CN1313191C - Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology - Google Patents
Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology Download PDFInfo
- Publication number
- CN1313191C CN1313191C CNB2004100667187A CN200410066718A CN1313191C CN 1313191 C CN1313191 C CN 1313191C CN B2004100667187 A CNB2004100667187 A CN B2004100667187A CN 200410066718 A CN200410066718 A CN 200410066718A CN 1313191 C CN1313191 C CN 1313191C
- Authority
- CN
- China
- Prior art keywords
- film
- polymer
- polymer microporous
- microporous film
- overcritical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005516 engineering process Methods 0.000 title claims description 12
- 239000012982 microporous membrane Substances 0.000 title 1
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000005266 casting Methods 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims description 43
- 239000012530 fluid Substances 0.000 claims description 25
- 229910001220 stainless steel Inorganic materials 0.000 claims description 23
- 239000010935 stainless steel Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007766 curtain coating Methods 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- 239000001569 carbon dioxide Substances 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 101100049199 Xenopus laevis vegt-a gene Proteins 0.000 description 1
- 101100049200 Xenopus laevis vegt-b gene Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 101150068675 vegt gene Proteins 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention discloses a method for preparing polymer microporous films by supercritical or near-critical CO2 technique. The method comprises the following steps: polymer is dissolved in different solvents to obtain film casting solutions with transparent homogeneous phases; the film casting solution flows and extends in a mould to form a film after film forming pretreatment; the mould is place in a film forming device by supercritical carbon dioxide, the mould is heated and pressurized to above the critical point of carbon dioxide, and the pressure os reduced to the normal pressure after film forming until a smooth white polymer microporous film is obtained. A polymer microporous film with controllable pore size and porosity can be obtained by controlling the temperature, the pressure and the polymer concentration. The present invention avoids the usage of a large quantity of solvent, a dry film is directly obtained without a changed micropore structure, and the solvent and the carbon dioxide can be utilized recurrently. The obtained polymer microporous film has the advantages that the porosity is greater than 70%, the average pore size is within the range of 0.1 to 10 microeters, and the mechanical strength is high. The polymer microporous film can be used as a separation film, a multiporous supporting film, or a diaphragm for Lithium ion secondary cells.
Description
Technical field
The present invention relates to polymer microporous film and preparation method thereof, relate in particular to a kind of overcritical or near critical CO
2Technology prepares the method for polymer microporous film, belongs to the preparing technical field of porous polymer separation membrane material.
Background technology
Along with extensive use and the development of membrane separation technique, also promoted the development of membrane preparation technology in fields such as chemical industry, pharmaceuticals industry, textile industry, paper industry and wastewater treatments.The preparation method of polymer microporous film mainly contains at present: pulling method, track etch method, template leaching method, phase inversion and coating process etc.The microporous barrier of different apertures and distribution, different porosities and structure can be prepared according to the requirement of using, also flat sheet membrane, hollow-fibre membrane and tubular membrane can be prepared.(document 1 that sees reference .Kesting R E, Synthetic Polymeric Membrane.Second Edition, John Wiley﹠amp; Sons, 1985)
Mostly the perforated membrane that is used for micro-filtration, ultrafiltration is to adopt phase inversion to prepare, the polymer solution of homogeneous phase experience temperature change or add non-solvent and be separated, the solution of homogeneous phase becomes polymer-rich phase and polymer-poor phase two-phase system, wherein solid-state polymer-rich phase becomes the main body of film, and liquid polymer-poor phase becomes the hole of film.US3,945,926 adopt phase inversion to prepare polycarbonate membrane; US3,945,926 come adjustment aperture and membrane structure by the relative concentration of strictness control solvent and non-solvent.US4,629,563, US4,774,039, US5, employing phase inversions such as 171,445 prepare the Kynoar anisotropic membrane, mainly as micro-filtration membrane and milipore filter.Adopt the intensity of polymer microporous film of this method preparation lower.
US4,247,498 adopt thermally induced phase separation to prepare a series of polymer microporous film, and the membrane aperture that obtains is 0.1-5 μ m and 0.2-1 μ m, and pore-size distribution is narrower, and the structure of film is three-dimensional uniformly cellular.But there is cortex in resulting film, is difficult to obtain the film of symmetrical structure, the cost of manufacture height.
Said method need use a large amount of organic solvents, causes the waste of solvent, and remains in the performance of the organic solvent influence film in the film, contaminated environment.
The method of not using solvent to prepare polymer microporous film has: the melt extruding-pulling method of (1) preparation polypropylene, polyethylene, poly tetrafluoroethylene, the membrane aperture scope is 0.1-3 μ m, the porosity of film can reach 90%, this method is only applicable to (partly) crystallization polymer, and need heat-treat, post processing such as stretching and thermal finalization; (2) nuclear track-etching method of preparation Merlon, poly terephthalic acid dimethyl ester, polyimide film, the membrane aperture scope is 0.02-10 μ m, but surface porosity factor very low (the most about 10%), can be less with the membrane material of this method.(document 2 that sees reference, Li Linyi, membrane technology basic principle, publishing house of Tsing-Hua University, 1999.).
In recent years, by supercritical CO
2The method of extracting the plasticizer in the polymer microporous film for extractant is noticeable.Supercritical fluid is meant that the temperature and pressure when fluid is in its critical pressure and critical-temperature when above, claims this fluid to be in supercriticality, distinguishes mutually with common liquids and gases and is called supercritical fluid.The interface of gas-liquid disappears when supercriticality, becomes the system of homogeneous, and the surface can be 0.Supercritical fluid has the density close with liquid, thereby very strong solvent strength is arranged, and it has the viscosity close with gas simultaneously, makes it be easier to spread in polymer, and mass tranfer coefficient is big.In addition, the density of fluid and viscosity can be regulated by the variation of pressure and temperature, thereby supercritical fluid has purposes very widely.(seeing document [3]-[6]).
[3]Berens?A?R,Huvard?G?S,Kortsmeyer?R?W,Kuing?F?W,Application?ofcompressed?carbon?dioxide?in?the?incorporation?of?additives?into?polymers,JAppl.Polym.Sci,1992,46:231~242
[4]Sarrade?S,Guizard?C,Rios?G?M,New?applications?of?supercritical?fluids?andsupercritical?fluids?progresses?in?separation,Separation?and?Purification?Technology,2003,32:57~63.
[5]Krause?B,Diekmann?K,Van?der?Vegt?N?F?A,Wessling?M,Open?nanoporousmorphologies?from?polymeric?blends?by?carbon?dioxide?foaming,Macromolecules,2002,35:1738~1745.
[6]Matsuyama?H,Yano?H,Maki?T,Teramoto?M,Mishima?K,Matsuyama?K,Formation?of?porous?fleet?membrane?by?phase?separation?with?supercritical?CO
2,JMembr?Sci,2001,194:157~163.
Along with the reinforcement of people's environmental consciousness, in the preparation process of polymer microporous film, should not use or use less as far as possible organic solvent.CO
2Have hypotoxicity, environment friendly and cheap and easy to get, adopt overcritical (closely critical) CO
2During for non-solvent (precipitating reagent), can one-step method obtain polymer microporous film, not need post processing, and solvent and CO
2Be easy to recyclingly, reduce environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind of overcritical or near critical CO
2Technology prepares the method for polymer microporous film.
The step of method is as follows:
1) with the organic solvent of the olefin polymer of 8-35wt% or esters polymer and 12-65wt% in 50-80 ℃ water bath with thermostatic control mechanical agitation 2-6 hour, obtain casting solution, stand-by after the vacuum defoamation;
2) with casting solution curtain coating or knifing in the stainless steel mould of U type, and level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, constant temperature 25-70 ℃, constant voltage 7.38-32MPa, time 0.5-4 hour;
3) open pressure-reducing valve, slowly step-down, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Advantage of the present invention is:
CO
2Critical-temperature be 31.5 ℃, critical pressure is 7.38Mpa, just can realize supercritical operation at a lower temperature.Adopt supercritical CO
2The preparation polymer microporous film has following advantage:
(1) as non-solvent, CO
2Be that other easier being diffused in the polymer of non-solvent of linear little molecular proportion removed CO
2Can reduce the cohesive energy of nearly all organic solvent, organic solvent is at supercritical CO
2In diffusion coefficient than the high 1-2 of a traditional liquid flux order of magnitude, the quality transfering rate of solvent and non-solvent accelerates then to have accelerated the speed that is separated, the therefore material that obtains having the micrometer grade hole structure;
(2) there is not gas-liquid interface in supercritical fluid, does not have surface tension, can make polymer film rapid draing and does not destroy its structure, and not have residue;
(3) can one-step method directly obtain polymer microporous film with this technology, not need post processing, simplify technical process by polymer solution.
(4) ratio of non-solvent and solvent was generally 30: 1 in phase inversion, thus the use of solvent can significantly reduce, and the decompression after be dissolved in overcritical (closely critical) CO
2In solvent and gas CO
2Separately, solvent and non-solvent (supercritical CO
2) can be recycled;
(5) CO
2Have hypotoxicity and environment friendly, chemical inertness is not flammable, and handling safety is cheap and easy to get.
Description of drawings
Fig. 1 is the LJX32-1 type supercritical CO that the present invention adopts
2Film forming experimental provision flow chart is among the figure: H01 steel cylinder, H02CO
2Pump, H03 heater 1, H04 heat-exchanger pump 1, H05 become membrane cisterna, H06 heater 2, H07 heat-exchanger pump 2, H08 separator, H09 filter, H10 cooling unit;
Fig. 2 is the stereoscan photograph of the embodiment of the invention 1 polymer microporous film, (a) is the stereoscan photograph of polymer microporous film upper surface among the figure, (b) being the stereoscan photograph of polymer microporous film lower surface, (c) is the stereoscan photograph in polymer microporous film cross section.
The specific embodiment
The present invention adopts supercritical CO
2Fluid is the non-solvent of preparation in the polymer microporous film, and polymer dissolution is obtained homogeneous phase, transparent viscous solution in solvent, and level places supercritical CO after curtain coating in stainless steel mould (blade coating) film forming
2Device in film forming, directly obtain drying, solid-state polymer microporous film.The concentration of regulating system pressure in the preparation process, temperature, polymer can prepare the polymer microporous film of different apertures and distribution, different structure.Purpose is to reduce the use of organic solvent and non-solvent in the polymer microporous film preparation process, CO
2And solvent can recycling use, reduces environmental pollution.In addition, can directly obtain dry film, and not need post processing, and dry run do not change the structure of microporous barrier, simplified technical process.
Olefin polymer of the present invention is: polystyrene, polyvinyl chloride, Kynoar, poly-(biasfluoroethylene-hexafluoropropylene), poly-(vinylidene-CTFE), poly-(vinylidene-tetrafluoroethene) or poly-(biasfluoroethylene-hexafluoropropylene-tetrafluoroethene).Esters polymer is: polymethyl methacrylate, PMA, polyvinylacrylate, polyvinyl acetate, Merlon or PET polyesters.Solvent is: acetone, butanone, oxolane, N-N dimethylacetylamide, N-N dimethyl formamide, N-methyl pyrrolidone, N-N dimethyl sulfoxide (DMSO), toluene, triethyl phosphate, trimethyl phosphate or tetramethylurea organic solvent.The concentration of polymer is in the casting solution: 8wt%-35wt%.
Overcritical or near critical CO of the present invention
2Fluid is the CO of purity>99.9%
2, temperature 25-70 ℃, pressure 7.38-32Mpa, the time of constant temperature and pressure is 0.5-4h, the step-down time is 0.5-4h.
Following embodiment is done more detailed description to the present invention, but described embodiment is not construed as limiting the invention.Determine performance described herein by following method.
(1) weight average molecular weight (Mw): measure according to the molecular weight of polystyrene by GPC.
GPC instrument: WATERS high performance liquid chromatograph pillar: GMHXL
Solvent: N, N-dimethylacetylamide temperature: 25 ℃
(2) porosity
Densimetry is measured.Cut out the film of certain size size after the microporous barrier drying, measure its length and width and thickness, claim quality, calculate the density (ρ of film thus
m).Density (the ρ of polymeric material
p) be 1.77g cm
-3Porosity is calculated as follows:
Embodiment 1
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 8wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the acetone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution curtain coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 25 ℃ of constant temperature, constant voltage 13.5MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Embodiment 2
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 20wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the acetone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution curtain coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 13.5MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.The average pore size of resulting polymer microporous film is 5 μ m, and porosity 85% is unsymmetric structure.
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 35wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the acetone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 13.5MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Embodiment 4
The polystyrene (Yuyao City great achievement plastics trading firm) of 20wt% is dissolved in the toluene, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 13.5MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Embodiment 5
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 20wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the butanone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 70 ℃ of constant temperature, constant voltage 13.5MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Embodiment 6
(IF850, Co., Ltd is imported and exported on new Great Wall, Zhejiang) is dissolved in the toluene with the polymethyl methacrylate of 20wt%, mechanical agitation under 80 ℃ of temperature, and the dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 13.5MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Embodiment 7
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 20wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the acetone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 7.38MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Embodiment 8
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 20wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the acetone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 32MPa, 2 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Embodiment 9
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 20wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the acetone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 13.5MPa, 0.5 hour time.Open pressure-reducing valve, slow 0.5 hour step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Example 10
Poly-(biasfluoroethylene-hexafluoropropylene) (Mw=4.5 * 10 with 20wt%
5, Mn=1.3 * 10
5, Tm=143 ℃) be dissolved in the acetone, mechanical agitation under 50 ℃ of temperature, dissolving back forms the solution of homogeneous phase, transparent, thickness fully; Deaeration is also removed impurity, under the normal temperature and pressure with the casting solution blade coating in stainless steel mould; In carbon dioxide atmosphere, the stainless steel mould level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, 35 ℃ of constant temperature, constant voltage 13.5MPa, 4 hours time.Open pressure-reducing valve, slow 2 hours step-down time, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Claims (4)
1. overcritical or near critical CO
2Technology prepares the method for polymer microporous film, it is characterized in that, the step of method is as follows:
1) with the organic solvent of the olefin polymer polymer of 8-35wt% and 12-65wt% in 50-80 ℃ water bath with thermostatic control mechanical agitation 2-6 hour, obtain casting solution, stand-by after the vacuum defoamation;
2) with casting solution curtain coating or knifing in the stainless steel mould of U type, and level places overcritical or near critical CO
2The one-tenth membrane cisterna in airtight, open CO
2Intake valve, pressurization, heating up makes CO in the jar
2Be in supercriticality, constant temperature 25-70 ℃, constant voltage 7.38-32MPa, time 0.5-4 hour;
3) open pressure-reducing valve, slowly step-down, supercritical CO
2Fluid emptying or recycling in the separator, organic solvent reclaims in separator, takes out polymer microporous film in becoming membrane cisterna, directly stores for future use.
Said olefin polymer is: Kynoar, poly-(biasfluoroethylene-hexafluoropropylene), poly-(vinylidene-CTFE), poly-(vinylidene-tetrafluoroethene) or poly-(biasfluoroethylene-hexafluoropropylene-tetrafluoroethene).
2. a kind of overcritical or near critical CO according to claim 1
2Technology prepares the method for polymer microporous film, it is characterized in that said solvent is: acetone, butanone, oxolane, N-N dimethylacetylamide, N-N dimethyl formamide, N-methyl pyrrolidone, N-N dimethyl sulfoxide (DMSO), triethyl phosphate, trimethyl phosphate or tetramethylurea organic solvent.
3. a kind of overcritical or near critical CO according to claim 1
2Technology prepares the method for polymer microporous film, it is characterized in that, the concentration of polymer is in the said casting solution: 8wt%-35wt%.
4. a kind of overcritical or near critical CO according to claim 1
2Technology prepares the method for polymer microporous film, it is characterized in that: said overcritical or near critical CO
2The temperature of fluid is 25-70 ℃, and pressure is 7.38-32Mpa, and the time of constant temperature and pressure is 0.5-4h, and the step-down time is 0.5-4h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100667187A CN1313191C (en) | 2004-09-24 | 2004-09-24 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100667187A CN1313191C (en) | 2004-09-24 | 2004-09-24 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1613548A CN1613548A (en) | 2005-05-11 |
CN1313191C true CN1313191C (en) | 2007-05-02 |
Family
ID=34764937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2004100667187A Expired - Fee Related CN1313191C (en) | 2004-09-24 | 2004-09-24 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1313191C (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101757687B (en) * | 2009-12-25 | 2014-11-26 | 中国科学院长春应用化学研究所 | Surface modification method of bio-absorbable material implanted in polyester |
CN102070793A (en) * | 2010-12-22 | 2011-05-25 | 大连理工大学 | Process for preparing polymer lithium ion battery microporous membrane by supercritical fluid phase separation |
CN103367674A (en) * | 2013-07-24 | 2013-10-23 | 北京化工大学常州先进材料研究院 | Lithium ion battery with polyvinylidene fluoride-hexafluoropropylene microporous membrane |
CN103401014A (en) * | 2013-07-24 | 2013-11-20 | 北京化工大学常州先进材料研究院 | Lithium ion battery with polypropylene micropore diaphragm |
CN103897212B (en) * | 2014-04-11 | 2016-06-15 | 厦门大学 | The preparation method of a kind of nano-porous polymer film |
CN105754131B (en) * | 2016-02-04 | 2019-02-05 | 青岛科技大学 | A kind of polymer supercritical gas foaming production line |
CN105642132B (en) * | 2016-04-15 | 2017-12-12 | 北京碧水源膜科技有限公司 | A kind of polyvinylidene fluoride film being modified through targetting synergy nano-functional material and preparation method thereof |
CN106693718A (en) * | 2017-01-22 | 2017-05-24 | 大连大学 | Method for preparing polymer microporous membrane by supercritical carbon dioxide extraction assisted thermally induced phase separation method |
CN109078500B (en) * | 2017-06-14 | 2020-10-20 | 宁波绿色方舟环境科技有限公司 | Fluorine-containing polymer flat membrane and preparation method thereof |
CN109078509B (en) * | 2017-06-14 | 2020-10-23 | 宁波绿色方舟环境科技有限公司 | Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003213425A (en) * | 2002-01-24 | 2003-07-30 | Utec:Kk | Apparatus and method for forming film |
CN1436807A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Supercritical CO2 process of preparing conductive composite polypyrrole film material |
CN1124308C (en) * | 2001-03-28 | 2003-10-15 | 中国科学院广州化学研究所 | Preparation of foamed material |
-
2004
- 2004-09-24 CN CNB2004100667187A patent/CN1313191C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1124308C (en) * | 2001-03-28 | 2003-10-15 | 中国科学院广州化学研究所 | Preparation of foamed material |
JP2003213425A (en) * | 2002-01-24 | 2003-07-30 | Utec:Kk | Apparatus and method for forming film |
CN1436807A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Supercritical CO2 process of preparing conductive composite polypyrrole film material |
Non-Patent Citations (4)
Title |
---|
Formation of porous flat membrane by phaseseparationwithsupercritical CO2 Hideto Matsuyama,Journal of membrane science 2001 * |
Formation of porous flat membrane by phaseseparationwithsupercritical CO2 Hideto Matsuyama,Journal of membrane science 2001;Formation of porous flat membrane by phaseseparationwithsupercritical CO2 Hideto Matsuyama,Journal of membrane science,Vol.194 2001;Matsuyama Formation of porous flat membrane by phaseseparation withsupercritical CO2 Hideto,Journla of mmbrane science,Vol.19 No.4 2001 * |
Formation of porous flat membrane by phaseseparationwithsupercritical CO2 Hideto Matsuyama,Journal of membrane science,Vol.194 2001 * |
Matsuyama Formation of porous flat membrane by phaseseparation withsupercritical CO2 Hideto,Journla of mmbrane science,Vol.19 No.4 2001 * |
Also Published As
Publication number | Publication date |
---|---|
CN1613548A (en) | 2005-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Poly (vinylidene fluoride) hollow fiber membrane for high-efficiency separation of dyes-salts | |
Bonyadi et al. | Flux enhancement in membrane distillation by fabrication of dual layer hydrophilic–hydrophobic hollow fiber membranes | |
Wang et al. | Porous PVDF asymmetric hollow fiber membranes prepared with the use of small molecular additives | |
Song et al. | Optimization of morphology and perf ormance of PVDF hollow fiber for direct contact membrane distillation using experimental design | |
CN1313191C (en) | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology | |
Hou et al. | Fabrication and characterization of hydrophobic PVDF hollow fiber membranes for desalination through direct contact membrane distillation | |
Jin et al. | Hydrophobic modification of poly (phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation | |
CN102245284A (en) | Hydrophobic ozone-stable membrane made of polyvinylidene fluoride | |
JPH06100720A (en) | Microporous film of superpermeable polypropylene and its production | |
CN101293185A (en) | Method for producing polyvinylidene fluoride porous membrane | |
CN108295667A (en) | A kind of positive osmosis composite membrane and preparation method thereof based on large aperture basement membrane | |
Jin et al. | Preparation of a poly (vinyl chloride) ultrafiltration membrane through the combination of thermally induced phase separation and non‐solvent‐induced phase separation | |
Bildyukevich et al. | Preparation of high-flux ultrafiltration polyphenylsulfone membranes | |
Li et al. | Study on the interfacial activation of dual surfactants in the process of forming porous membranes | |
Song et al. | Preparation of PVDF/CaCO3 hybrid hollow fiber membranes for direct contact membrane distillation through TIPS method | |
JP4761967B2 (en) | Vinylidene fluoride resin porous hollow fiber and method for producing the same | |
Li et al. | A new method for tailoring the surface pore size and internal pore structure of ultrafiltration membranes without using additives—Atomization-assisted nonsolvent induced phase separation method | |
CN1748844A (en) | Method for preparing polyvinylidene fluoride flat plate porous film by thermal phase separation process | |
Kumari et al. | Effect of polyvinylpyrrolidone on separation performance of cellulose acetate-polysulfone blend membranes | |
Elhaj et al. | Monolithic space-filling porous materials from engineering plastics by thermally induced phase separation | |
Ma et al. | Preparation, characterization and performance of a novel PVDF/PMMA/TPU blend hollow fiber membrane for wastewater treatment | |
Alsalhy | Influence of spinning conditions on the morphology, pore size, pore size distribution, mechanical properties, and performance of PVC hollow fiber membranes | |
CN116251483A (en) | Microgel composite membrane with self-cleaning and temperature responsiveness as well as preparation method and application thereof | |
Wang et al. | Effect of the highly asymmetric structure on the membrane characteristics and microfiltration performance of PTFE wrapped hollow fiber membrane | |
Bil’Dyukevich et al. | Investigation of the morphology of polymer-inorganic capillary membranes based on polysulfone |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070502 Termination date: 20110924 |