CN101961605B - Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin - Google Patents
Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin Download PDFInfo
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Abstract
The invention provides a preparation process for a diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and a resin with solvents of diethylene triaminepentaacetic acid dianhydride, sodium hydroxide, sodium borohydride, tetrabutyl ammonium bromide, p-toluenesulfonic acid, N,N-dimethylacetylamide, polyvinylpyrrolidone and the like as raw materials by utilizing a chemical blending/phase transfer process, which has the advantages of simple operation, uniform blending and the like. In the process, diethylene triaminepentaacetic acid multi-aminopolycarboxylic acid compounds are uniformly blended in the polyvinylidene fluoride separation membrane and the resin; the hydrophilic performance of the polyvinylidene fluoride separation membrane and the resin is improved; the elimination of complexing state heavy metal ions from waste water can be realized by utilizing the polyvinylidene fluoride separation membrane and the resin; the efficiency for purifying drinking water by utilizing the polyvinylidene fluoride separation membrane and the resin is enhanced; the elimination and the recycling utilization of the complexing state heavy metal ions in industrial waste water can be promoted; and the application of the polyvinylidene fluoride separation membrane and the resin in the field of water processing is expanded.
Description
Technical field
The present invention relates to the improved properties of Kynoar macromolecular material; Particularly relate to a kind of employing diethylene triamine pentacetic acid (DTPA) dianhydride, NaOH, sodium borohydride, TBAB, p-methyl benzenesulfonic acid, N; Reagent such as N-dimethylacetylamide are raw material; Applied chemistry blend/phase transfer of technology, the preparation technology that polyvinylidene fluoride separation membrane and resin are carried out modification.
Background technology
The polyvinylidene fluoride separation membrane technology has normal-temperature operation, do not have phase-state change, obvious energy-saving effect is arranged, and filtering accuracy is high, and production is polluted little, the advantage that water yield is big, matter is good.Through the screening and the crown_interception of film, suspended particulate in the water body and colloidal state pollutant there is good removal effect.Polyvinylidene fluoride separation membrane anti-pollution, anti-chemical oxidation function admirable can effectively be removed suspended particulate and colloid pollution thing in the water body, but conventional polyvinylidene fluoride separation membrane can not be realized the removal to water-soluble heavy metal ion.For effectively realizing that polyvinylidene fluoride separation membrane and resin to the removal of free state in the water body and organic complex attitude heavy metal contaminants, tackle it and carry out modification, will have in the functional group introducing diffusion barrier and resin of chelating coordination.
In the heavy metal pollution treatment process, there is the high and secondary pollution important disadvantages of processing cost in widely used chemical precipitation disposal technology.Absorption method comprises ion-exchange and absorption, is the control measures of heavy metal pollution in a kind of potential solution water body with application prospect, but conventional sorbing material such as active carbon, flyash etc. have the shortcoming that adsorption capacity is low, the rate of adsorption is slow.Thereby research and development and application has even aperture distribution, specific area is big, adsorption capacity is high, the rate of adsorption is fast, and the stable novel absorption material of physical and chemical performance is the important behave that solves heavy metal pollution of water body.Polyvinylidene fluoride separation membrane and resin have antipollution, chemically-resistant oxidation, to the stable advantage of microbial action, and mechanical performance is good, physical and chemical performance is stable.But conventional polyvinylidene fluoride separation membrane and resin can not be realized the removal to water-soluble heavy metal contaminants in the water body.
The diffusion barrier of function admirable and the research and development of novel absorption material are the emphasis of polymeric material field research always, just are being devoted to the research and development of novel diffusion barrier and sorbing material both at home and abroad.For heavy metal pollution improvement, wastewater treatment and reuse field, good, the anti-chemical agent oxidation of the diffusion barrier of Kynoar material and resin anti-fouling performance causes people's attention day by day.At present, the emphasis of tackling key problems for polyvinylidene fluoride material is surface graft modification research, the particularly improvement of polyvinylidene fluoride separation membrane and resin hydrophilicity.Improving the hydrophilicity of polyvinylidene fluoride separation membrane and resin, improve the handling property of diffusion barrier and resin, will be the difficult point and the emphasis of each developer and institute tackling key problem.Reagent such as many scholar's using polythene alcohol, acrylic acid, acrylamide and polyacrylic acid; Adopt technology such as radiation-induced, plasma-induced, ozone oxidation; Carried out the research of polyvinylidene fluoride separation membrane and resin surface hydrophilic modifying; At the hydroxy-acid group and the oh group of its surface grafting possess hydrophilic property ability, effectively improved the water-wet behavior of polyvinylidene fluoride separation membrane and resin, realized the absorption of free state heavy metal contaminants is removed.But surface graft modification can produce harmful effect to the physical property of diffusion barrier and resin; As change the microcellular structure and the pore-size distribution of diffusion barrier and resin surface; The hydrophilic radical of grafting can come off, and the polyvinylidene fluoride separation membrane of grafted propylene acid polymer and functional group of sulfonic acid and resin are low to complex state removal of heavy metal ions efficient in the water body.In addition; Adopt diethylene triamine pentacetic acid (DTPA) and melamine that polyvinylidene fluoride separation membrane and resin are carried out modification; Can realize with the polyamino polycarboxylic acid functional group blend of chelating coordination and be grafted to polyvinylidene fluoride separation membrane and resin in; But reaction often needs the high temperature more than 160 ℃, and reaction condition control requires very strict.The existence of these problems will influence the performance of polyvinylidene fluoride separation membrane and resin, finally limit the application in water treatment field of polyvinylidene fluoride separation membrane and resin.
Summary of the invention
In order to overcome the above-mentioned deficiency that prior art exists; The present invention provides the preparation technology of a kind of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and resin; Through chemical blend/phase transfer of technology, even doping diethylene triamine pentacetic acid (DTPA) polyamino multi-carboxylic acid compounds in polyvinylidene fluoride separation membrane and resin, make in polyvinylidene fluoride separation membrane and the resin even blend possess hydrophilic property can with the polyamino polycarboxylic acid functional group of chelating coordination property; Improved the hydrophilicity of diffusion barrier and resin; Realize the removal of free state and complex state heavy metal ion in the water body, further improved drinking water quality, removed and reclaimed the heavy metal ion in the industrial wastewater; Efficiently solve the heavy metal pollution of water environment, advanced the recycling of heavy metal contaminants.
The preparation technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and resin is:
1) the Kynoar preparation of used chemical liquids of alkalizing:
150～180g NaOH and 3～7g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
2) basification of Kynoar:
A. after treating that each component is all dissolved in the chemical alkaline solution; Its temperature slowly being raise, treat that temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins in the chemical alkaline solution with average grain diameter; Keeping solution temperature is 75～85 ℃, and the basification time is 8h;
B. alkalize behind the 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
3) adopting chemical blend/phase transfer of technology to prepare the blend casting liquid that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane adopted consists of:
A. diethylene triamine pentacetic acid (DTPA) dianhydride 120～200g/L, sodium borohydride 4～7g/L, the Kynoar 120～150g/L of basification, p-methyl benzenesulfonic acid 1～3g/L, polyvinylpyrrolidone 30～50g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the addition sequence of each reagent is: at first adding sodium borohydride, is the Kynoar of basification then, secondly is p-methyl benzenesulfonic acid, is diethylene triamine pentacetic acid (DTPA) dianhydride and polyvinylpyrrolidone at last successively;
4) adopt chemical blend/phase transfer of technology to prepare the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane:
A. adopt chemical blend/phase transfer of technology to prepare diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane, in three-neck flask, sodium borohydride is joined N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃; When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h; Behind the insulation 3h, will cast liquid temp and reduce to 40～50 ℃, and successively p-methyl benzenesulfonic acid and diethylene triamine pentacetic acid (DTPA) dianhydride joined in the above-mentioned casting liquid, stirring reaction 2h begins to join the whole process of stirring reaction 2h from p-methyl benzenesulfonic acid and need lead to nitrogen protection; After leading to nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation makes each components dissolved and abundant blend 6h in the casting liquid; Behind the stirring 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
B. diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride flat sheet membrane is at the medical scraper system film of smooth usefulness on glass; Film forming in water condensation is bathed then; Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride hollow-fibre membrane is to draw with spinning-drawing machine; Core liquid is 5% ethanol water, and flow velocity is 1.2～1.8ml/min; Casting liquid rate of extrusion is 1.3～1.5ml/min, and the filament length that per minute makes is 35 meters, and condensation is bathed and is deionized water, and its electrical conductivity is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃;
C. diethylene triamine pentacetic acid (DTPA) two anhydride modification vinylidene hollow-fibre membranes and flat sheet membrane are at first soaked 48h with deionized water; Be immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution;
5) adopting chemical blend/phase transfer of technology to prepare the blend casting liquid that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin adopted consists of:
A. diethylene triamine pentacetic acid (DTPA) dianhydride 150～230g/L, sodium borohydride 4～7g/L, the Kynoar 100～130g/L of basification, p-methyl benzenesulfonic acid 1～3g/L, polyvinylpyrrolidone 30～50g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the addition sequence of each reagent is: at first adding sodium borohydride, is the Kynoar of basification then, secondly is p-methyl benzenesulfonic acid, is diethylene triamine pentacetic acid (DTPA) dianhydride and polyvinylpyrrolidone at last successively;
6) adopt chemical blend/phase transfer of technology to prepare the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin:
A. adopt chemical blend/phase transfer of technology to prepare diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin, in three-neck flask, sodium borohydride is joined N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃; When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h; Behind the insulation 3h, will cast liquid temp and reduce to 40～50 ℃, and successively p-methyl benzenesulfonic acid and diethylene triamine pentacetic acid (DTPA) dianhydride joined in the above-mentioned casting liquid, stirring reaction 2h begins to join the whole process of stirring reaction 2h from p-methyl benzenesulfonic acid and need lead to nitrogen protection; After leading to nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation makes each components dissolved and abundant blend 6h in the casting liquid; Behind the stirring 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
B. the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin is: dropwise join in the deionized water with dropper the casting liquid after the deaeration of " a " step; And slowly stir; The deionization electrical conductivity of water is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃; Last casting liquid such as casting drop acceleration can not be too fast, and is necessary get in the deionized water, and could drip next drips casting liquid, and the granularity of resin microsphere is 1.2～1.7mm, and the average pore size of resin surface micropore is 0.18 μ m;
C. diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin at first soaks 48h with deionized water, is immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, and taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
The present invention is to adopting diethylene triamine pentacetic acid (DTPA) dianhydride, NaOH, sodium borohydride, TBAB, p-methyl benzenesulfonic acid, N; Reagent such as N-dimethylacetylamide are raw material; Applied chemistry blend/phase transfer of technology, it is suitable equally to carry out polysulfones diffusion barrier, polyethersulfone separating membrane, the modification of polyacrylonitrile diffusion barrier.
The invention has the beneficial effects as follows: this in Kynoar in diffusion barrier and the resin evenly the doping possess hydrophilic property can and chemical graft blend/phase transfer of technology of the polyamino multi-carboxylic acid compounds of chelating coordination property; Have advantages such as simple to operate, that blend is even; Improved the hydrophilicity of conventional polyvinylidene fluoride separation membrane and resin, realized its removal heavy metal contaminants in the water body.This invention has realized the removal to complex state heavy metal ion in the water body of polyvinylidene fluoride separation membrane and resin; Improved microfiltering separation film of polyvinylidene fluoride and resin efficient to drink water purifying; Realize the removal and the recycling of heavy metal contaminants in the industrial wastewater, expanded the application in water treatment field of polyvinylidene fluoride separation membrane and resin.
The specific embodiment
Following mask body combines embodiment, specifies the preparation technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and resin.
Embodiment
1, chemical blend/phase transfer of technology prepares the technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane
1) the Kynoar preparation of used chemical liquids of alkalizing:
170g NaOH and 5g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
2) Kynoar basification:
After treating that each component is all dissolved in the chemical alkaline solution, its temperature is slowly raise;
Treating that the alkaline solution temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins and carries out basification in the chemical alkaline solution with average grain diameter, and keeping solution temperature is 75～85 ℃, and the basification time is 8h;
Behind the basification 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
3) adopt chemical blend/phase transfer of technology to prepare the blend casting liquid preparation that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane is adopted:
In three-neck flask, the 0.5g sodium borohydride is joined 100g N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃;
When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the 13g basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h;
Behind the insulation 3h; To cast liquid temp and reduce to 40～50 ℃; Successively 0.2g p-methyl benzenesulfonic acid and 150g diethylene triamine pentacetic acid (DTPA) dianhydride are joined in the above-mentioned casting liquid, stirring reaction 2h, the whole process that begins to join stirring reaction 2h from p-methyl benzenesulfonic acid need be led to nitrogen protection;
Behind the logical nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation 6h makes each components dissolved and fully blend in the casting liquid;
Behind the 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
4) preparation of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane:
Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride flat sheet membrane is at the medical scraper system film of smooth usefulness on glass, then film forming in water condensation is bathed; The modified hollow tunica fibrosa is to draw with spinning-drawing machine, and core liquid is 5% ethanol water, and flow velocity is 1.2～1.8mL/min; Casting liquid rate of extrusion is 1.3～1.5mL/min, and the filament length that per minute makes is 35 meters, and condensation is bathed and is deionized water, and its electrical conductivity is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃;
5) processing of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and preservation:
Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride hollow-fibre membrane, flat sheet membrane; At first soak 48h with deionized water; Be immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
2, chemical blend/phase transfer of technology prepares the technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin
(1) the Kynoar preparation of used chemical liquids of alkalizing:
170g NaOH and 5g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
(2) Kynoar basification:
After treating that each component is all dissolved in the chemical alkaline solution, its temperature is slowly raise;
Treating that the alkaline solution temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins and carries out basification in the chemical alkaline solution with average grain diameter, and keeping solution temperature is 75～85 ℃, and the basification time is 8h;
Behind the basification 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
(3) adopt chemical blend/phase transfer of technology to prepare the blend casting liquid preparation that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin is adopted:
In three-neck flask, the 0.5g sodium borohydride is joined 100g N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃;
When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the 11g basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h begins to heat the whole process with insulation reaction 3h from solvent and will adopt condensing reflux;
Behind the insulation 3h; To cast liquid temp and reduce to 40～50 ℃; Successively 0.2g p-methyl benzenesulfonic acid and 180g diethylene triamine pentacetic acid (DTPA) dianhydride are joined in the above-mentioned casting liquid, stirring reaction 2h, the whole process that begins to join stirring reaction 2h from p-methyl benzenesulfonic acid need be led to nitrogen protection;
Behind the logical nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation 6h makes each components dissolved and fully blend in the casting liquid;
Behind the 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
(4) preparation of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin:
Casting liquid after the deaeration is dropwise joined in the deionized water with dropper, and slowly stir, the deionization electrical conductivity of water is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃;
Last casting liquid such as casting drop acceleration can not be too fast, and is necessary get in the deionized water, and could drip next drips casting liquid, and the granularity of mixed microsphere is 1.2～1.7mm, and the average pore size of resin surface micropore is 0.18 μ m;
(5) processing and the preservation of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin:
Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin at first soaks 48h with deionized water, is immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, and taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
Claims (2)
1. the preparation technology of a diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane makes blend in the polyvinylidene fluoride separation membrane that the polyamino polycarboxylic acid functional group of chelating coordination arranged, and it is characterized in that: this preparation technology may further comprise the steps:
1) the Kynoar preparation of used chemical alkaline solution of alkalizing:
150～180g NaOH and 3～7g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
2) basification of Kynoar:
A. after treating that each component is all dissolved in the chemical alkaline solution; Its temperature slowly being raise, treat that temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins in the chemical alkaline solution with average grain diameter; Keeping solution temperature is 75～85 ℃, and the basification time is 8h;
B. alkalize behind the 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
3) adopting chemical blend/phase transfer of technology to prepare the blend casting liquid that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane adopted consists of:
A. diethylene triamine pentacetic acid (DTPA) dianhydride 120～200g/L, sodium borohydride 4～7g/L, the Kynoar 120～150g/L of basification, p-methyl benzenesulfonic acid 1～3g/L, polyvinylpyrrolidone 30～50g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the addition sequence of each reagent is: at first adding sodium borohydride, is the Kynoar of basification then, secondly is p-methyl benzenesulfonic acid, is diethylene triamine pentacetic acid (DTPA) dianhydride and polyvinylpyrrolidone at last successively;
4) adopt chemical blend/phase transfer of technology to prepare the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane:
A. adopt chemical blend/phase transfer of technology to prepare diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane, in three-neck flask, sodium borohydride is joined N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃; When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the basification is joined in the solvent, keeping blend casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h; Behind the insulation 3h; Liquid temp is cast in blend reduced to 40～50 ℃; Successively p-methyl benzenesulfonic acid and diethylene triamine pentacetic acid (DTPA) dianhydride are joined in the above-mentioned blend casting liquid, stirring reaction 2h begins to join the whole process of stirring reaction 2h from p-methyl benzenesulfonic acid and need lead to nitrogen protection; After leading to nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation makes each components dissolved and abundant blend 6h in the blend casting liquid; Behind the stirring 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
B. diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride flat sheet membrane is at the medical scraper system film of smooth usefulness on glass; Film forming in water condensation is bathed then; Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride hollow-fibre membrane is to draw with spinning-drawing machine; Core liquid is 5% ethanol water, and flow velocity is 1.2～1.8mL/min; Blend casting liquid rate of extrusion is 1.3～1.5mL/min, and the filament length that per minute makes is 35 meters, and condensation is bathed and is deionized water, and its electrical conductivity is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃;
C. diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride hollow-fibre membrane and flat sheet membrane are at first soaked 48h with deionized water; Be immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution;
2. the preparation technology of a diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin makes blend in the polyvinylidene fluoride resin that the polyamino polycarboxylic acid functional group of chelating coordination arranged, and it is characterized in that: this preparation technology may further comprise the steps:
1) the Kynoar preparation of used chemical alkaline solution of alkalizing:
150～180g NaOH and 3～7g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
2) basification of Kynoar:
A. after treating that each component is all dissolved in the chemical alkaline solution; Its temperature slowly being raise, treat that temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins in the chemical alkaline solution with average grain diameter; Keeping solution temperature is 75～85 ℃, and the basification time is 8h;
B. alkalize behind the 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
3) adopting chemical blend/phase transfer of technology to prepare the blend casting liquid that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin adopted consists of:
A. diethylene triamine pentacetic acid (DTPA) dianhydride 150～230g/L, sodium borohydride 4～7g/L, the Kynoar 100～130g/L of basification, p-methyl benzenesulfonic acid 1～3g/L, polyvinylpyrrolidone 30～50g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the addition sequence of each reagent is: at first adding sodium borohydride, is the Kynoar of basification then, secondly is p-methyl benzenesulfonic acid, is diethylene triamine pentacetic acid (DTPA) dianhydride and polyvinylpyrrolidone at last successively;
4) adopt chemical blend/phase transfer of technology to prepare the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin:
A. adopt chemical blend/phase transfer of technology to prepare diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin, in three-neck flask, sodium borohydride is joined N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃; When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the basification is joined in the solvent, keeping blend casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h; Behind the insulation 3h; Liquid temp is cast in blend reduced to 40～50 ℃; Successively p-methyl benzenesulfonic acid and diethylene triamine pentacetic acid (DTPA) dianhydride are joined in the above-mentioned blend casting liquid, stirring reaction 2h begins to join the whole process of stirring reaction 2h from p-methyl benzenesulfonic acid and need lead to nitrogen protection; After leading to nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation makes each components dissolved and abundant blend 6h in the blend casting liquid; Behind the stirring 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
B. the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin is: dropwise join in the deionized water with dropper the casting of the blend after the deaeration of " a " step liquid; And slowly stir; The deionization electrical conductivity of water is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃; Last blend casting liquid such as blend casting drop acceleration can not be too fast, and is necessary get in the deionized water, and could drip next drips blend casting liquid, and the granularity of resin microsphere is 1.2～1.7mm, and the average pore size of resin surface micropore is 0.18 μ m;
C. diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin at first soaks 48h with deionized water, is immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, and taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
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