CN102553464A - Preparation method of modified polyvinylidene fluoride ultrafiltration membrane - Google Patents
Preparation method of modified polyvinylidene fluoride ultrafiltration membrane Download PDFInfo
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- CN102553464A CN102553464A CN2011104531561A CN201110453156A CN102553464A CN 102553464 A CN102553464 A CN 102553464A CN 2011104531561 A CN2011104531561 A CN 2011104531561A CN 201110453156 A CN201110453156 A CN 201110453156A CN 102553464 A CN102553464 A CN 102553464A
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- polyvinilidene fluoride
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Abstract
The invention discloses a preparation method of a modified polyvinylidene fluoride ultrafiltration membrane. The preparation method comprises the following steps of: firstly adding unisexual hydrophilic groups in polyvinylidene fluoride, uniformly mixing, and carrying out irradiation grafting; then dissolving a polyvinylidene fluoride membrane material in a solvent; adding an additive, and uniformly stirring; adding a pore-forming agent, uniformly stirring, and preparing and forming a casting film liquid, wherein the mass percents of the polyvinylidene fluoride membrane material, the solvent, the additive and the pore-forming agent are respectively 5-25%, 70-90%, 1-10% and 0-4%; and finally carrying out filtration and vacuum deaeration on the obtained casting film liquid, carrying out the scrape coating of the casting film liquid on a polyester non-woven fabric, placing the polyester non-woven fabric in the air for certain time, immersing the polyester non-woven fabric in gel bath, curing gel at the temperature of 0-35 DEG C, and preparing a plain filter membrane. The preparation method of the modified polyvinylidene fluoride ultrafiltration membrane disclosed by the invention has the advantages that the hydrophilism is enhanced and the pollution degree is reduced.
Description
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Technical field
The present invention relates to a kind of sewage disposal device, particularly a kind of preparation method of modified polyvinilidene fluoride milipore filter.
Background technology
Hyperfiltration technique receives extensive attention because of advantages such as its separation process does not have phase transformation, energy consumption is low and selectivity is good, non-secondary pollutions.Its core component milipore filter, the existing special engineered macromolecular materials that adopt more.This has overcome the shortcoming of early stage cellulose material, pollutes but in application, also can produce film, even has a strong impact on using for a long time and moving of milipore filter.
Kynoar (PVDF) is a kind of hydrophobic line style crystalline polymer; Have characteristics such as excellent processing characteristics, thermal stability and chemical resistance; Be a kind of separation membrane commonly used, be widely used in fields such as environmental protection, metallurgy, medicine, food processings
(1-3)The hydrophobicity of material but the problem that occurs is thereupon; Process the film surface with PVDF and also all present stronger hydrophobicity; In actual use; Be prone to produce reasons such as absorption owing to separated material at hydrophobic surface, cause film to pollute. make milipore filter itself have antifouling property, be solve that film pollutes the most effectively and one of essential method.
Summary of the invention
Goal of the invention:, the invention discloses a kind of hydrophily and strengthen, the preparation method of the modified polyvinilidene fluoride milipore filter that dustiness descends to the deficiency of prior art.
Technical scheme: the invention discloses a kind of preparation method of modified polyvinilidene fluoride milipore filter, this method comprises the steps:
(1) in Kynoar, adds the unisexuality hydrophilic radical, after mixing, carry out irradiation grafting
Under (2) 40～75 ℃, PVDF membrane material is dissolved in the solvent; Under 20～30 ℃, add additive, stir; Under 30-35 ℃, add pore-foaming agent, stir, be configured to casting solution; Wherein, the mass percent of PVDF membrane material, solvent, additive and four kinds of components of pore-foaming agent is respectively 5～25%, 70～90%, 1～10% and 0～4%;
(3) casting solution that obtains of step (2) through filter with vacuum defoamation after, with its blade coating on polyester non-woven fabric, in air, place certain hour after, in its immersion coagulation bath,, prepare the plain film filter membrane at 0～35 ℃ of following gel solidification.
Wherein, the Kynoar molecular weight is 20～600,000.
Wherein, the solvent described in the step (2) is dimethyl sulfoxide (DMSO), oxolane, N, dinethylformamide, N, the combination of any one in N-dimethylacetylamide, the N-methyl pyrrolidone or two or more arbitrary proportions.
Wherein, the additive described in the step (1) is the combination of any one or two or more arbitrary proportions in PVP, polyethylene glycol, hyperbranched poly (amine-ester), oxalic acid, formic acid, propionic acid and the chloroform.
Wherein, the PVP molecular weight is 1～50,000, and molecular weight polyethylene glycol is 600～40000, hyperbranched polyamine/ester molecule amount is 2000～30000.
Wherein, the pore-foaming agent described in the step (2) is the combination of any one or two or more arbitrary proportions in acetone, ether and the methyl alcohol.
Wherein, the coagulation bath described in the step (3) is the combination of any one or two or more arbitrary proportions in water, ethanol, propyl alcohol and the n-butanol.
Wherein, be 0～150 second the standing time in air described in the step (3).
Wherein, the described unisexuality hydrophilic radical of step (1) is maleic anhydride, styrene, polypyrrole alkane ketone or N, the N-2-Methacrylamide.
Wherein, the mass ratio 1-10:100 of Kynoar and unisexuality hydrophilic radical
Wherein, said irradiation dose is 0.1-0.35kGy, and irradiation intensity is 0.2-0.5kGy, percent grafting 0-20%.
Beneficial effect: the present invention discloses a kind of preparation method of modified polyvinilidene fluoride milipore filter, and hydrophily strengthens, and dustiness descends.
The specific embodiment
Below in conjunction with embodiment the present invention is done further explanation.
Embodiment 1
In Kynoar, add maleic anhydride, mass ratio is after 100:1 mixes, and carries out irradiation grafting, and irradiation intensity is 0.3kGy/h, and irradiation dose is 0.15kGy, and percent grafting reaches 1.5%; Under 60 ℃, PVDF membrane material is dissolved in the solvent, the Kynoar molecular weight is 500,000, and solvent is N, dinethylformamide, N, the combination of any one in the N-dimethylacetylamide or two or more arbitrary proportions; Under 25 ℃, add additive then, stir, additive is a PVP, and the PVP molecular weight is 30,000; Under 30 ℃, add pore-foaming agent, pore-foaming agent is an acetone, stirs, and is configured to casting solution; Wherein, the mass percent of PVDF membrane material, solvent, additive and four kinds of components of pore-foaming agent is respectively 18%, 72%, 5% and 5%; Casting solution after filtration and vacuum defoamation, on polyester non-woven fabric, is placed its blade coating after 15 seconds in air, it is immersed in coagulation bath, coagulation bath is a water, at 15 ℃ of following gel solidifications, prepares the plain film filter membrane.
Embodiment 2
In Kynoar, add styrene, after mixing, carry out irradiation grafting, mass ratio is after 50:1 mixes, and carries out irradiation grafting, and irradiation intensity is 0.25kGy/h, and irradiation dose is 0.2kGy, and percent grafting reaches 5%; Under 55 ℃, PVDF membrane material is dissolved in the solvent, the Kynoar molecular weight is 500,000, and solvent is N, N-dimethylacetylamide, N-methyl pyrrolidone and in the combination of any one or two or more arbitrary proportions; Under 25 ℃, add additive, stir, additive is a polyethylene glycol, and molecular weight polyethylene glycol is 400; Under 30 ℃, add pore-foaming agent, pore-foaming agent is an acetone, stirs, and is configured to casting solution; Wherein, the mass percent of PVDF membrane material, solvent, additive and four kinds of components of pore-foaming agent is respectively 16%, 75%, 6% and 3%; After filtration and vacuum defoamation, on polyester non-woven fabric, in air, place after 30 seconds its blade coating casting solution; It is immersed in the coagulation bath; Coagulation bath is the combination of any one or two or more arbitrary proportions in water, the ethanol, at 20 ℃ of following gel solidifications, prepares the plain film filter membrane.
Embodiment 3
In Kynoar, add polypyrrole alkane ketone, after mixing, carry out irradiation grafting, mass ratio is 75:1, and irradiation intensity is 0.3kGy/h, and irradiation dose is 0.25kGy, and percent grafting reaches 10%; Under 70 ℃, PVDF membrane material is dissolved in the solvent, the Kynoar molecular weight is 750,000, and solvent is the N-methyl pyrrolidone; Under 25 ℃, add additive, stir, additive is a polyethylene glycol, and molecular weight polyethylene glycol is 10,000; Under 30 ℃, add pore-foaming agent, pore-foaming agent is an acetone, stirs, and is configured to casting solution; Wherein, the mass percent of PVDF membrane material, solvent, additive and four kinds of components of pore-foaming agent is respectively 12%, 73%, 10% and 5%; After filtration and vacuum defoamation, on polyester non-woven fabric, in air, place after 50 seconds its blade coating casting solution; It is immersed in the coagulation bath; Coagulation bath is the combination of any one or two or more arbitrary proportions in water, the n-butanol, at 25 ℃ of following gel solidifications, prepares the plain film filter membrane.
Embodiment 4
In Kynoar, add N, the N-2-Methacrylamide after mixing, carries out irradiation grafting, and mass ratio is 90:1, and irradiation intensity is 0.5kGy/h, and irradiation dose is 0.35kGy, and percent grafting reaches 20%; Under 75 ℃, PVDF membrane material is dissolved in the solvent, the Kynoar molecular weight is 800,000, and solvent is dimethyl sulfoxide (DMSO), N, the N-dimethylacetylamide with in the combination of any one or two or more arbitrary proportions; Under 20 ℃, add additive, additive is an oxalic acid, stirs; Under 32 ℃, add pore-foaming agent, pore-foaming agent is a methyl alcohol, stirs, and is configured to casting solution; Wherein, the mass percent of PVDF membrane material, solvent, additive and four kinds of components of pore-foaming agent is respectively 20%, 71%, 5% and 4%; After filtration and vacuum defoamation, on polyester non-woven fabric, in air, place after 150 seconds its blade coating casting solution; It is immersed in the coagulation bath; Coagulation bath is the combination of any one or two or more arbitrary proportions in water, the ethanol, at 10 ℃ of following gel solidifications, prepares the plain film filter membrane.
The invention provides a kind of preparation method and thinking of modified polyvinilidene fluoride milipore filter; The method and the approach of concrete this technical scheme of realization are a lot; The above only is a preferred implementation of the present invention, should be pointed out that for those skilled in the art; Under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention, and all available prior art of each part not clear and definite in the present embodiment realizes.
Claims (11)
1. the preparation method of a modified polyvinilidene fluoride milipore filter is characterized in that, this method comprises the steps:
(1) in Kynoar, adds the unisexuality hydrophilic radical, after mixing, carry out irradiation grafting;
Under (2) 40～75 ℃, PVDF membrane material is dissolved in the solvent; Under 20～30 ℃, add additive, stir; Under 30-35 ℃, add pore-foaming agent, stir, be configured to casting solution; Wherein, the mass percent of PVDF membrane material, solvent, additive and four kinds of components of pore-foaming agent is respectively 5～25%, 70～90%, 1～10% and 0～4%;
(3) casting solution that obtains of step (2) through filter with vacuum defoamation after, with its blade coating on polyester non-woven fabric, in air, place certain hour after, in its immersion coagulation bath,, prepare the plain film filter membrane at 0～35 ℃ of following gel solidification.
2. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1 is characterized in that, the Kynoar molecular weight is 20～600,000.
3. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1; It is characterized in that; Solvent described in the step (2) is dimethyl sulfoxide (DMSO), oxolane, N; Dinethylformamide, N, the combination of any one in N-dimethylacetylamide, the N-methyl pyrrolidone or two or more arbitrary proportions.
4. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1 is characterized in that the additive described in the step (1) is the combination of any one or two or more arbitrary proportions in PVP, polyethylene glycol, hyperbranched poly (amine-ester), oxalic acid, formic acid, propionic acid and the chloroform.
5. according to the preparation method of claim 1 or 4 described a kind of modified polyvinilidene fluoride milipore filters; It is characterized in that the PVP molecular weight is 1～50,000, molecular weight polyethylene glycol is 600～40000, hyperbranched polyamine/ester molecule amount is 2000～30000.
6. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1 is characterized in that, the pore-foaming agent described in the step (2) is the combination of any one or two or more arbitrary proportions in acetone, ether and the methyl alcohol.
7. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1 is characterized in that the coagulation bath described in the step (3) is the combination of any one or two or more arbitrary proportions in water, ethanol, propyl alcohol and the n-butanol.
8. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1 is characterized in that be 0～150 second the standing time in air described in the step (2).
9. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1 is characterized in that, the described unisexuality hydrophilic radical of step (1) is maleic anhydride, acrylic acid, gather pyrrole irons alkane ketone or N, the N-2-Methacrylamide.
10. according to the preparation method of claim 1 or 9 described a kind of modified polyvinilidene fluoride milipore filters, it is characterized in that the mass ratio 1-10:100 of Kynoar and unisexuality hydrophilic radical.
11. the preparation method of a kind of modified polyvinilidene fluoride milipore filter according to claim 1 is characterized in that, said irradiation dose is 0.1-0.35kGy, and irradiation intensity is 0.2-0.5kGy, percent grafting 0-20%.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103861476A (en) * | 2012-12-18 | 2014-06-18 | 同济大学 | Preparation method of polyvinylidene fluoride (PVDF) composite mesoporous membrane |
| CN104043351A (en) * | 2014-06-16 | 2014-09-17 | 东北林业大学 | Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane |
| CN104524999A (en) * | 2015-01-16 | 2015-04-22 | 济南大学 | Panel type modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN105597712A (en) * | 2015-11-19 | 2016-05-25 | 天津工业大学 | Enhanced type oil-absorbing film material, and assembly and preparation method thereof |
| CN105709616A (en) * | 2016-03-09 | 2016-06-29 | 中国海洋大学 | Method for preparing organic-solvent-resistant ultrafiltration membrane, prepared ultrafiltration membrane and application of ultrafiltration membrane |
| CN107158970A (en) * | 2017-06-07 | 2017-09-15 | 江苏大学 | A kind of preparation method and its usage of super hydrophilic gel compound membrane |
| CN108043240A (en) * | 2017-12-29 | 2018-05-18 | 北京清大国华环境股份有限公司 | A kind of resistant to pollution PVDF Modified Membranes of high throughput and preparation method thereof |
| CN109437455A (en) * | 2018-12-25 | 2019-03-08 | 杭州蓝然环境技术股份有限公司 | The processing equipment and method of secondary clarifier effluent Treated sewage reusing |
| CN109603595A (en) * | 2019-01-15 | 2019-04-12 | 中国科学院上海应用物理研究所 | Graft modification Kynoar, ultrafiltration membrane and preparation method thereof |
| CN109675446A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of super hydrophilic modified polyvinilidene fluoride film and the preparation method and application thereof |
| CN110975649A (en) * | 2019-11-19 | 2020-04-10 | 江苏大孚膜科技有限公司 | Modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN116870701A (en) * | 2023-09-08 | 2023-10-13 | 杭州尚善若水环保科技有限公司 | Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861476A (en) * | 2012-12-18 | 2014-06-18 | 同济大学 | Preparation method of polyvinylidene fluoride (PVDF) composite mesoporous membrane |
| CN104043351A (en) * | 2014-06-16 | 2014-09-17 | 东北林业大学 | Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane |
| CN104524999A (en) * | 2015-01-16 | 2015-04-22 | 济南大学 | Panel type modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN105597712A (en) * | 2015-11-19 | 2016-05-25 | 天津工业大学 | Enhanced type oil-absorbing film material, and assembly and preparation method thereof |
| CN105597712B (en) * | 2015-11-19 | 2018-01-16 | 天津工业大学 | Enhanced oil suction membrane material, component and preparation method thereof |
| CN105709616A (en) * | 2016-03-09 | 2016-06-29 | 中国海洋大学 | Method for preparing organic-solvent-resistant ultrafiltration membrane, prepared ultrafiltration membrane and application of ultrafiltration membrane |
| CN105709616B (en) * | 2016-03-09 | 2019-05-14 | 中国海洋大学 | A kind of preparation method of organic solvent-resistant ultrafiltration membrane, prepared film and its application |
| CN107158970A (en) * | 2017-06-07 | 2017-09-15 | 江苏大学 | A kind of preparation method and its usage of super hydrophilic gel compound membrane |
| CN109675446A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of super hydrophilic modified polyvinilidene fluoride film and the preparation method and application thereof |
| CN108043240A (en) * | 2017-12-29 | 2018-05-18 | 北京清大国华环境股份有限公司 | A kind of resistant to pollution PVDF Modified Membranes of high throughput and preparation method thereof |
| CN109437455A (en) * | 2018-12-25 | 2019-03-08 | 杭州蓝然环境技术股份有限公司 | The processing equipment and method of secondary clarifier effluent Treated sewage reusing |
| CN109437455B (en) * | 2018-12-25 | 2024-05-31 | 杭州蓝然技术股份有限公司 | Treatment equipment and method for recycling secondary sedimentation tank effluent water |
| CN109603595A (en) * | 2019-01-15 | 2019-04-12 | 中国科学院上海应用物理研究所 | Graft modification Kynoar, ultrafiltration membrane and preparation method thereof |
| CN110975649A (en) * | 2019-11-19 | 2020-04-10 | 江苏大孚膜科技有限公司 | Modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN116870701A (en) * | 2023-09-08 | 2023-10-13 | 杭州尚善若水环保科技有限公司 | Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage |
| CN116870701B (en) * | 2023-09-08 | 2023-11-21 | 杭州尚善若水环保科技有限公司 | Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage |
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Application publication date: 20120711 |