CN100400144C - Production of liquid separating film - Google Patents
Production of liquid separating film Download PDFInfo
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- CN100400144C CN100400144C CNB2005100617125A CN200510061712A CN100400144C CN 100400144 C CN100400144 C CN 100400144C CN B2005100617125 A CNB2005100617125 A CN B2005100617125A CN 200510061712 A CN200510061712 A CN 200510061712A CN 100400144 C CN100400144 C CN 100400144C
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Abstract
The present invention discloses a preparation process of a liquid separating film, which comprises the steps of preparing filming liquid from aromatic high molecular polymer with sulfonyl (for example, polyethersulfone, polysulfone, etc.) on a main chain and the corresponding organic solvent and organic acid additive (for example, acetic acid, propionic acid, oxalic acid, citric acid, etc.); coating the film on non-woven polyester cloth by using a casting method; evaporating in air for a long time, and then immersing the film in the aqueous solution of salt with certain concentration (gel bath). The present invention has the advantages that in the process that the immersing gel converts to the film, the film casting liquid and the gel bath generate migration, diffusion and exchange of matter, and simultaneously, acid matter in the film casting liquid and alkali matter in the gel bath generate chemical reaction. Compared with the classic immersing phase conversion method for making the film, the preparation process of the present invention can regulate an asymmetric film structure in a certain degree as required, and thereby, the performance of the film is largely optimized.
Description
Technical field
The invention belongs to a kind of membrane separation technique field, refer in particular to a kind of preparation method of liquid separating film.
Background technology
Immersing gel phase conversion film-forming method is a kind of fluid separation applications membrane preparation method of classics.Though the industrialization of this film-forming method, and fields such as separation, purifying and enrichment have been widely used in by its prepared milipore filter, micro-filtration membrane.Shinde etc. are solvent with DMF, respectively with LiCl, ZnCl transforming in the process for preparing polyacrylonitrile ultrafiltration film by immersing gel phase
2, AlCl
3Deng being additive, utilize Li
+, Zn
2+, Al
3+Etc. the cation of different valence state the difference that influences, studied of the influence of the cationic additive of different valence state to gel process and film properties to compatibility between PAN and the DMF; B.Jung etc. are by after immersing gel phase and transforming the preparation polyacrylonitrile ultrafiltration film, and the hot water of the gained milipore filter being put into 80 ℃ soaks certain hour, improves the performance of film by heat treatment; And D.B.Mosqueda and J.menez etc. introduce film forming procedure with solvent evaporation and heat treatment etc. in by the process of immersing gel phase conversion method development poly (ether-sulfone) ultrafiltration membrane.The preparation of all these diffusion barriers has all obtained certain separating effect, but regrettably, it is narrow often can not to obtain pore-size distribution simultaneously by this method system film, the high diffusion barrier with comprehensive superperformance of flux.Lot of domestic and international research institution and enterprise do a lot of work aspect improved in that these classics preparation method is carried out in succession.
Summary of the invention
The present invention is directed to deficiency of the prior art, propose a kind of pore-size distribution that can effectively control diffusion barrier, improve the liquid film preparation method of the transit dose of water.
The present invention is accomplished by following technical proposals:
A kind of preparation method of liquid separating film specifically follows these steps to carry out:
(1) the aromatic polymer polymer that contains sulfuryl on the main chain is dissolved in the organic solvent between 0～80 ℃, and to be aided with certain organic acid is that nonsolvent additive is mixed with casting solution, is prepared into polymer concentration and is 8～30% casting solution;
(2) constant humidity in 40%～80%, constant temperature in 20～45 ℃ environment with even speed with casting solution equably curtain coating to polyester non-woven fabric, form the liquid film of 50～500 micron thickness;
(3) nonwoven that is coated with casting solution was positioned in the environment of 20～45 ℃ of constant humidity 40%～80%, constant temperature 10～600 seconds;
(4) leave standstill after, again the nonwoven that casting solution is arranged being immersed in temperature is that 2～50 ℃, concentration are 1%～50% inorganic salt solution.
The preparation method of above-mentioned a kind of liquid separating film, the described molecular weight that contains the aromatic polymer polymer of sulfuryl is 30,000～80,000.The polymer of the molecular weight in this scope in the process of preparation liquid film, can obtain the required film requirement of diffusion barrier, when the further again homogenising of the molecular weight of polymer, when being 40,000～60,000 at molecular weight, can obtain even more ideal effect certainly.
The preparation method of above-mentioned a kind of liquid separating film, described organic solvent is dimethyl formamide or dimethylacetylamide or dimethyl sulfoxide (DMSO) or N-vinyl pyrrolidone, when the high molecular polymer that contains sulfuryl because of main chain was dissolved in these organic solvents, solubility and speed can reach good effect.Certainly, of a great variety because of organic solvent according to the organic similar principle that mixes, outside the above-mentioned solvent that generally uses, also exists and the high molecular polymer phased soln that contains sulfuryl, can be used for preparing the present invention's liquid separating film equally.
The preparation method of above-mentioned a kind of liquid separating film, described nonsolvent additive is oxalic acid or acetic acid or citric acid or propionic acid, addition is that used casting solution system is to 10～80% of corresponding nonsolvent additive gel value.
The preparation method of above-mentioned a kind of liquid separating film, described constant humidity are 45%～65%, and constant temperature is 20～40 ℃, and thickness of liquid film is 100～300 microns.
The preparation method of above-mentioned a kind of liquid separating film, the described nonwoven that is placed with casting solution was distributed in the environment of 30～40 ℃ of constant humidity 50%～60%, constant temperature 100～300 seconds.
The preparation method of above-mentioned a kind of liquid separating film, described inorganic salt solution is a carbonate aqueous solution, equally when getting the aqueous solution such as potash or saleratus, also can obtain desirable effect.、
In the present invention, the condition control in the preparation membrane process is very important, in each step, and the phenomenon that all has physics and chemical process to carry out together.When polymer and solvent, nonsolvent additive mix when making casting solution mutually, need reach one and immerse the gel balance.For this reason, we are when adding nonsolvent additive, and according to the difference of the component in the casting solution system, pairing nonsolvent additive gel value is also different, so we determine its gel value according to certain theoretical value in advance, determines corresponding addition.
In the whole process, 1. the casting solution system is to the mensuration of corresponding nonsolvent additive gel value; 2. the preparation of casting solution; 3. the preparation of coagulation bath; 4. the coating of casting solution on polyester non-woven fabric; 5. evaporate, immerse gel and chemical reaction and modify film forming.Change in the membrane process immersing gel phase, the physical processes such as migration, diffusion and exchange of material have not only taken place between casting solution and the coagulation bath, but also be accompanied by the generation of chemical reaction; Physical processes such as the quantity of prepared anisotropic membrane structure not only can be by material when casting solution is coated on the nonwoven migration, diffusion and exchange, speed are regulated and control, but also chemical process such as intensity that can be by chemical reaction and speed is regulated and control.Exist just because of the controlled condition among the preparation method, can prepare the liquid film of different performance according to different requirements liquid separating film.
Beneficial effect of the present invention: the liquid separating film by the prepared gained of the present invention has bigger water flux, and the even aperture distribution of whole film can obtain better effect in liquid separation process.
Description of drawings
The test result of the pure water flux of Fig. 1 anisotropic membrane performance
Fig. 2 is to the rejection of film with different molecular weight polyethylene glycol
The test result of the pore-size distribution of the film that Fig. 3 is different
The electron-microscope scanning result on the film cross section of the film that Fig. 4 is different and surface, the cross section of film (left side) and surface (right side) photo
PES-0: concentration of sodium carbonate is 0wt% in the coagulation bath; PES-1: concentration of sodium carbonate is 1wt% in the coagulation bath;
PES-5: concentration of sodium carbonate is 5wt% in the coagulation bath; PES-10: concentration of sodium carbonate is 10wt% in the coagulation bath
The specific embodiment
The present invention is a kind of preparation method of liquid separating film, and step is as follows:
Whole process comprises: 1. according to the mensuration of the raw materials used casting solution system that will be mixed with to corresponding nonsolvent additive gel value;
2. the preparation of casting solution;
3. the preparation of coagulation bath;
4. the coating of casting solution on polyester non-woven fabric;
5. evaporate, immerse gel and chemical reaction and modify film forming.
2CH
3COOH+Na
2CO
3＝2CH
3COONa+CO
2↑+H
2O
After the inversion of phases process was complete, with prepared film deionized water cyclic washing, and wet method was preserved.
By implementing present embodiment with quadrat method, test result such as Fig. 1 of the pure water flux of prepared anisotropic membrane performance:
Fig. 2 is the test result to the present embodiment rejection, and used test is the rejection of different molecular weight polyethylene glycol:
Fig. 3 is the test result to the present embodiment pore-size distribution
Fig. 4 is to present embodiment prepared film cross section and surperficial electron-microscope scanning result, the cross section of film (left side) and surface (right side) photo:
We can obtain the film of different apertures, different rejection and water flux by to implementing the present invention under the controlled conditions such as different temperatures, humidity, different component proportioning ratios, constitute certain rules.
Certainly; the foregoing description only is to realize a part of the present invention, and comprising that the present invention protected is not limited to the foregoing description, as long as industry those of ordinary skill; the technical scheme that does not need creative work or can associate by the present invention should all belong to protection scope of the present invention.
Claims (8)
1. the preparation method of a liquid separating film specifically follows these steps to carry out:
(1) the aromatic polymer polymer that contains sulfuryl on the main chain is dissolved in the organic solvent between 0～80 ℃, and be aided with a kind of in oxalic acid or acetic acid or citric acid or the propionic acid for nonsolvent additive is mixed with casting solution, be prepared into polymer concentration and be 8～30% casting solution;
(2) constant humidity in 40%～80%, constant temperature in 20～45 ℃ environment with even speed with casting solution equably curtain coating to polyester non-woven fabric, form the liquid film of 50～500 micron thickness;
(3) nonwoven that is coated with casting solution was positioned in the environment of 20～45 ℃ of constant humidity 40%～80%, constant temperature 10～600 seconds;
(4) leave standstill after, again the nonwoven that casting solution is arranged being immersed in temperature is that 2～50 ℃, concentration are 1%～50% inorganic salt solution.
2. the preparation method of a kind of liquid separating film according to claim 1 is characterized in that the described molecular weight that contains the aromatic polymer polymer of sulfuryl is 30,000～80,000.
3. the preparation method of a kind of liquid separating film according to claim 1 and 2 is characterized in that the described molecular weight that contains the aromatic polymer polymer of sulfuryl is 40,000～60,000.
4. the preparation method of a kind of liquid separating film according to claim 1 is characterized in that described organic solvent is dimethyl formamide or dimethylacetylamide or dimethyl sulfoxide (DMSO) or N-vinyl pyrrolidone.
5. the preparation method of a kind of liquid separating film according to claim 1 is characterized in that described nonsolvent additive is oxalic acid or acetic acid or citric acid or propionic acid, and addition is that used casting solution system is to 10～80% of corresponding nonsolvent additive gel value.
6. the preparation method of a kind of liquid separating film according to claim 1 is characterized in that described thickness of liquid film is 100～300 microns.
7. the preparation method of a kind of liquid separating film according to claim 1 is characterized in that the described nonwoven that is placed with casting solution was distributed in the environment of 30～40 ℃ of constant humidity 50%～60%, constant temperature 100～300 seconds.
8. the preparation method of a kind of liquid separating film according to claim 1 is characterized in that described inorganic salt solution is a carbonate aqueous solution.
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| CNB2005100617125A CN100400144C (en) | 2005-11-28 | 2005-11-28 | Production of liquid separating film |
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| CNB2005100617125A CN100400144C (en) | 2005-11-28 | 2005-11-28 | Production of liquid separating film |
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| CN100400144C true CN100400144C (en) | 2008-07-09 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091880B (en) * | 2007-06-25 | 2010-05-19 | 南京工业大学 | Method for preparing porous separation membrane |
| CN101254414B (en) * | 2007-11-30 | 2010-04-14 | 华南理工大学 | Preparation of porous membrane |
| CN101829509A (en) * | 2010-05-11 | 2010-09-15 | 杭州水处理技术研究开发中心有限公司 | Preparation method of antibacterial porous membrane |
| CN103120901A (en) * | 2013-03-01 | 2013-05-29 | 北京工业大学 | Preparation method of polyacrylonitrile flat micro-filtration membrane |
| CN103611429A (en) * | 2013-11-21 | 2014-03-05 | 北京工业大学 | Preparation method of composite phase separated flat plate micro-filtration membrane |
| CN104307389B (en) * | 2014-10-11 | 2016-08-24 | 四川大学 | Polyether sulfone thermal stimulus response film and preparation method thereof |
| CN104492285B (en) * | 2014-11-20 | 2016-11-30 | 江苏凯米膜科技股份有限公司 | Antipollution, high-flux ultra-filtration membrane and preparation method thereof and casting solution used |
| CN105214523B (en) * | 2015-09-21 | 2017-05-10 | 中国海洋大学 | Method for preparing homogeneous organic-inorganic hybrid film |
| CN105833741B (en) * | 2016-04-25 | 2018-06-29 | 中国科学院兰州化学物理研究所 | A kind of preparation method of polyvinylidene fluoride porous membrane |
Citations (5)
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|---|---|---|---|---|
| CN1237475A (en) * | 1998-05-29 | 1999-12-08 | 中国科学院大连化学物理研究所 | Prepartion of composite gas separation membrane its application |
| CN1288776A (en) * | 2000-09-21 | 2001-03-28 | 华东理工大学 | Preparation of sulfonated polyether sulfone filtering film |
| JP2003080043A (en) * | 2001-09-07 | 2003-03-18 | Ube Ind Ltd | New polyimide selective permeable membrane |
| JP2005081226A (en) * | 2003-09-08 | 2005-03-31 | Institute Of Physical & Chemical Research | Nanofiltration membrane and production method therefor |
| JP2005137996A (en) * | 2003-11-05 | 2005-06-02 | Toyobo Co Ltd | Permselective separation membrane |
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2005
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237475A (en) * | 1998-05-29 | 1999-12-08 | 中国科学院大连化学物理研究所 | Prepartion of composite gas separation membrane its application |
| CN1288776A (en) * | 2000-09-21 | 2001-03-28 | 华东理工大学 | Preparation of sulfonated polyether sulfone filtering film |
| JP2003080043A (en) * | 2001-09-07 | 2003-03-18 | Ube Ind Ltd | New polyimide selective permeable membrane |
| JP2005081226A (en) * | 2003-09-08 | 2005-03-31 | Institute Of Physical & Chemical Research | Nanofiltration membrane and production method therefor |
| JP2005137996A (en) * | 2003-11-05 | 2005-06-02 | Toyobo Co Ltd | Permselective separation membrane |
Non-Patent Citations (2)
| Title |
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| 浸入沉淀相转化法制膜. 俞三传，高从堦.膜科学与技术，第20卷第5期. 2000 |
| 浸入沉淀相转化法制膜. 俞三传，高从堦.膜科学与技术，第20卷第5期. 2000 * |
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Owner name: HANGZHOU WATER TREATMENT TECHNOLOGY RESEARCH AND D Free format text: FORMER NAME OR ADDRESS: HANGZHOU WATER TREATMENT TECHNOLOGICAL RESEARCH DEVELOPMENT CENTER Owner name: HANGZHOU WATER TREATMENT TECHNOLOGICAL RESEARCH DE Free format text: FORMER NAME OR ADDRESS: STATE OCEANIC ADMINISTRATION, HANGZHOU WATER TREATMENT TECHNOLOGY RESEARCH AND DEVELOPMENT CENTER |
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Address after: No. 50 Wenhua Road, Zhejiang, Hangzhou Province, China: 310012 Patentee after: HANGZHOU WATER TREATMENT TECHNOLOGY DEVELOPMENT CENTER Co.,Ltd. Address before: No. 50 Wenhua Road, Zhejiang, Hangzhou Province, China: 310012 Patentee before: Hangzhou Water Treating Technology Research Development Center Address after: No. 50 Wenhua Road, Zhejiang, Hangzhou Province, China: 310012 Patentee after: Hangzhou Water Treating Technology Research Development Center Address before: No. 50 Wenhua Road, Zhejiang, Hangzhou Province, China: 310012 Patentee before: Hangzhou water treatment technology research and development center of State Oceanic Administration |
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