CN104607074B - A kind of preparation method containing azobenzene polyamide reverse osmosis composite film - Google Patents
A kind of preparation method containing azobenzene polyamide reverse osmosis composite film Download PDFInfo
- Publication number
- CN104607074B CN104607074B CN201510015750.0A CN201510015750A CN104607074B CN 104607074 B CN104607074 B CN 104607074B CN 201510015750 A CN201510015750 A CN 201510015750A CN 104607074 B CN104607074 B CN 104607074B
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- CN
- China
- Prior art keywords
- reverse osmosis
- azo
- monomer
- composite film
- osmosis composite
- 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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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 41
- 229920002647 polyamide Polymers 0.000 title claims abstract description 36
- 239000004952 Polyamide Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 66
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 65
- 239000012528 membrane Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001338 self-assembly Methods 0.000 claims abstract description 21
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 230000010148 water-pollination Effects 0.000 claims abstract description 6
- -1 Azo amide Chemical class 0.000 claims description 53
- 229920001519 homopolymer Polymers 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 36
- 210000004379 membrane Anatomy 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000002464 physical blending Methods 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 210000002469 basement membrane Anatomy 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 229920001002 functional polymer Polymers 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229940059939 kayexalate Drugs 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- 239000004697 Polyetherimide Substances 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims 1
- 229920002492 poly(sulfone) Polymers 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 229920001601 polyetherimide Polymers 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 20
- 238000005516 engineering process Methods 0.000 abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 230000004907 flux Effects 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 4
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 229940113088 dimethylacetamide Drugs 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000000707 layer-by-layer assembly Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Inorganic materials [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical class C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- HRMMNIKBLMRRJP-UHFFFAOYSA-N 2,4-dimethylpentane Chemical compound CC(C)[C]C(C)C HRMMNIKBLMRRJP-UHFFFAOYSA-N 0.000 description 1
- OITNBJHJJGMFBN-UHFFFAOYSA-N 4-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CCl)C=C1 OITNBJHJJGMFBN-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical compound CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- WFACWTZLXIFJCM-UHFFFAOYSA-N 5-(chloromethyl)-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(CCl)C=C1C=O WFACWTZLXIFJCM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007821 HATU Substances 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QARMSQRZTXVCAA-UHFFFAOYSA-N bis(2-nitrophenyl)diazene Chemical compound [O-][N+](=O)C1=CC=CC=C1N=NC1=CC=CC=C1[N+]([O-])=O QARMSQRZTXVCAA-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NNIYFVYSVUWTOA-UHFFFAOYSA-N copper hydrochloride Chemical compound Cl.[Cu] NNIYFVYSVUWTOA-UHFFFAOYSA-N 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Polyamides (AREA)
Abstract
The invention provides a kind of preparation method containing azobenzene polyamide reverse osmosis composite film.Particular by the introducing of the hydrophily functional groups such as serial azobenzene photoresponse group and carboxyl, sulfonic group, synthesis has the azo-type anion/cation polyamides amine functions self assembly molecule of ultraviolet light response and hydrophilicity concurrently, then by electrostatic self-assembled and interlayer original position photochemically reactive integrated with couple, both by layer-by-layer and ultraviolet light（UV）Curing technology combination of sciences, prepares that the number of plies is controllable, and interlayer covalent bond is firmly crosslinked, and membrane body is electrically charged, mechanical strength is good, salt rejection rate and water flux is high, antifouling property is strong polyamide reverse osmosis composite film containing azobenzene.
Description
Technical field
The present invention relates to reverse osmosis membrane preparation field, relates in particular to a kind of polyamide reverse osmosis composite film containing azobenzene
Production method.
Background technology
At present, the general counter-infiltration of domestic and international commercialization（RO）Film mostly is the polyamide-based composite membrane containing azobenzene, and which prepares master
Polyamine to be adopted and the interfacial polymerization of polynary acyl chlorides, but there is complicated process of preparation in which, and relatively costly, skin layer thickness is not
Easy to control, and the critical defect such as environmental pollution is serious.Therefore, further develop and apply novel high-performance reverse osmosis composite membrane,
The study hotspot of always scientific circles and industrial quarters.
The performance of reverse osmosis composite membrane is closely bound up with the component of its ultra-thin separating layer, structure and form.Therefore, select special
Color material of preparing and using science film build method preparing its ultra-thin separating layer, will obtain high-performance reverse osmosis composite membrane
The key breakthrough points.
LBL self-assembly (layer-by-layer assembly, LbL) technology, especially dynamic LBL self-assembly, is one
Plant simple and the Ultrathin Multilayer of practicality constructs technology.It can be adjusted by the design of assembled material, optimization of assembling condition etc.
Control means, are more conveniently realized the control to membrane structure and function in the range of molecular dimension, can be graded by change group again
Method realizes the integrated of difference in functionality, while also having concurrently, easy to operate, preparation technology and equipment are simple, raw material sources are extensive, ring
The advantages of border pollution is little, is particularly applied to preparing for seperation film with the obvious advantage.The separation characteristic of film is determined by the aperture of film
, the flux of film is inseparable with its skin thickness.Self-assembled film is then because the composition of energy effective control superthin layer, structure and shape
State, so that be easier to realize effective, the accurately dual regulation and control that separate membrane aperture and thickness.Further, since dividing prepared by LBL technology
From film, its membrane body carries electric charge, and according to Preferential adsorption capillary stream principle, which will have to organic matters such as bacterium, viruses
Good removal effect, so as to effectively improve the antifouling property of seperation film, increases the service life.
Although as described above, LBL technology is applied to the preparation of seperation film has unrivaled advantage, current LBL
Technology is based primarily upon electrostatic attraction layer-layer self assembly, weaker assembling driving force and unstable intermolecular interaction, causes
The stability of assembling film and intensity is not good enough.
Ultraviolet light（UV）Solidification is a kind of new material surface treatment advanced technology that developed recently gets up, and it has height
The advantages of effect, energy-conservation, economy, environmental protection, wide adaptability, and it is widely used in the industries such as coating, printing, membrane technology.But in LBL
In technology, still do not apply, how two kinds of technology to be combined, the reverse osmosis composite membrane for preparing high intensity and stability is current
Need the difficult problem that captures.
Content of the invention
The present invention is directed to deficiency of the prior art, and the technical barrier for existing, and has carried out the research and exploration of science, has carried
A kind of preparation method containing azobenzene polyamide reverse osmosis composite film is supplied.
A kind of preparation method containing azobenzene polyamide reverse osmosis composite film of the present invention.By diazonium-coupling, acyl
Amination, the design and optimization of free radical polymerization process route, by azobenzene group, amide group and anion/cation hydrophilic radical,
Introduced in function self assembly molecule respectively, prepare the side chain type anion/cation azobenzene for having ultraviolet light response and hydrophile function concurrently
Polyamide self-assembling function monomer layer by layer, and the collection by the physical blending method such as free radical solution polymerization and supersonic oscillations
Into the host-guest doping type copolymer for preparing Integrated Films, hydrophily, mechanical property, stability and ultraviolet light response in one is micro-
Hole basement membrane.Then in conjunction with the improvement dynamic layer-by-layer of ultraviolet light polymerization post processing, the preparation number of plies is controllable, layer
Between covalent bond be firmly crosslinked, the charged low stain of membrane body, high intensity, the new reverse osmosis of polyamide containing azobenzene of high stability
Saturating composite membrane.
Specifically preparation method is：
A kind of preparation method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
（1）P-aminoazobenzene derivative（A）Synthesis
Anil is chosen, is dissolved in water, its mass percent concentration in aqueous is 1% ~ 50%；Treat
After above-mentioned anil is dissolved completely in water, add in the aqueous solution with substituted aroma primary amine molal weight ratio be 1.0 ~
1.5 natrium nitrosum, stirring and dissolving prepare mixed liquor；Above-mentioned mixed liquor is poured slowly into mass percent concentration for 1% ~ 20%
HCl solution in, the Hcl solution temperatures be 0 ~ 5 DEG C, with substituted aroma primary amine mol ratio be 1.0 ~ 5.0, after reaction, with shallow lake
Completely whether, it is unnecessary in dereaction to be removed with the aqueous solution of urea that weight concentration is 1% ~ 20% for powder-potassium iodide starch paper inspection reaction
Nitrous acid；By above-mentioned reacting liquid filtering, the filtrate for obtaining is diazonium salt solution, and cooling is placed.
By the one kind in anil, it is dissolved in the water, its weight concentration in aqueous is 1% ~ 50%；To above-mentioned
The HCl for accounting for the lysate weight 0.05% ~ 5% being added in anil lysate, being stirred vigorously, reaction temperature is 0 ~ 60 DEG C,
Prepare mixed liquor；In the diazonium salt solution of the slow cooling by described in the addition 1. of above-mentioned mixed liquor, product is obtained to ammonia
Base azobenzene derivatives, treat that P-aminoazobenzene derivative is separated out completely, through filtering, recrystallizing and use saturated sodium-chloride successively
Solution, ethanol solution, deionized water are washed and then are dried in vacuum tank, obtain final product the product P-aminoazobenzene derivative
A.
The anil, can be neighbour/para-totuidine, acetyl group aniline, right/ortho-nitraniline, neighbour/to carboxyl benzene
Amine, neighbour/to aniline sulfonic acid, a kind of in substituted aromatic primary amine, preferably, substituted aromatic primary amine.
（2）Side chain type azo acid amides function monomer（B）Synthesis
Choose and carry carboxylic acid group（-COOH）Functional polymer, be dissolved in organic solvent, such as cyclohexanone, benzene first
Ether, tetrahydrofuran, acetonitrile, dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE（NMP）, N,N-dimethylformamide（DMF）、
Dimethyl acetamide（DMA）, dichloromethane（DCM）, in dioxane or diethylene glycol dimethyl ether, its weight in organic solution
Amount concentration is 5% ~ 50%, after above-mentioned functions macromolecule is completely dissolved, then is 0.5 ~ 20 by itself and carboxyl molal weight ratio successively
Add step（1）Middle products therefrom A, adds condensing agent by itself and carboxyl molal weight than 1 ~ 30, adds and with carboxyl mol ratio is
0.01 ~ 10 catalyst, reaction temperature are 0 ~ 100 DEG C, and the reaction time is 1 ~ 24h, by being condensed acylation reaction, prepares side chain type
Azo acid amides function monomer, as product B.
Described with carboxylic acid group（-COOH）Functional polymer can be methacrylic acid, acrylic acid, methacrylic acid,
One kind in paranitrobenzoic acid, benzoic acid or a- hydroxyacetic acids.
Described organic solvent can be organic solvent, such as cyclohexanone, methyl phenyl ethers anisole, tetrahydrofuran, acetonitrile, dimethyl sulfoxide (DMSO)
(DMSO), 1-METHYLPYRROLIDONE（NMP）, N,N-dimethylformamide（DMF）, dimethyl acetamide（DMA）, dichloromethane
（DCM）, one kind in dioxane or diethylene glycol dimethyl ether.
The condensing agent can be 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides（EDCI）, diisopropyl carbon two
Imines (DIC), O- (7- azepine BTA -1- bases)-two（Dimethylamino）Carbon hexafluorophosphate（HATU）Or O-（Benzene
And triazole -1- bases)-two（Dimethylamino）Carbon hexafluorophosphate（HBTU）Deng, in one or more mixing.
The catalyst can such as be N- diisopropylethylamine (DIEA), triethanolamine（TEA）, I-hydroxybenzotriazole
（HOBT）, 4-N, N- lutidines（DMAP）Or 1- hydroxy benzo triazoles (HOBt) etc..
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
In microwave（MI）Under the conditions of, using active/controllable ATRP（ATRP）Technology, in idol
In nitrogen monomer B/ catalysis-initiator systems and organic solvent, homopolymerization is carried out to above-mentioned product B and wherein reacts 10min ~ 2h, micro-
Wave radiation power is 300W～900W.Azo monomer B/ catalysis-initiator systems proportioning preferably 10 ~ 60/0.5 ~ 10/0.5 ~ 10/0.5
~10.Azo amide homopolymer of the serial end group of synthesis gained containing ω-halogen group is product C.
Described azo monomer B/ catalysis-initiator systems can be such as 2- isobutyl ethyl bromides（2-EbiB）Five first of/CuBr/
Base diethyl triamine（PMDETA）, p-chloromethyl benzoic acid (CMBA)/CuCl/2,2'- bipyridyls (bpy), 5- chloromethyl -2-
Hydroxy benzaldehyde (the CMHB)/iodo- 2,3- dimethylbutanes of CuBr/4,4'- bis--tertiary butyls -2,2'- bipyridyls (dTbpy), 2-/
Bis- (5- nonyls) -2 of CuI/4,4'- bis--n-heptyls -2,2'- bipyridyls (dHbpy) or paratoluensulfonyl chloride/CuCl/4,4'-,
2'- bipyridyls (dNbpy) etc..
Described organic solvent can be such as tetrahydrofuran, acetonitrile, dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE
（NMP）, N,N-dimethylformamide（DMF）, dimethyl acetamide（DMA）, dichloromethane（DCM）, dioxane or diethyl two
Diethylene glycol dimethyl ether etc..
（4）Azobenzene ＆ MMA block copolymers（D）Synthesis
In above-mentioned azo amide homopolymer synthetic system, the good flexible unit methyl methacrylate of addition filming performance
Ester（MMA）, wherein azo amide monomer is 1 with MMA molal weights ratio:1~1:10, remaining with（3）Described in consistent, synthesis is even
Pyridine ＆ MMA block copolymers are product D.
（5）Chain anion/cation azo amide homopolymer（E）Synthesis
On the basis of the synthesis of the azo amide homopolymer of ω-halogen group, using its halogen group and series with cloudy/
, there is nucleophilic substitution in the compound of positive functional group, introduce anion/cation functional groups respectively in azopolyamide structure
In, prepare side chain type anion/cation azo amide homopolymer, as product E.
Described band Yin/Yang functional compounds can be hexamethylene diamine, shitosan（CHI）, cetyl trimethyl chlorination
Ammonium, triethylbenzyl ammonium chloride, sodium sulfanilate, kayexalate（PSS）, phenol, acrylic or methacrylic
Acid.
（6）The powered micropore basal membrane of self assembly（F）Synthesis
Hydrophily, stability and the equal good filming thing of copolymerization performance are chosen as polymerized monomer M, hydrophily band is simultaneously introduced
Electricity Functional monomer, preferably acrylic acid（AA）, vinyl alcohol, ethylene glycol, in acrylamide etc. a kind of as polymerized monomer N, causing
In agent, and organic solvent, by the method for free radical solution polymerization, synthesize bulk copolymer needed for basement membrane, monomer ratio（M:N）
Molal weight ratio is 1:1~100:1, solvent load is 1 ~ 100 times of total weight of monomer, and initiator amount is total weight of monomer 0.05% ~ 2%,
Polymerization temperature is 0 ~ 100 DEG C, and polymerization time is 1h ~ 24h, after polymerisation terminates, adds step（4）Described in product D, and
By the method for the physical blendings such as supersonic oscillations, be well-dispersed in above-mentioned polymerization liquid, prepare concentration be 5% ~
The host-guest doping system copolymer casting solution of 20wt%, is then cast to this casting solution on 10 ~ 80 DEG C of glass support plate,
With gripper shoe to be put into rapidly after glass bar knifing freezing film in deionized water, the THICKNESS CONTROL of film at 50 ~ 100 μm, ethanol:
Deionized water:KOH weight proportions are 10 ~ 60: 40~20:50 ~ 20, temperature is 20 ~ 50 DEG C, is cleaned by ultrasonic 30min ~ 2h, then
Deionized water is fully embathed, nitrogen dry up standby, as powered micropore basal membrane needed for self assembly, as product F.
The initiator can be such as azodiisobutyronitrile（AIBN）, ABVN, benzoyl peroxide or sulfurous
Sour hydrogen sodium etc..
The organic solvent can be such as cyclohexanone, methyl phenyl ethers anisole, N,N-dimethylformamide（DMF）, dimethyl acetamide
（DMA）, dichloromethane（DCM）, dioxane or diethylene glycol dimethyl ether etc..
Further, the monomer ratio（M:N）For 1:1~20:1,1 ~ 30 times of solvent load preferred monomers gross weight, polymerization
Preferably 0 ~ 50 DEG C of reaction temperature, ethanol:Deionized water:KOH weight proportions are 10 ~ 30: 40~20: 50.
（7）Polyamide reverse osmosis composite film containing azobenzene（G）Synthesis
By step（5）Middle synthesis gained side chain type anion/cation azo amide homopolymer E is dissolved in deionized water, is prepared
Into the solution that concentration is 0.5 ~ 10mg/ml.Again by step（6）The powered micropore basal membrane F of middle synthesis gained is in above-mentioned product E（Side
Chain cationic azo amide homopolymer）In the aqueous solution, 2 ~ 60min of immersion carrys out self assembly side chain type cationic azo acid amides, takes out
Deionized water is cleaned, and nitrogen is dried up, then immerses product E（The side chain type anion azo amide homopolymer aqueous solution）2 ~ 60min,
Clean after taking-up and dry up, complete once to assemble circulation, repeat above operation, obtain self-assembled multilayer film.
Whole self assembling process is carried out under lucifuge.4 ~ 60 layers of azo acid amides film will be assembled again to use at 5 ~ 50cm of distance
The mercury lamp (365nm) of 25W, UV expose 10 ~ 60min, and exposure finishes rear film layer color burn.As self assembly reverse osmosis containing azobenzene
Saturating composite membrane G.
Beneficial effects of the present invention are：Method of the present invention will independently fill technology and ultraviolet light layer by layer（UV）Solidification skill
Art combination of sciences, prepares that the number of plies is controllable, and interlayer covalent bond is firmly crosslinked, membrane body is charged be prepared for mechanical strength good,
Salt rejection rate and the polyamide reverse osmosis composite film containing azobenzene that water flux is high, antifouling property is strong.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not constitutes any type of any restriction, more non-general to the real protection scope of the present invention
Protection scope of the present invention is confined to this.
Embodiment 1
A kind of production method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
（1）P-aminoazobenzene derivative（A）Synthesis
Take 5.5g（0.04mol）Paranitroanilinum, plus 16g（0.16mol）Dense HCl and 20gH20, the lower heating for dissolving of stirring,
Then cooled down with ice-water bath, make the fine crystals of precipitation hydrochloride.3.3g is separately taken（0.048mol）Natrium nitrosum, plus 18gH20 matches somebody with somebody
Into solution, fast drop is stirred vigorously 30 min of lower reaction in above-mentioned hydrochloride.With the inspection reaction of starch monoiod(in)ate potassium test paper
Whether completely, with urea except the unnecessary nitrous acid of generation in dereaction.By reacting liquid filtering, the yellow filtrate that clarifies is obtained i.e.
Diazonium salt solution for paranitroanilinum.
Take 8.3g（0.048mol）P-aminobenzene sulfonic acid and 1.0g（0.01mol）Concentrated hydrochloric acid, plus 30gH2O stirring and dissolvings, put
Cool down in ice bath, above-mentioned diazonium salt solution is slowly instilled under stirring, completion of dropping continues stirring 60min.Second is added in three batches
Sour sodium, every time plus 4.0g, every 30min plus once.Now there are a large amount of solids to separate out in solution.At being continually maintained in less than 5 DEG C
Stirring reaction 5 hours or so.By reactant liquor suction filtration, and washed with saturated nacl aqueous solution, ethanol solution, deionized water successively,
Then dry in vacuum tank, the pressed powder for obtaining is to amino azo nitrobenzene（A1）.
（2）Side chain type azo acid amides function monomer（B）Synthesis
Sequentially add in 150ml round-bottomed flasks and take 3.4g（0.04mol）Methacrylic acid, 9.7g（0.04mol）Step
（1）Middle products therefrom A1,70g（1.0mol）N,N-dimethylformamide（DMF）, after stirring and dissolving at 50 DEG C, then add successively
Enter catalyst 12g（0.08mol）Triethanolamine（TEA）, add condensing agent 1- (3- dimethylamino-propyls) -3- ethyl carbon in four batches
Diimine（EDCI）, every time plus 2.0g, every 30min plus once.Feed intake and finish, be continually maintained in stirring reaction at 50 DEG C
40min or so.After reaction terminates, in 30ml methyl alcohol Precipitation polymer, again by reactant liquor suction filtration, a large amount of deionizations washings
Wash, be vacuum dried.The pressed powder for obtaining is Methacrylamide azo nitrobenzene（B1）.
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
31.1g is weighed successively（0.1mol）Step（2）Described in azo monomer B1, 3.9g（0.02mol）2- isobutyl bromides
Ethyl ester（2-EbiB）/ 2.9g（0.02mol）CuBr/ 3.5g（0.02mol）Pentamethyldiethylenetriamine（PMDETA）It is catalyzed-draws
Agent is sent out in the two mouthfuls of round-bottomed flasks of 500ml with reflux, and adds 50ml cyclohexanone as solvent, add magnetic stir bar
After being sufficiently stirred for, it is put in the reactor equipped with carbon tetrachloride, and fills repeatedly under vacuo-take out in 4 ~ 6 cleared flasks of nitrogen
Oxygen and nitrogen charging gas shielded after flask mouth is sealed, adjust microwave power constant in 450W, irradiated heat makes carbon tetrachloride
Backflow (76.8 DEG C of b.p.), continuous irradiation 30min, rapid two mouthfuls of flasks of taking-up are put in refrigerator and are cooled down.Plus 50mlTHF is dilute then
Release polymer fluid, make precipitating agent by polymer fibrids out with the methyl alcohol of 150 ~ 200ml, during by volume 1/100（v/v）Plus
Hydrochloric acid copper removal.Suction filtration simultaneously washs filter cake with a large amount of methyl alcohol, and vacuum drying obtains end group containing ω-halogen group azo acid amides homopolymerization
Thing（C1）.
（4）Azobenzene ＆ MMA block copolymers（D）Synthesis
Press above-mentioned steps（3）Described in, weigh 5.0g respectively（0.05mol）Methyl methacrylate（MMA）And 15.6g
（0.05mol）Step（2）Described in azo monomer B1,Replace（3）Described in 31.1g（0.1mol）Step（2）Described in azo list
Body B1, remaining presses step（3）Described in consistent, synthesis azobenzene ＆ MMA block copolymers are product D1.
（5）Chain anion/cation azo amide homopolymer（E）Synthesis
Contain ω-halogen group azo amide homopolymer using end group（C1）In, the nucleophilic of halogen group and particular functional group
Substitution reaction, is introduced into anion/cation in azo amide structure.
A anion azo amide homopolymers（E）Synthesis
40g phenol, step are sequentially added in the 500ml there-necked flasks with reflux condensation mode with agitating device（3）Middle conjunction
Into products therefrom C178.2g, 150 ~ 200ml of solvent acetone, and stir, then fill repeatedly under vacuo-take out nitrogen
Oxygen in 4 ~ 6 cleared flasks, and flask mouth is sealed after nitrogen charging gas shielded, heating reflux reaction in 80 DEG C of oil baths is placed in,
After reaction 12h, reaction unit is pulled down, solution left standstill in bottle obtains upper strata yellow solution, is then carried out vacuum distillation, control
Vacuum processed is -0.09MPa, and unnecessary phenol and solvent acetone steams by vapo(u)rizing temperature≤65 DEG C successively, remaining be cloudy from
Sub- azo amide homopolymer（E1a）.
B cationic azo amide homopolymers（E）Synthesis
Press above-mentioned anion azo amide homopolymer（E1a）Synthesis described in, with 25g hexamethylene diamines replace 40g phenol, remaining
Constant, synthesizing cationic azo amide homopolymer（E1b）.
（6）The powered micropore basal membrane of self assembly（F）Synthesis
To in stirring, the 500ml four round flask of reflux, 5.5ml acrylic acid is separately added into successively（AA）、
47.4ml acrylonitrile（AN）, 233ml dimethyl sulfoxide (DMSO)s（DMSO）, and after stirring, constant temperature 3h in 30 DEG C of oil baths is placed in,
Then the oxygen for filling repeatedly under vacuo-taking out in 4 ~ 6 cleared flasks of nitrogen, adds 0.3284g azodiisobutyronitriles（AIBN）,
And flask mouth is sealed after nitrogen charging gas shielded, in 1h, then it is warming up to 60 DEG C.After continuing to keep 60 DEG C of reaction 10-11h, stop
Reaction.Then 20g steps are weighed（4）Middle synthesis products therefrom D1, add in above-mentioned polymerization liquid, and pass through supersonic oscillations
Deng the method for physical blending, product D is well-dispersed in above-mentioned polymerization liquid, prepares host-guest doping system copolymer
（P（AN-co-AA）- azobenzene ＆ MMA）Casting solution, casting solution is cast on 50 DEG C of glass support plate, is scraped with glass bar
After film, gripper shoe is put into rapidly freezing film in deionized water, the thickness of film is with being fixed on the poly- of known thickness in gripper shoe
Ester film（100 microns）It is controlled, is subsequently placed in 30 DEG C of temperature, by 30: 60:The ethanol of 10 weight proportions:Deionized water:
In KOH mixed liquors, be cleaned by ultrasonic 40min, then fully embathed with a large amount of deionized waters, nitrogen dry up standby, as self assembly institute
Need powered micropore basal membrane, as product F1.
（7）Polyamide reverse osmosis composite film containing azobenzene（G）Synthesis
By step（5）Middle synthesis gained side chain type anion/cation azo amide homopolymer E1a/1bDeionized water is dissolved in respectively
In, it is configured to the solution that concentration is 10mg/ml.Again by step（6）The powered micropore basal membrane F of middle synthesis gained1In above-mentioned E1b（Side
Chain cationic azo amide homopolymer）In the aqueous solution, immersion 30min carrys out self assembly side chain type cationic azo acid amides, takes out and uses
Deionized water is cleaned, and nitrogen is dried up, then immerses E1a（Side chain type anion azo amide homopolymer）Aqueous solution 30min, after taking-up
Clean and dry up, complete once to assemble circulation, repeat above operation 20 times, obtain assembling 20 layers of azo acid amides composite membrane.Then
Placed it at mercury lamp (365nm) 20cm away from 5W again, UV exposes 50min, exposure finishes rear film layer color burn.As layer by layer
Self assembly reverse osmosis composite membrane.
Assay method：It is 210 to determine contact angleo.This composite membrane（G1）In 2000ppmNaCl solution, 25 DEG C, pH is 7.5,
Under the conditions of pressure is 225psi, rejection 99.7% to NaCl, water flux is 1.00m3/m2.day.Through 1000ppmNaClO water
After solution immersion treatment 10h, its rejection to NaCl is still up to 95.2%.Meanwhile, long-time stain resistance reality is carried out to which
Test, under conditions of the aqueous solution of 225psi pressure, 25 DEG C of temperature, sodium chloride-containing 500ppm of pH7.0 ~ 7.5 and 50ppm milk
Continuous operation 2000 hours, acquired results are shown in Table 1.
Embodiment 2
A kind of production method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
（1）P-aminoazobenzene derivative（A）Synthesis
By 1 step of embodiment（1）Middle 5.5g（0.04mol）Paranitroanilinum replaces with 9.2g（0.04mol）P-aminophenyl
Sodium sulfonate, remaining is with embodiment 1.Products therefrom is to amino azosulfonic acid base benzene（A2）.
（2）Side chain type azo acid amides function monomer（B）Synthesis
By 1 step of embodiment（2）Middle 9.7g（0.04mol）Product A1, replaces with 13.5g（0.04mol）Product A2, remaining
With embodiment 1.Products therefrom is Methacrylamide azosulfonic acid base benzene（B2）.
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
By 1 step of embodiment（3）Middle 31.1g（0.1mol）Product B1, replaces with 40.5g（0.1mol）Product B2, remaining
With embodiment 1.Products therefrom is end group and contains ω-halogen group azo amide homopolymer（C2）.
Remaining steps are with embodiment 1.
Assay method：Its contact angle is determined for 20..The other the same as in Example 1 is identical, and acquired results are shown in Table 1.
Embodiment 3
A kind of production method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
（1）P-aminoazobenzene derivative（A）Synthesis
By 1 step of embodiment（1）Middle paranitroanilinum replaces with p-aminobenzoic acid, and remaining is with embodiment 1.The product for obtaining
Thing is to amino azo carboxyl benzene（A3）.
（2）Side chain type azo acid amides function monomer（B）Synthesis
With embodiment 1.Products therefrom is Methacrylamide azo carboxyl benzene（B3）.
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
With embodiment 1.Products therefrom is end group and contains ω-halogen group azo amide homopolymer（C3）.
（4）Azobenzene ＆ MMA block copolymers（D）Synthesis
With embodiment 1.
（5）Chain anion/cation azo amide homopolymer（E）Synthesis
40g phenol in embodiment 1 is replaced with 92g sodium sulfanilates, remaining is with embodiment 1.
（6）The powered micropore basal membrane of self assembly（F）Synthesis
With embodiment 1.
（7）Polyamide reverse osmosis composite film containing azobenzene（G）Synthesis
With embodiment 1.
Determination method side：Its contact angle is determined for 26..The other the same as in Example 1 is identical, and acquired results are shown in Table 1.
Embodiment 4:
A kind of production method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
(1) P-aminoazobenzene derivative（A）Synthesis
By 2 step of embodiment（1）Middle 8.3g（0.048mol）P-aminobenzene sulfonic acid replaces with 8.0g（0.048mol）N-(2-
Ethoxy)-N-ethylaniline, remaining is with embodiment 2.The product for obtaining is to amino azosulfonic acid base benzene（A4）.
（2）Side chain type azo acid amides function monomer（B）Synthesis
By 1 step of embodiment（2）Middle 3.4g（0.04mol）Methacrylic acid, replaces with 6.7g（0.04mol）P-nitrophenyl
Formic acid.Products therefrom is p-nitrophenyl acid amides azo carboxyl benzene（B4）.
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
By 1 step of embodiment（3）Middle 31.1g（0.1mol）Product B1, replace with 39.3g（0.1mol）Product B4, remaining is same
Embodiment 1.Products therefrom is end group and contains ω-halogen group azo amide homopolymer（C4）.
Remaining is with embodiment 3.
Determination method side：Its contact angle is determined for 30..The other the same as in Example 1 is identical, and acquired results are shown in Table 1.
Embodiment 5:
A kind of production method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
（1）P-aminoazobenzene derivative（A）Synthesis
With embodiment 1.
（2）Side chain type azo acid amides function monomer（B）Synthesis
By 1 step of embodiment（2）Middle 3.4g（0.04mol）Methacrylic acid, replaces with 2.9g（0.04mol）Acrylic acid.
Remaining is with embodiment 1.Products therefrom is acrylamide azo carboxyl benzene（B5）.
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
With embodiment 2.Products therefrom is end group and contains ω-halogen group azo amide homopolymer（C5）.
（4）Azobenzene ＆ MMA block copolymers（D）Synthesis
With embodiment 1.
（5）Chain anion/cation azo amide homopolymer（E）Synthesis
25g hexamethylene diamines in embodiment 1 are replaced with 35g shitosans, remaining is with embodiment 1.
（6）The powered micropore basal membrane of self assembly（F）Synthesis
With embodiment 1.
（7）Polyamide reverse osmosis composite film containing azobenzene（G）Synthesis
With embodiment 1.
Assay method：Its contact angle is determined for 28..The other the same as in Example 1 is identical, and acquired results are shown in Table 1.
Embodiment 6:
A kind of production method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
（1）P-aminoazobenzene derivative（A）Synthesis
By 1 step of embodiment（1）Middle 5.5g（0.04mol）Paranitroanilinum replaces with 4.3g（0.04mol）Para-totuidine,
Remaining is with embodiment 1.Products therefrom is to AAT（A6）.
（2）Side chain type azo acid amides function monomer（B）Synthesis
With embodiment 4.
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
With embodiment 4.
（4）Azobenzene ＆ MMA block copolymers（D）Synthesis
With embodiment 1.
（5）Chain anion/cation azo amide homopolymer（E）Synthesis
With embodiment 5.
（6）The powered micropore basal membrane of self assembly（F）Synthesis
With embodiment 1.
（7）Polyamide reverse osmosis composite film containing azobenzene（G）Synthesis
With embodiment 1.
Assay method：Its contact angle is determined for 22..With embodiment 1, acquired results are shown in Table 1 to test condition.
Embodiment 7
A kind of production method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：
（1）P-aminoazobenzene derivative（A）Synthesis
With embodiment 2.
（2）Side chain type azo acid amides function monomer（B）Synthesis
With embodiment 2.
（3）Azo amide homopolymer of the end group containing ω-halogen group（C）Synthesis
With embodiment 2.
（4）Azobenzene ＆ MMA block copolymers（D）Synthesis
With embodiment 1.
（5）Chain anion/cation azo amide homopolymer（E）Synthesis
40g phenol in embodiment 1 is replaced with 92g sodium sulfanilates, 25g hexamethylene diamines replace with 35g shells and gather
Sugar, remaining is with embodiment 1.
（6）The powered micropore basal membrane of self assembly（F）Synthesis
With embodiment 1.
（7）Polyamide reverse osmosis composite film containing azobenzene（G）Synthesis
With embodiment 1.
Assay method：Its contact angle is determined for 20..The other the same as in Example 1, acquired results such as table 1.
Table 1
As can be drawn from Table 1, the reverse osmosis composite membrane containing azobenzene for being prepared by the method for the invention, with obvious
The rejection to salt, water flux, chlorine resistance and resistant to pollution performance.
To sum up, method of the present invention, will independently fill technology and ultraviolet light layer by layer（UV）Curing technology combination of sciences, system
For going out, the number of plies is controllable, and interlayer covalent bond is firmly crosslinked, and the charged low stain of membrane body, high intensity, the new of high stability contain
Azobenzene polyamide reverse osmosis composite film.
In addition to above-mentioned case study on implementation, the present invention can also have other embodiment.All employing equivalents or equivalent transformation
Deng the technical scheme of formation, protection domain of the presently claimed invention is all fallen within.
Claims (7)
1. a kind of preparation method containing azobenzene polyamide reverse osmosis composite film, comprises the following steps：(1) P-aminoazobenzene spreads out
Biological synthesis；(2) the P-aminoazobenzene derivative for synthesizing the first step adds having for the functional polymer with carboxylic acid group
In machine solvent, and add condensing agent and catalyst that side chain type azo acid amides function monomer is obtained；(3) by the side synthesized in second step
Chain azo acid amides function monomer carries out homopolymerization under the conditions of azo monomer catalysis-initiator system and organic solvent, and end group is obtained
Azo amide homopolymer containing ω-halogen group；(4) in the synthetic system of the 3rd step homopolymers, methacrylic acid is added
Methylmethacrylate monomer, is obtained Ou Danben ＆MMA block copolymers；(5) the azo acyl by end group obtained in the 3rd step containing ω-halogen group
Amine homopolymers carries out nucleophilic substitution, and side chain type anion and cationic azo amide homopolymer is obtained；(6) the 4th step is used
In obtained Ou Danben ＆MMA block copolymers prepare the powered micropore basal membrane of self assembly as raw material；(7) by obtained in the 5th step
Side chain type anion and cationic azo amide homopolymer are configured to solution, with the powered micropore base of obtained self assembly in step 6
Film is reacted, and the synthesis containing azobenzene polyamide reverse osmosis composite film is obtained.
2. a kind of preparation method containing azobenzene polyamide reverse osmosis composite film as claimed in claim 1, it is characterised in that：Institute
The concrete grammar for stating step (5) is the halogen group of the azo amide homopolymer for making ω-halogen group and carries Yin/Yang functional group
Compound, there is nucleophilic substitution, be introduced into anion/cation functional groups respectively in azopolyamide structure, preparation
Side chain type anion and cationic azo amide homopolymer.
3. a kind of preparation method containing azobenzene polyamide reverse osmosis composite film as claimed in claim 1, it is characterised in that：Institute
The concrete grammar of step (6) is stated for hydrophily, stability and the equal good filming thing of copolymerization performance being chosen as polymerized monomer M, with
When introduce the powered function monomer of hydrophily, a kind of as polymerized monomer N in acrylic acid, vinyl alcohol, ethylene glycol, acrylamide,
In initiator and organic solvent, by the method for free radical solution polymerization, synthesize bulk copolymer needed for basement membrane, monomer ratio
(M:N) molal weight ratio is 1:1～100:1, solvent load is 1～100 times of total weight of monomer, and initiator amount is total weight of monomer
0.05%～2%, polymerization temperature is 0～100 DEG C, and polymerization time is 1h～24h, after polymerisation terminates, adds in step (4)
Products therefrom Ou Danben ＆MMA block copolymers, and the method by supersonic oscillations physical blending, are well-dispersed in
State in polymerization liquid, prepare the host-guest doping system copolymer casting solution that concentration is 5%～20wt%, then this is cast
Film liquid is cast on 10～80 DEG C of glass support plate, is solidified with being put into gripper shoe rapidly after glass bar knifing in deionized water
Film forming, the THICKNESS CONTROL of film at 50～100 μm, ethanol:Deionized water:KOH weight proportions are 10～60:40～20:50～20,
Temperature is 20～50 DEG C, is cleaned by ultrasonic 30min～2h, then deionized water is fully embathed, and nitrogen dries up standby, prepared self assembly
Required powered micropore basal membrane.
4. a kind of preparation method containing azobenzene polyamide reverse osmosis composite film as claimed in claim 1, it is characterised in that：Institute
The concrete grammar for stating step (7) is to be dissolved in the side chain type anion and cationic azo amide homopolymer of synthesis in step (5)
In deionized water, the solution that concentration is 0.5～10mg/ml, then the powered micropore basal membrane by synthesis gained in step (6) is configured to
2～60min self assembly side chain type cationic azo acyls are soaked in the above-mentioned side chain type cationic azo amide homopolymer aqueous solution
Amine, takes out deionized water and cleans, and nitrogen is dried up, then immerse the product side chain type anion azo amide homopolymer aqueous solution 2～
60min, cleans after taking-up and dries up, complete once to assemble circulation, repeats above operation, carries out the assembling of other layers, obtains preliminary
Self-assembled multilayer film, above-mentioned assembling process are carried out under lucifuge, then will assemble 4～60 layers of azo acid amides film distance 5～
Use the 365nm mercury lamps of 25W, UV to expose 10～60min at 50cm, obtain final product the polyamide reverse osmosis composite film containing azobenzene.
5. a kind of preparation method containing azobenzene polyamide reverse osmosis composite film as claimed in claim 2, it is characterised in that：Institute
The band Yin/Yang functional compounds that states refer to hexamethylene diamine, shitosan (CHI), hexadecyltrimethylammonium chloride, triethylbenzyl
Ammonium chloride, sodium sulfanilate, kayexalate (PSS), phenol, acrylic or methacrylic acid.
6. a kind of preparation method containing azobenzene polyamide reverse osmosis composite film as claimed in claim 3, it is characterised in that：Step
Suddenly the polymer monomer M described in (6) is acrylonitrile, polysulfones, poly- cellulose, polyvinyl alcohol, Kynoar, polyetherimide
Amine, SPSF, polyether sulfone, polyimides or poly-N-vinylcaprolactam；Described initiator refers to azodiisobutyronitrile
(AIBN), a kind of in ABVN, benzoyl peroxide or sodium hydrogensulfite.
7. a kind of preparation method containing azobenzene polyamide reverse osmosis composite film as claimed in claim 3, it is characterised in that：Step
Suddenly monomer ratio (M described in (6):N it is) 1:1～20:1,1～30 times of solvent load total weight of monomer, polymeric reaction temperature 0～50
DEG C, ethanol:Deionized water:KOH weight proportions are 10～30:40～20:50.
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| CN114832642B (en) * | 2022-04-11 | 2022-11-01 | 贵州省材料产业技术研究院 | PVDF (polyvinylidene fluoride) antibacterial nanofiltration membrane capable of realizing layer-by-layer self-assembly host-guest recognition and preparation method |
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