CN103611434B - Preparation method of tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film - Google Patents
Preparation method of tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film Download PDFInfo
- Publication number
- CN103611434B CN103611434B CN201310643072.3A CN201310643072A CN103611434B CN 103611434 B CN103611434 B CN 103611434B CN 201310643072 A CN201310643072 A CN 201310643072A CN 103611434 B CN103611434 B CN 103611434B
- Authority
- CN
- China
- Prior art keywords
- solution
- preparation
- phosphonic acid
- film
- tetramethylene phosphonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film, which comprises the following steps: by using tetrabutyl titanate, ethylenediamine tetra(methylenephosphonic acid), dimethylsulfoxide, polyvinylidene fluoride and the like as main raw materials, carrying out covalent bonding reaction on the tetrabutyl titanate and ethylenediamine tetra(methylenephosphonic acid) at the temperature of lower than 130 DEG C to prepare a blend casting solution for preparing the chelated film; and by using a physical blending/phase transition technique, scraping the blend casting solution into the chelated film, and blending the ethylenediamine tetra(methylenephosphonic acid) chelation group into the polyvinylidene fluoride separation film, thereby implementing adsorption and removal of heavy metal pollutants in a water environment. The method is simple to operate and low in cost; and the prepared chelated film has the advantages of high mechanical strength and favorable performance for adsorbing heavy metal ions, and can effectively alleviate adverse effects of the organic complexing agent in the water body on the adsorption and removal of the heavy metal pollutants.
Description
Technical field the present invention relates to the preparation method of Kynoar macromolecular material, particularly the preparation method of Kynoar chelating membrane.
Heavy metal contaminants form mutability in background technology water body, difficult for biological degradation, easily to accumulate in vivo, its have environmental hazard large, dispose difficult feature.Though the precipitation that chemical precipitation heavy metal treatment technology effectively can realize heavy metal contaminants is removed, there is the defect that operating cost is high, chemical precipitates disposes difficulty and there is secondary pollution.Conventional absorbtion technology, as charcoal absorption, ion exchange resin absorption, though the Adsorption of Heavy Metals in Waters pollutant can be realized, but when there is the organic complexing agents such as citric acid, succinic acid, ethylenediamine tetra-acetic acid in water body, its absorption property can significantly decline, and then reduces the efficiency of heavy metal contaminants Adsorption.Membrane separation technique have separative efficiency high, simple, easy and simple to handle without phase transformation, energy-conserving and environment-protective, equipment, take up an area and less, easily realize the obviously advantage such as Automated condtrol, it, as the efficient sewage disposal of one and water resources comprehensive utilization technology, obtains investigation and application comparatively widely in water treatment field.Membrane separation technique is normally according to the size being trapped material yardstick, by the effect such as screening, selected area update strategy of diffusion barrier, under the impetus of ambient pressure, electrical potential difference or difference in chemical potential, realize the separation of component each in mixed liquor, purification and enrichment, then can realize being separated of predetermined substance and component, purification and concentrated.
Membrane separation technique is used for the concern that the removal of heavy metal contaminants has caused Chinese scholars.The present situation being used for heavy metal pollution process with regard to current UF membrane is seen, the membrane separation technique for heavy metal contaminants process is only confined to electrodialysis, nanofiltration and counter-infiltration, but these technology exist the defects such as processing cost is high, pre-processing requirements is strict.Current engineer applied is conventional micro-filtration, Ultra filtration membrane technology comparatively widely, because it filters and rejection the subject of knowledge and the object of knowledge limit, still can not realize effective removal of water-soluble heavy metal contaminants.Chemical coagulation, Polymer adsorption, micelle enhanced ultrafiltration and microfiltration membranes isolation technics, although the disposal that effectively can realize heavy metal, its defect that there is heavy metal after-treatment and environment is existed to potential hazard.Thus, actively developing the study on the modification of conventional micro-filtration, ultra-filtration and separation film, realize its Adsorption to water-soluble heavy metal contaminants, is one of Important Action implementing Heavy Metal Pollution.
In the microfiltering separation film of numerous macromolecule material, polyvinylidene fluoride separation membrane, with its good chemical stability, resistance tocrocking and excellent mechanical property, gets most of the attention.Conventional polyvinylidene fluoride separation membrane can not realize the removal to water-soluble heavy metal ion, therefore the study on the modification of microfiltering separation film of polyvinylidene fluoride is carried out, heavy metal had the functional group grafting of absorption and coordination or be blended in vinylidene diffusion barrier, will the removal of each form heavy metal contaminants in water body be realized.In this regard, Chinese scholars has carried out many research work in succession, and achieves a series of valuable achievement in research.Patent manuscript CN102496732A provides a kind of preparation method of polyvinylidene fluoride grafted p-styrenesulfonic acid proton exchange membrane, first the alkali alcoholic solution of preparation containing phase transfer catalyst, and adopts this solution to carry out basification to Kynoar powder; Then the Kynoar powder of styrene sulfonate monomer and basification is joined in organic solvent; and under the effect of initator; under nitrogen protection atmosphere; styrene sulfonate is grafted on Kynoar strand, has prepared the polyvinylidene fluoride proton exchange membrane of styrene sulfonate graft modification.But this patented technology is mainly used in fuel cell field, and the removal effect of the modified polyvinilidene fluoride PEM adopting this patented technology to prepare to Heavy Metals in Waters is not satisfactory.Patent CN102527262A discloses a kind of preparation method of high-throughput polyvinylidene fluoride hollow fiber ultrafiltration membrane of chemical enhanced pore, this technology applied chemistry strengthening pore-foaming agent processes film silk, obtain a kind of high-throughout polyvinylidene fluoride hollow fiber ultrafiltration membrane, this patented technology, by optimizing the processes such as core liquid composition, gel phase conversion and post processing, has prepared the polyvinylidene fluoride (PVDF) ultrafiltration membrane of high flux, high strength, high rejection, good hydrophilic property.But casting solution preparation process is loaded down with trivial details, R&D costs are high shortcoming that this patented technology exists, and the diffusion barrier of preparation effectively can not realize the removal of Heavy Metals in Waters pollutant.
It is easy that patent CN101537315A and CN102527246A each provides a kind of preparation method, evenly blended, effectively can remove the preparation method of the Kynoar material chelating membrane of free state and complex state heavy metal ion in water environment, it adopts melamine and 3-aminopropyl trimethoxysilane and diethylene triamine pentacetic acid (DTPA) to react at dimethyl sulfoxide (DMSO) organic phase generation covalent bonding, Applied Physics is blended/phase transfer of technology, diethylene triamine pentacetic acid (DTPA) functional group heavy metal ion with chelating ligands effect is blended in polyvinylidene fluoride polymer, prepare modified polyvinilidene fluoride chelating membrane.The chelating membrane mechanical performance of the Kynoar material adopting above-mentioned patented technology to prepare is not good enough, there is the defect that chelating membrane breaks in use procedure.In addition, although the Kynoar chelating membrane adopting above-mentioned patented technology to prepare effectively achieves the Adsorption of free state heavy metal in water body, but when organic complexing agents such as having citric acid, succinic acid, ethylenediamine tetra-acetic acid in water body exists, the removal effect of its heavy metal significantly can be reduced.
Summary of the invention the object of the present invention is to provide the preparation method that a kind of preparation method is easy, blended evenly, effectively can remove the butyl titanate-ethylenediamine tetramethylene phosphonic acid/Kynoar chelating membrane of free state and complex state heavy metal ion in water environment.The present invention mainly reacts by the covalent bonding of butyl titanate and ethylenediamine tetramethylene phosphonic acid, Applied Physics is blended/phase transfer of technology, ethylenediamine tetramethylene phosphonic acid heavy metal ion with chelating ligands effect is blended in polyvinylidene fluoride separation membrane, lower than at the temperature of 130 DEG C, prepare butyl titanate-ethylenediamine tetramethylene phosphonic acid/Kynoar chelating membrane.
Preparation method of the present invention is as follows:
One, the preparation of blended casting liquid:
1, raw materials used:
Primary raw material comprises: ethylenediamine tetramethylene phosphonic acid, butyl titanate, Kynoar, polyvinylpyrrolidone and dimethyl sulfoxide (DMSO), and their consumption has following mass ratio relation:
Ethylenediamine tetramethylene phosphonic acid: butyl titanate: Kynoar: polyvinylpyrrolidone: dimethyl sulfoxide (DMSO)=5 ~ 7:1 ~ 2:7 ~ 9:1 ~ 1.5:60 ~ 63.
2, preparation method:
(1) addition sequence of above-mentioned various raw material is: first add dimethyl sulfoxide (DMSO), ethylenediamine tetramethylene phosphonic acid, then add butyl titanate, finally adds Kynoar, polyvinylpyrrolidone successively;
(2) preparation of blended casting liquid is carried out in atmosphere, first dimethyl sulfoxide solvent is poured in container, then ethylenediamine tetramethylene phosphonic acid is joined in dimethyl sulfoxide solvent, magnetic agitation, make it fully dissolve and mix, solution temperature controls at 70 DEG C ~ 80 DEG C; After ethylenediamine tetramethylene phosphonic acid dissolves mixing completely, solution temperature is slowly elevated to 120 DEG C ~ 130 DEG C with the heating rate of 5 DEG C/min, and butyl titanate is joined in above-mentioned solution, magnetic agitation, ethylenediamine tetramethylene phosphonic acid and butyl titanate are fully reacted; After reaction 1h, solution temperature is down to 70 DEG C ~ 80 DEG C by 120 DEG C ~ 130 DEG C, then joins in above-mentioned solution by Kynoar, polyvinylpyrrolidone successively, solution temperature controls at 70 DEG C ~ 80 DEG C all the time, magnetic agitation 6h, makes each components dissolved of solution and fully blended; Mixed solution is placed in water-bath deaeration 3 ~ 5h after 6h, bath temperature is 50 DEG C ~ 60 DEG C, obtains blended casting liquid.
Two, the preparation of dull and stereotyped chelating membrane:
1, above-mentioned blended casting liquid is poured on smooth glass, makes the uniform liquid film of thickness with medical scraper;
2, the liquid film made by medical scraper is placed in baking oven together with glass plate and carries out drying and processing, and oven temperature is 70 DEG C ~ 80 DEG C, and drying time is 4 ~ 6h;
3, the liquid film after oven dry is placed in the bath of the running water condensation after microfiltration membranes process and carries out gelation process, condensation bath water temperature is 40 DEG C ~ 50 DEG C;
4, until above-mentioned film from glass plate depart from after, first it is used distilled water immersion 48h, then being immersed in concentration is 24h in the hydrochloric acid solution of 0.1 ~ 0.5mol/L, and being immersed in volume ratio after being cleaned by its taking-up distilled water is afterwards preserve in the aqueous hydrogen peroxide solution of 0.5 ~ 2%.
The chelating ligands ability of ethylenediamine tetramethylene phosphonic acid heavy metal ion is better than conventional organic carboxyl acid, if the ligand complex constant of ethylenediamine tetramethylene phosphonic acid and hydration copper ion is respectively higher than ethylenediamine tetra-acetic acid and diethylene triamine pentacetic acid (DTPA) 4 and 2 orders of magnitude.Thus, ethylenediamine tetramethylene phosphonic acid is blended in polyvinylidene fluoride separation membrane, will the performance of polyvinylidene fluoride separation membrane Adsorption heavy metal contaminants be improved.
The present invention compared with prior art tool has the following advantages:
1, preparation temperature is low, simple to operate, with low cost;
2, blended effective, evenly blended polyamino polyphosphonic acid compound in polyvinylidene fluoride separation membrane, make polyamino polyphosphonic acid functional group and the coordination of Heavy Metals in Waters pollutant with chelating ligands performance, effectively achieve the removal of free state and complex state heavy metal ion in water environment; Effectively can overcome the adverse effect that organic complexing agent exists the generation of heavy metal Adsorption;
3, the Kynoar chelating membrane rupture strength prepared of the present invention is high, good mechanical performance;
4, expanded the application of polyvinylidene fluoride separation membrane in sewage treatment area, removal and the recycling of heavy metals in industrial wastewater pollutant can have been realized.
Detailed description of the invention
Embodiment 1
Pour in beaker by 600g dimethyl sulfoxide solvent, join in dimethyl sulfoxide solvent, magnetic agitation by 50g ethylenediamine tetramethylene phosphonic acid, make it fully dissolve and mix, it is 70 DEG C that solution temperature controls; After ethylenediamine tetramethylene phosphonic acid dissolves mixing completely, solution temperature is slowly elevated to 120 DEG C with the heating rate of 5 DEG C/min, and 10g butyl titanate is joined in above-mentioned solution, magnetic agitation, makes ethylenediamine tetramethylene phosphonic acid and butyl titanate fully react; After reaction 1h, solution temperature is down to 70 DEG C by 120 DEG C, then joins in above-mentioned solution by 80g Kynoar, 10g polyvinylpyrrolidone successively, solution temperature controls at 70 DEG C all the time, magnetic agitation 6h, makes each components dissolved of solution and fully blended; Then mixed solution is placed in 50 DEG C of water-bath deaeration 3h, namely obtains blended casting liquid.Blended casting liquid is poured on smooth glass by medical scraper masking, then the liquid film made by medical scraper is placed in baking oven together with glass plate and carries out drying and processing, oven temperature is 70 DEG C, drying time is 4h, again the liquid film after oven dry is placed in the bath of the running water condensation after microfiltration membranes process and carries out gelation process, condensation bath water temperature is 40 DEG C, until above-mentioned film after glass plate departs from, first it is used distilled water immersion 48h, then being immersed in concentration is 24h in the hydrochloric acid solution of 0.1mol/L, being immersed in volume ratio after being cleaned by its taking-up distilled water is afterwards preserve in the aqueous hydrogen peroxide solution of 0.5%.
Embodiment 2
Pour in beaker by 610g dimethyl sulfoxide solvent, join in dimethyl sulfoxide solvent, magnetic agitation by 60g ethylenediamine tetramethylene phosphonic acid, make it fully dissolve and mix, it is 70 DEG C that solution temperature controls; After ethylenediamine tetramethylene phosphonic acid dissolves mixing completely, solution temperature is slowly elevated to 125 DEG C with the heating rate of 5 DEG C/min, and 20g butyl titanate is joined in above-mentioned solution, magnetic agitation, makes ethylenediamine tetramethylene phosphonic acid and butyl titanate fully react; After reaction 1h, solution temperature is down to 70 DEG C by 125 DEG C, then joins in above-mentioned solution by 90g Kynoar, 15g polyvinylpyrrolidone successively, solution temperature controls at 70 DEG C all the time, magnetic agitation 6h, makes each components dissolved of solution and fully blended; Then mixed solution is placed in 55 DEG C of water-bath deaeration 4h, namely obtains blended casting liquid.Blended casting liquid is poured on smooth glass by medical scraper masking, then the liquid film that medical scraper is made is carried out drying and processing together with glass plate as in baking oven, oven temperature is 75 DEG C, drying time is 5h, again the liquid film after oven dry is placed in the bath of the running water condensation after microfiltration membranes process and carries out gelation process, condensation bath water temperature is 50 DEG C, until above-mentioned film after glass plate departs from, first it is used distilled water immersion 48h, then being immersed in concentration is 24h in the hydrochloric acid solution of 0.3mol/L, being immersed in volume ratio after being cleaned by its taking-up distilled water is afterwards preserve in the aqueous hydrogen peroxide solution of 1%.
Embodiment 3
Pour in beaker by 620g dimethyl sulfoxide solvent, join in dimethyl sulfoxide solvent, magnetic agitation by 50g ethylenediamine tetramethylene phosphonic acid, make it fully dissolve and mix, it is 80 DEG C that solution temperature controls; After ethylenediamine tetramethylene phosphonic acid dissolves mixing completely, solution temperature is slowly elevated to 130 DEG C with the heating rate of 5 DEG C/min, and 15g butyl titanate is joined in above-mentioned solution, magnetic agitation, makes ethylenediamine tetramethylene phosphonic acid and butyl titanate fully react; After reaction 1h, solution temperature is down to 80 DEG C by 130 DEG C, then joins in above-mentioned solution by 70g Kynoar, 10g polyvinylpyrrolidone successively, solution temperature controls at 80 DEG C all the time, magnetic agitation 6h, makes each components dissolved of solution and fully blended; Then mixed solution is placed in 60 DEG C of water-bath deaeration 5h, namely obtains blended casting liquid.Blended casting liquid is poured on smooth glass by medical scraper masking, then the liquid film that medical scraper is made is carried out drying and processing together with glass plate as in baking oven, oven temperature is 80 DEG C, drying time is 6h, again the liquid film after oven dry is placed in the bath of the running water condensation after microfiltration membranes process and carries out gelation process, condensation bath water temperature is 45 DEG C, until above-mentioned film after glass plate departs from, first it is used distilled water immersion 48h, then being immersed in concentration is 24h in the hydrochloric acid solution of 0.5mol/L, being immersed in volume ratio after being cleaned by its taking-up distilled water is afterwards preserve in the aqueous hydrogen peroxide solution of 2%.
Embodiment 4
Pour in beaker by 630g dimethyl sulfoxide solvent, join in dimethyl sulfoxide solvent, magnetic agitation by 70g ethylenediamine tetramethylene phosphonic acid, make it fully dissolve and mix, it is 75 DEG C that solution temperature controls; After ethylenediamine tetramethylene phosphonic acid dissolves mixing completely, solution temperature is slowly elevated to 125 DEG C with the heating rate of 5 DEG C/min, and 20g butyl titanate is joined in above-mentioned solution, magnetic agitation, makes ethylenediamine tetramethylene phosphonic acid and butyl titanate fully react; After reaction 1h, solution temperature is down to 75 DEG C by 125 DEG C, then joins in above-mentioned solution by 90g Kynoar, 15g polyvinylpyrrolidone successively, solution temperature controls at 75 DEG C all the time, magnetic agitation 6h, makes each components dissolved of solution and fully blended; Then mixed solution is placed in 60 DEG C of water-bath deaeration 3.5h, namely obtains blended casting liquid.Blended casting liquid is poured on smooth glass by medical scraper masking, then the liquid film that medical scraper is made is carried out drying and processing together with glass plate as in baking oven, oven temperature is 75 DEG C, drying time is 4.5h, again the liquid film after heat treatment is placed in the bath of the running water condensation after microfiltration membranes process and carries out gelation process, condensation bath water temperature is 48 DEG C, until above-mentioned film after glass plate departs from, first it is used distilled water immersion 48h, then being immersed in concentration is 24h in the hydrochloric acid solution of 0.4mol/L, being immersed in volume ratio after being cleaned by its taking-up distilled water is afterwards preserve in the aqueous hydrogen peroxide solution of 1.5%.
Claims (1)
1. a preparation method for butyl titanate-ethylenediamine tetramethylene phosphonic acid/polyvinylidene fluoride flat chelating membrane, is characterized in that:
(1) preparation of blended casting liquid:
1. raw materials used:
Primary raw material comprises: ethylenediamine tetramethylene phosphonic acid, butyl titanate, Kynoar, polyvinylpyrrolidone and dimethyl sulfoxide (DMSO), and their consumption has following mass ratio relation:
Ethylenediamine tetramethylene phosphonic acid: butyl titanate: Kynoar: polyvinylpyrrolidone: dimethyl sulfoxide (DMSO)=5 ~ 7:1 ~ 2:7 ~ 9:1 ~ 1.5:60 ~ 63;
2. preparation method:
The addition sequence of a, above-mentioned various raw material is: first add dimethyl sulfoxide (DMSO), ethylenediamine tetramethylene phosphonic acid, then add butyl titanate, finally add Kynoar, polyvinylpyrrolidone successively;
The preparation of b, blended casting liquid is carried out in atmosphere, first dimethyl sulfoxide solvent is poured in container, then ethylenediamine tetramethylene phosphonic acid is joined in dimethyl sulfoxide solvent, magnetic agitation, make it fully dissolve and mix, it is 70 DEG C ~ 80 DEG C that solution temperature controls; After ethylenediamine tetramethylene phosphonic acid dissolves mixing completely, solution temperature is slowly elevated to 120 DEG C ~ 130 DEG C with the heating rate of 5 DEG C/min, and butyl titanate is joined in above-mentioned solution, magnetic agitation, ethylenediamine tetramethylene phosphonic acid and butyl titanate are fully reacted; After reaction 1h, solution temperature is down to 70 DEG C ~ 80 DEG C by 120 DEG C ~ 130 DEG C, then joins in above-mentioned solution by Kynoar, polyvinylpyrrolidone successively, the final solution temperature that controls is at 70 DEG C ~ 80 DEG C, magnetic agitation 6h, makes each components dissolved of solution and fully blended; Mixed solution is placed in water-bath deaeration 3 ~ 5h after 6h, bath temperature is 50 DEG C ~ 60 DEG C, obtains blended casting liquid;
(2) preparation of dull and stereotyped chelating membrane:
1. blended casting liquid prepared by above-mentioned steps (1) is poured on smooth glass, makes the uniform liquid film of thickness with medical scraper;
2. the liquid film made by medical scraper is placed in baking oven together with glass plate and carries out drying and processing, and oven temperature is 70 DEG C ~ 80 DEG C, and drying time is 4 ~ 6h;
3. the film after above-mentioned oven dry is placed in the bath of the running water condensation after microfiltration membranes process and carries out gelation process, condensation bath water temperature is 40 DEG C ~ 50 DEG C;
4. until above-mentioned film from glass plate depart from after, first it is used distilled water immersion 48h, then being immersed in concentration is 24h in the hydrochloric acid solution of 0.1 ~ 0.5mol/L, and being immersed in volume ratio after being cleaned by its taking-up distilled water is afterwards preserve in the aqueous hydrogen peroxide solution of 0.5 ~ 2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310643072.3A CN103611434B (en) | 2013-12-03 | 2013-12-03 | Preparation method of tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310643072.3A CN103611434B (en) | 2013-12-03 | 2013-12-03 | Preparation method of tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103611434A CN103611434A (en) | 2014-03-05 |
| CN103611434B true CN103611434B (en) | 2015-04-08 |
Family
ID=50162166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310643072.3A Expired - Fee Related CN103611434B (en) | 2013-12-03 | 2013-12-03 | Preparation method of tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103611434B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801210B (en) * | 2015-04-03 | 2017-01-25 | 燕山大学 | Preparation method of ethylenediamine tetramethylenephosphonic acid modified polyvinylidene fluoride separating membrane |
| CN104772050B (en) * | 2015-04-03 | 2016-10-12 | 燕山大学 | Ethylenediamine tetramethylene phosphonic acid and the preparation method of diethylene triamine pentacetic acid modified polyvinylidene fluoride chelating membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5087372A (en) * | 1989-03-24 | 1992-02-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for removing heavy metal ions from contaminated water and a porous membrane usable therefor |
| CN101961605A (en) * | 2010-09-02 | 2011-02-02 | 燕山大学 | Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin |
| CN102527246A (en) * | 2011-12-06 | 2012-07-04 | 燕山大学 | Method for preparing 3-aminopropyl-trimethoxy-silane-diethylenetriamine-pentaacetic-acid/polyvinylidene-fluoride chelation film |
-
2013
- 2013-12-03 CN CN201310643072.3A patent/CN103611434B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5087372A (en) * | 1989-03-24 | 1992-02-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for removing heavy metal ions from contaminated water and a porous membrane usable therefor |
| CN101961605A (en) * | 2010-09-02 | 2011-02-02 | 燕山大学 | Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin |
| CN102527246A (en) * | 2011-12-06 | 2012-07-04 | 燕山大学 | Method for preparing 3-aminopropyl-trimethoxy-silane-diethylenetriamine-pentaacetic-acid/polyvinylidene-fluoride chelation film |
Non-Patent Citations (3)
| Title |
|---|
| DTPA 改性聚偏氟乙烯膜的制备与表征;宋来洲等;《高分子材料科学与工程》;20110228;第27卷(第2期);第166-170 * |
| Hierarchically meso-/macroporous titanium tetraphosphonate materials: Synthesis,photocatalytic activity and heavy metal ion adsorption;Tian-Yi Ma等;《Microporous and Mesoporous Materials》;20090409;第123卷;第234-242页 * |
| 朱传方等.含磷的金属鳌合剂N,N,N,N,-烃基二氨基四亚甲基膦酸的合成研究(III).《化学试剂》.1995,第17卷(第2期),第109-110页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103611434A (en) | 2014-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Arthanareeswaran et al. | Effect of solvents on performance of polyethersulfone ultrafiltration membranes: Investigation of metal ion separations | |
| CN102764596B (en) | Preparation method of hydrophilic ultra-filtration membrane | |
| CN109621739B (en) | Hydrophilic modification method for high-flux PVDF porous membrane | |
| CN104001436B (en) | A kind of preparation method of amino modified graphene oxide graft modification ultrafiltration micro-filtration film | |
| CN111450715B (en) | Loose nanofiltration membrane and preparation method and application thereof | |
| CN102614788A (en) | Preparation method for polyether sulfone/graphene oxide composite ultrafiltration membrane | |
| CN102068925B (en) | Preparation method of polyaniline nano composite film | |
| CN105032220B (en) | Preparation method of permanent hydrophilic type polysulfone ultrafiltration membrane | |
| CN110339733B (en) | Graphene oxide/polyaniline composite membrane and application thereof | |
| CN102527246B (en) | Method for preparing 3-aminopropyl-trimethoxy-silane-diethylenetriamine-pentaacetic-acid/polyvinylidene-fluoride chelation film | |
| JP6697205B2 (en) | Chelate microfiltration membrane manufacturing method, recycling method and application | |
| CN102389722B (en) | Method for preparing nano composite ultrafiltration membrane by using polyaniline nano material | |
| CN105435653A (en) | Composite nano filtration membrane with high selectivity on removing divalent ions and preparation method thereof | |
| Cui et al. | Preparation of pervaporation membranes by interfacial polymerization for acid wastewater purification | |
| CN110479109B (en) | Preparation method of polyvinylidene fluoride mixed matrix membrane with high flux and strong pollution resistance | |
| CN103394295A (en) | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof | |
| CN104772050B (en) | Ethylenediamine tetramethylene phosphonic acid and the preparation method of diethylene triamine pentacetic acid modified polyvinylidene fluoride chelating membrane | |
| CN107376673A (en) | One kind is loaded with TiO2PES milipore filters of nanotube and its preparation method and application | |
| CN103611434B (en) | Preparation method of tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film | |
| Gao et al. | Bimetallic polyphenol networks structure modified polyethersulfone membrane with hydrophilic and anti-fouling properties based on reverse thermally induced phase separation method | |
| CN110038536B (en) | Preparation method of chemical grafting modified polyvinylidene fluoride separation membrane | |
| CN106823824A (en) | Carry the preparation method of the polyether sulfone functional membrane of polyamino phosphonic acid functional groups | |
| CN109012214A (en) | A method of high-permeability ultrafiltration membrane is prepared based on chemical pore-forming | |
| CN104028122B (en) | The preparation method of GMA-TEPA/Kynoar anion-exchange membrane | |
| CN103599706B (en) | Preparation method of 3-aminopropyltrimethoxysilane-ethylenediamine tetramethylenephosphonic acid/polyvinylidene fluoride chelating membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150408 Termination date: 20171203 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |