CN102784567B - Modified polyvinylidene fluoride membrane coated with single-walled carbon nano tube and preparation method thereof - Google Patents
Modified polyvinylidene fluoride membrane coated with single-walled carbon nano tube and preparation method thereof Download PDFInfo
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- CN102784567B CN102784567B CN201210329689.3A CN201210329689A CN102784567B CN 102784567 B CN102784567 B CN 102784567B CN 201210329689 A CN201210329689 A CN 201210329689A CN 102784567 B CN102784567 B CN 102784567B
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Abstract
The invention provides a modified polyvinylidene fluoride membrane coated with a single-walled carbon nano tube and and a preparation method of the modified polyvinylidene fluoride membrane. The modified polyvinylidene fluoride membrane coated with the single-walled carbon nano tube comprises the following components in parts by weight: 10 to 20 parts of polyvinylidene fluoride, 3 to 7 parts of polyvinylpyrrolidone, and 0.01 to 0.08 parts of single-walled carbon nano tube. According to the invention, the polyvinylidene fluoride is used as a membrane forming main body of the modified membrane, a pore-forming agent is added, a wet method phase transformation method is used for preparing the membrane, the membrane surface is subjected to hydrophilization modification treatment by alkali liquor, and then the evenly dispersed single-walled carbon nano tube is coated on the surface of the membrane, so as to obtain the modified polyvinylidene fluoride membrane coated with the single-walled carbon nano tube; with the addition of the single-walled carbon nano tube, the hydrophily and the stain resistance of the membrane are enhanced, and the service life of the membrane is greatly prolonged. The preparation method of the modified membrane has simple process, is convenient to operate, does not need to change the existing apparatus, and has high operability.
Description
Technical field
The invention belongs to diffusion barrier modification technology field, particularly relate to a kind of SWCN and apply modified polyvinilidene fluoride film and preparation method thereof.
Background technology
Kynoar (PVDF) is as a kind of macromolecular material of function admirable, its outstanding chemical stability, radiation resistance, resistance tocrocking and heat resistance more make it at film separation field, show that it can, wherein PVDF microfiltration membranes and milipore filter are successfully applied to the fields such as chemical industry, electronics, weaving, food, biochemistry, but due to the surface of PVDF resin can be extremely low, hydrophobicity is extremely strong (contact angle is about 80 °), when processing water-based fluid, easily produce adsorption fouling, the growing of the deposition of for example inorganic matter fouling, colloidal solid thing, microorganism, chemical contamination and other problem.To sum up, because accumulation of pollutants causes film pollution to cause that transmembrane pressure raises in film surface and hole, membrane flux declines, the disposal ability of film reduces rapidly, cause membrane lifetime to shorten, have a strong impact on stability, security and the economy of film separation process, greatly limited its application.Therefore, film pollutes the bottleneck that has become restricting current membrane separation technique large-scale application, how successfully to address this problem the key that more becomes embrane method water treatment large-scale application, is also focus and the difficult point of membrane science technical research.
At present, development of new pollution-resistant membrane material is the research field that current research personnel pay close attention to the most, as patent 200510009860.2 discloses a kind of modification film of polyvinylidene fluoride and preparation method thereof, patent 200810061388.0 discloses a kind of method of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer, and patent 200910069485.9 discloses polyvinylidene fluoride/liquid crystal blending microporous membrane and preparation method thereof.
Current is mainly by the novel pollution-resistant membrane material of following two aspect developing:
The one, the matrix material before masking is carried out to modification, comprise blending and modifying and modification by copolymerization, these class methods are by introduce hydrophilic radical or hydroaropic substance in membrane material, fundamentally change the hydrophily of film;
The 2nd, the modifying surface to finished film, comprise surface coating modified, surface chemical modification, surface irradiation graft modification and surface plasma modification, thereby these class methods are to reach raising film hydrophily by introduce hydrophilic radical on film surface, wherein utilize the specific function of inorganic nano-particle, it is the important method that improves film contamination resistance that inorganic particulate and organic polymer blend are prepared to the polymeric membrane for separation with specific function, add inorganic nano-particle can improve the hydrophily of film, reducing film pollutes, simultaneously, can also improve film strength and toughness.At home and abroad, in existing relevant report, the inorganic nano-particle mainly adding has A1
2o
3, SiO
2, TiO
2deng, but from practical application effect, adopt said method and means also can only make the pollution of film be controlled effectively or the pollution time is continued, in embrane method water treatment procedure, membrane pollution problem thoroughly solves.
Patent 201210096520 discloses a kind of Kynoar-CNT composite separating film and preparation method thereof, this diffusion barrier is comprised of the following component in weight portion: Kynoar 10～20, N, N-dimethylacetylamide 60～80, CNT 0.1～3 and polyvinylpyrrolidone 2～5, described Kynoar-CNT composite separating film is to utilize ultrasonicly to add churned mechanically method even carbon nanotube is distributed in Kynoar, finally by wet method phase inversion, made the poly-vinylidene-fluoride composite film of doped carbon nanometer pipe, the surface that can finely improve Kynoar due to adding of CNT can, strengthen the hydrophily of film, improve the resistance tocrocking of film, therefore the pure water flux of film is greatly improved, but it is not obvious that the method exists modified effect, in Blending Processes, the more difficult dispersion of CNT, easily produce and reunite, and then can affect uniformity and the intensity of film, in order to improve the degree of scatter of CNT in system, need to increase substantially the time and intensity of blend.
Summary of the invention
The problem to be solved in the present invention is to provide and a kind ofly can effectively improves the hydrophily of film, and a kind of SWCN that improves film contamination resistance applies modified polyvinilidene fluoride film and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of SWCN applies modified polyvinilidene fluoride film, the surface of Kynoar rete is provided with single-wall carbon nanotube membrane layer, count by weight, described SWCN applies modified polyvinilidene fluoride film and is made by following component:
Kynoar 10-20
Polyvinylpyrrolidone 3-7
SWCN (SWCNTs) 0.01-0.08
Described Kynoar refers to that molecular weight ranges is the Kynoar of 430000-900000, in Modified Membrane of the present invention as the material of main part of film.
Described polyvinylpyrrolidone refers to that molecular weight ranges is the polyvinylpyrrolidone of 30000-40000, in Modified Membrane of the present invention as pore-foaming agent.
Described SWCN is to consist of individual layer column type graphite linings, and the distribution of its diameter is little, defect is few, has higher uniformity consistency.The diameter of SWCN is generally at 1～6nm, length can reach hundreds of nanometer to tens micron, therefore compare with multi-walled carbon nano-tubes, SWCN has larger specific area, has more functional group by modification the less addition in the situation that.
The draw ratio of described SWCN is (500-3000): 1, preferably (1000-2000): 1.Draw ratio is too small, although be easy to disperse, a little less than the interaction after applying between SWCN, easily produce and comes off; Draw ratio is excessive, and in modification dispersion process, easily generation is reunited, and is also not easy to apply evenly in coating procedure, therefore effect, selects above-mentioned range effect best with operation.
Preferably, described SWCN coating modified polyvinilidene fluoride film is flat sheet membrane.
The present invention also provides a kind of above-mentioned SWCN to apply the preparation method of modified polyvinilidene fluoride film, comprises the steps:
(1) Kynoar and polyvinylpyrrolidone are dissolved in DMA, obtain casting solution;
Preferably, the weight ratio scope of Kynoar, polyvinylpyrrolidone and DMA is: (10-20): (3-7): (100-130), and preferably (16-18): (6-7): (100-110);
(2) by above-mentioned casting solution at 25-45 ℃, preferably at 40 ℃, standing 18-48 hour, preferably deaeration in 24 hours;
(3) in the SWCN of above-mentioned parts by weight, add deionized water, ultrasonic dispersion 3-6 hour after mixing, preferably 5 hours, obtains homogeneous dispersion liquid;
Preferably, the weight ratio of SWCN and deionized water is (0.1-2.0) mg: 1g;
(4) by the casting solution after step (2) deaeration is processed, on glass plate, with knifing rod, scrape and make the homogeneous membrane being of uniform thickness;
(5) by homogeneous membrane standing 30-50s in air, immerse film forming in coagulating bath (deionized water), the DMA in film is removed;
(6) after 24h, take out, with after deionized water rinsing, be placed into and in strong base solution, place 1-4 hour; Strong base solution can be selected known alkali lye in the industry, as KOH, and NaOH, preferably KOH;
(7) film is taken out to the rear deionized water rinsing of using, the single-walled carbon nanotube dispersion liquid after step (3) is processed is sprayed on film, dry, obtain described SWCN and apply modified polyvinilidene fluoride film.
Preferably, in step (1), using the material of main part Kynoar as film with as the polyvinylpyrrolidone of pore-foaming agent, join solvent N, in N-dimethylacetylamide, after hand operated mixing 5 minutes, solution is placed in to the ultrasonic dispersion of ultrasonic washing instrument 4 hours, then change magnetic agitation into and extremely dissolve completely for 2 hours, obtain casting solution.Hand operated mixing can be avoided originally polymer conglomeration, and combination of ultrasound magnetic agitation can obtain the dispersion liquid of homogeneous sooner.
The present invention also provides above-mentioned SWCN to apply the application of modified polyvinilidene fluoride film in micro-filtration, ultrafiltration and nanofiltration process.
Modified Membrane of the present invention be take Kynoar as film forming main body, add pore-foaming agent, by wet method phase inversion, prepare film forming, with alkali lye, hydrophilic modification processing is carried out in film surface, then finely dispersed SWCN is coated to film surface, prepare SWCN and apply modified polyvinilidene fluoride film, SWCN add the further hydrophily of film and the contamination resistance of film of having improved, greatly extended the service life of film, preparation method's technique of Modified Membrane of the present invention is simple, easy to operate, do not need existing equipment to change, workable.Compare with the Kynoar-CNT composite separating film that adopts blend method to prepare, the Modified Membrane that the present invention adopts the mode of coating SWCN to prepare, not only overcome the drawback of blend inequality, and the SWCN adopting is better than multi-walled carbon nano-tubes from intrinsic performance, in addition, in Modified Membrane of the present invention, only need to add the seldom SWCN of amount and just can possess good performance.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1
SWCN applies a modified polyvinilidene fluoride film, and the surface of Kynoar rete is provided with single-wall carbon nanotube membrane layer, counts by weight, and described SWCN applies modified polyvinilidene fluoride film and made by following component:
Kynoar 15g
Polyvinylpyrrolidone 3g
SWCN (SWCNTs) 0.05g
The draw ratio of described SWCN is 1000: 1.
Described SWCN applies the preparation method of modified polyvinilidene fluoride film, comprises the steps:
(1) using the material of main part Kynoar 15g of film with as the polyvinylpyrrolidone 3g of pore-foaming agent, join 100g solvent N, in N-methylacetamide, after hand operated mixing 5 minutes, solution is placed in to the ultrasonic dispersion of ultrasonic washing instrument 4 hours, after change magnetic agitation 2 hours into dissolving completely, obtain casting solution;
(2) by the deaeration in standing 24 hours at 40 ℃ of above-mentioned casting solution;
(3) in the SWCN of 0.05g, add 100g deionized water, after mixing, ultrasonic dispersion is 5 hours, obtains homogeneous dispersion liquid;
(4) by the casting solution after step (2) deaeration is processed, on glass plate, with knifing rod, scrape and make the homogeneous membrane being of uniform thickness;
(5), by homogeneous membrane standing 30-50s in air, immerse film forming in coagulating bath (deionized water);
(6) after 24h, take out, with after deionized water rinsing, be placed in KOH solution and place 1 hour.
(7) film is taken out to the rear deionized water rinsing of using, the single-walled carbon nanotube dispersion liquid after step (3) is processed is sprayed on film, dry, obtain described SWCN and apply modified polyvinilidene fluoride film.
The above-mentioned SWCN for preparing is applied to the testing experiment that modified polyvinilidene fluoride film and pure polyvinylidene fluoride film carry out contact angle, experimental result shows, the contact angle of pure polyvinylidene fluoride film is 80.1 °, and the contact angle of Modified Membrane of the present invention is 57.5 °, show that the Modified Membrane hydrophily that the present invention prepares obviously improves, the contamination resistance of corresponding film is also improved.
Embodiment 2
SWCN applies a modified polyvinilidene fluoride film, and the surface of Kynoar rete is provided with single-wall carbon nanotube membrane layer, counts by weight, and described SWCN applies modified polyvinilidene fluoride film and made by following component:
Kynoar 15g
Polyvinylpyrrolidone 5g
SWCN (SWCNTs) 0.01g
The draw ratio of described SWCN is 500: 1.
Described SWCN applies the preparation method of modified polyvinilidene fluoride film, comprises the steps:
(1) using the material of main part Kynoar 15g of film with as the polyvinylpyrrolidone 5g of pore-foaming agent, join 100g solvent N, in N-dimethylacetylamide, after hand operated mixing 5 minutes, solution is placed in to the ultrasonic dispersion of ultrasonic washing instrument 4 hours, after change magnetic agitation 2 hours into dissolving completely, obtain casting solution;
(2) by the deaeration in standing 24 hours at 40 ℃ of above-mentioned casting solution;
(3) in the SWCN of 0.01g, add 100g deionized water, after mixing, ultrasonic dispersion is 5 hours, obtains homogeneous dispersion liquid;
(4) by the casting solution after step (2) deaeration is processed, on glass plate, with knifing rod, scrape and make the homogeneous membrane being of uniform thickness;
(5), by homogeneous membrane standing 30-50s in air, immerse film forming in coagulating bath (deionized water);
(6) after 24h, take out, with after deionized water rinsing, be placed in KOH solution and place 1 hour.
(7) film is taken out to the rear deionized water rinsing of using, the single-walled carbon nanotube dispersion liquid after step (3) is processed is sprayed on film, dry, obtain described SWCN and apply modified polyvinilidene fluoride film.
The above-mentioned SWCN for preparing is applied to the testing experiment that modified polyvinilidene fluoride film and pure polyvinylidene fluoride film carry out contact angle, experimental result shows, the contact angle of pure polyvinylidene fluoride film is 80.1 °, and the contact angle of Modified Membrane of the present invention is 65.5 °, show that the Modified Membrane hydrophily that the present invention prepares obviously improves, the contamination resistance of corresponding film is also improved.
Embodiment 3
SWCN applies a modified polyvinilidene fluoride film, and the surface of Kynoar rete is provided with single-wall carbon nanotube membrane layer, counts by weight, and described SWCN applies modified polyvinilidene fluoride film and made by following component:
Kynoar 15g
Polyvinylpyrrolidone 3g
SWCN (SWCNTs) 0.08g
The draw ratio of described SWCN is 3000: 1.
Described SWCN applies the preparation method of modified polyvinilidene fluoride film, comprises the steps:
(1) using the material of main part Kynoar 15g of film with as the polyvinylpyrrolidone 3g of pore-foaming agent, join 100g solvent N, in N-dimethylacetylamide, after hand operated mixing 5 minutes, solution is placed in to the ultrasonic dispersion of ultrasonic washing instrument 4 hours, after change magnetic agitation 2 hours into dissolving completely, obtain casting solution;
(2) by the deaeration in standing 24 hours at 40 ℃ of above-mentioned casting solution;
(3) in the SWCN of 0.08g, add 200g deionized water, after mixing, ultrasonic dispersion is 5 hours, obtains homogeneous dispersion liquid;
(4) by the casting solution after step (2) deaeration is processed, on glass plate, with knifing rod, scrape and make the homogeneous membrane being of uniform thickness;
(5), by homogeneous membrane standing 30-50s in air, immerse film forming in coagulating bath (deionized water);
(6) after 24h, take out, with after deionized water rinsing, be placed in KOH solution and place 1 hour.
(7) film is taken out to the rear deionized water rinsing of using, the single-walled carbon nanotube dispersion liquid after step (3) is processed is sprayed on film, dry, obtain described SWCN and apply modified polyvinilidene fluoride film.
The above-mentioned SWCN for preparing is applied to the testing experiment that modified polyvinilidene fluoride film and pure polyvinylidene fluoride film carry out contact angle, experimental result shows, the contact angle of pure polyvinylidene fluoride film is 80.1 °, and the contact angle of Modified Membrane of the present invention is 54.5 °, show that the Modified Membrane hydrophily that the present invention prepares obviously improves, the contamination resistance of corresponding film is also improved.
Above preferred embodiment of the present invention is had been described in detail, but described content is only preferred embodiment of the present invention, can not be considered to for limiting practical range of the present invention.All equalization variations of doing according to the present patent application scope and improvement etc., within all should still belonging to patent covering scope of the present invention.
Claims (5)
1. SWCN applies a preparation method for modified polyvinilidene fluoride film, it is characterized in that: comprise the steps:
(1) Kynoar and polyvinylpyrrolidone are dissolved in DMA, obtain casting solution;
(2) by above-mentioned casting solution at 25-45 ℃, standing 18-48 hour deaeration;
(3) in the SWCN of above-mentioned parts by weight, add deionized water, after mixing, ultrasonic dispersion obtains homogeneous dispersion liquid for 3-6 hour;
(4) by the casting solution after step (2) deaeration is processed, on glass plate, with knifing rod, scrape and make the homogeneous membrane being of uniform thickness;
(5), by homogeneous membrane standing 30-50s in air, immerse film forming in coagulating bath;
(6) after 24h, take out the film of processing through step (5), with after deionized water rinsing, be placed into and in strong base solution, place 1-4 hour;
(7) film is taken out to the rear deionized water rinsing of using, the single-walled carbon nanotube dispersion liquid after step (3) is processed is sprayed on film, dry, obtain described SWCN and apply modified polyvinilidene fluoride film;
Wherein the ratio of weight and number of Kynoar, polyvinylpyrrolidone, SWCN is: 10-20 part: 3-7 part: 0.01-0.08 part; The draw ratio of described SWCN is (500-3000): 1.
2. method according to claim 1, it is characterized in that: step (1) is: Kynoar and polyvinylpyrrolidone are joined to solvent N, in N-dimethylacetylamide, after hand operated mixing 5 minutes, solution is placed in to the ultrasonic dispersion of ultrasonic washing instrument 4 hours, then change magnetic agitation into and extremely dissolve completely for 2 hours, obtain casting solution.
3. method according to claim 1 and 2, is characterized in that: in step (1), the weight ratio scope of Kynoar, polyvinylpyrrolidone and DMA is: (10-20): (3-7): (100-130).
4. method according to claim 3, is characterized in that: in step (3), the weight ratio of SWCN and deionized water is (0.1-2.0) mg:1g.
5. method according to claim 4, is characterized in that: the strong base solution in step (6) is KOH solution.
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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 |
| CN103877868B (en) * | 2012-12-19 | 2016-07-06 | 中国科学院大连化学物理研究所 | A kind of preparation method separating film and high flux high intensity separation film |
| CN103084074B (en) * | 2013-01-16 | 2014-09-03 | 天津工业大学 | Hydrophilic polyvinylidene fluoride modified separation membrane and preparation method thereof |
| CN104230056B (en) * | 2014-09-21 | 2016-04-06 | 北京工业大学 | The method of Pollution of Ultrafiltration Membrane is alleviated in a kind of preoxidation and membrane modifying combined action |
| CN105107392B (en) * | 2015-08-28 | 2018-05-22 | 西南石油大学 | A kind of multi-walled carbon nanotube surface embedded type modified polyvinilidene fluoride film and preparation method |
| CN108554192A (en) * | 2018-05-03 | 2018-09-21 | 东莞市石鼓污水处理有限公司 | A kind of ceramic filter membrane of surface modification carbon nanotube |
| CN109569332B (en) * | 2018-12-27 | 2021-12-21 | 华南理工大学 | High-moisture-permeability and high-hydrophobicity graphite oxide composite membrane and preparation method thereof |
| CN110252155A (en) * | 2019-06-20 | 2019-09-20 | 西华大学 | Anti-pollution functionalized multi-walled carbon nanotube composite membrane and preparation method thereof |
| CN111911717A (en) * | 2020-07-13 | 2020-11-10 | 江苏海基新能源股份有限公司 | Fire extinguishing agent conveying pipe for lithium battery pack and preparation method thereof |
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| CN100337729C (en) * | 2005-10-22 | 2007-09-19 | 燕山大学 | Chemical modification technique for microfiltering separation film of polyvinylidene fluoride |
| US20100009165A1 (en) * | 2008-07-10 | 2010-01-14 | Zyvex Performance Materials, Llc | Multifunctional Nanomaterial-Containing Composites and Methods for the Production Thereof |
| CN101879418B (en) * | 2010-08-18 | 2012-07-04 | 天津工业大学 | Preparation method of polyvinylidene fluoride modified film |
| CN102614784A (en) * | 2012-04-05 | 2012-08-01 | 天津工业大学 | Polyvinylidene fluoride-carbon nano tube composite separation film and preparation method thereof |
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