CN103127841A - Polyvinylidene fluoride hydrophilic modified membrane and preparation method thereof - Google Patents
Polyvinylidene fluoride hydrophilic modified membrane and preparation method thereof Download PDFInfo
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- CN103127841A CN103127841A CN2011103850945A CN201110385094A CN103127841A CN 103127841 A CN103127841 A CN 103127841A CN 2011103850945 A CN2011103850945 A CN 2011103850945A CN 201110385094 A CN201110385094 A CN 201110385094A CN 103127841 A CN103127841 A CN 103127841A
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- kynoar
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Abstract
The invention discloses a polyvinylidene fluoride hydrophilic modified membrane and a preparation method of the polyvinylidene fluoride hydrophilic modified membrane. The polyvinylidene fluoride hydrophilic modified membrane is composed of 12-22% polyvinylidene fluoride hydrophilic, 0.5-15% hydrophilic polymer and 63-87.5% polarity good solvent. By means of the prepared polyvinylidene fluoride hydrophilic modified membrane, a pore-forming agent does not need to be added. Compared with the prior art, the polyvinylidene fluoride hydrophilic modified membrane and the preparation method of the polyvinylidene fluoride hydrophilic modified membrane have the advantages of being simple in operation method, big in water flux, relatively small in water contact angle, good in hydrophilicity, good in uniformity and the like. The prepared polyvinylidene fluoride hydrophilic modified membrane is suitable for being made into a composite type flat sheet membrane and used for a membrane bioreactor.
Description
Technical field
The invention belongs to membrane science and technology field of membrane materials, specifically relate to a kind of Kynoar hydrophilic modifying film and preparation method thereof.
Background technology
Kynoar (PVDF) has good chemical stability, heat resistance and mechanical property, and uvioresistant irradiation and the performance such as ageing-resistant, and dissolve in some intensive polar solvent, be easy to use the phase inversion masking, be a kind of novel film materials of high comprehensive performance, caused in membrane separation technique that in recent years people's very big interest is (referring to Zhang Kan etc., fine chemistry industry, 2001,18:100; Tang Guangjun etc., the chemical industry progress, 2004,23:480).But its strong-hydrophobicity makes PVDF can produce two problems when aqueous phase separation: the one, see through the membrane mass transfer driving force high, and energy consumption is large; The 2nd, very easily adsorb organic compound, protein etc. cause film to pollute, and water flux descends.Therefore, to the pvdf membrane hydrophilic modification, and then realize the reduction energy consumption, improve water flux, strengthen the film contamination resistance to be very necessary.
At present, the main method of pvdf membrane hydrophilic modification there are surface chemical modification, plasma modification, irradiation grafting modification and blending and modifying.
First three methods can be introduced polar group or large hydrophilic molecular chain on pvdf membrane, improve the hydrophily of film.Although these methods have advantage separately, but there is certain limitation.Surface chemical modification, although realized hydrophilic modification from the film surface, because the C-F bond energy is higher, the film surface chemical modification more difficult (referring to Shao Pinghai etc., water technology, 1995,21:26); Plasma modification, due to the motion of PVDF strand, the polar group of introducing can prolongation in time be transferred to membrane body, and modified effect is unstable (referring to Iwata etc., J. Membr. Sci. 1988,38:185; Wang etc., E. T. J. Membr. Sci. 2002,19:5103; Rafik etc. Eur. Polym. J. 2000,36:1911); The irradiation grafting modification, the disposable apparatus expense is high, be difficult to realize industrialization (referring to Zuo Danying etc., membrane science and technology, 2006,26:41); And compare, the blending and modifying of pvdf membrane can be avoided above-mentioned unfavorable factor, and blending and modifying is simple to operation, has industrial prospect, and is significant.
Blending and modifying refers under the prerequisite of not destroying the pvdf membrane structure, the method that hydrophilic polymer and PVDF combine with intermolecular force.By the character that complementation and the cooperative effect of character between different polymer are improved membrane material, utilize Compatibility Between Polymers difference regulation and control membrane structure.This method is easy and simple to handle, not only can improve the hydrophily of film, and has preserved the premium properties of pvdf membrane body.
Summary of the invention
Generally need to use simultaneously pore former and hydrophilic polymer in the Kynoar hydrophilic modification, pore former commonly used has polyvinylpyrrolidone, polyethylene glycol, lithium chloride and polyvinyl alcohol.
The object of the present invention is to provide and a kind ofly need not to add pore former and can realize preparation method to the hydrophilic modification of Kynoar.
For reaching this purpose, the present invention adopts following technical scheme:
A kind of formula of Kynoar hydrophilic modifying film is made of as following weight percent following component:
Kynoar 12～22%, hydrophilic polymer 0.5～15%, polarity good solvent 63～87.5%;
Described hydrophilic polymer is selected from one or more combinations in polymethyl methacrylate, polyacrylonitrile or cellulose acetate;
One or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE of described polarity good solvent.
As preferred embodiment, in the formula of above-mentioned Kynoar hydrophilic modifying film, contain Kynoar 16～18%, hydrophilic polymer 1～2%, polarity good solvent 80-83%.
Above-mentioned hydrophilic polymer is preferably polymethyl methacrylate, and the polarity good solvent is preferably dimethylacetylamide.
The present invention also provides a kind of preparation method of Kynoar hydrophilic modifying film, comprises the steps:
(1) preparation casting solution: casting solution is comprised of by mass percent following component: Kynoar 12～22%, hydrophilic polymer 0.5～15%, polarity good solvent 63～87.5%, described polarity good solvent is selected from one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE, described casting solution was dissolved in the baking oven of 50～60 ℃ 40～50 hours, discontinuous degassing forms homogeneous phase solution;
(2) preparation film: the described casting solution of step (1) is carried out at the uniform velocity knifing on glass plate, then soak film forming in water and/or ethanol medium, soaking time swap is 20～30 hours, namely gets Kynoar hydrophilic modifying film.
The Kynoar hydrophilic modifying film of the present invention's preparation is suitable as membrane for water treatment, can be prepared into compound flat sheet membrane on nonwoven by being attached to, and is used for membrane bioreactor.
Compared with prior art, the invention has the advantages that:
(1) general polyvinylidene fluoride resin all can be used for the present invention;
(2) need not to add pore former, easy and simple to handle;
(3) the Kynoar hydrophilic modifying film pure water flux of preparation has had significantly raising, the pure water contact angle also has obvious reduction, the hydrophilicity of Kynoar hydrophilic modifying film significantly improves, although mechanical property has a little to reduce, the Kynoar hydrophilic modifying film that possesses this mechanical property can satisfy the application aspect water treatment.
The method of testing of Kynoar hydrophilic modifying film of the present invention is as follows:
(1) hot strength and elongation at break method of testing
Adopt the universal electrical puller system to carry out Mechanics Performance Testing, test condition: temperature is 25 ℃, and rate of extension is 25 mm/min, and the flat sheet membrane specimen length is 100 mm, and gauge length is 60 mm.Adopt at last hot strength formula and elongation at break formula to calculate hot strength and elongation at break, computing formula is as follows:
Hot strength:
δ=F/S
S=a×b
Wherein: F is maximum pull, and S is cross-sectional area, and a is the width of flat sheet membrane, and b is the thickness of flat sheet membrane.
Elongation at break:
ρ?=?L/L
0
Wherein: L is the sample elongation, L
0Be the former length of sample.
(2) pure water flux method of testing
Flat sheet membrane is packed in the water flux tester, under 25 ℃, first adopt 0.15 MPa to its precompressed 30 min, the pure water quality that then sees through in 0.10 MPa lower-weighing 20 min, obtain its pure water flux by the water flux computing formula at last, the water flux computing formula is as follows:
J=see through liquid to amass/(film effective area * time) (L/ m
2H)
(3) rotary viscosity
PVDF is dissolved in DMAC, is mixed with the weak solution of 0.1 g/ml, then under 30 ℃, adopt rotation viscometer (NDJ-8SN) to measure its rotary viscosity.
(4) pure water contact angle
The method of dripping is measured the pure water contact angle on PVDF microporous barrier surface on OCA20 type video optics contact angle measurement with lying.1 μ L pure water drops in face, captures by the high speed video system of instrument the image photograph that drop is attached to the film surface.Adopt elliptic method (as shown below) to determine baseline, determine drop profile profile, choose suitable computational methods match appearance curve, calculate the pure water contact angle.
Description of drawings
Figure of description is partly measured the method for pure water contact angle for the available technology adopting elliptic method.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but do not limit the invention to these specific embodiment.One skilled in the art would recognize that the present invention contained all alternatives, improvement project and the equivalents that may comprise in claims scope.
Embodiment 1
Accurately take Kynoar 15g, dimethylacetylamide 84.5g, polymethyl methacrylate 0.5g is mixed with the blend casting solution, and solution temperature is 55
oC, dissolution time are 48 hours, the solution clear.Topple over casting solution and at the uniform velocity carry out knifing on glass plate, then soak film forming in water, time swap is 24 hours in water, finally makes Kynoar hydrophilic modifying film of the present invention.After tested, its hot strength=3.26MPa, elongation at break=58.5%, pure water flux=8.5L/m
2H(0.1MPa), rotary viscosity 2710mpas(30
oC), pure water contact angle=77.5
o
Embodiment 2
Accurately take Kynoar 15g, dimethylacetylamide 84g, polymethyl methacrylate 1g is mixed with the blend casting solution, and solution temperature is 55
oC, dissolution time are 48 hours, the solution clear.Topple over casting solution and at the uniform velocity carry out knifing on glass plate, then soak film forming in water, time swap is 24 hours in water, finally makes Kynoar hydrophilic modifying film of the present invention.After tested, its hot strength=2.26MPa, elongation at break=28.7%, pure water flux=19.8L/m
2H(0.1MPa), rotary viscosity 2870mpas(30
oC), pure water contact angle=75.9
o
Embodiment 3
Accurately take Kynoar 15g, dimethylacetylamide 83g, polymethyl methacrylate 2g is mixed with the blend casting solution, and solution temperature is 55
oC, dissolution time are 48 hours, the solution clear.Topple over casting solution and at the uniform velocity carry out knifing on glass plate, then soak film forming in water, time swap is 24 hours in water, finally makes Kynoar hydrophilic modifying film of the present invention.After tested, its hot strength=1.58MPa, elongation at break=21.8%, pure water flux=133.4L/m
2H(0.1MPa), rotary viscosity 2990 mpas(30
oC), pure water contact angle=69.9
o
Embodiment 4
Accurately take Kynoar 15g, dimethylacetylamide 80g, polymethyl methacrylate 5g is mixed with the blend casting solution, and solution temperature is 55
oC, dissolution time are 48 hours, the solution clear.Topple over casting solution and at the uniform velocity carry out knifing on glass plate, then soak film forming in water, time swap is 24 hours in water, finally makes Kynoar hydrophilic modifying film of the present invention.After tested, its hot strength=1.95MPa, elongation at break=20.4%, pure water flux=395.5L/m
2H(0.1MPa), rotary viscosity 3490 mpas(30
oC), pure water contact angle=64.2
o
Comparative example
Accurately take Kynoar 15g, dimethylacetylamide 85g is mixed with the blend casting solution, and solution temperature is 55
oC, dissolution time are 48 hours, the solution clear.Topple over casting solution and at the uniform velocity carry out knifing on glass plate, then soak film forming in water, time swap is 24 hours in water, finally makes Kynoar hydrophilic modifying film of the present invention.After tested, its hot strength=4.73MPa, elongation at break=72.1%, pure water flux=1.1L/m
2H(0.1MPa), rotary viscosity 2680mpas(30
oC), pure water contact angle=86.5
o
Table 1 Kynoar hydrophilic modifying film properties
the prepared Kynoar hydrophilic modifying film of the present invention is compared with embodiment 1-2 in Chinese patent CN 101147848A, in the situation that do not add the polyvinyl alcohol pore former, overcome film inhomogeneous, there are the shortcomings such as lamination, pure water flux has had significantly raising, the pure water contact angle also has obvious reduction, the hydrophilicity of Kynoar hydrophilic modifying film significantly improves, although mechanical property has a little reduction, but the Kynoar hydrophilic modifying film that possesses this mechanical property can satisfy the application aspect water treatment, simultaneously can also make up by Kynoar hydrophilic modifying film being attached to compound flat sheet membrane that nonwoven prepares the reduction of mechanical property.
Claims (7)
1. the formula of a Kynoar hydrophilic modifying film is characterized in that being comprised of as following weight percent following component:
Kynoar 12～22%, hydrophilic polymer 0.5～15%, polarity good solvent 63～87.5%;
Described hydrophilic polymer is selected from one or more combinations in polymethyl methacrylate, polyacrylonitrile or cellulose acetate;
One or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE of described polarity good solvent.
2. according to the formula of Kynoar hydrophilic modifying film claimed in claim 1, it is characterized in that containing Kynoar 16～18%, hydrophilic polymer 1～2%, polarity good solvent 80～83%.
3. according to the formula of Kynoar hydrophilic modifying film claimed in claim 1, it is characterized in that described hydrophilic polymer is polymethyl methacrylate, described polarity good solvent is dimethylacetylamide.
4. according to the preparation method of Kynoar hydrophilic modifying film claimed in claim 1, it is characterized in that comprising the steps:
(1) preparation casting solution: casting solution is comprised of by mass percent following component: Kynoar 12～22%, hydrophilic polymer 0.5～15%, polarity good solvent 63～87.5%, described polarity good solvent is selected from one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE, described casting solution was dissolved in the baking oven of 50～60 ℃ 40～50 hours, discontinuous degassing forms homogeneous phase solution;
(2) preparation film: the described casting solution of step (1) is carried out at the uniform velocity knifing on glass plate, then soak film forming in water and/or ethanol medium, soaking time swap is 20～30 hours, namely gets Kynoar hydrophilic modifying film.
5. according to the preparation method of Kynoar hydrophilic modifying film claimed in claim 4, it is characterized in that described polarity good solvent is dimethylacetylamide, described hydrophilic polymer is polymethyl methacrylate.
6. according to the application of the described Kynoar hydrophilic modifying of one of claim 1 to 5 film, it is characterized in that Kynoar hydrophilic modifying film is attached to and be prepared into compound flat sheet membrane on nonwoven.
7. according to the application of Kynoar hydrophilic modifying film claimed in claim 6, it is characterized in that described compound flat sheet membrane is used for membrane bioreactor.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248915A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Preparation method of enhanced flat composite microporous membrane for improving hydrophility |
| CN104524997A (en) * | 2014-12-31 | 2015-04-22 | 哈尔滨理工大学 | Hydrophilic modification method of PVDF multihole film |
| CN104971631A (en) * | 2015-07-24 | 2015-10-14 | 中南大学 | Preparation method of high-flux PVDF (polyvinylidene fluoride) porous membrane |
| CN105126635A (en) * | 2015-08-07 | 2015-12-09 | 东莞理工学院 | Novel hydrophilic composite tube type microfiltration membrane and preparation method thereof |
| CN107174964A (en) * | 2017-07-24 | 2017-09-19 | 上海应用技术大学 | A kind of use isopropanol coagulation bath regulates and controls the method that hydrophilic F127 PVDF are modified membrane structure |
| CN107297157A (en) * | 2016-12-30 | 2017-10-27 | 天津工业大学 | A kind of hydrophiling, the preparation method of anti-pollution PVDF seperation film |
| CN107349799A (en) * | 2017-08-03 | 2017-11-17 | 浙江工业大学 | A kind of preparation method of antipollution macromolecule inorganic hybrid membrane |
| CN108695474A (en) * | 2018-04-02 | 2018-10-23 | 河南工程学院 | A kind of preparation method of the porous pvdf membrane of battery diaphragm |
| CN109173743A (en) * | 2018-10-17 | 2019-01-11 | 常州大学 | A kind of hollow nano silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof |
| CN109485884A (en) * | 2018-11-02 | 2019-03-19 | 北京石油化工学院 | The preparation method of polyvinylidene difluoride film |
| CN110323396A (en) * | 2019-06-21 | 2019-10-11 | 王宽 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| CN111408277A (en) * | 2020-03-11 | 2020-07-14 | 宁波水艺膜科技发展有限公司 | Rapid crosslinking preparation method of super-hydrophilic polyvinylidene fluoride microporous membrane |
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| CN101239280A (en) * | 2007-11-27 | 2008-08-13 | 北京市射线应用研究中心 | Reinforced microporous filter membrane and method and device for preparing the same |
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| CN101879418A (en) * | 2010-08-18 | 2010-11-10 | 天津工业大学 | Preparation method of polyvinylidene fluoride modified film |
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| CN101239280A (en) * | 2007-11-27 | 2008-08-13 | 北京市射线应用研究中心 | Reinforced microporous filter membrane and method and device for preparing the same |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248915B (en) * | 2013-06-28 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of preparation method improving hydrophilic enhancement mode plate compounding microporous barrier |
| CN104248915A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Preparation method of enhanced flat composite microporous membrane for improving hydrophility |
| CN104524997A (en) * | 2014-12-31 | 2015-04-22 | 哈尔滨理工大学 | Hydrophilic modification method of PVDF multihole film |
| CN104971631A (en) * | 2015-07-24 | 2015-10-14 | 中南大学 | Preparation method of high-flux PVDF (polyvinylidene fluoride) porous membrane |
| CN104971631B (en) * | 2015-07-24 | 2017-03-29 | 中南大学 | A kind of preparation method of high flux PVDF perforated membranes |
| CN105126635A (en) * | 2015-08-07 | 2015-12-09 | 东莞理工学院 | Novel hydrophilic composite tube type microfiltration membrane and preparation method thereof |
| CN107297157A (en) * | 2016-12-30 | 2017-10-27 | 天津工业大学 | A kind of hydrophiling, the preparation method of anti-pollution PVDF seperation film |
| CN107174964A (en) * | 2017-07-24 | 2017-09-19 | 上海应用技术大学 | A kind of use isopropanol coagulation bath regulates and controls the method that hydrophilic F127 PVDF are modified membrane structure |
| CN107349799B (en) * | 2017-08-03 | 2020-06-09 | 浙江工业大学 | Preparation method of anti-pollution polymer-inorganic hybrid membrane |
| CN107349799A (en) * | 2017-08-03 | 2017-11-17 | 浙江工业大学 | A kind of preparation method of antipollution macromolecule inorganic hybrid membrane |
| CN108695474A (en) * | 2018-04-02 | 2018-10-23 | 河南工程学院 | A kind of preparation method of the porous pvdf membrane of battery diaphragm |
| CN108695474B (en) * | 2018-04-02 | 2021-05-04 | 河南工程学院 | Preparation method of porous PVDF film for battery diaphragm |
| CN109173743A (en) * | 2018-10-17 | 2019-01-11 | 常州大学 | A kind of hollow nano silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof |
| CN109173743B (en) * | 2018-10-17 | 2021-04-30 | 常州大学 | Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof |
| CN109485884A (en) * | 2018-11-02 | 2019-03-19 | 北京石油化工学院 | The preparation method of polyvinylidene difluoride film |
| CN109485884B (en) * | 2018-11-02 | 2021-07-09 | 北京石油化工学院 | Preparation method of polyvinylidene fluoride film |
| CN110323396A (en) * | 2019-06-21 | 2019-10-11 | 王宽 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| CN110323396B (en) * | 2019-06-21 | 2022-08-30 | 王宽 | Lithium ion battery composite diaphragm and preparation method thereof |
| CN111408277A (en) * | 2020-03-11 | 2020-07-14 | 宁波水艺膜科技发展有限公司 | Rapid crosslinking preparation method of super-hydrophilic polyvinylidene fluoride microporous membrane |
| CN111408277B (en) * | 2020-03-11 | 2022-02-18 | 宁波水艺膜科技发展有限公司 | Rapid crosslinking preparation method of super-hydrophilic polyvinylidene fluoride microporous membrane |
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Application publication date: 20130605 |