CN104470629A - 源自于多官能胺以及不同的多官能胺-反应性单体的组合的膜 - Google Patents
源自于多官能胺以及不同的多官能胺-反应性单体的组合的膜 Download PDFInfo
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- CN104470629A CN104470629A CN201380037799.5A CN201380037799A CN104470629A CN 104470629 A CN104470629 A CN 104470629A CN 201380037799 A CN201380037799 A CN 201380037799A CN 104470629 A CN104470629 A CN 104470629A
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- Prior art keywords
- amine
- reactive
- monomer
- polyfunctional amine
- acid
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- 150000001412 amines Chemical class 0.000 title claims abstract description 56
- 239000000178 monomer Substances 0.000 title claims abstract description 48
- 239000004952 Polyamide Substances 0.000 claims abstract description 34
- 229920002647 polyamide Polymers 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- -1 carboxylic acid halides Chemical class 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 6
- 150000004820 halides Chemical class 0.000 abstract description 4
- 150000003461 sulfonyl halides Chemical class 0.000 abstract 3
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000004760 aramid Substances 0.000 description 12
- 229920003235 aromatic polyamide Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229920002492 poly(sulfone) Polymers 0.000 description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 229940018564 m-phenylenediamine Drugs 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001263 acyl chlorides Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 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 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000001261 hydroxy acids Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000777 acyl halide group Chemical group 0.000 description 3
- 150000001266 acyl halides Chemical group 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- ILJDFBVQZFJJJS-UHFFFAOYSA-N butyl $l^{1}-oxidanylformate Chemical compound CCCCOC([O])=O ILJDFBVQZFJJJS-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- VDBLRYZZFGJCLY-UHFFFAOYSA-N 1,3-dioxo-2-benzofuran-5-sulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=C2C(=O)OC(=O)C2=C1 VDBLRYZZFGJCLY-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XYWDFUIKKLBQPL-UHFFFAOYSA-N ClC1=C(C(=O)Cl)C=CC=C1S(=O)(=O)Cl Chemical compound ClC1=C(C(=O)Cl)C=CC=C1S(=O)(=O)Cl XYWDFUIKKLBQPL-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 125000005647 linker group Chemical group 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052699 polonium Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- GPSHWNLDDARPCO-UHFFFAOYSA-N 10-chloro-10-oxodecanoic acid Chemical compound OC(=O)CCCCCCCCC(Cl)=O GPSHWNLDDARPCO-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
- 150000004999 2,4-diaminotoluenes Chemical class 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- OHFLNNVKHIOKKU-UHFFFAOYSA-N 3-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C(Cl)=O)=C1 OHFLNNVKHIOKKU-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
- AKRGLPCOXCYKNF-UHFFFAOYSA-N 5-chloro-5-oxopentanoic acid Chemical compound OC(=O)CCCC(Cl)=O AKRGLPCOXCYKNF-UHFFFAOYSA-N 0.000 description 1
- YJKJKJNKFIDCMN-UHFFFAOYSA-N 6-chloro-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(Cl)=O YJKJKJNKFIDCMN-UHFFFAOYSA-N 0.000 description 1
- YZOFOUXOAJQSIU-UHFFFAOYSA-N 8-chloro-8-oxooctanoic acid Chemical compound OC(=O)CCCCCCC(Cl)=O YZOFOUXOAJQSIU-UHFFFAOYSA-N 0.000 description 1
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- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
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- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 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
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
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- COQLPRJCUIATTQ-UHFFFAOYSA-N Uranyl acetate Chemical compound O.O.O=[U]=O.CC(O)=O.CC(O)=O COQLPRJCUIATTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
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- 150000007824 aliphatic compounds Chemical class 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- JTMZBRWRXFAITF-UHFFFAOYSA-N azane;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonic acid Chemical compound [NH4+].C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C JTMZBRWRXFAITF-UHFFFAOYSA-N 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 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 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
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- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1214—Chemically bonded layers, e.g. cross-linking
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyamides (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
用于制造包含多孔载体和薄膜聚酰胺层的复合聚酰胺膜的方法,其中所述方法包括以下步骤:向所述多孔载体的表面施加多官能胺单体以及胺反应性化合物的组合,和使所述成分反应以形成薄膜聚酰胺层,其中所述胺反应性化合物包括:i)包含两到三个选自酰卤、磺酰卤和酸酐的胺反应性部分的多官能胺反应性单体,ii)包含至少四个选自酰卤、磺酰卤和酸酐的胺反应性部分的多官能胺反应性单体,和iii)包含至少一个羧酸部分或其盐和至少一个选自酰卤和磺酰卤的胺反应性部分的酸化合物。
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)和多官能胺反应性(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。各种其它多官能胺反应性单体已被研究。例如,Cadotte的US 4259183描述了二和三官能酰卤单体的组合,例如间苯二酰氯或对苯二酰氯与均苯三甲酰氯的组合。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。四酰卤单体也已经在文献中描述,参见例如:i)Lei,Li等,Polyamide Thin Film Composite MembranesPrepared from Isomeric Biphenyl Tetraacyl Chloride and m-Phenylenediamine,Journal of Membrane Science,315(2008),20-27页;ii)R.J.Peterson,Composite Reverse Osmosis and NanofiltrationMembranes,Journal of Membrane Science,83(1993),81-150页(参见例如116-117页)和US 6162358,这二者描述了使用金刚烷-2,6二酮-1,3,5,7-四甲酰氯,和iii)CN 102219673,其描述了利用5,5'-亚甲基二间苯二酰氯、均苯三酰氯和哌嗪的组合形成纳米过滤膜。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。
将羧酸部分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(例如二氧化硅)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。多官能酰卤单体例如TMC的一部分酰卤基团在所述界面聚合期间或之后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可通过利用具有羧酸部分的胺反应性单体而进一步增加。参见例如WO 2010/120326(也参见US8177978)。不幸的是,引入这样的含羧酸单体的程度具有限制。WO 2010/120326证明了单水解均苯三甲酰氯的上限为0.02125wt%;超过这个限度所述聚酰胺结构将失去完整性(即注意到在WO2010/120326的图14中显示的盐截留率的极大丧失)。
发明内容
本发明包括复合聚酰胺膜及其制造和使用方法。在一种实施方式中,本发明包括用于制造包括多孔载体和薄膜聚酰胺层的复合聚酰胺膜的方法,所述方法包括以下步骤:向所述多孔载体的表面施加多官能胺单体以及胺反应性化合物组合,和使所述成分反应以形成薄膜聚酰胺层,其中所述胺反应性化合物包括:
i)包含两到三个选自酰卤、磺酰卤和酸酐的胺反应性部分的多官能胺反应性单体,
ii)包含至少四个选自酰卤、磺酰卤和酸酐的胺反应性部分的多官能胺反应性单体,和
iii)包含至少一个羧酸部分或其盐以及至少一个选自酰卤和磺酰卤的胺反应性部分的酸化合物。
描述了许多其他的实施方式。
发明具体描述
本发明不具体限于特定构造或形状的复合膜。例如,本发明适用于通常可用于反渗透(RO)的平板状、管状和中空纤维聚酰胺膜。RO膜对几乎所有的溶解盐相对不可渗透,并通常截留超过大约95%(优选大于96.5%、99%并且甚至99.5%)的单价离子盐,例如氯化钠。RO膜还通常截留超过约95%的无机分子以及分子量大于约100道尔顿的有机分子。
在一种实施方式中,本发明包括标准平板状构造,其包括无纺背衬网(例如PET纱)的底层(背面)、具有通常厚度约25-125μm的多孔载体中间层,和顶层(正面),所述顶层包含厚度优选小于约1微米、例如0.01微米至1微米但是更优选约0.01至0.1μm的薄膜聚酰胺层。所述多孔载体优选是聚合材料,其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多孔载体: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,和各种卤代聚合物例如聚偏氟乙烯。对于RO应用,所述多孔载体提供了强度,但是由于它比较高的孔隙度,对流体流动性提供较低的抗性。由于它比较薄,所述聚酰胺层经常根据它在多微孔载体上的涂层覆盖度或负载量描述,例如从约2至5000mg聚酰胺/平方米多孔载体表面积,并更优选约50至500mg/m2。如US 4277344和US 6878278所述,优选通过多官能胺单体和多官能胺反应性单体之间在多孔载体表面上进行界面缩聚反应,来制备聚酰胺层。更具体地说,可以通过多官能胺单体与多官能胺反应性单体(其中每个术语意图是指利用单一物质或多种物质二者)在多孔载体的至少一个表面上进行界面聚合,来制备所述聚酰胺膜层。在本文中使用时,术语“聚酰胺”是指沿着分子链存在酰胺键(—C(O)NH—)的聚合物。所述多官能胺和多官能胺反应性单体最通常通过从溶液进行涂布的步骤施加于多孔载体,其中所述多官能胺单体通常从水基或极性溶液涂布,而多官能胺反应性单体从有机基或非极性溶液涂布。虽然所述涂布步骤不需要按照特定的次序,但优选多官能胺单体首先涂布在多孔载体上,然后是多官能胺反应性单体。涂布可以通过喷涂、膜涂、辊涂或通过使用浸渍槽以及其它涂布技术完成。多余的溶液可以通过气刀、干燥器、烘箱等等从所述载体上除去。一旦彼此发生接触,所述酰卤和多官能胺单体在它们的表面处界面反应,形成聚酰胺层。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。所述多官能胺反应性单体与多官能胺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。除去多余的溶剂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。
所述多官能胺单体没有特别限制,代表性的实例包含至少两个伯或仲氨基,并且可以是芳族的(例如间苯二胺、对苯二胺、1,3,5-三氨基苯、1,3,4-三氨基苯、3,5-二氨基苯甲酸、2,4-二氨基甲苯、2,4-二氨基茴香醚、和二甲苯二胺)或脂族的(例如乙二胺、丙二胺和三(2-二氨基乙基)胺)。优选的例子包括包含两个或三个伯氨基的多官能胺单体。一种优选的多官能胺是间苯二胺(mPD)。多官能胺单体可以作为极性溶液施加于多孔载体。所述极性溶液可以含有约0.1至约20重量%并更优选约0.5至约8重量%的多官能胺单体。一旦涂布在多孔载体上,可以任选除去多余的溶液。
在一种实施方式中,本发明包括向多孔载体施加至少两种不同的多官能胺反应性单体的组合以及不同的酸化合物。所述各种成分可以单独地、例如相继涂布,但是优选合并并从共同的非极性溶液涂布。所述成分在非极性溶剂中的溶解范围可以从约0.01至10重量%、优选0.05至4重量%(当合并时),并可以作为连续或分批涂布操作的一部分进行传递。非极性溶剂的选择没有特别的限制并且可以使用多种溶剂的组合。所述溶剂优选在20℃(101kPa)下是液体。所述溶剂优选具有小于800ppm的水溶解度(并更优选小于500、400、300、或200,或在一些实施方式中,小于150ppm)。在本文中使用时,术语“水溶解度”是指通过ASTM D4928-11测量,在20℃(101kPa)下测量的可溶于选定烃溶剂中的水的浓度。可应用的溶剂的非限制性例子包括:链烷烃(例如己烷,环己烷,庚烷,辛烷,十二烷)、异链烷烃(例如ISOPARTM L)、芳烃(例如SolvessoTM芳族液体,VarsolTM未脱芳烃的液体,苯,烷基化苯(例如甲苯,二甲苯,三甲苯异构体,二乙苯))和卤代烃(例如FREONTM系列,氯苯,二和三氯苯)或其混合物。优选的溶剂包含1至40、2至20或3至15重量%的芳烃含量,例如1,3,5-三甲基苯。其他优选的溶液包含超过50重量%的链烷烃或异链烷烃,例如ISOPARTML。还有其他的实施方式符合前面这两个标准。
代表性的多官能胺反应性化合物没有特别的限制,并且可以是芳族或脂族的(直链或环状的),并且可以独自或组合使用。包含两到三个酰卤部分的芳族多官能胺反应性单体的非限制性例子包括:均苯三甲酰氯,对苯二甲酰氯,间苯二甲酰氯,联苯基二羧酰氯,萘二羧酰氯,吡啶-3,5-二甲酰氯,和吡啶-2,6-二甲酰氯。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。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。一种特别优选的多官能胺反应性单体是均苯三甲酰氯(TMC)。前述化合物中的一个或多个酰卤部分可以用磺酰卤或酸酐部分置换。代表性例子包括:3-(氯磺酰基)苯甲酸次氯酸酐(benzoic hypochlorousanhydride);3,5-双(氯磺酰基)苯甲酸次氯酸酐;1,3-二氧代-1,3-二氢异苯并呋喃-5-磺酰氯;和1,3-二氧代-1,3-二氢异苯并呋喃-5-甲酰氯。
包含至少四个胺反应性部分的多官能胺反应性单体可以是四酰卤单体,包括金刚烷-2,6-二酮-1,3,5,7-四甲酰氯、1,2,4,5-苯四羧酰氯、和萘-四甲酰氯。这样的单体的优选类别由式(I)表示:
式(I):
其中A选自:氧(-O-);碳(-C-);硅(-Si-);其各自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,优选氯。在优选实施方式中,A是未取代的碳,例如5,5’-亚甲基二间苯二甲酰氯。前述化合物中的一个或多个酰卤部分可以用磺酰卤或酸酐部分置换。代表性例子包括3-(氯磺酰基)苯甲酰氯,3,5-双(氯磺酰基)苯甲酰氯,1,3-二氧代-1,3-二氢异苯并呋喃-5-甲酰氯,1,3-二氧代-1,3-二氢异苯并呋喃-5-磺酰氯,苯并[1,2-c:4,5-c']二呋喃-1,3,5,7-四酮,和5-(氯代磺酰基)间苯二甲酰氯。酸化合物的选择没有特别的限制,但是全部包含:(a)至少一个羧酸部分或其盐和(b)至少一个酰卤或酸酐部分。在优选实施方式中,所述酸化合物不同于前述的多官能胺反应性单体。非限制性例子包括前述包含两到三个酰卤基团的多官能胺反应性单体的单和二水解对应物,以及包含至少四个胺反应性部分的多官能卤化物单体的单、二和三水解对应物。优选的酸化合物包括单水解的均苯三甲酰氯(mhTMC)和单水解的间苯二甲酰氯(mhIPC)。其它的例子包括由式(II)表示的:
式(II):
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(II)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。
包含至少一个酸酐基团和至少一个羧酸基团的酸化合物的代表性例子包括:3,5-双(((丁氧基羰基)氧基)羰基)苯甲酸,1,3-二氧代-1,3-二氢异苯并呋喃-5-羧酸,3-(((丁氧基羰基)氧基)羰基)苯甲酸,和4-(((丁氧基羰基)氧基)羰基)苯甲酸。
所述非极性涂层溶液优选包含至少0.1、0.2.、0.3、0.4或0.5wt%的所述包含两到三个胺反应性部分的多官能胺反应性单体。优选的范围是从0.1至0.3wt%。
所述非极性涂层溶液优选包含至少0.01、0.025、0.04、0.05和甚至0.6wt%的所述酸化合物。优选的范围是从0.02至0.6wt%。
所述非极性涂层溶液优选包含至少0.005、0.01、0.02或0.1wt%的所述包含至少四个胺反应性部分的单体。优选的范围是从0.005至0.02wt%。
所述非极性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。US 6878278、US 6723241、US 6562266和US 6337018描述了在进行界面聚合之前添加可与所述非极性溶液结合的广泛范围的代表性络合剂。一类这样的络合剂由式(III)表示:α(Lxβ)y
其中α是不含硫的结合芯,选自属于下列范围的元素:(a)IIIA-VIB族(即,IIIA、IVA、VA、VIA、VIIA、VIIIA、IB、IIB、IIIB、IVB、VB、VIB族)和(b)常规IUPAC元素周期表的3-6周期(即,以Na、K、Rb和Cs开始的周期)。常规IUPAC元素周期表形式的IIIA至VIB族对应于:“新符号”IUPAC元素周期表的3-16族和CAS版元素周期表的IIIB-VIA族。为了避免任何混淆,在此的进一步参考将利用常规IUPAC元素周期表,即IIIA族对应于以Sc、Y、La等开始的栏,VIB族对应于以O、S、Se、Te、Po开始的栏。具体例子包括:(1)下列金属:铝,钪,钛,钒,铬,锰,铁,钴,镍,铜,锌,镓,锗,砷,钇,锆,铌,钼,锝,钌,铑,钯,银,镉,铟,锡,锑,碲,镧,铈,镨,钕,钷,钐,铕,钆,铽,镝,钬,铒,铥,镱,镥,铪,钽,钨,铼,锇,铱,铂,金,汞,铊,铅,铋(铋通常不优选)和钋;(2)下列半导体:硅,硒和锗;以及(3)磷。特别优选的结合芯包括:Al、Si、P、As、Sb、Se和Te,以及金属例如:Fe、Cr、Co、Ni、Cu和Zn。L是任选的化学连接基团,相同或不同,选自例如下列的键:含碳部分,例如芳基、烷烃、烯烃、--O--、--S--、--N--、--H--、--P--、--O--P--、和--O--P--O--(各自可以是取代或未取代的)。β是相同或不同的增溶基团,包含1至12个碳原子,它可以是取代或未取代的并且可以包含由L定义的内部连接基团。例子包括具有1至6个碳原子的脂族和芳烃基团、芳基、杂环基和烷基。"x"是0至1的整数,“y”是1至5、优选2至4的整数。虽然取决于所使用的具体的溶剂和酰卤物质,但是下列络合剂通常可用于本发明:磷(例如膦、磷酸酯)、铋、砷和锑的三苯基衍生物;磷的烷氧酯,包括亚磷酸三丁酯和二丁酯;有机金属络合物,例如二茂铁和四乙基铅以及铁(II)、铁(III)、钴(III)和Cr(III)的乙酰丙酮络合物。这样的络合剂的优选类别由式(IV)表示。
式(IV):
其中“P”是磷,“O”是氧,R1、R2和R3独立地选自含碳部分。术语“含碳部分”是用来指支链和非支链的非环基团,例如甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、2-戊基、3-戊基、叔丁基等,它们可以是未取代的或取代的(例如用酰胺基、醚基、酯基、砜基、羰基、酸酐、氰化物、腈、异氰酸酯、氨基甲酸酯、β-羟基酯、双和三键等取代);和环状基团,例如环戊基、环己基、芳烃例如苯基、杂环(例如吡啶)等,它们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、酯等取代)。环部分可以通过脂族连接基团例如甲基、乙基等与磷原子连接。优选的含碳部分包括未取代的、支链或非支链的C1-C12基团,更优选C1-C8脂族基团,例如:甲基,乙基,丙基,异丙基,丁基,2-甲基丁基,3-甲基丁基,2-乙基丁基,戊基,己基等等。另外,所述部分包括苯基。当使用时,前述的络合剂优选以约0.001至2%w/w的浓度在涂层溶液内使用。
当利用2000ppm NaCl水溶液在225psi、25℃和pH 8下测试时,根据本方法制造的TFC膜优选具有大于95、98、99并且甚至99.5%的NaCl截留率。在其他实施方式中,当在相同的条件下测试时,根据本发明制造的TFC膜具有大于18、22或甚至25GFD的通量值。在又一组实施方式中,TFC膜具有前述的截留率和通量值的所有组合,例如截留率大于99.5%和通量大于18、22和甚至25GFD。
作为本方法的结果,可制造与文献中描述的相比较羧酸含量增加的薄膜聚酰胺层。在优选实施方式中,所述薄膜聚酰胺层特征为具有至少0.16、0.30、0.45、0.50、0.55mol/kg、并优选至少0.6mol/kg聚酰胺的解离羧酸根含量。所述聚酰胺层的“解离羧酸根含量”可通过银滴定和卢瑟福(Rutherford)背散射测量根据以下方法测定:
(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,所述膜的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,O.等在J.of Membrane Sci.2006,282,71-81和Environmental Science&Technology 2008,42(14),5260-5266中描述。模拟程序可用于拟合两层(厚的聚砜层在薄的聚酰胺层底下)或三层体系(聚砜,聚酰胺,和表面涂层)。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,可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。
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的聚酰胺质量和每单位面积的羧酸基团摩尔数来确定,例如通过下述的络合和定量方法。
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(WeiXie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。
实施例
下面描述的所有TFC膜都利用采用中试规模生产设备产生的聚砜多孔载体制造。所述聚砜载体切成片,附着于线框上并在水中浸大约30分钟。然后取出所述载体并在包含4.5wt%三乙基樟脑磺酸铵、0.06wt%十二烷基硫酸钠和4wt%mPD溶液的涂层水溶液中浸泡大约20分钟。所述载体然后放在塑料板顶部的纸巾上并用辊压掉多余的溶液。将密封垫和塑料片放在所述载体上并在四边夹紧以制成边缘防漏的密封。所述载体然后用非极性溶液涂布,所述溶液包含Isopar L、4wt%均三甲苯和均苯三甲酰氯(“TMC”),以及如下面表I或表II指示的各种量的mhTMC和5,5’-亚甲基间苯二甲酰氯(“Tetra”)或各种量的mh TMC和苯-1,2,4,5-四甲酰氯;然而,在每个实施例中,TMC和Tetra或苯-1,2,4,5-四甲酰氯(苯四酰氯)的总浓度保持在0.3wt%不变。然后倒掉剩余的涂层溶液并用80mL己烷清洗所述膜,空气干燥大约一分钟,并在试验之前储存在RO水中。从每个膜切出2个试件并在平面池台架测试试验工作台中在室温下利用2000ppm NaCl水溶液以225psi、25℃和pH 8进行试验。测量通量和NaCl截留率,结果概括在表I和表II中。
表I:
表II.
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 (8)
1.用于制造包含多孔载体和薄膜聚酰胺层的复合聚酰胺膜的方法,其中所述方法包括以下步骤:向所述多孔载体的表面施加多官能胺单体以及胺反应性化合物的组合,和使所述成分反应以形成薄膜聚酰胺层,其中所述胺反应性化合物包括:
i)包含两到三个选自酰卤、磺酰卤和酸酐的胺反应性部分的多官能胺反应性单体,
ii)包含至少四个选自酰卤、磺酰卤和酸酐的胺反应性部分的多官能胺反应性单体,和
iii)包含至少一个羧酸部分或其盐和至少一个选自酰卤和磺酰卤的胺反应性部分的酸化合物。
2.任一前述权利要求的方法,其中所述薄膜聚酰胺层特征为在pH 9.5时具有至少0.16mol/kg的解离羧酸根含量。
3.任一前述权利要求的方法,其中当利用2000ppm NaCl水溶液在225psi、25℃和pH 8下测试时,所述复合聚酰胺膜具有大于99%的NaCl截留率。
4.任一前述权利要求的方法,其中当利用2000ppm NaCl水溶液在225psi、25℃和pH 8下测试时,所述复合聚酰胺膜具有大于99.5%的NaCl截留率和大于24GFD的通量。
5.任一前述权利要求的方法,其中所述包含至少四个胺反应性部分的多官能胺反应性单体由式(I)表示:
其中A选自:氧(-O-)、碳(-C-)、硅(-Si-),其各自可以是未取代或用具有1-4个碳原子的烷基取代;或羰基(-C(O)-),和X是相同或不同的并选自卤素。
6.任一前述权利要求的方法,其中所述包含两到三个胺反应性部分的多官能胺反应性单体包含:均苯三甲酰氯。
7.任一前述权利要求的方法,其中所述酸化合物包含:单水解均苯三甲酰氯。
8.任一前述权利要求的方法,其中所述多官能胺反应性单体从包含至少0.025重量%所述酸化合物的共同非极性溶液涂布在所述多孔载体上。
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Cited By (1)
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Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9399196B2 (en) | 2011-08-31 | 2016-07-26 | Dow Global Technologies Llc | Composite polyamide membrane derived from monomer including amine-reactive and phosphorous-containing functional groups |
WO2013048764A1 (en) | 2011-09-29 | 2013-04-04 | Dow Global Technologies Llc | Method for preparing high purity mono-hydrolyzed acyl halide compound |
ES2806675T3 (es) | 2012-01-06 | 2021-02-18 | Ddp Specialty Electronic Mat Us Inc | Método de preparación de una membrana de poliamida de material compuesto |
US9630149B2 (en) | 2012-07-19 | 2017-04-25 | Dow Global Technologies Llc | Composite polyamide membrane with improved structure |
WO2014109947A1 (en) | 2013-01-14 | 2014-07-17 | Dow Global Technologies Llc | Composite polyamide membrane comprising substituted benzamide monomer |
WO2014109946A1 (en) * | 2013-01-14 | 2014-07-17 | Dow Global Technologies Llc | Composite polyamide membrane |
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 |
US9387442B2 (en) | 2013-05-03 | 2016-07-12 | Dow Global Technologies Llc | Composite polyamide membrane derived from an aliphatic acyclic tertiary amine compound |
EP3077088B1 (en) | 2013-12-02 | 2017-12-27 | Dow Global Technologies LLC | Method for forming a composite polyamide membrane post treated with nitrious acid |
WO2015084512A1 (en) | 2013-12-02 | 2015-06-11 | Dow Global Technologies Llc | Composite polyamide membrane treated with dihyroxyaryl compounds and nitrous acid |
WO2015105630A1 (en) * | 2014-01-07 | 2015-07-16 | Dow Global Technologies Llc | Treatment of aqueous mixtures containing anionic surfactants using fouling resistant reverse osmosis membrane |
CA2935685A1 (en) * | 2014-01-07 | 2015-07-16 | Dow Global Technologies Llc | Desalination of aqueous mixture containing nano-sized particles using fouling resistant reverse osmosis membrane |
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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 |
WO2015175254A1 (en) * | 2014-05-14 | 2015-11-19 | Dow Global Technologies Llc | Composite polyamide membrane post-treated with nitrous acid |
WO2015175256A1 (en) * | 2014-05-14 | 2015-11-19 | Dow Global Technologies Llc | Composite polyamide membrane post treated with nitrous acid |
CN106232216B (zh) * | 2014-05-14 | 2019-10-11 | 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 |
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 |
WO2018003943A1 (ja) * | 2016-06-29 | 2018-01-04 | 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 |
US12098280B2 (en) | 2017-09-07 | 2024-09-24 | Sabanci Universitesi | Zwitterionic thin film composite membranes with high performance |
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 |
AU2020207924A1 (en) * | 2019-01-18 | 2021-07-08 | Toray Industries, Inc. | Carbon membrane for fluid separation use |
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 |
KR102309228B1 (ko) * | 2019-12-27 | 2021-10-05 | 닛토덴코 가부시키가이샤 | 복합 반투막 |
AU2022341820A1 (en) * | 2021-09-09 | 2024-02-15 | 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 (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0556569A2 (en) * | 1992-01-22 | 1993-08-25 | Nitto Denko Corporation | Composite reverse osmosis membrane and novel acid chloride |
US6162358A (en) * | 1998-06-05 | 2000-12-19 | Nl Chemicals Technologies, Inc. | High flux reverse osmosis membrane |
CN1292723A (zh) * | 1999-01-14 | 2001-04-25 | 东丽株式会社 | 复合半透膜、其制造方法和使用它的水净化方法 |
CN1441693A (zh) * | 2000-04-17 | 2003-09-10 | 陶氏环球技术公司 | 复合膜及其制造方法 |
CN102219673A (zh) * | 2011-05-06 | 2011-10-19 | 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 |
WO2011152735A1 (en) * | 2010-06-04 | 2011-12-08 | Tom Nils Nilsen | Thin film composites |
Family Cites Families (109)
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 |
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 |
US4529646A (en) | 1984-07-30 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Production of composite membranes |
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 |
US4626468A (en) | 1986-04-23 | 1986-12-02 | E. I. Du Pont De Nemours And Company | Microporous support layer with interfacially polymerized copolyamide thereon |
US4719062A (en) | 1986-04-23 | 1988-01-12 | E. I. Du Pont De Nemours And Company | Extractant-surfactant post-treatments of permselective composite membranes |
US4812270A (en) | 1986-04-28 | 1989-03-14 | Filmtec Corporation | Novel water softening membranes |
US4812238A (en) * | 1987-01-15 | 1989-03-14 | The Dow Chemical Company | Membranes prepared via reaction of diazonium compounds or precursors |
US4888116A (en) | 1987-01-15 | 1989-12-19 | The Dow Chemical Company | Method of improving membrane properties 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 |
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 |
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 |
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 |
US5180802A (en) * | 1990-07-18 | 1993-01-19 | Rheox, Inc. | Monoamine capped non-reactive polyamide composition |
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 |
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 |
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 |
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 |
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 |
WO1999001208A1 (fr) | 1997-07-02 | 1999-01-14 | Nitto Denko Corporation | Membrane composite d'osmose inverse et procede de production |
US5876602A (en) | 1997-11-04 | 1999-03-02 | The Dow Chemical Company | Treatment of composite polyamide membranes to improve performance |
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 |
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 |
US7882963B2 (en) | 2006-05-12 | 2011-02-08 | 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 |
US8177978B2 (en) | 2008-04-15 | 2012-05-15 | Nanoh20, Inc. | Reverse osmosis membranes |
JP5856479B2 (ja) * | 2008-04-15 | 2016-02-09 | ナノエイチツーオー・インコーポレーテッド | 複合ナノ粒子tfc膜 |
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 |
US20110243851A1 (en) * | 2008-12-11 | 2011-10-06 | Agency For Science, Technology And Research | 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 |
JP5807547B2 (ja) | 2009-12-22 | 2015-11-10 | 東レ株式会社 | 半透膜およびその製造方法 |
WO2011078047A1 (ja) | 2009-12-24 | 2011-06-30 | 東レ株式会社 | 複合半透膜およびその製造方法 |
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 |
JP5516738B2 (ja) * | 2010-07-27 | 2014-06-11 | 株式会社村田製作所 | 高周波モジュール |
WO2012020680A1 (ja) | 2010-08-11 | 2012-02-16 | 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 |
WO2012090862A1 (ja) | 2010-12-28 | 2012-07-05 | 東レ株式会社 | 複合半透膜 |
EP2632577B1 (en) | 2011-01-24 | 2014-10-01 | Dow Global Technologies LLC | Method for making a composite polyamide membrane |
CN103328083B (zh) | 2011-01-24 | 2018-02-09 | 陶氏环球技术有限责任公司 | 复合聚酰胺膜 |
US20130287944A1 (en) * | 2011-01-24 | 2013-10-31 | Dow Global Technologies Llc | Composite polyamide membrane |
CN102151499B (zh) * | 2011-02-28 | 2013-01-30 | 浙江理工大学 | 一种聚酰胺复合纳滤膜及其制备方法 |
US9399196B2 (en) | 2011-08-31 | 2016-07-26 | Dow Global Technologies Llc | Composite polyamide membrane derived from monomer including amine-reactive and phosphorous-containing functional groups |
EP2565010A1 (en) * | 2011-09-05 | 2013-03-06 | Ptah AB | A moulding arrangement |
CN103328088B (zh) | 2011-09-29 | 2016-02-03 | 陶氏环球技术有限责任公司 | 用于在烃类溶剂中增溶含羧酸化合物的方法 |
KR101946792B1 (ko) * | 2011-09-29 | 2019-02-13 | 다우 글로벌 테크놀로지스 엘엘씨 | 카복실산 함유 아실 할라이드 단량체로부터 유도된 복합 폴리아미드 멤브레인 |
WO2013048764A1 (en) | 2011-09-29 | 2013-04-04 | Dow Global Technologies Llc | Method for preparing high purity mono-hydrolyzed acyl halide compound |
KR102004232B1 (ko) | 2011-09-29 | 2019-07-26 | 다우 글로벌 테크놀로지스 엘엘씨 | 가수분해된 아실 할라이드 화합물을 동일계내에서 제조하는 방법 |
ES2806675T3 (es) | 2012-01-06 | 2021-02-18 | Ddp Specialty Electronic Mat Us Inc | Método de preparación de una membrana de poliamida de material compuesto |
US9630149B2 (en) * | 2012-07-19 | 2017-04-25 | Dow Global Technologies Llc | Composite polyamide membrane with improved structure |
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 |
WO2014109946A1 (en) | 2013-01-14 | 2014-07-17 | Dow Global Technologies Llc | Composite polyamide membrane |
WO2014109947A1 (en) | 2013-01-14 | 2014-07-17 | Dow Global Technologies Llc | Composite polyamide membrane comprising substituted benzamide monomer |
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 |
US9387442B2 (en) * | 2013-05-03 | 2016-07-12 | Dow Global Technologies Llc | Composite polyamide membrane derived from an aliphatic acyclic tertiary amine compound |
ES2677994T3 (es) * | 2014-01-09 | 2018-08-08 | Dow Global Technologies Llc | Membrana de poliamida de material compuesto con contenido azoico preferido |
KR102293862B1 (ko) * | 2014-09-15 | 2021-08-25 | 삼성전자주식회사 | 반도체 소자의 제조 방법 |
-
2013
- 2013-07-03 US US14/407,366 patent/US9630149B2/en active Active
- 2013-07-03 WO PCT/US2013/049178 patent/WO2014014664A1/en active Application Filing
- 2013-07-03 CN CN201380037799.5A patent/CN104470629B/zh not_active Expired - Fee Related
- 2013-07-03 US US14/406,994 patent/US9610542B2/en active Active
- 2013-07-03 WO PCT/US2013/049182 patent/WO2014014668A1/en active Application Filing
- 2013-07-03 EP EP13737111.8A patent/EP2858740B8/en active Active
- 2013-07-03 US US14/407,013 patent/US9925500B2/en not_active Expired - Fee Related
- 2013-07-03 US US14/405,697 patent/US9643128B2/en active Active
- 2013-07-03 CN CN201380038497.XA patent/CN104470626B/zh active Active
- 2013-07-03 WO PCT/US2013/049180 patent/WO2014014666A1/en active Application Filing
- 2013-07-03 WO PCT/US2013/049176 patent/WO2014014662A1/en active Application Filing
- 2013-07-03 CN CN201380038531.3A patent/CN104470628A/zh active Pending
- 2013-07-03 CN CN201380038533.2A patent/CN104487160B/zh active Active
- 2013-07-03 US US14/405,711 patent/US9662615B2/en active Active
- 2013-07-03 JP JP2015523111A patent/JP6334522B2/ja active Active
- 2013-07-03 EP EP13737109.2A patent/EP2874733A1/en not_active Withdrawn
- 2013-07-03 WO PCT/US2013/049177 patent/WO2014014663A1/en active Application Filing
- 2013-07-03 US US14/407,362 patent/US20150157990A1/en not_active Abandoned
- 2013-07-03 CN CN201380038529.6A patent/CN104661733B/zh active Active
- 2013-07-03 CN CN201380038526.2A patent/CN104470627B/zh active Active
- 2013-07-03 WO PCT/US2013/049183 patent/WO2014014669A1/en active Application Filing
- 2013-07-03 JP JP2015523112A patent/JP6386456B2/ja not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0556569A2 (en) * | 1992-01-22 | 1993-08-25 | Nitto Denko Corporation | Composite reverse osmosis membrane and novel acid chloride |
US6162358A (en) * | 1998-06-05 | 2000-12-19 | Nl Chemicals Technologies, Inc. | High flux reverse osmosis membrane |
CN1292723A (zh) * | 1999-01-14 | 2001-04-25 | 东丽株式会社 | 复合半透膜、其制造方法和使用它的水净化方法 |
CN1441693A (zh) * | 2000-04-17 | 2003-09-10 | 陶氏环球技术公司 | 复合膜及其制造方法 |
WO2011152735A1 (en) * | 2010-06-04 | 2011-12-08 | Tom Nils Nilsen | Thin film composites |
CN102219673A (zh) * | 2011-05-06 | 2011-10-19 | 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 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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