CN101234305A - Polyphenylene sulfide porous film and preparation thereof - Google Patents
Polyphenylene sulfide porous film and preparation thereof Download PDFInfo
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- CN101234305A CN101234305A CNA2007100635372A CN200710063537A CN101234305A CN 101234305 A CN101234305 A CN 101234305A CN A2007100635372 A CNA2007100635372 A CN A2007100635372A CN 200710063537 A CN200710063537 A CN 200710063537A CN 101234305 A CN101234305 A CN 101234305A
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Abstract
The invention discloses a porous membrane of polyphenylene sulfide and a preparation method thereof. The porous membrane of polyphenylene sulfide provided by the invention is prepared by the polyphenylene sulfide with the inner pore diameter of 0.09 to 0.2Mum and porosity rate of 70 to 90 percent. The invention adopts the polyphenylene sulfide with excellent performance as the membrane material which is dissolved at the high temperature and then heterogeneous separated at low temperature to prepare the porous membrane of polyphenylene sulfide of high strength, high temperature resistance and solvent-resistance. Compared with the porous membranes of polyvinylidene fluoride, polyethylene and polypropylene, the porous membrane of polyphenylene sulfide has the advantages of narrowly distributed pore diameter, high porosity rate, high strength, high temperature resistance and solvent-resistance which can be widely applied to the fields such as micro-filtration and ultra-filtration, especially the membrane process of ultra-filtration and micro-filtration at high temperature, and even can replace the inorganic membrane.
Description
Technical field
The present invention relates to a kind of polyphenylene sulfide porous film and preparation method thereof.
Background technology
Thermally induced phase separation (TIPS) method is a kind of making miillpore filter method of rising the 1980s, and it is particularly useful for no suitable solvent under the normal temperature, can not be by the non-molten polymer that causes (NIPS) method film forming that is separated.Compare with dry method, the wet method of NIPS method, the TIPS method has following advantage at least: influence factor is few, film-forming process is easier to control, become that film strength is higher, porosity is more high.The TIPS method has obtained the application of industrialization through years of development, and the perforated membrane of TIPS method preparation is used for wastewater treatment, reclaimed water reuse mainly by membrane process such as micro-filtration, ultrafiltration, also is used for water treatment.
At present, the membrane material that adopts the TIPS legal system to be equipped with perforated membrane mainly contains polyethylene (PE), polypropylene (PP) and Kynoar (PVDF) etc., and the temperature tolerance and the solvent resistance of these materials are general.Chinese patent CN1613907, CN1356410 and CN1718627 disclose the method that thermally induced phase separation prepares polypropylene porous film.Main mineral oil, vegetable oil, atoleine, the phthalate of adopting mixes diluent as diluent with polypropylene, be heated into homogeneous phase solution, and the phase-splitting of lowering the temperature then forms loose structure.But because the restriction of membrane material self character, it is high temperature resistant, solvent resistance and bad, has limited its industrial applicability.
Summary of the invention
The purpose of this invention is to provide a kind of high temperature resistant, solvent-proof polyphenylene sulfide porous film and preparation method thereof.
Polyphenylene sulfide porous film provided by the present invention is made by polyphenylene sulfide, and inner aperture is 0.09～0.2 μ m, and porosity is 70～90%.
The preparation method of this polyphenylene sulfide porous film comprises the steps:
1), forms homogeneous phase solution with polyphenylene sulfide and mixing diluents; Described diluent is selected from one or more in diphenyl ether, benzophenone, diphenyl sulphone (DPS) and the styrax;
2) after the homogeneous phase solution deaeration, be coated on the template, cooling is separated homogeneous phase solution, freezing film;
3) with the diluent in the extractant extraction membrane, obtain described polyether-ether-ketone porous film.
Wherein, in the homogeneous phase solution, the mass content of polyphenylene sulfide is 5-50%; Be preferably 10-40%.Homogeneous phase solution forms under high-temperature stirring, and temperature is 220-280 ℃, is preferably 240-280 ℃.In order to guarantee the performance of gained film, generally selecting number-average molecular weight for use is the polyphenylene sulfide of 50000-150000.
In preparation process, step 2) cooling of being adopted can be adopted cooling naturally in air, also can adopt in the direct immersion cooling fluid and cool off, and selected cooling fluid is water, ethanol, ethylene glycol or propane diols; The step 3) extractant is alcohol compound or acetone; Wherein, alcohol compound commonly used is methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol, is preferably ethanol or propyl alcohol.After preparation finishes, the extractant that contains diluent is carried out rectifying separate, can reuse diluent and extractant.
Polyphenylene sulfide (PPS) is a kind of resistant to elevated temperatures semicrystalline polymeric, and its vitrification point is 103.9 ℃, and fusing point is 265.6 ℃, and is being insoluble to any organic solvent below 200 ℃.The high performance polyphenylene sulfide plate porous membrane that the present invention prepares, its pore structure can effectively be controlled by the change of the mass ratio of each component in diluent and the casting solution, pore structure in the polyphenylene sulfide plate porous membrane that obtains can be branch shape, spherocrystal shape, cell shape pore structure, porosity reaches 70～90%, and pore-size distribution is narrower, and the average diameter of internal holes (being non-surface holes) is 0.09～0.2 μ m; And, film high temperature resistant, solvent resistance is good.
The present invention adopts the polyphenylene sulfide with excellent properties as membrane material, dissolving at high temperature, then the low temperature phase-splitting prepare have high strength, high temperature resistant and solvent-proof polyphenylene sulfide porous film.Compare with perforated membranes such as Kynoar, polyethylene and polypropylene, it is narrow that polyphenylene sulfide porous film of the present invention has pore-size distribution, the porosity height, the intensity height, advantages such as high temperature resistant and anti-solvent, can be widely used in the membrane process such as ultrafiltration, micro-filtration under the fields such as micro-filtration and ultrafiltration, particularly high temperature, even alternative inoranic membrane.
Description of drawings
Fig. 1. the section pore structure electromicroscopic photograph of the polyphenylene sulfide plate porous membrane of embodiment 1.
Fig. 2. the section pore structure electromicroscopic photograph of the polyphenylene sulfide plate porous membrane of embodiment 2.
Fig. 3. the section pore structure electromicroscopic photograph of the polyphenylene sulfide plate porous membrane of embodiment 3.
Fig. 4. the section pore structure electromicroscopic photograph of the polyphenylene sulfide plate porous membrane of embodiment 4.
The specific embodiment
The present invention adopts PPS/ mixing diluents system to produce the polyphenylene sulfide plate porous membrane by thermally induced phase separation, and the typical operational procedure of this method is:
Polyphenylene sulfide and diluent mix in high-temperature kettle and are heated to congruent melting, stir, and obtain casting solution after the standing and defoaming, at high temperature casting solution is coated on the template, in air, slowly cools off or quenching then, again diluent in the film is extracted, drying obtains polyphenylene sulfide porous film.This method can form the good polyphenylene sulfide plate porous membrane of pore structure, and hole dimension is controlled, and the narrowly distributing in aperture, film high temperature resistant, solvent resistance is good.
Below in conjunction with embodiment technical scheme of the present invention is further detailed, but described embodiment is not construed as limiting the invention for example.Choose among the present invention and have excellent properties, high temperature resistant, solvent-proof polyphenylene sulfide is as membrane material, select suitable diluents (diphenyl ether, benzophenone, diphenyl sulphone (DPS) and styrax etc.) for use, prepare perforated membrane through thermally induced phase separation, in actual production, can add some additive as required again to improve some characteristic of film forming procedure or improvement gained film.
Embodiment 1
The polyphenylene sulfide number-average molecular weight is 90,000, and diluent is a diphenyl ether.Its component is a polyphenylene sulfide quality percentage composition 30%, diphenyl ether quality percentage composition 70%.Heat temperature raising to 260 ℃ in the high-temperature stirring still mixes.The polymer homogeneous phase solution that obtains directly is coated on the template.Cooling bath selects water as cooling fluid.Make solution phase-splitting film-forming in the immersion cooling fluid, dry behind acetone extract then.The thick 150 μ m of the plate porous membrane that obtains, the section pore structure of film is a branch shape pore structure, and inner average pore size is 0.09 μ m, and porosity is 80%, and its pore structure is as shown in Figure 1.Under 25 ℃ of conditions, pure water flux is 1000L/m
2Hr0.1MPa.Below 180 ℃, respectively film is soaked a week in acid solution (0.4mol/L sulfuric acid solution), alkali lye (0.4mol/L NaOH solution) after, pore structure and pure water flux are constant substantially.
Embodiment 2
The polyphenylene sulfide number-average molecular weight is 90,000, and diluent is diphenyl ether and benzophenone.Its component is a polyphenylene sulfide quality percentage composition 15%, diphenyl ether quality percentage composition 40%, benzophenone quality percentage composition 45%.Heat temperature raising to 260 ℃ in the high-temperature stirring still mixes.The polymer homogeneous phase solution that obtains directly is coated on the template.Cooling bath selects water as cooling fluid.Make solution phase-splitting film-forming in the immersion cooling fluid, dry behind acetone extract then.The thick 150 μ m of the plate porous membrane that obtains, the section pore structure of film is a branch shape pore structure, and inner average pore size is 0.2 μ m, and porosity is 85%, and its pore structure is as shown in Figure 2.Under 25 ℃ of conditions, pure water flux is 1500L/m
2Hr0.1MPa.Below 180 ℃, respectively film is soaked a week in acid solution (0.4mol/L sulfuric acid solution), alkali lye (0.4mol/L NaOH solution) after, pore structure and pure water flux are constant substantially.
Embodiment 3
The polyphenylene sulfide number-average molecular weight is 90,000, and diluent is a diphenyl sulphone (DPS).Its component is a polyphenylene sulfide quality percentage composition 40%, diphenyl sulphone (DPS) quality percentage composition 60%.Heat temperature raising to 260 ℃ in the high-temperature stirring still mixes.The polymer homogeneous phase solution that obtains directly is coated on the template.Cooling bath selects water as cooling fluid.Make solution phase-splitting film-forming in the immersion cooling fluid, dry behind acetone extract then.The thick 150 μ m of the plate porous membrane that obtains, the section pore structure of film is a spherocrystal shape pore structure, and inner average pore size is 0.15 μ m, and porosity is 80%, and its pore structure is as shown in Figure 3.Under 25 ℃ of conditions, pure water flux is 1200L/m
2Hr0.1MPa.Below 180 ℃, respectively film is soaked a week in acid solution (0.4mol/L sulfuric acid solution), alkali lye (0.4mol/L NaOH solution) after, pore structure and pure water flux are constant substantially.
Embodiment 4
The polyphenylene sulfide number-average molecular weight is 90,000, and diluent is a styrax.Its component is a polyphenylene sulfide quality percentage composition 10%, styrax quality percentage composition 90%.Heat temperature raising to 280 ℃ in the high-temperature stirring still mixes.The polymer homogeneous phase solution that obtains directly is coated on the template.Cooling bath selects water as cooling fluid.Make solution phase-splitting film-forming in the immersion cooling fluid, dry behind acetone extract then.The thick 180 μ m of the plate porous membrane that obtains, the section pore structure of film is a branch shape pore structure, and inner average pore size is 0.10 μ m, and porosity is 90%, and its pore structure is as shown in Figure 4.Under 25 ℃ of conditions, pure water flux is 1100L/m
2Hr0.1MPa.Below 180 ℃, respectively film is soaked a week in acid solution (0.4mol/L sulfuric acid solution), alkali lye (0.4mol/L NaOH solution) after, pore structure and pure water flux are constant substantially.
Comparative Examples 1
Polyethylene, weight average molecular weight are 90,000, and diluent is a crude mineral oils, and its component is a ultra-high molecular weight polyethylene quality percentage composition 15%, natural minerals oil quality percentage composition 85%.Heat temperature raising to 150 ℃ in the high-temperature stirring still mixes.The polymer homogeneous phase solution that obtains directly is coated on the template.Cooling bath selects water as cooling fluid.Make solution phase-splitting film-forming in the immersion cooling fluid, dry behind acetone extract then.The dull and stereotyped thickness 150 μ m that obtain, the section pore structure of film is a spherocrystal shape pore structure, and inner average pore size is 0.5 μ m, and porosity is 75%.Under 25 ℃ of conditions, pure water flux is 600L/m
2Hr0.1MPa.Below 180 ℃, after one week of immersion, pore structure is substantially all destroyed in acid solution (0.4mol/L sulfuric acid solution), alkali lye (0.4mol/L NaOH solution).
Claims (10)
1. a polyphenylene sulfide porous film is made by polyphenylene sulfide, and inner aperture is 0.09～0.2 μ m, and porosity is 70～90%.
2. polyphenylene sulfide porous film according to claim 1 is characterized in that: the number-average molecular weight of described polyphenylene sulfide is 50000-150000.
3. polyphenylene sulfide porous film according to claim 1 is characterized in that: described polyphenylene sulfide porous film prepares as follows:
1), forms homogeneous phase solution with polyphenylene sulfide and mixing diluents; Described diluent is selected from one or more in diphenyl ether, benzophenone, diphenyl sulphone (DPS) and the styrax;
2) after the homogeneous phase solution deaeration, be coated on the template, cooling is separated homogeneous phase solution, freezing film;
3) with the diluent in the extractant extraction membrane, obtain described polyphenylene sulfide porous film.
4. the preparation method of the described polyphenylene sulfide porous film of claim 1 comprises the steps:
1), forms homogeneous phase solution with polyphenylene sulfide and mixing diluents; Described diluent is selected from one or more in diphenyl ether, benzophenone, diphenyl sulphone (DPS) and the styrax;
2) after the homogeneous phase solution deaeration, be coated on the template, cooling is separated homogeneous phase solution, freezing film;
3) with the diluent in the extractant extraction membrane, obtain described polyphenylene sulfide porous film.
5. preparation method according to claim 4 is characterized in that: in the described homogeneous phase solution, the mass content of polyphenylene sulfide is 5-50%; Be preferably 10-40%.
6. preparation method according to claim 4 is characterized in that: described homogeneous phase solution forms under high-temperature stirring, and temperature is 220-280 ℃, is preferably 240-280 ℃.
7. preparation method according to claim 4 is characterized in that: the number-average molecular weight of described polyphenylene sulfide is 50000-150000.
8. according to the arbitrary described preparation method of claim 4-7, it is characterized in that: step 2) cooling adopted can adopt cooling naturally in air, also can adopt in the direct immersion cooling fluid and cool off, selected cooling fluid is water, ethanol, ethylene glycol or propane diols.
9. according to the arbitrary described preparation method of claim 4-7, it is characterized in that: the described extractant of step 3) is alcohol compound or acetone.
10. preparation method according to claim 9 is characterized in that: described alcohol compound is methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol, is preferably ethanol or propyl alcohol.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309930A (en) * | 2010-07-01 | 2012-01-11 | 东丽纤维研究所（中国）有限公司 | Preparation method of polyphenylene sulfide ultra-fine fiber porous membrane |
| CN103205123A (en) * | 2013-03-06 | 2013-07-17 | 珠海市赛纬电子材料有限公司 | Production method of polyphenylene sulfide diaphragm in lithium ion batteries |
| CN106062038A (en) * | 2014-03-18 | 2016-10-26 | 东丽株式会社 | Polyphenylene sulfide porous body and production method thereof, polyphenylene sulfide-thermoplastic resin block copolymer and production method thereof |
| CN106178972A (en) * | 2016-08-27 | 2016-12-07 | 太原市晋华恒远科技有限公司 | A kind of preparation method of high temperature resistant PPS gas separation membrane |
| CN106268348A (en) * | 2016-08-08 | 2017-01-04 | 太原市晋华恒远科技有限公司 | A kind of preparation method of super-hydrophobic polyphenylene sulfide film |
| CN107057353A (en) * | 2017-01-18 | 2017-08-18 | 北京信润新材料科技有限公司 | A kind of porous PPS films and preparation method thereof |
| CN109301133A (en) * | 2018-10-05 | 2019-02-01 | 中山大学 | A kind of diaphragm preparation method for high security, lithium ion battery with high energy density |
| CN112512673A (en) * | 2018-07-30 | 2021-03-16 | 东丽株式会社 | Separation membrane and method for producing separation membrane |
| CN114744368A (en) * | 2022-06-13 | 2022-07-12 | 四川新能源汽车创新中心有限公司 | Lithium battery diaphragm with compact structure and preparation method thereof |
| CN116617866A (en) * | 2023-06-13 | 2023-08-22 | 阿克菲姆膜材(嘉兴)有限公司 | Preparation method of high-porosity polyphenylene sulfide filtering membrane |
-
2007
- 2007-02-02 CN CNA2007100635372A patent/CN101234305A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309930A (en) * | 2010-07-01 | 2012-01-11 | 东丽纤维研究所（中国）有限公司 | Preparation method of polyphenylene sulfide ultra-fine fiber porous membrane |
| CN103205123A (en) * | 2013-03-06 | 2013-07-17 | 珠海市赛纬电子材料有限公司 | Production method of polyphenylene sulfide diaphragm in lithium ion batteries |
| CN106062038A (en) * | 2014-03-18 | 2016-10-26 | 东丽株式会社 | Polyphenylene sulfide porous body and production method thereof, polyphenylene sulfide-thermoplastic resin block copolymer and production method thereof |
| CN106268348B (en) * | 2016-08-08 | 2019-10-22 | 天津津纶新材料科技有限公司 | A kind of preparation method of super-hydrophobic polyphenylene sulfide film |
| CN106268348A (en) * | 2016-08-08 | 2017-01-04 | 太原市晋华恒远科技有限公司 | A kind of preparation method of super-hydrophobic polyphenylene sulfide film |
| CN106178972A (en) * | 2016-08-27 | 2016-12-07 | 太原市晋华恒远科技有限公司 | A kind of preparation method of high temperature resistant PPS gas separation membrane |
| CN106178972B (en) * | 2016-08-27 | 2019-09-27 | 天津津纶新材料科技有限公司 | A kind of preparation method of high temperature resistant PPS gas separation membrane |
| CN107057353A (en) * | 2017-01-18 | 2017-08-18 | 北京信润新材料科技有限公司 | A kind of porous PPS films and preparation method thereof |
| CN112512673A (en) * | 2018-07-30 | 2021-03-16 | 东丽株式会社 | Separation membrane and method for producing separation membrane |
| CN109301133A (en) * | 2018-10-05 | 2019-02-01 | 中山大学 | A kind of diaphragm preparation method for high security, lithium ion battery with high energy density |
| CN114744368A (en) * | 2022-06-13 | 2022-07-12 | 四川新能源汽车创新中心有限公司 | Lithium battery diaphragm with compact structure and preparation method thereof |
| CN114744368B (en) * | 2022-06-13 | 2022-08-30 | 四川新能源汽车创新中心有限公司 | Lithium battery diaphragm with compact structure and preparation method thereof |
| CN116617866A (en) * | 2023-06-13 | 2023-08-22 | 阿克菲姆膜材(嘉兴)有限公司 | Preparation method of high-porosity polyphenylene sulfide filtering membrane |
| CN116617866B (en) * | 2023-06-13 | 2023-11-28 | 阿克菲姆膜材(嘉兴)有限公司 | Preparation method of high-porosity polyphenylene sulfide filtering membrane |
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