CN102784567A - 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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- CN102784567A CN102784567A CN2012103296893A CN201210329689A CN102784567A CN 102784567 A CN102784567 A CN 102784567A CN 2012103296893 A CN2012103296893 A CN 2012103296893A CN 201210329689 A CN201210329689 A CN 201210329689A CN 102784567 A CN102784567 A CN 102784567A
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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 hear resistance more makes it show that at the film separation field it can; Wherein PVDF micro-filtration membrane and milipore filter successfully are applied to fields such as chemical industry, electronics, weaving, food, biochemistry; But since the surface of PVDF resin can be extremely low, hydrophobicity is extremely strong (contact angle is about 80 °); When handling water-based fluid, be prone to produce absorption and pollute, the growing of the deposition of for example inorganic matter fouling, colloidal solid thing, microorganism, chemical contamination and other problem.To sum up, because pollutant is deposited on the film surface and hole causes film pollution causing transmembrane pressure to raise, membrane flux descends; 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, also is the focus and the difficult point of membrane science technical research.
At present; Development of new pollution-resistant membrane material is the research field that the current research personnel pay close attention to the most; A kind of modification film of polyvinylidene fluoride and preparation method thereof is disclosed like patent 200510009860.2; Patent 200810061388.0 discloses a kind of method of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer, and patent 200910069485.9 discloses Kynoar/liquid crystal blending microporous membrane and preparation method thereof.
Current mainly is through following two aspect developing novel anti polluted membrane materials:
The one, the matrix material before the system film is carried out modification, comprise blending and modifying and modification by copolymerization, these class methods are through in membrane material, introducing hydrophilic radical or hydroaropic substance, fundamentally changing the hydrophily of film;
The 2nd, modification is carried out on the surface of 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 through introduce hydrophilic radical on the film surface; Wherein utilize the specific function of inorganic nano-particle, inorganic particulate and organic polymer blend are prepared the important method that the polymeric membrane for separation with specific function is a raising film contamination resistance, add hydrophily, the pollution of reduction film that inorganic nano-particle can improve film; Simultaneously, can also improve film strength and toughness.In the existing at home and abroad relevant report, the main inorganic nano-particle that adds 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 obtains continuity, thoroughly solution of membrane pollution problem in the embrane method water treatment procedure.
Patent 201210096520 discloses a kind of Kynoar-CNT composite separating film and preparation method thereof; This diffusion barrier is made up of the following component in weight portion: Kynoar 10～20, N, N-dimethylacetylamide 60～80, CNT 0.1～3 and polyvinylpyrrolidone 2～5, said Kynoar-CNT composite separating film utilize ultrasonicly to add churned mechanically method even carbon nanotube is distributed in the Kynoar; Make the poly-vinylidene-fluoride composite film of doped carbon nanometer pipe at last by the wet method phase inversion; Because the adding of CNT can finely improve the surface ability of Kynoar, the hydrophily of reinforcing membrane, the resistance tocrocking of raising film; Therefore make the pure water flux of film be greatly improved; But it is not obvious that this method exists modified effect, and in the blend process, CNT is difficult to be disperseed; Be easy to generate reunion; And then can influence the uniformity and the intensity of film, in order to improve the degree of scatter of CNT in system, need increase substantially the time and intensity of blend.
Summary of the invention
The problem that the present invention will solve provides a kind of hydrophily that can effectively improve film, and improves a kind of SWCN coating modified polyvinilidene fluoride film of film contamination resistance and preparation method thereof.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is: a kind of SWCN applies modified polyvinilidene fluoride film; The surface of Kynoar rete is provided with the single-wall carbon nanotube membrane layer; Count by weight, said SWCN applies modified polyvinilidene fluoride film and is processed by following component:
Kynoar 10-20
Polyvinylpyrrolidone 3-7
SWCN (SWCNTs) 0.01-0.08
Said Kynoar is meant 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.
Said polyvinylpyrrolidone is meant that molecular weight ranges is the polyvinylpyrrolidone of 30000-40000, in modified membrane of the present invention as pore-foaming agent.
Said SWCN is to be made up of individual layer column type graphite linings, and the distribution of its diameter is little, defective is few, has higher uniformity consistency.The diameter of SWCN is generally at 1～6nm; Length then can reach hundreds of nanometer to tens micron; Compare with multi-walled carbon nano-tubes, SWCN has bigger specific area, therefore under the situation of less addition, has more functional group through modification.
The draw ratio of said SWCN is (500-3000): 1, preferred (1000-2000): 1.Draw ratio is too small, though be easy to disperse, applies a little less than the interaction between the SWCN of back, is easy to generate to come off; Draw ratio is excessive, in the modification dispersion process, is easy to generate reunion, also is not easy in the coating procedure to apply evenly, therefore on effect, selects above-mentioned range effect best with operation.
Preferably, said SWCN coating modified polyvinilidene fluoride film is a 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 N, in the N-dimethylacetylamide, get casting solution;
Preferably, Kynoar, polyvinylpyrrolidone and N, the weight ratio scope of N-dimethylacetylamide is: (10-20): (3-7): (100-130), preferred (16-18): (6-7): (100-110);
(2) with above-mentioned casting solution at 25-45 ℃, under preferred 40 ℃, left standstill deaeration in preferred 24 hours 18-48 hour;
(3) in the SWCN of above-mentioned parts by weight, add deionized water, mix the ultrasonic dispersion in back 3-6 hour, preferred 5 hours, get the homogeneous dispersion liquid;
Preferably, the weight ratio of SWCN and deionized water is (0.1-2.0) mg: 1g;
(4) will be through the casting solution after step (2) deaeration is handled, on glass plate, scrape and process the homogeneous membrane that is of uniform thickness with the knifing rod;
(5) homogeneous membrane is left standstill 30-50s in air, immerse film forming in the coagulating bath (deionized water), the N in the film, the N-dimethylacetylamide is removed;
(6) behind the 24h, take out, behind deionized water rinsing, be placed in the strong base solution and placed 1-4 hour; Strong base solution can be selected known alkali lye in the industry for use, like KOH, and NaOH, preferred KOH;
(7) film is taken out the back and use deionized water rinsing, will spray on the film, dry, get said SWCN and apply modified polyvinilidene fluoride film through the SWCN dispersion liquid after step (3) is handled.
Preferably; To join solvent N as the material of main part Kynoar of film with as the polyvinylpyrrolidone of pore-foaming agent in the step (1); In the N-dimethylacetylamide, manually stir 5 minutes after, solution is placed the ultrasonic dispersion of ultrasonic washing instrument 4 hours; Change magnetic agitation dissolving extremely fully in 2 hours then into, obtain casting solution.Manually stirring can be avoided polymer conglomeration originally, and the 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 is the film forming main body with the Kynoar, adds pore-foaming agent, prepares film forming through the wet method phase inversion; With alkali lye hydrophilic modification is carried out on the film surface and handle, then finely dispersed SWCN is coated to the film surface, prepare SWCN and apply modified polyvinilidene fluoride film; The adding of SWCN has further improved the hydrophily of film and the contamination resistance of film; Prolonged the service life of film greatly, preparation method's technology of modified membrane of the present invention is simple, easy to operate; Need not change existing equipment, 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 uneven drawback of blend; And the SWCN that adopts is better than multi-walled carbon nano-tubes from intrinsic performance, and in addition, a SWCN that only needs in the modified membrane of the present invention to add very small amount just can possess good performance.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but does not limit protection scope of the present invention.
Embodiment 1
A kind of SWCN applies modified polyvinilidene fluoride film, and the surface of Kynoar rete is provided with the single-wall carbon nanotube membrane layer, counts by weight, and said SWCN applies modified polyvinilidene fluoride film and processed by following component:
Kynoar 15g
Polyvinylpyrrolidone 3g
SWCN (SWCNTs) 0.05g
The draw ratio of said SWCN is 1000: 1.
Said SWCN applies the preparation method of modified polyvinilidene fluoride film, comprises the steps:
(1) joins 100g solvent N with the material of main part Kynoar 15g of film with as the polyvinylpyrrolidone 3g of pore-foaming agent; In the N-methylacetamide; Manually stir after 5 minutes; Solution is placed the ultrasonic dispersion of ultrasonic washing instrument 4 hours, after change magnetic agitation 2 hours into to dissolving fully, obtain casting solution;
(2) above-mentioned casting solution is left standstill deaeration in 24 hours under 40 ℃;
(3) in the SWCN of 0.05g, add the 100g deionized water, mix the ultrasonic dispersion in back 5 hours, get the homogeneous dispersion liquid;
(4) will be through the casting solution after step (2) deaeration is handled, on glass plate, scrape and process the homogeneous membrane that is of uniform thickness with the knifing rod;
(5) homogeneous membrane is left standstill 30-50s in air, immerse film forming in the coagulating bath (deionized water);
(6) behind the 24h, take out, behind deionized water rinsing, be placed in the KOH solution and placed 1 hour.
(7) film is taken out the back and use deionized water rinsing, will spray on the film, dry, get said SWCN and apply modified polyvinilidene fluoride film through the SWCN dispersion liquid after step (3) is handled.
The above-mentioned SWCN for preparing is applied 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 °, shows that the modified membrane hydrophily that the present invention prepares obviously improves, and the contamination resistance of corresponding film also is improved.
Embodiment 2
A kind of SWCN applies modified polyvinilidene fluoride film, and the surface of Kynoar rete is provided with the single-wall carbon nanotube membrane layer, counts by weight, and said SWCN applies modified polyvinilidene fluoride film and processed by following component:
Kynoar 15g
Polyvinylpyrrolidone 5g
SWCN (SWCNTs) 0.01g
The draw ratio of said SWCN is 500: 1.
Said SWCN applies the preparation method of modified polyvinilidene fluoride film, comprises the steps:
(1) joins 100g solvent N with the material of main part Kynoar 15g of film with as the polyvinylpyrrolidone 5g of pore-foaming agent; In the N-dimethylacetylamide; Manually stir after 5 minutes; Solution is placed the ultrasonic dispersion of ultrasonic washing instrument 4 hours, after change magnetic agitation 2 hours into to dissolving fully, obtain casting solution;
(2) above-mentioned casting solution is left standstill deaeration in 24 hours under 40 ℃;
(3) in the SWCN of 0.01g, add the 100g deionized water, mix the ultrasonic dispersion in back 5 hours, get the homogeneous dispersion liquid;
(4) will be through the casting solution after step (2) deaeration is handled, on glass plate, scrape and process the homogeneous membrane that is of uniform thickness with the knifing rod;
(5) homogeneous membrane is left standstill 30-50s in air, immerse film forming in the coagulating bath (deionized water);
(6) behind the 24h, take out, behind deionized water rinsing, be placed in the KOH solution and placed 1 hour.
(7) film is taken out the back and use deionized water rinsing, will spray on the film, dry, get said SWCN and apply modified polyvinilidene fluoride film through the SWCN dispersion liquid after step (3) is handled.
The above-mentioned SWCN for preparing is applied 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 °, shows that the modified membrane hydrophily that the present invention prepares obviously improves, and the contamination resistance of corresponding film also is improved.
Embodiment 3
A kind of SWCN applies modified polyvinilidene fluoride film, and the surface of Kynoar rete is provided with the single-wall carbon nanotube membrane layer, counts by weight, and said SWCN applies modified polyvinilidene fluoride film and processed by following component:
Kynoar 15g
Polyvinylpyrrolidone 3g
SWCN (SWCNTs) 0.08g
The draw ratio of said SWCN is 3000: 1.
Said SWCN applies the preparation method of modified polyvinilidene fluoride film, comprises the steps:
(1) joins 100g solvent N with the material of main part Kynoar 15g of film with as the polyvinylpyrrolidone 3g of pore-foaming agent; In the N-dimethylacetylamide; Manually stir after 5 minutes; Solution is placed the ultrasonic dispersion of ultrasonic washing instrument 4 hours, after change magnetic agitation 2 hours into to dissolving fully, obtain casting solution;
(2) above-mentioned casting solution is left standstill deaeration in 24 hours under 40 ℃;
(3) in the SWCN of 0.08g, add the 200g deionized water, mix the ultrasonic dispersion in back 5 hours, get the homogeneous dispersion liquid;
(4) will be through the casting solution after step (2) deaeration is handled, on glass plate, scrape and process the homogeneous membrane that is of uniform thickness with the knifing rod;
(5) homogeneous membrane is left standstill 30-50s in air, immerse film forming in the coagulating bath (deionized water);
(6) behind the 24h, take out, behind deionized water rinsing, be placed in the KOH solution and placed 1 hour.
(7) film is taken out the back and use deionized water rinsing, will spray on the film, dry, get said SWCN and apply modified polyvinilidene fluoride film through the SWCN dispersion liquid after step (3) is handled.
The above-mentioned SWCN for preparing is applied 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 °, shows that the modified membrane hydrophily that the present invention prepares obviously improves, and the contamination resistance of corresponding film also is improved.
More than preferred embodiment of the present invention is specified, but said content is merely preferred embodiment of the present invention, can not be considered to be used to limit practical range of the present invention.All equalizations of doing according to application range of the present invention change and improve etc., all should still belong within the patent covering scope of the present invention.
Claims (9)
1. a SWCN applies modified polyvinilidene fluoride film, and it is characterized in that: the surface of Kynoar rete is provided with the single-wall carbon nanotube membrane layer, counts by weight, and said SWCN applies modified polyvinilidene fluoride film and processed by following component:
Kynoar 10-20
Polyvinylpyrrolidone 3-7
SWCN 0.01-0.08;
The draw ratio of said SWCN is (500-3000): 1.
2. SWCN according to claim 1 applies modified polyvinilidene fluoride film, it is characterized in that: the draw ratio of said SWCN is (1000-2000): 1.
3. SWCN according to claim 1 and 2 applies modified polyvinilidene fluoride film, it is characterized in that: it is flat sheet membrane that said SWCN applies modified polyvinilidene fluoride film.
4. the preparation method of each described SWCN coating modified polyvinilidene fluoride film of claim 1-3 is characterized in that: comprise the steps:
(1) Kynoar and polyvinylpyrrolidone are dissolved in N, in the N-dimethylacetylamide, get casting solution;
(2) with above-mentioned casting solution under 25-45 ℃, leave standstill deaeration in 18-48 hour;
(3) in the SWCN of above-mentioned parts by weight, add deionized water, mix the ultrasonic dispersion in back and got the homogeneous dispersion liquid in 3-6 hour;
(4) will be through the casting solution after step (2) deaeration is handled, on glass plate, scrape and process the homogeneous membrane that is of uniform thickness with the knifing rod;
(5) homogeneous membrane is left standstill 30-50s in air, immerse film forming in the coagulating bath;
(6) take out the film of handling through step (5) behind the 24h, behind deionized water rinsing, be placed in the strong base solution and placed 1-4 hour;
(7) film is taken out the back and use deionized water rinsing, will spray on the film, dry, get said SWCN and apply modified polyvinilidene fluoride film through the SWCN dispersion liquid after step (3) is handled.
5. method according to claim 4; It is characterized in that: step (1) is: Kynoar and polyvinylpyrrolidone are joined solvent N; In the N-methylacetamide, manually stir 5 minutes after, solution is placed the ultrasonic dispersion of ultrasonic washing instrument 4 hours; Change magnetic agitation dissolving extremely fully in 2 hours then into, obtain casting solution.
6. according to claim 4 or 5 described methods, it is characterized in that: in the step (1), Kynoar, polyvinylpyrrolidone and N, the weight ratio scope of N-dimethylacetylamide is: (10-20): (3-7): (100-130).
7. according to each described method of claim 4-6, it is characterized in that: in the step (3), the weight ratio of SWCN and deionized water is (0.1-2.0) mg:1g.
8. according to each described method of claim 4-7, it is characterized in that: the strong base solution in the step (6) is a KOH solution.
9. each described SWCN of claim 1-3 applies the application of modified polyvinilidene fluoride film in micro-filtration, ultrafiltration and nanofiltration process.
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| CN103084074A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Hydrophilic polyvinylidene fluoride modified separation membrane and preparation method thereof |
| CN103861476A (en) * | 2012-12-18 | 2014-06-18 | 同济大学 | Preparation method of polyvinylidene fluoride (PVDF) composite mesoporous membrane |
| CN103877868A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Separation membrane preparation method and high-flux and high-strength separation membrane |
| CN104230056A (en) * | 2014-09-21 | 2014-12-24 | 北京工业大学 | Method for relieving pollution to ultrafiltration membrane under joint action of pre-oxidation and membrane modification |
| CN105107392A (en) * | 2015-08-28 | 2015-12-02 | 西南石油大学 | Multiwalled carbon nanotube surface-embedded modified polyvinylidene fluoride (PVDF) membrane and preparation method thereof |
| 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 |
| CN109569332A (en) * | 2018-12-27 | 2019-04-05 | 华南理工大学 | Hydrophobic graphite oxide composite membrane of a kind of high moisture-inhibiting height and preparation method thereof |
| CN110252155A (en) * | 2019-06-20 | 2019-09-20 | 西华大学 | A kind of pollution-resistant multi-walled carbon nano-tube 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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| CN103861476A (en) * | 2012-12-18 | 2014-06-18 | 同济大学 | Preparation method of polyvinylidene fluoride (PVDF) composite mesoporous membrane |
| CN103877868A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Separation membrane preparation method and high-flux and high-strength separation membrane |
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| CN104230056A (en) * | 2014-09-21 | 2014-12-24 | 北京工业大学 | Method for relieving pollution to ultrafiltration membrane under joint action of pre-oxidation and membrane modification |
| 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 |
| CN105107392A (en) * | 2015-08-28 | 2015-12-02 | 西南石油大学 | Multiwalled carbon nanotube surface-embedded modified polyvinylidene fluoride (PVDF) membrane and preparation method thereof |
| 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 |
| CN109569332A (en) * | 2018-12-27 | 2019-04-05 | 华南理工大学 | Hydrophobic graphite oxide composite membrane of a kind of high moisture-inhibiting height and preparation method thereof |
| CN110252155A (en) * | 2019-06-20 | 2019-09-20 | 西华大学 | A kind of pollution-resistant multi-walled carbon nano-tube 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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