CN104014256A - Preparation method of anti-biological-pollution PVDF (polyvinylidene fluoride) film - Google Patents
Preparation method of anti-biological-pollution PVDF (polyvinylidene fluoride) film Download PDFInfo
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- CN104014256A CN104014256A CN201410168475.1A CN201410168475A CN104014256A CN 104014256 A CN104014256 A CN 104014256A CN 201410168475 A CN201410168475 A CN 201410168475A CN 104014256 A CN104014256 A CN 104014256A
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Abstract
The invention discloses a preparation method of a PVDF (polyvinylidene fluoride) film modified by silver phosphate modified nano negative ion powder. The preparation method comprises the steps of firstly, obtaining nano silver phosphate by adopting an ion exchange method, and modifying negative ion powder by nano silver phosphate to obtain negative ion powder with different silver carrying capacity; secondly, adding a proper amount of the silver-carrying negative ion powder into a PVDF casting film solution, and preparing the modified PVDF film containing the silver-carrying negative ion powder by adopting a phase inversion method. By virtue of peculiar nanometer size effect and surface energy of the silver-carrying negative ion powder, the PVDF film is endowed with effective anti-biological-pollution capability, the hydrophilicity of the PVDF film is improved, and the flux recovery rate of the PVDF film is increased; in addition, the preparation method of the modified PVDF film is simple and easy to adjust and control.
Description
Technical field
The invention belongs to polymer film modification field, its content relates to a kind of Kynoar membrane preparation method simultaneously with hydrophily and stable against biological contamination function of preparation.
Background technology
Embrane method water treatment is described as one of the optimization technique in Water Pollution Control Engineering field, has been widely used in drink water purifying and dirty waste water treatment and reuse etc., this mainly because of its can shortened process, improve that effluent quality is good and intensive degree is high.But in embrane method water treatment, during film pollutes and is intended to filter, the meeting such as the particulate in waste water, colloidal particle, organic matter or protein and membrane material generation physics chemical action, or be enriched in film surface because concentration polarization makes above-mentioned substance, and cause absorption in hole, deposition, cause aperture to diminish or stop up, this not only increases membrane resistance, reduce separative efficiency, and shorten membrane lifetime, improve operating cost., overcome or decelerating membrane pollution becomes the key point of Membrane Separation for Water Treatment scale application, be also one of problem of tool challenge in film Separation Research for this reason.
In polymeric film material, Kynoar (PVDF) because thering is good in oxidation resistance, mechanical performance is high, thermally-stabilised and the characteristic such as easy film forming is widely used as membrane material.Yet PVDF is hydrophobic polymer, its surface can be low, and easily in adsorbed water, all kinds of materials bring out film pollution.Therefore, explore hydrophilic modification pvdf membrane, decelerating membrane pollution effectively, reduce costs, improve separative efficiency, the application of the Membrane Separation for Water Treatment of, low consumption efficient for realizing in fields such as biochemical, medicine, chemical industry and water purification provides technical support, also highlighted important social effect and construction value.
By approach such as grafting, copolymerization, crosslinked, surperficial coating and blend, it is the main method of hydrophilic modification polymer film.Wherein utilize inorganic nano material blending and modifying polymer film to highlight many sharp points, as do not needed intrinsic filming technology, by the otherness of organic and inorganic mixed system inversion of phases, on the microscopic pattern basis of reconstruct film, give its new function as hydrophily and stability etc.But nano material and polymer-compatible are not good enough, and self easily reunite, thereby cause pore defect to increase, connectedness is obstructed, and affects its hydrophily and separation function.Publication number CN102863721A patent provides a kind of preparation method of antibiotic property polyvinylidene fluoride film, in described polyvinylidene fluoride film, contains silver molecular sieve, thereby makes film surface present antibacterial functions.But the hydrophily of the film after modification and the variation of physical property have been ignored.Publication number CN103331107A patent has disclosed the attapulgite modified pvdf membrane of 1-dimention nano, by regulation and control order of addition and quality, has given film hydrophily.Yet for the research of its specified conditions, there is limitation to annotating Modified Membrane separation property in its result.Publication number CN103084074A patent has been described the result of study of CNT and Graphene modification pvdf membrane, high spot reviews the variation of film surface water contact angle, separative efficiency is evaluated.In addition, the preprocessing process of CNT and graphene oxide is complicated, and the regularity that affects of pvdf membrane structure and performance is difficult to determine.Publication number CN102114389A patent has shown preparation and the performance of silver-loaded nano-titanium dioxide/polrvinyl chloride membrane.Its result shows, the biocidal property of Modified Membrane, pure water flux and antifouling property etc. are all improved, but ignored, inquires into silver carrying amount to improving the impact of film properties.
Nanometer anion powder belongs to a kind of natural mixed mineral matter, has higher hydrophily, and wide material sources, is easy to batch production.Nanometer silver orthophosphate (Ag
3pO
4) be conductor photocatalysis material, there is very strong sunshine response.For this reason, silver orthophosphate decorated nanometer negative ion powder is done to additive and PVDF blend, realize the hydrophilic while of pvdf membrane, also improve its separative efficiency and stable against biological contamination ability.
Summary of the invention
The object of the invention is, based on existing method of modifying deficiency, by preparation nanometer silver orthophosphate, to modify negative ion powder, to alleviate it, in solvent, reunite, and prepare stable against biological contamination modification pvdf membrane with Kynoar (PVDF) blend.This process is simple, easily control, and to equipment and environment without specific (special) requirements.
The invention provides each constituent mass of modification pvdf membrane casting solution than as follows:
Described organic solvent is selected from N, N-acetic acid dimethylamide, N, N-diformamide and 1-METHYLPYRROLIDONE any one.Preferred N, N-acetic acid dimethylamide or N, N-diformamide.
Described pore-foaming agent be selected from polyvinylpyrrolidone, polyethylene glycol and perchlorate any one.Preferably polyethylene pyrrolidones.
Modified polyvinilidene fluoride film, is characterized in that: described pvdf membrane can be microfiltration membranes or milipore filter.
Another object of the present invention is to provide the method that silver orthophosphate is modified negative ion powder and modification pvdf membrane thereof, and its step is as follows:
1) nanometer anion powder is joined in 40～60mL distilled water to ultrasonic dispersion 1～2 hour;
2) under lucifuge and continuous stirring, difference being measured to ammonium dihydrogen phosphate (ADP) and silver nitrate adds successively in above-mentioned suspension and completes ion-exchange reactions, approximately 5～8 hours time;
3) above-mentioned suspension filtered, second alcohol and water wash products is extremely neutral, in 40～60 ℃ of vacuum drying, within 20～24 hours, obtain load silver orthophosphate negative ion powder;
Advantage of the present invention is: above-mentioned preparation method is gentle, and easily control, and negative ion powder surface band negative electricity has not only suppressed silver orthophosphate self and reunited, and can impel silver orthophosphate load capacity to increase.General its load capacity can reach 0.2～1.6wt.%;
3) will carry in right amount silver orthophosphate negative ion powder and join in organic solvent, within ultrasonic 1～2 hour, form even mixed liquor, add in turn subsequently pore-foaming agent and PVDF, in 40～60 ℃ of stirred in water bath, within 12～24 hours, obtain PVDF casting solution;
4) by the deaeration in standing 1～2 day at 20～30 ℃ of this casting solution, room temperature knifing, in air, stop after 10～100 seconds and be impregnated into lentamente film forming in water-setting solid-liquid, repeatedly change water with desolvation and pore-foaming agent, finally obtain carrying silver orthophosphate negative ion powder modification pvdf membrane.
The biocidal property experiment of pvdf membrane is with inhibition zone evaluation.Select Escherichia coli as model microorganism, by its constant temperature culture on nutrient agar panel.Its result shows, modification pvdf membrane can form obvious inhibition zone, and inhibition zone (as Fig. 5) does not appear in pure pvdf membrane, this means that modification pvdf membrane has deactivation ability to microorganism, and microorganism is difficult in the survival of film surface under certain condition.
The hydrophily experiment of pvdf membrane is with water contact angle and pure water flux evaluation.Its result shows, the contact angle of modification pvdf membrane obviously reduces (as Fig. 1, Fig. 2, Fig. 3, Fig. 4); And pure water flux significantly increases (as Fig. 7), mean that modification pvdf membrane hydrophily strengthens, modified effect is obvious.
Characteristic of the present invention is: compare with pvdf membrane, modification pvdf membrane has been given surperficial can increasing because carrying the nanometer size effect of silver orthophosphate negative ion powder.In addition, because the electrical effect of silver orthophosphate has suppressed negative ion powder polymerization, thereby cause it to be easy in casting solution, disperse and migration, pure water flux and biocidal property are all improved.Obviously, modified condition provided by the invention is controlled, easily implements.
Accompanying drawing explanation
The pvdf membrane that Fig. 1 provides for embodiment 1 (M, 87 °) water contact angle figure.
The silver orthophosphate modification pvdf membrane that Fig. 2 provides for the embodiment of the present invention 2 (M1,76 °) water contact angle figure.
The negative ion powder modification pvdf membrane that Fig. 3 provides for the embodiment of the present invention 3 (M2,64 °) water contact angle figure.
Silver orthophosphate modification negative ion powder modification pvdf membrane (M3,58 °) the water contact angle figure that Fig. 4 provides for the embodiment of the present invention 4.
Fig. 5 is under lucifuge and 37 ℃ of conditions, cultivates the antibacterial loop graph that pvdf membrane and modification pvdf membrane surface form through 24 hours; Respectively: pure pvdf membrane (M); Silver orthophosphate modification pvdf membrane (M1); Negative ion powder modification pvdf membrane (M2); Silver orthophosphate is modified negative ion powder modification pvdf membrane (M3).Modification pvdf membrane all presents the inhibition zone of different radii, and wherein the inhibition zone radius of M1 is about 1.5 millimeters, and the inhibition zone radius of M2 is about 3 millimeters, and the inhibition zone radius of M3 is about 5 millimeters.
Fig. 6 is the AFM figure that pure pvdf membrane (M) and silver orthophosphate are modified negative ion powder modification pvdf membrane (M3), show that modification pvdf membrane surface roughness reduces, illustrate that the silver orthophosphate modification negative ion powder adding is evenly dispersed in pvdf membrane, and made up its blemish.
Fig. 7 is the initial pure water flux contrast of pvdf membrane and modification pvdf membrane.
Fig. 8 is flux decline (Jt/J0) temporal evolution that pvdf membrane and modification pvdf membrane filter 10mg/L humic acid (HA).
Fig. 9 is for filtering the flux recovery rate contrast of the rear contaminated pvdf membrane of 10mg/L humic acid (HA) and modification pvdf membrane.
The specific embodiment
In conjunction with example, the present invention is done to full and accurate elaboration:
Embodiment 1:
1.0 grams of polyvinylpyrrolidones (PVP) and 9.0 grams of PVDF are dissolved in 40 grams of DMAs (DMAc), and in 65 ℃ of water-baths, continuous stirring obtains PVDF casting solution in 24 hours, by the deaeration in 2 days of its sealing and standing.Under room temperature, on clean glass plate, with self-control scraper, control liquid measure knifing, in air, stop and be promptly impregnated into water coagulating bath in approximately 30 seconds, repeatedly change water with desolvation and pore-foaming agent, make described pvdf membrane (M).Its feature: with each component optimal proportion preparation PVDF casting solution, all the performance of diffusion barrier obtaining is thus more excellent.
Embodiment 2:
Be dispersed in 39.5 grams of N by 0.5 gram of nanometer silver orthophosphate is ultrasonic, in N-dimethylacetylamide (DMAC) 2 hours, add successively 9.0 grams of PVDF and 1.0 grams of polyvinylpyrrolidones (PVP), in 65 ℃ of water-baths, continuous stirring obtains the PVDF casting solution of phosphoric acid silver for 24 hours, by the deaeration in 2 days of its sealing and standing.Under room temperature, on clean glass plate, with self-control scraper, control liquid measure knifing, in air, stop and be promptly impregnated into water coagulating bath in approximately 30 seconds, repeatedly change water with desolvation and pore-foaming agent, make described modification pvdf membrane (M1).
Embodiment 3:
Be dispersed in 39.5 grams of N by 0.5 gram of negative ion powder is ultrasonic, in N-dimethylacetylamide (DMAC) 2 hours, add successively 9.0 grams of PVDF and 1.0 grams of polyvinylpyrrolidones (PVP), in 65 ℃ of water-baths, continuous stirring obtains the PVDF casting solution of phosphoric acid silver for 24 hours, by the deaeration in 2 days of its sealing and standing.Under room temperature, on clean glass plate, with self-control scraper, control liquid measure knifing, in air, stop and be promptly impregnated into water coagulating bath in approximately 30 seconds, repeatedly change water with desolvation and pore-foaming agent, make described modification pvdf membrane (M2).
Embodiment 4:
0.5 gram of silver orthophosphate is modified to negative ion powder is ultrasonic is dispersed in 39.5 grams of N, in N-dimethylacetylamide (DMAC) 2 hours, add successively 9.0 grams of PVDF and 1.0 grams of polyvinylpyrrolidones (PVP), in 65 ℃ of water-baths, continuous stirring obtains the PVDF casting solution of phosphoric acid silver for 24 hours, by the deaeration in 2 days of its sealing and standing.Under room temperature, on clean glass plate, with self-control scraper, control liquid measure knifing, in air, stop and be promptly impregnated into water coagulating bath in approximately 30 seconds, repeatedly change water with desolvation and pore-foaming agent, make described modification pvdf membrane (M3).
Claims (3)
1. a preparation method of carrying silver orthophosphate nanometer anion powder modified polyvinilidene fluoride (PVDF) film, its process contains as follows:
1) feature of modified polyvinilidene fluoride film is: by carrying silver orthophosphate nanometer anion powder, obtain properties, its casting solution is prepared by following mass ratio:
Wherein Kynoar solvent is selected from N, N-acetic acid dimethylamide, N, in N-diformamide and 1-METHYLPYRROLIDONE any one; In the optional polyvinylpyrrolidone of pore-foaming agent, polyethylene glycol or perchlorate any one;
2) get a year silver orthophosphate negative ion powder and be dispersed in organic solvent, within ultrasonic 1～2 hour, form even mixed liquor, add in turn subsequently pore-foaming agent and PVDF, in 40～60 ℃ of stirring in water bath, within 5～24 hours, obtain homogeneous phase PVDF casting solution;
3) above-mentioned PVDF casting solution is in 20～30 ℃ of deaerations in standing 1～2 day;
4) under room temperature on glass plate knifing, in air, stop after 10～100 seconds lentamente film forming in steep water solidification liquid, repeatedly change water with desolvation and pore-foaming agent;
5) from water coagulating bath, take out and obtain the different Series P VDF films that carry the modification of silver orthophosphate amount negative ion powder.
2. carry according to claim 1 the preparation method of silver orthophosphate negative ion powder, its technical process is as follows:
1) commercially available nanometer anion powder is distributed in 40～60mL distilled water to ultrasonic 1～2 hour, under lucifuge and continuous stirring, add successively different amount ammonium dihydrogen phosphate (ADP)s and silver nitrate to carry out ion-exchange reactions, after approximately 5～8 hours time, obtain the negative ion powder suspension containing different silver orthophosphate load capacity;
2) above-mentioned suspension after filtration, second alcohol and water cleans to product neutrality, within 20～24 hours, finally obtains series carry silver-colored negative ion powder in 40～60 ℃ of vacuum drying.
3. modified polyvinilidene fluoride film according to claim 1, is characterized in that: described Modified Membrane can be microfiltration membranes or milipore filter.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383820A (en) * | 2014-11-10 | 2015-03-04 | 华南师范大学 | Visible-light-response antibacterial and antifouling polyvinylidene fluoride film and preparation method thereof |
| CN105521715A (en) * | 2015-12-29 | 2016-04-27 | 天津工业大学 | Blend polyvinylidene fluoride hollow fiber film and making method thereof |
| CN107118477A (en) * | 2017-05-12 | 2017-09-01 | 合肥工业大学 | A kind of carbon-coated metallic nano-particles load pvdf membrane and its preparation method and application |
| CN107983167A (en) * | 2017-12-15 | 2018-05-04 | 陕西麦可罗生物科技有限公司 | A kind of anti-WSSV membrane materials and preparation method thereof |
| CN108310983A (en) * | 2018-02-02 | 2018-07-24 | 山西大学 | A kind of preparation of antibacterial pollution-resistant PVDF ultrafiltration membrane and regeneration method |
| CN112007520A (en) * | 2019-05-28 | 2020-12-01 | 中国石油化工股份有限公司 | Reverse osmosis membrane resistant to biological pollution and preparation method and application thereof |
| CN115382396A (en) * | 2022-08-15 | 2022-11-25 | 无锡零界净化设备股份有限公司 | Preparation method of casting solution of hydrophilic PVDF (polyvinylidene fluoride) microporous filter membrane |
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- 2014-04-23 CN CN201410168475.1A patent/CN104014256A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383820A (en) * | 2014-11-10 | 2015-03-04 | 华南师范大学 | Visible-light-response antibacterial and antifouling polyvinylidene fluoride film and preparation method thereof |
| CN105521715A (en) * | 2015-12-29 | 2016-04-27 | 天津工业大学 | Blend polyvinylidene fluoride hollow fiber film and making method thereof |
| CN105521715B (en) * | 2015-12-29 | 2018-06-12 | 天津工业大学 | A kind of blending polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
| CN107118477B (en) * | 2017-05-12 | 2019-06-14 | 合肥工业大学 | A kind of carbon-coated metallic nano-particles load pvdf membrane and its preparation method and application |
| CN107118477A (en) * | 2017-05-12 | 2017-09-01 | 合肥工业大学 | A kind of carbon-coated metallic nano-particles load pvdf membrane and its preparation method and application |
| CN107983167A (en) * | 2017-12-15 | 2018-05-04 | 陕西麦可罗生物科技有限公司 | A kind of anti-WSSV membrane materials and preparation method thereof |
| CN107983167B (en) * | 2017-12-15 | 2020-11-20 | 陕西麦可罗生物科技有限公司 | anti-WSSV membrane material and preparation method thereof |
| CN108310983A (en) * | 2018-02-02 | 2018-07-24 | 山西大学 | A kind of preparation of antibacterial pollution-resistant PVDF ultrafiltration membrane and regeneration method |
| CN108310983B (en) * | 2018-02-02 | 2021-02-02 | 山西大学 | Preparation and regeneration method of antibacterial and anti-pollution PVDF ultrafiltration membrane |
| CN112007520A (en) * | 2019-05-28 | 2020-12-01 | 中国石油化工股份有限公司 | Reverse osmosis membrane resistant to biological pollution and preparation method and application thereof |
| CN112007520B (en) * | 2019-05-28 | 2023-03-24 | 中国石油化工股份有限公司 | Reverse osmosis membrane resistant to biological pollution and preparation method and application thereof |
| CN115382396A (en) * | 2022-08-15 | 2022-11-25 | 无锡零界净化设备股份有限公司 | Preparation method of casting solution of hydrophilic PVDF (polyvinylidene fluoride) microporous filter membrane |
| CN115382396B (en) * | 2022-08-15 | 2024-02-23 | 无锡零界净化设备股份有限公司 | Preparation method of membrane casting solution of hydrophilic PVDF microporous filter membrane |
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