CN102872730B - Method for preparing polyvinylidene fluoride alloy film - Google Patents
Method for preparing polyvinylidene fluoride alloy film Download PDFInfo
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- CN102872730B CN102872730B CN201210362623.4A CN201210362623A CN102872730B CN 102872730 B CN102872730 B CN 102872730B CN 201210362623 A CN201210362623 A CN 201210362623A CN 102872730 B CN102872730 B CN 102872730B
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- polyvinylidene fluoride
- caprolactam
- fluoride alloy
- alloy membrane
- casting solution
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Abstract
The invention relates to a method for preparing a polyvinylidene fluoride alloy film, which comprises the following steps: 1), uniformly mixing polyvinylidene fluoride, hydrophilic copolymers and caprolactam; 2, heating the mixed polyvinylidene fluoride, hydrophilic copolymers and caprolactam under the protection of nitrogen to a solution temperature, and maintaining for 0.5-2 h at the temperature; 3), after the polyvinylidene fluoride, hydrophilic copolymers and caprolactam are completely solved, stirring for 0.5-1.5 h and then standing to obtain a casting solution, and saving the casting solution at the solution temperature; 4), fabricating the casting solution to a film which is then placed in the air for natural cooling until complete solidification; and 5), finally, extracting caprolactam, actually the polyvinylidene fluoride alloy film, through an extracting agent. The method has the advantages of simple technology, zero contamination and lower cost. The prepared polyvinylidene fluoride alloy film has the advantages of superior chemical stability, high mechanical strength, contamination resistance and easiness in cleaning. The method provided by the invention can provide high-performance alloy film products for the MBR technology in the filed of sewage disposal and water resource recycle, and has an extensive application in the fields of industry, medicine, sewage disposal and the like.
Description
Technical field
Patent of the present invention belongs to macromolecular material and manufactures field, specifically, relates to a kind of method preparing polyvinylidene fluoride alloy membrane, belongs to thermally induced phase separation.
Background technology
Kynoar (PVDF) has outstanding solvent resistance, resistance to acids and bases, UV resistant and weatherability, is a kind of membrane material of excellence.In recent years, polyvinylidene fluoride alloy membrane obtains good application at the dirty water decontamination handles and biochemical pharmacy industry.
Polyvinylidene fluoride alloy membrane is a kind of polymer porous film.The preparation of polymer porous film has multiple method, mainly contains phase inversion, pulling method, sintering process and irradiation method etc., and wherein phase inversion comprises again thermally induced phase separation, phase separation method etc.Phase inversion is one of modal method, it is the method being transformed film forming by the liquid-liquid phase separation of control polymer solution, according to the difference of the mode of being separated, thermal induction precipitated phase partition method, solution evaporative precipitation phase separation method, gaseous phase deposition phase separation method and immersion precipitation phase separation method can be divided into again.
Thermally induced phase separation (TIPS) obtains the attention of people gradually in membrane separation technique in recent years.Thermally induced phase separation (TIPS) is that the one proposed by Castro the eighties in 20th century is caused being separated by temperature change and prepares the method for perforated membrane (as microfiltration membranes, milipore filter).Use higher boiling, low-molecular-weight single or mixed diluent at high temperature forms homogeneous phase solution with high polymer, during cooling, homogeneous phase solution generation solid-liquid or liquid-liquid phase separation, then remove diluent, thus obtain the high polymer microcellular film with a fixed structure.Compare with other film-forming method, the film that suitable diluent can make thermally induced phase separation obtained has that intensity is good, porosity is high, aperture is easy to the advantages such as regulation and control, therefore receives the concern of people and obtains comparatively systematic research.The diluent of current employing mostly is water-insoluble cosolvent, water insoluble, so also they must be extracted with other extractant after film forming, complex process, and unfriendly to environment.In addition, due to the hydrophobicity of PVDF, simple pvdf membrane when applying easily by the Organic Pollution in water, and not easy cleaning.
Summary of the invention
Technical problem to be solved by this invention is, for the deficiencies in the prior art, provides a kind of technique simple, pollution-free, the lower-cost method preparing polyvinylidene fluoride alloy membrane.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of method preparing polyvinylidene fluoride alloy membrane, comprises the following steps:
1) Kynoar, hydrophilic macromolecule and caprolactam are mixed, wherein, the weight percentage of Kynoar is 15 ~ 25%, and the weight percentage of hydrophilic macromolecule is 1 ~ 4%, and the weight percentage of caprolactam is 70 ~ 85%;
2) mixed Kynoar, hydrophilic macromolecule and caprolactam are heated to solution temperature under nitrogen protection, and keep 0.5 ~ 2h at such a temperature;
3) after Kynoar, hydrophilic macromolecule and caprolactam dissolve completely, under solution temperature, stir 0.5 ~ 1.5h, leave standstill, obtain casting solution, casting solution is preserved under solution temperature;
4) above-mentioned casting solution is made film forming, place and naturally cool in atmosphere, until solidify completely;
5) last, extract caprolactam by extractant, namely obtain polyvinylidene fluoride alloy membrane.
Preferably, described hydrophilic macromolecule is one or more in polyethylene glycol oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP).
Preferably, in step 2) and step 3) in, the temperature range of described solution temperature is 140 ~ 170 DEG C.
Preferably, in step 5), described extractant is water or ethanol.
Preferably, in step 5), the thickness of described polyvinylidene fluoride alloy membrane is 20 ~ 200 μm.
Preferably, the thickness of described polyvinylidene fluoride alloy membrane is 100 ~ 140 μm.
Compared with prior art, the invention has the advantages that: (1) present invention utilizes " high-temperature digestion, low temperature phase-splitting " principle, using caprolactam as diluent, with hydrophilic macromolecule polyethylene glycol oxide (PEO), one or more in polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) are as additive, by Kynoar, at high temperature mixed dissolution stir into uniform casting solution after hydrophilic macromolecule mixes with caprolactam, again casting solution is made film forming, place to naturally cool in atmosphere and solidify completely, make casting solution system generation liquid-liquid or solid-liquid separation, the bicontinuous structure of PVDF and diluent is formed after polymeric system solidification, after this, caprolactam extraction on film is fallen, caprolactam position is formed poroid, the polymer backbone of remainder is then retained, (2) the present invention with the addition of hydrophilic macromolecule in the feed, improve the hydrophily of film, polyvinylidene fluoride alloy membrane is made to keep the performance of permanent hydrophilic, compared with the traditional polyvinylidene fluoride alloy membrane not adding hydrophilic macromolecule, anti-pollution, easy cleaning, and after cleaning, the performance recovery such as water flux, rejection of film is better, little on the impact of performance, (3) polyvinylidene fluoride alloy membrane obtained by the inventive method is co-continuous network structure but not common chondritic, and compared with chondritic, the mechanical strength of the film of co-continuous network structure is better, (4) the diluent caprolactam adopted is water miscible, with water or ethanol extraction caprolactam, can avoid adopting ketone, ester class etc. as extractant, thus reduces the production cost of polyvinylidene fluoride alloy membrane and also pollution-free to environment, environmental protection, and be solid under water miscible caprolactam room temperature, be easy to recycle, (5) film-forming method technique of the present invention is simple, pollution-free, cost is lower, preparation polyvinylidene fluoride alloy membrane has excellent chemical stability, mechanical strength is high, can be the MBR(note in sewage disposal, water resource recycling field: MBR, i.e. Membrane Bio-Reactor, also known as membrane bioreactor) technique provides high performance alloy film product, is widely used in fields such as industry, medical treatment, sewage disposals.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the appearance structure of polyvinylidene fluoride alloy membrane prepared by the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1: precise caprolactam 185g, Kynoar 60g, polyvinylpyrrolidone 2.5g; pour in 500mL band plug wide-mouth bottle after above three kinds of raw materials are stirred; under slowly leading to nitrogen protection condition; employing oil bath is heated; used oil bath temperature is 140 DEG C; heating makes raw material dissolve completely; and keep 45 minutes at 140 DEG C; then electric mixer agitating solution is used 30 minutes; standing and defoaming in oil bath afterwards; obtain casting solution, then casting solution is incubated preservation at 140 DEG C.Obtained casting solution is poured into striking film forming in template, place and naturally cool in atmosphere, until solidify completely, then put into water and diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 125 μm.
The SEM figure of the appearance structure of polyvinylidene fluoride alloy membrane prepared by the embodiment of the present invention 1 is shown in Fig. 1, and as seen from Figure 1, obtained polyvinylidene fluoride alloy membrane is co-continuous network structure, but not common chondritic.
The pure water flux of polyvinylidene fluoride alloy membrane 25 DEG C time that the present embodiment 1 obtains is 84.0L/(m
2h), contact angle is 57.6
o, and the contact angle not adding the pure pvdf membrane of hydrophilic macromolecule polyvinylpyrrolidone is 78
o.
Embodiment 2: precise caprolactam 182.5g, Kynoar 62.5g, polyvinylpyrrolidone 5.1g; pour in 500mL band plug wide-mouth bottle after above three kinds of raw materials are stirred; under slowly leading to nitrogen protection condition; employing oil bath is heated; used oil bath temperature is 150 DEG C; heating makes raw material dissolve completely; and 1h is kept at 150 DEG C; then electric mixer agitating solution is used 30 minutes; standing and defoaming in oil bath afterwards; obtain casting solution, then casting solution is incubated preservation at 150 DEG C.Obtained casting solution is poured into striking film forming in template, place and naturally cool in atmosphere, until solidify completely, then put into water and diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 120 μm.
The pure water flux of polyvinylidene fluoride alloy membrane 25 DEG C time that the present embodiment 2 obtains is 89.0L/(m
2h), contact angle is 54.0
o.
Embodiment 3: precise caprolactam 177.5g, Kynoar 62.5g, polyvinylpyrrolidone 10g; pour in 500mL band plug wide-mouth bottle after above three kinds of raw materials are stirred; under slowly leading to nitrogen protection condition; employing oil bath is heated; used oil bath temperature is 160 DEG C; heating makes raw material dissolve completely; and 1.5h is kept at 160 DEG C; then electric mixer agitating solution is used 45 minutes; standing and defoaming in oil bath afterwards; obtain casting solution, then casting solution is incubated preservation at 160 DEG C.Obtained casting solution is poured into striking film forming in template, place and naturally cool in atmosphere, until solidify completely, then put into water and diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 115 μm.
The pure water flux of polyvinylidene fluoride alloy membrane 25 DEG C time that the present embodiment 3 obtains is 109.5L/(m
2h), contact angle is 50.4
o.
Embodiment 4: precise caprolactam 108g, Kynoar 32g, polyvinyl alcohol 4g; pour in 250mL band plug wide-mouth bottle after above three kinds of raw materials are stirred; under slowly leading to nitrogen protection condition, adopt oil bath heating, used oil bath temperature is 160 DEG C; heating makes raw material dissolve completely; and 1h is kept at 160 DEG C, then use electric mixer agitating solution 1h, afterwards standing and defoaming in oil bath; obtain casting solution, then casting solution is incubated preservation at 160 DEG C.Obtained casting solution is poured into striking film forming in template, place and naturally cool in atmosphere, until solidify completely, then put into water and diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 110 μm.
The pure water flux of polyvinylidene fluoride alloy membrane 25 DEG C time that the present embodiment 4 obtains is 214.1 L/ (m
2h).
Embodiment 5: precise caprolactam 178g, Kynoar 62g, polyvinylpyrrolidone 10g; pour in 500mL band plug wide-mouth bottle after above three kinds of raw materials are stirred; under slowly leading to nitrogen protection condition, adopt oil bath heating, used oil bath temperature is 150 DEG C; heating makes raw material dissolve completely; and 0.5h is kept at 150 DEG C, then use electric mixer agitating solution 30 minutes, afterwards standing and defoaming in oil bath; obtain casting solution, then casting solution is incubated preservation at 150 DEG C.Obtained casting solution is poured into striking film forming in template, place and naturally cool in atmosphere, until solidify completely, then put into water and diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 110 μm.
The pure water flux of polyvinylidene fluoride alloy membrane 25 DEG C time that the present embodiment 5 obtains is 109.4L/(m
2h).
Embodiment 6: precise caprolactam 164g, Kynoar 30g, polyethylene glycol oxide 6g; pour in 500mL band plug wide-mouth bottle after above three kinds of raw materials are stirred; under slowly leading to nitrogen protection condition, adopt oil bath heating, used oil bath temperature is 150 DEG C; heating makes raw material dissolve completely; and 0.5h is kept at 150 DEG C, then use electric mixer agitating solution 40 minutes, afterwards standing and defoaming in oil bath; obtain casting solution, then casting solution is incubated preservation at 150 DEG C.Obtained casting solution is poured into striking film forming in template, place and naturally cool in atmosphere, until solidify completely, then put into water and diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 100 μm.
The pure water flux of polyvinylidene fluoride alloy membrane 25 DEG C time that the present embodiment 6 obtains is 728.5L/(m
2h).
Claims (4)
1. prepare a method for polyvinylidene fluoride alloy membrane, it is characterized in that comprising the following steps:
1) Kynoar, hydrophilic macromolecule and caprolactam are mixed, wherein, the weight percentage of Kynoar is 15 ~ 25%, and the weight percentage of hydrophilic macromolecule is 1 ~ 4%, and the weight percentage of caprolactam is 70 ~ 85%;
2) mixed Kynoar, hydrophilic macromolecule and caprolactam are heated to solution temperature under nitrogen protection, and keep 0.5 ~ 2h at such a temperature;
3) after Kynoar, hydrophilic macromolecule and caprolactam dissolve completely, under solution temperature, stir 0.5 ~ 1.5h, leave standstill, obtain casting solution, casting solution is preserved under solution temperature;
4) above-mentioned casting solution is made film forming, place and naturally cool in atmosphere, until solidify completely;
5) last, extract caprolactam by extractant, namely obtain polyvinylidene fluoride alloy membrane;
Described hydrophilic macromolecule is one or more in polyethylene glycol oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP);
In step 2) and step 3) in, the temperature range of described solution temperature is 140 ~ 170 DEG C.
2. a kind of method preparing polyvinylidene fluoride alloy membrane according to claim 1, is characterized in that: in step 5) in, described extractant is water or ethanol.
3. a kind of method preparing polyvinylidene fluoride alloy membrane according to claim 1, is characterized in that: in step 5) in, the thickness of described polyvinylidene fluoride alloy membrane is 20 ~ 200 μm.
4. a kind of method preparing polyvinylidene fluoride alloy membrane according to claim 3, is characterized in that: the thickness of described polyvinylidene fluoride alloy membrane is 100 ~ 140 μm.
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|---|---|---|---|
| CN201210362623.4A CN102872730B (en) | 2012-09-26 | 2012-09-26 | Method for preparing polyvinylidene fluoride alloy film |
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|---|---|---|---|
| CN201210362623.4A CN102872730B (en) | 2012-09-26 | 2012-09-26 | Method for preparing polyvinylidene fluoride alloy film |
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| CN102872730A CN102872730A (en) | 2013-01-16 |
| CN102872730B true CN102872730B (en) | 2015-01-21 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415671B (en) * | 2013-09-09 | 2017-07-14 | 宁波大学 | A kind of method that composite thermotropic phase separation method prepares polyvinylidene fluoride alloy membrane |
| CN105126648B (en) | 2015-09-21 | 2018-03-09 | 江苏凯米膜科技股份有限公司 | A kind of method that network hole polyvinylidene fluoride film is prepared based on polyvinyl alcohol gel |
| CN107297156B (en) * | 2016-04-16 | 2021-05-25 | 宁波大学 | Preparation method of composite forward osmosis membrane based on interfacial polymerization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU617213B2 (en) * | 1988-09-01 | 1991-11-21 | Membrana Gmbh | Process for producing membranes |
| CN101269302A (en) * | 2008-05-06 | 2008-09-24 | 南京奥特高科技有限公司 | Non-crystallization permanent hydrophilic PVDF membrane material and preparation method thereof |
| CN101342468A (en) * | 2008-08-22 | 2009-01-14 | 清华大学 | Preparation method for beta crystal phase polyvinylidene fluoride hollow fiber porous membrane |
| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | Method for preparing polyvinylidene fluoride porous membrane |
-
2012
- 2012-09-26 CN CN201210362623.4A patent/CN102872730B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU617213B2 (en) * | 1988-09-01 | 1991-11-21 | Membrana Gmbh | Process for producing membranes |
| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | Method for preparing polyvinylidene fluoride porous membrane |
| CN101269302A (en) * | 2008-05-06 | 2008-09-24 | 南京奥特高科技有限公司 | Non-crystallization permanent hydrophilic PVDF membrane material and preparation method thereof |
| CN101342468A (en) * | 2008-08-22 | 2009-01-14 | 清华大学 | Preparation method for beta crystal phase polyvinylidene fluoride hollow fiber porous membrane |
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