrogel is made up of polymer three-dimensional network and water.The mechanical strength of most of artificial Common hydrogels is very poor, is easily out of shape, and along with water content difference occur swelling and deswelling.Hydrogel has splendid hydrophily, because it more than 80 percent is all water, if the film this kind of hydrogel being prepared into water treatment not only fundamentally can solve the hydrophily problem of film, various environmental stimulus factor can also be utilized to change the size of fenestra, thus the filtration behavior of regulation and control film.Sodium alginate is a kind of natural polymer extracted from brown alga, containing α-Isosorbide-5-Nitrae structure L-type guluronic acid and β-Isosorbide-5-Nitrae structure D type mannuronic acid two kinds of construction units in its strand.Its water soluble, and be insoluble to organic solvent, hydrogel can be formed by ionomer.Sodium alginate has good biocompatibility, thickening property, film forming, stability, flocculability and sequestering, has been widely used in the various fields such as industry, agricultural, medicine.The research of sodium alginate in membrane material is only limitted to the report in amberplex and evaporating-osmosis film mostly.Sodium alginate aqueous solution and cellulosic copper ammon solution have been mixed with amberplex by Zhang Lina etc., this film has successfully adsorbed strontium ion and cadmium ion, and this amberplex reproducible [Journal ofMembrane Science, 1999,162:103-109.].Sodium alginate film and various inorganic ions are cross-linked by Y.M.Huang and M.H.Jochen etc., this film of preparation is used successfully to the evaporating-osmosis dehydration of the mixture of second alcohol and water and the mixture of isopropyl alcohol and water, obtain comparatively high permeating flux and separation [Journal of Membrane Science, 1999,160:101-113].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 have prepared a kind of Hybridization hydrogel flat membrane for water filtration in work before, 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, and the Flat Membrane obtained after washing away pore-foaming agent, for water filtration, has 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 residue 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, and mechanical strength is low, film is being subject to pressure thinning thus is making Pore Blocking, and therefore under the pressure of more than 0.16MPa, flux no longer increases with pressure and increases.In addition, the calcium alginate hydrogel Flat Membrane fenestra merely through calcium ion crosslinking is excessive, is difficult to the material retaining small-molecular-weight.
For pure ionomer hydrogel filter membrane poor stability, mechanical strength is low, fenestra is excessive, radical polymerization gel mould pore-foaming agent is difficult to the problems such as wash-out, a kind of filtration chemistry of this patent design preparation and ionomer alginate hydrogel Flat Membrane, this Flat Membrane take into sodium alginate as film base material, take water soluble compound as pore-foaming agent, add chemical cross-linking agent and ion crosslinking agent, make sodium alginate simultaneously by covalent bond and ionomer to improve the stability of film.Mechanical strength and the fenestra size of film is regulated by the kind and proportioning changing chemical cross-linking agent and ion crosslinking agent, and the stability in electrolyte solution.Preparation technology is simple for this hydrogel Flat Membrane, cost is low, do not have organic liquid waste to produce, the hydrogel Flat Membrane obtained can the pressure of resistance to 0.2-1MPa, and the separation field easily producing fouling membrane at water-oil separating, Separation of Proteins, filtration of biological samples etc. has good application prospect.
Now widely used polymeric membrane is difficult to biodegradation, therefore often problem of environmental pollution is brought after discarding, and hydrogel Flat Membrane key component prepared by the present invention is alginate, using rear direct abandonment can be degradable by microorganism, can not cause environmental hazard.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is pure ionomer hydrogel filter membrane poor stability, mechanical strength is low, fenestra is excessive, gel mould pore-foaming agent prepared by radical polymerization is difficult to wash-out, and common polymeric membrane is difficult to the problems such as biodegradation.
The present invention solves described pure ionomer hydrogel filter membrane poor stability, mechanical strength is low, fenestra is excessive, gel mould pore-foaming agent prepared by radical polymerization is difficult to wash-out, and the technical scheme that common polymeric membrane is difficult to the problems such as biodegradation is a kind of filtration chemistry of design and ionomer alginate hydrogel Flat Membrane.
The invention provides a kind of filtration chemistry and ionomer alginate hydrogel Flat Membrane and preparation method thereof, it is characterized in that comprising the following steps:
A) take 1-5g sodium alginate, the pore-foaming agent of sodium alginate mass percent 1%-100%, pour in 100ml deionized water together, stirring and dissolving 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 0.01%-10%, as ion crosslinking agent; The chemical cross-linking agent aqueous solution of preparation mass percent 0.1%-5%;
C) casting solution 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 hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is dipped into step b) in the chemical cross-linking agent aqueous solution that obtains, regulate the pH of the chemical cross-linking agent aqueous solution between 1-12, temperature between 4 DEG C-90 DEG C, to control the degree of chemical crosslink reaction; After chemical crosslinking 1-36h, film being taken out, is reentered into step b) in the ionomer agent solution that obtains, crosslinked 0.1-24h, obtains the chemistry containing pore-foaming agent and ionomer alginate hydrogel Flat Membrane; The aqueous solution volume ratio of chemical cross-linking agent and ion crosslinking agent is 1: 20-10: 1; If pore-foaming agent can react with chemical cross-linking agent, first wash away pore-foaming agent by deionized water and be cross-linked with chemical cross-linking agent again;
E) by steps d) obtain containing the chemistry of pore-foaming agent and ionomer alginate hydrogel Flat Membrane at 4 DEG C-90 DEG C with deionized water concussion wash-out 8-48h, removing pore-foaming agent and unreacted crosslinking agent, obtain water filtration chemistry and ionomer alginate hydrogel Flat Membrane.
Aqueous metal salt of the present invention is any one or two or more mixture in zinc chloride, barium chloride, iron chloride, aluminium chloride, calcium chloride, calcium dihydrogen phosphate, calcium nitrate aqueous solution; Described chemical cross-linking agent is one or more mixtures in epoxychloropropane, glutaraldehyde, Geniposide, carbodiimide, succinyl oxide, hexamethylene diisocyanate; Described pore-foaming agent is any one or two or more mixture in polyacrylamide, PVP, polyethylene glycol, urea, polyvinyl alcohol, PVP, gelatin, water soluble starch.
Preparation technology is simple for this hydrogel Flat Membrane, cost is low, organic liquid waste is not had to produce, the hydrogel Flat Membrane obtained can the pressure of resistance to 0.2-1MPa, good stability, there is high contamination resistance, than pure ionomer alginate hydrogel film, there is better stability and mechanical strength simultaneously, micromolecular rejection is also significantly improved.The separation field that this chemistry and ionomer alginate hydrogel Flat Membrane easily produce fouling membrane at water-oil separating, Separation of Proteins, filtration of biological samples etc. has good application prospect.
Detailed description of the invention
Introduce specific embodiments of the invention below, but the present invention is not by the restriction of embodiment.
Embodiment 1. 1 kinds of filtration glutaraldehydes and calcium ion crosslinking alginate hydrogel Flat Membrane and preparation method thereof
A) take 5g sodium alginate, the polyethylene glycol pore-foaming agent of sodium alginate mass percent 5%, pour in 100ml deionized water together, stirring and dissolving 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 solution of 10%, as ion crosslinking agent; The glutaraldehyde water solution of preparation mass percent 5%, as chemical cross-linking agent;
C) casting solution is poured on the sheet glass of dry cleansing, scrape with knifing rod the uniform film that thickness is 600 μm, vacuum outgas is steeped, and is dipped into step b together with sheet glass) in the calcium chloride solution that obtains, reaction 8h, obtains the hydrogel Flat Membrane of ionomer; Then polyethylene glycol is washed away by deionized water.
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is dipped into step b) in the chemical cross-linking agent aqueous solution that obtains, the pH regulating the chemical cross-linking agent aqueous solution is 4, and temperature, at 30 DEG C, carries out chemical crosslinking; After chemical crosslinking 1h, film being taken out, is reentered into step b) in the ionomer agent solution that obtains, crosslinked 2h, obtains the chemistry containing polyethylene glycol and ionomer alginate hydrogel Flat Membrane; The aqueous solution volume ratio of chemical cross-linking agent and ion crosslinking agent is 10: 1;
E) by steps d) chemistry that obtains and ionomer alginate hydrogel Flat Membrane with deionized water concussion wash-out 2h, remove unreacted crosslinking agent, obtain water filtration glutaraldehyde and calcium ion crosslinking alginate hydrogel Flat Membrane at 25 DEG C.
Embodiment 2. 1 kinds of filtration glutaraldehydes and barium ions cross-linked alginate hydrogel Flat Membrane and preparation method thereof
A) take 2.5g sodium alginate, the PVP pore-foaming agent of sodium alginate mass percent 3%, pour in 100ml deionized water together, stirring and dissolving is even, is positioned over after leaving standstill froth breaking in the closed container of 25 DEG C and obtains casting solution;
B) preparing barium ions mass percent is the barium chloride solution of 1%, as ion crosslinking agent; The chemical cross-linking agent glutaraldehyde water solution of preparation mass percent 1%;
C) casting solution is poured on the sheet glass of dry cleansing, scrape with knifing rod the uniform film that thickness is 20 μm, vacuum outgas is steeped, and is dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1h, obtains the hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is dipped into step b) in the chemical cross-linking agent aqueous solution that obtains, the pH regulating the chemical cross-linking agent aqueous solution is 3.5, temperature at 90 DEG C, to carry out chemical crosslink reaction; After chemical crosslinking 3h, film being taken out, is reentered into step b) in the ionomer agent solution that obtains, crosslinked 3h, obtains the chemistry containing PVP and ionomer alginate hydrogel Flat Membrane; The aqueous solution volume ratio of chemical cross-linking agent and ion crosslinking agent is 1: 10;
E) by steps d) obtain containing the chemistry of PVP and ionomer alginate hydrogel Flat Membrane at 25 DEG C with deionized water concussion wash-out 24h, removing PVP and unreacted crosslinking agent, obtain water filtration glutaraldehyde and barium ions cross-linked alginate hydrogel Flat Membrane.
Embodiment 3. 1 kinds of filtration hexamethylene diisocyanates and aluminium ion cross-linked alginate hydrogel Flat Membrane and preparation method thereof
A) take 1g sodium alginate, the urea of sodium alginate mass percent 100%, pour in 100ml deionized water together, stirring and dissolving is even, is positioned over after leaving standstill froth breaking in the closed container of 4 DEG C and obtains casting solution;
B) preparing aluminium ion mass percent is the aluminum chloride aqueous solution of 0.01%, as ion crosslinking agent; The chemical cross-linking agent hexamethylene diisocyanate aqueous solution of preparation mass percent 5%;
C) casting solution is poured on the sheet glass of dry cleansing, scrape with knifing rod the uniform film that thickness is 2000 μm, vacuum outgas is steeped, and is dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 10h, obtains the hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is dipped into step b) in the chemical cross-linking agent aqueous solution that obtains, the pH regulating the chemical cross-linking agent aqueous solution is 5, temperature at 30 DEG C, to control chemical crosslink reaction; After chemical crosslinking 1-36h, film being taken out, is reentered into step b) in the ionomer agent solution that obtains, crosslinked 4h, obtains urea-containing chemistry and ionomer alginate hydrogel Flat Membrane; The aqueous solution volume ratio of chemical cross-linking agent and ion crosslinking agent is 20: 1
E) by steps d) the urea-containing chemistry that obtains and ionomer alginate hydrogel Flat Membrane at 25 DEG C with deionized water concussion wash-out 48h, removing urea and unreacted crosslinking agent, obtain water filtration hexamethylene diisocyanate and aluminium ion cross-linked alginate hydrogel Flat Membrane.
Embodiment 4. 1 kinds of filtration succinyl oxides and zinc ion cross-linked alginate hydrogel Flat Membrane and preparation method thereof
A) take 4.5g sodium alginate, the polyacrylamide pore-foaming agent of sodium alginate mass percent 4%, pour in 100ml deionized water together, stirring and dissolving is even, is positioned over after leaving standstill froth breaking in the closed container of 30 DEG C and obtains casting solution;
B) preparing zinc ion mass percent is the solder(ing)acid of 6%, as ion crosslinking agent; The chemical cross-linking agent succinyl oxide aqueous solution of preparation mass percent 1.75%;
C) casting solution is poured on the sheet glass of dry cleansing, scrape with knifing rod the uniform film that thickness is 1000 μm, vacuum outgas is steeped, and is dipped into step b together with sheet glass) in the ionomer agent solution that obtains, reaction 12h, obtains the hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is dipped into step b) in the chemical cross-linking agent aqueous solution that obtains, the pH regulating the chemical cross-linking agent aqueous solution is 6, temperature at 45 DEG C, to control the degree of chemical crosslink reaction; After chemical crosslinking 8h, film being taken out, is reentered into step b) in the ionomer agent solution that obtains, crosslinked 5h, obtains the chemistry containing polyacrylamide and ionomer alginate hydrogel Flat Membrane; The aqueous solution volume ratio of chemical cross-linking agent and ion crosslinking agent is 5: 1;
E) by steps d) obtain containing the chemistry of polyacrylamide and ionomer alginate hydrogel Flat Membrane at 25 DEG C with deionized water concussion wash-out 12h, removing polyacrylamide and unreacted crosslinking agent, obtain water filtration succinyl oxide and zinc ion cross-linked alginate hydrogel Flat Membrane.
Claims (4)
1. filter the preparation method with chemistry and ionomer alginate hydrogel Flat Membrane, it is characterized in that comprising the following steps:
A) take 1-5g sodium alginate, the pore-foaming agent of sodium alginate mass percent 1%-100%, pour in 100ml deionized water together, stirring and dissolving 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 0.01%-10%, as ion crosslinking agent; The chemical cross-linking agent aqueous solution of preparation mass percent 0.1%-5%;
C) casting solution 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 hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is dipped into step b) in the chemical cross-linking agent aqueous solution that obtains, regulate the pH of the chemical cross-linking agent aqueous solution between 1-12, temperature between 4 DEG C-90 DEG C, to control the degree of chemical crosslink reaction; After chemical crosslinking 1-36h, film being taken out, is reentered into step b) in the ionomer agent solution that obtains, crosslinked 0.1-24h, obtains the chemistry containing pore-foaming agent and ionomer alginate hydrogel Flat Membrane; The aqueous solution volume ratio of chemical cross-linking agent and ion crosslinking agent is 1: 20-10: 1; If pore-foaming agent can react with chemical cross-linking agent, first wash away pore-foaming agent by deionized water and be cross-linked with chemical cross-linking agent again;
E) by steps d) obtain containing the chemistry of pore-foaming agent and ionomer alginate hydrogel Flat Membrane at 4 DEG C-90 DEG C with deionized water concussion wash-out 8-48h, removing pore-foaming agent and unreacted crosslinking agent, obtain water filtration chemistry and ionomer alginate hydrogel Flat Membrane.
2. a kind ofly to filter by chemistry and the preparation method of ionomer alginate hydrogel Flat Membrane as claimed in claim 1, it is characterized in that described aqueous metal salt is any one or two or more mixture in zinc chloride, barium chloride, iron chloride, aluminium chloride, calcium chloride, calcium dihydrogen phosphate, calcium nitrate aqueous solution.
3. a kind of preparation method filtered with chemistry and ionomer alginate hydrogel Flat Membrane as claimed in claim 1, is characterized in that described chemical cross-linking agent is one or more mixtures in glutaraldehyde, Geniposide, carbodiimide, succinyl oxide, hexamethylene diisocyanate.
4. a kind ofly to filter by chemistry and the preparation method of ionomer alginate hydrogel Flat Membrane as claimed in claim 1, 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, PVP, gelatin, water soluble starch.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998002204A1 (en) * | 1996-07-11 | 1998-01-22 | Hercules Incorporated | Medical devices comprising ionically and non-ionically cross-linked polymer hydrogels having improved mechanical properties |
| CN102335455A (en) * | 2010-07-26 | 2012-02-01 | 中国科学院化学研究所 | Biomacromolecular hydrogel biological stent and preparation method thereof |
| CN103170250A (en) * | 2013-04-02 | 2013-06-26 | 天津工业大学 | Hybridization hydrogel flat membrane for water filtration and preparation method thereof |
| CN103191657A (en) * | 2013-04-02 | 2013-07-10 | 天津工业大学 | Hybridized gel film for filtration of organic solvent and preparation method thereof |
Family Cites Families (1)
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| US8946194B2 (en) * | 2010-10-08 | 2015-02-03 | Board Of Regents, University Of Texas System | One-step processing of hydrogels for mechanically robust and chemically desired features |
-
2013
- 2013-09-13 CN CN201310424397.2A patent/CN103446897B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998002204A1 (en) * | 1996-07-11 | 1998-01-22 | Hercules Incorporated | Medical devices comprising ionically and non-ionically cross-linked polymer hydrogels having improved mechanical properties |
| CN102335455A (en) * | 2010-07-26 | 2012-02-01 | 中国科学院化学研究所 | Biomacromolecular hydrogel biological stent and preparation method thereof |
| CN103170250A (en) * | 2013-04-02 | 2013-06-26 | 天津工业大学 | Hybridization hydrogel flat membrane for water filtration and preparation method thereof |
| CN103191657A (en) * | 2013-04-02 | 2013-07-10 | 天津工业大学 | Hybridized gel film for filtration of organic solvent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 褐藻酸膜的制作工艺和性能研究;刘邻渭等;《包装工程》;19951231;第16卷;第21页右栏第1-17行、第22页右栏最后1行至第24页右栏最后1行 * |
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