CN103406032B - A kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane and preparation method thereof - Google Patents
A kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane and preparation method thereof Download PDFInfo
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- CN103406032B CN103406032B CN201310320944.2A CN201310320944A CN103406032B CN 103406032 B CN103406032 B CN 103406032B CN 201310320944 A CN201310320944 A CN 201310320944A CN 103406032 B CN103406032 B CN 103406032B
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- polyvinyl chloride
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Abstract
The present invention relates to a kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane and preparation method thereof, described blend film is made up of the polyvinyl chloride of mass ratio 1:9-9:1 and sulfonated polyether sulfone.Preparation method: the polyvinyl chloride of mass ratio 1:9-9:1 and sulfonated polyether sulfone are dissolved in solvent, under 80-85 DEG C of condition, stirring and dissolving, leave standstill, deaeration, obtains casting solution; Room temperature, ambient humidity is under the condition of 50-55%, is scraped by the casting solution of 80-85 DEG C and makes liquid film, then put into the water-bath of 10-25 DEG C, and after film separation, take out, washing, soak, natural drying, to obtain final product.The inventive method technique is simple, and cost is low, is easy to industrialization; Blend film permeability prepared by the present invention is good, and water flux is large, and intensity is high, has good antifouling property, has a good application prospect.
Description
Technical field
The invention belongs to blend film and preparation field, particularly a kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is adopted to have many documents and patent report as material of preparing.Zhao Fangbo, thank to the people such as high honour, Zhang Xiaohui and report hydrophilic polyvinyl chloride membrane and preparation method thereof (application number: CN101513593), its technology of preparing adopts polyvinyl chloride, dissolving solventless polyvinyl chloride, vinyl acetate, nano aluminium oxide, pore former and calgon or neopelex or citric acid, makes according to percentage by weight, the people such as Zhu Fangqin report a kind of PVC hollow fiber membrane and preparation method thereof (application number: CN102343222A), its technology of preparing is first synthesizing styrene-vinyl acetate-maleic list poly glycol monomethyl ether ester polymer, again by polyvinyl chloride membrane material and this mixed with polymers even, then by the mixture both this, pore-foaming agent and casting solution solvent mixed preparing casting solution, casting solution is sprayed by shower nozzle with inner gel medium at 20 DEG C of-60 DEG C of temperature simultaneously, be stop 2-10s in the air of 50%-60% in humidity, then at the uniform velocity immerse in the outer gel media coagulating bath of 20 DEG C-30 DEG C, in the outer gel media of 20 DEG C-30 DEG C, more than 8h is soaked after shaping, namely hollow-fibre membrane is obtained, Zhao Fangbo, Qiu Feng, thank to the people such as high honour and report silver-loaded nano-titanium dioxide/polrvinyl chloride membrane and preparation method thereof (application number: CN102114389A), its technology of preparing is for solvent with N-N dimethylacetylamide, calgon is dispersant, polyvinylpyrrolidone is pore former and ethanolic solution is solidification liquid, and with polyvinyl chloride and Ag-carried nanometer titanium dioxide for raw material obtains, Peng Yuelian, Liu Shuxiu, the people such as Sui Yan report Crossblend separation membrane for polyvinyl chloride in high pass quantity and preparation method thereof (application number: CN1562451), its technology of preparing is dissolved in mass percent altogether for 66-87% organic solvent by polyvinyl acetaldehyde high polymer or halogenebe-fattyene alcoholysate and polyvinyl chloride with mass ratio 1/9 ~ 9/1, the organic additive of the inorganic additive or mass percent 1-20% that add mass percent 0.01-8% again dissolves and obtains blend solution post curing, casting film-forming, coagulation bath is put into after evaporation, Crossblend separation membrane for polyvinyl chloride in high pass quantity is obtained after automatic stripping.The people such as Gao Sulian report the polyvinyl chloride/development of cellulose acetate alloy nano filtering membrane and the document of Characterization of Interfacial Properties thereof, but it just makes the filler of filled column with the blend solution of this bi-material instead of make Flat Membrane to study.And the patent of polyvinyl chloride/sulfonated polyethersulfone blending membrane has no report.
Sulfonated polyether sulfone (SPES) good hydrophilic property, have excellent heat-resisting, hydrolysis and dimensional stability, anti-fouling performance is good.And polyvinyl chloride (PVC) physicochemical stability is good, acid and alkali-resistance and biological etch, but hydrophobicity is too strong, easily by the Organic Pollution such as grease, protein.Therefore, in conjunction with advantage each other, the novel film materials of applicable sewage disposal can be developed by both are blended.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane and preparation method thereof, and the method technique is simple, and cost is low, is easy to industrialization; The blend film permeability of preparation is good, and water flux is large, and intensity is high, has good antifouling property, has a good application prospect.
A kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane of the present invention, described blend film is that the polyvinyl chloride of 1:9-9:1 and sulfonated polyether sulfone form by mass ratio.
Described blend film thickness is that under 60-340 μm, 0.18MPa pressure, pure water flux is 7.33-7254Lm
-2h
-1, hot strength is 90.8-497.1Ncm
-2.
The preparation method of a kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane of the present invention, comprising:
(1) be that the polyvinyl chloride of 1:9-9:1 and sulfonated polyether sulfone are dissolved in solvent by mass ratio, under 80-85 DEG C of condition, stirring and dissolving, leave standstill, deaeration, obtains casting solution;
(2) room temperature, ambient humidity is under the condition of 50-55%, is scraped by the casting solution of 80-85 DEG C and makes liquid film, then put into the water-bath of 10-25 DEG C, after film separation, take out, washing, soak, natural drying, obtains polyvinyl chloride and sulfonated polyether sulfone blend film.
In described step (1), the mass ratio of polyvinyl chloride and sulfonated polyether sulfone is 7:3.
In described step (1), solvent is one or more in dimethyl formamide, dimethylacetylamide, METHYLPYRROLIDONE.
In described step (1), polyvinyl chloride and sulfonated polyether sulfone gross mass percent concentration are 14%-20%.
In described step (2), casting solution flat membrane casting equipment is scraped and is made liquid film.
In described step (2), the thickness of liquid film is 60 ~ 340 μm.
In described step (2), washing is distilled water washing, soaks for soaking in the glycerine water solution of 50vol%.
Striking liquid film method: the clean temperature of scraping lamina membranacea, flat membrane casting equipment panel and casting solution is consistent, set and scrape film thickness and knifing speed, knifing speed is 3000 ~ 5000mm/min, the casting solution prepared is poured over the one end of scraping lamina membranacea, startup knifing machine is scraped and is made the liquid film that thickness is 60 ~ 340 μm.
beneficial effect
(1) present invention process is simple, and cost is low, is easy to industrialization;
(2) the blend film transparent performance prepared of the present invention is good, and water flux is high, and intensity is high, has good antifouling property, has good application prospect.
Accompanying drawing explanation
Fig. 1 is polymer content is 14wt%, and coagulation bath temperature is 25 ° of C, when casting solution temperature is 80 ° of C, and the section structure electron-microscope scanning figure of pure PVC film;
Fig. 2 is polymer content is 14wt%, and coagulation bath temperature is 25 ° of C, when casting solution temperature is 80 ° of C, and the section structure electron-microscope scanning figure of pure SPES film;
Fig. 3 is polymer content is 14wt%, and coagulation bath temperature is 25 ° of C, and when casting solution temperature is 80 ° of C, mass ratio is the section structure electron-microscope scanning figure of the PVC/SPES blend film of 9:1;
Fig. 4 is polymer content is 14wt%, and coagulation bath temperature is 25 ° of C, and when casting solution temperature is 80 ° of C, mass ratio is the section structure electron-microscope scanning figure of the PVC/SPES blend film of 8:2;
Fig. 5 is polymer content is 14wt%, and coagulation bath temperature is 25 ° of C, and when casting solution temperature is 80 ° of C, mass ratio is the section structure electron-microscope scanning figure of the PVC/SPES blend film of 7:3;
Fig. 6 is polymer content is 14wt%, and coagulation bath temperature is 25 ° of C, and when casting solution temperature is 80 ° of C, mass ratio is the section structure electron-microscope scanning figure of the PVC/SPES blend film of 6:4;
Fig. 7 is polymer content is 14wt%, and coagulation bath temperature is 25 ° of C, and when casting solution temperature is 80 ° of C, mass ratio is the section structure electron-microscope scanning figure of the PVC/SPES blend film of 5:5.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Be that to join mass concentration be in 86wt%N, N-dimethylacetylamide for 14wt% polyvinyl chloride and sulfonated polyether sulfone by total mass concentration, be placed in water-bath and stir until dissolve completely under constant temperature 80 ° of C, then leave standstill, deaeration, obtain casting solution, for subsequent use; The clean temperature of scraping lamina membranacea, flat membrane casting equipment panel and casting solution is consistent, and set and scrape film thickness and knifing speed, scraping film thickness is 0.3mm, and knifing speed is 4000mm/min.The casting solution prepared is poured over the one end of scraping lamina membranacea, start knifing machine and scrape the liquid film made thickness and be about 0.3mm, put into 25 ° of C water-bath film forming immediately, take out from water-bath after film separation, fully wash with distilled water, soak the solvent removing and remain in film, soak 24h with the glycerine water solution of 50vol% again, finally take out and naturally dry in atmosphere.
Described in said method, the mass ratio of polyvinyl chloride/sulfonated polyether sulfone is respectively 10:0,9:1,8:2,7:3,6:4,5:5,4:6,3:7,2:8,1:9,0:10, and the Flat Membrane of institute's striking measures its pure water flux under 0.18MPa pressure, pure water flux (the L ﹒ m of gained
-2﹒ h
-1) analog value is respectively 0.27,7.33,9.00,174.00,307.20,1245.60,7254.00,6400.00,411.60,240.00,101.50; Hot strength (N ﹒ cm
-2) analog value is respectively 324.35,349.61,373.17,379.11,251.91,112.76,90.80,321.02,360.60,400.29,497.10.Result shows, the mass ratio of polyvinyl chloride/sulfonated polyether sulfone is that the Flat Membrane combination property of 7:3 is best.
The mass ratio measuring polyvinyl chloride/sulfonated polyether sulfone further is respectively 10:0,9:1,8:2,7:3,6:4,5:5,4:6,3:7, the contact angle on 2:8,1:9,0:10 Flat Membrane surface, the contact angle data of gained are 72.19 °, 70.33 °, 67.57 °, 62.57 °, 62.48 °, 55.12 °, 50.02 °, 46.80 °, 45.31 °, 40.20 °, 41.2 °.Result shows, the hydrophily of blend film is than the good hydrophilic property of PVC film, and SPES adds the hydrophily improving PVC film.
Claims (5)
1. a polyvinyl chloride/sulfonated polyethersulfone blending membrane, is characterized in that: described blend film is made up of the polyvinyl chloride of mass ratio 7:3 and sulfonated polyether sulfone; Wherein said blend film thickness is that under 60-340 μm, 0.18MPa pressure, pure water flux is 174.00Lm
-2h
-1, hot strength is 379.11Ncm
-2.
2. a preparation method for polyvinyl chloride/sulfonated polyethersulfone blending membrane, comprising:
(1) polyvinyl chloride of mass ratio 7:3 and sulfonated polyether sulfone are dissolved in solvent, under 80-85 DEG C of condition, stirring and dissolving, leave standstill, deaeration, obtains casting solution; Wherein polyvinyl chloride and sulfonated polyether sulfone gross mass percent concentration are 14%;
(2) room temperature, ambient humidity is under the condition of 50-55%, is scraped by the casting solution of 80-85 DEG C and makes liquid film, then put into the water-bath of 10-25 DEG C, after film separation, take out, washing, soak, natural drying, obtains polyvinyl chloride and sulfonated polyether sulfone blend film.
3. the preparation method of a kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane according to claim 2, is characterized in that: in described step (1), solvent is one or more in dimethyl formamide, dimethylacetylamide, METHYLPYRROLIDONE.
4. the preparation method of a kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane according to claim 2, is characterized in that: in described step (2), casting solution flat membrane casting equipment is scraped and made liquid film.
5. the preparation method of a kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane according to claim 2, is characterized in that: in described step (2), washing is distilled water washing, soaks for soaking in the glycerine water solution of 50vol%.
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| CN103977718B (en) * | 2014-06-06 | 2016-03-02 | 中国科学技术大学 | Positive osmosis composite membrane of a kind of high water flux and preparation method thereof |
| CN104548973A (en) * | 2014-12-18 | 2015-04-29 | 东华大学 | Preparation and catalytic regeneration of functionalized graphene oxide/polyether sulfone blended ultrafiltration membrane |
| CN106009377A (en) * | 2016-06-17 | 2016-10-12 | 安庆市天虹新型材料科技有限公司 | Polyvinyl chloride film |
| CN107486039A (en) * | 2017-08-02 | 2017-12-19 | 同济大学 | It is a kind of suitable for modification NF membrane of industrial effluent reusing and its preparation method and application |
| CN110523304A (en) * | 2019-09-04 | 2019-12-03 | 德蓝水技术股份有限公司 | A kind of preparation method of high throughput antipollution special type tubular ultra-filtration membrane |
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| CN1765981A (en) * | 2005-11-25 | 2006-05-03 | 东华大学 | Polyvinylidene fluoride and polyethersulfone blending membrane, production method and uses |
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