CN105860375A - 耐苛性碱薄膜 - Google Patents
耐苛性碱薄膜 Download PDFInfo
- Publication number
- CN105860375A CN105860375A CN201610236990.8A CN201610236990A CN105860375A CN 105860375 A CN105860375 A CN 105860375A CN 201610236990 A CN201610236990 A CN 201610236990A CN 105860375 A CN105860375 A CN 105860375A
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- CN
- China
- Prior art keywords
- film
- percentage
- acrylic
- weights
- polymer
- Prior art date
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Links
- 239000003518 caustics Substances 0.000 title claims abstract description 20
- 239000012528 membrane Substances 0.000 title abstract description 8
- 239000002033 PVDF binder Substances 0.000 claims abstract description 42
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 229920001400 block copolymer Polymers 0.000 claims abstract description 7
- 229920005623 miscible polymer blend Polymers 0.000 claims abstract description 5
- 229920001897 terpolymer Polymers 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000013060 biological fluid Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003204 osmotic effect Effects 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002952 polymeric resin Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 61
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 15
- 239000010409 thin film Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000013638 trimer Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- -1 perfluorinated methyl ethylene ether Chemical compound 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000015110 jellies Nutrition 0.000 description 3
- 239000008274 jelly Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical class C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920006370 Kynar Polymers 0.000 description 2
- 229920007485 Kynar® 761 Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- 229920000120 polyethyl acrylate Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000000807 solvent casting Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- GVIVQCNNFDHBAG-UHFFFAOYSA-N 2,2-dimethyl-1,3-dioxole Chemical compound CC1(C)OC=CO1 GVIVQCNNFDHBAG-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical group CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical compound FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 206010003671 Atrioventricular Block Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 208000010271 Heart Block Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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Abstract
耐苛性碱薄膜。提供了一种耐苛性碱的薄膜,包括一种均相聚合物共混物,该均相聚合物共混物由以下组分组成:a)按重量计75百分比到90百分比的至少一种聚偏氟乙烯PVDF聚合物或共聚物;以及b)按重量计10百分比到25百分比的至少一种丙烯酸类聚合物,所述丙烯酸类聚合物选自下述:(1)三元共聚物;和(2)丙烯酸嵌段共聚物;所述薄膜是微多孔的,孔径为0.01‑10微米。
Description
本发明专利申请是国际申请号为PCT/US2007/082795,国际申请日为2007年10月29日,进入中国国家阶段的申请号为200780042899.1,名称为“耐苛性碱薄膜”的发明专利申请的分案申请。
发明领域
本发明涉及耐苛性碱薄膜,该苛性碱薄膜是通过用溶剂流铸一种或多种聚偏氟乙烯共聚物与一种或多种丙烯酸类聚合物的一种共混物而形成的。
发明背景
聚偏氟乙烯(PVDF)薄膜正逐渐用于微孔过滤和超滤法的应用中,并且已经描述在美国专利例如US 6,013,688和US 6,110,309中。PVDF树脂是化学上和生物上非常惰性的并且具有出色的机械性能。它是耐氧化环境的,例如,广泛用于水的杀菌中的氯和臭氧。PVDF薄膜还高度地耐大多数无机和有机酸类、脂肪族和芳香族烃类、醇类、以及卤化的溶剂引起的腐蚀。该树脂在一些溶剂中是可溶的并且可以容易地进行溶液流铸,以使用相转化法形成多孔膜。PVDF薄膜可以按平板或中空纤维的构型进行流铸。
聚偏氟乙烯微孔膜(总体上作为具有基本均一厚度的薄片形成)具有包含无数互通的通道的一种海绵状内部结构,这些通道具有在窄的限度之内的基本上均一的宽度。总体上是控制这些膜孔尺寸以使其在一个非常小的范围上相对地均一。总体上,这些孔的尺寸范围落在从0.01微米到约10微米的更大的概括范围内。
已经对PVDF薄膜进行了改性(薄膜形成之后)以改进具体的特性。US6,734,386描述了通过在PVDF薄膜的表面上聚合丙烯酸单体的该薄膜的后处理。后处理反应是复杂的并且在生产方法中增加了昂贵的步骤。
已知PVDF与不同的丙烯酸树脂形成易混合的掺杂物。这些包括聚甲基丙烯酸甲酯(PMMA)、聚丙烯酸甲酯(PMA)、聚甲基丙烯酸乙酯(PEMA)、聚丙烯酸乙酯(PEA)、以及这些树脂与其他丙烯酸类共聚物的共聚物类。这些易混合的共混物在长时间内是稳定的。这些丙烯酸类聚合物和共聚物不是水溶性的,并且不会随着长期暴露于水而迁移。(聚乙烯吡咯烷酮(PVP)是与PVDF易混合的另一种聚合物树脂,然而,这种树脂是水溶性的,并且将随着长期暴露于水中而迁移出共混物。因此,在水过滤的应用中,PVDF-PVP共混物在长时间内将不会久稳定。)这些丙烯酸树脂有其独特的良好的耐化学腐蚀性,并且确切地说将不经历当暴露于苛性碱溶液时PVDF所发生的毁坏性脱氟化氢作用。
US 4,377,481描述了PVDF-丙烯酸树脂共混物用于聚合物薄膜的用途,其中丙烯酸树脂是包含至少一种单体的一种共聚物,该单体如果聚合则与PVDF不相容,例如包含磺酸或氨基基团的(甲基)丙烯酸单体。
US 6,074,718描述了还可以与一种第二聚合物共混的PVDF的空心纤维薄膜。所描述的甲基丙烯酸甲酯聚合物是从最终薄膜中提取出的一种成孔材料。在这种应用中,并非旨在使其保留在最终薄膜中,因此对该薄膜没有做出重要的贡献。
PVDF薄膜的一个主要的限制是起因于碱类例如氢氧化钠、氢氧化钾、有机胺类、以及其他碱类的腐蚀的苛性碱耐受性。氢氧化钠溶液经常用于清洗过滤膜以除去生物学的污垢。此清洗循环缩短了PVDF薄膜的寿命并且可能导致薄膜失效。随着对,存在着对苛性碱清洗具有增加的耐受性的PVDF薄膜的一种需要,以大大地改进PVDF薄膜组件的性能和寿命。对薄膜过滤装置来说,过滤组件的寿命是一个主要的经济方面的考虑。
出人意料地,已经发现由均相PVDF-丙烯酸共混物制成的薄膜具有改进的苛性碱耐受性。
发明概述
本发明涉及一种耐苛性碱薄膜,包括一种均相聚合物共混物,该均相聚合物共混物包括:
a)按重量计百分之50到百分之99的至少一种聚偏氟乙烯(PVDF)聚合物或共聚物;以及
b)按重量计百分之1到百分之50的至少一种丙烯酸酯类聚合物。
本发明还涉及将这种耐苛性碱薄膜用于处理水、废弃的液体、生物学流体以及工作流体的物品。
附图简要说明
图1:是一个纯KYNAR薄膜(对比的)的薄膜截面的SEM照片。
图2:是一个KYNAR-丙烯酸薄膜的薄膜截面的SEM照片。本发明的薄膜没有孔隙和裂纹。SEM照片示出了类似的海绵状的形态。KYNAR-丙烯酸薄膜没有显示出任何聚合物相分离。
发明详细说明
如此处所使用,在涉及PVDF-丙烯酸共混物以及由其形成的薄膜时,“均相的”是指在溶液中PVDF与丙烯酸类聚合物形成一个单相,并且是指在薄膜中该共混物是均一的。
本发明涉及一种丙烯酸类聚合物/PVDF共混物用于溶液流铸成高分子膜的用途。在该共混物中,丙烯酸类聚合物的水平是在按重量计1百分比和50百分比之间,优选是按重量从10百分比到25百分比,其中PVDF的水平在50重量百分比到99重量百分比,并且优选是从75重量百分比到90重量百分比。
聚偏氟乙烯树脂可以是通过将偏二氟乙烯(VDF)进行聚合而制成的一种均聚物、以及偏二氟乙烯的共聚物、三聚物以及更高的聚合物的的一种或多种,其中,这些偏二氟乙烯单元包括大于所有在该聚合物中的单体单元的总重量的百分之70,并且更优选包括这些单元的总重量的百分之75。偏二氟乙烯的共聚物、三聚物以及更高的聚合物可以通过使偏二氟乙烯与一种或多种单体进行反应而制成,该一种或多种单体来自下组,其构成为:氟乙烯,三氟乙烯,四氟乙烯,一种或多种部分或完全氟化的α-烯烃,例如3,3,3-三氟-1-丙烯、1,2,3,3,3-五氟丙烯、3,3,3,4,4-五氟-1-丁烯,以及六氟丙烯,部分氟化的烯烃六氟异丁烯,全氟化的乙烯醚,例如全氟甲基乙烯醚、全氟乙基乙烯醚、全氟正丙基乙烯醚、以及全氟-2-丙氧基丙基乙烯醚,氟化的间二氧杂环戊烯类,例如全氟(1,3-间二氧杂环戊烯)以及全氟(2,2-二甲基-1,3-间二氧杂环戊烯)、烯丙基,部分氟化的烯丙基,或氟化的烯丙基单体,例如2-羟乙基烯丙基醚、或3-烯丙氧基丙二醇,以及乙烯或丙烯。优选的共聚物或三聚物是与氟乙烯、三氟乙烯、四氟乙烯(TFE)、以及六氟丙烯(HFP)形成的。
优选的共聚物是VDF,包括从约71重量百分比到约99重量百分比的VDF,和相应地从约1百分比到约29百分比的TFE;从约71重量百分比到约99重量百分比的VDF,和相应地从约1百分比到约29百分比的HFP(例如在U.S.Pat.No.3,178,399中披露的);以及从约71重量百分比到99重量百分比的VDF,和相应地从约1重量百分比到29重量百分比的三氟乙烯。
优选的三聚物是VDF、HFP、和TFE的三聚物,以及VDF、三氟乙烯、和TFE的三聚物。尤其优选的三聚物具有至少71重量百分比的VDF,以及可能以变化的比例存在的其他共聚单体,但同时它们包含高达该三聚物的29重量百分比。
聚偏氟乙烯还可以是通过共聚反应或者后聚合反应官能化作用生产的一种官能化的PVDF。另外,PVDF可以是一种接枝共聚物,例如像一种辐射接枝的马来酸酐共聚物。
一种或多种PVDF聚合物与一种或多种丙烯酸类聚合物进行共混。“丙烯酸类聚合物”,如此处所使用,是指包括由甲基丙烯酸烷基酯和丙烯酸烷基酯的单体、以及它们的混合物形成的聚合物、共聚物、以及三聚物。术语“(甲基)丙烯酸酯”在此使用以表示丙烯酸酯、甲基丙烯酸酯、或它们的一种混合物。甲基丙烯酸烷基酯单体优选是甲基丙烯酸甲酯,它可以组成从百分之50到百分之100的单体混合物。0到50百分比的其他丙烯酸酯和甲基丙烯酸酯单体或其他烯键式不饱和单体包括但不限于苯乙烯、α甲基苯乙烯、丙烯腈、并且交联剂也可能以低水平存在于该单体混合物中。在该单体混合物中有用的其他甲基丙烯酸酯以及丙烯酸酯单体包括但不限于丙烯酸甲酯、丙烯酸乙酯以及甲基丙烯酸乙酯、丙烯酸丁酯以及甲基丙烯酸丁酯、甲基丙烯酸异辛酯以及丙烯酸异辛酯、丙烯酸月桂酯以及甲基丙烯酸月桂酯、丙烯酸十八酯以及甲基丙烯酸十八酯、丙烯酸异冰片酯以及甲基丙烯酸异冰片酯、丙烯酸甲氧乙酯以及甲基丙烯酸甲氧乙酯、丙烯酸2-乙氧乙酯以及甲基丙烯酸2-乙氧乙酯、丙烯酸二甲氨基乙酯以及甲基丙烯酸二甲氨基乙酯单体。烷基(甲基)丙烯酸类(例如甲基丙烯酸以及丙烯酸)可以用于该单体混合物。优选,丙烯酸类聚合物是一种无规共聚物,该无规共聚物包含70重量百分比到99重量百分比,并且更优选90重量百分比到99重量百分比的甲基丙烯酸甲酯单元,以及从1重量百分比到30重量百分比,并且更优选1重量百分比到10重量百分比的一种或多种丙烯酸C1-4烷基酯单元。特别地,一种确切的有用的三聚物包含约95.5重量百分比到98.5重量百分比的甲基丙烯酸甲酯单元,1重量百分比到3重量百分比的(甲基)丙烯酸单元以及0.5重量百分比到1.5重量百分比的丙烯酸乙酯单元的一种三聚物。
在另一个优选的实施方案中,少量的从0.5重量百分比到10重量百分比,并且优选从1重量百分比到5重量百分比的(甲基)丙烯酸作为与甲基丙烯酸甲酯的共聚单体使用。由于酸官能性的存在,所形成的共聚物包含增强的亲水性。
在另一个实施方案中,丙烯酸类聚合物是可能为二-或三嵌段共聚物的一种嵌段共聚物。在薄膜形成中,该嵌段共聚物结构可以提供一种改进的形态学的控制,导致受控的结构域尺寸、以及受控的微结构构造。这导致了改进的孔隙率控制和改进的稳定性,同时提供导致优异的机械性能的更好的官能团分布。这些丙烯酸类嵌段共聚物可以使用受控的自由基聚合技术来制成,这些自由基聚合技术包括但不限于原子转移自由基聚合(ATRP)、可逆加成断裂链转移聚合(RAFT)、氮氧介导聚合(NMP)、硼介导聚合、以及催化链转移聚合(CCT)。在来自氮氧族的一种稳定自由基的存在下制备共聚物的一种方法描述于US 6,255,402中。氮氧介导的稳定自由基已经被用于生产受控的嵌段共聚物,如在US 6,255,448和US 2002/0040117中所描述。这些参考文献通过引用结合在此。
原则上,任何与所选单体相容的活性或受控聚合技术均可用于制造嵌段共聚物。受控的自由基聚合的一个优选的方法是氮氧介导的CRP。氮氧介导的CRP是优选的,因为它允许在三嵌段共聚物中使用更多种单体,并且尤其有益于聚丙烯酸酯类和酸功能的聚丙烯酸酯类。在一个实施方案中,三嵌段丙烯酸聚合物是通过一种受控的自由基聚合来形成的,该三嵌段丙烯酸聚合物具有丙烯酸丁酯的中心嵌段且包括5重量百分比到50重量百分比的三嵌段聚合物,以及末端基团,这些末端基团包括具有75百分比到100百分比的甲基丙烯酸甲酯和从0重量百分比到25重量百分比的一种或多种丙烯酸C1-4烷基酯或丙烯酸的一种均聚物或共聚物,其中每个末端基团组成了25重量百分比到47.5重量百分比的三嵌段聚合物。
总体上,在共混物中使用的PVDF聚合物具有在从100,000g/mol到5,000,000g/mol范围内的分子量,并且丙烯酸类聚合物具有在从30,000到500,000范围内的分子量。若一种或多种丙烯酸类聚合物的分子量过高,则对于在薄膜中使用来说该聚合物将过于脆。当使用丙烯酸类共聚物时,具有更高水平的丙烯酸烷基酯时,Tg更低并且可以容许更高的分子量。
将PVDF和丙烯酸类聚合物与一种溶剂一起混合,以形成一种共混的聚合物溶液。PVDF和丙烯酸类聚合物可以一起共混,随后进行溶解,或这些聚合物可以单独地溶解在相同或不同的溶剂中,并且将这些溶剂溶液一起共混。溶解本发明的这些溶液中有用的溶剂包括,但不限于N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、丙酮、二甲基甲酰胺、四氢呋喃、甲基乙基酮、四甲基脲、二甲亚砜、磷酸三乙酯、N-辛基-吡咯烷酮、γ丁内酯、N,N’-二甲基-亚丙基-脲、碳酸二甲酯、以及它们的混合物。
该聚合物溶液典型地具有从10百分比到30百分比的固体水平,优选15百分比到22百分比,并且最优选从17百分比到20百分比。该溶液是通过混合并且任选在高达80℃,并且典型地从50℃到80℃的温度下加热而形成的。
除PVDF和丙烯酸类聚合物以及溶剂之外,可以将其他添加剂加入该聚合物溶液中,基于该总溶液,典型地是从1重量百分比到20重量百分比,并且更优选从5重量百分比到10重量百分比。典型的添加剂包括但不限于成孔剂,这些成孔剂典型地是亲水性的水可提取的化合物,例如金属盐类(例如锂、钙、以及锌的盐类)、醇类、乙二醇类(例如聚乙二醇、聚丙二醇);硅石、纳米碳管以及可以或不可提取的其他纳米材料;以及为了便于加工薄膜材料,用来增加溶液粘度的化合物。
可以调整溶液粘度以获得最好的加工条件。对于平板来说,调整所有的配制品以获得对于扁平片流铸而言最好的粘度。在空心纤维的形成中,该方法实际上为一种挤出形式,并且更高的粘度是有益的。
然后,通过本领域已知的典型的方法使PVDF/丙烯酸溶液形成薄膜,以形成平板、有载体的平板或空心纤维膜。在一种典型的方法中,PVDF/丙烯酸溶液被溶剂流铸并且拉伸到一个基片上。此薄膜可以是有载体的或无载体的,例如是流铸在一个多孔载体网上,如一种纺织的或非纺织的聚烯烃或聚酯。然后,该薄膜通过相分离方法形成,其中该流铸薄膜溶液的热力学被破坏,这样使这些聚合物凝胶和相从该溶剂中分离出。热力学上的变化经常是通过部分溶剂蒸发,和/或将该薄膜暴露到高湿度的环境开始的。然后,将该薄膜放置在一个对于该聚合物来说为非溶剂的例如水、醇、或它们的混合物中,并且将溶剂除去,则留下了一个多孔的膜。孔的尺寸可以如本领域中已知的通过添加剂的使用以及聚合物的浓度进行调整。例如高分子量的添加剂可以导致大的孔尺寸,而使用锂盐添加剂可以产生小的孔尺寸。
本发明的PVDF/丙烯酸薄膜总体上是75微米到200微米,并且优选是从100微米厚到150微米厚。
当不被任何具体的理论所束缚时,相信该共混物中的丙烯酸类聚合物在聚偏氟乙烯的非晶相的(而不是结晶的)区域浓缩。因此,该丙烯酸类聚合物可用来增强PVDF的较弱的非晶相区域而导致性质上的改进。
另外,PVDF和丙烯酸类聚合物是可熔融混合的,这表明该共混物在固态时在热力学方面是相容的。这意味着由该共混物形成的薄膜将不会相分离并且应保持稳定。
当暴露于苛性碱溶液时,由这些PVDF-丙烯酸的共混物产生的薄膜比单独的PVDF薄膜表现出小得多的变色性。变色指示了脱氟化氢作用,这最终导致机械性能的损失、减小的薄膜寿命、以及差的分离性能。苛性碱暴露是指在从20℃到90℃范围的温度下,用浓度范围从0.5%到50%的氢氧化钠(或类似的碱)溶液浸没或洗涤这些薄膜。这些是经常在薄膜清洗循环中使用的条件。
本发明的薄膜可以用于许多应用中,包括但不限于:水净化、多种生物学流体的纯化、废水处理、渗透蒸馏、以及工作流体过滤。
实例
称出KYNAR 761树脂(12.0g)(Arkema Inc.)加入250ml的罐中,随后是3g的丙烯酸树脂(具有大致2%的甲基丙烯酸的PMMA共聚物)。然后,将77g的二甲基乙酰胺加入,将该罐密封,并且放置在辊上以完全溶解这些树脂。单独地称出聚乙二醇(2.5份,400MW)、水(3.0份)、以及聚乙二醇(2.5份,8000MW)的一种混合物,并且混合直到所有的都完全溶解。将KYNAR/丙烯酸树脂溶液加热到70℃,并且用一个顶置式搅拌器搅拌。然后将聚乙二醇/水溶液逐滴加入该热的聚合物溶液中。加入后,在70℃下让该混合物进行30分钟的混合。然后,通过在粘稠物溶液上抽轻度的真空,将它除气以除去气泡。在流铸之前,允许将除气的薄膜胶状物冷却到环境温度。
通过以下程序流铸薄膜:
将薄膜胶状物倾倒在一个清洁的玻璃板上并且通过拉伸方块进行拉伸。湿薄膜厚度范围是从5密耳到20密耳。然后,将湿薄膜暴露到高湿度(65℃水浴之上的环境蒸气)中从30秒到2分钟。在暴露于湿度后,将玻璃板浸入热水浴中以完成相转化并且使薄膜凝固。薄膜的形成迅速发生,并且所形成的薄膜自发地离开了玻璃板。
替代地,该湿流铸薄膜可以立即在热水浴中淬火而不经任何湿度的暴露。另一个替代的程序涉及在环境温度下的水浴中淬火或暴露到更低的湿度水平(在水提取器的橱中约60%的RH)下。代替玻璃板,薄膜可以被流铸在一个聚酯隔离膜上、一个聚丙烯片上、或在一种非纺织的聚酯织物上。
将这些薄膜在水中冲洗,随后用醇冲洗,然后在空气中干燥。
如上制备另外的薄膜配制品,但是用下列丙烯酸树脂:a)一种PMMA丙烯酸类共聚物,用聚丙烯酸乙酯作为次要组分;b)一种丙烯酸三嵌段共聚物(b-PMMA/b-聚丙烯酸丁酯/b-PMMA,以大致35:30:35的组成)
最后,用15g的KYNAR 761并且不加入丙烯酸制备了一种配制品。
对由所有这些配制品流铸的薄膜进行对苛性碱暴露的测试。
苛性碱暴露测试
将这些薄膜的片(约20mm x 50mm)切开并且放入小瓶中。将10重量百分比的氢氧化钠在水中的溶液加入每个小瓶中。将这些小瓶盖上并且振荡(不是搅拌),然后在环境温度下置于一边。每隔几天目测一下这些样品。两周之后除去这些薄膜,用去离子水漂洗,然后简单地浸渍在异丙醇中并且允许风干。将干燥后的薄膜样品在Hunter Labscan XE色度计上进行变色分析。
如在表1中可见,当暴露于苛性碱溶液时,纯PVDF薄膜变色。取决于薄膜胶状物配制品的类型,反应性非常迅速地发生(<30分钟)或几天后才显著。在两种情况下,可比较的这些PVDF-丙烯酸薄膜的变色少得多。因此,这些PVDF-丙烯酸薄膜是更耐苛性碱的。对于表1中示出的这些薄膜来说,在暴露一整夜后,纯PVDF薄膜显示了红棕色的变色(由大的ΔE*证明)。然而,本发明的这些薄膜的变色少得多,这由更低的ΔE*值证明。
表1
苛性碱处理的薄膜的变色数据
亨特色标
Claims (8)
1.一种耐苛性碱的薄膜,包括一种均相聚合物共混物,该均相聚合物共混物由以下组分组成:
a)按重量计75百分比到90百分比的至少一种聚偏氟乙烯PVDF聚合物或共聚物;以及
b)按重量计10百分比到25百分比的至少一种丙烯酸类聚合物,所述丙烯酸类聚合物选自下述:
(1)三元共聚物,该三元共聚物由从90重量百分比到99重量百分比的甲基丙烯酸甲酯单体单元、0.5-9.5重量百分比的一种或多种丙烯酸C1-4烷基酯类和0.5-5重量百分比的(甲基)丙烯酸单元组成,其中这些丙烯酸单体的总和等于100%;和
(2)丙烯酸嵌段共聚物,所述丙烯酸类嵌段共聚物全部由丙烯酸类单体组成,其中至少一个端基嵌段由从75重量百分比到100重量百分比的甲基丙烯酸甲酯单体单元和从0重量百分比到25重量百分比的一种或多种丙烯酸C1-4烷基酯类和/或(甲基)丙烯酸组成;
所述薄膜是微多孔的,孔径为0.01-10微米。
2.如权利要求1所述的薄膜,其中所述PVDF聚合物包括一种共聚物,该共聚物具有85摩尔百分比到95摩尔百分比的聚偏氟乙烯以及5摩尔百分比到15摩尔百分比的六氟丙烯。
3.如权利要求1所述的薄膜,其中所述PVDF聚合物具有从100,000g/mol到5,000,000g/mol的分子量。
4.如权利要求1所述的薄膜,其中所述丙烯酸类聚合物具有从30,000g/mol到500,000g/mol的分子量。
5.如权利要求1所述的薄膜,其中所述丙烯酸类嵌段共聚物是一种三嵌段共聚物,该三嵌段共聚物具有一个聚丙烯酸丁酯中心嵌段以及作为端基嵌段的甲基丙烯酸甲酯或甲基丙烯酸甲酯共聚物类。
6.如权利要求1所述的薄膜,其中,这些PVDF和丙烯酸类聚合物树脂是按适当比例进行预混,这是通过将熔融物挤压成一种粒化形式并且再随后用于该薄膜的制备。
7.如权利要求1所述的薄膜,其中所述薄膜是一种空心纤维膜、一种有载体的空心纤维膜、一种扁平的无载体的薄膜、或一种扁平的有载体的薄膜。
8.如权利要求1所述的薄膜,包括用于水净化、多种生物学流体的纯化、废水处理、渗透蒸馏、以及工作流体过滤的一种物品。
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CN101970992A (zh) | 2011-02-09 |
US20110017661A1 (en) | 2011-01-27 |
CN105860375B (zh) | 2021-07-09 |
EP2108107A2 (en) | 2009-10-14 |
WO2009091351A3 (en) | 2016-06-09 |
EP2108107B1 (en) | 2020-04-08 |
WO2009091351A2 (en) | 2009-07-23 |
US9327247B2 (en) | 2016-05-03 |
JP5378235B2 (ja) | 2013-12-25 |
JP2010526885A (ja) | 2010-08-05 |
EP2108107A4 (en) | 2017-04-05 |
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