CN102872730A - Method for preparing polyvinylidene fluoride alloy film - Google Patents
Method for preparing polyvinylidene fluoride alloy film Download PDFInfo
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- CN102872730A CN102872730A CN2012103626234A CN201210362623A CN102872730A CN 102872730 A CN102872730 A CN 102872730A CN 2012103626234 A CN2012103626234 A CN 2012103626234A CN 201210362623 A CN201210362623 A CN 201210362623A CN 102872730 A CN102872730 A CN 102872730A
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- polyvinylidene fluoride
- caprolactam
- alloy membrane
- fluoride alloy
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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 makes the field, specifically, relates to a kind of method for 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 has obtained good application at the dirty water decontamination handles and biochemical pharmacy industry.
Polyvinylidene fluoride alloy membrane is a kind of polymer porous film.Polymer porous film be prepared with several different methods, mainly contain phase inversion, pulling method, sintering process and irradiation method etc., wherein phase inversion comprises again thermally induced phase separation, phase separation method etc.Phase inversion is one of modal method, it is the method for coming conversion film by the liquid-liquid phase separation of control polymer solution, according to the difference of the mode of being separated, can be divided into again thermal induction precipitated phase partition method, solution evaporation precipitated phase partition method, gaseous phase deposition phase separation method and immersion precipitation phase separation method.
Thermally induced phase separation (TIPS) obtains people's attention gradually in membrane separation technique in recent years.Thermally induced phase separation (TIPS) is a kind of method that is caused being separated to prepare perforated membrane (such as micro-filtration membrane, milipore filter) by temperature change that is proposed by Castro the eighties in 20th century.Use higher boiling, low-molecular-weight single or mixed diluent at high temperature to form homogeneous phase solution with high polymer, homogeneous phase solution generation solid-liquid or liquid-liquid phase separation during cooling then remove diluent, thereby obtain having the high polymer microcellular film of a fixed structure.With other film-forming method relatively, the film that suitable diluent can make thermally induced phase separation make has that intensity is good, porosity is high, the aperture is easy to the advantages such as regulation and control, so receives people's concern and obtain comparatively systematic research.The diluent that adopts at present mostly is water-insoluble cosolvent, and is water insoluble, thus also must extract them with other extractant after the film forming, complex process, and unfriendly to environment.In addition because the hydrophobicity of PVDF, simple pvdf membrane when using easily by the Organic Pollution in the water, and easy cleaning not.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, to provide a kind of technique simple, pollution-free, the lower-cost method for preparing polyvinylidene fluoride alloy membrane.
The present invention solves the problems of the technologies described above the technical scheme that adopts: a kind of method for preparing polyvinylidene fluoride alloy membrane may further comprise the 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 under this temperature, keep 0.5～2h;
3) after Kynoar, hydrophilic macromolecule and caprolactam dissolve fully, 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, be placed on naturally cooling in the air, until solidify fully;
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), the polyvinylpyrrolidone (PVP).
Preferably, in step 2) and step 3) in, the temperature range of described solution temperature is 140～170 ℃.
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 μ m.
Preferably, the thickness of described polyvinylidene fluoride alloy membrane is 100～140 μ m.
Compared with prior art, the invention has the advantages that: (1) the present invention has utilized the principle of " high-temperature digestion; low temperature phase-splitting ", with caprolactam as diluent, with hydrophilic macromolecule polyethylene glycol oxide (PEO), in polyvinyl alcohol (PVA) or the polyvinylpyrrolidone (PVP) one or more are as additive, with Kynoar, mixed dissolution and stir into uniform casting solution at high temperature after hydrophilic macromolecule and caprolactam mix, again casting solution is made film forming, be placed on to naturally cool in the air fully and solidify, casting solution system generation liquid-liquid or solid-liquid are separated, after solidifying, polymeric system forms the bicontinuous structure of PVDF and diluent, after this, caprolactam on the film is extracted, and the caprolactam position forms poroid, and remaining polymer backbone then is retained; (2) the present invention has added hydrophilic macromolecule in raw material, improve the hydrophily of film, make polyvinylidene fluoride alloy membrane keep the performance of permanent hydrophilic, compare with the traditional polyvinylidene fluoride alloy membrane that does not add hydrophilic macromolecule, anti-pollution, easy cleaning, and after cleaning, the performance recoveries such as the water flux of film, rejection are better, and are little on the impact of performance; (3) the prepared polyvinylidene fluoride alloy membrane of the inventive method is that co-continuous network structure but not common chondritic are compared with chondritic, and the mechanical strength of the film of co-continuous network structure is better; (4) the diluent caprolactam that adopts is water miscible, and water or ethanol extraction caprolactam can avoid adopting ketone, ester class etc. as extractant, thereby has reduced the production cost of polyvinylidene fluoride alloy membrane and also pollution-free to environment, environmental protection; And be solid under the 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, the polyvinylidene fluoride alloy membrane of preparation has good chemical stability, mechanical strength is high, can annotate for the MBR(in sewage disposal, water resource recycling field: MBR, be Membrane Bio-Reactor, claiming again membrane bioreactor) technique provides high performance alloy film product, is widely used in fields such as industry, medical treatment, sewage disposals.
Description of drawings
Fig. 1 is the SEM figure of appearance structure of the polyvinylidene fluoride alloy membrane of the embodiment of the invention 1 preparation.
The specific embodiment
Embodiment is described in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1: accurate weighing caprolactam 185g, Kynoar 60g, polyvinylpyrrolidone 2.5g; pour into after above three kinds of raw materials are stirred in the 500mL band plug wide-mouth bottle; under slowly logical nitrogen protection condition; employing oil bath heating; the used oil bath temperature is 140 ℃; heating is dissolved raw material fully; and 140 ℃ of lower maintenances 45 minutes; then used the electric mixer agitating solution 30 minutes; standing and defoaming in oil bath afterwards; obtain casting solution, then casting solution is preserved 140 ℃ of lower insulations.Pour resulting casting solution in template striking film forming, be placed on naturally cooling in the air, until solidify fully, then put into water the diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 125 μ m.
The SEM figure of the appearance structure of the polyvinylidene fluoride alloy membrane of the embodiment of the invention 1 preparation sees Fig. 1, and as seen from Figure 1, prepared polyvinylidene fluoride alloy membrane is the co-continuous network structure, but not common chondritic.
The pure water flux of the polyvinylidene fluoride alloy membrane that present embodiment 1 makes in the time of 25 ℃ is 84.0L/(m
2H), contact angle is 57.6
o, and the contact angle that does not add the pure pvdf membrane of hydrophilic macromolecule polyvinylpyrrolidone is 78
o
Embodiment 2: accurate weighing caprolactam 182.5g, Kynoar 62.5g, polyvinylpyrrolidone 5.1g; pour into after above three kinds of raw materials are stirred in the 500mL band plug wide-mouth bottle; under slowly logical nitrogen protection condition; employing oil bath heating; the used oil bath temperature is 150 ℃; heating is dissolved raw material fully; and at 150 ℃ of lower 1h that keep; then used the electric mixer agitating solution 30 minutes; standing and defoaming in oil bath afterwards; obtain casting solution, then casting solution is preserved 150 ℃ of lower insulations.Pour resulting casting solution in template striking film forming, be placed on naturally cooling in the air, until solidify fully, then put into water the diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 120 μ m.
The pure water flux of the polyvinylidene fluoride alloy membrane that present embodiment 2 makes in the time of 25 ℃ is 89.0L/(m
2H), contact angle is 54.0
o
Embodiment 3: accurate weighing caprolactam 177.5g, Kynoar 62.5g, polyvinylpyrrolidone 10g; pour into after above three kinds of raw materials are stirred in the 500mL band plug wide-mouth bottle; under slowly logical nitrogen protection condition; employing oil bath heating; the used oil bath temperature is 160 ℃; heating is dissolved raw material fully; and at 160 ℃ of lower 1.5h that keep; then used the electric mixer agitating solution 45 minutes; standing and defoaming in oil bath afterwards; obtain casting solution, then casting solution is preserved 160 ℃ of lower insulations.Pour resulting casting solution in template striking film forming, be placed on naturally cooling in the air, until solidify fully, then put into water the diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 115 μ m.
The pure water flux of the polyvinylidene fluoride alloy membrane that present embodiment 3 makes in the time of 25 ℃ is 109.5L/(m
2H), contact angle is 50.4
o
Embodiment 4: accurate weighing caprolactam 108g, Kynoar 32g, polyvinyl alcohol 4g; pour into after above three kinds of raw materials are stirred in the 250mL band plug wide-mouth bottle; under slowly logical nitrogen protection condition, adopt the oil bath heating, the used oil bath temperature is 160 ℃; heating is dissolved raw material fully; and at 160 ℃ of lower 1h that keep, then use electric mixer agitating solution 1h, afterwards standing and defoaming in oil bath; obtain casting solution, then casting solution is preserved 160 ℃ of lower insulations.Pour resulting casting solution in template striking film forming, be placed on naturally cooling in the air, until solidify fully, then put into water the diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 110 μ m.
The pure water flux of the polyvinylidene fluoride alloy membrane that present embodiment 4 makes in the time of 25 ℃ is 214.1 L/ (m
2H).
Embodiment 5: accurate weighing caprolactam 178g, Kynoar 62g, polyvinylpyrrolidone 10g; pour into after above three kinds of raw materials are stirred in the 500mL band plug wide-mouth bottle; under slowly logical nitrogen protection condition, adopt the oil bath heating, the used oil bath temperature is 150 ℃; heating is dissolved raw material fully; and at 150 ℃ of lower 0.5h that keep, then used the electric mixer agitating solution 30 minutes, afterwards standing and defoaming in oil bath; obtain casting solution, then casting solution is preserved 150 ℃ of lower insulations.Pour resulting casting solution in template striking film forming, be placed on naturally cooling in the air, until solidify fully, then put into water the diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 110 μ m.
The pure water flux of the polyvinylidene fluoride alloy membrane that present embodiment 5 makes in the time of 25 ℃ is 109.4L/(m
2H).
Embodiment 6: accurate weighing caprolactam 164g, Kynoar 30g, polyethylene glycol oxide 6g; pour into after above three kinds of raw materials are stirred in the 500mL band plug wide-mouth bottle; under slowly logical nitrogen protection condition, adopt the oil bath heating, the used oil bath temperature is 150 ℃; heating is dissolved raw material fully; and at 150 ℃ of lower 0.5h that keep, then used the electric mixer agitating solution 40 minutes, afterwards standing and defoaming in oil bath; obtain casting solution, then casting solution is preserved 150 ℃ of lower insulations.Pour resulting casting solution in template striking film forming, be placed on naturally cooling in the air, until solidify fully, then put into water the diluent caprolactam is dissolved out, namely obtain polyvinylidene fluoride alloy membrane, the thickness of this polyvinylidene fluoride alloy membrane is 100 μ m.
The pure water flux of the polyvinylidene fluoride alloy membrane that present embodiment 6 makes in the time of 25 ℃ is 728.5L/(m
2H).
Claims (6)
1. method for preparing polyvinylidene fluoride alloy membrane is characterized in that may further comprise the 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 under this temperature, keep 0.5～2h;
3) after Kynoar, hydrophilic macromolecule and caprolactam dissolve fully, 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, be placed on naturally cooling in the air, until solidify fully;
5) last, extract caprolactam by extractant, namely obtain polyvinylidene fluoride alloy membrane.
2. a kind of method for preparing polyvinylidene fluoride alloy membrane according to claim 1, it is characterized in that: described hydrophilic macromolecule is one or more in polyethylene glycol oxide (PEO), polyvinyl alcohol (PVA), the polyvinylpyrrolidone (PVP).
3. a kind of method for preparing polyvinylidene fluoride alloy membrane according to claim 1 and 2 is characterized in that: in step 2) and step 3) in, the temperature range of described solution temperature is 140～170 ℃.
4. a kind of method for preparing polyvinylidene fluoride alloy membrane according to claim 1 and 2, it is characterized in that: in step 5), described extractant is water or ethanol.
5. a kind of method for preparing polyvinylidene fluoride alloy membrane according to claim 1 and 2, it is characterized in that: in step 5), the thickness of described polyvinylidene fluoride alloy membrane is 20～200 μ m.
6. a kind of method for preparing polyvinylidene fluoride alloy membrane according to claim 5, it is characterized in that: the thickness of described polyvinylidene fluoride alloy membrane is 100～140 μ m.
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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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415671A (en) * | 2013-09-09 | 2015-03-18 | 宁波大学 | Method for preparing polyvinylidene fluoride alloy film by adopting compound thermally induced phase separation process |
| WO2017050019A1 (en) * | 2015-09-21 | 2017-03-30 | 江苏凯米膜科技股份有限公司 | Method for preparing polyvinyl alcohol gel based meshed polyvinylidene fluoride film |
| CN107297156A (en) * | 2016-04-16 | 2017-10-27 | 宁波大学 | A kind of preparation method of the compound forward osmosis membrane based on interfacial polymerization |
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| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415671A (en) * | 2013-09-09 | 2015-03-18 | 宁波大学 | Method for preparing polyvinylidene fluoride alloy film by adopting compound thermally induced phase separation process |
| WO2017050019A1 (en) * | 2015-09-21 | 2017-03-30 | 江苏凯米膜科技股份有限公司 | Method for preparing polyvinyl alcohol gel based meshed polyvinylidene fluoride film |
| US10335741B2 (en) | 2015-09-21 | 2019-07-02 | Jiangsu Kaimi Membrane Technology Co., Ltd | Method for preparing the network-pore polyvinylidene fluoride membrane based on polyvinyl alcohol gel |
| CN107297156A (en) * | 2016-04-16 | 2017-10-27 | 宁波大学 | A kind of preparation method of the compound forward osmosis membrane based on interfacial polymerization |
| CN107297156B (en) * | 2016-04-16 | 2021-05-25 | 宁波大学 | Preparation method of composite forward osmosis membrane based on interfacial polymerization |
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