CN101003004A - Process for preparing polyacrylic acid-Kynoar polyblend separation film and polyblend resin - Google Patents
Process for preparing polyacrylic acid-Kynoar polyblend separation film and polyblend resin Download PDFInfo
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- CN101003004A CN101003004A CN 200610102284 CN200610102284A CN101003004A CN 101003004 A CN101003004 A CN 101003004A CN 200610102284 CN200610102284 CN 200610102284 CN 200610102284 A CN200610102284 A CN 200610102284A CN 101003004 A CN101003004 A CN 101003004A
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Abstract
A process for preparing polyacrylic acid-polyvinylidene fluoride mixed separating membrane and mixed resin features that the polyvinylidene fluoride, acrylic acid, N, N-dimethyl acetylamine, polyethanediol, polyvinyl pyrrolidone, acrylamide, and p-phenyldimethylacyl are used as raw materials and the acrylic acid polymer is uniformed doped in said separating film and resin to improve their hydrophilicity.
Description
Technical field
The present invention relates to a kind of improved properties of macromolecular material, particularly relate to the preparation technology of a kind of poly acrylic acid-poly vinylidene blending isolation film and blending resin.
Background technology
Polyvinylidene fluoride separation membrane technology normal-temperature operation, do not have phase-state change, obvious energy-saving effect arranged, have the filtering accuracy height, produce pollute little, the advantage that water yield is big, matter is good.By screening, 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 remove suspended particulate and colloid pollution thing in the water body, become one of macromolecular material research and development emphasis, but conventional polyvinylidene fluoride separation membrane can not be realized the removal to water-soluble heavy metal ion.The processing procedure of conventional drinking water be former water through chemical coagulation, precipitation and filter, last chlorination, a part of so tiny flco, colloid pollution thing and part heavy metal ion still remain in the water body.Long-term drinking, these residual pollutants can cause the grievous injury to health.Poly acrylic acid-poly vinylidene blending isolation film can not only effectively be removed tiny flco residual in the drinking water and colloid pollution thing, and has realized the absorption of heavy metal ion is removed, and has improved drinking water quality.On the other hand, the processing of sewage should not rest on the qualified discharge, and answers regeneration after the advanced treating.Poly acrylic acid-poly vinylidene blending isolation film has been cut down the suspended material in the sewage, colloid pollution thing, and the COD of suspension, BOD
5Deng, and realized removal to residual heavy metal ion in the water body further having improved quality of reused water, expanded the application of recycle-water.Diffusion barrier sewage disposal and reuse big carrying out of advancing China's sewage recycling work to the utmost alleviated the shortage of water resource, guaranteed sustainable water supply, ensured social sustainable development.
In the heavy metal pollution treatment process, absorption method comprises ion-exchange and absorption, be 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 channel that solves heavy metal pollution of water body.Polyvinylidene fluoride resin has 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 resin can not be realized the removal to water-soluble heavy metal contaminants in the water body, utilize solution heat-induced aggregation and phase transfer blending technology, evenly be blended into acrylate copolymer in the polyvinylidene fluoride resin, realized that polyvinylidene fluoride resin removes the absorption of water-soluble heavy metal ion, this recycling to the control of heavy metal pollution in the water body and heavy metal is significant.
In the municipal sewage treatment process, 66%～84% heavy metal ion is moved in the mud by the microbial action in the activated sludge in the sewage.Like this,, caused content of beary metal severe overweight in the mud, thereby brought difficulty for the disposal of mud though concentration of heavy metal ion is on the low side in the water outlet.Poly acrylic acid-poly vinylidene blend film and blending resin are in the process of sewage disposal, realization is to removal, the elimination of heavy metal ion or effectively suppress the migration of heavy metal ion in mud and transform, when realizing that wastewater efficient is handled, will lay a solid foundation for the disposal and the utilization of mud.In the municipal sewage treatment process, mud is handled be used for agricultural production effectively, will be for boosting agricultural yield and promoting the rural economy prosperity to establish solid material base.Thereby the mud that effectively utilizes the municipal sewage plant is the inevitable requirement of each Regional Economic Sustainable Development, also is the objective requirement of social economy capable of circulation.
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 drink water purifying, 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 hydrophilicity.Improving the hydrophilicity of polyvinylidene fluoride separation membrane, improve the handling property of diffusion barrier, 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 surface hydrophilic modification, at the hydroxy-acid group and the oh group of its surface grafting possess hydrophilic property energy, effectively improved the water-wet behavior of polyvinylidene fluoride separation membrane.But surface graft modification can produce harmful effect to the physical property of diffusion barrier, as change the microcellular structure and the pore-size distribution of separation membrane surface, under some situation, the hydrophilic radical of grafting can come off etc., the existence of these problems will influence the performance of polyvinylidene fluoride separation membrane, finally limit the application of polyvinylidene fluoride separation membrane in each field.
Summary of the invention
In order to overcome the prior art above shortcomings, the invention provides the preparation technology of a kind of poly acrylic acid-poly vinylidene blending isolation film and blending resin, by solution heat-induced aggregation and phase transfer blending technology, even doping acrylate copolymer in polyvinylidene fluoride separation membrane and resin, make in polyvinylidene fluoride separation membrane and the resin evenly the blend possess hydrophilic property can with the carboxylic acid group functional group of ion-exchange performance, improve the hydrophilicity of diffusion barrier, realization is removed the absorption of heavy metal ion in the water body, suppresses and slows down in the conventional sewage biological treatment system heavy metal to the migration and the conversion of mud.
The preparation technology of poly acrylic acid-poly vinylidene blending isolation film and blending resin is:
1) the blend casting liquid that is adopted consists of:
A. acrylic acid 50～80ml/L, acrylamide 15～25g/L, paraphenylene terephthalamide 10～15g/L, polyvinylpyrrolidone 30～50g/L; Polyethylene glycol 5～20g/L, Kynoar 100～130g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the preparation of chemistry casting liquid can be carried out in air, also can carry out under the protection of inert nitrogen gas;
D. the addition sequence of each reagent is: at first being Kynoar, polyvinylpyrrolidone, polyethylene glycol, is acrylic acid, acrylamide then, is the paraphenylene terephthalamide at last;
2) preparation of poly acrylic acid-poly vinylidene blending isolation film and blending resin
A. solution heat-induced aggregation and phase transfer blending technology are adopted in the preparation of poly acrylic acid-poly vinylidene blending isolation film and blending resin.Control blend casting liquid temp is in 50 ℃～60 ℃, and Kynoar, polyvinylpyrrolidone, polyethylene glycol are fully dissolved, and adds acrylic acid, acrylamide again, makes its dissolving, adds the paraphenylene terephthalamide at last.Wait to cast after each component is fully dissolved in the liquid, the casting liquid temp that slowly raises, the control temperature is cast liquid with blend behind the 2h and is placed water-bath deaeration 3～5h at 70 ℃～80 ℃, and bath temperature is 40 ℃～50 ℃;
B. dull and stereotyped blend film is at the medical scraper system film of smooth usefulness on glass, then film forming in water condensation is bathed;
The doughnut blend film 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 the running water after handling through micro-filtration membrane, and water temperature is 35 ℃～45 ℃;
The preparation process of poly acrylic acid-poly vinylidene blending resin is: dropwise join in deionized water with dropper the casting liquid after the deaeration of (a) step, and slowly stir, casting drop acceleration can not be too fast, must etc. last one the casting liquid enter in the deionized water, could drip next and drip casting liquid, the granularity of mixed microsphere is 1.5～2mm, and average pore size is 0.23 μ m;
C. poly acrylic acid-poly vinylidene doughnut blend film, dull and stereotyped blend film and poly acrylic acid-poly vinylidene blending resin at first soak 48h with deionized water, be immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, take out to be immersed in the aqueous hydrogen peroxide solution that concentration is 0.5～2% (volume ratio) after cleaning and preserve.
The present invention is suitable equally to polysulfones diffusion barrier, polyethersulfone separating membrane, polyacrylonitrile diffusion barrier and acrylic acid blend.
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 the solution heat-induced aggregation and the phase transfer blending technology of ion-exchange performance acrylate copolymer, have advantages such as simple to operate, that blend is even, improved the hydrophilicity of conventional polyvinylidene fluoride separation membrane.This invention has realized the removal to water-soluble heavy metal ion of polyvinylidene fluoride separation membrane and resin, improved microfiltering separation film of polyvinylidene fluoride and resin efficient to drink water purifying, suppressed in the biological treatment system heavy metal ion and expanded polyvinylidene fluoride separation membrane and resin application in the disposal and the utilization of sewage disposal, utilization and mud to the migration and the conversion of mud.
The specific embodiment
Following mask body describes poly acrylic acid-poly vinylidene blending isolation film and blending resin preparation technology in conjunction with the embodiments in detail.
Embodiment
1) preparation of blend casting liquid:
The process for preparation of 1L blend casting liquid is: with 120g Kynoar, 35g polyvinylpyrrolidone, 10g polyethylene glycol, use N, the dissolving of N-dimethylacetylamide;
After treating that solution temperature is cold slightly, add acrylic acid 60ml, acrylamide 20g, stir fully dissolving;
And then the 15g paraphenylene terephthalamide joined in the mixed liquor fully dissolving;
In the course of dissolution, control blend casting liquid temp is 50 ℃～60 ℃, wait to cast after each component is fully dissolved in the liquid, and the casting liquid temp that slowly raises, the control temperature is cast liquid with blend behind the 2h and is placed water-bath deaeration 3～5h at 70 ℃～80 ℃, and bath temperature is 40 ℃～50 ℃;
2) preparation of poly acrylic acid-poly vinylidene blending isolation film:
Dull and stereotyped blend film is at the medical scraper system film of smooth usefulness on glass, then film forming in water condensation is bathed; The doughnut blend film 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 the running water after handling through micro-filtration membrane, and water temperature is 35 ℃～45 ℃;
3) preparation of poly acrylic acid-poly vinylidene blending resin
Casting liquid after the deaeration is dropwise joined in the deionized water with dropper, and slowly stir, casting drop acceleration can not be too fast, must etc. last one the casting liquid enter in the deionized water, could drip next and drip casting liquid, the granularity of mixed microsphere is 1.5～2mm, and average pore size is 0.23 μ m.
4) processing of poly acrylic acid-poly vinylidene blending isolation film and blending resin and preservation:
Poly acrylic acid-poly vinylidene doughnut blend film, dull and stereotyped blend film, and blending resin at first soaks 48h with deionized water, be immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, take out to be immersed in the aqueous hydrogen peroxide solution that concentration is 0.5～2% (volume ratio) after cleaning and preserve.
Claims (1)
1. the preparation technology of poly acrylic acid-poly vinylidene blending isolation film and blending resin, adopt Kynoar, acrylic acid, N, the N-dimethylacetylamide, polyethylene glycol, polyvinylpyrrolidone, acrylamide, paraphenylene terephthalamide's reagent is raw material, by solution heat-induced aggregation and phase transfer blending technology, even doping acrylate copolymer in polyvinylidene fluoride separation membrane and resin, make in polyvinylidene fluoride separation membrane and the resin evenly the blend possess hydrophilic property can with the carboxylic acid group functional group of ion-exchange performance, it is characterized in that: this preparation technology may further comprise the steps:
1) the blend casting liquid that is adopted consists of:
A. acrylic acid 50～80ml/L, acrylamide 15～25g/L, paraphenylene terephthalamide 10～15g/L, polyvinylpyrrolidone 30～50g/L, polyethylene glycol 5～20g/L, Kynoar 100～130g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the preparation of chemistry casting liquid can be carried out in air, also can carry out under the protection of inert nitrogen gas;
D. the addition sequence of each reagent is: at first being Kynoar, polyvinylpyrrolidone, polyethylene glycol, is acrylic acid, acrylamide then, is the paraphenylene terephthalamide at last;
2) preparation of poly acrylic acid-poly vinylidene blending isolation film and blending resin:
A. solution heat-induced aggregation and phase transfer blending technology are adopted in the preparation of poly acrylic acid-poly vinylidene blending isolation film and blending resin, control blend casting liquid temp is in 50 ℃～60 ℃, Kynoar, polyvinylpyrrolidone, polyethylene glycol are fully dissolved, add acrylic acid, acrylamide again, make its dissolving, add the paraphenylene terephthalamide at last; Wait to cast after each component is fully dissolved in the liquid, the casting liquid temp that slowly raises, the control temperature is cast liquid with blend behind the 2h and is placed water-bath deaeration 3～5h at 70 ℃～80 ℃, and bath temperature is 40 ℃～50 ℃;
B. dull and stereotyped blend film is at the medical scraper system film of smooth usefulness on glass, then film forming in water condensation is bathed; The doughnut blend film 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, the filament length that per minute makes is 35 meters, and condensation is bathed and is the running water after handling through micro-filtration membrane, and water temperature is 35 ℃～45 ℃; The preparation process of poly acrylic acid-poly vinylidene blending resin is: dropwise join in deionized water with dropper the casting liquid after the deaeration of (a) step, and slowly stir, casting drop acceleration can not be too fast, must etc. last one the casting liquid enter in the deionized water, could drip next and drip casting liquid, the granularity of mixed microsphere is 1.5～2mm, and average pore size is 0.23 μ m;
C. poly acrylic acid-poly vinylidene doughnut blend film, dull and stereotyped blend film and blending resin 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 concentration after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101022840A CN100430117C (en) | 2006-12-18 | 2006-12-18 | Process for preparing polyacrylic acid-Kynoar polyblend separation film and polyblend resin |
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| CNB2006101022840A CN100430117C (en) | 2006-12-18 | 2006-12-18 | Process for preparing polyacrylic acid-Kynoar polyblend separation film and polyblend resin |
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| CN101003004A true CN101003004A (en) | 2007-07-25 |
| CN100430117C CN100430117C (en) | 2008-11-05 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103611436A (en) * | 2013-12-11 | 2014-03-05 | 天津工业大学 | PVDF (Polyvinylidene Fluoride)/Fe-Pd bi-metal nanoparticle hybrid membrane and preparation method thereof |
| CN103638827A (en) * | 2013-12-11 | 2014-03-19 | 天津工业大学 | Iron-heavy metal nano particle/PVDF (polyvinylidene fluoride) hybrid membrane and preparation method thereof |
| CN105032203A (en) * | 2015-07-28 | 2015-11-11 | 苏州科技学院 | Preparation method of membrane adsorbent for removing ammonia nitrogen in wastewater |
| CN110963547A (en) * | 2019-12-11 | 2020-04-07 | 天津市环境保护技术开发中心 | Preparation method of hollow fiber membrane for removing heavy metals from industrial wastewater |
| CN111135733A (en) * | 2020-01-13 | 2020-05-12 | 北京赛诺膜技术有限公司 | MOFs polymer hollow fiber composite membrane and preparation method thereof |
-
2006
- 2006-12-18 CN CNB2006101022840A patent/CN100430117C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103611436A (en) * | 2013-12-11 | 2014-03-05 | 天津工业大学 | PVDF (Polyvinylidene Fluoride)/Fe-Pd bi-metal nanoparticle hybrid membrane and preparation method thereof |
| CN103638827A (en) * | 2013-12-11 | 2014-03-19 | 天津工业大学 | Iron-heavy metal nano particle/PVDF (polyvinylidene fluoride) hybrid membrane and preparation method thereof |
| CN105032203A (en) * | 2015-07-28 | 2015-11-11 | 苏州科技学院 | Preparation method of membrane adsorbent for removing ammonia nitrogen in wastewater |
| CN105032203B (en) * | 2015-07-28 | 2017-06-16 | 苏州科技学院 | The preparation method of the membrane adsorbent of ammonia nitrogen in a kind of removal waste water |
| CN110963547A (en) * | 2019-12-11 | 2020-04-07 | 天津市环境保护技术开发中心 | Preparation method of hollow fiber membrane for removing heavy metals from industrial wastewater |
| CN111135733A (en) * | 2020-01-13 | 2020-05-12 | 北京赛诺膜技术有限公司 | MOFs polymer hollow fiber composite membrane and preparation method thereof |
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| CN100430117C (en) | 2008-11-05 |
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Granted publication date: 20081105 Termination date: 20111218 |