CN100523077C - Blending film, producing method and use thereof - Google Patents
Blending film, producing method and use thereof Download PDFInfo
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- CN100523077C CN100523077C CNB2008100557170A CN200810055717A CN100523077C CN 100523077 C CN100523077 C CN 100523077C CN B2008100557170 A CNB2008100557170 A CN B2008100557170A CN 200810055717 A CN200810055717 A CN 200810055717A CN 100523077 C CN100523077 C CN 100523077C
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 title abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 94
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 81
- 238000002360 preparation method Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims description 51
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 38
- 229920001038 ethylene copolymer Polymers 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000000605 extraction Methods 0.000 claims description 30
- -1 ethylene-chlorotrifluoro-ethylene Chemical group 0.000 claims description 23
- 230000004907 flux Effects 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000010865 sewage Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003490 calendering Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009997 thermal pre-treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- 239000010841 municipal wastewater Substances 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 abstract description 17
- 239000012528 membrane Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000001471 micro-filtration Methods 0.000 abstract description 13
- 238000002145 thermally induced phase separation Methods 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract 3
- CRWBOACCCUOPSJ-UHFFFAOYSA-N ClC(=C(F)F)F.CC Chemical group ClC(=C(F)F)F.CC CRWBOACCCUOPSJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010840 domestic wastewater Substances 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 15
- 229910052698 phosphorus Inorganic materials 0.000 description 15
- 239000011574 phosphorus Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 230000003628 erosive effect Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000007844 bleaching agent Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 229920001780 ECTFE Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a polyvinylidene fluoride/ ethane-trifluorochloroethylene copolymer blend membrane which is prepared through adopting a thermally induced phase separation, and the process for preparation and the usage. Polyvinylidene fluoride/ ethane-trifluorochloroethylene copolymer blend membrane is prepared through the thermally induced phase separation through the blending of the copolymer of polyvinylidene fluoride and ethane-trifluorochloroethylene. The invention can dramatically improve the performance of polyvinylidene fluoride, can obtain microfiltration membrane which has the advantages of excellent corrosion resistance, narrow pore size distribution and high intensity, thereby meeting the requirements of water handling of practical production and domestic wastewater better.
Description
[technical field]
The present invention relates to a kind of microfiltration membrane technical field.More specifically, the present invention relates to a kind of polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film that adopts the thermally induced phase separation preparation, the production method of described film and purposes.
[background technology]
The membrane sepn process is subjected to the general attention of people because of it is efficient, simple, energy-conservation.Especially, the known microfiltration membrane of people has been widely used for industrial technology fields such as chemical industry, medicine, food, electronics, and they are used for desalt, separate and recycle.Usually the microfiltration membrane preparation method who adopts is a wet method.Described wet method is based on the macromolecular solution phase separation principle, promptly the macromolecular solution by polymkeric substance and solvent composition is a homogeneous system, when macromolecular solution contacts with non-solvent, solvent in non-solvent and the macromolecular solution exchanges, non-solvent diffuses in the macromolecular solution, the solubleness of polymkeric substance reduces, and at this moment macromolecular solution is separated, and forms to be rich in polymer phase and to be rich in solvent phase; Behind the solvent in removing its solution, formed microvoid structure in the solid polymer membrane with certain pore size and pore distribution.Because when the macromolecular solution surface contacted with non-solvent, this surface can be solidified rapidly in the extremely short time, forms cortex.Non-solvent diffuses in the macromolecular solution by cortex subsequently, forms porous support layer below cortex.Usually the aperture of cortex is less, and the aperture of supporting layer is bigger.By adding the aperture that additive can increase cortex, still, along with the increase in cortex aperture, the aperture of supporting layer also becomes greatly, and film strength also descends thereupon.Therefore, the microfiltration membrane intensity made from wet method is lower.
It is thermally induced phase separation (TIPS) that the important technology of a preparation microfiltration membrane improves.The basic fundamental of thermally induced phase separation is, earlier polymer and thinner at high temperature is mixed and made into homogeneous phase solution, reduces temperature then and makes the macromolecular solution cooling curing, and polymer and thinner are separated in temperature-fall period.With extraction agent the polymer of thinner behind cooling curing extracted mutually again, promptly obtain vesicular structure.Because heat passage very fast, the surface of macromolecular solution and inner phase-splitting simultaneously in the temperature-fall period, therefore even, porosity is high with the microfiltration membrane pore distribution that thermally induced phase separation is made, and also intensity is good.Thermally induced phase separation generally adopts semicrystalline polymerics such as polypropylene, polyvinylidene difluoride (PVDF) as material of preparing.Polyvinylidene difluoride (PVDF) particularly is because its higher intensity and erosion resistance and be used for water treatment more and more preferably.But, along with the extensive application of polyvinylidene fluoride microporous filtering film in sewage disposal, to the also raising thereupon of erosion resistance requirement of film.The erosion resistance of improving film is the problem that presses for solution at present.Can know that from prior art a kind of method that improves the film erosion resistance is to adopt polymer blended method.For this reason, the inventor has carried out a large amount of experimental studies, has made the present invention finally.
[summary of the invention]
[problem that invention will solve]
The purpose of this invention is to provide a kind of polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film.
Another object of the present invention provides the preparation method of a kind of described polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film.
Another object of the present invention provides the purposes of described polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film.
[technical scheme]
Purpose of the present invention mainly is the problem that solves the corrosion-resistant of existing polyvinylidene fluoride microporous filtering film in the prior art.The fusing point of polyvinylidene difluoride (PVDF) is 160 ℃, and the fusing point of ethylene-chlorotrifluoro-ethylene copolymer is higher, about 240 ℃, also has better erosion resistance simultaneously.Therefore, by with the ethylene-chlorotrifluoro-ethylene copolymer blend, adopt thermally induced phase separation to prepare polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film, might obviously improve the performance of polyvinylidene fluoride film, promptly obtain good corrosion resistance, pore size distribution is narrow, intensity is high microfiltration membrane, thereby satisfy the needs of actual production and sanitary sewage disposal better.
The present invention realizes by following manner:
A kind of polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film is characterized in that the weight ratio 35:1-2:1 of polyvinylidene difluoride (PVDF) and ethylene-chlorotrifluoro-ethylene copolymer in this blend film, and the film thickness of this blend film is 0.20-0.40 millimeter, water flux 8-40L/m
2.h, mean pore size 0.05-0.30 micron, stretching strength retentivity 60-90%.
Here, should be noted that in the described blend film that the weight ratio of polyvinylidene difluoride (PVDF) and ethylene-chlorotrifluoro-ethylene copolymer is to implement essential to the inventionly, the erosion resistance of this blend film is improved not obvious or is difficult to make the film of the better performances of homogeneous if this weight ratio surpasses its scope.
The film thickness of described blend film also be implement essential to the invention, if this thickness less than 0.20 millimeter, then this blend film strength is relatively poor; If this thickness is greater than 0.40 millimeter, then the water flux of this blend film is lower.
Similarly, water flux, mean pore size, stretching strength retentivity also are that enforcement is essential to the invention.If water flux is too low, blend film does not just have practical value.If mean pore size is too little, water flux will be too low; If mean pore size is too big, just do not reach the filtration requirement of expection.If stretching strength retentivity is too low, will shorten the work-ing life of film.
Preferably, the weight ratio 20:1-2:1 of polyvinylidene difluoride (PVDF) and ethylene-chlorotrifluoro-ethylene copolymer in this blend film, the film thickness of this blend film are 0.20-0.40 millimeter, water flux 8-35L/m
2.h, mean pore size 0.05-0.20 micron, stretching strength retentivity 65-90%.
More preferably, the weight ratio 10:1-4:1 of polyvinylidene difluoride (PVDF) and ethylene-chlorotrifluoro-ethylene copolymer in this blend film, the film thickness of this blend film are 0.20-0.40 millimeter, water flux 8-30L/m
2.h, mean pore size 0.05-0.15 micron, stretching strength retentivity 70-90%.
The invention still further relates to the preparation method of a kind of polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film, it is characterized in that the step of this method is as follows:
The preparation of a, preparation liquid: 20-35 weight % polyvinylidene difluoride (PVDF), 1-10 weight % ethylene-chlorotrifluoro-ethylene copolymer, 60-78 weight % thinner stirred 2-12 hour down at melt mix temperature 100-300 ℃, obtained uniform preparation liquid;
B, deaeration are handled: described even preparation liquid left standstill under 100-300 ℃ 0.5-12 hour;
C, mould pre-treatment: forming mould temperature 100-300 ℃ following thermal pretreatment 5-60 minute;
D, moulding: the deaeration preparation liquid that step b) obtains is poured in the step c) preheated mold, and this preparation liquid calendering formation cooled off 1-12 hour in cooling environment then;
E, extraction: the cooling forming film is at ambient temperature with extraction agent extraction 1-14 days;
F, drying: spe membrane carries out drying treatment, removes extraction agent wherein, obtains polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film like this.
The present invention adopts the ethylene-chlorotrifluoro-ethylene copolymer and the polyvinylidene blending of high strength and erosion resistance, can guarantee the physical strength of film, can improve the erosion resistance of film again, create condition for the present invention adopts thermally induced phase separation to prepare polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film.
All higher because of the fusing point of polyvinylidene difluoride (PVDF) and ethylene-chlorotrifluoro-ethylene copolymer, be respectively about 160 ℃ and 240 ℃, and their decomposition temperature all is higher than 300 ℃.Therefore, preparation liquid need be under comparatively high temps but should be lower than under the temperature of decomposition temperature and be prepared.
According to a kind of preferred embodiment, the melt mix temperature of described preparation liquid is preferably 200-280 ℃, and stirs 2-10 hour under this temperature.
More preferably, the melt mix temperature of described preparation liquid is 220-270 ℃, and stirs 2-8 hour under this temperature.
In addition, when preparation film liquid, need add thinner.
On meaning of the present invention, described thinner should be appreciated that it is can not dissolve described macromolecular material at low temperatures, but can at high temperature dissolve described macromolecular material and form the agent of homogeneous solution.
According to a kind of preferred embodiment, described thinner is one or more thinners that are selected from dibutyl phthalate, gamma-butyrolactone, propylene glycol carbonic ether, trimethyl phosphate.
Preferably, the thinner in the described preparation liquid is the thinner that is selected from dibutyl phthalate or gamma-butyrolactone.
More preferably, the thinner in the described preparation liquid is a dibutyl phthalate.
In addition, after making uniform preparation liquid, for not having defective in the film that guarantees to obtain, for example the pin hole known usually of people etc. needs that also this film liquid is carried out deaeration and handles.This deaeration is handled normally after preparation liquid mixes, and stops to stir, and is incubated down at temperature 100-300 ℃ and leaves standstill 0.5-12 hour.
Preferably, this deaeration processing is to leave standstill 2-10 hour in a temperature 200-280 ℃ insulation.
More preferably, this deaeration processing is to leave standstill 2-8 hour in a temperature 220-270 ℃ insulation.
On the other hand, described preparation liquid is poured in the mould before the calendering formation, need be carried out thermal pretreatment mould.Can be put into mould in temperature 100-300 ℃ the baking oven thermal pretreatment 5-60 minute.
On meaning of the present invention, described mould should be appreciated that the normally used mould of people when being the dull and stereotyped microfiltration membrane of preparation, promptly keeps certain space between two parallel stainless steel plates.The thickness of microfiltration membrane is by the distance decision between stainless steel plate, and its shape and size depend on the shape and the size of stainless steel plate.
Therefore, adopting the microfiltration membrane of the present invention's preparation can be the microfiltration membrane with different thickness, shape and size.
Preferably, described mould is in temperature 150-300 ℃ baking oven thermal pretreatment 5-60 minute.
More preferably, described mould is in temperature 150-260 ℃ baking oven thermal pretreatment 20-60 minute.
Then, the deaeration preparation liquid is poured in the above-mentioned preheated mold, calendering formation, and be placed on cooling cooling in the cooling environment.
According to a kind of preferred embodiment, described cooling environment is air or water, ice, dry ice or a liquid nitrogen at ambient temperature, and be 1-12 hour its cooling time.
Preferably, described cooling environment is air or a water, ice at ambient temperature, and be 1-12 hour its cooling time.
More preferably, described cooling environment is water or an ice at ambient temperature, and be 1-12 hour its cooling time.
After treating that mould cools off fully, the blend film of making is taken out from mould, and put into extraction agent extraction thinner wherein.
On meaning of the present invention, described extraction agent should be appreciated that it is to dissolve described thinner, but can not dissolve the solvent of described macromolecular material.
According to a kind of preferred embodiment, described extraction agent is one or more extraction agents that are selected from water, Virahol, ethylene glycol or dehydrated alcohol, and the extraction time is 1-14 days.
Preferably, described extraction agent is the extraction agent that is selected from dehydrated alcohol or Virahol, and the extraction time is 1-7 days.
More preferably, described extraction agent is a Virahol, and the extraction time is 1-7 days.
Then, the film after the extraction is carried out drying treatment,, promptly get polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film to remove extraction agent wherein.
According to a kind of preferred embodiment, described drying treatment is meant that blend film of the present invention spontaneous combustion in air dries or heating, drying in baking oven.
On meaning of the present invention, described drying should be appreciated that be this blend film after drying treatment wherein the content of extraction agent be equal to or less than 0.05 weight %.
If the content of extraction agent is higher than 0.05 weight % in this blend film, then this blend film water flux after long-time the placement can reduce.
The content of described extraction agent is according to the change calculations of blend film weight before and after the high temperature drying.
When heating, drying was handled in baking oven, its bake out temperature was 90-105 ℃, and drying time is 2-10 hour.The baking oven that uses for example is that Tianjing Huabei Laboratory Apparatus Co., Ltd. is with trade(brand)name electric drying oven with forced convection product sold.
The present invention has carried out the mensuration of thickness, pure water flux, mean pore size and erosion resistance to prepared blend film.
The thickness of described blend film is to use the opticmicroscope of band scale to measure, and used opticmicroscope is that the XTT that instrument electric light instrument plant of Beijing section produces becomes times stereoscopic microscope.
The cup type ultra-fine filter of SCM type that the pure water flux of described blend film is to use Shanghai Inst. of Applied Physics Chinese Academy of Sciences to produce is tested under 0.1MPa pressure.
The mean pore size of described blend film is to use semidrying pore size determination instrument to measure.
The tensile strength variation that the erosion resistance of described blend film is to use clorox to soak front and back compares definite.Particularly, blend film of the present invention was soaked 15 days down for 30 ℃ in temperature in the 5000ppm aqueous sodium hypochlorite solution, then, change definite its stretching strength retentivity by measuring this blend film tensile strength before and after this test.The stretching strength retentivity of this blend film is high more, and erosion resistance is just good more.
The commodity that tensile strength is to use Shijiazhuang Zhongshi Detection Equipment Co., Ltd. to sell are called the product of WDT-5 electronics pulling experiment machine.Its tensile strength is to measure according to the operational condition of described instrument working instructions regulation.
Stretching strength retentivity is defined as follows:
Stretching strength retentivity=(tensile strength before the tensile strength/immersion after the immersion) * 100%
Adopt the present invention to prepare polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film, have simple, the easy row of filming technology, not high to equipment requirements, technological process is easy to characteristics such as control.The film toughness height of making thus, erosion resistance is strong, and water flux is big.Be particularly suitable for the processing reuse of sewage.
Polyvinylidene difluoride (PVDF)/the purposes of ethylene-chlorotrifluoro-ethylene copolymer blend film in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment that the invention still further relates to described polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film or prepare by the inventive method.
[beneficial effect]
The present invention is by polyvinylidene difluoride (PVDF) and ethylene-chlorotrifluoro-ethylene copolymer blend, adopt thermally induced phase separation to prepare polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film, can obviously improve the performance of polyvinylidene difluoride (PVDF), promptly obtain good corrosion resistance, pore size distribution is narrow, intensity is high microfiltration membrane, thereby satisfy the needs of actual production and sanitary sewage disposal better.Blend film strength and erosion resistance obviously are better than the polyvinylidene fluoride film of one-component, and this is easy to from embodiment 1,2 and comparative example 1, and embodiment 3-7 and comparative example 2 find out.
When using prepared blend film to carry out the sanitary sewage disposal of office building or office building, treated water reaches the landscape water standard of national regulation, reclaimed water reuse such as can be used as greening, view, clean, flush the toilet.
[embodiment]
Following non-limiting example is used to illustrate in greater detail the present invention.
Embodiment 1:
According to using raw material gross weight meter, 30 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, the ethylene-chlorotrifluoro-ethylene copolymer of the trade mark HALAR that 10 weight %SOLVAY companies produce, the dibutyl phthalate that 60 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 6 hours down 250 ℃ of temperature, make uniform preparation liquid, this preparation liquid was 250 ℃ of following standing and defoaming of temperature 5 hours then.
In addition, with flat plate mold preheating 40 minutes under 250 ℃ of temperature, then the deaeration preparation liquid is poured in this mould into this preparation liquid calendering formation.
Then flat plate mold is inserted in the frozen water, place after 12 hours, take out the blend film of calendering formation.
Place this blend film Virahol to soak 7 days again, extract the dibutyl phthalate that wherein contains.
This blend film placed under the room temperature dry 3 days.
The thickness of making blend film is 0.25 millimeter, water flux 16L/m
2.h, 0.12 micron of mean pore size, tensile strength 4.3MPa.Tensile strength 3.6MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 84%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, reclaimed water reuse such as water outlet can be used as cleaning, flush the toilet.When influent quality is COD
Cr65mg/L, BOD
5When 7mg/L, ammonia nitrogen 22mg/L, total phosphorus 3mg/L, total nitrogen 24mg/L, its effluent quality is as follows: COD
Cr30mg/L, BOD
52mg/L, ammonia nitrogen 5mg/L, total phosphorus 0.5mg/L, total nitrogen 9mg/L.
Wherein:
COD
CrBe to adopt dichromate titration to measure.
BOD
5Be to adopt dilution and inoculation 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 light-intensity method [GB 7479-87] to measure.
Embodiment 2:
According to using raw material gross weight meter, 35 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, the ethylene-chlorotrifluoro-ethylene copolymer of the trade mark HALAR that 5 weight %SOLVAY companies produce, the dibutyl phthalate that 60 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 8 hours down 250 ℃ of temperature, make uniform preparation liquid, this preparation liquid was 250 ℃ of following standing and defoaming of temperature 8 hours then.
In addition, with flat plate mold preheating 40 minutes under 250 ℃ of temperature, then the deaeration preparation liquid is poured in this mould into this preparation liquid calendering formation;
Then flat plate mold is inserted in the frozen water, place after 10 hours, take out the blend film of calendering formation.
Place this blend film Virahol to soak 8 days again, extract the dibutyl phthalate that wherein contains.
This blend film placed under the room temperature dry 3 days.
The thickness of making blend film is 0.25 millimeter, water flux 11L/m
2.h, 0.08 micron of mean pore size, tensile strength 3.8MPa.Tensile strength 2.8MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 74%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, reclaimed water reuse such as water outlet can be used as cleaning, flush the toilet.When influent quality is COD
Cr65mg/L, BOD
5When 7mg/L, ammonia nitrogen 22mg/L, total phosphorus 3mg/L, total nitrogen 24mg/L, its effluent quality is as follows: CODCr22mg/L, BOD
51mg/L, ammonia nitrogen 3mg/L, total phosphorus 0.3mg/L, total nitrogen 5mg/L.Its water-quality determination method is identical with embodiment 1.
The comparative example 1:
According to using raw material gross weight meter, 40 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, the dibutyl phthalate that 60 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 8 hours down for 250 ℃ in temperature, make uniform preparation liquid, this preparation liquid was 250 ℃ of following standing and defoaming of temperature 8 hours then.
In addition, with flat plate mold preheating 40 minutes under 250 ℃ of temperature, then the deaeration preparation liquid is poured in this mould into this preparation liquid calendering formation;
Then flat plate mold is inserted in the frozen water, place after 12 hours, take out the blend film of calendering formation.
Place this blend film Virahol to soak 7 days again, extract the dibutyl phthalate that wherein contains.
This blend film placed under the room temperature dry 3 days.
The thickness of making blend film is 0.25 millimeter, water flux 9L/m
2.h, 0.09 micron of mean pore size, tensile strength 3.5MPa.Tensile strength 2.3MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 66%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, reclaimed water reuse such as water outlet can be used as cleaning, flush the toilet.When influent quality is COD
Cr65mg/L, BOD
5When 7mg/L, ammonia nitrogen 22mg/L, total phosphorus 3mg/L, total nitrogen 24mg/L, its effluent quality is as follows: COD
Cr25mg/L, BOD
52mg/L, ammonia nitrogen 4mg/L, total phosphorus 0.5mg/L, total nitrogen 8mg/L.Its water-quality determination method is identical with embodiment 1.
Embodiment 3:
According to using raw material gross weight meter, 22 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, the ethylene-chlorotrifluoro-ethylene copolymer of the trade mark HALAR that 8 weight %SOLVAY companies produce, the dibutyl phthalate that 70 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 6 hours down 260 ℃ of temperature, make uniform preparation liquid, this preparation liquid was 250 ℃ of following standing and defoaming of temperature 5 hours then.
In addition, with flat plate mold preheating 35 minutes under 260 ℃ of temperature, then the deaeration preparation liquid is poured in this mould into this preparation liquid calendering formation;
Then flat plate mold is inserted in 25 ℃ of water, place after 4 hours, take out the blend film of calendering formation.
Place this blend film Virahol to soak 5 days again, extract the dibutyl phthalate that wherein contains.
This blend film placed under the room temperature dry 2 days.
The thickness of making blend film is 0.23 millimeter, water flux 28L/m
2.h, 0.24 micron of mean pore size, tensile strength 2.9MPa.Tensile strength 2.1MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 72%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, water outlet can be used as landscape water.When influent quality is COD
Cr58mg/L, BOD
5When 6mg/L, ammonia nitrogen 10mg/L, total phosphorus 1mg/L, total nitrogen 21mg/L, its effluent quality is as follows: COD
Cr30mg/L, BOD
53mg/L, ammonia nitrogen 5mg/L, total phosphorus 0.5mg/L, total nitrogen 12mg/L.Its water-quality determination method is identical with embodiment 1.
Embodiment 4:
According to using raw material gross weight meter, 28 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, the ethylene-chlorotrifluoro-ethylene copolymer of the trade mark HALAR that 2 weight %SOLVAY companies produce, the dibutyl phthalate that 70 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 4 hours down 260 ℃ of temperature, make uniform preparation liquid, this preparation liquid was 260 ℃ of following standing and defoaming of temperature 4 hours then.
In addition, with flat plate mold preheating 15 minutes under 260 ℃ of temperature, then the deaeration preparation liquid is poured in this mould into this preparation liquid calendering formation;
Then flat plate mold is inserted in 25 ℃ of water, place after 8 hours, take out the blend film of calendering formation.
Place this blend film Virahol to soak 5 days again, extract the dibutyl phthalate that wherein contains.
This blend film placed under the room temperature dry 2 days.
The thickness of making blend film is 0.23 millimeter, water flux 22L/m
2.h, 0.18 micron of mean pore size, tensile strength 2.6MPa.Tensile strength 1.7MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 65%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, water outlet can be used as landscape water.When influent quality is COD
Cr58mg/L, BOD
5When 6mg/L, ammonia nitrogen 10mg/L, total phosphorus 1mg/L, total nitrogen 21mg/L, its effluent quality is as follows: COD
Cr26mg/L, BOD
52mg/L, ammonia nitrogen 4mg/L, total phosphorus 0.4mg/L, total nitrogen 9mg/L.Its water-quality determination method is identical with embodiment 1.
Embodiment 5:
According to using raw material gross weight meter, 28.5 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, 1.5 the ethylene-chlorotrifluoro-ethylene copolymer of the trade mark HALAR that weight %SOLVAY company produces, the dibutyl phthalate that 70 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 4 hours down 260 ℃ of temperature, make uniform preparation liquid, this preparation liquid was 260 ℃ of following standing and defoaming of temperature 3 hours then.Other filming technology is identical with embodiment 4.
The thickness of making blend film is 0.23 millimeter, water flux 21.5L/m
2.h, 0.17 micron of mean pore size, tensile strength 2.5MPa.Tensile strength 1.6MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 64%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, water outlet can be used as landscape water.When influent quality and embodiment 4 were identical, its effluent quality was as follows: COD
Cr25mg/L, BOD
52mg/L, ammonia nitrogen 4mg/L, total phosphorus 0.4mg/L, total nitrogen 8mg/L.Its water-quality determination method is identical with embodiment 1.
Embodiment 6:
According to using raw material gross weight meter, 28.8 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, 1.2 the ethylene-chlorotrifluoro-ethylene copolymer of the trade mark HALAR that weight %SOLVAY company produces, the dibutyl phthalate that 70 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 4 hours down 260 ℃ of temperature, make uniform preparation liquid, this preparation liquid was 260 ℃ of following standing and defoaming of temperature 3 hours then.Other filming technology is identical with embodiment 4.
The thickness of making blend film is 0.23 millimeter, water flux 20.4L/m
2.h, 0.16 micron of mean pore size, tensile strength 2.5MPa.Tensile strength 1.6MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 64%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, water outlet can be used as landscape water.When influent quality and embodiment 4 were identical, its effluent quality was as follows: COD
Cr24mg/L, BOD
52mg/L, ammonia nitrogen 4mg/L, total phosphorus 0.4mg/L, total nitrogen 8mg/L.Its water-quality determination method is identical with embodiment 1.
Embodiment 7:
According to using raw material gross weight meter, 29.1 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, 0.9 the ethylene-chlorotrifluoro-ethylene copolymer of the trade mark HALAR that weight %SOLVAY company produces, the dibutyl phthalate that 70 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 4 hours down 260 ℃ of temperature, make uniform preparation liquid, this preparation liquid was 260 ℃ of following standing and defoaming of temperature 3 hours then.Other filming technology is identical with embodiment 4.
The thickness of making blend film is 0.23 millimeter, water flux 19.6L/m
2.h, 0.15 micron of mean pore size, tensile strength 2.4MPa.Tensile strength 1.5MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 63%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, water outlet can be used as landscape water.When influent quality and embodiment 4 were identical, its effluent quality was as follows: COD
Cr22mg/L, BOD
51.5mg/L, ammonia nitrogen 4mg/L, total phosphorus 0.4mg/L, total nitrogen 7mg/L.Its water-quality determination method is identical with embodiment 1.
The comparative example 2:
According to using raw material gross weight meter, 30 weight % Shanghai three are shown tender care for the polyvinylidene fluoride resin of the trade mark FR904 of Materials Co., Ltd's production, the dibutyl phthalate that 70 weight % Jiangsu, seven leaf latex company limiteds produce, put in the pyroreaction still, stirred 4 hours down for 260 ℃ in temperature, make uniform preparation liquid, this preparation liquid was 260 ℃ of following standing and defoaming of temperature 3 hours then.Other filming technology is identical with embodiment 4.
The thickness of making blend film is 0.23 millimeter, water flux 18L/m
2.h, 0.14 micron of mean pore size, tensile strength 2.3MPa.Tensile strength 1.3MPa in the chlorine bleach liquor of 5000ppm after soaking 15 days under 30 ℃ adopts formula noted earlier to calculate stretching strength retentivity 57%.
Use the blend film of this embodiment preparation to carry out the sanitary sewage disposal of office building, water outlet can be used as landscape water.When influent quality and embodiment 4 were identical, its effluent quality was as follows: COD
Cr21mg/L, BOD
51mg/L, ammonia nitrogen 4mg/L, total phosphorus 0.4mg/L, total nitrogen 6mg/L.Its water-quality determination method is identical with embodiment 1.
Claims (8)
1, a kind of polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film, it is characterized in that the weight ratio 35:1-2:1 of polyvinylidene difluoride (PVDF) and ethylene-chlorotrifluoro-ethylene copolymer in this blend film, the film thickness of this blend film is 0.20-0.40 millimeter, water flux 8-40L/m
2.h, mean pore size 0.05-0.30 micron, stretching strength retentivity 60-90%, wherein, the cup type ultra-fine filter of SCM type that described water flux is to use Shanghai Inst. of Applied Physics Chinese Academy of Sciences to produce is tested under 0.1MPa pressure; Described stretching strength retentivity is defined as:
Stretching strength retentivity=(tensile strength before the tensile strength/immersion after the immersion) * 100%.
2, the preparation method of a kind of polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film is characterized in that the step of this method is as follows:
The preparation of a, preparation liquid: 20-35 weight % polyvinylidene difluoride (PVDF), 1-10 weight % ethylene-chlorotrifluoro-ethylene copolymer, 60-78 weight % thinner stirred 2-12 hour down at melt mix temperature 100-300 ℃, obtain uniform preparation liquid, described thinner is one or more thinners that are selected from dibutyl phthalate, gamma-butyrolactone, propylene glycol carbonic ether, trimethyl phosphate;
B, deaeration are handled: described even preparation liquid left standstill under 100-300 ℃ 0.5-12 hour;
C, mould pre-treatment: forming mould temperature 100-300 ℃ following thermal pretreatment 5-60 minute;
D, moulding: the deaeration preparation liquid that step b) obtains is poured in the step c) preheated mold, and this preparation liquid calendering formation cooled off 1-12 hour in cooling environment then, and described cooling environment is air or water, ice, dry ice or a liquid nitrogen at ambient temperature;
E, extraction: with extraction agent extraction 1-14 days, described extraction agent was one or more extraction agents that are selected from water, Virahol, ethylene glycol or dehydrated alcohol to the cooling forming film at ambient temperature;
F, drying: the film after the extraction is carried out drying treatment, remove extraction agent wherein, obtain polyvinylidene difluoride (PVDF)/ethylene-chlorotrifluoro-ethylene copolymer blend film like this.
3, method according to claim 2 is characterized in that stirring 2-10 hour down at melt mix temperature 200-280 ℃.
4, method according to claim 3 is characterized in that stirring 2-8 hour down at melt mix temperature 220-270 ℃.
5, method according to claim 2 is characterized in that described thinner is the thinner that is selected from dibutyl phthalate or gamma-butyrolactone.
6, method according to claim 2 is characterized in that described extraction agent is the extraction agent that is selected from dehydrated alcohol or Virahol.
7, the polyvinylidene difluoride (PVDF) according to claim 1/purposes of ethylene-chlorotrifluoro-ethylene copolymer blend film in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment.
8, the polyvinylidene difluoride (PVDF)/purposes of ethylene-chlorotrifluoro-ethylene copolymer blend film in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment for preparing according to the described method of arbitrary claim among the claim 2-6.
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| CN108057346B (en) * | 2017-12-08 | 2020-12-25 | 南京工业大学 | High-flux polymer separation membrane, preparation method, diluent composition and application |
| CN108479414B (en) * | 2018-04-12 | 2020-12-25 | 南京工业大学 | Hollow fiber polymer membrane, preparation method and application thereof in brine refining |
| CN111992052A (en) * | 2020-08-12 | 2020-11-27 | 北京中环膜材料科技有限公司 | Thermotropic phase hollow fiber blend membrane and preparation method thereof |
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