CN104661733B - 具有羧酸官能团的复合聚酰胺膜 - Google Patents
具有羧酸官能团的复合聚酰胺膜 Download PDFInfo
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- CN104661733B CN104661733B CN201380038529.6A CN201380038529A CN104661733B CN 104661733 B CN104661733 B CN 104661733B CN 201380038529 A CN201380038529 A CN 201380038529A CN 104661733 B CN104661733 B CN 104661733B
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- Prior art keywords
- carboxylic acid
- thin film
- film
- polyamide layer
- film polyamide
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 38
- 229920002647 polyamide Polymers 0.000 title claims abstract description 38
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 150000001732 carboxylic acid derivatives Chemical group 0.000 title abstract description 14
- 239000010409 thin film Substances 0.000 claims abstract description 23
- 239000012634 fragment Substances 0.000 claims abstract description 21
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 claims abstract description 11
- 230000004044 response Effects 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 52
- -1 carboxylic acid halides Chemical class 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010494 dissociation reaction Methods 0.000 claims description 10
- 230000005593 dissociations Effects 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001266 acyl halides Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000002835 absorbance Methods 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 239000004760 aramid Substances 0.000 description 18
- 229920003235 aromatic polyamide Polymers 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000539 dimer Substances 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001263 acyl chlorides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012695 Interfacial polymerization Methods 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000001261 hydroxy acids Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MMCOTMRRXSOFLF-UHFFFAOYSA-N 2-(3,5-dichlorophenyl)-2-oxoacetic acid Chemical compound OC(=O)C(=O)C1=CC(Cl)=CC(Cl)=C1 MMCOTMRRXSOFLF-UHFFFAOYSA-N 0.000 description 2
- OHFLNNVKHIOKKU-UHFFFAOYSA-N 3-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C(Cl)=O)=C1 OHFLNNVKHIOKKU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000000777 acyl halide group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
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- 238000004448 titration Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- NNIJZQYSYZQFDZ-UHFFFAOYSA-N (2,3-dibutylphenyl) dihydrogen phosphate Chemical compound CCCCC1=CC=CC(OP(O)(O)=O)=C1CCCC NNIJZQYSYZQFDZ-UHFFFAOYSA-N 0.000 description 1
- RFBZPOTVVHLWBP-UHFFFAOYSA-N 11-chloro-11-oxoundecanoic acid Chemical compound OC(=O)CCCCCCCCCC(Cl)=O RFBZPOTVVHLWBP-UHFFFAOYSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- OYEQKMASMPBQMP-UHFFFAOYSA-N 4-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=C(C(Cl)=O)C=C1 OYEQKMASMPBQMP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
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- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
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- MYTYKMBAJLQHLQ-UHFFFAOYSA-N butyl heptyl hexyl phosphate Chemical compound CCCCCCCOP(=O)(OCCCC)OCCCCCC MYTYKMBAJLQHLQ-UHFFFAOYSA-N 0.000 description 1
- DJQFQXHRKYELGT-UHFFFAOYSA-N butyl heptyl hydrogen phosphate Chemical compound CCCCCCCOP(O)(=O)OCCCC DJQFQXHRKYELGT-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Abstract
薄膜复合聚酰胺膜，其包括多孔载体和薄膜聚酰胺层，所述薄膜聚酰胺层是间苯二胺(mPD)和均苯三甲酰氯(TMC)的反应产物，其中所述膜的特征在于所述薄膜聚酰胺层在pH 9.5时具有至少0.18mol/kg的解离羧酸含量，并且其中所述薄膜聚酰胺层在650℃时的热解造成火焰电离检测器对在212m/z和237m/z处产生的碎片的响应比率小于2.8。
Description
发明领域
本发明涉及薄膜复合膜及其制造和使用方法。
发明背景
复合聚酰胺膜用于各种流体分离。一种类别包括具有“薄膜”聚酰胺层的多孔载体。这些膜统称为“薄膜复合”(TFC)膜。所述薄膜聚酰胺层可以通过多官能胺(例如间苯二胺)和多官能酰卤(例如均苯三甲酰氯)单体用不混溶溶液顺序涂布在载体上后二者之间界面缩聚反应而形成，参见例如Cadotte的US 4277344。WO 2010/120326描述了使用均苯三甲酰氯与它的单和二水解对应物的组合。另外的成分也已经添加到所述涂层溶液以改善膜性能。例如，Mickols的US 6878278描述了向所述酰卤涂层溶液添加磷酸三烃基酯化合物。
将羧酸官能团引入所述聚酰胺层中赋予了所述层更多的负电荷，这被认为提高了某些溶质(例如NaCl，硝酸盐)的截留以及赋予所述膜对某些污垢(例如腐殖酸)的提高的抗性。多官能酰卤单体的一部分酰卤基团在所述界面聚合期间不可避免地变得水解(例如通过与大气中存在的水或与所述胺涂层溶液中存在的水反应)。所述聚酰胺层的总羧酸含量(“解离的羧酸根含量”)可通过利用包含羧酸官能团的酰卤单体而进一步增加。参见例如WO2010/120326。可以增加所述聚酰胺层的羧酸含量的其他方法包括用氯化剂后处理(参见例如：US 4277344，US 4761234，US 5051178和US 5876602)或后施加带电荷的涂层。不幸的是，后处理步骤增加了膜制备的成本和复杂性。另外，后氯化可危害长期膜性能。
发明内容
在一种实施方式中，本发明包括薄膜复合聚酰胺膜，其包括多孔载体和薄膜聚酰胺层，所述聚酰胺层是间苯二胺(mPD)和均苯三甲酰氯(TMC)的反应产物，其中所述膜特征在于所述薄膜聚酰胺层在pH 9.5时具有至少0.18mol/kg的解离羧酸含量，并且其中所述薄膜聚酰胺层在650℃时的热解造成火焰电离检测器对在212m/z和237m/z处产生的碎片的响应比率小于2.8。在另一种实施方式中，本发明包括制造薄膜复合膜的方法，所述方法包括向多孔载体的表面施加间苯二胺的极性溶液和包含均苯三甲酰氯的非极性溶液以形成薄膜聚酰胺层，其中所述非极性溶液还包含：i)包含至少一个酰卤部分和至少一个羧酸部分的酰卤反应物，和ii)磷酸三烃基酯化合物。描述了许多其他的实施方式。
附图说明
图1是代表性薄膜聚酰胺层的热解GC-MS响应(a)随着对应于代表性薄膜聚酰胺层的温度(b)的变化的曲线。
发明具体描述
本发明包括薄膜复合膜及其制造和使用方法。本发明不具体限于特定类型、构造或形状的复合膜或应用。例如，本发明适用于可用于各种应用包括正渗透(FO)、反渗透(RO)和纳滤(NF)的平板状、管状和中空纤维聚酰胺膜。RO复合膜对于几乎所有的溶解盐相对不可渗透，并通常截留超过大约95％的单价离子盐，例如氯化钠。RO复合膜还通常截留超过大约95％的无机分子以及分子量大于约100道尔顿的有机分子。NF复合膜比RO复合膜更可渗透，并通常截留小于约95％的单价离子盐，同时根据二价离子的种类，截留超过约50％(并经常超过90％)的二价离子盐。NF复合膜还通常截留纳米范围的粒子以及分子量大于约200至500道尔顿的有机分子。
本方法包括在多孔载体上形成薄膜聚酰胺层。所述多孔载体没有特别的限制并优选包括聚合材料，所述聚合材料具有的孔隙尺寸足以允许渗透物基本上不受限制地通过，然而并非大得足以妨碍在其上形成的薄膜聚酰胺膜层的桥接。例如，所述载体的孔隙尺寸优选从大约0.001至0.5μm。多孔载体的非限制性例子包括由下列材料制成的那些：聚砜，聚醚砜，聚酰亚胺，聚酰胺，聚醚酰亚胺，聚丙烯腈，聚(甲基丙烯酸甲酯)，聚乙烯，聚丙烯，和各种卤化聚合物例如聚偏氟乙烯。
所述薄膜聚酰胺层是通过间苯二胺(mPD)和均苯三甲酰氯(TMC)之间在多孔载体表面上的界面缩聚反应而制备的，如US 4277344和US 6878278所述。术语“聚酰胺”是指沿着分子链存在酰胺键(—C(O)NH—)的聚合物。MPD和TMC可以通过涂布步骤从溶液施加于多孔载体，其中mPD优选从水基或极性涂层溶液涂布，而TMC从有机基或非极性涂层溶液涂布。所述极性涂层溶液优选包含约0.1至约20重量％并更优选约0.5至约6重量％的mPD。所述非极性溶液优选包含约0.1至10重量％并更优选0.3至3重量％的TMC。一旦彼此发生接触，所述单体在它们的表面处界面反应，形成聚酰胺层或膜。这种层，经常被称为聚酰胺“辨别层”或“薄膜层”，提供了具有从溶剂(例如水性进料)中分离溶质(例如盐)的主要手段的复合膜。所述单体的反应时间可以小于一秒，但是接触时间通常在约1至60秒，之后可以任选通过气刀、水浴、干燥器等除去多余的液体。除去多余的溶液可以通过在升高的温度下、例如约40℃至约120℃下干燥来完成，但是也可以利用在环境温度下空气干燥。虽然涂布步骤不需要按照特定的次序，但优选首先涂布mPD，然后是TMC。涂布可通过喷涂、膜涂、辊涂或通过使用浸渍槽以及其他涂布技术完成。
所述界面聚合在酰卤反应物存在下进行。所述反应物可以从单独的涂层溶液涂布，或者在一些实施方式中，合并并从前述非极性涂层溶液涂布。所述酰卤反应物包含至少一个酰卤部分和至少一个羧酸部分(或其盐)。酰卤反应物的非限制性例子包括如下所述的多官能酰卤单体的单和二水解对应物以及如下所述的四酰卤单体的单、二和三水解对应物。优选的酰卤反应物包括单水解的均苯三甲酰氯(mhTMC)，即1-羧基-3,5-二氯甲酰苯，和单水解的间苯二甲酰氯(mhIPC)。其它的例子包括由式(I)表示的：
其中X是卤素(优选氯)和n是1至10的整数。代表性的物质包括：4-(氯代羰基)丁酸；5-(氯代羰基)戊酸；6-(氯代羰基)己酸；7-(氯代羰基)庚酸；8-(氯代羰基)辛酸；9-(氯代羰基)壬酸和10-(氯代羰基)癸酸。虽然酰卤和羧酸基团显示在末端位置，但它们之一或二者可以沿着所述脂肪链位于其它位置。虽然式(I)中没有显示，但所述脂族反应物可以包含另外的羧酸和酰卤基团。另外，可以使用的相应的芳族物质，其包括3-羧基苯甲酰氯和4-羧基苯甲酰氯。
可以水解形成所述反应物的非限制性多官能酰卤单体包括：对苯二甲酰氯，间苯二甲酰氯，联苯基二羧酰氯，和萘二羧酰氯。脂族化合物的非限制性例子包括己二酰氯、丙二酰氯、戊二酰氯和癸二酰氯。脂环族多官能酰卤的非限制性例子包括：环丙烷三羧酰氯，环戊烷三羧酰氯，环己烷三羧酰氯，环戊烷二羧酰氯，环丁烷二羧酰氯，环己烷二羧酰氯，和四氢呋喃二羧酰氯。代表性的多官能酰卤单体还包括如式(II)表示的四酰卤单体：
其中A选自：氧(-O-)、碳(-C-)、硅(-Si-)、硫(-S-)和氮(-N-)，其可以是未取代或例如用1-4个碳原子的烷基取代；或羰基(-C(O)-)。X是相同或不同的并选自卤素。在优选实施方式中，每个X是氯。在另一种优选实施方式中，A是未取代的碳，即所述单体是5,5'-亚甲基二间苯二甲酰氯。
所述酰卤反应物和TMC优选从总酰卤含量为至少0.10wt％(例如0.10至5wt％)的共同非极性涂层溶液涂布。在本文中使用时，术语“酰卤含量”是指包含至少一个酰卤部分的化合物的浓度，通过重量和通常稀释实践来测量。所述涂层溶液中的所述酰卤反应物的浓度优选为至少0.001wt％和在一些实施方式中至少0.005、0.01、0.02、0.04或0.07wt％。该反应物优选的上限是0.25wt％、0.15wt％、0.010wt％，并且在一些实施方式中，等于或小于0.08wt％。所述涂层溶液可以作为连续或分批涂布操作的一部分施加于多孔载体。合适的非极性溶剂是能够溶解所述酰卤反应物并且与水不混溶的那些，例如己烷、环己烷、庚烷和卤代烃例如FREON系列。优选的溶剂包括对臭氧层造成很小威胁并在经历常规加工时闪点和可燃性方面足够安全而不需要采取特殊防范的溶剂。优选的溶剂是ISOPARTM，可得自Exxon Chemical Company。所述涂层溶液可以任选包含其它物质，包括共溶剂、相转移剂、增溶剂和络合剂，其中单个添加剂可以起到多种功能。代表性的共溶剂包括：苯，甲苯，二甲苯，均三甲苯，乙苯，二乙二醇二甲醚，环己酮，乙酸乙酯，丁基卡必醇TM乙酸酯，月桂酸甲酯和丙酮。在一种实施方式中，用于涂布所述多官能酰卤的非极性涂层溶液包含4至100wt％均三甲苯作为共溶剂以及溶剂例如异链烷烃。
在另一种实施方式中，本方法包括在磷酸三烃基酯化合物存在下进行界面聚合的步骤。向多孔载体施加所述磷酸三烃基酯化合物的手段没有特别的限制，例如所述磷酸三烃基酯化合物可以包含在前述的涂层溶液之一或二者中，或者可以在界面聚合之前或期间从单独的涂层溶液涂布。在优选实施方式中，所述磷酸三烃基酯化合物添加到用于向多孔载体施加TMC的非极性涂层溶液中。
在优选实施方式中，所述磷酸三烃基酯化合物在界面聚合期间与TMC以至少0.1:1、0.5:1、1:1、1.1:1、1.2:1、1.5:1或2:1的摩尔比存在。摩尔比(磷酸三烃基酯化合物与TMC的比率)的优选范围包括：1:1至5:1，1.2:1至4:1，1.5:至3:1和2:1至3:1。
可适用的磷酸三烃基酯化合物的代表性例子在US 6878278中描述。这种化合物的优选类别包括式(III)表示的那些。
其中“P”是磷，“O”是氧，R1、R2和R3独立地选自氢和包含1至10个碳原子的烃基，条件是R1、R2和R3中不超过一个是氢。R1、R2和R3优选独立地选自脂族和芳族基团。可适用的脂族基团包括支链和非支链的物质二者，例如甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、2-戊基、3-戊基。可适用的环状基团包括环戊基和环己基。可适用的芳族基团包括苯基和萘基。环状和芳族基团可以通过脂族连接基团例如甲基、乙基等与磷原子相连。前述的脂族和芳族基团可以是未取代的或取代的(例如用甲基、乙基、丙基、羟基、酰胺、醚、砜、羰基、酯、氰化物、腈、异氰酸酯、氨基甲酸酯、β-羟基酯等取代)；然而，优选具有3至10个碳原子的未取代烷基。磷酸三烃基酯化合物的具体例子包括：磷酸三丙酯，磷酸三丁酯，磷酸三戊酯，磷酸三己酯，磷酸三苯酯，磷酸丙基二苯基酯，磷酸二丁基苯基酯，磷酸丁基二乙基酯，磷酸氢二丁基酯，磷酸氢丁基庚基酯和磷酸丁基庚基己基酯。
在优选实施方式中，所述薄膜聚酰胺层特征在于，通过后文在实施例章节描述的卢瑟福(Rutherford)背散射测量技术测量，在pH 9.5时具有至少0.18、0.20、0.22、0.3和在一些实施方式中至少0.4mol/kg聚酰胺的解离羧酸根含量。虽然在本试验中未使用，但TFC聚酰胺膜的羧酸含量(mol/kg聚酰胺)还可以利用所测量的每单位面积聚酰胺质量和每单位面积羧酸基团摩尔数确定，例如通过也在实施例章节中描述的络合和定量方法。
在另一种优选实施方式中，所述薄膜聚酰胺层在650℃热解导致火焰电离检测器对在212m/z和237m/z处产生的碎片的响应比率小于2.8，并更优选小于2.6。在212和237m/z处产生的碎片分别由式IV和V表示。
该碎片比率被认为指示了提供通量、盐通过率或完整性改善的聚合物结构(特别对于具有比较高的羧酸含量的膜，例如在pH 9.5下解离羧酸根含量为至少0.18、0.20、0.22、0.3和在一些实施方式中至少0.4mol/kg聚酰胺)。参考图1，研究显示，在低于500℃的热解温度期间主要形成二聚体碎片212m/z，而在超过500℃的热解温度下主要形成二聚体碎片237m/z。这表明二聚体碎片212来源于只有单键裂解占优势的端基，而二聚体碎片237基本上来源于发生多重键裂解并还原的主体(bulk)物质。因此，二聚体碎片212与237的比率可用作相对转化率的度量。
优选的热解方法利用具有质谱检测的气相色谱质谱进行，例如Fr ontier Lab2020iD热解器安装在Agilent 7890GC上，利用LECO飞行时间(TruTOF)质谱仪检测。峰面积检测利用火焰电离检测器(FID)进行。通过将聚酰胺样品杯向下放置到设定在650℃的热解炉中6秒以单脉冲方式进行热解。利用出自Varian(FactorFour VF-5MS CP8946)的30M X0.25mm id柱进行分离，所述柱具有1um 5％苯基甲基硅氧烷内相。组分识别通过匹配碎片峰的相对保留时间与用LECO飞行时间质谱仪进行的相同分析的相对保留时间(或任选通过匹配质谱与NIST数据库或文献的参考资料)来进行。利用能够测量至0.001mg的MettlerE20微型天平，称重膜样品放入Frontier Labs二氧化硅内衬的不锈钢杯中。样品重量目标是200ug+/-50ug。气相色谱条件如下：Agilent 6890GC(SN：CN10605069)，具有30M X0.25mm，1μm 5％二甲基聚硅氧烷相(Varian FactorFour VF-5MS CP8946)；进样端口320℃，检测端口：320℃，分流进样器流量比50:1，GC柱温箱条件：以6℃/min从40℃至100℃，以30℃/min从100℃至320℃，320℃下8min；0.6mL/min的恒定流量的氦载气提供5.0psi的背压。LECO TruTOF质谱仪参数如下：电子电离源(正EI模式)，扫描速率为20次扫描/秒，扫描范围：14–400m/z；检测器电压＝3200(超过调整电压(tune volt age)400V)；MS采集延迟＝1min；发射电压–70V。碎片212m/z和碎片237m/z的峰面积相对于样品重量归一化。归一化峰面积用于确定碎片212m/z与237m/z的比率。此外，碎片212m/z的归一化峰面积除以所有其他碎片的归一化峰面积的总和，提供了所述m/z 212碎片相对于聚酰胺的分率，并且通常通过乘以100而称为组成百分率。优选该值小于12％。
在另一种优选实施方式中，所述薄膜聚酰胺层特征在于ATRIR羧酸羰基伸缩/酰胺羰基伸缩(在此称为COOH/酰胺)小于0.1并更优选0.08。该测量值被认为指示了提供改善的通量、盐通过率或完整性的聚合物结构(特别是对于羧酸含量比较高的膜)。优选的ATR IR方法通过首先将聚酰胺层与背衬板层离，从而首先使所述聚酰胺层与多孔载体分离来进行。所述层离的膜浸在适合于溶解所述多孔载体的溶剂(例如二甲基甲酰胺)中。溶解所述多孔载体之后，通过过滤收集不可溶的聚酰胺，用二甲基甲酰胺洗涤2次，用DI水洗涤2次，和用甲醇洗涤2次，然后在真空烘箱中在50℃下干燥20小时。层离的聚酰胺层的红外光谱用Perkin Elmer Spectrum One FT-IR和Universal ATR取样辅助设备以4cm-1的额定分辨率和16次扫描(大致采集时间为90秒)获取。Universal ATR取样辅助设备配备有单反射(single bounce)金刚石/ZnSe结晶。羧酸峰高在1706cm-1处测量，单点基线在1765cm-1处。酰胺峰高在1656cm-1处测量，单点基线在1765cm-1处。
在又一种优选实施方式中，如下所述利用标准ζ-电位测量法测量，所述膜具有小于或等于4.3、4.2、4.1、4、3.8、3.6或在一些实施方式中3.5的等电点(IEP)。
在另一种优选实施方式中，所述膜与不使用所述酰卤反应物制备的对比膜相比，例如当用盐水溶液(2000ppm NaCl)在150psi、25℃和pH 8下测试时，具有改善的通量。在另一种实施方式中，当利用2000ppmNaCl水溶液在150psi、25℃和pH 8下测试时，所述膜也保持了相当的NaCl通过率值。在另一种实施方式中，当在这样的条件下测试时，所述膜具有小于5％的NaCl通过率值。
在另一种优选实施方式中，所述复合膜没有经受使用氯化剂的后处理。
虽然在许多优选实施方式中可以结合本发明使用后施加涂层，但可以不使用这样的涂层，即没有聚丙烯酸或聚乙酸乙烯酯涂层。
实施例
利用中试规模膜生产线制备样品膜。聚砜载体从在二甲基甲酰胺(DMF)中的16.5wt％溶液浇铸，随后浸泡在3.5wt％的间苯二胺(mPD)水溶液中。然后将所生成的载体恒速牵拉通过反应台，同时施加非极性涂层溶液的均匀薄层。所述非极性涂层溶液包含异链烷溶剂(ISOPARL)、以及均苯三甲酰氯(TMC)和1-羧基-3,5-二氯甲酰苯(mhTMC)以各种比率的组合，同时保持总酰氯含量为0.26wt％、以及磷酸三丁酯(TBP)与TMC以1.1:1恒定化学计量摩尔比。除去多余的非极性溶液，所生成的复合膜通过水清洗槽和干燥炉。然后利用盐水溶液(2000ppmNaCl)在150psi、PH8和25℃下对所述样品膜的试件进行标准测试。还测定了样品膜的解离羧酸根含量、等电点(IEP)、二聚体碎片比率(212m/z:237m/z)和羧酸/酰胺(COOH:酰胺)比率(按照本文中描述的方法)。结果概括在表1中。不使用TBP制备第二组类似的膜，结果概括在表2中。通量和NaCl通过率的标准偏差提供在括号中。除了用3-(氯羰基)苯甲酸即“单水解间苯二甲酰氯”或“mhIPC”代替1-羧基-3,5-二氯甲酰苯(mhTMC)以外，第三组膜以与第一组相同的方式制备。还测定样品膜的解离羧酸根含量和二聚体碎片比率(212m/z:237m/z)(按照本文中描述的方法)。结果概括在表3中。
表1：
表2：
表3：
样品膜的聚酰胺层的“解离羧酸根含量”通过银滴定法和如下所述的卢瑟福(Rutherford)背散射测量来确定。
(i)膜样品(1英寸x 6英寸)在去离子水(800mL)中煮30分钟，然后放入甲醇和水的50/50w/w溶液(800mL)中浸泡过夜。接着，这些膜的1英寸x 1英寸大小样品浸在pH调节到9.5的20mL的1x 10-4M AgNO3溶液中30分钟。含银离子的容器以条带包裹以限制曝光。用所述银离子溶液浸泡之后，通过在2份干净的20mL无水甲醇中各浸泡所述膜5分钟，除去未结合的银。最后，让所述膜在氮气氛中干燥至少30分钟。
(ii)卢瑟福背散射(RBS)测量：膜样品安装在导热和导电的双面带上，将其进而安装到充当散热片的硅片上。所用的带是Chromerics Thermattach T410或3M铜带。RBS测量值用Van de Graff加速器(High Voltage Engineering Corp.，Burlington，MA)得到；直径3mm的A 2MeV He+室温射束以入射角22.5°、出射角52.5°、散射角150°和40纳安(nAmp)射束电流使用。膜样品安装到活动样品台上，其在测量期间连续移动。这种移动让离子通量保持低于3x 1014He+/cm2。
(iii)数据分析：利用可商购的模拟程序进行从RBS得到的光谱的分析。它从RO/NF膜的RBS分析获取元素组成的用途说明由Coronell等在J.of MembraneSci.2006，282，71-81和Environmental Science&Technology 2008，42(14)，5260-5266中描述。利用模拟程序拟合两层体系(厚的聚砜层在薄的聚酰胺层底下)获得表中的数据，而拟合三层体系(聚砜，聚酰胺，和表面涂层)可使用相同的方式。所述两层(在添加聚酰胺层之前的聚砜，和最终TFC聚酰胺层的表面)的原子分数组成首先通过XPS测量以提供所述拟合值的界限。因为XPS不能测量氢，使用得自所提出的所述聚合物的分子式的H/C比率，聚砜为0.667，聚酰胺在0.60–0.67的范围。虽然用硝酸银滴定所述聚酰胺只引入少量的银，但银的散射截面明显高于其他低原子序数的元素(C，H，N，O，S)，并且尽管以低得多的浓度存在，但峰的尺寸大得与所述其他元素不成比例，因此提供了良好的灵敏度。银的浓度在中利用两层模型化方法确定，所述方法通过固定所述聚砜的组成和拟合所述银峰值，同时保持所述聚酰胺层组成的窄的窗口(层2，范围利用XPS预先确定)。从所述模拟确定所述聚酰胺层中元素(碳，氢，氮，氧和银)的摩尔浓度。所述银浓度是在所述试验条件的pH下可用于结合银的所述羧酸根摩尔浓度的直接反映。
羧酸基团摩尔数/单位面积膜是通过透过所述膜的物质所引起的相互作用值的指示，较大的值因此将有利地影响盐通过率。该值可以通过所测量的羧酸根含量乘以所测量的厚度并乘以聚酰胺密度来计算。或者，羧酸根数量/单位面积膜(mol/m2)可以通过测量已知面积内的总络合金属的方法更直接确定。利用乙酸双氧铀和甲苯胺蓝O染料二者的方法描述于：Tiraferri等，Journal of Membrane Science，2012，389，499-508。通过聚合物灰化确定膜中络合阳离子(钠或钾)含量的方法描述于(Wei Xie等，Polymer，53卷，第7期，2012年3月22日，1581-1592页)。
确定薄膜聚酰胺膜在pH 9.5下每单位面积膜的解离羧酸根数量的优选方法如下。膜样品在去离子水中煮30分钟，然后放入50wt％的甲醇水溶液中浸泡过夜。接下来，所述膜样品浸在用NaOH调节pH到9.5的1x 10-4M AgNO3溶液中30分钟。浸泡在所述银离子溶液中之后，通过在无水甲醇中两次浸泡所述膜30分钟，除去未结合的银。每单位面积的银量优选通过灰化确定，如Wei所述，并重新溶解供通过ICP测量。优选地，pH 9.5时每平方米膜的解离羧酸根数量大于6x10-5，8x10-5，1x10-4，1.2x10-4，1.5x10-4，2x10-4，或甚至3x10-4mol/m2。
样品膜的等电点利用Desal Nano HS仪器，利用标准ζ-电位技术用石英池通过电泳光散射(ELS)测定。膜样品(2英寸x 1英寸)首先在DI水中煮20分钟，然后用室温DI水充分清洗并在室温下储存在新鲜的DI溶液中过夜。所述样品然后按照以下参考资料装载：2008“User’s Manual for the DelsaTMNano Submicron Particle Size and ZetaPotential,”和Beckmann Coulter提供对于相同仪器的“Pre-Course Reading”。pH滴定在pH 10至pH 2的范围内进行，并且在ζ电位变成零的pH下确定等电点。
已经描述了本发明的许多实施方式，并且在有些情况下，某些实施方式、选择、范围、成分或其他特征已经被表征为“优选的”。“优选”特征的表征决不能被解释为认为这样的特征是本发明要求的、必需的或关键的。前述美国专利文献每一个的全部主题通过引用完全并入本文。
Claims (5)
1.薄膜复合聚酰胺膜，其包含多孔载体和薄膜聚酰胺层，所述薄膜聚酰胺层包含间苯二胺(mPD)和均苯三甲酰氯(TMC)的反应产物，其中所述膜的特征在于所述薄膜聚酰胺层在pH 9.5时具有至少0.3mol/kg的解离羧酸根含量，并且其中所述薄膜聚酰胺层在650℃时的热解造成火焰电离检测器对在212m/z和237m/z处产生的碎片的响应比率小于2.8。
2.权利要求1的膜，其中所述薄膜聚酰胺层在650℃时的热解造成火焰电离检测器对在212m/z和237m/z处产生的碎片的响应比率小于2.6。
3.任一前述权利要求的膜，其中薄膜聚酰胺层的ATR IR产生小于0.1的COOH C＝O伸缩/酰胺C＝O伸缩吸光度比率。
4.用于制造薄膜复合膜的方法，所述方法通过向多孔载体的表面施加间苯二胺的极性溶液和包含均苯三甲酰氯的非极性溶液以聚合并形成薄膜聚酰胺层，其中所述非极性溶液的特征还在于包含：
至少0.15重量％的酰卤反应物，其包含至少一个酰卤部分和至少一个羧酸部分，以及
其中所述聚合在磷酸三烃基酯化合物存在下发生，所述磷酸三烃基酯化合物与均苯三甲酰氯的摩尔比为至少0.5:1至5:1，
式(III)：
其中“P”是磷，“O”是氧，R1、R2和R3独立地选自氢和包含1至10个碳原子的烃基，条件是R1、R2和R3中不超过一个是氢。
5.权利要求4的方法，其中所述酰卤反应物包含单水解的均苯三甲酰氯。
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| CN201380038497.XA Active CN104470626B (zh) | 2012-07-19 | 2013-07-03 | 羧酸官能团增加的复合聚酰胺膜 |
| CN201380038533.2A Active CN104487160B (zh) | 2012-07-19 | 2013-07-03 | 结构改善的复合聚酰胺膜 |
| CN201380038531.3A Pending CN104470628A (zh) | 2012-07-19 | 2013-07-03 | 源自于四官能酰卤单体的薄膜复合膜 |
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| CN201380038533.2A Active CN104487160B (zh) | 2012-07-19 | 2013-07-03 | 结构改善的复合聚酰胺膜 |
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Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6054968B2 (ja) | 2011-08-31 | 2016-12-27 | ダウ グローバル テクノロジーズ エルエルシー | アミン−反応性およびリン−含有官能基を含むモノマーから誘導された複合ポリアミド膜 |
| US9029600B2 (en) | 2011-09-29 | 2015-05-12 | Dow Global Technologies Llc | Method for preparing high purity mono-hydrolyzed acyl halide compound |
| WO2013103666A1 (en) | 2012-01-06 | 2013-07-11 | Dow Global Technologies Llc | Composite polyamide membrane |
| CN104470627B (zh) * | 2012-07-19 | 2018-05-11 | 陶氏环球技术有限责任公司 | 复合聚酰胺膜 |
| CN104918687A (zh) * | 2013-01-14 | 2015-09-16 | 陶氏环球技术有限责任公司 | 使用非极性溶剂的掺合物经由界面聚合制造复合聚酰胺膜 |
| WO2014109947A1 (en) | 2013-01-14 | 2014-07-17 | Dow Global Technologies Llc | Composite polyamide membrane comprising substituted benzamide monomer |
| US9051417B2 (en) | 2013-03-16 | 2015-06-09 | Dow Global Technologies Llc | Method for solubilizing carboxylic acid-containing compound in hydrocarbon solvent |
| US9289729B2 (en) | 2013-03-16 | 2016-03-22 | Dow Global Technologies Llc | Composite polyamide membrane derived from carboxylic acid containing acyl halide monomer |
| US8969259B2 (en) | 2013-04-05 | 2015-03-03 | Reg Synthetic Fuels, Llc | Bio-based synthetic fluids |
| WO2014179024A1 (en) | 2013-05-03 | 2014-11-06 | Dow Global Technologies Llc | Composite polyamide membrane derived from an aliphatic acyclic tertiary amine compound |
| CN106170333B (zh) | 2013-12-02 | 2019-02-15 | 陶氏环球技术有限责任公司 | 用二羟基芳基化合物和亚硝酸处理的复合聚酰胺膜 |
| CN105873665B (zh) | 2013-12-02 | 2019-01-01 | 陶氏环球技术有限责任公司 | 用亚硝酸后处理的复合聚酰胺膜 |
| CA2935680C (en) * | 2014-01-07 | 2022-01-18 | Dow Global Technologies Llc | Treatment of aqueous mixtures containing anionic surfactants using fouling resistant reverse osmosis membrane |
| EP3092056B1 (en) * | 2014-01-07 | 2018-08-01 | Dow Global Technologies LLC | Desalination of aqueous mixture containing nano-sized particles using fouling resistant reverse osmosis membrane |
| KR102273550B1 (ko) | 2014-01-09 | 2021-07-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 아조 함량 및 높은 산 함량을 갖는 복합 폴리아미드 막 |
| US9616392B2 (en) | 2014-01-09 | 2017-04-11 | Dow Global Technologies Llc | Composite polyamide membrane having high acid content and low azo content |
| JP6535010B2 (ja) | 2014-01-09 | 2019-06-26 | ダウ グローバル テクノロジーズ エルエルシー | 好ましいアゾ含有量を有する複合ポリアミド皮膜 |
| CN106257977B (zh) | 2014-04-28 | 2019-10-29 | 陶氏环球技术有限责任公司 | 用亚硝酸后处理的复合聚酰胺膜 |
| KR102359211B1 (ko) | 2014-05-14 | 2022-02-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 아질산으로 후처리된 복합 폴리아미드 막 |
| KR102357884B1 (ko) * | 2014-05-14 | 2022-02-03 | 다우 글로벌 테크놀로지스 엘엘씨 | 아질산으로 후-처리된 복합 폴리아미드 멤브레인 |
| KR102358648B1 (ko) * | 2014-05-14 | 2022-02-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 아질산으로 후처리된 복합 폴리아미드 막 |
| KR101716045B1 (ko) * | 2014-09-30 | 2017-03-22 | 주식회사 엘지화학 | 투과유량 특성이 우수한 폴리아미드계 수처리 분리막의 제조 방법 및 상기 제조 방법으로 제조된 수처리 분리막 |
| EP3374065B1 (en) * | 2015-11-12 | 2021-05-26 | Getpreecharsawas, Jirachai | Ultra-thin nanometer-scale polymeric membranes |
| JP6943180B2 (ja) * | 2016-06-29 | 2021-09-29 | 東レ株式会社 | 複合半透膜及び複合半透膜の製造方法 |
| CN107376667B (zh) * | 2017-08-25 | 2020-11-27 | 上海城市水资源开发利用国家工程中心有限公司 | 一种制备纳滤/正渗透两栖性能cta膜的方法及装置 |
| JP7300810B2 (ja) * | 2017-09-15 | 2023-06-30 | 日東電工株式会社 | 複合半透膜及びその製造方法 |
| CN110605035A (zh) * | 2018-06-14 | 2019-12-24 | 中国科学院大连化学物理研究所 | 一种高通量聚酰胺纳滤或反渗透复合膜及其制备 |
| CN113272049A (zh) * | 2019-01-18 | 2021-08-17 | 东丽株式会社 | 流体分离用碳膜 |
| CN110092454A (zh) * | 2019-05-27 | 2019-08-06 | 长安大学 | 一种废水的处理装置、制造方法及利用该装置处理废水的方法 |
| EP3842127B1 (en) * | 2019-12-27 | 2023-05-03 | Nitto Denko Corporation | Composite semipermeable membrane |
| WO2023038538A1 (en) * | 2021-09-09 | 2023-03-16 | Qatar Foundation For Education, Science And Community Development | Method, apparatus and system for seawater treatment |
| CN114656356B (zh) * | 2022-03-28 | 2023-10-13 | 中国科学院长春应用化学研究所 | 一种螺环二茚满四酰氯及其制备方法、复合膜及其制备方法 |
| CN115055064A (zh) * | 2022-08-17 | 2022-09-16 | 苏州苏瑞膜纳米科技有限公司 | 一种高性能聚酰胺复合反渗透膜的制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0467533A1 (en) * | 1990-07-18 | 1992-01-22 | Rheox International, Inc. | Polyamide compositions and sealant formulations comprising them |
| US6406626B1 (en) * | 1999-01-14 | 2002-06-18 | Toray Industries, Inc. | Composite semipermeable membrane, processfor producing the same, and method of purifying water with the same |
| CN102151499A (zh) * | 2011-02-28 | 2011-08-17 | 浙江理工大学 | 一种聚酰胺复合纳滤膜及其制备方法 |
Family Cites Families (112)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH462993A (de) | 1961-06-12 | 1968-09-30 | Ciba Geigy | Verfahren zur Herstellung von Küpenfarbstoffen |
| FR1587787A (zh) | 1968-10-02 | 1970-03-27 | ||
| US3694390A (en) | 1970-03-30 | 1972-09-26 | Alfred Edwards Winslow | Epoxidized polyamide resin forming stable aqueous solutions of high concentration |
| JPS5223346B2 (zh) | 1972-08-30 | 1977-06-23 | ||
| JPS53146275A (en) | 1977-05-27 | 1978-12-20 | Teijin Ltd | Production of selective permeative-membrane of high water permeability |
| US4259183A (en) | 1978-11-07 | 1981-03-31 | Midwest Research Institute | Reverse osmosis membrane |
| US4277344A (en) | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
| US4606943A (en) | 1983-03-18 | 1986-08-19 | Culligan International Company | Method for preparation of semipermeable composite membrane |
| US4529646A (en) | 1984-07-30 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Production of composite membranes |
| US4643829A (en) | 1984-07-30 | 1987-02-17 | E. I. Du Pont De Nemours And Company | Multilayer reverse osmosis membrane in which one layer is poly-meta-phenylene cyclohexane-1,3,5-tricarboxamide |
| US4761234A (en) | 1985-08-05 | 1988-08-02 | Toray Industries, Inc. | Interfacially synthesized reverse osmosis membrane |
| US4758343A (en) | 1985-09-20 | 1988-07-19 | Toray Industries, Inc. | Interfacially synthesized reverse osmosis membrane |
| US4719062A (en) | 1986-04-23 | 1988-01-12 | E. I. Du Pont De Nemours And Company | Extractant-surfactant post-treatments of permselective composite membranes |
| US4626468A (en) | 1986-04-23 | 1986-12-02 | E. I. Du Pont De Nemours And Company | Microporous support layer with interfacially polymerized copolyamide thereon |
| US4812270A (en) | 1986-04-28 | 1989-03-14 | Filmtec Corporation | Novel water softening membranes |
| US4888116A (en) | 1987-01-15 | 1989-12-19 | The Dow Chemical Company | Method of improving membrane properties via reaction of diazonium compounds or precursors |
| US4812238A (en) * | 1987-01-15 | 1989-03-14 | The Dow Chemical Company | Membranes prepared via reaction of diazonium compounds or precursors |
| US4830885A (en) | 1987-06-08 | 1989-05-16 | Allied-Signal Inc. | Chlorine-resistant semipermeable membranes |
| US4769148A (en) | 1987-11-18 | 1988-09-06 | The Dow Chemical Company | Novel polyamide reverse osmosis membranes |
| US4783346A (en) | 1987-12-10 | 1988-11-08 | E. I. Du Pont De Nemours And Company | Process for preparing composite membranes |
| JPH01180208A (ja) | 1988-01-11 | 1989-07-18 | Toray Ind Inc | 複合半透膜の製造方法およびその膜 |
| US4948507A (en) | 1988-09-28 | 1990-08-14 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
| US4872984A (en) | 1988-09-28 | 1989-10-10 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
| CN1035338A (zh) | 1988-12-16 | 1989-09-06 | 北京市海洋综合技术开发部 | 塑胶无胎卷材 |
| GB2247419B (en) | 1989-10-30 | 1993-08-25 | Aligena Ag | Semipermeable composite membranes |
| US5015382A (en) | 1989-04-20 | 1991-05-14 | E. I. Du Pont De Nemours And Company | Microporous support layer with interfacially polymerized copolyamide membrane thereon |
| US5015380A (en) | 1989-04-20 | 1991-05-14 | E. I. Du Pont De Nemours And Company | Microporous support layer with interfacially polymerized copolyamide membrane thereon |
| US4950404A (en) | 1989-08-30 | 1990-08-21 | Allied-Signal Inc. | High flux semipermeable membranes |
| US4960517A (en) | 1989-12-13 | 1990-10-02 | Filmtec Corporation | Treatment of composite polyamide membranes via substitution with amine reactive reagents |
| US4964998A (en) * | 1989-12-13 | 1990-10-23 | Filmtec Corporation | Use of treated composite polyamide membranes to separate concentrated solute |
| US5019264A (en) | 1990-07-31 | 1991-05-28 | E. I. Du Pont De Nemours And Company | Multilayer reverse osmosis membrane of polyamide-urea |
| JP3031763B2 (ja) | 1990-09-14 | 2000-04-10 | 日東電工株式会社 | 複合逆浸透膜およびその製造方法 |
| US5254261A (en) | 1991-08-12 | 1993-10-19 | Hydranautics | Interfacially synthesized reverse osmosis membranes and processes for preparing the same |
| US5290452A (en) | 1991-12-05 | 1994-03-01 | Exxon Research & Engineering Co. | Crosslinked polyester amide membranes and their use for organic separations |
| US5246587A (en) | 1991-12-23 | 1993-09-21 | Hydranautics | Interfacially synthesized reverse osmosis membranes and processes for preparing the same |
| JPH05261259A (ja) * | 1992-01-22 | 1993-10-12 | Nitto Denko Corp | 複合逆浸透膜 |
| CA2087421A1 (en) | 1992-01-22 | 1993-07-23 | Hisao Hachisuka | Composite reverse osmosis membrane and novel acid chloride |
| JP3242185B2 (ja) * | 1993-03-03 | 2001-12-25 | 東洋紡績株式会社 | ポリアミド系複合中空糸型逆浸透膜の製造方法 |
| US5616249A (en) | 1993-05-20 | 1997-04-01 | Ionics, Incorporated | Nanofiltration apparatus and processes |
| JP3006976B2 (ja) | 1993-06-24 | 2000-02-07 | 日東電工株式会社 | 高透過性複合逆浸透膜の製造方法 |
| JPH07178327A (ja) | 1993-11-12 | 1995-07-18 | Nitto Denko Corp | 複合半透膜及びその製造方法 |
| JPH0810595A (ja) * | 1994-06-29 | 1996-01-16 | Nitto Denko Corp | 複合逆浸透膜 |
| US5783079A (en) | 1994-08-29 | 1998-07-21 | Toyo Boseki Kabushiki Kaisha | Composite hollow fiber membrane and process for its production |
| US5693227A (en) | 1994-11-17 | 1997-12-02 | Ionics, Incorporated | Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method |
| US5614099A (en) | 1994-12-22 | 1997-03-25 | Nitto Denko Corporation | Highly permeable composite reverse osmosis membrane, method of producing the same, and method of using the same |
| JP3489922B2 (ja) | 1994-12-22 | 2004-01-26 | 日東電工株式会社 | 高透過性複合逆浸透膜の製造方法 |
| US5582725A (en) | 1995-05-19 | 1996-12-10 | Bend Research, Inc. | Chlorine-resistant composite membranes with high organic rejection |
| US5989426A (en) * | 1995-07-05 | 1999-11-23 | Nitto Denko Corp. | Osmosis membrane |
| KR0183370B1 (ko) | 1995-07-07 | 1999-04-15 | 김은영 | 방향족 폴리에스테르 또는 방향족 폴리에스테르와 폴리아미드 공중합체의 활성층을 갖는 역삼투용 복합막 |
| US5755964A (en) * | 1996-02-02 | 1998-05-26 | The Dow Chemical Company | Method of treating polyamide membranes to increase flux |
| JP3681214B2 (ja) | 1996-03-21 | 2005-08-10 | 日東電工株式会社 | 高透過性複合逆浸透膜 |
| CN1093428C (zh) * | 1997-03-26 | 2002-10-30 | 中国科学院大连化学物理研究所 | 微孔尼龙膜的化学改性及其带组氨酸配基亲和膜的制备 |
| IL121046A (en) | 1997-06-10 | 2001-07-24 | Weizmann Kiryat Membrane Prod | Semipermeable encapsulated membranes with improved acid and base stability and process for their manufacture and their use |
| DE69814891T2 (de) | 1997-07-02 | 2004-05-13 | Nitto Denko Corp., Ibaraki | Zusammengesetzte umkehrosmosemembran und verfahren zu ihrer herstellung |
| US5876602A (en) | 1997-11-04 | 1999-03-02 | The Dow Chemical Company | Treatment of composite polyamide membranes to improve performance |
| US6162358A (en) | 1998-06-05 | 2000-12-19 | Nl Chemicals Technologies, Inc. | High flux reverse osmosis membrane |
| JP2000202257A (ja) * | 1999-01-14 | 2000-07-25 | Toray Ind Inc | 複合半透膜およびその製造方法 |
| JP4404988B2 (ja) | 1999-04-21 | 2010-01-27 | 住友精化株式会社 | ポリアミド樹脂水性分散液の製造方法 |
| US6245234B1 (en) | 1999-06-03 | 2001-06-12 | Saehan Industries Incorporation | Composite polyamide reverse osmosis membrane and method of producing the same |
| US6280853B1 (en) | 1999-06-10 | 2001-08-28 | The Dow Chemical Company | Composite membrane with polyalkylene oxide modified polyamide surface |
| US6464873B1 (en) | 1999-06-15 | 2002-10-15 | Hydranautics | Interfacially polymerized, bipiperidine-polyamide membranes for reverse osmosis and/or nanofiltration and process for making the same |
| CN1195576C (zh) | 1999-09-28 | 2005-04-06 | 东丽株式会社 | 复合半透膜的制造方法 |
| US6337018B1 (en) * | 2000-04-17 | 2002-01-08 | The Dow Chemical Company | Composite membrane and method for making the same |
| US7279097B2 (en) | 2003-06-18 | 2007-10-09 | Toray Industries, Inc. | Composite semipermeable membrane, and production process thereof |
| CN1263535C (zh) * | 2004-06-12 | 2006-07-12 | 国家海洋局杭州水处理技术研究开发中心 | 新型聚酰胺反渗透复合膜及其制备方法 |
| US7479300B2 (en) * | 2005-03-30 | 2009-01-20 | Woongjin Chemical Co., Ltd. | Composite polyamide reverse osmosis membrane and method of producing the same |
| US8092918B2 (en) * | 2005-08-16 | 2012-01-10 | Ge Osmonics, Inc. | Polyamide matrices and methods for their preparation and use |
| US20070251883A1 (en) | 2006-04-28 | 2007-11-01 | Niu Q Jason | Reverse Osmosis Membrane with Branched Poly(Alkylene Oxide) Modified Antifouling Surface |
| WO2007133362A1 (en) | 2006-05-12 | 2007-11-22 | Dow Global Technologies Inc. | Modified membrane |
| WO2008035524A1 (fr) * | 2006-09-20 | 2008-03-27 | Ntn Corporation | Procédé de trempe restreinte pour un élément annulaire |
| CN100443150C (zh) | 2006-09-22 | 2008-12-17 | 中国科学院长春应用化学研究所 | 含联苯结构的芳香聚酰胺反渗透复合膜 |
| JP4921565B2 (ja) | 2007-02-05 | 2012-04-25 | ダウ グローバル テクノロジーズ エルエルシー | 修飾ポリアミド膜 |
| US7806275B2 (en) | 2007-05-09 | 2010-10-05 | The United States Of America As Represented By The Secretary Of The Interior, The Bureau Of Reclamation | Chlorine resistant polyamides and membranes made from the same |
| JP2009006279A (ja) * | 2007-06-28 | 2009-01-15 | Nitto Denko Corp | 複合半透膜及びその製造方法 |
| EP3144054B1 (en) * | 2008-04-15 | 2022-11-02 | NanoH2O, Inc. | Polyamide tfc membranes prepared using mono-hydrolyzed trimesoyl chloride |
| US8177978B2 (en) | 2008-04-15 | 2012-05-15 | Nanoh20, Inc. | Reverse osmosis membranes |
| CN101601975A (zh) | 2008-06-10 | 2009-12-16 | 贵阳时代汇通膜科技有限公司 | 一种复合反渗透膜 |
| US8147735B2 (en) | 2008-07-09 | 2012-04-03 | Eltron Research & Development, Inc. | Semipermeable polymers and method for producing same |
| US7815987B2 (en) | 2008-12-04 | 2010-10-19 | Dow Global Technologies Inc. | Polyamide membrane with coating of polyalkylene oxide and polyacrylamide compounds |
| SG171985A1 (en) * | 2008-12-11 | 2011-07-28 | Agency For Science Techonology And Res | Glucose-peg conjugates for reducing glucose transport into a cell |
| JP5262668B2 (ja) * | 2008-12-15 | 2013-08-14 | 東レ株式会社 | 複合ナノろ過膜 |
| WO2011008549A2 (en) * | 2009-06-29 | 2011-01-20 | NanoH2O Inc. | Improved hybrid tfc ro membranes with nitrogen additives |
| US20110049055A1 (en) | 2009-08-31 | 2011-03-03 | General Electric Company | Reverse osmosis composite membranes for boron removal |
| CN102665883A (zh) | 2009-12-22 | 2012-09-12 | 东丽株式会社 | 半透膜及其制造方法 |
| SG181590A1 (en) | 2009-12-24 | 2012-07-30 | Toray Industries | Composite semipermeable membrane and method for producing same |
| KR101928256B1 (ko) | 2010-02-23 | 2018-12-11 | 도레이 카부시키가이샤 | 복합 반투막 및 그의 제조 방법 |
| US8733558B2 (en) | 2010-05-24 | 2014-05-27 | Dow Global Technologies Llc | Composite membrane with coating comprising polyalkylene oxide and biguanide-type compounds |
| NO335286B1 (no) | 2010-06-04 | 2014-11-03 | Tom-Nils Nilsen | Tynnfilmkompositter |
| WO2012014643A1 (ja) * | 2010-07-27 | 2012-02-02 | 株式会社村田製作所 | 高周波モジュール |
| JP5895838B2 (ja) | 2010-08-11 | 2016-03-30 | 東レ株式会社 | 分離膜エレメントおよび複合半透膜の製造方法 |
| KR20140005885A (ko) | 2010-12-28 | 2014-01-15 | 도레이 카부시키가이샤 | 복합 반투막 |
| ES2524318T3 (es) * | 2011-01-24 | 2014-12-05 | Dow Global Technologies Llc | Método para preparar una membrana de poliamida de material compuesto |
| WO2012102942A1 (en) | 2011-01-24 | 2012-08-02 | Dow Global Technologies Llc | Composite polyamide membrane |
| ES2523453T3 (es) | 2011-01-24 | 2014-11-26 | Dow Global Technologies Llc | Método para preparar una membrana de material compuesto de poliamida |
| CN102219673B (zh) | 2011-05-06 | 2014-07-02 | 中国科学院长春应用化学研究所 | 荷正电纳滤复合膜及其制备方法 |
| JP6054968B2 (ja) * | 2011-08-31 | 2016-12-27 | ダウ グローバル テクノロジーズ エルエルシー | アミン−反応性およびリン−含有官能基を含むモノマーから誘導された複合ポリアミド膜 |
| EP2565010A1 (en) * | 2011-09-05 | 2013-03-06 | Ptah AB | A moulding arrangement |
| JP6030657B2 (ja) | 2011-09-29 | 2016-11-24 | ダウ グローバル テクノロジーズ エルエルシー | 加水分解アシルハライド化合物を調製するためのインサイチュ法 |
| US9029600B2 (en) | 2011-09-29 | 2015-05-12 | Dow Global Technologies Llc | Method for preparing high purity mono-hydrolyzed acyl halide compound |
| WO2013048765A1 (en) * | 2011-09-29 | 2013-04-04 | Dow Global Technologies Llc | Composite polyamide membrane derived from carboxylic acid containing acyl halide monomer |
| WO2013048763A1 (en) | 2011-09-29 | 2013-04-04 | Dow Global Technologies Llc | Method for solubilizing carboxylic acid-containing compound in hydrocarbon solvent |
| WO2013103666A1 (en) | 2012-01-06 | 2013-07-11 | Dow Global Technologies Llc | Composite polyamide membrane |
| CN104470627B (zh) | 2012-07-19 | 2018-05-11 | 陶氏环球技术有限责任公司 | 复合聚酰胺膜 |
| CN104918687A (zh) | 2013-01-14 | 2015-09-16 | 陶氏环球技术有限责任公司 | 使用非极性溶剂的掺合物经由界面聚合制造复合聚酰胺膜 |
| WO2014109947A1 (en) | 2013-01-14 | 2014-07-17 | Dow Global Technologies Llc | Composite polyamide membrane comprising substituted benzamide monomer |
| JP6272905B2 (ja) | 2013-01-14 | 2018-01-31 | ダウ グローバル テクノロジーズ エルエルシー | トリ−ヒドロカルビルホスフェートを含む複合ポリアミド膜 |
| US9051412B2 (en) * | 2013-03-14 | 2015-06-09 | Bayer Materialscience Llc | Base-catalyzed, long chain, active polyethers from short chain DMC-catalyzed starters |
| US9289729B2 (en) * | 2013-03-16 | 2016-03-22 | Dow Global Technologies Llc | Composite polyamide membrane derived from carboxylic acid containing acyl halide monomer |
| US8999449B2 (en) | 2013-03-27 | 2015-04-07 | Dow Global Technologies Llc | Composite polyamide membrane derived from aromatic monomer including anhydride and sulfonyl halide functional groups |
| WO2014179024A1 (en) | 2013-05-03 | 2014-11-06 | Dow Global Technologies Llc | Composite polyamide membrane derived from an aliphatic acyclic tertiary amine compound |
| JP6535010B2 (ja) * | 2014-01-09 | 2019-06-26 | ダウ グローバル テクノロジーズ エルエルシー | 好ましいアゾ含有量を有する複合ポリアミド皮膜 |
| KR102293862B1 (ko) * | 2014-09-15 | 2021-08-25 | 삼성전자주식회사 | 반도체 소자의 제조 방법 |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0467533A1 (en) * | 1990-07-18 | 1992-01-22 | Rheox International, Inc. | Polyamide compositions and sealant formulations comprising them |
| US6406626B1 (en) * | 1999-01-14 | 2002-06-18 | Toray Industries, Inc. | Composite semipermeable membrane, processfor producing the same, and method of purifying water with the same |
| CN102151499A (zh) * | 2011-02-28 | 2011-08-17 | 浙江理工大学 | 一种聚酰胺复合纳滤膜及其制备方法 |
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