CN101912740A - Method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane - Google Patents
Method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane Download PDFInfo
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- CN101912740A CN101912740A CN 201010265038 CN201010265038A CN101912740A CN 101912740 A CN101912740 A CN 101912740A CN 201010265038 CN201010265038 CN 201010265038 CN 201010265038 A CN201010265038 A CN 201010265038A CN 101912740 A CN101912740 A CN 101912740A
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Abstract
The invention provides a method for performing hydrophilic modification on the surface of a polyvinylidene fluoride micro-porous membrane. The method is characterized by comprising the following specific steps of: cleaning a polyvinylidene fluoride micro-porous filter membrane with deionized water, dipping the cleaned filter membrane in solution of ethanol, dipping the dipped filter membrane in the deionized water, adding the polyvinylidene fluoride micro-porous membrane into solution of an alkali oxidant and reacting at the temperature of between 20 and 80 DEG C for 20 to 60 minutes, wherein the alkali oxidant contains alkali and potassium permanganate serving as an oxidant; dipping the polyvinylidene fluoride micro-porous membrane treated in the step one in solution of an acid reducing agent to remove the alkali and the potassium permanganate serving the oxidant on the surface, cleaning the dipped membrane with the deionized water and drying the cleaned membrane; and dipping the polyvinylidene fluoride micro-porous membrane treated in the step two in 5 to 20 volume percent solution of glycerin, reacting at normal temperature for 5 to 20 minutes, cleaning the membrane with the deionized water and drying the cleaned membrane. The method has the advantages of simple and efficient process, capability of improving the hydrophility of the polyvinylidene fluoride membrane and lasting effect.
Description
Technical field
The present invention relates to a kind of method of performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane, belong to film performing hydrophilic modification on surface technical field.
Background technology
Membrane separation technique is to be the fluid separation element operating technology of representative with the polymeric membrane for separation, is a kind of novel frontier branch of science new and high technology.Because membrane separation technique has the unexistent advantage of many other isolation technics: concentrating does not need in a disguised form, and separation is big, and separation selectivity is strong, and does not need evaporimeter or freezing equipment, so cost of investment is low, energy resource consumption is few; Especially,, protect original color, nutrition and the mouthfeel of separated material easily owing to be not heated in the separation process for the processing of the material (as food, medicine or Bio-engineering Products) of those thermal sensitivitys.Aspect membrane separation technique importance, there is the expert that its application and development are called " industrial revolution for the third time " abroad; U.S. official also says " not having a technology to use so widely as membrane separation technique at present "; Also popular in the world the saying of " who is grasping membrane technology, and who just grasps the future of chemical industry ".Because membrane separation technique has many advantages and importance, exists huge productive potentialities and application prospect, all many-sides such as biology and food industry, medical industry, environmental project have been widely used in.
Kynoar is a kind of crystalline polymer of function admirable, because its outstanding chemical stability, corrosion resistance and hear resistance more makes it exhibit one's skill to the full at the film separation field, formed a series of polyvinylidene fluoride separation membrane, wherein polyvinylidene fluoride microporous filtering film and milipore filter successfully are applied to fields such as chemical industry, electronics, weaving, food, biochemistry.Along with the range of application of polyvinylidene fluoride film constantly enlarges, the researcher of various countries is the development of all kinds of novel diffusion barriers of membrane material carrying out with the Kynoar, thereby its excellent performance is not fully exerted, can satisfies the requirement of some special film process and special dimension.Than other membrane material, the most outstanding characteristics of Kynoar are to have extremely strong hydrophobicity, this becomes the principal element of restriction polyvinylidene fluoride film in a lot of fields large-scale application, when especially being applied in aspects such as water-oil separating, protide separation, because polyvinylidene fluoride surface can be extremely low, and extremely strong hydrophobicity is arranged, easily produce absorption and pollute, make membrane flux descend the service life of having reduced film.
In order to improve the hydrophily of polyvinylidene fluoride film, it can efficiently be utilized for a long time, people are inquiring into all kinds of method of modifying always, and on the whole, the modification purpose of polyvinylidene fluoride film is intended to improve its surface hydrophilicity, increases the surface energy, thereby prevents to form pollution layer.Its method of modifying comprises: physical modification, low-temperature plasma modified, chemical modification etc.
Wherein, physical modification is a hydrophily of improving the polyvinylidene fluoride film surface by the method for physical blending or face coat, blending and modifying belongs to the body modification, the mechanical strength of polyvinylidene fluoride film, modulus, elongation at break etc. after compatibility between the blend and the content influence modification.Simultaneously, participate in the big molecule of blend if having huge side group, also can impact membrane aperture, these factors all await inquiring into and studying to the flux of modification caudacoria and the influence of rejection.And the greatest problem of surface coating process is to add or the grafting or the block copolymer that apply easily break away from from macromolecule surface, can not obtain nonvolatil modified effect.
Low-temperature plasma modified is that development in recent years gets method faster, and it does not influence the bulk properties of material, by introducing oxygen containing polar group at material surface, thereby has improved surperficial hydrophily.Simple plasma treatment, its hydrophilic effect is uncertain, and retention time is short.
Surface chemical modification is simple, efficient.This is because the polymer surface that surface modification is only limited at solid carries out, the body part of material still maintains the original state and does not participate in reaction, product after the modification, because of the top layer different with the structure of body interior, it is a kind of composite of surface modification, because the Kynoar membrane body is the membrane material of a class function admirable, therefore its modification is mainly concentrated on surface modification.It is convenient and easy adopting the advantage of surface chemical modification method, does not need special device and equipment, with low cost, is easy to realize extensive industrialization, can " fix " needed hydrophilicity muchly.
Summary of the invention
The objective of the invention is can be low at polyvinylidene fluoride film surface, and extremely strong hydrophobicity is arranged, and easily produce absorption and pollute, thereby the characteristics that membrane flux is descended proposes a kind of method of performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane.
In order to achieve the above object, the invention provides a kind of method of performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane, it is characterized in that, concrete steps are:
The first step, use the washed with de-ionized water polyvinylidene fluoride microporous filtering film, it is dipped in the ethanolic solution that concentration expressed in percentage by volume is 50-90% then and soaks 12-36hr, again it is immersed in deionized water;
Second goes on foot, the polyvinylidene fluoride microporous film after the first step processing is joined in the alkaline oxygenated agent solution, reacts 20-60min down at 20-80 ℃, wherein, contains alkali and oxidant potassium permanganate in the described alkaline oxidiser;
The 3rd goes on foot, the polyvinylidene fluoride microporous film after the processing of second step is immersed remove surperficial alkali and oxidant potassium permanganate in the acidic reduction agent solution, uses washed with de-ionized water, oven dry;
It is in the glycerite of 5-20% that the 4th step, the polyvinylidene fluoride microporous film after the 3rd step handled immerse concentration of volume percent, reacts 5-20min at normal temperatures, use washed with de-ionized water, dries.
Alkaline oxygenated agent solution described in second step is made up of alkali, oxidant potassium permanganate, phase transfer catalyst TBAB and water.Described alkali is potassium hydroxide, and the weight percent concentration of potassium hydroxide is 10-50%, and the weight percent concentration of potassium permanganate is 1-5%, and the concentration of TBAB is 2000mg/l-5000mg/l.
Acidic reduction agent solution described in the 3rd step is made up of sulfuric acid, reducing agent sodium hydrogensulfite and water.The concentration of volume percent of sulfuric acid is 1-3%, and the weight percent concentration of sodium hydrogensulfite is 1-3%.
Compared with prior art, advantage of the present invention is:
(1) adopt the necleophilic reaction of potassium hydroxide/potassium permanganate system and sulfuric acid/sodium hydrogensulfite to introduce hydroxyl on the film surface, and then use glycerine water solution to handle and introduce bigger hydrophilic radical or side chain, can form more stable hydrophilic layer on the film surface, on the basis that keeps the original premium properties of Kynoar, effectively improved the hydrophily of polyvinylidene fluoride film, effect is lasting.
(2) technology is simple, efficient, does not need special device and equipment, and is with low cost, is easy to realize extensive industrialization.
The specific embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1
(1) with polyvinylidene fluoride microporous filtering film with washed with de-ionized water 10 times, be dipped in then in 70% the ethanolic solution and soak 24hr, again it is immersed in deionized water;
(2) polyvinylidene fluoride film of above-mentioned processing be impregnated in to add phase transfer catalyst be in the alkali/oxidizing agent solution of TBAB, react 40min under 50 ° of C, wherein, alkali is potassium hydroxide, and weight percent concentration is 20%; Oxidant is a potassium permanganate, and weight percent concentration is 3%, and the concentration of TBAB is 3000mg/l;
(3) polyvinylidene fluoride film with above-mentioned processing impregnated in the vitriolated sodium hydrogensulfite, removes the potassium permanganate and the potassium hydroxide on surface, and with washed with de-ionized water 10 times, oven dry, wherein, the concentration of volume percent of sulfuric acid is 1%, and the weight percent concentration of sodium hydrogensulfite is 3%.
(4) film immersion with above-mentioned processing is in 10% glycerite in concentration of volume percent, reacts 15min at normal temperatures, washed with de-ionized water 10 times of reaction back, oven dry.
Embodiment 2
(1) with polyvinylidene fluoride microporous filtering film with washed with de-ionized water 10 times, be dipped in then in 70% the ethanolic solution and soak 24hr, again it is immersed in deionized water;
(2) polyvinylidene fluoride film of above-mentioned processing be impregnated in to add phase transfer catalyst be in the alkali/oxidizing agent solution of TBAB, react 60min under 60 ° of C, wherein, alkali is potassium hydroxide, and weight percent concentration is 30%; Oxidant is a potassium permanganate, and weight percent concentration is 2%, and the concentration of TBAB is 5000mg/l;
(3) polyvinylidene fluoride film with above-mentioned processing impregnated in the vitriolated sodium hydrogensulfite, removes the potassium permanganate and the potassium hydroxide on surface, and with washed with de-ionized water 10 times, oven dry, wherein, the concentration of volume percent of sulfuric acid is 2%, and the weight percent concentration of sodium hydrogensulfite is 2%.
(4) film immersion with above-mentioned processing is in 15% glycerite in concentration of volume percent, reacts 10min at normal temperatures, washed with de-ionized water 10 times of reaction back, oven dry.
Embodiment 3
(1) with polyvinylidene fluoride microporous filtering film with washed with de-ionized water 10 times, be dipped in then in 70% the ethanolic solution and soak 24hr, again it is immersed in deionized water;
(2) polyvinylidene fluoride film of above-mentioned processing be impregnated in to add phase transfer catalyst be in the alkali/oxidizing agent solution of TBAB, react 50min under 40 ° of C, wherein, alkali is potassium hydroxide, and weight percent concentration is 40%; Oxidant is a potassium permanganate, and weight percent concentration is 3%, and the concentration of TBAB is 4000mg/l;
(3) polyvinylidene fluoride film with above-mentioned processing impregnated in the vitriolated sodium hydrogensulfite, removes the potassium permanganate and the potassium hydroxide on surface, and with washed with de-ionized water 10 times, oven dry, wherein, the concentration of volume percent of sulfuric acid is 2.5%, and the weight percent concentration of sodium hydrogensulfite is 3%.
(4) film immersion with above-mentioned processing is in 20% glycerite in concentration of volume percent, reacts 20min at normal temperatures, washed with de-ionized water 10 times of reaction back, oven dry.
Embodiment 4
(1) with polyvinylidene fluoride microporous filtering film with washed with de-ionized water 10 times, be dipped in then in 70% the ethanolic solution and soak 24hr, again it is immersed in deionized water;
(2) polyvinylidene fluoride film being impregnated in the adding phase transfer catalyst is in the alkali/oxidizing agent solution of TBAB, reacts 20min under 20 ° of C, and wherein, alkali is potassium hydroxide, and weight percent concentration is 10%; Oxidant is a potassium permanganate, and weight percent concentration is 1%, and the concentration of TBAB is 2000mg/l;
(3) polyvinylidene fluoride film with above-mentioned processing impregnated in the vitriolated sodium hydrogensulfite, removes the potassium permanganate and the potassium hydroxide on surface, and with washed with de-ionized water 10 times, oven dry, wherein, the concentration of volume percent of sulfuric acid is 1%, and the weight percent concentration of sodium hydrogensulfite is 1%.
(4) film immersion with above-mentioned processing is in 20% glycerite in concentration of volume percent, reacts 20min at normal temperatures, washed with de-ionized water 10 times of reaction back, oven dry.
Embodiment 5
(1) with polyvinylidene fluoride microporous filtering film with washed with de-ionized water 10 times, be dipped in then in 70% the ethanolic solution and soak 24hr, again it is immersed in deionized water;
(2) polyvinylidene fluoride film being impregnated in the adding phase transfer catalyst is in the alkali/oxidizing agent solution of TBAB, reacts 60min under 80 ° of C, and wherein, alkali is potassium hydroxide, and weight percent concentration is 50%; Oxidant is a potassium permanganate, and weight percent concentration is 5%, and the concentration of TBAB is 3500mg/l;
(3) polyvinylidene fluoride film with above-mentioned processing impregnated in the vitriolated sodium hydrogensulfite, removes the potassium permanganate and the potassium hydroxide on surface, and with washed with de-ionized water 10 times, oven dry, wherein, the concentration of volume percent of sulfuric acid is 3%, and the weight percent concentration of sodium hydrogensulfite is 3%.
(4) film immersion with above-mentioned processing is in 5% glycerite in concentration of volume percent, reacts 20min at normal temperatures, washed with de-ionized water 10 times of reaction back, oven dry.
Utilize the size of contact angle to characterize the hydrophily of polyvinylidene fluoride film, method of testing is:
Adopt the JC 2000A contact angle measurement of Shanghai Zhongchen digital technology equipment Co., Ltd, entirely be affixed on sample bench on two-sided tape the Kynoar diaphragm, drop is dropped in the film surface with the micro-amounts of liquids injector, the quick freezing image goes out the static contact angle of sample through the computer The Fitting Calculation.Each sample is surveyed 8 times at least, after removal maximum and the minimum of a value, surveys its mean value.The results are shown in Table 1.
Table 1
Can be illustrated by test result: to be reduced to mean value from 123.9 ° be 43.3 ° to contact angle after the polyvinylidene fluoride film modification, hydrophily has all obtained improving preferably, and with the prolongation of standing time, when be 60 days standing time, contact angle rises to 53.2 ° of mean values from 43.3 ° of mean values, only improve 9.9 °, the polyvinylidene fluoride film modification is described after hydrophily have persistence preferably.
Claims (6)
1. the method for a performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane is characterized in that, concrete steps are:
The first step, use the washed with de-ionized water polyvinylidene fluoride microporous filtering film, it is dipped in the ethanolic solution that concentration expressed in percentage by volume is 50-90% then and soaks 12-36hr, again it is immersed in deionized water;
Second goes on foot, the polyvinylidene fluoride microporous film after the first step processing is joined in the alkaline oxygenated agent solution, reacts 20-60min down at 20-80 ℃, wherein, contains alkali and oxidant potassium permanganate in the described alkaline oxidiser;
The 3rd goes on foot, the polyvinylidene fluoride microporous film after the processing of second step is immersed remove surperficial alkali and oxidant potassium permanganate in the acidic reduction agent solution, uses washed with de-ionized water, oven dry;
It is in the glycerite of 5-20% that the 4th step, the polyvinylidene fluoride microporous film after the 3rd step handled immerse concentration of volume percent, reacts 5-20min at normal temperatures, use washed with de-ionized water, dries.
2. the method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane as claimed in claim 1 is characterized in that, the alkaline oxygenated agent solution described in second step is made up of alkali, oxidant potassium permanganate, phase transfer catalyst TBAB and water.
3. the method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane as claimed in claim 2, it is characterized in that, described alkali is potassium hydroxide, the weight percent concentration of potassium hydroxide is 10-50%, the weight percent concentration of potassium permanganate is 1-5%, and the concentration of TBAB is 2000mg/l-5000mg/l.
4. the method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane as claimed in claim 1 is characterized in that, the acidic reduction agent solution described in the 3rd step is made up of sulfuric acid, reducing agent sodium hydrogensulfite and water.
5. the method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane as claimed in claim 4 is characterized in that, the concentration of volume percent of sulfuric acid is 1-3%, and the weight percent concentration of sodium hydrogensulfite is 1-3%.
6. the method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane as claimed in claim 1 is characterized in that, the glycerite concentration of volume percent described in the 4th step is 5-20%, and the reaction time is 5-20min at normal temperatures.
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| CN102786140A (en) * | 2011-05-20 | 2012-11-21 | 北京师范大学 | Surface modification method of polypropylene biological filling material |
| CN103272495A (en) * | 2013-06-22 | 2013-09-04 | 南昌航空大学 | Method for preparing hydrophilic polyvinylidene fluoride hollow fiber membrane |
| CN103272496A (en) * | 2013-06-22 | 2013-09-04 | 南昌航空大学 | Method for preparing hydrophilic polyvinylidene fluoride flat sheet membrane |
| CN103521090A (en) * | 2013-09-25 | 2014-01-22 | 中山朗清膜业有限公司 | Production process of hydrophilic polyvinylidene fluoride hollow fiber membrane |
| CN104292490A (en) * | 2014-09-29 | 2015-01-21 | 常州回天新材料有限公司 | Method for modifying PDVF thin film |
| CN105597576A (en) * | 2015-12-25 | 2016-05-25 | 西南石油大学 | Preparation method of beta-cyclodextrin grafted polyvinylidene fluoride ultrafiltration membrane |
| CN106902641A (en) * | 2017-03-21 | 2017-06-30 | 亚美滤膜（南通）有限公司 | The hydrophilically modified processing method of semi-permeable filter membrane and macromolecule plastic film |
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| CN109046035A (en) * | 2018-08-28 | 2018-12-21 | 浙江工业大学 | A kind of hydrophilic modifying Kynoar filter membrane and its application |
| CN110694487A (en) * | 2019-11-27 | 2020-01-17 | 大连交通大学 | Device and method for electrochemically modifying polyvinylidene fluoride membrane |
| CN110841488A (en) * | 2019-12-05 | 2020-02-28 | 江苏美能膜材料科技有限公司 | Preparation method of hydrophilic polyvinylidene fluoride hollow fiber dry film filament |
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2010
- 2010-08-30 CN CN 201010265038 patent/CN101912740A/en active Pending
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| 《高分子材料科学与工程》 20100630 黎聪等 《聚偏氟乙烯膜亲水化改性及在酪蛋白分离中的应用》 100 1-6 第26卷, 第6期 2 * |
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| CN102786140B (en) * | 2011-05-20 | 2014-04-30 | 北京师范大学 | Surface modification method of polypropylene biological filling material |
| CN102786140A (en) * | 2011-05-20 | 2012-11-21 | 北京师范大学 | Surface modification method of polypropylene biological filling material |
| CN103272495A (en) * | 2013-06-22 | 2013-09-04 | 南昌航空大学 | Method for preparing hydrophilic polyvinylidene fluoride hollow fiber membrane |
| CN103272496A (en) * | 2013-06-22 | 2013-09-04 | 南昌航空大学 | Method for preparing hydrophilic polyvinylidene fluoride flat sheet membrane |
| CN103521090A (en) * | 2013-09-25 | 2014-01-22 | 中山朗清膜业有限公司 | Production process of hydrophilic polyvinylidene fluoride hollow fiber membrane |
| CN104292490A (en) * | 2014-09-29 | 2015-01-21 | 常州回天新材料有限公司 | Method for modifying PDVF thin film |
| CN105597576A (en) * | 2015-12-25 | 2016-05-25 | 西南石油大学 | Preparation method of beta-cyclodextrin grafted polyvinylidene fluoride ultrafiltration membrane |
| CN106902641B (en) * | 2017-03-21 | 2021-04-02 | 亚美滤膜（南通）有限公司 | Hydrophilic modification treatment method for semi-permeable filter membrane and high-molecular plastic film |
| CN106902641A (en) * | 2017-03-21 | 2017-06-30 | 亚美滤膜（南通）有限公司 | The hydrophilically modified processing method of semi-permeable filter membrane and macromolecule plastic film |
| CN106943894A (en) * | 2017-04-21 | 2017-07-14 | 北京师范大学 | High performance ultra filtration composite membrane that a kind of graphene oxide is modified and preparation method thereof |
| CN106943894B (en) * | 2017-04-21 | 2019-10-22 | 北京师范大学 | A kind of high performance ultra filtration composite membrane and preparation method thereof that graphene oxide is modified |
| CN109046035A (en) * | 2018-08-28 | 2018-12-21 | 浙江工业大学 | A kind of hydrophilic modifying Kynoar filter membrane and its application |
| CN110694487A (en) * | 2019-11-27 | 2020-01-17 | 大连交通大学 | Device and method for electrochemically modifying polyvinylidene fluoride membrane |
| CN110694487B (en) * | 2019-11-27 | 2021-12-17 | 大连交通大学 | Device and method for electrochemically modifying polyvinylidene fluoride membrane |
| CN110841488A (en) * | 2019-12-05 | 2020-02-28 | 江苏美能膜材料科技有限公司 | Preparation method of hydrophilic polyvinylidene fluoride hollow fiber dry film filament |
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Open date: 20101215 |