CN101357304B - Surface modification method of polyvinylidene fluoride membrane - Google Patents
Surface modification method of polyvinylidene fluoride membrane Download PDFInfo
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- CN101357304B CN101357304B CN2008101371840A CN200810137184A CN101357304B CN 101357304 B CN101357304 B CN 101357304B CN 2008101371840 A CN2008101371840 A CN 2008101371840A CN 200810137184 A CN200810137184 A CN 200810137184A CN 101357304 B CN101357304 B CN 101357304B
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Abstract
A surface modification method of a polyvinylidene fluoride membrane relates to a surface modification method of a membrane. The surface modification method solves the problems of the existing polyvinylidene fluoride membranes of poor hydrophilicity, easy pollution, low water production rate and complex modification process. The surface modification method comprises the following steps: a. a polyvinylidene fluoride membrane is soaked in mixed solution of an oxidant and strong alkali, and washed; b; the washed polyvinylidene fluoride membrane is soaked in nano oxide sol and washed, and then thesurface modified polyvinylidene fluoride membrane is obtained. The modification method improves anti-pollution capability of the polyvinylidene fluoride membrane, prolongs the service life by 20%-35%, causes the polyvinylidene fluoride membrane to have good hydrophilicity and improves the water flux by 17%-40%, and the process of the method is simple.
Description
Technical field
The present invention relates to a kind of surface modifying method of film.
Background technology
Compare with traditional water treatment technology, membrane separation technique have take up an area of little, energy consumption is low, effluent quality is excellent, treatment effect is good, to characteristics such as ambient influnence are little, be the new and high technology that solves the contemporary energy, resource and environmental problem.But because film pollutes, problem such as the life-span of film is short has limited membrane separation technique further in the extensive use of water treatment field.
In the present employed membrane material, macromolecule organic polymer Kynoar (PVDF) has advantages such as good resistance to impact, wearability and chemical stability.But because polyvinylidene fluoride surface can be low, the film hydrophily for preparing is poor, relatively is easy to generate the absorption pollution in water treatment procedure, thereby has reduced the aquifer yield of film, has increased the cleaning difficulty, shortens the life-span of film.At present, there are the physics of employing or chemical method that polyvinylidene fluoride film is carried out modification, but complex process.
Summary of the invention
The present invention seeks to have poor, the easy pollution of polyvinylidene fluoride film hydrophilically, the low problem that reaches the complex process of modification of water flux now, and a kind of surface modifying method of polyvinylidene fluoride film is provided in order to solve.
The surface modifying method of polyvinylidene fluoride film is realized according to the following steps: a, polyvinylidene fluoride film be impregnated in the mixed solution of oxidant and highly basic, under 30～90 ℃ condition, reacts 3～30min, then with deionized water rinsing to going out clarification of water; B, the polyvinylidene fluoride film after will washing impregnated in 5～30min in the nano-oxide colloidal sol, use deionized water rinsing then 1～3 time, promptly get the polyvinylidene fluoride film of surface modification; Wherein oxidant is potassium permanganate, hydrogen peroxide, clorox, sodium chlorate or potassium chlorate among the step a; Highly basic is potassium hydroxide or NaOH; In the mixed solution of oxidant and highly basic, the volume ratio of oxidant and highly basic is 1～3: 1～10 among the step a, and the mass concentration of oxidant is 0.5～10%, and the molar concentration of highly basic is 1～10mol/L; Nano-oxide colloidal sol is nano aluminium oxide colloidal sol, nano titanic oxide sol or nano silicon dioxide sol among the step b.
The present invention utilizes nano-oxide that polyvinylidene fluoride film is carried out modification, polyvinylidene fluoride film after the modification has not only kept the original good characteristic of polyvinylidene fluoride film, and improved the surface property of polyvinylidene fluoride film, improved contamination resistance, to prolong 20%～35% service life, good hydrophilic property shows that contact angle drops to 58 °～65 ° from 80 °, water flux has improved 17%～40%, and technology of the present invention is simple.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the surface modifying method of present embodiment polyvinylidene fluoride film is realized according to the following steps: a, polyvinylidene fluoride film be impregnated in the mixed solution of oxidant and highly basic, under 30～90 ℃ condition, react 3～30min, then with deionized water rinsing to going out clarification of water; B, the polyvinylidene fluoride film after will washing impregnated in 5～30min in the nano-oxide colloidal sol, use deionized water rinsing then 1～3 time, promptly get the polyvinylidene fluoride film of surface modification; Wherein oxidant is potassium permanganate, hydrogen peroxide, clorox, sodium chlorate or potassium chlorate among the step a; Highly basic is potassium hydroxide or NaOH; In the mixed solution of oxidant and highly basic, the volume ratio of oxidant and highly basic is 1～3: 1～10 among the step a, and the mass concentration of oxidant is 0.5～10%, and the molar concentration of highly basic is 1～10mol/L; Nano-oxide colloidal sol is nano aluminium oxide colloidal sol, nano titanic oxide sol or nano silicon dioxide sol among the step b.
Used polyvinylidene fluoride film can be existing various polyvinylidene fluoride films in the present embodiment.
The specific embodiment two: what present embodiment and the specific embodiment one were different is to react 10～20min among the step a under 40～80 ℃ condition.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is to react 15min among the step a under 60 ℃ condition.Other step and parameter are identical with the specific embodiment one.
The specific embodiment four: present embodiment and the specific embodiment one are different is that the volume ratio of oxidant and highly basic is 2: 5 among the step a, and the mass concentration of oxidant is 5%, and the molar concentration of highly basic is 5mol/L.Other step and parameter are identical with the specific embodiment one.
The specific embodiment five: present embodiment and the specific embodiment one are different is that polyvinylidene fluoride film after will washing among the step b impregnated in 15min in the nano-oxide colloidal sol, uses deionized water rinsing then 2 times.Other step and parameter are identical with the specific embodiment one.
The specific embodiment six: present embodiment and the specific embodiment one are different be among the step b in the nano-oxide colloidal sol particle diameter of oxide be 1nm～900nm.Other step and parameter are identical with the specific embodiment one.
The specific embodiment seven: the surface modifying method of present embodiment polyvinylidene fluoride film is realized according to the following steps: a, polyvinylidene fluoride film be impregnated in the mixed solution of potassium permanganate and potassium hydroxide, under 60 ℃ condition, react 15min, then with deionized water rinsing to going out clarification of water; B, the polyvinylidene fluoride film after will washing impregnated in 15min in the nano aluminium oxide colloidal sol, use deionized water rinsing then 2 times, promptly get the polyvinylidene fluoride film of surface modification; Wherein in the mixed solution of step a potassium permanganate and potassium hydroxide, the volume ratio of oxidant and highly basic is 2: 5, and the mass concentration of oxidant is 5%, and the molar concentration of highly basic is 5mol/L.
The polyvinylidene fluoride film of surface modification in the present embodiment, water flux improves 17% after tested, and contamination resistance strengthens, and prolongs 22% service life.
The specific embodiment eight: the surface modifying method of present embodiment polyvinylidene fluoride film is realized according to the following steps: a, polyvinylidene fluoride film be impregnated in the mixed solution of potassium permanganate and potassium hydroxide, under 40 ℃ condition, react 20min, then with deionized water rinsing to going out clarification of water; B, the polyvinylidene fluoride film after will washing impregnated in 20min in the nano titanic oxide sol, use deionized water rinsing then 3 times, promptly get the polyvinylidene fluoride film of surface modification; Wherein in the mixed solution of step a potassium permanganate and potassium hydroxide, the volume ratio of oxidant and highly basic is 1: 4, and the mass concentration of oxidant is 4%, and the molar concentration of highly basic is 3mol/L.
The polyvinylidene fluoride film of surface modification in the present embodiment, surface property improves after tested, and good hydrophilic property shows that contact angle drops to 58 ° from 80 °.
Claims (5)
1. the surface modifying method of polyvinylidene fluoride film, the surface modification that it is characterized in that polyvinylidene fluoride film realizes according to the following steps: a, polyvinylidene fluoride film be impregnated in the mixed solution of oxidant and highly basic, under 30～90 ℃ condition, react 3～30min, then with deionized water rinsing to going out clarification of water; B, the polyvinylidene fluoride film after will washing impregnated in 5～30min in the nano-oxide colloidal sol, use deionized water rinsing then 1～3 time, promptly get the polyvinylidene fluoride film of surface modification; Wherein oxidant is potassium permanganate, hydrogen peroxide, clorox, sodium chlorate or potassium chlorate among the step a; Highly basic is potassium hydroxide or NaOH; In the mixed solution of oxidant and highly basic, the volume ratio of oxidant and highly basic is 1～3: 1～10 among the step a, and the mass concentration of oxidant is 0.5～10%, and the molar concentration of highly basic is 1～10mol/L; Nano-oxide colloidal sol is nano aluminium oxide colloidal sol, nano titanic oxide sol or nano silicon dioxide sol among the step b; Among the step b in the nano-oxide colloidal sol particle diameter of oxide be 1nm～900nm.
2. the surface modifying method of polyvinylidene fluoride film according to claim 1 is characterized in that reacting 10～20min among the step a under 40～80 ℃ condition.
3. the surface modifying method of polyvinylidene fluoride film according to claim 1 is characterized in that reacting 15min among the step a under 60 ℃ condition.
4. the surface modifying method of polyvinylidene fluoride film according to claim 1 is characterized in that the volume ratio of oxidant and highly basic is 2: 5 among the step a, and the mass concentration of oxidant is 5%, and the molar concentration of highly basic is 5mol/L.
5. the surface modifying method of polyvinylidene fluoride film according to claim 1, the polyvinylidene fluoride film after it is characterized in that will washing among the step b impregnated in 15min in the nano-oxide colloidal sol, uses deionized water rinsing then 2 times.
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| CN2008101371840A CN101357304B (en) | 2008-09-24 | 2008-09-24 | Surface modification method of polyvinylidene fluoride membrane |
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| CN2008101371840A CN101357304B (en) | 2008-09-24 | 2008-09-24 | Surface modification method of polyvinylidene fluoride membrane |
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| CN101357304B true CN101357304B (en) | 2011-04-20 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837251B (en) * | 2010-04-07 | 2012-05-23 | 南京工业大学 | Method for hydrophilic modification on polyvinylidene fluoride porous film surface by amphipathic molecule |
| CN102199306B (en) * | 2011-05-12 | 2013-01-30 | 苏州斯迪克新材料科技股份有限公司 | Membrane for sealing bag on inner wall of large airplane and surface treatment method thereof |
| CN102179190A (en) * | 2011-06-17 | 2011-09-14 | 上海应用技术学院 | Thermalsynthesis method and use of polyvinylidene fluoride composite mesoporous 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 |
| CN105126647B (en) * | 2015-09-10 | 2017-06-30 | 南京大学 | A kind of high efficiency oil-water separates the preparation method of composite hyperfiltration membrane |
| CN105617883B (en) * | 2015-12-28 | 2018-04-20 | 山东省科学院海洋仪器仪表研究所 | A kind of method using alumine hydroxide colloid to polypropylene filter hydrophilic modifying |
| CN105884079A (en) * | 2016-05-18 | 2016-08-24 | 南京海益环保工程有限公司 | Brackish water reverse osmosis treatment technique |
| CN107213803B (en) * | 2017-05-08 | 2020-01-14 | 武汉理工大学 | Polyvinylidene fluoride membrane surface grafting coating composite modification method |
| CN108837711B (en) * | 2018-06-20 | 2021-06-11 | 华南师范大学 | Preparation method and application of nanoparticle modified PVDF flat membrane |
| CN110180415A (en) * | 2019-05-27 | 2019-08-30 | 武汉纳霏膜科技有限公司 | A kind of method of hydrophilizing of reverse osmosis 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 |
| CN111717983B (en) * | 2020-07-06 | 2022-04-26 | 苏州汇博龙环保科技有限公司 | Process and equipment for modifying wastewater filler material and process for treating wastewater |
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