CN104918688A - 包含经取代苯甲酰胺单体的复合聚酰胺膜 - Google Patents
包含经取代苯甲酰胺单体的复合聚酰胺膜 Download PDFInfo
- Publication number
- CN104918688A CN104918688A CN201480004562.1A CN201480004562A CN104918688A CN 104918688 A CN104918688 A CN 104918688A CN 201480004562 A CN201480004562 A CN 201480004562A CN 104918688 A CN104918688 A CN 104918688A
- Authority
- CN
- China
- Prior art keywords
- monomer
- acyl halide
- substituted
- functional group
- benzamide
- 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.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 71
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004952 Polyamide Substances 0.000 title claims abstract description 24
- 229920002647 polyamide Polymers 0.000 title claims abstract description 24
- 150000003936 benzamides Chemical class 0.000 title claims abstract description 21
- 239000012528 membrane Substances 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 45
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 150000007942 carboxylates Chemical class 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000008064 anhydrides Chemical group 0.000 claims description 7
- 150000003009 phosphonic acids Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000010408 film Substances 0.000 description 16
- -1 phosphono, phosphinyl Chemical group 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 210000004379 membrane Anatomy 0.000 description 15
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 12
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 11
- 229940018564 m-phenylenediamine Drugs 0.000 description 11
- 239000008139 complexing agent Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000001728 nano-filtration Methods 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 239000006184 cosolvent Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 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
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent 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
- 238000002474 experimental method Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N lysine Chemical compound NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 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
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 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
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical class COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-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
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-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 compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- BHCZMPWVHPXAKA-UHFFFAOYSA-N C(=O)ClC=O Chemical compound C(=O)ClC=O BHCZMPWVHPXAKA-UHFFFAOYSA-N 0.000 description 1
- PVTBNVWWDWOVNI-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1CCC1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1CCC1 PVTBNVWWDWOVNI-UHFFFAOYSA-N 0.000 description 1
- CFCVIOUVUKYMBG-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.O1CCCC1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.O1CCCC1 CFCVIOUVUKYMBG-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VWRNJWAKPLFEJR-UHFFFAOYSA-N OS(c(cc(cc1)NC(c2cc(C(Cl)=O)cc(C(Cl)=O)c2)=O)c1-c(c(S(O)(=O)=O)c1)ccc1NC(c1cc(C(Cl)=O)cc(C(Cl)=O)c1)=O)(=O)=O Chemical compound OS(c(cc(cc1)NC(c2cc(C(Cl)=O)cc(C(Cl)=O)c2)=O)c1-c(c(S(O)(=O)=O)c1)ccc1NC(c1cc(C(Cl)=O)cc(C(Cl)=O)c1)=O)(=O)=O VWRNJWAKPLFEJR-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 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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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
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- 239000005864 Sulphur Substances 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
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- 230000002596 correlated effect Effects 0.000 description 1
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- XWALRFDLDRDCJG-UHFFFAOYSA-N cyclobutane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1(C(Cl)=O)C(Cl)=O XWALRFDLDRDCJG-UHFFFAOYSA-N 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- YKXAGRCDGMWYRO-UHFFFAOYSA-N cyclopropane-1,1,2-tricarboxylic acid Chemical compound OC(=O)C1CC1(C(O)=O)C(O)=O YKXAGRCDGMWYRO-UHFFFAOYSA-N 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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Abstract
一种制造包含多孔支撑物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：向多孔支撑物表面施用包含多官能胺单体的极性溶液和包含多官能酰基卤单体的非极性溶液，且将所述单体界面聚合以形成薄膜聚酰胺层。所述方法的特征在于在所述非极性溶液内包括经取代苯甲酰胺单体。
Description
技术领域
本发明大体上涉及复合聚酰胺膜以及制造和使用其的方法。
背景技术
复合聚酰胺膜用于多种流体分离。一种常见类别的膜包括用“薄膜”聚酰胺层涂布的多孔支撑物。薄膜层可以通过多官能胺(例如间苯二胺)单体与多官能酰基卤(例如均苯三甲酰基氯)单体之间的界面聚缩合反应形成，所述单体依次由不可混溶的溶液涂布在支撑物上，参见例如卡多特(Cadotte)的US 4277344。多种组分可以添加到涂布溶液中的一或两者以改进膜性能。举例来说，卡多特的US 4259183描述双官能和三官能酰基卤单体(例如间苯二甲酰基氯或对苯二甲酰基氯与均苯三甲酰基氯)的组合的使用。米可罗(Mickols)的US 6878278描述添加各种络合剂到酰基卤涂布溶液，包括多种含磷物质。US 2011/0049055描述添加由磺酰基、亚磺酰基、次磺酰基、硫酰基、磷酰基、膦酰基、氧膦基、硫代磷酰基、硫代膦酰基和碳酰卤化物衍生的部分。US 6521130描述在聚合之前添加羧酸(例如脂肪族和芳香族羧酸)或羧酸酯到一种或两种单体涂布溶液。类似地，US 6024873、US 5989426、US 5843351和US 5576057描述添加溶解度参数为8到14(cal/cm3)1/2的所选醇、醚、酮、酯、卤化烃、含氮化合物和含硫化合物到涂布溶液中的一者。US 2009/0107922描述添加多种“链封端试剂”到一种或两种涂布溶液，例如1，3丙磺酸内酯、苯甲酰氯、1，2-双(溴乙酰氧基)乙烷等。US 4606943和US6406626描述使用多官能胺和多官能酰基卤以及多官能酸酐卤化物(例如偏苯三酸酐酰基氯)形成薄膜聚酰胺。WO2012/102942、WO2012/102943和WO2012/102944描述添加多种单体，包括羧酸和胺反应性官能团。US 2009/0272692、US 2010/0062156、US2011/0005997、US 2012/0261344和US 8177978描述多种多官能酰基卤和其相应部分水解对应物的使用。US 7806275描述用吸电子基团改性酰基卤单体以使氯化减到最少。卡多特的US 4812270描述用磷酸后处理膜。US 5582725描述使用酰基卤(如苯甲酰氯)的类似后处理。继续探索进一步改进膜性能的新单体。
发明内容
本发明包括一种制造包含多孔支撑物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：向多孔支撑物表面施用包含多官能胺单体的极性溶液和包含多官能酰基卤单体的非极性溶液的步骤，且将所述单体界面聚合以形成薄膜聚酰胺层。所述方法的特征在于在所述非极性溶液内包括经取代苯甲酰胺单体，其中所述经取代苯甲酰胺单体与所述多官能酰基卤单体不同且由式(IIIa和IIIb)中的至少一者表示：
式(IIIa)：
式(IIIb)：
其中：
i)X、X′、X″和X″′独立地选自以下官能团：位于苯甲酰胺基的间位、邻位或对位的酰基卤、羧酸、羧酸酯和磺酸，或a)X和X′和b)X″和X″′中的一者或两者共同形成酸酐基团；其限制条件为X、X′、X″和X″′中的至少两者选自酰基卤和酸酐官能团；且
ii)Z是选自以下各者中的至少一者：芳基、烷基、烯基和烷氧基，其中各自可未经取代或经选自羧酸、羧酸酯、膦酸和磺酸的官能团取代；
iii)其限制条件为经取代苯甲酰胺单体包含至少一个选自羧酸、羧酸酯、膦酸和磺酸的官能团。
描述许多附加实施例，包括此类膜的应用。
具体实施方式
本发明未特别局限于特定类型、构造或形状的复合膜或应用。举例来说，本发明适用于多种应用中所用的平板、管状和中空纤维聚酰胺膜，包括正向渗透(FO)、反向渗透(RO)、纳米过滤(NF)、超滤(UF)、微滤(MF)和压力延迟流体分离。然而，本发明特别适用于设计用于RO和NF分离的膜。RO复合膜相对不可渗透几乎全部溶解盐且通常阻挡超过约95％的单价离子盐，如氯化钠。RO复合膜也通常阻挡超过约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复合膜更可渗透且通常阻挡小于约95％的单价离子盐，同时阻挡大于约50％(并且常常大于90％)的二价离子盐，视二价离子的种类而定。NF复合膜也通常阻挡在纳米范围中的粒子以及分子量大于约200到500道尔顿的有机分子。
复合聚酰胺膜的实例包括膜技术公司(FilmTec Corporation)FT-30TM型膜，即包含非织造背衬网(例如PET纱布)的底层(背侧)、具有约25-125μm典型厚度的多孔支撑物的中间层和包含厚度通常小于约1微米(例如0.01微米到1微米，但更通常约0.01到0.1μm)的薄膜聚酰胺层的顶层(前侧)的平板复合膜。多孔支撑物通常是具有一定孔径的聚合材料，所述孔径具有足以准许渗透物基本上不受限制的通过的尺寸，但并未大到足以干扰上面形成的薄膜聚酰胺层的桥接。举例来说，支撑物的孔径优选地介于约0.001到0.5μm范围内。多孔支撑物的非限制性实例包括由以下制成的多孔支撑物：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、聚丙烯和多种卤化聚合物(如聚偏二氟乙烯)。对于RO和NF应用来说，多孔支撑物提供强度，但由于其相对高的孔隙度而几乎无流体流动阻力。
由于其相对薄，聚酰胺层常常依据其在多孔支撑物上的涂布覆盖率或负载量加以描述，例如每平方米多孔支撑物表面积约2到5000mg聚酰胺并且更优选的是约50到500mg/m2。如US 4277344和US 6878278中所述，聚酰胺层优选地通过多官能胺单体与多官能酰基卤单体之间的界面聚缩合反应在多孔支撑物表面上制备。更确切地说，聚酰胺膜层可以通过在多孔支撑物的至少一个表面上界面聚合多官能胺单体与多官能酰基卤单体(其中每一术语意图指代使用单一物质或多个物质)而制备。如本文所用，术语“聚酰胺”是指沿着分子链出现酰胺键(-C(O)NH-)的聚合物。多官能胺和多官能酰基卤单体最常借助于涂布步骤由溶液施用到多孔支撑物，其中所述多官能胺单体通常由水基或极性溶液涂布并且所述多官能酰基卤由有机基或非极性溶液涂布。尽管涂布步骤无需遵循特定顺序，但多官能胺单体优选地首先涂布在多孔支撑物上，接着是多官能酰基卤。涂布可以通过喷雾、涂膜、辊涂或经由在其它涂布技术当中使用浸渍罐而实现。可以通过空气刀、干燥器、烘箱等从支撑物去除过量溶液。
多官能胺单体包含至少两个伯氨基或仲氨基并且可以是芳香族(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、2，4-二氨基苯甲醚和二甲苯二胺)或脂肪族(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)和具有两个氨基的仲脂肪族胺(如哌嗪)。一种优选的多官能胺是间苯二胺(mPD)。多官能胺单体可以极性溶液形式施用到多孔支撑物。极性溶液可以含有约0.1到约10w/v％并且更优选地约1到约6w/v％多官能胺单体。一旦涂布在多孔支撑物上，可以任选地去除过量溶液。
多官能酰基卤单体包含至少两个酰基卤基团，并且优选地由有机基或非极性溶剂涂布，但多官能酰基卤可以由气相传递(例如对于具有足够蒸气压的多官能酰基卤)。多官能酰基卤不受特别限制并且芳香族或脂环族多官能酰基卤可以与其组合一起使用。芳香族多官能酰基卤的非限制性实例包括：均苯三甲酰基氯、对苯二甲酸酰基氯、间苯二甲酸酰基氯、联苯二甲酸酰基氯和萘二甲酸二氯化物。脂环族多官能酰基卤的非限制性实例包括：环丙烷三甲酸酰基氯、环丁烷四甲酸酰基氯、环戊烷三甲酸酰基氯、环戊烷四甲酸酰基氯、环己烷三甲酸酰基氯、四氢呋喃四甲酸酰基氯、环戊烷二甲酸酰基氯、环丁烷二甲酸酰基氯、环己烷二甲酸酰基氯和四氢呋喃二甲酸酰基氯。一种优选的多官能酰基卤为均苯三甲酰基氯(TMC)。多官能酰基卤可以约0.01到10w/v％、优选地0.05到3w/v％的范围溶解于非极性溶剂中，并且可以作为连续涂布操作的一部分传递。适合的溶剂是能够溶解多官能酰基卤且与水不可混溶的溶剂，例如己烷、环己烷、庚烷和卤化烃(如FREON系列)。优选的溶剂包括对臭氧层几乎不造成威胁且在闪点和可燃性方面安全到足以在不采用特殊防护措施的情况下进行常规加工的溶剂。优选的溶剂是可购自埃克森化学公司(Exxon Chemical Company)的ISOPARTM。
非极性溶液可以包括额外物质，包括共溶剂、相转移剂、增溶剂、络合剂和除酸剂，其中个别添加剂可以提供多个功能。代表性共溶剂包括：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carbitolTM乙酸酯、月桂酸甲酯和丙酮。代表性除酸剂包括N，N-二异丙基乙胺(DIEA)。US 6878278、US 6723241、US 6562266和US 6337018描述了添加可在进行界面聚合之前与非极性溶液组合的广泛范围的代表性络合剂。一类所述络合剂由式(I)表示。
式(I)：α(Lxβ)y
其中α是含非硫的结合核心，其选自常规IUPAC周期表中以下各者当中的元素：(a)第IIIA-VIB族(即，第IIIA族、第IVA族、第VA族、第VIA族、第VIIA族、第VIIIA族、第IB族、第IIB族、第IIIB族、第IVB族、第VB族、第VIB族)和(b)第3-6周期(即，以Na、K、Rb和Cs开始的周期)。常规IUPAC形式周期表的第IIIA到VIB族对应于：“新符号”IUPAC周期表的第3-16族和CAS版周期表的第IIIB-VIA族。为了避免任何混淆，本文中进一步提及将使用常规IUPAC周期表，即，第IIIA族对应于以Sc、Y、La等开始的栏，且第VIB族对应于以O、S、Se、Te、Po开始的栏。尤其优选的结合核心包括：Al、Si、P、As、Sb、Se和Te以及金属，如：Fe、Cr、Co、Ni、Cu和Zn。L是任选的化学连接基团，相同或不同，选自如以下各者的键：含碳部分，例如芳香族基团、烷烃、烯烃、--O--、--S--、--N--、--H--、--P--、--O--P--和--O--P--O--(其中的每一者可以经取代或未经取代)。β是增溶基团，相同或不同，且包括1到12个碳原子，所述碳原子可经取代或未经取代且可包括如由L定义的内部连接基团。实例包括具有1到6个碳原子的脂肪族和芳烃基团、芳香族基团、杂环基团和烷基。“x”是0到1的整数，且“y”是1到5、优选地2到4的整数。尽管视所用的特定溶剂和酰基卤种类而定，但以下络合剂通常适用于本发明：磷(例如膦、磷酸酯)、铋、砷和锑的三苯基衍生物；磷的烷烃氧基酯，包括亚磷酸三丁酯和亚磷酸二丁酯；有机金属络合物，如二茂铁和四乙基铅以及铁(II)、铁(III)、钴(III)和Cr(III)的乙酰基丙酮酸盐络合物。所述络合剂的优选的类别由式(II)表示。
式(II)：
其中“P”是磷，“O”是氧，且R1、R2和R3独立地选自含碳部分。术语“含碳部分”打算意指支链和非支链非环状基团，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，其可未经取代或经取代(例如经取代酰胺基、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、双键和三键等)；和环状基团，例如环戊基、环己基、芳香族物，例如苯基、杂环(例如吡啶)等，其可未经取代或经取代(例如经取代甲基、乙基、丙基、羟基、酰胺、醚、砜、羰基、酯等)。环部分可经由脂肪族连接基团(例如甲基、乙基等)键联到磷原子。优选的含碳部分包括未经取代的支链或非支链C1-C12基团，且更优选地为C1-C8脂肪族基团，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。另外，部分包括苯基。当使用时，上述络合剂优选地以与多官能酰基卤单体约1∶5到5∶1(且1∶1到3∶1为优选的)的比率添加到含有多官能酰基卤的有机基或非极性涂布溶液中。在另一优选实施例中，涂布溶液内的络合剂的浓度是约0.001w/v％到2w/v％。
一旦彼此接触，多官能酰基卤单体和多官能胺单体在其表面界面处反应以形成聚酰胺层或膜。这一层常常被称作聚酰胺“辨别层”或“薄膜层”，给复合膜提供其用于使溶质(例如盐)与溶剂(例如水性进料)分离的主要构件。
多官能酰基卤和多官能胺单体的反应时间可以小于一秒，但是接触时间通常介于约1秒到60秒范围内，之后可任选地经由空气刀、水浴、干燥器等来移除过量液体。可在例如约40℃到约120℃的高温下干燥(然而可使用在环境温度下的空气干燥)实现过量溶剂的移除。
本发明方法的特征在于在非极性溶液内包括经取代苯甲酰胺单体以及多官能酰基卤单体。虽然两种单体可包括多个酰基卤官能团，但彼此不同。举例来说，多官能酰基卤单体优选地不包括苯甲酰胺基。非极性溶液优选地包含至少0.001w/v％的经取代苯甲酰胺单体。在另一实施例中，非极性溶液包含约0.001到0.25w/v％的经取代苯甲酰胺单体。在另一实施例中，非极性溶液包含摩尔比为约0.001∶1到1∶1，优选地0.01∶1到0.1∶1且更优选地0.001∶1到0.01∶1的苯甲基单体和多官能酰基卤。非极性溶液可包括额外组分，包括如先前所述的共溶剂和络合剂。
经取代苯甲酰胺单体由式(IIIa和IIIb)中的至少一者表示：
式(IIIa)：
式(IIIb)：
其中：
i)X、X′、X″和X″′独立地选自以下官能团：位于苯甲酰胺基的间位、邻位或对位的酰基卤、羧酸、羧酸酯(即，羧酸的盐和酯)、膦酸和磺酸，或a)X和X′和b)X″和X″′中的一者或两者共同形成酸酐基团；其限制条件为X、X′、X″和X″′中的至少两者选自酰基卤和酸酐官能团；且
ii)Z是选自以下各者中的至少一者：芳基、烷基、烯基和烷氧基，其中各自可未经取代或经选自羧酸、羧酸酯、膦酸和磺酸的官能团取代；
iii)其限制条件为经取代苯甲酰胺单体包含至少一个选自羧酸、羧酸酯、膦酸和磺酸的官能团。
经取代苯甲酰胺单体优选地包含2到5个苯基，且在若干实施例中，包含至少三个苯基。经取代苯甲酰胺单体也应充分可溶于非极性溶液内以促进并入，视需要通过使用共溶剂、表面活性剂或相转移试剂来辅助溶解度。在最优选实施例中，经取代苯甲酰胺单体的分子量为370到900道尔顿，且更优选为400到800道尔顿。优选的单体子类由式(IV)表示。
式(IV)：
其中A、A′、A″和A″′独立地选自卤素和羟基。在实施例的优选子组中，A、A′、A″和A″′中的至少三者(且在一些情况下所有)是选自卤素(例如Cl)。代表性种类表示在式(V)-(XI)中。
式(V)：
式(VI)：
式(VII)：
式(VIII)：
式(IX)：
式(X)：
式(XI)：
在实施例的另一子类中，a)X和X′和b)X″和X″共同形成酸酐基团。非限制性种类由式(XII)-(XIII)表示。
式(XII)：
式(XIII)：
另一可适用单体由式(XIV)表示：
式(XIV)：
制备经取代苯甲酰胺单体的方法不受特定限制且包括使二胺和多官能酰基卤或酸酐化合物反应。举例来说，式(XI)中所示的单体可通过使1，3-二氧代-1，3-二氢异苯并呋喃-5-羰酰氯与2，6-二氨基己酸反应来制备。其它实例包括使氨基酸(例如精氨酸、组氨酸、鸟氨酸等)与如上文所述的多官能酰基卤单体反应。
薄膜聚酰胺层可以任选地在其表面的至少一部分上包括吸湿聚合物。此类聚合物包括聚合表面活性剂、聚丙烯酸、聚乙烯醇、聚乙酸乙烯酯、聚环氧烷化合物、聚(噁唑啉)化合物、聚丙烯酰胺和如US 6280853、US 7815987、US 2009/0220690和US 2008/0185332中大体描述的相关反应产物。在一些实施例中，此类聚合物可以掺合和/或反应并且可以由常见溶液涂布或以其它方式施用到聚酰胺膜或依次施用。
已经描述了本发明的多个实施例并且在一些情况下已将某些实施例、选择、范围、组分或其它特征表征为“优选的”。“优选”特点的表征决不应解释为将此类特点视作对本发明来说所需的、必需的或至关重要的。
实例
所有聚酰胺复合膜样品均在聚砜超滤支撑物上手动浇铸。聚砜支撑物通过将聚砜(P-3500)(约15％)于二甲基甲酰胺中的溶液涂布到连续非纺织PET网状物表面上而形成。通过将经涂布的网状物浸没在水中来开始倒相。所得支撑物薄片由在PET网状物(约150微米)上的不对称超滤膜层(约50微米)组成。将支撑物薄片切成片(11英寸×7英寸)，附着于线框(10英寸×7.5英寸)，且浸渍在RO水中约30分钟。接着从水中移出安装的支撑物薄片，且将其浸没在3w/v％MPD水溶液中持续至少约20分钟。接着，将纸巾置放在平坦塑料矩形板上。将MPD浸泡的支撑物(网状物侧向下)置于纸巾顶部上，且通过在支撑物的聚砜表面上滚动橡胶辊来剪断过量溶液。将矩形聚硅氧橡胶垫圈置于聚砜表面上，且将类似形状的矩形塑料框置放在垫圈上且将四侧夹紧以在边缘制得防漏密封。接着，将60ml包括TMC与经取代苯甲酰胺单体(参见下文)溶液组合的非极性溶液(Isopar L)倾倒在MPD浸泡的支撑物上，且使其反应约1分钟。接着，从所得反渗透膜薄片的顶表面倾倒掉过量液体。薄片用80mL己烷冲洗，风干约1分钟，且接着储存在RO水中直到测试。对于每一样品膜，切割两个试片且在室温和225psi下使用2000ppm NaCl溶液用平坦单元测试实验台测试。
两种不同的经取代苯甲酰胺单体用于实验。一种通过将过量TMC(约10∶1摩尔比)添加到含3，5-二氨基苯甲酸(DAB)的Isopar L中来制备(样品第2-4和9-10号)，且另一种通过将过量TMC(约10∶1摩尔比)添加到含赖氨酸的Isopar L中来制备(样品第6-7和12-13号)。将所得苯甲酰胺溶液过滤且与TMC溶液(在Isopar L中)组合以形成上文所述的非极性涂布溶液。非极性涂布溶液的总酰氯浓度在所有实验中保持恒定在0.13w/v％。经取代苯甲酰胺单体浓度是基于与非极性涂布溶液的总体积相比经取代苯甲酰胺单体溶液的体积分率。除酸剂(即N，N-二异丙基乙胺(DIEA))包括在用于样品第9和13号的非极性涂布溶液中(与用于形成经取代苯甲酰胺单体的二胺的摩尔比为2∶1)。增溶剂/络合剂(磷酸三丁酯(TBP))包括在样品第10和12号中(与用于形成经取代苯甲酰胺单体的二胺的摩尔比为1.5∶1)。
表1
表2
表3
表4
如表1-4中所提供的数据所示，用本发明经取代苯甲酰胺单体制备的样品膜与未用所述单体制备的对照膜相比展示出通常较低的NaCl通过率值。
Claims (4)
1.一种制造包含多孔支撑物和薄膜聚酰胺层的复合聚酰胺膜的方法，其中所述方法包含以下步骤：向多孔支撑物表面施用包含多官能胺单体的极性溶液和包含多官能酰基卤单体的非极性溶液，且将所述单体界面聚合以形成薄膜聚酰胺层，其中所述方法的特征在于在所述非极性溶液内包括经取代苯甲酰胺单体，其中所述经取代苯甲酰胺单体与所述多官能酰基卤单体不同且由式(IIIa和IIIb)中的至少一者表示：
其中：
i)X、X′、X″和X″′独立地选自以下官能团：位于苯甲酰胺基的间位、邻位或对位的酰基卤、羧酸、羧酸酯和磺酸，或a)X和X′和b)X″和X″′中的一者或两者共同形成酸酐基团；其限制条件为X、X′、X″和X″′中的至少两者选自酰基卤和酸酐官能团；且
ii)Z是选自以下各者中的至少一者：芳基、烷基、烯基和烷氧基，其中各自可未经取代或经选自羧酸、羧酸酯、膦酸和磺酸的官能团取代；
iii)其限制条件为所述经取代苯甲酰胺单体包含至少一个选自羧酸、羧酸酯、膦酸和磺酸的官能团。
2.根据权利要求1所述的方法，其中所述经取代苯甲酰胺单体包含至少三个苯基。
3.根据权利要求1所述的方法，其中X、X′、X″和X″′中的至少三者是酰基卤官能团。
4.根据权利要求1所述的方法，其中所述经取代苯甲酰胺单体具有370到900道尔顿的分子量
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| CN113398781A (zh) * | 2021-06-18 | 2021-09-17 | 中国农业科学院农业质量标准与检测技术研究所 | 一种微孔滤膜材料及其制备方法与应用 |
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| CN104918688B (zh) | 2016-12-14 |
| WO2014109947A1 (en) | 2014-07-17 |
| US9895666B2 (en) | 2018-02-20 |
| US20150298066A1 (en) | 2015-10-22 |
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