CN103328081B - 复合聚酰胺膜 - Google Patents
复合聚酰胺膜 Download PDFInfo
- Publication number
- CN103328081B CN103328081B CN201280006174.8A CN201280006174A CN103328081B CN 103328081 B CN103328081 B CN 103328081B CN 201280006174 A CN201280006174 A CN 201280006174A CN 103328081 B CN103328081 B CN 103328081B
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- CN
- China
- Prior art keywords
- monomer
- carboxylic acid
- chlorocarbonyl
- acid halides
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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 31
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 103
- 150000001412 amines Chemical class 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims abstract description 14
- 239000010409 thin film Substances 0.000 claims abstract description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- -1 carboxylic acid halides Chemical class 0.000 claims description 60
- 125000000524 functional group Chemical group 0.000 claims description 15
- AKRGLPCOXCYKNF-UHFFFAOYSA-N 5-chloro-5-oxopentanoic acid Chemical compound OC(=O)CCCC(Cl)=O AKRGLPCOXCYKNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- GPSHWNLDDARPCO-UHFFFAOYSA-N 10-chloro-10-oxodecanoic acid Chemical compound OC(=O)CCCCCCCCC(Cl)=O GPSHWNLDDARPCO-UHFFFAOYSA-N 0.000 claims description 4
- YJKJKJNKFIDCMN-UHFFFAOYSA-N 6-chloro-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(Cl)=O YJKJKJNKFIDCMN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001260 acyclic compounds Chemical class 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- RFBZPOTVVHLWBP-UHFFFAOYSA-N 11-chloro-11-oxoundecanoic acid Chemical compound OC(=O)CCCCCCCCCC(Cl)=O RFBZPOTVVHLWBP-UHFFFAOYSA-N 0.000 claims description 2
- YZOFOUXOAJQSIU-UHFFFAOYSA-N 8-chloro-8-oxooctanoic acid Chemical compound OC(=O)CCCCCCC(Cl)=O YZOFOUXOAJQSIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 150000001334 alicyclic compounds Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 29
- 150000001266 acyl halides Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 239000010408 film Substances 0.000 description 30
- 150000001263 acyl chlorides Chemical class 0.000 description 18
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000008139 complexing agent Substances 0.000 description 10
- 229940018564 m-phenylenediamine Drugs 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000001728 nano-filtration Methods 0.000 description 8
- 238000001223 reverse osmosis Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000002015 acyclic group Chemical group 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 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
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 125000000962 organic group Chemical group 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
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 2
- UUOFSRVHZJTWDE-UHFFFAOYSA-N 3-chloro-3-oxopropanoic acid Chemical compound OC(=O)CC(Cl)=O UUOFSRVHZJTWDE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 239000007864 aqueous solution Substances 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 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 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 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
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 238000001471 micro-filtration Methods 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
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011780 sodium chloride 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
- 238000005507 spraying Methods 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 238000000108 ultra-filtration 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
- 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
- VZURCUDRBDOEMA-UHFFFAOYSA-N 2,3-dimethylbutanedioyl dichloride Chemical compound ClC(=O)C(C)C(C)C(Cl)=O VZURCUDRBDOEMA-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- FNHMKBLWJZMQPH-UHFFFAOYSA-N 2,4-dioxo-3-oxabicyclo[3.3.1]nonane-7-carboxylic acid Chemical compound C1C2CC(C(=O)O)CC1C(=O)OC2=O FNHMKBLWJZMQPH-UHFFFAOYSA-N 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 class NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-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
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- 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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-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
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- YTDXMRNXRNNDAK-UHFFFAOYSA-N [O].C(C)(=O)Br Chemical compound [O].C(C)(=O)Br YTDXMRNXRNNDAK-UHFFFAOYSA-N 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
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- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- Transplantation (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyamides (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
制造复合聚酰胺膜的方法，其中所述方法包括以下步骤：向多孔载体的表面施加多官能胺单体和多官能酰卤单体，并且界面聚合所述单体以形成薄膜聚酰胺层，其中所述方法包括如下步骤中的至少一个：i)在包含至少一个羧酸官能团或其盐和单个胺反应性官能团的C2-C20脂族单体存在下进行界面聚合；和ii)向所述薄膜聚酰胺层施加包含至少一个羧酸官能团或其盐和单个胺反应性官能团的C2-C20脂族单体。本发明描述了许多其他的实施方式，包括这样的膜的应用。
Description
技术领域
本发明总的涉及复合聚酰胺膜及其制造和使用方法
背景技术
复合聚酰胺膜用于各种流体分离。一种常见类别的膜包括涂有“薄膜”聚酰胺层的多孔载体。所述薄膜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)单体之间的界面缩聚反应而形成，所述单体不混溶溶液顺序涂布在载体上，参见例如Cadotte的US4277344。为了改善膜性能，涂层溶液之一或二者中可以添加各种成分。例如，Cadotte的US4259183描述了使用二和三官能酰卤单体，例如间苯二酰氯或对苯二酰氯与均苯三甲酰氯的组合。Mickols的US6878278描述了向酰卤涂层溶液添加广泛范围的络合剂，包括各种含磷物质。US2011/0049055描述了添加来源于磺酰(sulfonyl)、亚磺酰、亚硫酰(sulfenyl)、磺酰(sulfuryl)、磷酰、膦酰、氧膦基、硫代磷酰、硫代膦酰和碳酰卤化物的部分。US6521130描述了在聚合之前，向一种或这两种单体涂层溶液添加羧酸(例如脂族和芳族羧酸)或羧酸酯。类似地，US6024873、US5989426、US5843351和US5576057描述了向涂层溶液之一添加选择的溶解度参数为8至14(cal/cm3)1/2的醇、醚、酮、酯、卤代烃、含氮化合物和含硫化合物。US2009/0107922描述了向一种或这两种涂层溶液添加各种“链封端试剂”，例如1，3-丙磺酸内酯、苯甲酰氯、1，2-双(溴乙酰氧基)乙烷等等。US4606943和US6406626描述了利用多官能胺和多官能酰卤与多官能酸酐卤化物(例如偏苯三酸酐酰氯)一起形成薄膜聚酰胺。US2009/0272692、US2010/0062156、US2011/0005997、WO2009/129354、WO2010/120326和WO2010/120327描述了使用各种多官能酰卤和它们相应的部分水解相应物。Cadotte的US4812270描述了用磷酸对所述膜进行后处理。US5582725描述了用酰卤例如苯甲酰氯进行类似的后处理。
发明概述
本发明包括制造复合聚酰胺膜的方法，所述方法包括以下步骤：向多孔载体表面施加多官能胺和酰卤单体，和所述单体界面聚合形成薄膜聚酰胺层。所述方法还包括以下步骤中的至少一个：i)在包含至少一个羧酸官能团或其盐和单个胺反应性官能团的C2-C20脂族单体存在下进行界面聚合；和/或ii)向所述薄膜聚酰胺层施加这样的脂族单体。本发明包括许多其他的实施方式。
发明详述
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，本发明适用于可在各种应用包括正向渗透(FO)、逆渗透(RO)、纳滤(NF)、超滤(UF)和微滤(MF)流体分离中使用的平片、管状和中空纤维聚酰胺膜。然而，本发明对设计用于RO和NF分离的膜特别有用。RO复合膜对几乎所有的溶解盐相对不可渗透，并通常阻隔超过约95％的单价离子盐，例如氯化钠。RO复合膜还通常阻隔超过约95％的无机分子以及分子量大于约100道尔顿的有机分子。NF复合膜比RO复合膜更可渗透，并通常阻隔小于约95％的单价离子盐，同时取决于二价离子的种类，阻隔超过约50％(并经常超过90％)的二价离子盐。NF复合膜还通常阻隔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。
复合聚酰胺膜的实例包括FilmTec Corporation FT-30TM型膜，即平片复合膜，其包括无纺背衬网(例如PET纱)的底层(背面)、通常厚度约25-125μm的多孔载体中间层、和包含厚度通常小于约1微米例如从0.01微米至1微米但更通常从大约0.01至0.1μm的薄膜聚酰胺层的顶层(正面)。所述多孔载体通常是聚合材料，其孔径大小足以允许渗透物基本不受限制地通过，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，所述载体的孔径优选从约0.001至0.5μm。多孔载体的非限制性实例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和NF应用而言，所述多孔载体提供了强度，但由于它比较高的孔隙率，提供的抗流体流动性很小。
由于它比较薄，所述聚酰胺层根据它在多孔载体上的涂层覆盖量或负载量经常被描述为例如约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US4277344和US6878278所述，优选通过多官能胺单体和多官能酰卤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，可以通过多官能胺单体与多官能酰卤单体(其中每个术语意图是指利用单个物质或多个物质两者)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酰卤单体最通常通过溶液涂布步骤的方式施加于多孔载体，其中所述多官能胺单体通常从水基或极性溶液涂布，而多官能酰卤从有机基或非极性溶液涂布。虽然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，然后是多官能酰卤。可以通过喷涂、薄膜涂布、辊涂或通过使用浸渍槽以及其它涂布技术完成涂布。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。
所述多官能胺单体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)。优选的多官能胺单体的实例包括具有两个或三个氨基的伯胺，例如间苯二胺，和具有两个氨基的脂族仲胺，例如哌嗪。一种优选的多官能胺是间苯二胺(mPD)。多官能胺单体可以以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6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。
所述多官能酰卤单体包含至少两个酰卤基团并优选从有机基或非极性溶剂涂布，但是所述多官能酰卤可以从气相递送(例如，对于具有充分的蒸气压的多官能酰卤)。所述多官能酰卤没有特别的限制，可以使用芳族或脂环族的多官能酰卤及其组合。芳族多官能酰卤的非限制性实例包括：均苯三甲酰氯、对苯二甲酰氯、间苯二甲酰氯、联苯二羧酰氯和萘二羧酰氯。脂环族多官能酰卤的非限制性实例包括：环丙烷三羧酰氯，环丁烷四羧酰氯，环戊烷三羧酰氯，环戊烷四羧酰氯，环己烷三羧酰氯，四氢呋喃四羧酰氯，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。一种优选的多官能酰卤是均苯三甲酰氯(TMC)。多官能酰卤在非极性溶剂中溶解的范围可以为约0.01至10重量％、优选0.05至3重量％，并可以作为连续涂层操作的一部分进行递送。适合的溶剂是能够溶解多官能酰卤并与水不混溶的溶剂，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很少形成威胁并在经历常规加工时闪点和可燃性方面足够安全不需要采取特殊防范的溶剂。优选的溶剂是可得自Exxon ChemicalCompany的ISOPARTM。
非极性溶液可以包括其他材料，包括其中个体添加剂可以起到多种功能的共溶剂、相转移剂、增溶剂和络合剂。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。US6878278、US6723241、US6562266和US6337018描述了在进行界面聚合之前添加可以与非极性溶液合并的广泛范围的代表性络合剂。一类这样的络合剂由式(I)表示。
式(I)：
α(Lxβ)y
其中α是不含硫的结合芯，选自落入如下之内的元素：(a)IIIA-VIB族(即，IIIA、IVA、VA、VIA、VIIA、VIIIA、IB、IIB、IIIB、IVB、VB、VIB族)和(b)常规IUPAC周期表的3-6周期(即，以Na、K、Rb和Cs开始的周期)。常规IUPAC周期表形式的IIIA至VIB族对应于：“新符号”IUPAC周期表的3-16族和CAS版本周期表的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周期表，即IIIA族对应于以Sc、Y、La等开始的列，VIB族对应于以O、S、Se、Te、Po开始的列。具体的实例包括：(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，选自例如下面的连接：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，并包含1至12个碳原子，它可以是取代或未取代的并且可以包含如L定义的内部连接基团。实例包括具有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溶剂和酰卤，但是下面的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(II)表示。
式(II)：
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”是用来指支链和无支链的无环基团和环状基团，所述无环基团为例如甲基、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)；所述环状基团为例如环戊基、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、支链或无支链的C1-C12基团，并且更优选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，前述的络合剂优选添加到包含所述多官能酰卤的有机基或非极性涂层溶液中，与多官能酰卤单体的比率为约1∶5至5∶1，优选1∶1至3∶1。在另一种优选实施方式中，涂层溶液内络合剂的浓度是约0.001至2重量％。
一旦彼此发生接触，所述多官能酰卤和多官能胺单体在它们的表面界面处反应，形成聚酰胺层或薄膜。这种层，经常被称为聚酰胺“识别层”或“薄膜层”，提供了其主要功能是从溶剂(例如水性进料)中分离溶质(例如盐)的复合膜。
多官能酰卤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风干。
在一种实施方式中，所述方法包括向多孔载体表面施加多官能胺单体和多官能酰卤单体并将所述单体界面聚合以形成薄膜聚酰胺层的步骤。所述方法特征为包括如下步骤中的至少一个：i)在包含至少一个羧酸官能团或其盐和单个胺反应性官能团的C2-C20脂族单体存在下进行界面聚合；和ii)在界面聚合基本完成之后，向薄膜聚酰胺层施加包含至少一个羧酸官能团或其盐和单个胺反应性官能团的C2-C20脂族单体。术语“胺反应性”官能团是指界面聚合期间，即形成薄膜聚酰胺层期间存在的时间段和条件时期，与多官能胺单体的胺官能团反应的官能团。这通常要求在室温和标准大气压下接触的数秒之内明显反应。胺反应性官能团的代表性实例包括：酰卤，酸酐，异氰酸酯和环氧。在优选实施方式中，胺反应性官能团是酰卤，优选是酰氯。
当在界面聚合期间存在时，所述主题脂族单体被认为掺入所生成的聚酰胺结构内(即主题脂族单体和多官能胺和酰卤单体形成反应产物)。当在聚酰胺形成之后施加时，所述主题脂族单体据信与薄膜聚酰胺中存在的残留胺基反应。
所述脂族单体不同于前述的多官能酰卤和多官能胺单体，优选包含2至20个碳原子，并可以是脂环族的或无环的，并可以是饱和的或不饱和的。除了包含至少一个羧酸官能团和胺反应性官能团之外，所述脂族单体还可以是未取代的或被非胺反应性官能团例如卤素、羟基、醚、腈、硝基和乙烯基取代。如果是脂环族的，所述化合物可以是直链或支链的。在一种优选实施方式中，所述脂族单体是无环的和不饱和的。在另一种实施方式中，所述脂族单体包含单个羧酸官能团。优选的脂族单体类别在下面式(III)中表示。
式(III)：
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位于沿着所述脂族链的其它位置。虽然没有显示在式(III)中，但所述脂族单体可以包含附加的羧酸官能团以及如上所述任选的非胺反应性官能团。
另一种优选的脂族单体类别包括无环化合物。这样的化合物的实例包括5和6元无环化合物以及稠环结构。在一组实施方式中，所述无环化合物包含单个羧酸官能团。优选实施方式的类别在下面式(IV和V)中表示。
式(IV)： 式(V)：
其中X是卤素(优选氯)。羧酸和酰卤官能团在环上的位置没有特别的限制(例如间位、对位和邻位)。虽然没有显示，但所述环可以包含饱和碳，但优选不是芳族的。所述环还可以包含非胺反应性官能团，例如卤素、羟基以及具有1至12个碳原子烷基和烯基，所述烷基和烯基可以是未取代的或被例如羟基、腈和醚基的部分取代。
如之前所述，向多孔载体的表面施加多官能单体的步骤优选包括施加包含多官能胺单体的极性溶液和包含多官能酰卤单体的非极性溶液。施加溶液的步骤优选包括通过喷涂、薄膜涂布、辊涂、或通过使用浸渍槽进行涂布。在一种实施方式中，所述主题脂族单体在施加步骤之前，例如在多孔载体上涂布非极性溶液之前，添加到所述非极性溶液。在这样的实施方式中，所述非极性溶液优选包含至少0.001重量/体积的脂族单体。在另一种实施方式中，所述非极性溶液包含约0.001至0.1重量/体积的脂族单体。在又一种实施方式中，所述非极性溶液包含的脂族单体和多官能酰卤的摩尔比为约0.0001∶1至1∶1，优选0.001∶1至0.1∶1，更优选0.001∶1至0.01∶1。所述非极性溶液可以包括其他成分，包括如上所述的络合剂以及少量水(例如50至500ppm，在一些实施方式中至少100ppm)。
在另一种实施方式中，所述主题脂族单体在界面聚合基本完成之前、期间或之后，单独施加于多孔载体的表面(例如从单独的溶液施加)。在这种实施方式中，所述涂层溶液优选是如前所述的非极性溶液，并优选包含浓度约0.5至5％重量/体积、或更优选约1至3％重量/体积的脂族单体。所述溶液可以包括其他成分，包括如上所述的络合剂以及少量水(例如50至500ppm，在一些实施方式中至少100ppm)。
所述主题脂族单体可以在涂层溶液内原位形成，例如通过酰卤官能团的水解反应，或者预先形成并添加到涂层溶液中。
用所述主题脂族单体制备的膜当与不用所述主题脂族单体制备的基本上类似的膜相比较时，表现出较低的溶质透过率。令人惊讶的是，用所述主题脂族单体制备的膜当与用包含两个而不是一个胺反应性官能团的类似脂族单体制备的基本上类似的膜相比较时，表现出较高的通量。
虽然不局限于具体类型的聚酰胺膜，但本发明特别适合应用于复合膜，例如通常用于RO和NF应用的复合膜，更尤其是用在RO和NF应用中的平片复合聚酰胺膜。所述薄膜聚酰胺层可以任选在它的至少一部分表面上包含吸湿性聚合物。这样的聚合物包括聚合物表面活性剂、聚丙烯酸、聚乙酸乙烯酯、聚氧化烯化合物、聚(噁唑啉)化合物、聚丙烯酰胺和相关的反应产物，如总体描述在Mickols和Niu的US6280853、US7815987、US2009/0220690以和US2008/0185332中的。在一些实施方式中，这样的聚合物可以掺合和/或反应，并且可以从共同的溶液涂布或以其它方式施加于聚酰胺膜，或相继施加。已经描述了本发明的许多实施方式，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表征为“优选的”。“优选的”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并入本文。
实施例：
除非另外指出，否则所有样品膜都利用中试规模膜生产线生产。聚砜载体从二甲基甲酰胺(DMF)中的16.5wt％溶液浇铸，随后浸泡在3.5wt％的间苯二胺(mPD)的水溶液中。然后将所生成的载体恒速牵拉通过反应台，同时施加非极性溶液的均匀薄层。所述非极性溶液包含异链烷(ISOPARL)、均苯三甲酰氯(TMC)和下面指出的其他单体。所述非极性溶液还含有相对于TMC的化学计量比为1∶1.4的TBP(磷酸三丁酯)(除了实施例3，其中比率是1∶1.1，和实施例7，其中不包含TBP)。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(2000ppm NaCl)，在150psi、pH8和室温下对所述样品膜的试件进行标准试验。试验结果概括在下面提供的表中。
实施例1：
复合聚酰胺膜样品利用4-(氯代羰基)丁酸作为“主题单体”进行制备。用来制备各个样品的非极性溶液的总酰氯含量保持在0.24％w/v不变。所述主题单体的浓度从0到0.03％w/v变化，同时剩余的酰氯含量只由TMC提供。如表1所示，随着4-(氯代羰基)丁酸的浓度增加，盐透过率从0.99％降低到0.52％。
表1：
实施例2：
复合聚酰胺膜样品利用2-(氯代羰基)乙酸作为主题单体进行制备。用来制备各个样品的非极性溶液的总酰氯含量保持在0.24％w/v不变。所述主题单体的浓度从0到0.03％w/v变化，同时剩余的酰氯含量只由TMC提供。如表2所示，随着2-(氯代羰基)乙酸浓度增加，盐透过率从1.46％降低到0.73％。
表2：
实施例3：
复合聚酰胺膜样品利用5-氯代羰基戊酸作为主题单体进行制备(样品10和12)。为了比较，还用1，4-二氯代羰基丁烷和TMC制备了膜(比较样品9和11)。用来制备各个样品的非极性溶液的总酰氯含量保持在0.175％w/v不变。所述主题单体的浓度从0到0.02％w/v变化，同时剩余的酰氯含量只由TMC提供。如表3所示，用主题单体5-氯代羰基戊酸制备的膜(样品10和12)与用结构类似的1，4-二氯代羰基丁烷添加剂制备的样品比较，表现出盐透过率改进了30％。
表3：
实施例4：
利用9-氯代羰基壬酸作为主题单体制备复合聚酰胺膜样品。为了比较，还制备了没有所述主题单体的对照膜。用来制备各个样品的非极性溶液的总酰氯含量保持在0.21％w/v不变。所述主题单体的浓度是0.011％w/v，同时剩余的酰氯含量只由TMC提供。如表4所示，用9-氯代羰基壬酸制备的膜在盐透过率上比对照膜改进了超过26％。
表4：
实施例5：
复合聚酰胺膜样品利用2，4-二氧代-3-氧杂双环[3.3.1]壬烷-7-羧酸作为主题单体进行制备。为了比较，还制备了没有所述主题单体的对照膜。用来制备各个样品的非极性溶液的总酰氯含量保持在0.24％w/v不变。所述主题单体的浓度是0.03％w/v，同时剩余的酰氯含量只由TMC提供。如表6所示，与只用TMC制成的膜相比较，所述主题单体显示出盐透过率改进。
表5：
实施例6：(比较)
利用1，8-二氯代羰基辛烷制备复合聚酰胺膜样品。为了比较，还制备了没有1，8-二氯代羰基辛烷的对照膜。用来制备各个样品的非极性溶液的总酰氯含量保持在0.21％w/v不变。所述比较单体的浓度是0.011％w/v，同时剩余的酰氯含量只由TMC提供。如表6所示，所述比较单体没有显示盐透过率的显著改进。
表6：
实施例7：
利用3.5wt％的mPD水溶液以及在异链烷溶剂(ISOPAR L)内包含TMC和作为主题单体的4-(氯代羰基)丁酸的非极性溶液，制备复合聚酰胺膜样品。用来制备各个样品的非极性溶液的TMC含量保持在0.11％w/v不变。没有样品包含TBP。所述主题单体的浓度在样品16中是大约0.01％w/v，在对照中是0％。所述非极性溶液还含有4％均三甲苯作为共溶剂。在用4-(氯代羰基)丁酸制备的样品中，盐透过率降低。
表7
Claims (9)
1.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：向多孔载体的表面施加多官能胺单体和多官能酰卤单体，并且界面聚合所述单体以形成薄膜聚酰胺层，其中所述方法特征在于包括如下步骤中的至少一个：
i)在其它单体存在下进行所述界面聚合，所述其它单体包含不同于前述多官能胺和酰卤单体并进一步包含至少一个羧酸官能团或其盐和单个胺反应性官能团的C2-C20脂族单体，并且其中所述其它单体和多官能酰卤单体从这两者共同的非极性溶液以0.0001∶1至1∶1的摩尔比施加；和
ii)向所述薄膜聚酰胺层施加其它单体，所述其它单体包含不同于前述多官能胺和酰卤单体并进一步包含至少一个羧酸官能团或其盐和单个胺反应性官能团的C2-C20脂族单体，并且其中所述其它单体以0.5至5％重量/体积的浓度从它的非极性溶液施加。
2.权利要求1的方法，其中所述胺反应性官能团选自：酰卤，酸酐，异氰酸酯和环氧。
3.权利要求1的方法，其中所述其它单体包含单个羧酸官能团。
4.权利要求1的方法，其中所述其它单体是脂环族化合物。
5.权利要求1的方法，其中所述其它单体是无环化合物。
6.权利要求1的方法，其中所述其它单体由式(III)表示：
式(III)：
其中X是卤素和n是1至10的整数。
7.权利要求1的方法，其中所述其它单体选自：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。
8.权利要求1的方法，其中所述其它单体由式(IV和V)的至少一个表示：
其中X是卤素。
9.权利要求1的方法，其中向多孔载体的表面施加多官能单体的步骤包括施加包含多官能胺单体的极性溶液和包含多官能酰卤单体的非极性溶液；并且其中所述非极性溶液还包含所述其它单体。
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| US8968828B2 (en) | 2015-03-03 |
| JP5912133B2 (ja) | 2016-04-27 |
| CN103328081A (zh) | 2013-09-25 |
| EP2632577B1 (en) | 2014-10-01 |
| US20130287945A1 (en) | 2013-10-31 |
| KR20140016274A (ko) | 2014-02-07 |
| KR101920194B1 (ko) | 2019-02-08 |
| ES2523453T3 (es) | 2014-11-26 |
| EP2632577A1 (en) | 2013-09-04 |
| JP2014510619A (ja) | 2014-05-01 |
| WO2012102944A1 (en) | 2012-08-02 |
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