CN102585282A - Method for preparing organic/inorganic composite nanowire filtering membrane - Google Patents
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Abstract
The invention discloses a method for preparing an organic/inorganic composite nanowire filtering membrane. The method comprises the following steps of: dissolving metal salt in an aqueous solution of ethanolamine to prepare a metal hydroxide nanowire; adding a heparin solution into a metal hydroxide nanowire solution to prepare a core-shell structured composite nanowire solution; fixing a polymer porous membrane in a filtering container, keeping a membrane surface upward, adding the core-shell structured composite nanowire solution into the filtering container, and filtering under reduced pressure; and drying. Negatively charged heparin is fixed on the surface of the positively charged metal hydroxide nanowire through electrostatic action to form the core-shell structured composite nanowire taking the nanowire as a core and the heparin as a shell, and the composite nanowire is deposited on the surface of the polymer porous membrane by a dynamic membrane preparation method to form the organic/inorganic composite nanowire filtering membrane with antibacterial property and blood compatibility. The nanowire has small diameter, small pore size when loaded, and high pore density, and the preparation process is simple and low in cost.
Description
Technical field
The present invention relates to the composite filtering film technical field, relate in particular to a kind of preparation method of organic/inorganic composite nano-line filtering membrane.
Background technology
Membrane sepn is to occur in 20 beginnings of the century; A new technology that emerges rapidly after the sixties in 20th century, membrane separation technique had both had separations concurrently, had concentrated, purifying and purified function, had again efficiently; Energy-saving and environmental protection, molecular level are filtered and filtration procedure is simple, be easy to characteristic such as control.At present; Membrane separation technique has been widely used in food, medicine, biology, environmental protection, chemical industry, metallurgy, the energy, oil, water treatment, electronics, field such as bionical; Produce huge economic benefit and social benefit, become one of most important means in the current separation science.The membrane process of having developed at present has micro-filtration, ultrafiltration, nanofiltration, r-o-, electrodialysis, dialysis, gas delivery, infiltration evaporation etc.Mould material is the core of membrane technique, and the character of mould material directly affects the materialization stability and the separation performance of film, can it be divided into organic high molecular layer (being polymeric film) and mineral membrane two big classes according to forming.
Polymeric membrane has advantages such as easy, the good mechanical property of preparation, selection kind are many; Therefore; The nf membrane product is many at present is main with macromolecular nano filtering membrane; Account for more than 95%, macromolecule member material commonly used mainly contains modified-cellulose class, polyolefine, polysulfones, polymeric amide, polycarbonate, Vestolen PP 7052 nitrile, PEMULEN TR2 and fluoropolymer etc.Polymer porous film also exists some urgent problems in actual application, the film serious like easy formation pollutes, the cutoff performance span is difficult to separate specific system greatly, and permeation flux is little not high with physical strength.Therefore, the various countries investigator is making great efforts to seek and develop novel porous film.
Along with the development of nanotechnology, utilize method of electrostatic spinning to prepare micro-filtration/ultra-filtration membrane and receive publicity day by day.Electrostatic spinning claims that again electricity spins, and is a kind of spining technology that simply, efficiently and fast prepares ultra-fine fibre; Advantages such as resulting tunica fibrosa porosity is high, specific surface area is big, hole connectivity and homogeneity are good are widely used in every field, still; The diameter of nano wire is difficult to reduce in the 100nm, and membrane pore size is big, so nano fibrous membrane is difficult to surpass/nf membrane; Therefore, the preparation diameter is littler becomes the target of research to form the nano wire of small through hole more.
Recently, Izumi Ichinose seminar has reported cadmium hydroxide, verditer, zinc hydroxide and manganous hydroxide nano wire successively, and nanowire diameter is little; The surface has a large amount of positive charges; Can be directly or indirect negative load electronegative species, as: AS, anionic dyestuff; Protein, polymkeric substance etc.Wherein, copper and zine ion are again a kind of bacteriocidal substances commonly used, though sterilizing ability a little less than silver ions, price is more reasonable, therefore, Application Areas enlarges day by day.Heparin; It is a kind of polyanionic polysaccharide; Has superior anticoagulation function; Can be fixed on the surface of biomaterial for medical purpose through specific method, can improve the surperficial anti-freezing performance and the biocompatibility of material, reach its range of application of expansion, improve its security in clinical application and the purpose of practicality.
Therefore, in order to overcome the deficiency of traditional filtering membrane surface modification, the present invention makes full use of the characteristic of metal hydroxides nano wire and heparin, and preparation has the organic/inorganic composite nano-line filtering membrane of bacterinertness and blood compatibility double effects.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of organic/inorganic composite nano-line filtering membrane is provided.
The preparation method of organic/inorganic composite nano-line filtering membrane comprises the steps:
(1) preparation of heparin solution:
It is that strength of solution is 0.2～2.5 grams per liter in 6.0～10 the phosphate buffer soln that heparin sodium is dissolved in the pH value;
(2) preparation of metal hydroxides nano wire solution:
With 1～6 mmole/liter metal-salt be dissolved in 0.4～2.4 isopyknic mmole/liter thanomin in, magnetic agitation 1 minute under 4～25 degrees centigrade, was grown 1～30 day, prepared the metal hydroxides nano wire solution of clear;
(3) preparation of nucleocapsid structure composite nano-line solution:
Heparin solution slowly is added in the metal hydroxides nano wire solution, magnetic agitation 0.5～24 hour, the heparin that makes bear electricity is fixed on the metal hydroxides nanowire surface of lotus positive electricity through electrostatic interaction, forms the composite nano-line solution of nucleocapsid structure;
(4) preparation of composite filtering film:
The polyalcohol stephanoporate basement membrane is fixed in the filtration vessel; Face adds 10～200 milliliters of nucleocapsid structure composite nano-line solution, filtration under diminished pressure under 0.01～0.1 megapascal (MPa) pressure up in the filtration vessel; Flushing, drying obtains organic/inorganic composite nano-line filtering membrane.
Described polyalcohol stephanoporate basement membrane is pvdf, polysulfones or polyethersulfone porous basement membrane.Described metal hydroxides nano wire is metallic copper, metallic zinc, cadmium metal or manganese metal hydroxide nano line.Described metal-salt is nitrate trihydrate copper, Cadmium chloride fine powder, zinc nitrate or manganous nitrate., said organic/inorganic composite nano-line filtering membrane is microfiltration membrane, ultra-filtration membrane or nf membrane.
The present invention passes through the dynamic system embrane method at polymer porous film surface filtration metal refining hydroxide nano line-heparin nucleocapsid structure composite nano-line; Realization is to the surface-treated of polymer porous film; With the composite filtering film of preparation high comprehensive performance, it is little both to have made full use of nanowire diameter, and the aperture that forms during load is little; Hole density is high, makes full use of the bacterinertness of metals ion and the blood compatibility characteristic of heparin again.Preparation technology is simple, cost is low, can realize scale operation.
Description of drawings
Fig. 1 is the sem photograph of verditer nano wire;
Fig. 2 (a) is the surface scan Electronic Speculum figure of polyvinylidene fluoride microporous filtering film;
Fig. 2 (b) is the surface scan Electronic Speculum figure after the polyvinylidene fluoride microporous filtering film modification;
Fig. 3 (a) is a sem photograph behind the polysulphones hyperfiltration membrane platelet adhesion;
Fig. 3 (b) is a sem photograph behind the platelet adhesion after the polysulphones hyperfiltration membrane modification;
Fig. 4 (a) is a poly (ether-sulfone) ultrafiltration membrane bactericidal property photo;
Fig. 4 (b) is the bactericidal property photo after the poly (ether-sulfone) ultrafiltration membrane modification.
Embodiment
The present invention at first prepares lotus positive electricity metal hydroxides nano wire; Again the heparin of bear electricity is fixed on the metal hydroxides nanowire surface of lotus positive electricity through electrostatic interaction; Prepare the composite nano-line of nucleocapsid structure; Through the dynamic system embrane method its filtration under diminished pressure is deposited on the polymer porous film again, forms organic/inorganic composite nano-line filtering membrane with bacterinertness and blood compatibility double effects.
The preparation method of organic/inorganic composite nano-line filtering membrane comprises the steps:
(1) preparation of heparin solution:
With heparin sodium be dissolved in the pH value be in 6.0～10 the phosphate buffer soln concentration be the heparin solution of 0.2～2.5 grams per liter;
(2) preparation of metal hydroxides nano wire solution:
With 1～6 mmole/liter metal-salt be dissolved in 0.4～2.4 isopyknic mmole/liter thanomin in, magnetic agitation 1 minute under 4～25 degrees centigrade, was grown 1～30 day, prepared the metal hydroxides nano wire solution of clear;
(3) preparation of nucleocapsid structure composite nano-line solution:
Heparin solution slowly is added in the metal hydroxides nano wire solution, magnetic agitation 0.5～24 hour, the heparin that makes bear electricity is fixed on the metal hydroxides nanowire surface of lotus positive electricity through electrostatic interaction, forms the composite nano-line solution of nucleocapsid structure;
(4) preparation of composite filtering film:
The polyalcohol stephanoporate basement membrane is fixed in the filtration vessel; Face adds 10～200 milliliters of nucleocapsid structure composite nano-line solution, filtration under diminished pressure under 0.01～0.1 megapascal (MPa) pressure up in the filtration vessel; Flushing, drying obtains organic/inorganic composite nano-line filtering membrane.
Described polyalcohol stephanoporate basement membrane is pvdf, polysulfones or polyethersulfone porous basement membrane.Described metal hydroxides nano wire is metallic copper, metallic zinc, cadmium metal or manganese metal hydroxide nano line.Described metal-salt is nitrate trihydrate copper, Cadmium chloride fine powder, zinc nitrate or manganous nitrate.Described organic/inorganic composite nano-line filtering membrane is microfiltration membrane, ultra-filtration membrane or nf membrane.
Characterize through membrane pore structure observation, surface chemistry compositional analysis, water contact angle measurement, water flux mensuration, platelet adhesion experiment and antibacterial experiment structure and performance modified polymer microporous film.Characterizing method is respectively:
Membrane pore structure characterizes: adopt sem (S-4800) to observe, observe before earlier with the sample vacuum metallizing;
Water flux: the water flux of flat sheet membrane is measured and in the ultrafiltration cup, is carried out, and measuring stress is 0.1 megapascal (MPa), before measuring with alcohol immersion 30 minutes;
Water contact angle: the surface water contact angle of polymer porous film adopts contact angle measurement (Dataphysics OCA20, Germany), measures through sessile drop method.
Platelet adhesion experiment: refrigerated is rich in hematoblastic adult's blood plasma in 37 degrees centigrade of water-baths, behind the quick-thawing, drips on diaphragm and hatched 30 minutes, clean diaphragm 3 times, remove the unstable thrombocyte of absorption with phosphate buffer solution.Diaphragm was immersed in the glutaraldehyde solution fixing 30 minutes, clean diaphragm with ultrapure water then, and dehydrate, and use scanning electron microscopic observation with ethanol/water mixed solution gradient.
Antibacterial experiment: diaphragm is joined in the bacterial solution, and hatching is 24 hours in 37 degrees centigrade of constant-temperature shaking water-baths, and cultivated 48 hours on nutrient agar the dilution back successively, and the number colony count is taken pictures.
To combine embodiment and accompanying drawing that the present invention is done more detailed description below, but said embodiment is not construed as limiting the invention.From disclosed by the invention content associated to or all distortion of deriving, all think protection scope of the present invention.
Embodiment 1:
It is in 7.4 the phosphate buffer soln that heparin sodium is dissolved in pH, obtains the heparin solution that concentration is 0.2～2.5 grams per liter; With 4 mmoles/liter the nitrate trihydrate copper dissolution in 1.6 isopyknic mmoles/liter thanomin in, magnetic agitation 1 minute, the verditer nano wire solution of clear is prepared in 4～25 degrees centigrade of down growths 1～7 day; 0～7 milliliter of heparin solution is joined in 40 milliliters of verditer nano wire solution magnetic agitation 0.5～3 hour, preparation nucleocapsid structure composite nano-line solution; The clip diameter is 5 centimetres a polyvinylidene fluoride microporous filtering film; Clean oven dry, in 95% ethanol, soaked 1 hour deionized water rinsing 3 times; Be fixed in the filtration vessel again; Face adds 10～40 milliliters of above-mentioned nucleocapsid structure composite nano-line solution, 0.08～0.1 megapascal (MPa) filtration under diminished pressure up in container; Take out, deionized water rinsing 3 times, room temperature is dried, and is subsequent use.The performance characterization result sees table 1 before and after the polyvinylidene fluoride microporous filtering film modification, and the pattern of verditer nano wire is seen accompanying drawing 1, and the pattern of polyvinylidene fluoride microporous filtering film surface topography and 1-5 sample is respectively like accompanying drawing 2 (a) with (b).
Table 1: polyvinylidene fluoride microporous filtering film performance before and after the modification of verditer nano wire compares
Embodiment 2:
It is in 6 the phosphate buffer soln that heparin sodium is dissolved in pH, obtains the heparin solution that concentration is 1.0～2.5 grams per liters; With 4 mmoles/liter the nitrate trihydrate copper dissolution in 1.6 isopyknic mmoles/liter thanomin in, magnetic agitation 1 minute, the verditer nano wire solution of clear is prepared in 4～25 degrees centigrade of growths 3～30 days; 0～20 milliliter of heparin solution is joined in 40 milliliters of verditer nano wire solution magnetic agitation 1～5 hour, preparation nucleocapsid structure composite nano-line solution; The clip diameter is 5 centimetres a polysulphones hyperfiltration membrane; Clean oven dry, in 95% ethanol, soaked 1 hour deionized water rinsing 3 times; Be fixed in the filtration vessel again; Face adds 10～60 milliliters of above-mentioned nucleocapsid structure composite nano-line solution, 0.04～0.1 megapascal (MPa) filtration under diminished pressure up in container; Take out, deionized water rinsing 3 times, room temperature is dried, and is subsequent use.The performance characterization result sees table 2 before and after the polysulphones hyperfiltration membrane modification, and Fig. 3 (a) is the sem photograph behind the PSF ultra-filtration membrane platelet adhesion, and Fig. 3 (b) is the sem photograph behind the 2-4 platelet adhesion.
Table 2: polysulphones hyperfiltration membrane performance before and after the modification of verditer nano wire compares
Embodiment 3:
It is in 10 the phosphate buffer soln that heparin sodium is dissolved in pH, obtains the heparin solution that concentration is 1.0～2.5 grams per liters; With 4 mmoles/liter the nitrate trihydrate copper dissolution in 1.6 isopyknic mmoles/liter thanomin in, magnetic agitation 1 minute, the verditer nano wire solution of clear is prepared in 15～25 degrees centigrade of growths 1～30 day; 0～100 milliliter of heparin solution is joined in 100 milliliters of verditer nano wire solution magnetic agitation 5～24 hours, preparation nucleocapsid structure composite nano-line solution; The clip diameter is 5 centimetres a poly (ether-sulfone) ultrafiltration membrane; Clean oven dry, in 95% ethanol, soaked 1 hour deionized water rinsing 3 times; Be fixed in the filtration vessel again; Face adds 0～200 milliliter of above-mentioned nucleocapsid structure composite nano-line solution, 0.04～0.1 megapascal (MPa) filtration under diminished pressure up in container; Take out, deionized water rinsing 3 times, room temperature is dried, and is subsequent use.The performance characterization result sees table 3 before and after the poly (ether-sulfone) ultrafiltration membrane modification, and Fig. 4 (a) is a PES ultra-filtration membrane bactericidal property photo, and Fig. 4 (b) is the bactericidal property photo of 3-2 modified membrane.
Table 3: poly (ether-sulfone) ultrafiltration membrane performance before and after the modification of cupric oxide nano line compares
Embodiment 4:
It is in 7.4 the phosphate buffer soln that heparin sodium is dissolved in pH, obtains the heparin solution that concentration is 1.0～2.5 grams per liters; With 4 mmoles/liter Cadmium chloride fine powder be dissolved in 1.6 isopyknic mmoles/liter thanomin in, magnetic agitation 1 minute, the cadmium hydroxide nano wire solution of clear is prepared in 15～25 degrees centigrade of growths 1～30 day; 0～50 milliliter of heparin solution is joined in 50 milliliters of verditer nano wire solution magnetic agitation 5～10 hours, preparation nucleocapsid structure composite nano-line solution; The clip diameter is 5 centimetres a poly (ether-sulfone) ultrafiltration membrane; Clean oven dry, in 95% ethanol, soaked 1 hour deionized water rinsing 3 times; Be fixed in the filtration vessel again; Face adds 0～100 milliliter of above-mentioned nucleocapsid structure composite nano-line solution, 0.05～0.1 megapascal (MPa) filtration under diminished pressure up in container; Take out, deionized water rinsing 3 times, room temperature is dried, and is subsequent use.
Table 4: poly (ether-sulfone) ultrafiltration membrane performance before and after the modification of Cadmium oxide nano wire compares
Embodiment 5:
It is in 7.1 the phosphate buffer soln that heparin sodium is dissolved in pH, obtains the heparin solution that concentration is 0.2～1.5 grams per liter; With 4 mmoles/liter zinc nitrate be dissolved in 0.8 isopyknic mmole/liter thanomin in, magnetic agitation 1 minute, the verditer nano wire solution of clear is prepared in 4～25 degrees centigrade of down growths 1～3 day; 0～10 milliliter of heparin solution is joined in 80 milliliters of zinc hydroxide nano-wire solution magnetic agitation 0.5～1 hour, preparation nucleocapsid structure composite nano-line solution; The clip diameter is 5 centimetres a polyvinylidene fluoride microporous filtering film; Clean oven dry, in 95% ethanol, soaked 1 hour deionized water rinsing 3 times; Be fixed in the filtration vessel again; Face adds 10～90 milliliters of above-mentioned nucleocapsid structure composite nano-line solution, 0.05～0.1 megapascal (MPa) filtration under diminished pressure up in container; Take out, deionized water rinsing 3 times, room temperature is dried, and is subsequent use.
Table 5: polyvinylidene fluoride microporous filtering film performance before and after the zinc hydroxide nano-wire modification compares
Embodiment 6:
It is in 8.5 the phosphate buffer soln that heparin sodium is dissolved in pH, obtains the heparin solution that concentration is 0.5～2.5 grams per liter; With 4 mmoles/liter manganous nitrate be dissolved in 1.2 isopyknic mmoles/liter thanomin in, magnetic agitation 1 minute, the verditer nano wire solution of clear is prepared in 4～15 degrees centigrade of growths 1～10 day; 0～80.0 milliliter of heparin solution is joined in 80 milliliters of verditer nano wire solution magnetic agitation 1～12 hour, preparation nucleocapsid structure composite nano-line solution; The clip diameter is 5 centimetres a polysulphones hyperfiltration membrane; Clean oven dry, in 95% ethanol, soaked 1 hour deionized water rinsing 3 times; Be fixed in the filtration vessel again; Face adds 40～160 milliliters of above-mentioned nucleocapsid structure composite nano-line solution, 0.02～0.1 megapascal (MPa) filtration under diminished pressure up in container; Take out, deionized water rinsing 3 times, room temperature is dried, and is subsequent use.
Table 2: polysulphones hyperfiltration membrane performance before and after the modification of manganous hydroxide nano wire compares
Claims (5)
1. the preparation method of an organic/inorganic composite nano-line filtering membrane
,Its characteristic comprises the steps:
(1) preparation of heparin solution:
With heparin sodium be dissolved in the pH value be in 6.0～10 the phosphate buffer soln concentration be the heparin solution of 0.2～2.5 grams per liter;
(2) preparation of metal hydroxides nano wire solution:
With 1～6 mmole/liter metal-salt be dissolved in 0.4～2.4 isopyknic mmole/liter thanomin in, magnetic agitation 1 minute under 4～25 degrees centigrade, was grown 1～30 day, prepared the metal hydroxides nano wire solution of clear;
(3) preparation of nucleocapsid structure composite nano-line solution:
Heparin solution slowly is added in the metal hydroxides nano wire solution, magnetic agitation 0.5～24 hour, the heparin that makes bear electricity is fixed on the metal hydroxides nanowire surface of lotus positive electricity through electrostatic interaction, forms the composite nano-line solution of nucleocapsid structure;
(4) preparation of composite filtering film:
The polyalcohol stephanoporate basement membrane is fixed in the filtration vessel, and face adds 10～200 milliliters of nucleocapsid structure composite nano-line solution up in the filtration vessel; 0.01 filtration under diminished pressure under～0.1 megapascal (MPa) pressure; Flushing, drying obtains organic/inorganic composite nano-line filtering membrane.
2. the preparation method of a kind of organic/inorganic composite nano-line filtering membrane according to claim 1 is characterized in that, described polyalcohol stephanoporate basement membrane is pvdf, polysulfones or polyethersulfone porous basement membrane.
3. the preparation method of a kind of organic/inorganic composite nano-line filtering membrane according to claim 1 is characterized in that, described metal hydroxides nano wire is metallic copper, metallic zinc, cadmium metal or manganese metal hydroxide nano line.
4. the preparation method of a kind of organic/inorganic composite nano-line filtering membrane according to claim 1 is characterized in that, described metal-salt is nitrate trihydrate copper, Cadmium chloride fine powder, zinc nitrate or manganous nitrate.
5. the preparation method of a kind of organic/inorganic composite nano-line filtering membrane according to claim 1 is characterized in that, said organic/inorganic composite nano-line filtering membrane is microfiltration membrane, ultra-filtration membrane or nf membrane.
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| CN103100308A (en) * | 2013-01-17 | 2013-05-15 | 浙江大学 | Preparation method of gelatin thin film and composite thin film for single-walled gelatin carbon nanometer tube |
| CN103223299A (en) * | 2013-05-17 | 2013-07-31 | 厦门大学 | Macromolecular negative-charge ultrafiltration membrane and preparation method thereof |
| CN105771695A (en) * | 2016-04-13 | 2016-07-20 | 南京工业大学 | Method for improving polyamide reverse osmosis membrane performance through surface modification |
| CN106582330A (en) * | 2016-12-12 | 2017-04-26 | 四川煜天石油机械设备有限公司 | Heavy metal-containing floating oil filter membrane |
| CN109304099A (en) * | 2018-11-02 | 2019-02-05 | 南京工业大学 | A kind of polymer-metal hydroxide nano line laminated film and preparation method thereof |
| CN111664970A (en) * | 2020-05-28 | 2020-09-15 | 浙江大学 | Self-powered flexible pressure sensing device and preparation method thereof |
| CN114502263A (en) * | 2019-07-15 | 2022-05-13 | 新加坡国立大学 | Ceramic membranes for water and wastewater treatment |
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| CN103100308A (en) * | 2013-01-17 | 2013-05-15 | 浙江大学 | Preparation method of gelatin thin film and composite thin film for single-walled gelatin carbon nanometer tube |
| CN103223299A (en) * | 2013-05-17 | 2013-07-31 | 厦门大学 | Macromolecular negative-charge ultrafiltration membrane and preparation method thereof |
| CN105771695A (en) * | 2016-04-13 | 2016-07-20 | 南京工业大学 | Method for improving polyamide reverse osmosis membrane performance through surface modification |
| CN106582330A (en) * | 2016-12-12 | 2017-04-26 | 四川煜天石油机械设备有限公司 | Heavy metal-containing floating oil filter membrane |
| CN106582330B (en) * | 2016-12-12 | 2019-05-31 | 安徽启迪清源新材料有限公司 | A kind of filter membrane of oil slick containing heavy metal |
| CN109304099A (en) * | 2018-11-02 | 2019-02-05 | 南京工业大学 | A kind of polymer-metal hydroxide nano line laminated film and preparation method thereof |
| CN114502263A (en) * | 2019-07-15 | 2022-05-13 | 新加坡国立大学 | Ceramic membranes for water and wastewater treatment |
| CN111664970A (en) * | 2020-05-28 | 2020-09-15 | 浙江大学 | Self-powered flexible pressure sensing device and preparation method thereof |
| CN111664970B (en) * | 2020-05-28 | 2021-06-11 | 浙江大学 | Self-powered flexible pressure sensing device and preparation method thereof |
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