CN110882634A - Formula of ethylene-chlorotrifluoroethylene copolymer microporous membrane and method for preparing microporous membrane by using formula - Google Patents
Formula of ethylene-chlorotrifluoroethylene copolymer microporous membrane and method for preparing microporous membrane by using formula Download PDFInfo
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- CN110882634A CN110882634A CN201811040596.2A CN201811040596A CN110882634A CN 110882634 A CN110882634 A CN 110882634A CN 201811040596 A CN201811040596 A CN 201811040596A CN 110882634 A CN110882634 A CN 110882634A
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- ethylene
- membrane
- microporous membrane
- chlorotrifluoroethylene copolymer
- film
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- 229920001780 ECTFE Polymers 0.000 title claims abstract description 97
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 title claims abstract description 88
- 239000012982 microporous membrane Substances 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 24
- 239000012510 hollow fiber Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- 239000002667 nucleating agent Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 3
- 239000010865 sewage Substances 0.000 claims abstract description 3
- 238000011282 treatment Methods 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 106
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 44
- 238000005266 casting Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 21
- CHJAYYWUZLWNSQ-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;ethene Chemical group C=C.FC(F)=C(F)Cl CHJAYYWUZLWNSQ-UHFFFAOYSA-N 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000009472 formulation Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 8
- 239000004156 Azodicarbonamide Substances 0.000 claims description 7
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 7
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 7
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical class ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- ISNKSXRJJVWFIL-UHFFFAOYSA-N (sulfonylamino)amine Chemical class NN=S(=O)=O ISNKSXRJJVWFIL-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000012648 alternating copolymerization Methods 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001087 glyceryl triacetate Substances 0.000 claims description 3
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012802 nanoclay Substances 0.000 claims description 3
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229960002622 triacetin Drugs 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical group [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- LDVAXRWOGUHMKM-UHFFFAOYSA-N benzene-1,3-disulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC(S(=O)(=O)NN)=C1 LDVAXRWOGUHMKM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000006260 foam Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention discloses a film preparation formula for preparing an ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous film, which comprises 20-80 wt% of ethylene-chlorotrifluoroethylene copolymer, 0.05-50 wt% of diluent, 0.05-15 wt% of foaming agent and 0.05-25 wt% of nucleating agent. According to the invention, the foaming agent is added into the film preparation formula, so that the ethylene-chlorotrifluoroethylene copolymer microporous film can form uniform and continuous foam pores, and the ethylene-chlorotrifluoroethylene copolymer microporous film not only has good mechanical property, but also has higher water flux, and can be suitable for sewage treatment and separation and purification of organic solvents.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a film preparation formula for preparing a microporous film by a micro-preparation method, and particularly relates to a film preparation formula for preparing an ethylene-chlorotrifluoroethylene copolymer microporous film.
Background
Ethylene chlorotrifluoroethylene copolymer (ECTFE) is an alternating copolymer of chlorotrifluoroethylene and ethylene close to 1:1, and has excellent properties in mechanical strength, heat resistance, chemical resistance, weather resistance and alkali resistance, for example, ethylene chlorotrifluoroethylene copolymer is not soluble in existing organic solvents at temperatures below 120 ℃, is suitable for high-temperature and highly corrosive separation environments, and is a potentially ideal membrane material.
When the ethylene-chlorotrifluoroethylene copolymer is prepared into a film, the ethylene-chlorotrifluoroethylene copolymer film has excellent performances such as high mechanical strength, thermal stability, flame retardance, chemical stability and the like. As for the preparation method of the ethylene-chlorotrifluoroethylene copolymer film, the following reports are reported in the prior art:
U.S. Pat. No. 4,4394460 reports a process for preparing an ethylene-chlorotrifluoroethylene copolymer membrane by dissolving an ethylene-chlorotrifluoroethylene copolymer in chlorotrifluoroethylene at a high temperature, adding silica powder, melt-extruding, quenching to form a membrane, extracting chlorotrifluoroethylene with trichloroethane and removing silica with hot sodium hydroxide to obtain an ethylene-chlorotrifluoroethylene copolymer porous membrane. The method has the advantages of complex process, expensive and toxic diluent chlorotrifluoroethylene, and difficult control of membrane aperture;
the Chinese patent CN1638851A improves the method, changes the diluent with high toxicity into citric acid ethyl ester or triacetyl glycerine, and prepares the ethylene-chlorotrifluoroethylene copolymer porous membrane by a TIPS method. Although the method solves the problem of toxicity of the diluent, the method still has the problems of complex preparation process and difficult control of membrane aperture;
U.S. Pat. No. 5,7247238 also modified the diluent to replace the more toxic diluent with dibutyl phthalate (DBP) to obtain porous membranes of ethylene-chlorotrifluoroethylene copolymer with different pore structures by controlling the quenching temperature. The method has simple process, is easy to control, and can control the pore structure size of the ethylene-chlorotrifluoroethylene copolymer porous membrane, but the prepared ethylene-chlorotrifluoroethylene copolymer porous membranes have spore pore structures, the porosity of the structure is low, and the mechanical property is poor;
chinese patent CN102228805 uses high temperature solvent diethyl phthalate as diluent, and prepares porous membrane of ethylene-chlorotrifluoroethylene copolymer by TIPS method. The membrane prepared by the method has good mechanical property, but the structure of the pores is not easy to control in the preparation process, and the connectivity of the pores is poor, if the membrane is slightly thick, the pores can not be communicated, and the membrane separation can not be carried out;
therefore, there is a need for further improvements in the preparation of microporous ethylene chlorotrifluoroethylene copolymer membranes.
Disclosure of Invention
The first purpose of the invention is to provide a film preparation formula of an ethylene-chlorotrifluoroethylene copolymer microporous film, and the ethylene-chlorotrifluoroethylene copolymer microporous film prepared by the film preparation formula can have uniform and continuous foam pores and can eliminate byproduct HF generated at high temperature.
The second object of the present invention is to provide a method for preparing an ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane using the above membrane-forming formulation.
The third purpose of the invention is to provide a preparation method for preparing the ethylene-chlorotrifluoroethylene copolymer flat microporous membrane by using the membrane preparation formula.
The fourth purpose of the invention is to provide the application of the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane or the flat microporous membrane prepared by the membrane preparation formula.
The ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane or the flat microporous membrane prepared by the invention has the characteristics of high elongation, high tensile strength, high water flux, good separation effect and the like.
Therefore, the invention adopts the following technical scheme:
a film-making formulation for an ethylene chlorotrifluoroethylene copolymer microporous film, the film-making formulation comprising:
20-80 wt% of ethylene-chlorotrifluoroethylene copolymer;
0.05-50 wt% of diluent;
0.05-15 wt% of foaming agent;
0.05-25 wt% of nucleating agent;
the foaming agent is at least one selected from bicarbonate, nitrite, azo compounds, nitrosoamine compounds and sulfonyl hydrazine compounds.
The foaming agent used in the film forming formulation of the present invention may be at least one selected from the group consisting of bicarbonate, nitrite, azo compounds, nitrosoamine compounds and sulfonyl hydrazide compounds, that is: the compound can be any one or a mixture of any several of bicarbonate, nitrite, azo compounds, nitrosoamine compounds and sulfonyl hydrazine compounds mixed in any proportion.
By bicarbonate is meant a bicarbonate that can be used as a blowing agent. Preferably, the bicarbonate is selected from at least one of sodium bicarbonate and ammonium bicarbonate, namely: can be a mixture of any one or two of sodium bicarbonate and ammonium bicarbonate in any proportion.
The nitrite is a nitrite that can be used as a foaming agent. Preferably, the nitrite is selected from ammonium nitrite.
The azo compound is an azo compound that can be used as a blowing agent. Preferably, the azo-based compound is at least one selected from the group consisting of azodicarbonamide, azobisisobutyronitrile, isopropyl azodicarboxylate, diethyl azodicarboxylate, diazoaminobenzene, and barium azodicarboxylate, that is: can be any one or a mixture of any several of azodicarbonamide, azodiisobutyronitrile, isopropyl azodicarboxylate, diethyl azodicarboxylate, diazoaminobenzene and barium azodicarboxylate in any proportion.
The nitrosoamine compound refers to a nitrosoamine compound that can be used as a blowing agent. Preferably, the nitrosamine-based compound is selected from at least one of N, N-dinitrosopentamethylenetetramine and N, N-dimethyl-diterephthalandiamine, that is: it may be any one or a mixture of two selected from the group consisting of N, N-dinitrosopentamethylenetetramine and N, N-dimethyl-diterephthalandiamine in any ratio.
The sulfonyl hydrazide compound refers to a sulfonyl hydrazide compound which can be used as a foaming agent. Preferably, the sulfonyl hydrazide compound is at least one selected from the group consisting of 4, 4-disulfonyl hydrazide diphenyl ether, p-benzenesulfonyl hydrazide, 3-disulfonyl hydrazide diphenyl sulfone, 4-diphenyl disulfonyl hydrazide, 1, 3-benzene disulfonyl hydrazide and 1, 4-benzene disulfonyl hydrazide, that is: can be any one or a mixture of any several of 4, 4-disulfonyl hydrazide diphenyl ether, p-benzenesulfonyl hydrazide, 3-disulfonyl hydrazide diphenyl sulfone, 4-diphenyldisulfonyl hydrazide, 1, 3-benzenesulfonyl hydrazide and 1, 4-benzenesulfonyl hydrazide in any proportion.
In order to enable the microporous membrane of the ethylene-chlorotrifluoroethylene copolymer prepared by the membrane preparation formula to have uniform and continuous pores, the ethylene-chlorotrifluoroethylene copolymer is preferably an ethylene-chlorotrifluoroethylene copolymer prepared by the 1:1 alternating copolymerization of ethylene and chlorotrifluoroethylene monomers, and is further preferably an ethylene-chlorotrifluoroethylene copolymer prepared by the 1:1 alternating copolymerization of ethylene and chlorotrifluoroethylene monomers, wherein the melt index of the ethylene-chlorotrifluoroethylene copolymer at 275 ℃ and 2.16kg is 5-200 g.
The diluent used in the film-forming formulation of the present invention may be at least one selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl sebacate, triacetin and tributyl citrate, that is: can be any one or a mixture of any several of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl sebacate, glyceryl triacetate and tributyl citrate which are mixed in any proportion.
The nucleating agent used in the film preparation formula of the invention can be at least one selected from nano clay, nano silicon dioxide, carbon nano tube, calcium carbonate powder, magnesium carbonate powder, nano titanium dioxide and talcum powder, namely: can be any one or a mixture of any several of nano clay, nano silicon dioxide, carbon nano tube, calcium carbonate powder, magnesium carbonate powder, nano titanium dioxide, kaolin powder and talcum powder which are mixed in any proportion.
In the invention, the higher the content of the ethylene-chlorotrifluoroethylene copolymer is, the better the mechanical property of the finally prepared microporous membrane is, but the porosity can be reduced and the membrane forming is not good, and in order to obtain the microporous membrane with better mechanical property, overall performances such as porosity, water flux and the like, the mass percent of the ethylene-chlorotrifluoroethylene copolymer in the membrane preparing formula is controlled to be 20-80 wt%.
In order to obtain a uniform membrane casting solution and make the membrane casting solution easily extruded from a die head, the mass percentage of the diluent in the membrane preparation formula is controlled to be 0.05-50 wt%.
The microporous membrane has the advantages that the amount of the foaming agent is too small, the number of cells of the microporous membrane is too large, the foaming agent is too much, the mechanical strength of the microporous membrane is reduced, and in order to obtain the microporous membrane with better mechanical properties, porosity, water flux and other overall properties, the mass percentage of the foaming agent in the membrane preparation formula is controlled to be 0.05-15 wt%.
The microporous membrane with too small amount of the nucleating agent has few cells, too many nucleating agents, the content of the ethylene-chlorotrifluoroethylene copolymer is reduced, the mechanical strength of the membrane is reduced, and in order to obtain the microporous membrane with better mechanical property, porosity, water flux and other overall properties, the mass percentage of the nucleating agent in the membrane preparation formula is controlled to be 0.05-25 wt%.
The method for preparing the ethylene-chlorotrifluoroethylene copolymer microporous membrane by using the membrane preparation formula is characterized by comprising the following steps of:
(1) uniformly mixing ethylene-chlorotrifluoroethylene copolymer, a diluent, a foaming agent and a nucleating agent in proportion, and heating to a molten state at the temperature of 180-270 ℃ to obtain a casting solution;
(2) extruding the membrane casting solution through a die head to form a membrane, so as to obtain a hollow fiber microporous membrane,
or blade-coating the casting solution on a flat plate to obtain a flat microporous membrane;
(3) and (3) placing the hollow fiber microporous membrane and/or the flat microporous membrane in a gel bath at the temperature of 10-150 ℃ for curing, and rinsing with an organic solvent and water to obtain the hollow fiber microporous membrane and/or the flat microporous membrane.
The method for preparing the ethylene-chlorotrifluoroethylene copolymer microporous membrane by using the membrane preparation formula is characterized by comprising the following steps of:
(1) uniformly mixing an ethylene-chlorotrifluoroethylene copolymer, a diluent, a foaming agent and a nucleating agent in proportion, and heating to a molten state at the temperature of 190-260 ℃ to obtain a casting solution;
(2) extruding the membrane casting solution through a die head of a double-screw extruder to form a membrane, so as to obtain a hollow fiber microporous membrane, or blade-coating the membrane casting solution on a glass flat plate, so as to obtain a flat microporous membrane;
(3) and (3) placing the hollow fiber microporous membrane and/or the flat microporous membrane in a gel bath at the temperature of 10-150 ℃ for curing, and rinsing with an organic solvent and water to obtain the hollow fiber microporous membrane and/or the flat microporous membrane.
The method for preparing the ethylene-chlorotrifluoroethylene copolymer microporous membrane by using the membrane preparation formula is characterized by comprising the following steps of:
(1) uniformly mixing ethylene-chlorotrifluoroethylene copolymer, a diluent, a foaming agent and a nucleating agent in proportion, and heating to a molten state at the temperature of 180-270 ℃ to obtain a casting solution;
(2) extruding the membrane casting solution through a die head of a double-screw extruder to form a membrane, so as to obtain a hollow fiber microporous membrane, or blade-coating the membrane casting solution on a glass flat plate, so as to obtain a flat microporous membrane;
(3) the hollow fiber microporous membrane and/or the flat plate microporous membrane are placed in a gel bath at the temperature of 10-150 ℃ for solidification, and then are rinsed by an organic solvent and water to obtain the hollow fiber microporous membrane and/or the flat plate microporous membrane, wherein the gel bath is selected from at least one of water, ethanol, isobutanol, ethylene glycol and glycerol, and the organic solvent is selected from at least one of ethanol, isopropanol, butanol, acetone and butyl ether.
The temperature range of the casting solution prepared by the preparation method is 180-270 ℃, and preferably 190-260 ℃. The temperature selection for a particular process implementation is related to the selection of the diluent.
The ethylene-chlorotrifluoroethylene microporous membrane prepared by the invention comprises a hollow fiber microporous membrane and a flat microporous membrane, and has the tensile strength of 1-15 MPa, the elongation at break of 20-150% and the water flux of 0.1-1200L/m2.h。
The preferable ethylene-chlorotrifluoroethylene microporous membrane comprises a hollow fiber microporous membrane and a flat microporous membrane, the tensile strength is 2-12 MPa, the elongation at break is 50-120%, and the water flux is 1-1000L/m2.h。
The ethylene-chlorotrifluoroethylene microporous membrane prepared by the invention is suitable for sewage treatment and separation and purification of organic solvents.
Compared with the prior art, the ethylene-chlorotrifluoroethylene copolymer film preparation formula provided by the invention is suitable for preparing the ECTFE microporous film by a thermal phase separation method, and has good water flux while maintaining the excellent mechanical property of the microporous film.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
According to the mass percentage, 70 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 120g at 275 ℃ and 2.16kg, 25 parts of diethyl phthalate, 3.5 parts of calcium carbonate powder with the particle size of 0.5 micron and 1.5 parts of azodicarbonamide are uniformly stirred, added into a screw machine, a casting solution is formed at 200 ℃, hollow fiber membrane wires are obtained through a die head, the hollow fiber membrane wires are quickly immersed into water at 30 ℃, then the membrane wires are put into ethanol to clean the diethyl phthalate in the hollow fiber membrane wires, the membrane wires are cleaned by pure water and dried, and the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane with the membrane wire wall thickness of 0.4 mm is obtained.
The properties of the ethylene chlorotrifluoroethylene copolymer hollow fiber microporous membranes prepared were tested according to standard GB/T32360-2015, as given in Table 1.
Example 2
The ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane obtained in example 1 was immersed in a 2% sodium hydroxide solution for 48 hours, membrane filaments were cleaned with pure water, and after air-drying, the performance of the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane was tested according to standard GB/T32360-.
Example 3
According to the mass percentage, 80 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 150g at 275 ℃ and 2.16kg, 15 parts of diethyl phthalate, 4 parts of calcium carbonate powder with the particle size of 0.5 micron and 10 parts of ammonium bicarbonate powder are uniformly stirred, added into a screw machine to form a membrane casting solution at 205 ℃, a hollow fiber membrane wire is obtained through a die head and is rapidly immersed into water at 40 ℃, then the membrane wire is put into ethanol to wash the diethyl phthalate in the hollow fiber membrane wire, the membrane wire is washed clean by pure water and dried, and the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane with the membrane wire wall thickness of 0.4 millimeter is obtained.
The properties of the ethylene chlorotrifluoroethylene copolymer hollow fiber microporous membranes prepared were tested according to standard GB/T32360-2015, as given in Table 1.
Example 4
According to the mass percentage, 70 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 160g at 275 ℃ and 2.16kg, 25 parts of diethyl phthalate, 2 parts of calcium carbonate powder with the particle size of 2 microns, 2 parts of kaolin with the particle size of 1 micron and 2 parts of azodicarbonamide are uniformly stirred, added into a screw machine to form a casting solution at 215 ℃, a flat membrane is obtained through a die head, the flat membrane is rapidly immersed into a mixed solution of water and glycerol at 70 ℃, then the membrane is put into ethanol, the diethyl phthalate in the membrane is cleaned, the membrane is cleaned by pure water and dried, and the ethylene-chlorotrifluoroethylene copolymer flat microporous membrane with the membrane thickness of 0.4 mm is obtained.
The properties of the flat microporous films of ethylene chlorotrifluoroethylene copolymer prepared were tested according to standard GB/T32360-2015, as given in Table 1.
Example 5
According to mass percentage, 40 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 170g at 275 ℃ and 2.16kg, 35 parts of diethyl phthalate, 20 parts of tributyl acetate, 1 part of calcium carbonate powder with the particle size of 0.5 micron and 1 part of isopropyl azodicarboxylate are uniformly stirred, added into a screw machine to form a casting solution at 205 ℃, a hollow fiber membrane wire is obtained through a die head, the hollow fiber membrane wire is quickly immersed into water at 40 ℃, then the membrane wire is put into ethanol to clean the diethyl phthalate in the hollow fiber membrane wire, the membrane wire is cleaned by pure water and dried to obtain the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane with the membrane wire wall thickness of 0.4 mm.
The properties of the ethylene chlorotrifluoroethylene copolymer hollow fiber microporous membranes prepared were tested according to standard GB/T32360-2015, as given in Table 1.
Example 6
According to the mass percentage, 70 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 120g at 275 ℃ and 2.16kg, 25 parts of diethyl phthalate, 3.5 parts of nano silicon dioxide and 1.5 parts of azodicarbonamide are uniformly stirred, added into a screw machine, a casting solution is formed at 200 ℃, hollow fiber membrane filaments are obtained through a die head, the hollow fiber membrane filaments are quickly immersed into water at 30 ℃, then the membrane filaments are put into ethanol to clean the diethyl phthalate in the hollow fiber membrane filaments, the membrane filaments are cleaned by pure water and dried, and the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane with the membrane filament wall thickness of 0.4 mm is obtained.
Example 7
According to the mass percentage, 70 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 160g at 275 ℃ and 2.16kg, 25 parts of diethyl phthalate, 3 parts of kaolin with the particle size of 1 micron and 2 parts of azodicarbonamide are uniformly stirred, added into a screw machine to form a casting solution at 205 ℃, a flat membrane is obtained through a die head, the flat membrane is rapidly immersed into a mixed solution of water and glycerol with the temperature of 70 ℃, then the membrane is put into ethanol, the diethyl phthalate in the membrane is cleaned, the membrane is cleaned by pure water and dried, and the ethylene-chlorotrifluoroethylene copolymer flat microporous membrane with the membrane thickness of 0.4 mm is obtained.
The properties of the flat microporous films of ethylene chlorotrifluoroethylene copolymer prepared were tested according to standard GB/T32360-2015, as given in Table 1.
Comparative example 1
Adding 70 parts by mass of ethylene-chlorotrifluoroethylene copolymer with the melt index of 120g at 275 ℃ and 2.16kg and 25 parts by mass of diethyl phthalate into a screw machine, forming a casting solution at 200 ℃, passing through a die head to obtain hollow fiber membrane filaments, quickly immersing the hollow fiber membrane filaments into water with the temperature of 30 ℃, putting the membrane filaments into ethanol to wash the diethyl phthalate in the hollow fiber membrane filaments, washing the membrane filaments with pure water, and airing to obtain the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane with the membrane filament wall thickness of 0.4 mm.
The properties of the ethylene chlorotrifluoroethylene copolymer hollow fiber microporous membranes prepared were tested according to standard GB/T32360-2015, as given in Table 1.
Comparative example 2
According to the mass percentage, 70 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 120g at 275 ℃ and 2.16kg, 25 parts of diethyl phthalate, 3.5 parts of nano silicon dioxide and 1 part of titanium dioxide powder with the particle size of 3 microns are added into a screw machine to form a membrane casting solution at 200 ℃, a hollow fiber membrane wire is obtained through a die head and is rapidly immersed into water with the temperature of 30 ℃, then the membrane wire is put into ethanol to wash the diethyl phthalate in the hollow fiber membrane wire, the membrane wire is washed clean by pure water and dried, and the ethylene-chlorotrifluoroethylene copolymer hollow fiber microporous membrane with the membrane wire wall thickness of 0.4 mm is obtained.
The properties of the ethylene chlorotrifluoroethylene copolymer hollow fiber microporous membranes prepared were tested according to standard GB/T32360-2015, as given in Table 1.
Comparative example 3
According to the mass percentage, 70 parts of ethylene-chlorotrifluoroethylene copolymer with the melt index of 160g at 275 ℃ and 2.16kg, 25 parts of diethyl phthalate, 2 parts of calcium carbonate powder with the particle size of 2 microns, 2 parts of kaolin with the particle size of 1 micron are uniformly stirred, added into a screw machine, a casting solution is formed at 215 ℃, a flat membrane is obtained through a die head, the flat membrane is rapidly immersed into a mixed solution of water and glycerol with the temperature of 70 ℃, then the membrane is put into ethanol, the diethyl phthalate in the membrane is cleaned, the membrane is cleaned by pure water and dried, and the ethylene-chlorotrifluoroethylene copolymer flat microporous membrane with the membrane thickness of 0.4 mm is obtained.
The properties of the flat microporous films of ethylene chlorotrifluoroethylene copolymer prepared were tested according to standard GB/T32360-2015, as given in Table 1.
TABLE 1 Properties of ECTFE film
| Examples | Tensile strength/MPa | Elongation at break/% | Water flux/L/m2.h |
| Example 1 | 8.5 | 105 | 830 |
| Example 2 | 6.9 | 83 | 750 |
| Example 3 | 8.3 | 98 | 660 |
| Example 4 | 8.1 | 95 | 820 |
| Example 5 | 7.9 | 82 | 720 |
| Example 6 | 8.6 | 107 | 780 |
| Examples | 8.5 | 97 | 760 |
| Comparative example 1 | 8.7 | 106 | 200 |
| Comparative example 2 | 8.8 | 102 | 198 |
| Comparative example 3 | 8.2 | 99 | 196 |
The data of the above examples show that the ethylene-chlorotrifluoroethylene copolymer microporous membrane prepared by the membrane preparation formula provided by the invention has good mechanical properties, higher water flux and higher water flux after being soaked in an alkaline solution.
Claims (10)
1. A film preparation formula of an ethylene-chlorotrifluoroethylene copolymer microporous film is characterized by comprising the following components in percentage by weight:
the foaming agent is at least one selected from bicarbonate, nitrite, azo compounds, nitrosoamine compounds and sulfonyl hydrazine compounds.
2. A film-forming formulation for an ethylene-chlorotrifluoroethylene copolymer microporous film according to claim 1, wherein the blowing agent comprises:
the bicarbonate is at least one selected from sodium bicarbonate and ammonium bicarbonate;
the nitrite is selected from ammonium nitrite;
the azo compound is at least one selected from azodicarbonamide, azodiisobutyronitrile, isopropyl azodicarboxylate, diethyl azodicarboxylate, diazoaminobenzene and barium azodicarboxylate;
the nitrosamine compound is at least one selected from N, N-dinitrosopentamethylenetetramine and N, N-dimethyl-di-p-xylylenediamine;
the sulfonyl hydrazide compound is at least one selected from 4, 4-disulfonyl hydrazide diphenyl ether, p-benzenesulfonyl hydrazide, 3-disulfonyl hydrazide diphenyl sulfone, 4-diphenyl disulfonyl hydrazide, 1, 3-benzene disulfonyl hydrazide and 1, 4-benzene disulfonyl hydrazide.
3. The film-forming formulation for an ethylene-chlorotrifluoroethylene copolymer microporous film as claimed in claim 2, wherein said blowing agent is selected from azo compounds.
4. A film-forming formulation for an ethylene-chlorotrifluoroethylene copolymer microporous film according to claim 1, wherein:
the ethylene-chlorotrifluoroethylene copolymer is an ethylene-chlorotrifluoroethylene copolymer prepared by 1:1 alternating copolymerization of ethylene and chlorotrifluoroethylene monomers;
the diluent is selected from at least one of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl sebacate, glyceryl triacetate and tributyl citrate;
the nucleating agent is selected from at least one of nano clay, nano silicon dioxide, carbon nano tube, calcium carbonate powder, magnesium carbonate powder, nano titanium dioxide and talcum powder.
5. The film-forming formulation for an ethylene-chlorotrifluoroethylene copolymer microporous film according to claim 1, wherein the ethylene-chlorotrifluoroethylene copolymer has a melt index at 275 ℃ and 2.16kg of 5 to 200 g.
6. A method of preparing an ethylene chlorotrifluoroethylene copolymer microporous membrane using the film-forming formulation of claim 1, characterized in that the method comprises:
(1) uniformly mixing ethylene-chlorotrifluoroethylene copolymer, a diluent, a foaming agent and a nucleating agent in proportion, and heating to a molten state at the temperature of 180-270 ℃ to obtain a casting solution;
(2) extruding the membrane casting solution through a die head to form a membrane, so as to obtain a hollow fiber microporous membrane,
or blade-coating the casting solution on a flat plate to obtain a flat microporous membrane;
(3) and (3) placing the hollow fiber microporous membrane and/or the flat microporous membrane in a gel bath at the temperature of 10-150 ℃ for curing, and rinsing with an organic solvent and water to obtain the hollow fiber microporous membrane and/or the flat microporous membrane.
7. A method of preparing an ethylene chlorotrifluoroethylene copolymer microporous membrane using the film-forming formulation of claim 1, characterized in that the method comprises:
(1) uniformly mixing an ethylene-chlorotrifluoroethylene copolymer, a diluent, a foaming agent and a nucleating agent in proportion, and heating to a molten state at the temperature of 190-260 ℃ to obtain a casting solution;
(2) extruding the membrane casting solution through a die head of a double-screw extruder to form a membrane, so as to obtain a hollow fiber microporous membrane, or blade-coating the membrane casting solution on a glass flat plate, so as to obtain a flat microporous membrane;
(3) and (3) placing the hollow fiber microporous membrane and/or the flat microporous membrane in a gel bath at the temperature of 10-150 ℃ for curing, and rinsing with an organic solvent and water to obtain the hollow fiber microporous membrane and/or the flat microporous membrane.
8. A method of preparing an ethylene chlorotrifluoroethylene copolymer microporous membrane using the film-forming formulation of claim 1, characterized in that the method comprises:
(1) uniformly mixing ethylene-chlorotrifluoroethylene copolymer, a diluent, a foaming agent and a nucleating agent in proportion, and heating to a molten state at the temperature of 180-270 ℃ to obtain a casting solution;
(2) extruding the membrane casting solution through a die head of a double-screw extruder to form a membrane, so as to obtain a hollow fiber microporous membrane, or blade-coating the membrane casting solution on a glass flat plate, so as to obtain a flat microporous membrane;
(3) the hollow fiber microporous membrane and/or the flat plate microporous membrane are placed in a gel bath at the temperature of 10-150 ℃ for solidification, and then are rinsed by an organic solvent and water to obtain the hollow fiber microporous membrane and/or the flat plate microporous membrane, wherein the gel bath is selected from at least one of water, ethanol, isobutanol, ethylene glycol and glycerol, and the organic solvent is selected from at least one of ethanol, isopropanol, butanol, acetone and butyl ether.
9. The microporous film of ethylene-chlorotrifluoroethylene copolymer produced by the film-forming formulation according to claim 1, wherein the microporous film of ethylene-chlorotrifluoroethylene has a tensile strength of 1 to 15MPa, an elongation at break of 20 to 150%, and a water permeabilityThe amount of the surfactant is 0.1 to 1200L/m2.h。
10. Use of an ethylene chlorotrifluoroethylene copolymer microporous membrane prepared using the film-forming formulation as claimed in claim 1, characterized in that the ethylene chlorotrifluoroethylene microporous membrane is used for sewage treatment and separation and purification of organic solvents.
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