CN101279211A - Preparation of polyvinylidene fluoride dewatering microporous film - Google Patents
Preparation of polyvinylidene fluoride dewatering microporous film Download PDFInfo
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- CN101279211A CN101279211A CNA2008100560188A CN200810056018A CN101279211A CN 101279211 A CN101279211 A CN 101279211A CN A2008100560188 A CNA2008100560188 A CN A2008100560188A CN 200810056018 A CN200810056018 A CN 200810056018A CN 101279211 A CN101279211 A CN 101279211A
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Abstract
The invention relates to a preparation method for a PVDF hydrophobic microporous membrane and belongs to the field of separation membrane and membrane separation. The invention aims at solving the problem of relatively low flux in the prior art and providing the preparation method for a PVDF microporous membrane with hydrophobic nature, which prepares the PVDF hydrophobic microporous membrane through the following steps: 1) preparing a casting solution adding with an alkoxy silane reagent; 2) placing the membrane in water with a moisture ranging from 60 percent to 85 percent or a steam atmosphere with a pH value of 0.5 to 3 or 10 to 13 for 1 to 4 min after scraping the casting membrane into a liquid membrane with a thickness ranging from 0.12 to 0.15mm; 3) immersing the membrane into water at room temperature or a coagulation bath with the pH value of 0.5 to 3 or 9 to 11. The method of the invention is simple in operation, low in cost, with the surface of the membrane prepared being a network cellular structure and accompanied by spherical particles and the cross section being a symmetrical spongy structure, while the hydrophobic nature and the pure water flux of the membrane are greatly improved.
Description
Technical field
The invention belongs to diffusion barrier and film separation field, be specifically related to the preparation method of strong-hydrophobicity polyvinylidene fluoride microporous film.
Background technology
Film distillation (Membrane Distillation is called for short MD) is the new membrane separation process of membrane technology and volatilization process combination.The sixties, Findly at first introduced this isolation technics.This technology is based on the effect of film both sides water vapor pressure difference, and the water vapour of hot side enters cold side by fenestra, and under the cold side condensation, this process is the same with the evaporation-transmission-condensation process in the conventional distillation then.Compare with other film separation processes, the film distillation has the distinct advantages that can separate under the condition of normal pressure and a little higher than normal temperature, can make full use of the energy at a low price such as solar energy, industrial exhaust heat and used heat, and equipment is simple, easy to operate.Can be used for all many-sides such as seawater and brackish water desalination, ultra-pure water preparation, concentrated aqueous solution and medicine, environmental protection, so the development of film distillation technology more and more causes people's attention.Why the film distillation competitiveness of comparing with other isolation technics is not strong at present, one very chief reason be that to be used for the film cost that film distills higher.The film still-process generally is porosity higher (70%～80%) to the requirement of film, and the aperture is between 0.2～0.3 μ m, therefore presses for to develop to have good separation performance and cheap film to adapt to the development of film distillation.
Kynoar (PVDF) has good chemical stability, and heat endurance and mechanical strength are the good separation membrane materials of a kind of combination property.Its hydrophobicity, hear resistance, solubility and be easy to characteristics such as preparation than polytetrafluoroethylene (PTFE) and polypropylene (PP) make it to become the ideal material that utilizes phase inversion to prepare film distillation dewatering microporous film.
More aperture and the voidage that improves film by the morphosis that changes film that concentrate on of people's research in recent years reaches the purpose that improves film distillation performance with expectation.Kong Ying etc. are additive preparation polyvinylidene fluoride film (Kong Ying with inorganic salts lithium chloride (LiCl), Wu Yong is strong, Yang Jinrong, Deng. be used for the preparation and the morphology studies thereof of the hydrophobic polyvinylidene fluoride microporous film of film distillation. membrane science and technology, 1990,10 (3)), improved because of polymeric additive residual shortcoming in film easily, the result shows, prepared film has high porosity, low aperture and high rejection, the hydrophobicity of film also obviously improve, and obvious variation has taken place the morphosis of film, have finger and spongelike structure concurrently, but the problem that exists is: because the less membrane flux that makes of film average pore size is not high; Du Qiyun etc. are with sal-ammoniac (NH
4Cl) saturated aqueous solution is additive preparation polyvinylidene fluoride film (Du Qiyun, Wu Liqun. the pore effect of the aqueous solution in film forming procedure. water technology, 1996,22 (6)), the maximum average pore size that makes film is 0.28um, but the problem that exists is: because inorganic salts NH
4Cl adds with the form of the aqueous solution, and the introducing of water makes film forming speed accelerate, and the surface forms compacted zone easily, causes that the aperture diminishes, the cortex thickening, and inorganic salts do not play due pore effect; Mao Peng etc. prepare PVDF porous hydrophobic membrane (Mao Peng by changing gelation condition, LiHongbing, Wu Lijuan, etal.Porous Poly (Vinylidene Fluoride) Membrane withHighly Hydrophobic Surface.Applied Polymer Science, 2005,98.), promptly utilize the mixed solution of water/DMAC to replace the pure water coagulation bath and gel replacement immersion precipitation gel in air respectively, the result shows, when making coagulation bath greater than 50% mixed solution with DMAC content, because the gel process of film slows down, cause the surface compact cortex to disappear, the film section is symmetrical spongelike structure, and the upper and lower surface contact angle of film all reaches 140 °, improved the hydrophobicity of film, made that as coagulation bath organic solvent DMAC consumption is too big but shortcoming is a mixed solution; And the film of preparing gel makes contact angle reach 144 °～149 ° because face forms micron and nanometer composite structure in air.
Water vapour induces the difference of film forming and immersion precipitation film forming to be that immersion precipitation is directly liquid film to be immersed in (commonly used is water) in the high molecular precipitating reagent, solvent in (normally tens of second) precipitating reagent and liquid film exchanges in a short period of time, high-molecular gel or film-forming, and water vapour to induce ratio juris be that liquid film directly is placed in the air of certain humidity, airborne water vapor diffusion enters liquid film, when wherein the content of water reaches a certain numerical value, high-molecular gel or film-forming.Water vapour is induced in the film forming procedure because water in air content is not high, and the speed that spreads in liquid film extremely slow (with respect to immersion precipitation), film forming speed than immersion precipitation slowly many, can obtain not having the symmetric membrane of dense layer surface usually.Hyun utilizes steam to induce the method for film forming to prepare PS membrane (Hyun Chae Park, YoonPo Kim, Hwa Yong Kim, Yong Soo Kang.Membrane formation by water vaporinduced phase inversion.Membr Sci, 1999,156), be higher than the spongelike structure that the film that forms under 65% the humidity has symmetry, but the problem that exists is: the fenestra of formation does not connect substantially, and pure water flux is extremely low.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, the preparation method of a kind of strong-hydrophobicity, high porosity and high-throughout polyvinylidene fluoride dewatering microporous film is provided.Film of the present invention is mainly used in film distillation and related film process.
The preparation method of polyvinylidene fluoride dewatering microporous film provided by the present invention may further comprise the steps:
1) with Kynoar PVDF, solvent N, N-dimethylacetylamide DMAC, alkoxy silane and LiCl Additive stirred the casting solution that obtains clarifying 6～7 hours; In the casting solution, the content of PVDF is 10%～20wt%, and the content of alkoxy silane is 8%～22wt%, and the content of LiCl Additive is 3%～5wt%, and the content of solvent DMAC is 53%～79wt%; Then casting solution is placed 50 ℃ of baking ovens to leave standstill 24～48h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained is after spreading to it thick liquid film of 0.12～0.15mm with scraper on the glass plate, at once glass plate being placed relative humidity is 60%～85% steam atmosphere, allow liquid film in the steam atmosphere, leave standstill 1～4min, obtain the nascent state film;
3) with step 2) the nascent state film of preparation immerses in 15～20 ℃ the coagulation bath, treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 20～30min, film is transferred in the deionized water soaked then, promptly obtain polyvinylidene fluoride dewatering microporous film.
Wherein, alkoxy silane described in the step 1) is selected from MTES, dimethyldiethoxysilane, tetraethoxysilane, tetramethoxy-silicane, MTMS, ethyl triethoxysilane, VTES, vinyltrimethoxy silane.Described alkoxysilane reagent can be dissolved each other with arbitrary proportion with solvent, but water insoluble, hydrolytic-polymeric reaction can take place in water generate high polymer; Hydrolytic polymerization speeds up under acidity or alkali condition, and the product of its polymerisation helps the crystallization of PVDF.
Step 2) steam described in is water vapour, acidity or alkaline steam; Described acid vapors is the acidic aqueous solution steam of pH=0.5～3; Described alkaline steam is the alkaline aqueous solution steam of pH=10～13.
Coagulation bath described in the step 3) is water, acidity or alkaline aqueous solution; Described acidic aqueous solution is the acidic aqueous solution of pH=0.5～3; Described alkaline aqueous solution is the alkaline solution of pH=9～11.The acidity at steam and coagulation bath two places or alkaline environment all can promote the hydrolysis or the polymerization of alkoxy silane.
The present invention has added the alkoxysilane reagent of the film gelation rate that can slow down in organic casting solution, in steam, added the soda acid composition, make in the film gel solidification, alkoxy silane generation hydrolysis and polymerisation, inorganic polymer that generates and macromolecular chain form inierpeneirating network structure, help the crystallization of high molecular polymer simultaneously, finally change the structure of film, reach the purpose of hydrophobically modified.
Compared with prior art, the present invention has the following advantages:
1) the inventive method is simple to operate, and cost is low;
2) water vapour is induced film forming and is added the gelation condition that alkoxysilane reagent has changed film, and film forming speed has slowed down;
3) structure that content by changing alkoxy silane and control steam gel time and air humidity can controlling diaphragms;
4) Zhi Bei film surface is mesh structural porous structure, and with spherical particle, section is symmetrical spongelike structure, and the hydrophobicity of film is greatly improved;
5) Zhi Bei film upper surface water contact angle CA reaches 100～141.4 °, and porosity reaches 70～86%, and pure water flux reaches 56m
3/ (m
2.h.MPa) more than.
Description of drawings
The sem photograph (a) of the polyvinylidene fluoride dewatering microporous film of Fig. 1, the embodiment of the invention 1 preparation and the side view (b) of water contact angle;
The sem photograph (a) of the polyvinylidene fluoride dewatering microporous film of Fig. 2, the embodiment of the invention 4 preparations and the side view (b) of water contact angle;
Sem photograph Quanta 200-EDAX Genesis 2000 type electron scanning Electronic Speculum (SEM) Observe; Water contact angle (CA) adopts DSA100 type optical method droplet profile analytical system to measure.
The invention will be further described below in conjunction with the drawings and the specific embodiments.
The specific embodiment:
Embodiment 1
Earlier in alkali steam behind the gel in acid the preparing gel polyvinylidene fluoride dewatering microporous film
1) the casting solution total amount is total to 100g, at first PVDF (10wt%), DMAC (70wt%), LiCl (4wt%), tetraethoxysilane TEOS (16wt%) are mixed, used magnetic stirrer 6 hours, the casting solution that obtains clarifying, be placed on then in 50 ℃ of baking ovens and leave standstill 48h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained is after spreading to it thick liquid film of 0.15mm with scraper on the glass plate, at once glass plate being placed pH=12, relative humidity is 85% NaOH alkali steam atmosphere, allow liquid film in alkali steam atmosphere, keep 4min, obtain the nascent state film;
3) then the nascent state film is immersed in the hydrochloric acid coagulation bath of (20 ℃, pH=1), treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 30min, transfer in the deionized water then and soak, obtain polyvinylidene fluoride dewatering microporous film.
SEM photo (accompanying drawing 1) shows that film surface compact cortex disappears, and be mesh structural porous structure and have a large amount of spheric granules, and grain diameter is bigger; Section is the spongelike structure of symmetry; CA is 138.3 °, and porosity is 76.06%, and pure water flux reaches 85m
3/ (m
2.h.MPa).
Embodiment 2
Earlier in alkali steam behind the gel in acid the preparing gel polyvinylidene fluoride dewatering microporous film
1) the casting solution total amount is total to 100g, at first PVDF (10wt%), DMAC (64wt%), LiCl (4wt%), TEOS (22wt%) are mixed, used magnetic stirrer 6 hours, the casting solution that obtains clarifying, be placed on then in 50 ℃ of baking ovens and leave standstill 48h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained is after spreading to it thick liquid film of 0.15mm with scraper on the glass plate, at once glass plate being placed pH=13, relative humidity is 85% NaOH alkali steam atmosphere, allow liquid film in alkali steam atmosphere, keep 4min, obtain the nascent state film;
3) then the film of nascent state is immersed in the hydrochloric acid coagulation bath of (20 ℃, pH=3), treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 30min, transfer in the deionized water then and soak, obtain polyvinylidene fluoride dewatering microporous film.
The SEM photo shows that the film surface is mesh structural porous structure, has a large amount of spheric granules in the no dense layer surface, face and fenestra; Section is the spongelike structure of symmetry; CA is 141.4 °, and porosity is 73.24%, and pure water flux reaches 88m
3/ (m
2.h.MPa).
Embodiment 3
Earlier in water vapour behind the gel in acid the preparing gel polyvinylidene fluoride dewatering microporous film
1) the casting solution total amount is total to 100g, at first PVDF (10wt%), DMAC (73wt%), LiCl (5wt%), TEOS (12wt%) are mixed, used magnetic stirrer 7 hours, the casting solution that obtains clarifying, be placed on then in 50 ℃ of baking ovens and leave standstill 48h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained places water vapour atmosphere (relative humidity 80%) to glass plate at once after it being spread to the thick liquid film of 0.15mm with scraper on the glass plate, allows liquid film keep 3min in the water vapour atmosphere, obtains the nascent state film;
3) then the film of nascent state is immersed in the hydrochloric acid coagulation bath of (18 ℃, pH=0.5), treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 30min, transfer in the deionized water then and soak, obtain polyvinylidene fluoride dewatering microporous film.
The SEM photo shows that the film surface is mesh structural porous structure and has particle aggregate, no dense layer surface; Section is the spongelike structure of symmetry; CA is 123.8 °, and porosity is 83.73%, and pure water flux reaches 76m
3/ (m
2.h.MPa).
Embodiment 4
Earlier in water vapour behind the gel in acid the preparing gel polyvinylidene fluoride dewatering microporous film
1) the casting solution total amount is total to 100g, at first PVDF (10wt%), DMAC (70wt%), LiCl (4wt%), TEOS (16wt%) is mixed, and uses magnetic stirrer 7 hours, the casting solution that obtains clarifying; Be placed on then in 50 ℃ of baking ovens and leave standstill 48h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained places water vapour atmosphere (relative humidity 85%) to glass plate at once after it being spread to the thick liquid film of 0.15mm with scraper on the glass plate, allows liquid film keep 4min in the water vapour atmosphere, obtains the nascent state film;
3) then the film of nascent state is immersed in the aqueous hydrochloric acid solution of (20 ℃, pH=1), treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 30min, transfer in the deionized water then and soak, obtain polyvinylidene fluoride dewatering microporous film.
SEM photo (accompanying drawing 2) shows that the film surface is mesh structural porous structure and has spheric granules, no dense layer surface; Section is the spongelike structure of symmetry; CA is 130.5 °, and porosity is 85.42%, and pure water flux reaches 83m
3/ (m
2.h.MPa).
Earlier in alkali steam behind the gel in water the preparing gel polyvinylidene fluoride dewatering microporous film
1) the casting solution total amount is total to 100g, at first PVDF (12wt%), DMAC (73wt%), LiCl (3wt%), VTES (12wt%) is mixed, and uses magnetic stirrer 6 hours, the casting solution that obtains clarifying; Be placed on then in 50 ℃ of baking ovens and leave standstill 24h, make its abundant slaking, deaeration;
2) system is during film, with scraper with casting solution after spreading to the thick liquid film of 0.15mm on the glass plate, at once glass plate is placed ammonia steam atmosphere (pH=10, relative humidity 60%), allow liquid film in ammonia steam atmosphere, keep 3min, obtain the nascent state film;
3) then the film of nascent state is immersed during (15 ℃) hydrogel bathes, treat that film is peeled off from glass plate fully after, continue in hydrogel is bathed, to soak 30min, transfer in the deionized water then and soak, obtain polyvinylidene fluoride dewatering microporous film.
The SEM photo shows that film surface compact cortex disappears, and is loose structure; Section is the spongelike structure of symmetry; CA is 107.4 °, and porosity is 86%, and pure water flux reaches 63m
3/ (m
2.h.MPa).
Embodiment 6.
Earlier in acid vapor behind the gel in alkali the preparing gel polyvinylidene fluoride dewatering microporous film
1) the casting solution total amount is total to 100g, at first PVDF (20wt%), DMAC (67wt%), LiCl (5wt%), TEOS (8wt%) are mixed, used magnetic stirrer 7 hours, the casting solution that obtains clarifying, be placed on then in 50 ℃ of baking ovens and leave standstill 24h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained is after spreading to it thick liquid film of 0.15mm with scraper on the glass plate, at once glass plate is placed hydrochloric acid vapour atmosphere (pH=3, relative humidity 85%), allow liquid film in the steam atmosphere, keep 1min, obtain the nascent state film;
3) then the film of nascent state is immersed in the NaOH coagulation bath of (20 ℃, pH=9), treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 30min, transfer in the deionized water then and soak, obtain polyvinylidene fluoride dewatering microporous film.
The SEM photo shows that film surface compact cortex disappears, and is loose structure, the embedded irregular particle of face; Section is the spongelike structure of symmetry; CA is 105.7 °, and porosity is 85.79%, and pure water flux reaches 59m
3/ (m
2.h.MPa).
Earlier in acid vapor behind the gel in alkali the preparing gel polyvinylidene fluoride dewatering microporous film
1) the casting solution total amount is total to 100g, at first PVDF (20wt%), DMAC (60wt%), LiCl (4wt%), TEOS (16wt%) are mixed, used magnetic stirrer 7 hours, the casting solution that obtains clarifying, be placed on then in 50 ℃ of baking ovens and leave standstill 24h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained is after spreading to it thick liquid film of 0.15mm with scraper on the glass plate, at once glass plate is placed acetic acid steam atmosphere (pH=0.5, relative humidity 75%), allow liquid film in the steam atmosphere, keep 3min, obtain the nascent state film;
3) then the film of nascent state is immersed in the NaOH coagulation bath of (20 ℃, pH=11), treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 30min, transfer in the deionized water then and soak, obtain polyvinylidene fluoride dewatering microporous film.
The SEM photo shows that film surface compact cortex disappears, and is porous network structure; Section is the spongelike structure of symmetry; CA is 112.3 °, and porosity is 84.8%, and pure water flux reaches 71m
3/ (m
2.h.MPa).
Claims (8)
1, a kind of preparation method of polyvinylidene fluoride dewatering microporous film is characterized in that, may further comprise the steps:
1) with Kynoar PVDF, solvent N, N-dimethylacetylamide DMAC, alkoxy silane and LiCl Additive are mixed, stirred 6～7 hours, the casting solution that obtains clarifying, in the casting solution, the content of PVDF is 10～20wt%, and the content of alkoxy silane is 8～22wt%, the content of LiCl Additive is 3～5wt%, and the content of solvent DMAC is 53～79wt%; Again casting solution is placed 50 ℃ of baking ovens to leave standstill 24～48h, make its abundant slaking, deaeration;
2) casting solution that step 1) is obtained is after spreading to it thick liquid film of 0.12～0.15mm with scraper on the glass plate, at once glass plate being placed relative humidity is 60%～85% steam atmosphere, allow liquid film in the steam atmosphere, leave standstill 1～4min, obtain the nascent state film;
3) with step 2) the nascent state film of preparation immerses in 15～20 ℃ the coagulation bath, treat that film is peeled off from glass plate fully after, continue in coagulation bath, to soak 20～30min, film is transferred in the deionized water soaked then, promptly obtain polyvinylidene fluoride dewatering microporous film.
2, method according to claim 1, it is characterized in that, alkoxy silane described in the step 1) is selected from MTES, dimethyldiethoxysilane, tetraethoxysilane, tetramethoxy-silicane, MTMS, ethyl triethoxysilane, VTES or vinyltrimethoxy silane.
3, method according to claim 1 is characterized in that step 2) described in steam be water vapour, acidity or alkaline steam.
4, method according to claim 3 is characterized in that, described acid vapors is the acidic aqueous solution steam of pH=0.5～3.
5, method according to claim 3 is characterized in that, described alkaline steam is the alkaline aqueous solution steam of pH=10～13.
6, method according to claim 1 is characterized in that, the coagulation bath described in the step 3) is water, acidity or alkaline aqueous solution.
7, method according to claim 6 is characterized in that, described acidic aqueous solution is the acidic aqueous solution of pH=0.5～3.
8, method according to claim 6 is characterized in that, described alkaline aqueous solution is the alkaline aqueous solution of pH=9～11.
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| CN102061049A (en) * | 2010-11-30 | 2011-05-18 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN102179188A (en) * | 2011-03-24 | 2011-09-14 | 北京工业大学 | Super hydrophobic modification method for polyvinylidene fluoride hydrophobic membranes |
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| CN102061049B (en) * | 2010-11-30 | 2013-03-27 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN102061049A (en) * | 2010-11-30 | 2011-05-18 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
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| CN102512984A (en) * | 2011-12-29 | 2012-06-27 | 武汉大学 | Preparation method for oxygen removal polymer film for water supplied for boiler |
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| CN106964264A (en) * | 2017-04-27 | 2017-07-21 | 苏州捷尔沃科技有限公司 | Self-supporting with superhydrophobic breathable property and the pvdf membrane containing substrate |
| CN112295409A (en) * | 2019-07-31 | 2021-02-02 | 天津工业大学 | Super-hydrophobic membrane with open network surface structure and preparation method thereof |
| CN112295409B (en) * | 2019-07-31 | 2022-04-05 | 天津工业大学 | Super-hydrophobic membrane with open network surface structure and preparation method thereof |
| CN112691555A (en) * | 2020-11-30 | 2021-04-23 | 北京碧水源膜科技有限公司 | Casting solution for producing microporous membrane, method for producing microporous membrane, and microporous membrane |
| CN113248780A (en) * | 2021-06-16 | 2021-08-13 | 中国科学院生态环境研究中心 | Hydrophobic PVDF (polyvinylidene fluoride) membrane, preparation method and application thereof |
| CN115275505A (en) * | 2022-05-16 | 2022-11-01 | 烟台泰和新材料股份有限公司 | Low-closed-pore high-film-breaking aramid fiber lithium battery diaphragm and preparation method thereof |
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