CN101249391B - Hollow fiber film, and preparation and use thereof - Google Patents
Hollow fiber film, and preparation and use thereof Download PDFInfo
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- CN101249391B CN101249391B CN2007101784603A CN200710178460A CN101249391B CN 101249391 B CN101249391 B CN 101249391B CN 2007101784603 A CN2007101784603 A CN 2007101784603A CN 200710178460 A CN200710178460 A CN 200710178460A CN 101249391 B CN101249391 B CN 101249391B
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Abstract
The invention relates to a hydrophilic polyvinylidene fluoride/sulphonated polyphenyl ether hollow fiber membrane, which has the intensity and the corrosion resistance of polyvinylidene fluoride and the hydrophilicity of sulphonated polyphenyl. The invention further relates to a method for manufacturing the membrane and the uses of the membrane in treatment of municipal sewage and industrial effluent and advanced treatment. The quality of the outgoing water reaches the water standard for scenery of the Effluent Standard of Pollutions for Town Sewage Treatment Plants (GB189.8-2002) and the water standard for scenery of the Regeneration and Utilization of Municipal Sewage (GB/T18920-2002).
Description
[technical field]
The present invention relates to technical field of waste water processing, more specifically, the present invention relates to a kind of hydrophilic Kynoar/sulfonated poly (phenylene oxide) hollow-fibre membrane, the production method of described film and purposes.
[background technology]
The film separation process is replacing traditional separation process, is widely used in separating of gas and liquid, handles especially for municipal wastewater, also is used for the wastewater treatment of industrial circles such as chemical industry, food, medicine, electronics.Macromolecular material has become main membrane material because of its processing wide in variety, easy, function admirable.The macromolecular material that is generally used for making film has cellulose diacetate, Triafol T, polyacrylonitrile, polysulfones, polyvinyl chloride, Kynoar etc.Different applications has proposed different requirements to film properties, in municipal wastewater or other wastewater treatment, has both required corrosion resistance, the intensity of film, requires film to have certain hydrophily again.Kynoar (PVDF) has good corrosion resistance and higher intensity, but hydrophily is relatively poor.By mixing with hydrophilic polymer is a kind of method of simply and effectively improving the film hydrophilicity.Report in the document that the polymer that is used for hydrophilic modifying has polyacrylonitrile (PAN), SPSF (SPS), cellulose acetate (CA), polymethyl methacrylate (PMMA) etc., though about PVDF and the existing bibliographical information of sulfonated poly (phenylene oxide) blend, but only limit to prepare the proton exchange flat sheet membrane (US5989742 and 6103414, CN 96199414.2) that fuel cell is used.Because municipal wastewater or other wastewater treatment complexity, condition changes greatly, to the requirement of film far above fuel cell, so the inventor passes through a large amount of experimental studies, has made the present invention finally.
[summary of the invention]
[technical problem that will solve]
The objective of the invention is to propose a kind of hydrophilic Kynoar/sulfonated poly (phenylene oxide) hollow-fibre membrane, this film had both had the intensity and the corrosion resistance of Kynoar, had the hydrophily of sulfonated poly (phenylene oxide) again.
Another object of the present invention is the production method that proposes a kind of described film.
Another object of the present invention is to propose the purposes of described film in municipal wastewater and Industrial Wastewater Treatment and advanced treating.The waste water quality that adopts film of the present invention to handle reaches the landscape water standard in " urban wastewater treatment firm pollutant emission standard (GB189.8-2002) ", and the landscape water standard in " urban sewage reutilization (GB/T18920-2002) ".
[technical scheme]
The present invention relates to a kind of hollow-fibre membrane, this film is made up of Kynoar and sulfonated poly (phenylene oxide) polymer blend, and the mass ratio of Kynoar and sulfonated poly (phenylene oxide) is 2 in this polymer blend: 1-50: 1.
Preferably, the mass ratio of Kynoar and sulfonated poly (phenylene oxide) is 2 in this polymer blend: 1-20: 1.
This film section is two cortex spongelike structures, the porosity 55-85% of its doughnut external diameter 0.2-3 millimeter, wall thickness 0.05-1 millimeter, this film, average pore size 0.005-0.5 micron, rupture strength 0.1-1MPa, under the condition of 0.1MPa and 25 ℃, the test pure water flux is 100-200L/m
2.h.
The present invention relates to a kind of production method of hollow-fibre membrane, it is characterized in that this method comprises the steps:
A) use solvent to prepare 10-40 weight % Kynoar solution;
B) use solvent to prepare 5-50 weight % sulfonated polyphenyl ethereal solution;
C) with above-mentioned a) solution and b of preparation) solution of preparation mixes and obtains a kind of mixed solution, and to make the Kynoar in this mixed solution and the mass ratio of sulfonated poly (phenylene oxide) be 2: 1-50: 1;
D) use the solvent preparation to contain the solution of pore former and surfactant, then the solution that obtains is added to above-mentioned c) preparation mixed solution in make a kind of spinning solution, and make that the total concentration of Kynoar and sulfonated poly (phenylene oxide) is 15-25 weight % in the spinning solution, the concentration of pore former is 0-20 weight %, and surfactant concentrations is 0-1 weight %;
E) use the mixture of non-solvent or non-solvent and solvent to prepare core liquid, wherein said non-solvent is 100: 0 to 10: 90 with the solvent quality ratio;
F) use the mixture of non-solvent or non-solvent and solvent to prepare coagulating bath, wherein said non-solvent is 100: 0 to 10: 90 with the solvent quality ratio;
G) adopt dry-wet spinning method, at dry-spinning path 1-15cm, the temperature 20-90 of described spinning solution ℃, under described core liquid and coagulation bath temperature 20-90 ℃ the condition, use above-mentioned e) core liquid and the above-mentioned f of preparation) coagulating bath for preparing, with above-mentioned d) spinning solution that obtains prepares described hollow-fibre membrane, the mass ratio of Kynoar and sulfonated poly (phenylene oxide) is 2 in this film: 1-50: 1, this film section is two cortex spongelike structures, its doughnut external diameter 0.2-3 millimeter, wall thickness 0.05-1 millimeter, the porosity 55-85% of this film, average pore size 0.005-0.5 micron, rupture strength 0.1-1MPa.
The dry-wet spinning method that the present invention adopts is to utilize phase transfer pore-forming mechanism.The phase transfer pore-forming is based on the phase separation principle of Polymer Solution: Polymer Solution is the homogeneous system by polymer and solvent composition.When Polymer Solution contacted with non-solvent, the solvent in non-solvent and the Polymer Solution exchanged, and non-solvent diffuses in the Polymer Solution, and the solubility of polymer reduces, and Polymer Solution can be separated into and be polymer-rich phase and solvent-rich phase; Behind the rich in polymers solidifying, remove solvent and just obtained loose structure.
Implement the employed doughnut spinning-drawing machine of described dry-wet spinning method and for example produced by the new three-dimensional films technology in Tianjin Co., Ltd, its spinning technique flow process as shown in Figure 1.Above-mentioned spinning solution is extruded simultaneously by the spinning head and the core liquid in the pore of spinning head center of doughnut spinning-drawing machine, entered then in the outer coagulating bath.Feed liquid still 2 is equipped with described spinning solution, and core flow container 3 is equipped with described core liquid.Spinning solution enters spinning head 4 under the nitrogen pressure of steel cylinder 1, described core liquid enters in the center pore of spinning head.Described spinning solution and described core liquid are extruded through spinning head 4 simultaneously, enter then in the coagulating tank 5.By with the exchange of coagulating bath, the solvent in the described spinning solution enters coagulating bath mutually with pore former, and coagulating bath diffuses in the spinning solution.Polymer in the described spinning solution is separated out because of solubility reduces by the phase transfer precipitation, thereby is spun into Kynoar/sulfonated poly (phenylene oxide) blend hollow fiber membrane.Made hollow-fibre membrane is wrapped on the wire wrapping wheel 8 through guide wheel 7.Wire wrapping wheel is in rotation process, and hollow-fibre membrane is through the further gel solidification of deionized water in the wrapping wire rinse bath 9.
On meaning of the present invention, described solvent should be appreciated that it is to dissolve described polymer, and obtains the solvent of homogeneous solution.
On meaning of the present invention, described non-solvent should be appreciated that it is the non-solvent that can not dissolve described polymer.
According to a kind of preferred embodiment, described solvent is one or more solvents that are selected from dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO).
Preferably, described solvent is one or more solvents that are selected from dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO).
More preferably, described solvent is dimethyl formamide or dimethylacetylamide.
According to a kind of preferred embodiment, described pore former is inorganic pore former or macromolecule pore former, or the mixture of the two.
On meaning of the present invention, described pore former should be appreciated that it is to help Polymer Solution to form the agent in hole in the gel solidification process.
Described inorganic pore former can be lithium nitrate, calcium nitrate, lithium chloride, calcium chloride, sodium nitrate, sodium acetate etc.The mass content of inorganic pore former in spinning solution can be 0-10%.
Described organic polymer pore former can be a PVP, polyethylene glycol, polyvinyl alcohol, methylcellulose water soluble polymer.The mass content of organic polymer pore former in spinning solution can be 0-20%.
Preferably, described pore former is one or more pore formers that are selected from lithium nitrate, calcium nitrate, lithium chloride, calcium chloride, PVP, polyethylene glycol, polyvinyl alcohol or methylcellulose.
More preferably, described pore former is one or more pore formers that are selected from lithium nitrate, calcium nitrate, lithium chloride, calcium chloride, polyethylene glycol, polyvinyl alcohol or methylcellulose.
Most preferably, described pore former is one or more pore formers that are selected from lithium nitrate, lithium chloride, calcium chloride, polyethylene glycol or methylcellulose.
According to a kind of preferred embodiment, described core liquid is with the preparation of the mixture of non-solvent or non-solvent and solvent.
On meaning of the present invention, described core liquid should be appreciated that it is the shape that can help to keep doughnut in spinning process, impels the gel solidification of Polymer Solution simultaneously, and forms the solution in hole.
Wherein, described non-solvent is one or more non-solvents that are selected from water, ethanol, methyl alcohol, propyl alcohol, butanols, ethylene glycol or glycerine.
Preferably, described non-solvent is one or more non-solvents that are selected from water, ethanol, propyl alcohol, ethylene glycol or glycerine.
More preferably, described non-solvent is one or more non-solvents that are selected from water, ethanol, propyl alcohol or glycerine.
According to a kind of preferred embodiment, described outer coagulating bath is with the preparation of the mixture of non-solvent or non-solvent and solvent.
On meaning of the present invention, described outer coagulating bath should be appreciated that it is to make the Polymer Solution gel solidification in spinning process, and forms the bath of hollow-fibre membrane.
Wherein, described non-solvent is one or more non-solvents that are selected from water, ethanol, methyl alcohol, propyl alcohol, butanols, ethylene glycol or glycerine.
Preferably, described non-solvent is one or more non-solvents that are selected from water, ethanol, propyl alcohol, ethylene glycol or glycerine.
More preferably, described non-solvent is one or more non-solvents that are selected from water, ethanol, propyl alcohol or glycerine.
For the stability of raising spinning solution and the uniformity of film forming, in spinning solution, can add surfactant, and in core liquid, outer coagulating bath, can not add surfactant, but also can add surfactant.
On meaning of the present invention, described surfactant should be appreciated that it is to help core liquid, outer coagulating bath and spinning solution to form the agent of homogeneous solution.
According to a kind of preferred embodiment; described surfactant is that one or more are selected from lauryl sodium sulfate, dodecyl sodium sulfate, Tween-80, N, the surfactant of N-dimethyl lauryl amine second lactone, sodium N methyl N oleyltaurate or oleoyl amino carboxylic acid sodium.
Preferably, described surfactant is one or more surfactants that are selected from lauryl sodium sulfate, dodecyl sodium sulfate, Tween-80, sodium N methyl N oleyltaurate or oleoyl amino carboxylic acid sodium.
More preferably, described surfactant is one or more surfactants that are selected from lauryl sodium sulfate, dodecyl sodium sulfate, Tween-80 or oleoyl amino carboxylic acid sodium.
After adopting the inventive method to make described hollow-fibre membrane, the present invention has also measured these technical parameters of external diameter, wall thickness, voidage, average pore size, rupture strength and pure water flux of hollow-fibre membrane.
Wherein external diameter and wall thickness are to use the light microscope determining of band scale, and used light microscope is that the XTT that instrument electric light instrument plant of Beijing section produces becomes times stereomicroscope.
Voidage is to use weight method to measure, and promptly weighs up the weight of dry front and back hollow-fibre membrane respectively, calculates the volume fraction that water takies then, promptly obtains voidage.The instrument that uses of weighing is the AL204 assay balance of plum Teller-Tuo benefit group.
Average pore size, rupture strength and pure water flux are to use semidry method pore size determination instrument, pneumatic process rupture strength analyzer and doughnut pure water flux analyzer to measure respectively.
The invention still further relates to the purposes of described hollow-fibre membrane in municipal wastewater and Industrial Wastewater Treatment.
[beneficial effect]
Good effect of the present invention is the hydrophily of sulfonated poly (phenylene oxide) is combined with the corrosion resistance and the intensity of Kynoar, the hollow-fibre membrane that makes had both had the intensity and the corrosion resistance of Kynoar, the hydrophily that has sulfonated poly (phenylene oxide) again can be used in the processing and the advanced treating of municipal wastewater and industrial wastewater.Its effluent quality reaches the landscape water standard in " urban wastewater treatment firm pollutant emission standard (GB189.8-2002) ", and the landscape water standard in " urban sewage reutilization (GB/T18920-2002) ".Reclaimed water reuse such as can be used as greening, view, clean, flush the toilet.It is as follows mainly to go out water quality standard:
COD
Cr50mg/L, BOD
56mg/L, ammonia nitrogen 5mg/L, total phosphorus 0.5mg/L, total nitrogen 15mg/L.
[description of drawings]
Fig. 1 is the spinning technique flow process of doughnut spinning-drawing machine.
Wherein: 1: the nitrogen pressure steel cylinder; 2: the feed liquid still; 3, core flow container; 4, spinning head; 5, coagulating tank; 6, hollow-fibre membrane guide wheel; 7, guide wheel; 8, wire wrapping wheel; 9, wrapping wire rinse bath.
[specific embodiment]
Following non-limiting example is used to illustrate in greater detail the present invention.
Embodiment 1:
15 gram Kynoar, 5 gram sulfonated poly (phenylene oxide)s and 5 gram polyethylene glycol are dissolved in respectively in 40 grams, 15 grams and the 10 gram dimethylacetylamides, solution temperature is 80 ℃, then they are mixed, adopt dry-wet spinning method again, dry-spinning path is 6cm, extruding volume flow rate is 2mL/min, the spinning solution temperature is 60 ℃, and core liquid employing weight concentration is 10% the dimethylacetylamide aqueous solution, and deionized water is adopted in coagulating bath, coagulation bath temperature is 50 ℃, promptly obtains said blend hollow fiber membrane; Its structure is two cortex constructions, and the pure water flux of film is 120L/m
2.h.bar, average pore size is 0.06 micron.This film is used for the recycling of municipal wastewater, and water outlet is as the greening reclaimed water reuse.When influent quality is COD
Cr60mg/L, BOD
5When 5mg/L, ammonia nitrogen 18mg/L, total phosphorus 2mg/L, total nitrogen 19mg/L, its effluent quality is as follows: COD
Cr35mg/L, BOD
51mg/L, ammonia nitrogen 3mg/L, total phosphorus 0.5mg/L, total nitrogen 7mg/L.
Wherein:
COD
CrBe to adopt dichromate titration to measure.
BOD
5Be to adopt dilution and inocalation method [GB7488-87] to measure.
Ammonia nitrogen is to adopt gas-phase molecular absorption spectrometry method [HJ/T 195-2005] to measure.
Total phosphorus is to adopt the ammonium molybdate spectrophotometry.
Total nitrogen is to adopt nessler reagent photometry [GB 7479-87] to measure.
Embodiment 2:
13 gram Kynoar, 6 gram sulfonated poly (phenylene oxide)s and 10 gram polyethylene glycol are dissolved in respectively in 45 grams, 16 grams and the 10 gram dimethylacetylamides, solution temperature is 80 ℃, mix then, adopt dry-wet spinning method, dry-spinning path is 6cm, extruding volume flow rate is 3mL/min, the spinning solution temperature is 80 ℃, and core liquid employing weight concentration is 20% the dimethylacetylamide aqueous solution, and deionized water is adopted in coagulating bath, coagulation bath temperature is 50 ℃, promptly obtains said blend hollow fiber membrane; Its structure is two cortex constructions, and the pure water flux of film is 160L/m
2.h, average pore size is 0.08 micron.This film is used for the sanitary sewage disposal of office building, and water outlet is as reclaimed water reuses such as cleaning, flush the toilet.When influent quality is COD
Cr58mg/L, BOD
5When 7mg/L, ammonia nitrogen 21mg/L, total phosphorus 4mg/L, total nitrogen 23mg/L, its effluent quality is as follows: COD
Cr39mg/L, BOD
52mg/L, ammonia nitrogen 4mg/L, total phosphorus 0.5mg/L, total nitrogen 9mg/L.Its water-quality determination method is identical with embodiment 1.
Embodiment 3:
17 gram Kynoar, 3 gram sulfonated poly (phenylene oxide)s and 15 gram PVPs are dissolved in respectively in 55 grams, 15 grams and the 5 gram dimethylacetylamides, solution temperature is 80 ℃, mix then, adopt dry-wet spinning method, dry-spinning path is 4cm, extruding volume flow rate is 2.5mL/min, the spinning solution temperature is 80 ℃, and core liquid employing weight concentration is 15% the dimethylacetylamide aqueous solution, and deionized water is adopted in coagulating bath, coagulation bath temperature is 45 ℃, promptly obtains said blend hollow fiber membrane; Its structure is two cortex constructions, and the pure water flux of film is 190L/m
2.h, average pore size is 0.09 micron.This film is used for the sanitary sewage disposal of residential quarters, and water outlet is as landscape water.When influent quality is COD
Cr72mg/L, BOD
5When 9mg/L, ammonia nitrogen 13mg/L, total phosphorus 4mg/L, total nitrogen 27mg/L, its effluent quality is as follows: COD
Cr43mg/L, BOD
54mg/L, ammonia nitrogen 5mg/L, total phosphorus 0.5mg/L, total nitrogen 11mg/L.Its water-quality determination method is identical with embodiment 1.
Embodiment 4-9:
Parameters such as the composition of film formula of liquid, core liquid and the coagulating bath of embodiment 4 to embodiment 9 and filming performance are referring to table 1 and table 2, and other parts are participated in embodiment 3.When influent quality is COD
Cr83mg/L, BOD
5When 15mg/L, ammonia nitrogen 18mg/L, total phosphorus 4mg/L, total nitrogen 32mg/L, its effluent quality all can reach the landscape water standard of " urban wastewater treatment firm pollutant emission standard (GB189.8-2002) ", and the landscape water standard of " urban sewage reutilization (GB/T18920-2002) ".Be COD
Cr≤ 50mg/L, BOD
5≤ 6mg/L, ammonia nitrogen≤5mg/L, total phosphorus≤0.5mg/L, total nitrogen≤15mg/L.Its water-quality determination method is identical with embodiment 1.
Table 1: preparation liquid prescription and filming performance among the present invention
Table 2: the composition of core liquid of the present invention and coagulating bath
| Embodiment | Core | Coagulating bath | |
| 4 and 5 | 10% dimethyl formamide, 5% ethanol, 1% |
5% dimethyl formamide, 2% ethanol, 1% |
|
| 6 and 7 | 20% dimethylacetylamide, 10% propyl alcohol, 1% lauryl sodium sulfate | 10% dimethylacetylamide, 4% propyl alcohol, 1% lauryl sodium sulfate | |
| 8 and 9 | 15% dimethyl sulfoxide (DMSO), 4% glycerine, 1% lauryl sodium sulfate | 10% dimethyl sulfoxide (DMSO), 2% glycerine, 1% lauryl sodium sulfate |
Annotate: other composition in core liquid and the coagulating bath is a water.
Claims (10)
1. hollow-fibre membrane, it is characterized in that this film is made up of Kynoar and sulfonated poly (phenylene oxide) polymer blend, the mass ratio of Kynoar and sulfonated poly (phenylene oxide) is 2 in this polymer blend: 1-50: 1, this film section is two cortex spongelike structures, the porosity 55-85% of its doughnut external diameter 0.2-3 millimeter, wall thickness 0.05-1 millimeter, this film, average pore size 0.005-0.5 micron, rupture strength 0.1-1MPa, under 1 crust and 25 ℃ condition, the test pure water flux is 100-200L/m
2H.
2. hollow-fibre membrane according to claim 1 is characterized in that the mass ratio of Kynoar and sulfonated poly (phenylene oxide) is 2 in this polymer blend: 1-50: 1.
3. the production method of a hollow-fibre membrane is characterized in that this method comprises the steps:
A) use solvent to prepare 10-40 weight % Kynoar solution;
B) use solvent to prepare 5-50 weight % sulfonated polyphenyl ethereal solution;
C) with above-mentioned a) solution and b of preparation) solution of preparation mixes and obtains a kind of mixed solution, and to make the Kynoar in this mixed solution and the mass ratio of sulfonated poly (phenylene oxide) be 2: 1-50: 1;
D) use the solvent preparation to contain the solution of pore former and surfactant, then the solution that obtains is added to above-mentioned c) preparation mixed solution in make a kind of spinning solution, and make that the total concentration of Kynoar and sulfonated poly (phenylene oxide) is 15-25 weight % in the spinning solution, the concentration of pore former is greater than 0 to smaller or equal to 20 weight %, and surfactant concentrations is to smaller or equal to 1 weight % greater than 0;
E) use the mixture of non-solvent or non-solvent and solvent to prepare core liquid, described non-solvent is 100: 0 to 10: 90 with the solvent quality ratio;
F) use the mixture of non-solvent or non-solvent and solvent to prepare coagulating bath, described non-solvent is 100: 0 to 10: 90 with the solvent quality ratio;
G) adopt dry-wet spinning method, at dry-spinning path 1-15cm, the temperature 20-90 of described spinning solution ℃, under described core liquid and coagulation bath temperature 20-90 ℃ the condition, use above-mentioned e) core liquid and the above-mentioned f of preparation) coagulating bath for preparing, with above-mentioned d) spinning solution that obtains prepares described hollow-fibre membrane, the mass ratio of Kynoar and sulfonated poly (phenylene oxide) is 2 in this film: 1-50: 1, this film section is two cortex spongelike structures, its doughnut external diameter 0.2-3 millimeter, wall thickness 0.05-1 millimeter, the porosity 55-85% of this film, average pore size 0.005-0.5 micron, rupture strength 0.1-1MPa.
4. production method according to claim 3 is characterized in that described solvent is one or more solvents that are selected from dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO).
5. production method according to claim 3 is characterized in that described non-solvent is one or more non-solvents that are selected from water, ethanol, methyl alcohol, propyl alcohol, butanols, ethylene glycol or glycerine.
6. production method according to claim 3 is characterized in that described pore former is one or more pore formers that are selected from lithium nitrate, calcium nitrate, lithium chloride, calcium chloride, PVP, polyethylene glycol, polyvinyl alcohol or methylcellulose.
7. according to the described production method of each claim in the claim 3 to 6; it is characterized in that described surfactant is that one or more are selected from lauryl sodium sulfate, dodecyl sodium sulfate, Tween-80, N, the surfactant of N-dimethyl lauryl amine second lactone, sodium N methyl N oleyltaurate or oleoyl amino carboxylic acid sodium.
8. production method according to claim 3 is characterized in that described core liquid and described coagulating bath contain described surfactant.
9. hollow-fibre membrane according to claim 1 and 2 or the purposes of hollow-fibre membrane in municipal wastewater and Industrial Wastewater Treatment of producing according to the described method of arbitrary claim in claim 3-6 and 8.
10. the purposes of hollow-fibre membrane in municipal wastewater and Industrial Wastewater Treatment of producing according to the described method of claim 7.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101791525B (en) * | 2009-12-24 | 2011-11-09 | 北京碧水源膜科技有限公司 | Polyvinylidene fluoride hollow fiber membrane with base material and production method thereof |
| CN101961606B (en) * | 2010-09-02 | 2012-07-04 | 燕山大学 | Process for preparing ethylenediaminetetraacetic dianhydride modified polyvinylidene fluoride separation membrane and resin |
| CN101961605B (en) * | 2010-09-02 | 2012-06-27 | 燕山大学 | Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin |
| CN102430344A (en) * | 2011-11-07 | 2012-05-02 | 东华大学 | Hollow polyvinylidene fluoride fibrous membrane and preparation method as well as application thereof |
| CN108525531A (en) * | 2017-03-02 | 2018-09-14 | 天津工业大学 | A kind of method that non-solvent induction gel phase separation method prepares polymer blend membrane |
| CN114959930B (en) * | 2022-05-26 | 2023-08-04 | 浙江毅聚新材料有限公司 | Spinning forming method |
| CN117679954B (en) * | 2024-02-01 | 2024-05-03 | 自然资源部天津海水淡化与综合利用研究所 | High-flux anti-pollution polyether sulfone flat microporous membrane and preparation method and application thereof |
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| CN1206503A (en) * | 1995-12-28 | 1999-01-27 | 纽约州立大学研究基金会 | Blend membranes based on sulfonated poly (phenylene oxide) for enhanced polymer electrochemical cells |
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