CN106232216A - 用亚硝酸后处理的复合聚酰胺膜 - Google Patents
用亚硝酸后处理的复合聚酰胺膜 Download PDFInfo
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- CN106232216A CN106232216A CN201580022591.5A CN201580022591A CN106232216A CN 106232216 A CN106232216 A CN 106232216A CN 201580022591 A CN201580022591 A CN 201580022591A CN 106232216 A CN106232216 A CN 106232216A
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- acid
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- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000004952 Polyamide Substances 0.000 title claims abstract description 27
- 229920002647 polyamide Polymers 0.000 title claims abstract description 27
- 239000012528 membrane Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000012805 post-processing Methods 0.000 title description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 25
- 239000004760 aramid Substances 0.000 claims abstract description 22
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 9
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- -1 methoxyl group Chemical group 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 150000003335 secondary amines Chemical class 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 150000003141 primary amines Chemical class 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QPEJHSFTZVMSJH-UHFFFAOYSA-N 3-amino-5-hydroxybenzoic acid Chemical compound NC1=CC(O)=CC(C(O)=O)=C1 QPEJHSFTZVMSJH-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- FZRKAZHKEDOPNN-UHFFFAOYSA-N Nitric oxide anion Chemical compound O=[N-] FZRKAZHKEDOPNN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- WFNVGXBEWXBZPL-UHFFFAOYSA-N 3,5-diaminophenol Chemical compound NC1=CC(N)=CC(O)=C1 WFNVGXBEWXBZPL-UHFFFAOYSA-N 0.000 claims description 2
- DCOZZPQKAZEDBO-UHFFFAOYSA-N 3-N,3-N-dimethylbenzene-1,3,5-triamine Chemical compound CN(C1=CC(=CC(=C1)N)N)C DCOZZPQKAZEDBO-UHFFFAOYSA-N 0.000 claims description 2
- RSCVHPBMEDSBLL-UHFFFAOYSA-N 3-amino-5-methoxybenzenesulfonic acid Chemical compound COC1=CC(N)=CC(S(O)(=O)=O)=C1 RSCVHPBMEDSBLL-UHFFFAOYSA-N 0.000 claims description 2
- DBEMTZANGFGKMX-UHFFFAOYSA-N 3-amino-5-methoxybenzoic acid Chemical compound COC1=CC(N)=CC(C(O)=O)=C1 DBEMTZANGFGKMX-UHFFFAOYSA-N 0.000 claims description 2
- 229940018563 3-aminophenol Drugs 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims description 2
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 claims description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 2
- SHCTVTZAVRBWEL-UHFFFAOYSA-N 3-amino-5-hydroxybenzenesulfonic acid Chemical compound NC1=CC(O)=CC(S(O)(=O)=O)=C1 SHCTVTZAVRBWEL-UHFFFAOYSA-N 0.000 claims 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims 1
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 claims 1
- 230000001588 bifunctional effect Effects 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 22
- 239000002585 base Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical class ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001728 nano-filtration Methods 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000008569 process Effects 0.000 description 3
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000006149 azo coupling reaction Methods 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
- 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
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material 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
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- WXYMNDFVLNUAIA-UHFFFAOYSA-N 1,8-dichlorooctane Chemical compound ClCCCCCCCCCl WXYMNDFVLNUAIA-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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ANRCFKDSDRXMCZ-UHFFFAOYSA-N [Cl].C(C1=CC=C(C(=O)N)C=C1)(=O)N Chemical compound [Cl].C(C1=CC=C(C(=O)N)C=C1)(=O)N ANRCFKDSDRXMCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-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
- 150000001555 benzenes Chemical class 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- DJQFQXHRKYELGT-UHFFFAOYSA-N butyl heptyl hydrogen phosphate Chemical compound CCCCCCCOP(O)(=O)OCCCC DJQFQXHRKYELGT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000012954 diazonium Substances 0.000 description 1
- 125000001752 diazonium salt group Chemical group 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VVOSATWFENUSTP-UHFFFAOYSA-N ethylbenzene;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound CCC1=CC=CC=C1.COCCOCCOC VVOSATWFENUSTP-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
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Abstract
一种用于制造包含多孔载体和聚酰胺层的复合聚酰胺膜的方法，其包括以下步骤：i)将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施加到多孔载体的表面上，并且使所述单体界面聚合以形成聚酰胺层；以及ii)使所述薄膜聚酰胺层暴露于亚硝酸；其中所述方法的特征在于以下各者中的至少一者：在主题胺化合物存在下进行步骤i)的界面聚合，或在步骤ii)之前将主题胺化合物施加到所述界面聚合的聚酰胺层，其中所述主题胺化合物与所述多官能酰基卤和多官能胺单体不同。
Description
技术领域
本发明大体上涉及复合聚酰胺膜以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中。一种常见类别的膜包括用“薄膜”聚酰胺层涂布的多孔载体。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（例如均苯三甲酰氯）单体之间的界面缩聚反应来形成，所述单体依次从不可混溶的溶液涂布在载体上，参看例如Cadotte的US 4277344。多种组分可以添加到涂布溶液中的一者或两者以改进膜性能。举例来说，Mickols的US 6878278描述添加各种添加剂到一种或两种涂布溶液，包括多种磷酸三烃酯化合物。US2013/0287944、US2013/0287945、US2013/0287946、WO2013/048765以及WO2013/103666描述添加各种单体，所述单体包括羧酸和胺反应性官能团以及各种磷酸三烃酯化合物。
Cadotte的US 4888116描述双官能和三官能酰基卤单体（例如间苯二甲酰氯或对苯二甲酰氯与均苯三甲酰氯）的组合的使用。随后用试剂（亚硝酸）后处理所得聚酰胺层以从未反应的侧接胺基形成重氮盐基团和对应的衍生物（例如偶氮键）。还参看WO2013/047398、US2013/0256215、US2013/0126419、US2012/0305473、US2012/0261332以及US2012/0248027。膜中偶氮基团的浓度和位置特定于胺端基数目和其沿着聚合物链的分布以及重氮盐水解和偶氮偶合的相对速率。因此，可能的偶氮基团的数目受到限制并且链间交联形成仅经由两个不同聚合物链中间的端基进行。因此，此途径限制可能的偶氮基团的数目并且仅经由两个不同聚合物链中间的端基引入链间交联。
在一个实施例中，本发明消除此限制并且提供合成途径以增加偶氮基团数目并且还经由聚合物主链上的多个位点引入链内交联。此产生较紧密并且较均匀的聚合物网状结构。在另一个实施例中，本发明消除上文所提到的限制并且提供合成途径以增加优先靠近聚合物表面分布的偶氮基团的数目。相比于均匀地在整个聚合物中分布偶氮交联，此实施例优先“收紧”膜表面而不是整体。因此，保护整体聚合物的开放性并且产生从进料面表面到聚砜载体对向表面的交联密度梯度，其中膜的进料面更加交联。此独特结构改进水与盐传输之间的选择性。确切地说，在不牺牲膜通量的情况下更高效地阻挡中等和较大分子。
发明内容
本发明包括一种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：i）将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施加到多孔载体的表面上并且使所述单体界面聚合以形成聚酰胺层；以及ii）使所述薄膜聚酰胺层暴露于亚硝酸。所述方法的特征在于以下各者中的至少一者：在主题胺化合物存在下进行步骤i）的界面聚合，或在步骤ii）之前将主题胺化合物施加到所述界面聚合的聚酰胺层，其中所述主题胺化合物与所述多官能胺单体不同并且由下式表示：
其中：
Z选自：羟基、烷氧基、酯、仲胺或叔胺以及酮酰胺；
Y选自：氢、羧酸、磺酸或其盐、卤素以及具有1到12个碳原子的烷基；并且
A、A'、A"和A"'独立地选自：Z、氢、胺，其限制条件为A、A'、A"和A"'中的至少一者是伯胺或仲胺以及Y、A或A"中的至少一者是氢。
描述许多其它实施例。
具体实施方式
本发明不受膜或应用的特定类型、构造或形状的特定限制。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，本发明尤其适用于制备经设计用于RO和NF分离的不对称膜。RO膜相对不可渗透几乎所有溶解盐并且典型地阻挡超过约95%的单价离子盐，如氯化钠。RO复合膜还典型地阻挡超过约95%的无机分子以及分子量大于约100AMU（道尔顿）的有机分子。NF膜比RO膜片更可渗透并且典型地阻挡小于约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，这取决于二价离子的种类。NF膜还典型地阻挡在纳米范围内的粒子以及分子量大于约200到500AMU的有机分子。
复合聚酰胺膜的实例包括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典型厚度的多孔载体的中间层和包含厚度典型地小于约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。多孔载体典型地是孔径尺寸足以允许渗透物基本上不受限制通过，但并未大到足以干扰其上所形成的薄膜聚酰胺层桥接的聚合材料。举例来说，载体的孔径优选地介于约0.001到0.5μm范围内。多孔载体的非限制性实例包括由：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如聚偏二氟乙烯制备的那些。对于RO和NF应用来说，多孔载体提供强度，但由于其相对较高的孔隙度而几乎无流体流动阻力。
由于其相对较薄，聚酰胺层常常依据其在多孔载体上的涂布覆盖率或负载量加以描述，例如每平方米多孔载体表面积约2到5000mg聚酰胺，并且更优选的是约50到500mg/m2。如US 4277344和US 6878278中所描述，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缩聚反应在多孔载体表面上制备。更确切地说，聚酰胺膜层可以通过在多孔载体的至少一个表面上使多官能胺单体与多官能酰基卤单体（其中每个术语意图指代使用单一物质或多个物质）界面聚合而制备。如本文所用，术语“聚酰胺”是指酰胺键（—C(O)NH—）沿着分子链存在的聚合物。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载体，其中所述多官能胺单体典型地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载体上，继而涂布多官能酰基卤。涂布可以通过喷雾、涂膜、辊涂或经由使用浸渍槽以及其它涂布技术而实现。过量溶液可以通过气刀、干燥器、烘箱等从载体去除。
多官能胺单体包含至少两个伯氨基并且可以是芳香族（例如间苯二胺（mPD）、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、2,4-二氨基苯甲醚以及二甲苯二胺）或脂肪族（例如乙二胺、丙二胺、环己烷-1,3-二胺以及三(2-二氨基乙基)胺）。二胺是优选的。一种尤其优选的多官能胺是间苯二胺（mPD）。多官能胺单体可以按极性溶液形式施加到多孔载体。极性溶液可以含有约0.1到约10重量%并且更优选地约1到约6重量%多官能胺单体。在一组实施例中，极性溶液包括至少2.5重量%（例如2.5到6重量%）多官能胺单体。一旦涂布在多孔载体上，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并且优选不包含羧酸官能团并且可以由非极性溶剂涂布，但多官能酰基卤可以可替代地由气相传递（例如，对于具有充足蒸气压力的多官能酰基卤）。多官能酰基卤不受特别限制，并且可以使用芳香族或脂环族多官能酰基卤以及其组合。芳香族多官能酰基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、联苯二甲酰氯和萘二甲酰二氯。脂环族多官能酰基卤的非限制性实例包括：环丙烷三甲酰氯、环丁烷四甲酰氯、环戊烷三甲酰氯、环戊烷四甲酰氯、环己烷三甲酰氯、四氢呋喃四甲酰氯、环戊烷二甲酰氯、环丁烷二甲酰氯、环己烷二甲酰氯和四氢呋喃二甲酰氯。一种优选的多官能酰基卤是均苯三甲酰氯（TMC）。多官能酰基卤可以以约0.01到10重量%、优选0.05到3重量%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。在多官能胺单体浓度小于3重量%的一组实施例中，多官能酰基卤少于0.3重量%。
适合的非极性溶剂是能够溶解多官能酰基卤并且与水不可混溶的溶剂；例如烷烃（例如己烷、环己烷、庚烷、辛烷、十二烷）、异烷烃（例如ISOPARTML）、芳族物（例如SolvessoTM芳香族流体、VarsolTM非脱芳香族流体、苯、烷基化苯（例如甲苯、二甲苯、三甲苯异构体、二乙苯））以及卤化烃（例如FREONTM系列、氯苯、二氯苯和三氯苯）或其混合物。优选的溶剂包括对臭氧层几乎不造成威胁并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。优选溶剂是可购自埃克森化学公司（Exxon ChemicalCompany）的ISOPARTM。非极性溶液可以包括额外成分，包括共溶剂、相转移剂、增溶剂、络合剂以及除酸剂，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、丁基卡必醇TM乙酸酯（butylcarbitolTM acetate）、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）。非极性溶液还可以包括少量水或其它极性添加剂，但是浓度优选低于其在非极性溶液中的溶解度极限。
极性和非极性涂布溶液中的一者或两者可以另外包括如由式I表示的磷酸三烃酯化合物：
式（I）：
其中“P”为磷，“O”为氧，并且R1、R2和R3独立地选自氢和包含1到10个碳原子的烃基，其限制条件为R1、R2和R3中不超过一者是氢。R1、R2和R3优选地独立地选自脂肪族和芳香族基团。可适用的脂肪族基团包括支链和非支链种类，例如甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、2-戊基、3-戊基。可适用的环状基团包括环戊基和环己基。可适用的芳香族基团包括苯基和萘基。环状基团和芳香族基团可以借助于例如甲基、乙基等的脂肪族键联基团键联到磷原子。前述脂肪族和芳香族基团可以是未经取代或经取代的（例如，经取代的甲基、乙基、丙基、羟基、酰胺、醚、砜、羰基、酯、氰化物、腈、异氰酸酯、氨基甲酸酯、β-羟基酯等）；然而，具有3到10个碳原子的未经取代的烷基是优选的。磷酸三烃酯化合物的具体实例包括：磷酸三乙酯、磷酸三丙酯、磷酸三丁酯、磷酸三戊酯、磷酸三己酯、磷酸三苯酯、磷酸丙酯联苯酯、磷酸二丁酯苯酯、磷酸丁酯二乙酯、磷酸氢二丁酯、磷酸氢丁酯庚酯和磷酸丁酯庚酯己酯。所选择的种类应至少部分地可溶于由其涂布的溶液（即极性对非极性涂布溶液）中。其它实例是US 6878278、US 6723241、US 6562266和US 6337018中所描述的此类化合物。在一个优选实施例中，非极性溶液可以包括0.001到10重量%并且更优选地0.01到1重量%磷酸三烃酯化合物。在另一个实施例中，非极性溶液包括与多官能酰基卤单体呈1:5到5:1并且更优选1:1到3:1摩尔（化学计量）比的磷酸三烃酯化合物。
除多官能胺和酰基卤单体以外，在界面聚合中可以任选地包括额外含羧酸单体。代表性实例描述于US2013/0287944、US2013/0287945、US2013/0287946、WO2013/048765和WO2013/103666中。
一旦彼此接触，多官能酰基卤单体和多官能胺单体即在其表面界面处反应，形成聚酰胺层或膜。这一层，常常被称为聚酰胺“区别层”或“薄膜层”，向复合膜提供其用于使溶质（例如盐）与溶剂（例如水性进料）分离的主要方式。多官能酰基卤与多官能胺单体的反应时间可以小于一秒，但是接触时间典型地介于约1到60秒范围内。可以通过用水冲洗膜并且接着在例如约40℃到约120℃的高温下干燥来实现过量溶剂的去除，但可以使用在环境温度下的空气干燥。然而，出于本发明的目的，膜优选地不允许干燥，并且仅用水冲洗或浸渍于水中并且任选地在湿润状态下储存。
本发明进一步包括添加如以下式II所表示的“主题”胺化合物。主题胺化合物与前述包括多官能胺单体的单体不同。在一个实施例中，主题胺化合物在多官能胺与酰基卤单体的界面聚合期间存在，例如借助于与多官能胺单体组合并且由极性溶液涂布以使得化合物并入整个所得聚酰胺层中。在一个替代性实施例中，主题胺化合物在聚酰胺层形成之后例如借助于后续涂布步骤而施加到其。在这一替代性实施例中，主题胺化合物优先与聚酰胺层表面上存在的残余酰氯基反应。在又另一个实施例中，主题胺化合物在界面聚合期间存在并且也施加到所得聚酰胺层上。用于添加或施加主题胺化合物的特定技术不受特定限制，并且包括由极性或非极性溶液施加胺化合物（例如10-20000ppm）或将聚酰胺层浸泡于含有主题胺化合物的浸渍槽中以使得聚酰胺层变得被化合物浸透。在用主题胺化合物处理之后，使聚酰胺层暴露于亚硝酸。
主题胺化合物可以由式II表示。
式II：
其中：
Z选自：羟基（-OH）、烷氧基（例如包括具有1到5个碳的烷基，优选甲氧基-OCH3）、酯（例如-O-CO-CH3）、仲胺或叔胺（例如-NHR、-NRR'，其中R和R'是优选具有1到5个碳原子的烷基）以及酮酰胺（例如-NH-CO-CH2-CO-CH3）；
Y选自：氢（-H）、羧酸（-COOH）、磺酸或其盐（-SO3H）、卤素（-F、-Cl、-Br、-I）以及具有1到12个碳原子的烷基；并且
A、A'、A"和A"'独立地选自：Z、氢和胺（伯胺、仲胺或叔胺，但优选伯胺或仲胺，包括具有1到5个碳原子的烷基），其限制条件为A、A'、A"和A"'中的至少一者是胺（伯胺或仲胺）以及Y、A或A"中的至少一者是氢。
在一子组优选实施例中：1）Z和A'或A"'中的至少一者是羟基，其限制条件为A或Y中的至少一者是氢；2）Z和A'或A"'中的至少一者是仲胺或叔胺，其限制条件为A或Y中的至少一者是氢；3）Z选自：羟基或甲氧基；Y选自：氢、卤素或羧酸；并且A、A'、A"和A"'独立地选自：氢和胺，其限制条件为A、A'、A"和A"'中的至少一者是伯胺或仲胺以及A或A"中的至少一者是氢；4）Z选自羟基，A'选自羟基，并且A是氢，其限制条件为A"、A'"或Y中的至少一者是胺；以及5）Z选自羟基，A”'选自羟基，Y是氢，其限制条件为A、A'或A"中的至少一者是伯胺或仲胺。在每种情况下，羟基可以“受保护”为乙酸酯或经取代的硅烷（例如叔丁基-二甲基硅烷）。“受保护”基团可以随后在用亚硝酸后处理之前通过简单地用水溶液洗涤膜而去除。
优选的主题胺化合物种类包括：3,5-二氨基苯酚、2,4-二氨基苯酚、3-氨基苯酚、2-氨基苯酚、4-氨基苯酚、5-氨基苯-1,3-二醇、3-氨基-5-羟基苯甲酸、3-氨基-5-羟基苯磺酸、5-甲氧基苯-1,3-二胺、4-甲氧基苯-1,3-二胺、3-甲氧基苯胺、2-甲氧基苯胺、4-甲氧基苯胺、3-氨基-5-甲氧基苯甲酸、3-氨基-5-甲氧基苯磺酸、、N1,N1-二甲基苯-1,3-二胺、N1,N1-二甲基苯-1,3,5-三胺、N1,N1,N3,N3-四甲基苯-1,3,5-三胺、N,N'-(5-氨基-1,3-亚苯基)双(3-氧代丁酰胺)、N-(4-氨基苯基)-3-氧代丁酰胺、5-氨基-1,3-亚苯基双(2,2,2-三氟乙酸酯)、5-氨基-1,3-亚苯基二乙酸酯、3,5-双((叔丁基二甲基硅烷基)氧基)苯胺、(3,5-双((叔丁基二甲基硅烷基)氧基)苯基)甲胺、2-(3,5-双((叔丁基二甲基硅烷基)氧基)苯基)乙胺。代表性化学式如下：
多种可适用的用亚硝酸后处理聚酰胺层的技术描述于US 4888116中，并且以引入的方式并入本文中。据信，亚硝酸与存在于聚酰胺区别层中的残余伯氨基反应以形成重氮盐基团，其一部分与主题活性胺化合物、聚酰胺层中的残余未反应胺或苯酚反应，导致重氮盐水解形成偶氮基团，即在聚酰胺结构中形成交联。代表性反应方案提供如下。
在一个实施例中，将亚硝酸的水溶液施加到薄膜聚酰胺层上。尽管水溶液可以包括亚硝酸，但是其优选包括当场形成亚硝酸的试剂，例如含碱金属亚硝酸盐的酸溶液或亚硝酰硫酸。因为亚硝酸是挥发性的并且易分解，所以其优选地通过使含碱金属亚硝酸盐的酸性溶液与聚酰胺区别层接触的反应而形成。一般来说，如果水溶液的pH小于约7（优选地小于约5），那么碱金属亚硝酸盐将反应以释放亚硝酸。亚硝酸钠在水溶液中与盐酸或硫酸反应是用于形成亚硝酸所尤其优选的。水溶液可以进一步包括湿润剂或表面活性剂。亚硝酸在水溶液中的浓度优选地是0.01到1重量%。一般来说，亚硝酸在5℃下比在20℃下可溶性更高，并且略微较高浓度的亚硝酸可在较低温度下操作。只要膜不受有害影响并且可以安全地操纵溶液，则较高浓度是可操作的。一般来说，亚硝酸浓度高于约二分之一（0.5）百分比由于处置这些溶液的困难而并非优选的。优选地，亚硝酸由于其在大气压下的有限溶解度而以约0.1重量百分比或更小的浓度存在。膜接触时的温度可以在宽范围变化。由于亚硝酸并非特别稳定，所以一般需要使用约0℃到约30℃范围内的接触温度，其中0℃到约20℃范围内的温度是优选的。高于这一范围的温度可能增加处理溶液上方通风或超大气压的需要。低于优选范围的温度一般导致反应速率和扩散速率降低。
一种优选的施加技术涉及使亚硝酸水溶液以连续流形式经过膜表面。这允许使用相对低浓度的亚硝酸。当亚硝酸从处理介质耗尽时，其可以补充并且使介质再循环到膜表面以便额外处理。分批处理也是可操作的。用于施加亚硝酸水溶液的特定技术不受特别限制并且包括喷雾、涂膜、辊涂或经由使用浸渍槽以及其它施加技术。一旦经处理，则膜可以用水洗涤并且在使用前湿润或干燥储存。
一旦亚硝酸扩散到膜中，则亚硝酸与聚酰胺层伯氨基之间的反应相对快速地进行。扩散所需的时间和需要进行的反应将取决于亚硝酸浓度、膜的任何预湿润程度、所存在伯氨基的浓度、膜的3维结构以及进行接触的温度。接触时间可以在数分钟到数天的范围内变化。对于特定膜和处理来说，可以容易地凭经验确定最优反应时间。在残余胺部分转化为重氮盐之后，pH可以升高到6-9并且温度增加到25℃，以起始一部分重氮盐向苯酚的水解以及重氮盐、苯酚或来源于主题胺并入的官能化环之间的偶氮偶合。
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、聚丙烯酰胺以及如US 6280853、US 7815987、US 7918349和US 7905361中概述的相关反应产物。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另外施加到聚酰胺膜或依次施加。
已经描述了本发明的多个实施例并且在一些情况下，已经将某些实施例、选择、范围、成分或其它特征表征为“优选的”。“优选”特征的表征决不应解释为将此类特征视作是本发明所需的、必需的或至关重要的。
Claims (10)
1.一种用于制造包含多孔载体和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：
i)将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施加到多孔载体的表面上，并且使所述单体界面聚合以形成聚酰胺层；以及
ii)使所述薄膜聚酰胺层暴露于亚硝酸；
其中所述方法的特征在于以下各者中的至少一者：
a)在主题胺化合物存在下进行步骤i)的界面聚合，和
b)在步骤ii)之前将主题胺化合物施加到所述界面聚合的聚酰胺层，
其中所述主题胺化合物与所述多官能胺单体不同并且由下式表示：
其中：
Z选自：羟基、烷氧基、酯、仲胺或叔胺以及酮酰胺；
Y选自：氢、羧酸、磺酸或其盐、卤素、胺以及具有1到12个碳原子的烷基；并且
A、A'、A"和A"'独立地选自：Z、氢、胺，其限制条件为A、A'、A"和A"'中的至少一者是伯胺或仲胺以及Y、A或A"中的至少一者是氢。
2.根据权利要求1所述的方法，其中Z和A'或A"'中的至少一者是羟基，其限制条件为A或Y中的至少一者是氢。
3.根据权利要求1所述的方法，其中Z和A'或A"'中的至少一者是仲胺或叔胺，其限制条件为A或Y中的至少一者是氢。
4.根据权利要求1所述的方法，其中：Z选自：羟基或甲氧基；Y选自：氢、卤素或羧酸；并且A、A'、A"和A"'独立地选自：氢和胺，其限制条件为A、A'、A"和A"'中的至少一者是伯胺或仲胺以及A或A"中的至少一者是氢。
5.根据权利要求1所述的方法，其中：Z选自羟基，A'选自羟基，并且A是氢，其限制条件为A"、A"'或Y中的至少一者是伯胺或仲胺。
6.根据权利要求1所述的方法，其中：Z选自羟基，A"'选自羟基，Y是氢，其限制条件为A、A'或A"中的至少一者是伯胺或仲胺。
7.根据权利要求1所述的方法，其中所述多官能胺是双官能胺。
8.根据权利要求1所述的方法，其中所述极性和非极性溶液中的至少一者进一步包含由下式表示的磷酸三烃酯化合物：
其中R1、R2和R3独立地选自氢和包含1到10个碳原子的烃基，其限制条件为R1、R2和R3中不超过一者是氢
9.根据权利要求1所述的方法，其中所述主题胺化合物与所述多官能胺单体组合于步骤i)的所述极性溶液内。
10.根据权利要求1所述的方法，其中所述主题胺化合物选自以下各者中的至少一者：3,5-二氨基苯酚、2,4-二氨基苯酚、3-氨基苯酚、2-氨基苯酚、4-氨基苯酚、5-氨基苯-1,3-二醇、3-氨基-5-羟基苯甲酸、3-氨基-5-羟基苯磺酸、5-甲氧基苯-1,3-二胺、4-甲氧基苯-1,3-二胺、3-甲氧基苯胺、2-甲氧基苯胺、4-甲氧基苯胺、3-氨基-5-甲氧基苯甲酸、3-氨基-5-甲氧基苯磺酸、、N1,N1-二甲基苯-1,3-二胺、N1,N1-二甲基苯-1,3,5-三胺、N1,N1,N3,N3-四甲基苯-1,3,5-三胺、N,N'-(5-氨基-1,3-亚苯基)双(3-氧代丁酰胺)、N-(4-氨基苯基)-3-氧代丁酰胺、5-氨基-1,3-亚苯基双(2,2,2-三氟乙酸酯)、5-氨基-1,3-亚苯基二乙酸酯、3,5-双((叔丁基二甲基硅烷基)氧基)苯胺、(3,5-双((叔丁基二甲基硅烷基)氧基)苯基)甲胺以及2-(3,5-双((叔丁基二甲基硅烷基)氧基)苯基)乙胺。
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| CN110404417A (zh) * | 2019-07-19 | 2019-11-05 | 中国石油大学(华东) | 聚酰胺膜的改性方法及改性聚酰胺膜 |
| CN111569676A (zh) * | 2020-06-02 | 2020-08-25 | 四川大学 | 超滤膜、纳滤膜及其制备和超滤-纳滤可逆转换的方法 |
| CN111569676B (zh) * | 2020-06-02 | 2021-07-27 | 四川大学 | 超滤膜、纳滤膜及其制备和超滤-纳滤可逆转换的方法 |
| CN115228290A (zh) * | 2022-08-03 | 2022-10-25 | 万华化学集团股份有限公司 | 一种耐清洗反渗透膜的制备方法 |
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| US9943810B2 (en) | 2018-04-17 |
| JP6640739B2 (ja) | 2020-02-05 |
| KR102359211B1 (ko) | 2022-02-07 |
| KR20170009883A (ko) | 2017-01-25 |
| WO2015175258A1 (en) | 2015-11-19 |
| CN106232216B (zh) | 2019-10-11 |
| US20170203259A1 (en) | 2017-07-20 |
| JP2017518174A (ja) | 2017-07-06 |
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