JP6170493B2 - ポリマーブレンド物の膜 - Google Patents
ポリマーブレンド物の膜 Download PDFInfo
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- JP6170493B2 JP6170493B2 JP2014524038A JP2014524038A JP6170493B2 JP 6170493 B2 JP6170493 B2 JP 6170493B2 JP 2014524038 A JP2014524038 A JP 2014524038A JP 2014524038 A JP2014524038 A JP 2014524038A JP 6170493 B2 JP6170493 B2 JP 6170493B2
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- JP
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- Prior art keywords
- membrane
- pvdf
- molecular weight
- measured
- polymethyl methacrylate
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims description 100
- 229920002959 polymer blend Polymers 0.000 title 1
- 239000002033 PVDF binder Substances 0.000 claims description 65
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000035699 permeability Effects 0.000 claims description 9
- 238000001542 size-exclusion chromatography Methods 0.000 claims description 9
- 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
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000000691 measurement method Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000002459 porosimetry Methods 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229920006187 aquazol Polymers 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 238000009285 membrane fouling Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229920005735 poly(methyl vinyl ketone) Polymers 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- 239000013505 freshwater Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229920001897 terpolymer Polymers 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 metal salts (eg Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- DMUPYMORYHFFCT-UPHRSURJSA-N (z)-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound F\C=C(/F)C(F)(F)F DMUPYMORYHFFCT-UPHRSURJSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical class C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 description 1
- YKWORVRLPTZONH-UHFFFAOYSA-N 1-ethenoxy-1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)OC=C YKWORVRLPTZONH-UHFFFAOYSA-N 0.000 description 1
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical compound FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- KKNLARLTLMDINT-UHFFFAOYSA-N 4,4,4-trifluoro-2-methylbut-2-enoic acid Chemical compound OC(=O)C(C)=CC(F)(F)F KKNLARLTLMDINT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- ZVUDQVJACUOJPE-UHFFFAOYSA-N fluoroethene;1,1,2-trifluoroethene Chemical compound FC=C.FC=C(F)F ZVUDQVJACUOJPE-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- AFFZTFNQQHNSEG-UHFFFAOYSA-N trifluoromethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)F AFFZTFNQQHNSEG-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0011—Casting solutions therefor
- B01D67/00111—Polymer pretreatment in the casting solutions
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
a.1〜99重量パーセントの、極めて高い分子量(Mw>580,000、サイズ排除クロマトグラフィーによる測定値)のポリフッ化ビニリデン、および
b)99〜1重量パーセントの、より低い分子量のPVDF(Mw<580,000、サイズ排除クロマトグラフィーによる測定値)、および
c)0〜40重量パーセントのその他の添加剤、
ここで、その膜の中の細孔は、5nmから最高100ミクロンまでの範囲であってよい。
以下の成分を混合容器の中に秤り込み、オイルバス上55〜65℃で4時間加熱混合する:
高MwPVDF(Mw>600K、Mn>280) 8.0g
PVDF樹脂(Mw:450〜550K、Mn:150〜200K) 12.0g
ポリビニルピロリドン(K17、Mw:12,000、BASF) 5.0g
ジメチルアセトアミド 75.0g
以下の成分を混合容器の中に秤り込み、オイルバス上55〜65℃で4時間加熱混合する:
高MwPVDF(Mw>600K、Mn>280) 12.0g
PVDF樹脂(Mw:450〜550K、Mn:150〜200K) 8.0g
ポリビニルピロリドン(K17、Mw:12,000、BASF) 5.0g
ジメチルアセトアミド 75.0g
以下の成分を混合容器の中に秤り込み、オイルバス上55〜65Cで4時間加熱混合する:
高MwPVDF(Mw>600K、Mn>280) 8.0g
PVDF樹脂(Mw:450〜550K、Mn:150〜200K) 12.0g
ポリビニルピロリドン(K17、Mw:12,000、BASF) 5.0g
N−メチルピロリドン 75.0g
以下の成分を混合容器の中に秤り込み、オイルバス上55〜65Cで4時間加熱混合する:
高MwPVDF(Mw>600K、Mn>280) 12.0g
PVDF樹脂(Mw:450〜550K、Mn:150〜200K) 8.0g
ポリビニルピロリドン(K17、Mw:12,000、BASF) 5.0g
N−メチルピロリドン 75.0g
以下の成分を混合容器の中に秤り込み、オイルバス上55〜65Cで4時間加熱混合する:
PVDF樹脂(Mw:450〜550K、Mn:150〜200K) 20.0g
ポリビニルピロリドン(K17、Mw:12,000、BASF) 5.0g
ジメチルアセトアミド 5.0g
以下の成分を混合容器の中に秤り込み、オイルバス上55〜65Cで4時間加熱混合する:
PVDF樹脂(Mw:450〜550K、Mn:150〜200K) 20.0g
ポリビニルピロリドン(K17、Mw:12,000、BASF) 5.0g
N−メチルピロリドン 75.0g
以下の成分を混合容器の中に秤り込み、オイルバス上55〜65Cで4時間加熱混合する:
高MwPVDF(Mw>600K、Mn>280) 20.0g
ポリビニルピロリドン(K17、Mw:12,000、BASF) 5.0g
ジメチルアセトアミド 75.0g
PMI毛管流多孔度計を使用し、ペルフルオロポリエーテル濡らし液(Galwick)を使用して、実施例1〜6で作成した膜の孔径を測定した。この方法は、膜科学に携わるものには公知である。毛管流多孔度計からは、バブルポイント(最大細孔径)および平均細孔径が得られるであろう。バブルポイント径は、膜産業においては周知の計量値であって、膜における細孔径の限界値が求められる。ここではそれを、各種の膜をそれらの限界径の範囲で比較するための一般的な目安として使用している。
本願発明者らは、次の手順を使用し、水のクロスフロー濾過によって膜の試験をした。膜をイソプロパノールの中に2分間浸漬させてから、脱イオン水中で洗浄した。次いでそれらの膜をSepa CF042 クロスフローセル(Sterlitech)の中に組み込んで、クロスフロー濾過を開始した。6psigで16時間濾過することによって、膜を圧縮させた。次いで圧力を下げて3psiとし、さらに6時間濾過を続けた。最後の1時間の間の濾液を集めて、それを使用して、すべての膜について濾過性能を比較した。次の表に、リットル/m2−hr−bar(Lmhb)の単位で表した濾過結果を示す。比較のために、バブルポイントのデータも示している。
Claims (11)
- 多孔質膜であって、
a)30〜70重量パーセントの、極めて高い重量平均分子量(Mw>580,000、サイズ排除クロマトグラフィーによる測定値)のポリフッ化ビニリデン、および
b)70〜30重量パーセントの、より低い重量平均分子量のPVDF(Mw=150,000〜550,000、サイズ排除クロマトグラフィーによる測定値)、および
c)0〜40重量パーセントのその他の添加剤、
を含み、
前記添加剤が、ポリビニルピロリドン、ポリエチレングリコール、エチレングリコール、ポリ−2−エチルオキサゾリン、プロピレングリコール、ヒドロキシエチルセルロース、ヒドロキシメチルセルロース、ブチルセロソルブ、リチウム塩、カルシウム塩、ナトリウム塩、マグネシウム塩、ポリメチルビニルケトン、ポリメチルメタクリレート、ポリメチルメタクリレート−コ−エチルアクリレート、ポリメチルメタクリレート−コ−ブチルアクリレート、ポリメチメタクリレート−コ−ブチルアクリレート−コ−ヒドロキシエチルメタクリレート、ポリメチルメタクリレート−コ−ブチルアクリレート−コ−メトキシポリエチレングリコール−メタクリレート、ポリメチルメタクリレート−コ−メタクリル酸、ポリメチルメタクリレート−コ−ブチルアクリレート−コ−メタクリル酸、ポリメチルメタクリレート−コ−アミノプロパンスルホン酸、ポリメチルメタクリレート−コ−アミノプロパンスルホン酸ナトリウム塩、からなる群より選択され、
前記膜の中の細孔が、0.137ミクロンの最大細孔径を有し、前記多孔質膜が75〜150ミクロンの厚さである、
前記多孔質膜。 - 前記のより低い分子量のPVDFが、サイズ排除クロマトグラフィーによる測定値で、450,000〜550,000の間の重量平均分子量(Mw)を有する、請求項1の膜。
- 前記のより低い分子量のPVDFが、サイズ排除クロマトグラフィーによる測定値で、350,000〜450,000の間の重量平均分子量(Mw)を有する、請求項1の膜。
- 前記のより低い分子量のPVDFが、サイズ排除クロマトグラフィーによる測定値で、250,000〜350,000の間の重量平均分子量(Mw)を有する、請求項1の膜。
- 前記のより低い分子量のPVDFが、サイズ排除クロマトグラフィーによる測定値で、150,000〜250,000の間の重量平均分子量(Mw)を有する、請求項1の膜。
- 前記多孔質膜の水透過性が、いずれかのPVDFから別々に作成した多孔質膜よりも高い水透過性を有する、請求項1の膜。
- 前記個々のPVDF樹脂成分から調製された膜に比較して、膜の汚損が抑制されている、請求項1の膜。
- 前記膜が、前記個々のPVDF樹脂成分から作成された同様の膜に比較して、より高い水透過性を有する、より小さい限界径を含む、請求項1の膜。
- 前記膜が、請求項1に記載の前記PVDFブレンド物を使用することによって、前記個々のPVDF樹脂成分から調製した膜と比較して、毛管流多孔度計法、水銀圧入多孔度測定法、水圧入多孔度測定法、または顕微鏡法のいずれの方法で測定しても、より均質な孔径分布を有している、請求項1の膜。
- 中空繊維である、請求項1に記載の膜。
- フラットシートである、請求項1に記載の膜。
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AU2013315547A1 (en) * | 2012-09-14 | 2015-02-26 | Evoqua Water Technologies Llc | A polymer blend for membranes |
AU2015292907B2 (en) | 2014-07-22 | 2020-05-07 | Arkema Inc. | High toughness hollow fiber membranes based on vinylidene fluoride polymers |
TWI669152B (zh) | 2014-11-03 | 2019-08-21 | 美商3M新設資產公司 | 微孔性聚偏二氟乙烯平面膜及其製造方法 |
CN104587842A (zh) * | 2014-12-23 | 2015-05-06 | 江苏蓝天沛尔膜业有限公司 | 一种用于工业污水处理的mbr平片滤膜的制备方法 |
JP2018012058A (ja) * | 2016-07-20 | 2018-01-25 | 三菱ケミカル株式会社 | 多孔質膜 |
CN108043240A (zh) * | 2017-12-29 | 2018-05-18 | 北京清大国华环境股份有限公司 | 一种高通量抗污染的pvdf改性膜及其制备方法 |
CN111244364B (zh) * | 2020-01-18 | 2020-11-13 | 江苏厚生新能源科技有限公司 | 一种pvdf涂覆隔膜及其制备方法、锂离子电池 |
KR20230019099A (ko) * | 2020-05-29 | 2023-02-07 | 도레이 카부시키가이샤 | 다공질막 및 복합막 |
CN112691555A (zh) * | 2020-11-30 | 2021-04-23 | 北京碧水源膜科技有限公司 | 用于制造微孔膜的铸膜液、微孔膜制造方法和微孔膜 |
KR102525810B1 (ko) * | 2021-04-21 | 2023-04-26 | 한국화학연구원 | 다공성 불소계 분리막 및 이의 제조 방법 |
WO2023127417A1 (ja) * | 2021-12-28 | 2023-07-06 | 日本ゼオン株式会社 | 多孔質体及び多孔質体の製造方法 |
WO2024006133A1 (en) * | 2022-06-30 | 2024-01-04 | Arkema Inc. | Triethylphosphate/n-methylpyrrolidone solvent blends for making pvdf membranes |
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US3178399A (en) | 1961-08-10 | 1965-04-13 | Minnesota Mining & Mfg | Fluorine-containing polymers and preparation thereof |
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US5746916A (en) * | 1994-01-26 | 1998-05-05 | Mitsubishi Rayon Co., Ltd. | Microporous membrane made of non-crystalline polymers and method of producing the same |
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