CN101745324A - Preparation method of dry high-hydrophilic polyvinylidene fluoride hollow fibrous membrane - Google Patents
Preparation method of dry high-hydrophilic polyvinylidene fluoride hollow fibrous membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a dry high-hydrophilic polyvinylidene fluoride hollow fibrous membrane, comprising the following steps: 1) heating and stirring polyvinylidene fluoride resin, solvent and additive to prepare casting solution, and preparing coating solution by an amphiphilic polymer, polyvinylidene fluoride and solvent; 2) extruding the casting solution, the coating solution and core liquid out to form hollow cellosilk by a three-layer bushing spinning nozzle; 3) dipping a solvent gel bath into the hollow cellosilk by air evaporation to be exchanged into an original membrane; 4) dipping the original membrane into a first hydrophilic bath and a second hydrophilic bath for hydrophilization; and finally drying naturally membrane silk to prepare polyvinylidene fluoride hollow fibrous membrane supported by a high-hydrophilic filtering layer and a spongy structure. The three-layer bushing spinning nozzle adopted by the invention has the advantages of self design, novel structure, simple and feasible membrane manufacturing process and easily controlled technical flow; and the prepared membrane product can be stored in a dry state and has large flux, high retention rate and strong pollution-resistant and pressure-resistant performance.
Description
Technical field
The present invention relates to the preparation method of film, relate in particular to a kind of preparation method of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane.
Background technology
Kynoar (PVDF) has excellent chemical stability, heat endurance and anti-radiation property, and strong oxidizer such as acid and alkali, alkali and halogen corrosion has at room temperature become main micro-filtration and milipore filter material.Polyvinylidene fluoride porous film is as long as be separated and be separated two kinds of methods preparation of calorific value by solution.Chinese patent CN1203119 discloses wet method or has done-wet method spinning Kynoar doughnut perforated membrane, and its nominal pore size is 0.1-1.0 μ m, and the pure water permeation flux reaches 300-1000L/m
2.h. (0.1MPa).Chinese patent CN1583232 discloses the method for making of immersing gel method spinning external-compression type Kynoar hollow fiber ultrafiltration membrane, casting solution is extruded into hollow fiber by two sleeve pipe spinning heads, carry out two-stage phase-separating coagulations then, rinsing makes the external-compression type hollow-fibre membrane of two cortexes, complete spongy supporting layer.The company of Asahi Chemical Industry of Japan discloses a kind of method of utilizing thermally induced phase separation to prepare polyvinylidene fluoride porous film in the U.S. Patent No. 5022990 of U. S. application, this method comprises polyvinylidene fluoride resin and organic liquid and inorganic granular mixing, and then the blend of gained melt extruded into hollow fiber, tubulose or flat film, at last organic liquid and inorganic pellet are extracted.Subsequently, the Chinese patent CN1265048 of Asahi Chemical Industry application improved that above-mentioned United States Patent (USP) makes that the film internal diameter is less, resistance to pressure difference and the not high shortcoming of flux.
At present, commercial Kynoar hollow fiber ultrafiltration membrane major part all is a hydrophobic membrane, and hydrophobic membrane needs often to carry out physics and Chemical cleaning in running, increases the cost of operation; Oily matter forms dirty stifledly easily in the long-term use on the film surface, causes film seriously polluted in the relatively poor MBR system of water quality especially, and membrane flux reduces sharply, and can not recover, and has shortened the service life of film.The second, the polyvinylidene fluoride (PVDF) ultrafiltration membrane dry state that solwution method prepares keeps problem.The exodermis of milipore filter is a dense layer surface, the contraction of subsiding of film a large amount of cortex micropore in dry run, film is immersed in water or the ethanolic solution, these micropores that shrink that subside can't recover, the flux of film is acutely descended, little molecule, higher boiling alcohols aqueous solution soaking Kynoar hollow fiber ultrafiltration membrane such as general industrial employing glycerine, the film silk is in dry run, glycerine occupies the cortex micropore, prevents the contraction of subsiding of a large amount of micropores.Though solved the polyvinylidene fluoride (PVDF) ultrafiltration membrane cortex micropore contraction problem of subsiding; but the film silk contains a large amount of glycerine; the water quality (high COD) of water outlet is filtered in influence, needs before therefore need dispatching from the factory to pour into sodium hydrogensulfite protection liquid then with clorox rinsing glycerine.Like this, increased the transport difficulty of polyvinylidene fluoride (PVDF) ultrafiltration membrane assembly and raise the cost, also had under the low temperature environment, the freezing assembly and the film silk of causing of protection liquid damages.The 3rd, the microstructure of polyvinylidene fluoride (PVDF) ultrafiltration membrane is based on two cortex finger-like pore structures, because the existence of big finger-like pore causes film silk crushing resistance poor, in a single day the use mediopellis breaks, and contaminant deposition causes the film silk to be scrapped easily, influences the water quality of water outlet.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane is provided.
The preparation method of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane comprises the steps:
1) be that 16～22% polyvinylidene fluoride resin, percentage by weight are that 56～65% solvent, percentage by weight are that 15～22% additive adds in the casting solution reactor with percentage by weight, stirred 12～24 hours at 60～90 ℃, filtration, vacuum defoamation obtained casting solution in 12～36 hours, and the number-average molecular weight of polyvinylidene fluoride resin is 1 * 10
5～1.0 * 10
6
2) be that 2～6% amphipathic copolymer hydrophilic modifying agent methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymers, percentage by weight are that 12～20% polyvinylidene fluoride resins, percentage by weight are that 56～75% solvents and percentage by weight are that 10～18% additives add in the coating liquid reactor with percentage by weight, stirred 12～16 hours at 60～80 ℃, filtration, vacuum defoamation obtained coating liquid in 12～36 hours, and the Kynoar number-average molecular weight is 1 * 10
5～6.0 * 10
5
3) be that 65～90 ℃ casting solution and coating liquid and temperature are that 15～40 ℃ core liquid carries out coextrusion by three layers of bushing type spinning head with temperature, cool off through 2～14cm air, the coagulation bath exchange system that immerses 20～40 ℃ gets former film, the composition of coagulating bath wherein: percentage by weight is 15～50% dimethylacetylamide, and percentage by weight is 50～85% water;
4) former film being immersed temperature earlier is that the second hydrophilic bath 2～3 minutes is immersed in 20～60 ℃ of first hydrophilic bath again after 1～2 minute, make the agent of amphipathic copolymer hydrophilic modifying form hydrogel layer, again the film silk is dried naturally, make the dry high-hydrophilic polyvinylidene fluoride hollow fiber ultrafiltration membrane at last.
Described solvent is one or both in dimethylacetylamide, dimethyl formamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), trimethyl phosphate or the triethyl phosphate.Consisting of of described core liquid: percentage by weight is 25～60% dimethylacetylamide, percentage by weight is 10～25% alcohols, percentage by weight is 25～50% water, and wherein alcohols is a kind of in ethanol, ethylene glycol, glycerine, isopropyl alcohol or the n-butanol.The first hydrophilic bath percentage by weight is 10～30% ethanol, and the water of the dimethylacetylamide of percentage by weight 5～20% and percentage by weight 50～70% is formed.Be weight percentage methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymer solution, 20～40% ethanol of percentage by weight and 40～70% water of percentage by weight of 5～20% of the second hydrophilic bath.
Three layers of self-service design of sleeve pipe spinning head, novel structure that the present invention is used, adopt the preparation of three grades of precipitate gel and hydrophilic technology to have the Kynoar hollow fiber ultrafiltration membrane (see figure 2) of strongly hydrophilic filter course and spongelike structure support, the product that makes can dry state be deposited, its film stretching＞300g, porosity is 70-80%, average pore size 0.01-0.06 μ m, dry film pure water flux are 310-600L/m
2.H (0.1MPa, 25 ℃).
Description of drawings
Fig. 1 is three layers of sleeve pipe spinning head schematic diagram of the present invention;
Fig. 2 is the electromicroscopic photograph in Hollow Fiber Ultrafiltration localized membrane of the present invention cross section;
Fig. 3 is the electromicroscopic photograph of hollow fiber ultrafiltration membrane outer surface of the present invention;
Fig. 4 is the electromicroscopic photograph of the local outer surface of hollow fiber ultrafiltration membrane of the present invention;
Fig. 5 is the electromicroscopic photograph of hollow fiber ultrafiltration membrane inner surface of the present invention.
The specific embodiment
Embodiment 1: with polyvinylidene fluoride resin (the Belgian Su Wei SolvaySolexis of company 6020 of percentage by weight 18%, weight average molecular weight 750000), percentage by weight is that 30% dimethylacetylamide (Kingsoft, Shanghai longitude and latitude chemical industry Co., Ltd) and percentage by weight are 30% triethyl phosphate (Jiangsu normal surplus chemical industry Co., Ltd), percentage by weight 9% (Henan universal love newly increase income K-30), polyethylene glycol of percentage by weight 12% (Hangzhou converge general chemical industry Instr Ltd. molecular weight 600) and percentage by weight 1% Tween-80 (Aladdin reagent company) add in the reactor 90 ℃ of stirrings of heating and make casting solution.With percentage by weight is 5% methyl methacrylate-amphipathic copolymer of monomethyl ether polyethylene glycol oxide methyl methacrylate, polyvinylidene fluoride resin (the Belgian Su Wei Solvay Solexis of company 1015, weight average molecular weight 400000) be 16%, percentage by weight is 53% dimethylacetylamide and 10% triethyl phosphate, and percentage by weight is that the polyvinylpyrrolidone of 10% polyethylene glycol (Hangzhou converge general chemical industry Instr Ltd. molecular weight 200) and 6% joins in other 85 ℃ of reactors dissolving and stirs and make coating liquid.By three layers of bushing type spinning head (see figure 1) casting solution, coating liquid and core liquid together are extruded into hollow fibre filament at 85 ℃.Core liquid is 45% (percentage by weight) solvent, and 15% alcohols and 40% water are formed.The hollow fibre filament of extruding immerses in the coagulation bath that solvent strength is 40% (percentage by weight) through the evaporation of 4cm air section and is exchanged into former film, and the coagulation bath temperature is 25 ℃.Former film immerses 20% (percentage by weight) ethanol, 10% dimethylacetylamide, and the first hydrophilic bath that 70% water is formed, further precipitate gel and preliminary hydrophiling, hydrophilic bath temperature is 50 ℃.At last, immerse 8% (percentage by weight) methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymer, the second hydrophilic bath of 35% ethanol and 57% water makes the film highly-hydrophilicization, hydrophilic bath temperature is 40 ℃, the film silk is dried naturally, making the film external diameter is 1.4mm, internal diameter 0.75mm again, stretching 320g, porosity is 80%, average pore size 0.04 μ m, and the dry film pure water flux is 550L/m
2.H (0.1MPa, 25 ℃).
Embodiment 2: step such as embodiment 1, polyvinylidene fluoride resin in the casting solution is changed into the HSV900 model of French Arkema (Arkema), weight average molecular weight 1000000, making the film external diameter is 1.4mm, internal diameter 0.75mm, stretching 340g, porosity is 76%, average pore size 0.03 μ m, the dry film pure water flux is 450L/m
2.H (0.1MPa, 25 ℃).
Embodiment 3: step such as embodiment 1, polyvinylidene fluoride resin percentage by weight in the casting solution is brought up to 22%, and the percentage by weight of triethyl phosphate is reduced to 26%, making the film external diameter is 1.4mm, internal diameter 0.75mm, stretching 367g, porosity is 73%, average pore size 0.01 μ m, the dry film pure water flux is 310L/m
2.H (0.1MPa, 25 ℃).
Embodiment 4: with polyvinylidene fluoride resin (the Belgian Su Wei SolvaySolexis of company 6020 of percentage by weight 16%, weight average molecular weight 750000), percentage by weight is that 30% dimethylacetylamide and percentage by weight are 33% triethyl phosphate, percentage by weight 7% (Henan universal love newly increase income K-30), polyethylene glycol of percentage by weight 13% (molecular weight 600) and percentage by weight 1% Tween-80 add in the reactor 90 ℃ of stirrings of heating and make casting solution.With percentage by weight is 5% methyl methacrylate-amphipathic copolymer of monomethyl ether polyethylene glycol oxide methyl methacrylate, polyvinylidene fluoride resin (the HSV900 model of French Arkema (Arkema), weight average molecular weight 1000000) be 12%, percentage by weight is 53% dimethylacetylamide and 12% triethyl phosphate, and percentage by weight is that the polyvinylpyrrolidone of 10% polyethylene glycol (molecular weight 200) and 8% joins in other 85 ℃ of reactors dissolving and stirs and make coating liquid.By three layers of bushing type spinning head casting solution, coating liquid and core liquid together are extruded into hollow fibre filament at 85 ℃.Core liquid is 40% (percentage by weight) solvent, and 15% alcohols and 45% water are formed.The hollow fibre filament of extruding immerses in the coagulation bath that solvent strength is 30% (percentage by weight) through the evaporation of 6cm air section and is exchanged into former film, and the coagulation bath temperature is 25 ℃.Former film immerses 20% (percentage by weight) ethanol, 10% dimethylacetylamide, and the first hydrophilic bath that 70% water is formed, further precipitate gel and preliminary hydrophiling, hydrophilic bath temperature is 50 ℃.At last, immerse 12% (percentage by weight) methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymer, the second hydrophilic bath of 35% ethanol and 53% water makes the film highly-hydrophilicization, hydrophilic bath temperature is 60 ℃, the film silk is dried naturally, making the film external diameter is 1.4mm, internal diameter 0.75mm again, stretching 290g, porosity is 81%, average pore size 0.06 μ m, and the dry film pure water flux is 600L/m
2.H (0.1MPa, 25 ℃).
Embodiment 5: with polyvinylidene fluoride resin (the Belgian Su Wei SolvaySolexis of company 6020 of percentage by weight 18%, weight average molecular weight 750000), percentage by weight is that 30% dimethyl formamide (Korea S's Samsung fine chemistry industry) and percentage by weight are 33% triethyl phosphate, and the polyethylene glycol of percentage by weight 8% and percentage by weight 11% (molecular weight 600) adds in the reactor 90 ℃ of stirrings of heating and makes casting solution.With percentage by weight is 6% methyl methacrylate-amphipathic copolymer of monomethyl ether polyethylene glycol oxide methyl methacrylate, polyvinylidene fluoride resin (the HSV900 model of French Arkema (Arkema), weight average molecular weight 1000000) be 14%, percentage by weight is 51% dimethyl formamide and 12% triethyl phosphate, and percentage by weight is that the polyvinylpyrrolidone of 10% polyethylene glycol (molecular weight 200) and 7% joins in other 85 ℃ of reactors dissolving and stirs and make coating liquid.By three layers of bushing type spinning head casting solution, coating liquid and core liquid together are extruded into hollow fibre filament at 85 ℃.Core liquid is 40% (percentage by weight) solvent, and 15% alcohols and 45% water are formed.The hollow fibre filament of extruding immerses in the coagulation bath that solvent strength is 30% (percentage by weight) through the evaporation of 6cm air section and is exchanged into former film, and the coagulation bath temperature is 35 ℃.Former film immerses 20% (percentage by weight) ethanol, 10% dimethylacetylamide, and the first hydrophilic bath that 70% water is formed, further precipitate gel and preliminary hydrophiling, hydrophilic bath temperature is 50 ℃.At last, immerse 14% (percentage by weight) methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymer, the second hydrophilic bath of 35% ethanol and 51% water makes the film highly-hydrophilicization, hydrophilic bath temperature is 50 ℃, the film silk is dried naturally, making the film external diameter is 1.4mm, internal diameter 0.75mm again, stretching 320g, porosity is 78%, average pore size 0.05 μ m, and the dry film pure water flux is 540L/m
2.H (0.1 MPa, 25 ℃).
Embodiment 6: step such as embodiment 5, polyvinylidene fluoride resin percentage by weight in the coating liquid is brought up to 20%, to make the film external diameter be 1.4mm and the percentage by weight of dimethyl formamide is reduced to 45%, internal diameter 0.75mm, stretching 335g, porosity is 76%, average pore size 0.03 μ m, and the dry film pure water flux is 370L/m
2.H (0.1MPa, 25 ℃).
Embodiment 7: step such as embodiment 5, dimethyl formamide in the casting solution is changed into N-methyl pyrrolidone (Hangzhou converge general chemical industry Instr Ltd.), and making the film external diameter is 1.4mm, internal diameter 0.75mm, stretching 310g, porosity is 82%, average pore size 0.05 μ m, the dry film pure water flux is 580L/m
2.H (0.1MPa, 25 ℃).
Embodiment 8: with polyvinylidene fluoride resin (the Belgian Su Wei SolvaySolexis of company 1015 of percentage by weight 18%, weight average molecular weight 400000), percentage by weight is that 25% dimethylacetylamide and percentage by weight are 35% triethyl phosphate, percentage by weight 8%, casting solution is made in 90 ℃ of stirrings of heating in polyethylene glycol of percentage by weight 13% (molecular weight 600) and the percentage by weight 1% Tween-80 adding reactor.With percentage by weight is 8% methyl methacrylate-amphipathic copolymer of monomethyl ether polyethylene glycol oxide methyl methacrylate, polyvinylidene fluoride resin (the Belgian Su Wei Solvay Solexis of company 1015, weight average molecular weight 400000) be 14%, percentage by weight is 52% dimethylacetylamide and 10% triethyl phosphate, and percentage by weight is that the polyvinylpyrrolidone of 8% polyethylene glycol (molecular weight 200) and 8% joins in other 85 ℃ of reactors dissolving and stirs and make coating liquid.By three layers of bushing type spinning head casting solution, coating liquid and core liquid together are extruded into hollow fibre filament at 85 ℃.Core liquid is 45% (percentage by weight) solvent, and 15% alcohols and 40% water are formed.The hollow fibre filament of extruding immerses in the coagulation bath that solvent strength is 40% (percentage by weight) through the evaporation of 4cm air section and is exchanged into former film, and the coagulation bath temperature is 40 ℃.Former film immerses 20% (percentage by weight) ethanol, 10% dimethylacetylamide, and the first hydrophilic bath that 70% water is formed, further precipitate gel and preliminary hydrophiling, hydrophilic bath temperature is 50 ℃.At last, immerse 10% (percentage by weight) methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymer, the second hydrophilic bath of 35% ethanol and 55% water makes the film highly-hydrophilicization, hydrophilic bath temperature is 40 ℃, the film silk is dried naturally, making the film external diameter is 1.4mm, internal diameter 0.75mm again, stretching 300g, porosity is 78%, average pore size 0.05 μ m, and the dry film pure water flux is 600L/m
2.H (0.1MPa, 25 ℃).
Embodiment 9: with polyvinylidene fluoride resin (the Belgian Su Wei SolvaySolexis of company 1015 of percentage by weight 19.5%, weight average molecular weight 400000), percentage by weight is that 20% dimethylacetylamide and percentage by weight are 40% triethyl phosphate, percentage by weight 9.5%, casting solution is made in 90 ℃ of stirrings of heating in polyethylene glycol of percentage by weight 12% (molecular weight 200) and the percentage by weight 1% Tween-80 adding reactor.With percentage by weight is 6% methyl methacrylate-amphipathic copolymer of monomethyl ether polyethylene glycol oxide methyl methacrylate, polyvinylidene fluoride resin (the Belgian Su Wei Solvay Solexis of company 1015, weight average molecular weight 400000) be 17%, percentage by weight is 55% dimethylacetylamide and 6% triethyl phosphate, and percentage by weight is that the polyvinylpyrrolidone of 10% polyethylene glycol (molecular weight 200) and 6% joins in other 85 ℃ of reactors dissolving and stirs and make coating liquid.By three layers of bushing type spinning head casting solution, coating liquid and core liquid together are extruded into hollow fibre filament at 85 ℃.Core liquid is 30% (percentage by weight) solvent, and 15% alcohols and 55% water are formed.The hollow fibre filament of extruding immerses in the coagulation bath that dimethylacetylamide concentration is 40% (percentage by weight) through the evaporation of 4cm air section and is exchanged into former film, and the coagulation bath temperature is 20 ℃.Former film immerses 20% (percentage by weight) ethanol, 10% dimethylacetylamide, and the first hydrophilic bath that 70% water is formed, further precipitate gel and preliminary hydrophiling, hydrophilic bath temperature is 50 ℃.At last, immerse 10% (percentage by weight) methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymer, the second hydrophilic bath of 40% ethanol and 50% water makes the film highly-hydrophilicization, hydrophilic bath temperature is 40 ℃, the film silk is dried naturally, making the film external diameter is 1.4mm, internal diameter 0.75mm again, stretching 300g, porosity is 75%, average pore size 0.01 μ m, and the dry film pure water flux is 350L/m
2.H (0.1 MPa, 25 ℃).
Claims (8)
1. the preparation method of a dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane is characterized in that comprising the steps:
1) be that 16～22% polyvinylidene fluoride resin, percentage by weight are that 56～65% solvent, percentage by weight are that 15～22% additive adds in the casting solution reactor with percentage by weight, stirred 12～24 hours at 60～90 ℃, filtration, vacuum defoamation obtained casting solution in 12～36 hours, and the number-average molecular weight of polyvinylidene fluoride resin is 1 * 10
5～1.0 * 10
6
2) be that 2～6% amphipathic copolymer hydrophilic modifying agent methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymers, percentage by weight are that 12～20% polyvinylidene fluoride resins, percentage by weight are that 56～75% solvents and percentage by weight are that 10～18% additives add in the coating liquid reactor with percentage by weight, stirred 12～16 hours at 60～80 ℃, filtration, vacuum defoamation obtained coating liquid in 12～36 hours, and the Kynoar number-average molecular weight is 1 * 10
5～1.0 * 10
6
3) be that 65～90 ℃ casting solution and coating liquid and temperature are that 15～40 ℃ core liquid carries out coextrusion by three layers of bushing type spinning head with temperature, through the cooling of 2～14cm air, the coagulation bath exchange system that immerses 20～40 ℃ gets former film;
4) former film being immersed temperature earlier is that the second hydrophilic bath 2～3 minutes is immersed in 20～60 ℃ of first hydrophilic bath again after 1～2 minute, make the agent of amphipathic copolymer hydrophilic modifying form hydrogel layer, again the film silk is dried naturally, make the dry high-hydrophilic polyvinylidene fluoride hollow fiber ultrafiltration membrane at last.
2. the preparation method of a kind of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane according to claim 1, it is characterized in that consisting of of described core liquid: percentage by weight is 25～60% dimethylacetylamide, percentage by weight is 10～25% alcohols, and percentage by weight is 25～50% water.
3. the preparation method of a kind of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane according to claim 1, it is characterized in that the composition of described coagulating bath: percentage by weight is 15～50% dimethylacetylamide, and percentage by weight is 50～85% water.
4. the preparation method of a kind of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane according to claim 1, it is characterized in that the described first hydrophilic bath percentage by weight is 10～30% ethanol, the water of the dimethylacetylamide of percentage by weight 5～20% and percentage by weight 50～70% is formed.
5. the preparation method of a kind of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane according to claim 1, it is characterized in that be weight percentage methyl methacrylate-monomethyl ether polyethylene glycol oxide methylmethacrylate copolymer solution, 20～40% ethanol of percentage by weight and 40～70% water of percentage by weight of 5～20% of the described second hydrophilic bath.
6. the preparation method of a kind of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane according to claim 1 is characterized in that described solvent is one or both in dimethylacetylamide, dimethyl formamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), trimethyl phosphate or the triethyl phosphate.
7. according to the preparation method of the described a kind of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane of claim 1, it is characterized in that described additive is in polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol or the Tween-80 type emulsifying agent two or three.
8. the preparation method of a kind of dry high-hydrophilic polyvinylidene fluoride hollow-fibre membrane according to claim 2 is characterized in that described alcohols is ethanol, ethylene glycol, glycerine, isopropyl alcohol or n-butanol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509804A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Method for preparing composite hollow fibre membrane |
| CN1583232A (en) * | 2003-08-06 | 2005-02-23 | 浙江欧美环境工程有限公司 | Manufacture and products of hollow fiber membrane of outer pressured polyvinylidene fluoride by immersion gelation |
| WO2007119913A1 (en) * | 2006-03-16 | 2007-10-25 | Sk Chemicals Co., Ltd. | Hollow fiber membrane and preparing method thereof |
| CN101190401A (en) * | 2007-06-13 | 2008-06-04 | 海南立昇净水科技实业有限公司 | Hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof |
-
2009
- 2009-12-10 CN CN200910155288.9A patent/CN101745324B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509804A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Method for preparing composite hollow fibre membrane |
| CN1583232A (en) * | 2003-08-06 | 2005-02-23 | 浙江欧美环境工程有限公司 | Manufacture and products of hollow fiber membrane of outer pressured polyvinylidene fluoride by immersion gelation |
| WO2007119913A1 (en) * | 2006-03-16 | 2007-10-25 | Sk Chemicals Co., Ltd. | Hollow fiber membrane and preparing method thereof |
| CN101190401A (en) * | 2007-06-13 | 2008-06-04 | 海南立昇净水科技实业有限公司 | Hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102366714B (en) * | 2011-10-21 | 2013-08-21 | 湖州森蓝环境工程有限公司 | Preparation method for hollow fiber microporous membrane with small aperture and high flux and product thereof |
| CN102366714A (en) * | 2011-10-21 | 2012-03-07 | 湖州森蓝环境工程有限公司 | Preparation method for hollow fiber microporous membrane with small aperture and high flux and product thereof |
| CN104069744A (en) * | 2014-07-21 | 2014-10-01 | 云南城投碧水源水务科技有限责任公司 | Reinforced hollow fiber membrane with hydrophilic cellular structure, as well as preparation method and production device of reinforced hollow fiber membrane |
| CN104069744B (en) * | 2014-07-21 | 2016-01-27 | 云南城投碧水源水务科技有限责任公司 | There is the enhancement type hollow fiber film of hydrophily honeycomb, its preparation method and process units |
| CN107635651A (en) * | 2015-06-03 | 2018-01-26 | 乐天化学株式会社 | Doughnut film manufacturing method and hollow-fibre membrane |
| CN109012239A (en) * | 2018-07-05 | 2018-12-18 | 绍兴齐英膜科技有限公司 | A kind of Organic inorganic film and preparation method thereof |
| CN109012239B (en) * | 2018-07-05 | 2020-12-22 | 绍兴齐英膜科技有限公司 | Organic-inorganic composite membrane and preparation method thereof |
| CN111530286B (en) * | 2020-04-28 | 2022-02-11 | 南京工业大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN111530286A (en) * | 2020-04-28 | 2020-08-14 | 南京工业大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN113828162A (en) * | 2020-06-23 | 2021-12-24 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN113828162B (en) * | 2020-06-23 | 2022-12-20 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN112370977A (en) * | 2020-11-24 | 2021-02-19 | 苏州富淼膜科技有限公司 | Treatment method of dry polyvinylidene fluoride hollow fiber ultrafiltration membrane |
| CN112370977B (en) * | 2020-11-24 | 2023-08-04 | 苏州富淼膜科技有限公司 | Treatment method of dry polyvinylidene fluoride hollow fiber ultrafiltration membrane |
| CN113877441A (en) * | 2021-11-12 | 2022-01-04 | 江苏巨之澜科技有限公司 | Composite hollow fiber braided tube filter membrane for fuel cell and preparation method and application thereof |
| CN113877441B (en) * | 2021-11-12 | 2024-02-23 | 江苏巨之澜科技有限公司 | Composite hollow fiber woven tube filter membrane for fuel cell and preparation method and application thereof |
| CN114870643A (en) * | 2022-04-27 | 2022-08-09 | 中科南京绿色制造产业创新研究院 | Polymer hollow fiber membrane and preparation method and application thereof |
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