CN105327624A - Preparation method of modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane - Google Patents

Preparation method of modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane Download PDF

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CN105327624A
CN105327624A CN201510856941.XA CN201510856941A CN105327624A CN 105327624 A CN105327624 A CN 105327624A CN 201510856941 A CN201510856941 A CN 201510856941A CN 105327624 A CN105327624 A CN 105327624A
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casting solution
membrane
polyvinyl alcohol
polyvinylidene fluoride
kynoar
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陈桂娥
徐孙杰
许振良
朱维纬
吴琼
孙威广
沈倩
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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Abstract

The invention relates to a preparation method of a modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane. The preparation method comprises the following steps of preparing membrane casting solution, wherein the membrane casting solution is prepared by polyvinylidene fluoride powder, polyvinyl alcohol powder, carboxylation multiwalled carbon nanotubes and dimethyl sulfoxide solvent; fully dispersing the carboxylation multiwalled carbon nanotube in the dimethyl sulfoxide solvent, then sequentially adding binary membrane materials prepared by the polyvinylidene fluoride powder and the polyvinyl alcohol powder, controlling the temperature to be 95 to 105 DEG C, mechanically stirring and dissolving, and obtaining uniform membrane casting solution; then after fully defoaming the obtained membrane casting solution at the temperature of 40 to 60 DEG C, scraping the membrane on a glass plate; immersing the glass plate with a membrane casting solution thin layer into coagulation bath with the temperature of 25 to 35 DEG C to split phases to form the membrane, taking out after soaking in deionized water for 5 to 7 days, naturally drying, and storing. According to the binary composite ultrafiltration membrane provided by the invention, the flux recovery rate can achieve 81.2 percent, and the binary composite ultrafiltration membrane has good hydrophilic and antifouling property.

Description

A kind of preparation method of polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of modification
Technical field
The invention belongs to materialogy field, relate to a kind of film, the preparation method of the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of a kind of modification specifically.
Background technology
At present, the preparation technology of macromolecule member material obtains unprecedented development, such as, and polyether sulfone (PES), polysulfones (PSF), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN) and PLA (PLA) etc.Kynoar (PVDF) has acidproof, alkaline-resisting, corrosion-resistant and excellent mechanical performance, be widely used, simultaneously, because the surface energy of PVDF material is low, hydrophobicity is polluted by force, easily, affect the service life of polyvinylidene fluoride film, therefore promote the hydrophily of polyvinylidene fluoride film by different physics, chemical modification method, thus improve the contamination resistance of film.Polyvinyl alcohol (PVA) is known by people, and its nontoxic degradable, makes it almost pollution-free to environment, and in addition, it has unique oil resistivity, wearability, solvent resistance, the performance that especially hydro carbons and film forming etc. are outstanding.In addition, along with developing rapidly of nano material, carbon nanomaterial becomes study hotspot in recent years.Carbon nanomaterial of a great variety, has his own strong points, common are Graphene, graphene oxide, CNT, carbon nanometer micro ball and their derivative products.Functionalized multi-wall carbonnanotubes has excellent thermal stability, mechanical property and dispersiveness good in macromolecular material, and its tube wall outside is containing abundant carboxyl and these hydrophilic functional groups of hydroxyl, can provide more excellent hydrophily, resistance tocrocking and mechanical performance for macromolecule member material.
Poor without the hydrophily of the polyvinylidene fluoride film of modification at present, thus cause the antifouling property of film poor.The general contact angle without the polyvinylidene fluoride film of modification is all more than 75 °.The contact angle of the pure polyvinylidene fluoride film of the preparation such as Wang Zhonghua is 79.2 °.(see ZonghuaWang, etal.NovelGO-blendedPVDFultrafiltrationmembranes [J] .Desalination, 2012,299:50-54.).And it is usual less than 50% without the flux recovery rate of the polyvinylidene fluoride film of modification.The flux recovery rate only 40% of the polyvinylidene fluoride film of the preparation such as Li Jianhua.(see Jian-HuaLi, etal.ThedoubleeffectsofsilvernanoparticlesonthePVDFmembr ane:Surfacehydrophilicityandantifoulingperformance [J] .AppliedSurfaceScience, 2013,265:663-670.).
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation method of polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of modification, the hydrophily that the preparation method of the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of described this modification solves the polyvinylidene fluoride film without modification of the prior art is poor, thus causes the technical problem of the antifouling property difference of film.
The invention provides a kind of preparation method of polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of modification, comprise the step that is prepared casting solution, described casting solution is by Kynoar powder, pva powder, functionalized multi-wall carbonnanotubes and dimethyl sulfoxide (DMSO) composition, in described casting solution, the mass percent of Kynoar powder is 13.5wt.% ~ 17.1wt.%, the mass percent of pva powder is 0.9wt.% ~ 4.5wt.%, the mass percent of functionalized multi-wall carbonnanotubes is 0.03wt.% ~ 0.15wt.%, surplus is dimethyl sulfoxide (DMSO), the mass percent of quality sum in described casting solution of described Kynoar and pva powder is 18wt.%, fully disperseed in dimethyl sulfoxide solvent by functionalized multi-wall carbonnanotubes, then add Kynoar and pva powder composition binary membrane material successively, control temperature 95 ~ 105 DEG C, mechanical agitation is dissolved, and obtains uniform casting solution, then by the casting solution of gained at 40 ~ 60 DEG C after abundant deaeration, knifing on glass plate, glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 25 ~ 35 DEG C, then water soaking took out after 5 ~ 7 days in deionization, preserved after naturally drying.
Further, described coagulation bath is the deionized water of employing 25 ~ 35 DEG C.
The invention provides a kind of method of blended high molecular weight hydrophilic polymer material and Novel Carbon Nanomaterials, blending method technological process is simple, and low for equipment requirements, preparation condition is easy to control, is easy to produce in enormous quantities simultaneously.Can prepare the milipore filter of highly-hydrophilic, antifouling property excellence by the method, its flux recovery rate can reach 81.2%.The polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of functionalized multi-wall carbonnanotubes modification of the present invention has good hydrophily and antifouling property.The advantages such as this preparation method has raw material and easily obtains, simple to operate, and film-formation result is good.
Compared with prior art, the invention has the beneficial effects as follows:
1) have employed two kinds of macromolecule member materials in the present invention, the blended composite hyperfiltration membrane preparing highly-hydrophilic, improves the hydrophobic property on pvdf membrane surface simultaneously, owing to adding functionalized multi-wall carbonnanotubes, improves the combination property of composite hyperfiltration membrane; And environmentally friendly, pollution-free, material easily obtains, and reduces cost to a great extent.
2) the present invention due in preparation process with Kynoar and polyvinyl alcohol composition binary membrane material for membrane material, dimethyl sulfoxide (DMSO) is solvent, and the binary membrane material of Kynoar and polyvinyl alcohol composition and functionalized multi-wall carbonnanotubes can be made fully to dissolve.Namely control being evenly distributed of hydrophilic functional group in binary composite membrane well, finally obtain the composite membrane that antifouling property is strong.
3) the present invention is by regulating the addition of functionalized multi-wall carbonnanotubes, can control front and the cross-section morphology of institute's film forming, thus improves pure water flux and flux recovery rate.
Accompanying drawing explanation
The composite membrane of Fig. 1 obtained by different case study on implementation carries out the result of infrared test.
The flux recovery rate situation of the composite membrane of Fig. 2 obtained by different case study on implementation.
The scanning electron microscopic picture of the composite membrane of Fig. 3 obtained by different case study on implementation.
Fig. 4 is the scanning electron microscopic picture of functionalized multi-wall carbonnanotubes.
Detailed description of the invention
The following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way.
embodiment 1
0.03wt.% functionalized multi-wall carbonnanotubes is joined in 82wt.% dimethyl sulfoxide solvent, ultrasonic disperse 10min; Then add total amount 18wt.% Kynoar and pva powder composition binary membrane material successively, control temperature 95 DEG C, mechanical agitation 12h dissolves and obtains casting solution;
Then by the casting solution of gained at 50 DEG C after abundant deaeration, knifing on a glass;
Then the glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 25 DEG C, then take out after soaking 7 days by deionized water, in air, naturally dry the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane obtaining functionalized multi-wall carbonnanotubes modification;
In the binary membrane material of Kynoar used and polyvinyl alcohol composition, the mass percent of shared casting solution pressed by Kynoar and polyvinyl alcohol, and Kynoar is 16.2wt.%, and polyvinyl alcohol is 1.8wt.%;
Described coagulation bath is pure deionized water.
Carry out the result of infrared test as Fig. 1 (B), flux recovery rate test result is as Fig. 2 (B), and the front of the composite membrane using surface sweeping electron microscopic observation to obtain and section, just looking like Fig. 3 (C), section is as Fig. 3 (D).
embodiment 2
0.06wt.% functionalized multi-wall carbonnanotubes is joined in 82wt.% dimethyl sulfoxide solvent, ultrasonic disperse 10min; Then add total amount 18wt.% Kynoar and pva powder composition binary membrane material successively, control temperature 105 DEG C, mechanical agitation 12h dissolves and obtains casting solution;
Then by the casting solution of gained at 60 DEG C after abundant deaeration, knifing on a glass;
Then the glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 30 DEG C, then take out after soaking 5 days by deionized water, in air, naturally dry the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane obtaining functionalized multi-wall carbonnanotubes modification;
In the binary membrane material of Kynoar used and polyvinyl alcohol composition, the mass percent of shared casting solution pressed by Kynoar and polyvinyl alcohol, and Kynoar is 15.3wt.%, and polyvinyl alcohol is 2.7wt.%;
Described coagulation bath is pure deionized water.
Carry out the result of infrared test as Fig. 1 (C), flux recovery rate test result is as Fig. 2 (C), and the front of the composite membrane using surface sweeping electron microscopic observation to obtain and section, just looking like Fig. 3 (E), section is as Fig. 3 (F).
embodiment 3
0.09wt.% functionalized multi-wall carbonnanotubes is joined in 82wt.% dimethyl sulfoxide solvent, ultrasonic disperse 10min; Then add total amount 18wt.% Kynoar and pva powder composition binary membrane material successively, control temperature 100 DEG C, mechanical agitation 12h dissolves and obtains casting solution;
Then by the casting solution of gained at 60 DEG C after abundant deaeration, knifing on a glass;
Then the glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 30 DEG C, then take out after soaking 5 days by deionized water, in air, naturally dry the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane obtaining functionalized multi-wall carbonnanotubes modification;
In the binary membrane material of Kynoar used and polyvinyl alcohol composition, the mass percent of shared casting solution pressed by Kynoar and polyvinyl alcohol, and Kynoar is 16.2wt.%, and polyvinyl alcohol is 1.8wt.%;
Described coagulation bath is pure deionized water.
Carry out the result of infrared test as Fig. 1 (D), flux recovery rate test result is as Fig. 2 (D), and the front of the composite membrane using surface sweeping electron microscopic observation to obtain and section, just looking like Fig. 3 (G), section is as Fig. 3 (H).
embodiment 4
0.12wt.% functionalized multi-wall carbonnanotubes is joined in 80wt.% dimethyl sulfoxide solvent, ultrasonic disperse 10min; Then add total amount 18wt.% Kynoar and pva powder composition binary membrane material successively, control temperature 100 DEG C, mechanical agitation 12h dissolves and obtains casting solution;
Then by the casting solution of gained at 45 DEG C after abundant deaeration, knifing on a glass;
Then the glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 35 DEG C, then take out after soaking 6 days by deionized water, in air, naturally dry the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane obtaining functionalized multi-wall carbonnanotubes modification;
In the binary membrane material of Kynoar used and polyvinyl alcohol composition, the mass percent of shared casting solution pressed by Kynoar and polyvinyl alcohol, and Kynoar is 13.5wt.%, and polyvinyl alcohol is 4.5wt.%;
Described coagulation bath is pure deionized water.
Carry out the result of infrared test as Fig. 1 (E), flux recovery rate test result is as Fig. 2 (E), and the front of the composite membrane using surface sweeping electron microscopic observation to obtain and section, just looking like Fig. 3 (I), section is as Fig. 3 (J).
embodiment 5
0.15wt.% functionalized multi-wall carbonnanotubes is joined in 80wt.% dimethyl sulfoxide solvent, ultrasonic disperse 10min; Then add total amount 18wt.% Kynoar and pva powder composition binary membrane material successively, control temperature 105 DEG C, mechanical agitation 12h dissolves and obtains casting solution;
Then by the casting solution of gained at 55 DEG C after abundant deaeration, knifing on a glass;
Then the glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 35 DEG C, then take out after soaking 6 days by deionized water, in air, naturally dry the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane obtaining functionalized multi-wall carbonnanotubes modification;
In the binary membrane material of Kynoar used and polyvinyl alcohol composition, the mass percent of shared casting solution pressed by Kynoar and polyvinyl alcohol, and Kynoar is 14.4wt.%, and polyvinyl alcohol is 3.6wt.%;
Described coagulation bath is pure deionized water.
Carry out the result of infrared test as Fig. 1 (F), flux recovery rate test result is as Fig. 2 (F), and the front of the composite membrane using surface sweeping electron microscopic observation to obtain and section, just looking like Fig. 3 (K), section is as Fig. 3 (L).
comparative example
A kind of polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of functionalized multi-wall carbonnanotubes modification and preparation method, it is by following preparation process: in 82wt.% dimethyl sulfoxide solvent, adding total amount 18wt.% Kynoar and pva powder composition binary membrane material successively, (namely the addition of functionalized multi-wall carbonnanotubes is (0.00wt.%) control temperature 100 DEG C, and mechanical agitation 12h dissolving obtains casting solution;
Then by the casting solution of gained at 40 DEG C after abundant deaeration, knifing on a glass; Then the glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 25 DEG C, then take out after soaking 7 days by deionized water, in air, naturally dry the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane obtaining functionalized multi-wall carbonnanotubes modification;
In the binary membrane material of Kynoar used and polyvinyl alcohol composition, the mass percent of shared casting solution pressed by Kynoar and polyvinyl alcohol, and Kynoar is 17.1wt.%, and polyvinyl alcohol is 0.9wt.%;
Described coagulation bath is pure deionized water.
Carry out the result of infrared test as Fig. 1 (A), flux recovery rate test result is as Fig. 2 (B), and the front of the composite membrane using surface sweeping electron microscopic observation to obtain and section, just looking like Fig. 3 (A), section is as Fig. 3 (B).
As can be seen from above-mentioned experiment, the effect that embodiment 3 obtains is best, illustrates that the mass ratio of Kynoar and polyvinyl alcohol in binary membrane material and the addition of functionalized multi-wall carbonnanotubes are for optimum.Meanwhile, operating condition optimum selected in embodiment 3, thus make the composite membrane front of formation and the structure of section reach optimum, the surface hydrophilicity of composite membrane is significantly improved, and flux recovery rate reaches maximum.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.

Claims (2)

1. the preparation method of the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of a modification, it is characterized in that: comprise the step that is prepared casting solution, described casting solution is by Kynoar powder, pva powder, functionalized multi-wall carbonnanotubes and dimethyl sulfoxide (DMSO) composition, in described casting solution, the mass percent of Kynoar powder is 13.5wt.% ~ 17.1wt.%, the mass percent of pva powder is 0.9wt.% ~ 4.5wt.%, the mass percent of functionalized multi-wall carbonnanotubes is 0.03wt.% ~ 0.15wt.%, surplus is dimethyl sulfoxide (DMSO), the mass percent of quality sum in described casting solution of described Kynoar and pva powder is 18wt.%, fully disperseed in dimethyl sulfoxide solvent by functionalized multi-wall carbonnanotubes, then add Kynoar and pva powder composition binary membrane material successively, control temperature 95 ~ 105 DEG C, mechanical agitation is dissolved, and obtains uniform casting solution, then by the casting solution of gained at 40 ~ 60 DEG C after abundant deaeration, knifing on glass plate, glass plate with casting solution thin layer is immersed phase-splitting film forming in the coagulation bath of 25 ~ 35 DEG C, then water soaking took out after 5 ~ 7 days in deionization, preserved after naturally drying.
2. the preparation method of the polyvinylidene fluoride-polyvinyl alcohol binary composite hyperfiltration membrane of a kind of modification according to claim 1, is characterized in that: described coagulation bath is the deionized water of employing 25 ~ 35 DEG C.
CN201510856941.XA 2015-11-30 2015-11-30 Preparation method of modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane Pending CN105327624A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113083031A (en) * 2021-04-27 2021-07-09 贵州省材料产业技术研究院 Electrically neutral polyvinylidene fluoride ultrafiltration membrane and preparation method thereof
CN114773753A (en) * 2022-04-29 2022-07-22 华南理工大学 Polyether-ether-ketone-polyvinylidene fluoride composite membrane and preparation method and application thereof

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CN103785304A (en) * 2014-01-15 2014-05-14 天津工业大学 Hydrophilic grafted multiwalled carbon nanotube modified polyvinylidene fluoride film and preparation method thereof
CN103785305A (en) * 2014-01-15 2014-05-14 天津工业大学 Multi-walled composite conductive carbon nanotube-polyvinylidene fluoride ultrafiltration membrane and preparation method thereof

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WO2002038256A1 (en) * 2000-11-13 2002-05-16 Usf Filtration And Separations Group Inc. Modified membranes
CN101147848A (en) * 2007-07-20 2008-03-26 天津工业大学 Polyvinylidene fluoride film hydrophilically modified method
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
CN103464004A (en) * 2013-06-21 2013-12-25 浙江海洋学院 High strength nanometer modified ultrafilter membrane and preparation method thereof
CN103785304A (en) * 2014-01-15 2014-05-14 天津工业大学 Hydrophilic grafted multiwalled carbon nanotube modified polyvinylidene fluoride film and preparation method thereof
CN103785305A (en) * 2014-01-15 2014-05-14 天津工业大学 Multi-walled composite conductive carbon nanotube-polyvinylidene fluoride ultrafiltration membrane and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113083031A (en) * 2021-04-27 2021-07-09 贵州省材料产业技术研究院 Electrically neutral polyvinylidene fluoride ultrafiltration membrane and preparation method thereof
CN114773753A (en) * 2022-04-29 2022-07-22 华南理工大学 Polyether-ether-ketone-polyvinylidene fluoride composite membrane and preparation method and application thereof
CN114773753B (en) * 2022-04-29 2023-05-02 华南理工大学 Polyether-ether-ketone-polyvinylidene fluoride composite membrane and preparation method and application thereof

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