CN109289557A - A kind of decoloration film and its preparation method and application - Google Patents
A kind of decoloration film and its preparation method and application Download PDFInfo
- Publication number
- CN109289557A CN109289557A CN201811299757.XA CN201811299757A CN109289557A CN 109289557 A CN109289557 A CN 109289557A CN 201811299757 A CN201811299757 A CN 201811299757A CN 109289557 A CN109289557 A CN 109289557A
- Authority
- CN
- China
- Prior art keywords
- sodium
- film
- decoloration
- aqueous phase
- preparation
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- 239000012528 membrane Substances 0.000 claims abstract description 62
- 239000008346 aqueous phase Substances 0.000 claims abstract description 58
- 239000012071 phase Substances 0.000 claims abstract description 55
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 15
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 87
- 238000000108 ultra-filtration Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- -1 polyetheramine Chemical compound 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 239000005416 organic matter Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002464 physical blending Methods 0.000 claims description 12
- 150000001263 acyl chlorides Chemical class 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 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 claims description 7
- 239000004697 Polyetherimide Substances 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 229920001601 polyetherimide Polymers 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 150000001409 amidines Chemical group 0.000 claims description 5
- CSVUNXDXKHELCR-UHFFFAOYSA-L disodium;3-carboxy-4-oxidobenzenesulfonate Chemical compound [Na+].[Na+].OC(=O)C1=CC(S([O-])(=O)=O)=CC=C1[O-] CSVUNXDXKHELCR-UHFFFAOYSA-L 0.000 claims description 5
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 239000000176 sodium gluconate Substances 0.000 claims description 4
- 235000012207 sodium gluconate Nutrition 0.000 claims description 4
- 229940005574 sodium gluconate Drugs 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- FCSPFOUVWHEDSS-UHFFFAOYSA-N CC(C(O)=CC=C1)=C1O.N=C=O.N=C=O Chemical compound CC(C(O)=CC=C1)=C1O.N=C=O.N=C=O FCSPFOUVWHEDSS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229940045998 sodium isethionate Drugs 0.000 claims description 3
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- HWJJKWDAKXZNEA-UHFFFAOYSA-N [Na].ON1C(CCC1=O)=S Chemical compound [Na].ON1C(CCC1=O)=S HWJJKWDAKXZNEA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims 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 claims description 2
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- NBPUSGBJDWCHKC-UHFFFAOYSA-M sodium 3-hydroxybutyrate Chemical compound [Na+].CC(O)CC([O-])=O NBPUSGBJDWCHKC-UHFFFAOYSA-M 0.000 claims description 2
- 239000001540 sodium lactate Substances 0.000 claims description 2
- 229940005581 sodium lactate Drugs 0.000 claims description 2
- 235000011088 sodium lactate Nutrition 0.000 claims description 2
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 2
- FTCLAXOKVVLHEG-UHFFFAOYSA-N sodium;3-sulfanylpropane-1-sulfonic acid Chemical compound [Na].OS(=O)(=O)CCCS FTCLAXOKVVLHEG-UHFFFAOYSA-N 0.000 claims description 2
- XUIVKWAWICCWIQ-UHFFFAOYSA-M sodium;formaldehyde;hydrogen sulfite Chemical compound [Na+].O=C.OS([O-])=O XUIVKWAWICCWIQ-UHFFFAOYSA-M 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- 229940024606 amino acid Drugs 0.000 claims 1
- OLINJIZFBLZETG-UHFFFAOYSA-L disodium;3-sulfonatobenzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC(S([O-])(=O)=O)=C1 OLINJIZFBLZETG-UHFFFAOYSA-L 0.000 claims 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 229960001790 sodium citrate Drugs 0.000 claims 1
- 229960004025 sodium salicylate Drugs 0.000 claims 1
- 239000000049 pigment Substances 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000001728 nano-filtration Methods 0.000 description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012178 vegetable wax Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- SIXWAZNKRKLCNN-UHFFFAOYSA-M CNC(CC)S(=O)(=O)[O-].[Na+] Chemical compound CNC(CC)S(=O)(=O)[O-].[Na+] SIXWAZNKRKLCNN-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002385 Sodium hyaluronate Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- CZCSLHYZEQSUNV-UHFFFAOYSA-N [Na].OB(O)O Chemical compound [Na].OB(O)O CZCSLHYZEQSUNV-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GMUQJDAYXZXBOT-UHFFFAOYSA-M sodium;4-amino-2-hydroxybenzoate;dihydrate Chemical compound O.O.[Na+].NC1=CC=C(C([O-])=O)C(O)=C1 GMUQJDAYXZXBOT-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of decoloration films and its preparation method and application, the active separating layer that the decoloration film includes supporting layer and is carried on supporting layer, the active separating layer includes the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes amine-containing monomer and polyelectrolyte.The preparation method of the decoloration film is the support membrane that supporting layer is impregnated with aqueous phase reactions object solution, takes out support membrane and removes surface solution, then carry out interface polymerization reaction with oily phase reaction object solution dipping support membrane, obtains the decoloration film.The preparation method is easy to repeat, and is conducive to industrialized production, and decoloration film high temperature resistant, the anti-pollution being prepared, and has high flux and pigment rejection.
Description
Technical field
The invention belongs to technical field of membrane separation, and in particular to a kind of decoloration film and its preparation method and application.
Background technique
With the development of industry, people are higher and higher for the presentation quality of product and the pursuit of class, how to decolourize
As frequently problem in the industrial productions such as food service industry, daily use chemicals industry, chemical industry, textile industry.Membrane separation technique
A kind of selective penetrated property using film, make mixture the concentration difference the effects of under extraction, purifying or enrichment reached by separation
And other effects high efficient separation technology, have many advantages, such as that low energy consumption, low emission, high degree of automation, occupied area are small, answer extensively
Used in decoloration field.
CN107803116A discloses a kind of method decolourized using commercialization nanofiltration membrane to vegetable wax, the method
Include the following steps: to provide the material liquid of vegetable wax and the first nanofiltration membrane for selectively penetrating, by by the material liquid and institute
The contact of the first nanofiltration membrane is stated, the first penetrating fluid and the first trapped fluid is formed, finally pigment is enriched in trapped fluid.
CN107325016A discloses a kind of ornithine extracting method of high quality, and described method includes following steps: micro-
It filters filter, decolorization, concentration, adjust pH, condensing crystallizing, washing process, drying process and crystallization crushing.Wherein decolourize
It is the nanofiltration membrane that molecular cut off is 100-1000 or so used by the organic decoloration membranous system for handling part.
CN107937628A discloses a kind of cane sugar manufacture system and its processing method that full constituent utilizes, the system packet
Include pretreatment unit, multistage membrane filtration system and concentrate processing unit.Wherein decoloration film is used in multistage membrane filtration system
A kind of seperation film.
CN108404679A discloses a kind of preparation method of decolorizing printing and dyeing waste water film, by a water copper acetate, ten water boric acid
Sodium, Dopamine hydrochloride, 2- bromine isobutyl acylbromide, nano-titanium dioxide, hydrazine hydrate, chitosan, monoxone, silver nitrate, beta cyclodextrin,
The raw materials such as polyacrylic acid are made, and the present invention embeds obtained Argent grain loading chitosan and beta cyclodextrin etc., pass through electrostatic
Spinning and heat cross-linking form stable fiber membrane structure, and thus obtained tunica fibrosa introduces the nanometer two of graft modification using dipping
Titanium oxide using a large amount of active sites increase in its surface and the contact surface that reacts of waste water, then passes through a water copper acetate dip loading
One layer of plating nanocrystalline Cu film.
But currently used decoloration film is mostly commercialized nanofiltration membrane, although having higher rejection to pigment,
It is to cause the flux of feed liquid small since the molecular cut off of nanofiltration membrane is small, and be only applicable to the small target product of molecular weight.And
Different commercialized nanofiltration membranes also will appear not anti-pollution, non-anti-chlorine, not antibacterial the disadvantages of.Therefore develop a kind of anti-pollution,
Chlorine-resistant, high temperature resistant and the easily prepared decoloration film dedicated for pigment removal are significantly.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of decoloration film and preparation method thereof and answer
With.
In order to achieve the above objectives, the invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of decoloration film, the work that the decoloration film includes supporting layer and is carried on supporting layer
Property separating layer, the active separating layer includes the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, the aqueous phase reactions
Object includes amine-containing monomer and polyelectrolyte.
Polyelectrolyte contains the functional group that can participate in interface polymerization reaction, and the decoloration film properties being prepared can be made steady
It is fixed, high temperature resistant, it can flux still with higher and pigment rejection in high-temperature process sample, and polyelectrolyte is hydrophilic
Property substance, can also be improved decoloration film contamination resistance.
In the present invention, the amine-containing monomer includes at least containing there are two the aromatic series organic matter of amidine functional group, at least
Containing there are two the aliphatic organic matter of amidine functional group or at least containing there are two appointing in the alicyclic organic matter of amidine functional group
It anticipates a kind of or at least two combinations.
Preferably, the amine-containing monomer includes piperazine, polyetheramine, ethylenediamine, propane diamine, diethylenetriamine, triethylene four
In amine, polyvinylamine, polyethyleneimine, cyclohexanediamine, phenylenediamine or benzene triamine any one or at least two combination；Institute
State at least two combination such as piperazine and polyetheramine, ethylenediamine and propane diamine, diethylenetriamine and triethylene tetramine, polyethylene
Amine and polyethyleneimine and cyclohexanediamine etc..
In the present invention, the polyelectrolyte contains the functional group for participating in interface polymerization reaction.
Preferably, the polyelectrolyte includes sodium isethionate, diphenylamine sulfonic acid sodium salt, 4- amino -1-naphthalene sulfonic aicd sodium, 3-
Carboxyl benzene sulfonate, N- hydroxy thiosuccinimide sodium salt, sulfosalicylic acid sodium salt, formaldehyde-sodium bisulphite adduct, Tris
Ethanesulfonic acid sodium, 3-sulfydryl-1-propane sulfonic acid sodium, 4- sodium hydroxybenzenesulfonate, N-2- hydroxyethyl piperazine-N'-2- ethanesulfonic acid sodium, three hydroxyls
It is base methylamino propane sulfonic acid sodium salt, 2- (4- anisyl) diazanyl sodium sulfonate, sodium indigotindisulfonate, amino acid, sodium citrate, transparent
It is matter acid sodium, sodium alginate, 2- Sodium γ-Hydroxybutrate, sodium gluconate, 3-hydroxybutyrate sodium, sodium lactate, P-hydroxybenzoic acid sodium, right
In paramisan sodium or sulfosalicylic acid sodium salt any one or at least two combination.Described at least two combination is for example
Sodium isethionate and diphenylamine sulfonic acid sodium salt, trihydroxy methylamino propane sulfonic acid sodium salt and sulfosalicylic acid sodium salt, sodium citrate and thoroughly
Bright matter acid sodium, sodium gluconate and 2- (4- anisyl) diazanyl sodium sulfonate and sodium alginate etc..
In the present invention, the oily phase reaction object includes at least containing there are two the aromatic series organic matter of carboxylic acid halides functional group, extremely
The aliphatic organic matter of few carboxylic acid halides functional group containing there are two at least contains in the alicyclic organic matter there are two carboxylic acid halides functional group
Any one or at least two combination.
Preferably, the oily phase reaction object includes o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, equal benzene
Three formyl chlorides, methylresorcinol diisocyanate, three formyl chloride of 1,3,5- hexamethylene, three acyl chlorides of biphenyl, four acyl chlorides of biphenyl, 5- oxygen first
In acyl chlorides-isophthaloyl chlorine or 5- isocyanates-isophthaloyl chlorine any one or at least two combination.Described at least two
Combine such as o-phthaloyl chloride and m-phthaloyl chloride, paraphthaloyl chloride and pyromellitic trimethylsilyl chloride, three acyl chlorides of biphenyl and connection
Three acyl chlorides of four acyl chlorides of benzene, methylresorcinol diisocyanate and three formyl chloride of 1,3,5- hexamethylene and biphenyl etc..
In the present invention, the supporting layer is porous ultrafiltration support membrane.
Preferably, the molecular cut off of the porous ultrafiltration support membrane be 10000-100000, such as 10000,20000,
30000,40000,50000,60000,70000,80000,90000 or 100000 etc..
Preferably, the material of the porous ultrafiltration support membrane include polyethylene, polyamide, polyimides, polyetherimide,
In polytetrafluoroethylene (PTFE), Kynoar, polysulfones or polyether sulfone any one or at least two combination.Described at least two
Combination is such as polyethylene and polyamide, polyimides and polyetherimide, polytetrafluoroethylene (PTFE) and Kynoar and polysulfones.
On the other hand, the present invention provides a kind of as described above preparation method of decoloration film, the preparation method include with
Lower step:
It with the support membrane of aqueous phase reactions object solution dipping supporting layer, takes out support membrane and removes surface solution, then is opposite with oil
It answers object solution dipping support membrane to carry out interface polymerization reaction, obtains the decoloration film.
Decoloration film of the present invention in such a way that interfacial polymerization prepares composite membrane, by supporting layer and active separating layer with
And polyelectrolyte, amine-containing monomer and the carboxylic acid halides organic matter in active separating layer carry out separating design, are then coupled, the preparation
Method is easy to repeat, and is conducive to industrialized production.In order to keep interfacial polymerization layer more stable, needed after having impregnated support membrane with water phase
Take out supporting layer removal surface solution.
In the present invention, the preparation method of the aqueous phase reactions object solution is physical blending process.
Preferably, in aqueous phase reactions object solution described in every 100g containing 0.1-3g (such as 0.1g, 0.2g, 0.3g, 0.4g,
0.6g, 0.8g, 1g, 2g or 3g etc.) solute.
Preferably, the solvent of the oily phase reaction object solution is petroleum ether, n-hexane, hexamethylene, paraxylene.
Preferably, in oil phase reaction object solution described in every 100mL containing 0.1-3g (such as 0.1g, 0.2g, 0.3g, 0.4g,
0.6g, 0.8g, 1g, 2g or 3g etc.) solute.
In the present invention, the time with the support membrane of aqueous phase reactions object solution dipping supporting layer is 1-60min, such as
1min, 5min, 10min, 20min, 30min, 40min, 50min or 60min etc., preferably 1-20min.
Preferably, it is described carry out interface polymerization reaction time be 2-300s, such as 2s, 10s, 20s, 50s, 100s,
150s, 180s, 200s, 250s or 300s etc., preferably 2-180s.
Preferably, film is heat-treated and is soaked in deionized water after the completion of the interface polymerization reaction.
Preferably, the temperature of the heat treatment is 25-80 DEG C, such as 25 DEG C, 30 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60
DEG C, 65 DEG C, 70 DEG C or 80 DEG C etc..
Preferably, the time of the heat treatment is 5-120min.
Preferably, the mode of the heat treatment is baking oven heating or heater plate.
Preferably, the time being soaked in deionized water be 2-24h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h,
16h, 18h, 20h, 22h or for 24 hours etc..
It is described heat treatment be in order to keep interface polymerization reaction complete, be soaked in deionized water be will be unreacted on support membrane
Acyl chlorides hydrolysis.
As the preferred technical solution of the present invention, the preparation method specifically includes the following steps:
(1) the aqueous phase reactions object solution containing amine-containing monomer and polyelectrolyte is prepared using physical blending process, so that often
Solute containing 0.1-3g in aqueous phase reactions object solution described in 100g；
(2) organic solvent is selected to match liquefaction phase reaction object solution, so that containing in oil phase reaction object solution described in every 100mL
The solute of 0.1-3g；
(3) support membrane of supporting layer is cleaned；
(4) it with the support membrane 1-60min of aqueous phase reactions object solution dipping supporting layer, takes out support membrane and removes surface solution,
Interface polymerization reaction is carried out with oily phase reaction object solution dipping support membrane 2-300s again；
(5) film is heat-treated 5- in a manner of baking oven or heating plate at 25-80 DEG C after the completion of interface polymerization reaction
120min, and it is soaked in 2-24h in deionized water, obtain the decoloration film.
In another aspect, the present invention provides application of the decoloration film as described above in product decoloration.
Preferably, the product is the product of food service industry, daily use chemicals industry, chemical industry, environmental protection industry (epi) or textile industry.
Compared with prior art, the present invention is at least had the advantages that
The polyelectrolyte contained in decoloration film of the present invention has and can participate in the functional group of interface polymerization reaction, can be with
Stablize the decoloration film properties being prepared, high temperature resistant, it can flux and color still with higher in high-temperature process sample
Plain rejection.
Meanwhile polyelectrolyte is hydroaropic substance, and the contamination resistance of decoloration film can be improved.
In addition, in such a way that interfacial polymerization prepares composite membrane, supporting layer and activity are divided for decoloration film of the present invention
Polyelectrolyte, amine-containing monomer and carboxylic acid halides organic matter in absciss layer and active separating layer carry out separating design, are then coupled,
The preparation method is easy to repeat, and is conducive to industrialized production.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer and polyelectrolyte.Preparation method includes the following steps:
Aqueous phase reactions object solution containing piperazine and Pehanorm base propanesulfonate is prepared using physical blending process, is made
Obtain the solute containing 0.5g in aqueous phase reactions object solution described in every 100g；The preparation of n-hexane solvent is selected to contain pyromellitic trimethylsilyl chloride
Oily phase reaction object solution, so that the solute containing 0.2g in oil phase reaction object solution described in every 100mL；With aqueous phase reactions object solution
Poly (ether-sulfone) ultrafiltration membrane 10min is impregnated, ultrafiltration membrane is taken out and removes surface solution, then impregnate ultrafiltration membrane 20s with oily phase reaction object solution
Carry out interface polymerization reaction；After the completion of interface polymerization reaction film is heat-treated 10min at 50 DEG C in a manner of heating plate, and impregnated
The 2h in deionized water obtains the decoloration film.
Embodiment 2
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer and polyelectrolyte.Preparation method includes the following steps:
Aqueous phase reactions object solution containing piperazine and sodium gluconate is prepared using physical blending process, so that described in every 100g
Solute containing 1g in aqueous phase reactions object solution；Petroleum ether solvent is selected to prepare molten containing pyromellitic trimethylsilyl chloride oil phase reaction object
Liquid, so that the solute containing 0.4g in oil phase reaction object solution described in every 100mL；Polysulfones ultrafiltration is impregnated with aqueous phase reactions object solution
Film 20min takes out ultrafiltration membrane and removes surface solution, then with oily phase reaction object solution impregnates ultrafiltration membrane 5s to carry out interfacial polymerization anti-
It answers；Film is heat-treated 10min in a manner of baking oven heating at 80 DEG C after the completion of interface polymerization reaction, and is soaked in deionized water
In for 24 hours, obtain the decoloration film.
Embodiment 3
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer and polyelectrolyte.Preparation method includes the following steps:
Aqueous phase reactions object solution containing piperazine and Sodium Hyaluronate is prepared using physical blending process, so that described in every 100g
Solute containing 0.4g in aqueous phase reactions object solution；N-hexane solvent is selected to prepare the oily phase reaction object containing pyromellitic trimethylsilyl chloride
Solution, so that the solute containing 0.1g in oil phase reaction object solution described in every 100mL；Polyethers acyl is impregnated with aqueous phase reactions object solution
Imines ultrafiltration membrane 10min takes out ultrafiltration membrane and removes surface solution, then carries out boundary with oily phase reaction object solution dipping ultrafiltration membrane 20s
Face polymerization reaction；Film is heat-treated 120min at 25 DEG C with baking oven drying mode after the completion of interface polymerization reaction, and is soaked in
In deionized water for 24 hours, the decoloration film is obtained.
Embodiment 4
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer and polyelectrolyte.Preparation method includes the following steps:
Aqueous phase reactions object solution containing piperazine and lysine is prepared using physical blending process, so that water phase described in every 100g
Contain the solute of 0.6g in reactant solution；It selects n-hexane solvent to prepare and contains pyromellitic trimethylsilyl chloride oil phase reaction object solution,
So that the solute containing 0.3g in oil phase reaction object solution described in every 100mL；Polyetherimide is impregnated with aqueous phase reactions object solution
Ultrafiltration membrane 10min takes out ultrafiltration membrane and removes surface solution, then carries out interface with oily phase reaction object solution dipping ultrafiltration membrane 20s and gather
Close reaction；Film is heat-treated 60min at 25 DEG C with baking oven drying mode after the completion of interface polymerization reaction, and is soaked in deionization
48h in water obtains the decoloration film.
Embodiment 5
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer and polyelectrolyte.Preparation method includes the following steps:
The aqueous phase reactions object for containing m-phenylene diamine (MPD) and 2- (4- anisyl) diazanyl sodium sulfonate is prepared using physical blending process
Solution, so that the solute containing 0.1g in aqueous phase reactions object solution described in every 100g；It selects n-hexane solvent to prepare and contains equal benzene
The oily phase reaction object solution of three formyl chlorides, so that the solute containing 0.2g in oil phase reaction object solution described in every 100mL；Use water phase
Reactant solution impregnates Polyetherimide Uf Membrane 10min, takes out ultrafiltration membrane and removes surface solution, then with oil phase reaction object solution
It impregnates ultrafiltration membrane 5s and carries out interface polymerization reaction；Film is heat-treated in a manner of baking oven at 25 DEG C after the completion of interface polymerization reaction
60min, and it is soaked in 48h in deionized water, obtain the decoloration film.
Embodiment 6
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer and polyelectrolyte.Preparation method includes the following steps:
Aqueous phase reactions object solution containing ethylenediamine and diphenylamine sulfonic acid sodium salt is prepared using physical blending process, so that every 100g
Solute containing 3g in the aqueous phase reactions object solution；It selects petroleum ether solvent to prepare and contains o-phthaloyl chloride and terephthaldehyde
The oily phase reaction object solution of acyl chlorides, so that the solute containing 3g in oil phase reaction object solution described in every 100mL；With aqueous phase reactions object
Solution impregnates Polyetherimide Uf Membrane 60min, takes out ultrafiltration membrane and removes surface solution, then is super with oily phase reaction object solution dipping
Filter membrane 300s carries out interface polymerization reaction；After the completion of interface polymerization reaction by film at 80 DEG C in a manner of heater plate at heat
5min is managed, and is soaked in 12h in deionized water, obtains the decoloration film.
Embodiment 7
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer and polyelectrolyte.Preparation method includes the following steps:
Aqueous phase reactions object solution containing polyvinylamine and 3- carboxyl benzene sulfonate is prepared using physical blending process, so that often
Solute containing 1.5g in aqueous phase reactions object solution described in 100g；It selects cyclohexane solvent to prepare and contains three acyl chlorides of biphenyl and isophthalic
The oily phase reaction object solution of dimethyl chloride, so that the solute containing 1.5g in oil phase reaction object solution described in every 100mL；Use water phase
Reactant solution impregnates Polyetherimide Uf Membrane 1min, takes out ultrafiltration membrane and removes surface solution, then with oil phase reaction object solution
It impregnates ultrafiltration membrane 2s and carries out interface polymerization reaction；Film is heat-treated in a manner of baking oven at 60 DEG C after the completion of interface polymerization reaction
10min, and it is soaked in 2h in deionized water, obtain the decoloration film.
Comparative example 1
The present embodiment provides a kind of decoloration film, the decoloration film includes supporting layer and the activity separation being carried on supporting layer
Layer, the active separating layer include the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes
Amine-containing monomer.Preparation method includes the following steps:
Aqueous phase reactions object solution containing piperazine is prepared using physical blending process, so that aqueous phase reactions object described in every 100g is molten
Contain the solute of 2g in liquid；N-hexane solvent is selected to prepare the oily phase reaction object solution containing pyromellitic trimethylsilyl chloride, so that often
Solute containing 2g in oil phase reaction object solution described in 100mL；Poly (ether-sulfone) ultrafiltration membrane 20min is impregnated with aqueous phase reactions object solution,
It takes out ultrafiltration membrane and removes surface solution, then carry out interface polymerization reaction with oily phase reaction object solution dipping ultrafiltration membrane 30s；Interface is poly-
Film is heat-treated 20min after the reaction was completed by conjunction at 50 DEG C in a manner of baking oven, and is soaked in 48h in deionized water, is obtained described
Decolourize film.
Embodiment 8
The rejection of water flux and sodium sulphate is tested the decoloration film that embodiment 1-7 and comparative example 1 are obtained at 25 DEG C, and
Test maximum transmembrane pressure when each decoloration film handles molasses feed liquid under 60 DEG C, the constant current speed of 0.13ml/min, Brix retention
Rate (refers to soluble solid content rejection), pigment removal rate, fouling membrane situation.It is as described in Table 1 to test your result.
Table 1
As seen from the results in Table 1:
The decoloration film as made from embodiment 1-7 is more stable relative to decoloration film properties made from comparative example 1, more resistant to high temperature,
Can in high-temperature process sample flux (maximum transmembrane pressure is small) still with higher and pigment removal rate, and antipollution
Ability is stronger.
The Applicant declares that the present invention is explained by the above embodiments decoloration film of the invention and preparation method thereof and answering
With, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention must rely on above-described embodiment and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of each raw material of product of the present invention
And addition, selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
Claims (10)
1. a kind of decoloration film, which is characterized in that the active separating layer that the decoloration film includes supporting layer and is carried on supporting layer,
The active separating layer includes the interfacial polymerization product of aqueous phase reactions object and oily phase reaction object, and the aqueous phase reactions object includes amine-containing
Monomer and polyelectrolyte.
2. decoloration film as described in claim 1, which is characterized in that the amine-containing monomer includes at least containing there are two amido functions
The aromatic series organic matter of group, at least the aliphatic organic matter of amidine functional group or the amidine functional group at least containing there are two containing there are two
Alicyclic organic matter in any one or at least two combination；
Preferably, the amine-containing monomer includes piperazine, polyetheramine, ethylenediamine, propane diamine, diethylenetriamine, triethylene tetramine, gathers
In vinylamine, polyethyleneimine, cyclohexanediamine, phenylenediamine or benzene triamine any one or at least two combination.
3. decoloration film as claimed in claim 1 or 2, which is characterized in that the polyelectrolyte contains participation interface polymerization reaction
Functional group；
Preferably, the polyelectrolyte includes sodium isethionate, diphenylamine sulfonic acid sodium salt, 4- amino -1-naphthalene sulfonic aicd sodium, 3- carboxyl
Benzene sulfonic acid sodium salt, N- hydroxy thiosuccinimide sodium salt, sulfosalicylic acid sodium salt, formaldehyde-sodium bisulphite adduct, Tris second sulphur
Sour sodium, 3-sulfydryl-1-propane sulfonic acid sodium, 4- sodium hydroxybenzenesulfonate, N-2- hydroxyethyl piperazine-N'-2- ethanesulfonic acid sodium, trihydroxy first
Amido propane sulfonic acid sodium salt, 2- (4- anisyl) diazanyl sodium sulfonate, sodium indigotindisulfonate, amino acid, sodium citrate, hyaluronic acid
Sodium, sodium alginate, 2- Sodium γ-Hydroxybutrate, sodium gluconate, 3-hydroxybutyrate sodium, sodium lactate, P-hydroxybenzoic acid sodium, to amino
In sodium salicylate or sulfosalicylic acid sodium salt any one or at least two combination.
4. decoloration film as claimed in any one of claims 1-3, which is characterized in that the oil phase reaction object includes at least containing
The aromatic series organic matter of two carboxylic acid halides functional groups, at least containing containing there are two the aliphatic organic matter of carboxylic acid halides functional group or at least two
In the alicyclic organic matter of a carboxylic acid halides functional group any one or at least two combination；
Preferably, the oily phase reaction object includes o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, equal benzene front three
Acyl chlorides, methylresorcinol diisocyanate, three formyl chloride of 1,3,5- hexamethylene, three acyl chlorides of biphenyl, four acyl chlorides of biphenyl, 5- oxygen formyl
In chloro- isophthaloyl chlorine or 5- isocyanates-isophthaloyl chlorine any one or at least two combination.
5. such as decoloration film of any of claims 1-4, which is characterized in that the supporting layer is porous ultrafiltration support
Film；
Preferably, the molecular cut off of the porous ultrafiltration support membrane is 10000-100000；
Preferably, the material of the porous ultrafiltration support membrane includes polyethylene, polyamide, polyimides, polyetherimide, poly- four
In vinyl fluoride, Kynoar, polyacrylonitrile, polysulfones or polyether sulfone any one or at least two combination.
6. the preparation method of decoloration film according to any one of claims 1 to 5, which is characterized in that the preparation method includes
Following steps:
It with the support membrane of aqueous phase reactions object solution dipping supporting layer, takes out support membrane and removes surface solution, then with oil phase reaction object
Solution impregnates support membrane and carries out interface polymerization reaction, obtains the decoloration film.
7. the preparation method of decoloration film as claimed in claim 6, which is characterized in that the preparation side of the aqueous phase reactions object solution
Method is physical blending process；
Preferably, the solute containing 0.1-3g in aqueous phase reactions object solution described in every 100g；
Preferably, the solvent of the oily phase reaction object solution is petroleum ether, n-hexane, hexamethylene, paraxylene；
Preferably, the solute containing 0.1-3g in oil phase reaction object solution described in every 100mL.
8. the preparation method of decoloration film as claimed in claims 6 or 7, which is characterized in that the aqueous phase reactions object solution soaks
The time of the support membrane of stain supporting layer is 1-60min, preferably 1-20min；
Preferably, the time for carrying out interface polymerization reaction is 2-300s, preferably 2-180s；
Preferably, film is heat-treated and is soaked in deionized water after the completion of the interface polymerization reaction；
Preferably, the temperature of the heat treatment is 25-80 DEG C；
Preferably, the time of the heat treatment is 5-120min；
Preferably, the mode of the heat treatment is baking oven heating or heater plate；
Preferably, the time being soaked in deionized water is 2-24h.
9. the preparation method of the decoloration film as described in any one of claim 6-8, which is characterized in that the preparation method is specific
The following steps are included:
(1) the aqueous phase reactions object solution containing amine-containing monomer and polyelectrolyte is prepared using physical blending process, so that every 100g institute
State the solute containing 0.1-3g in aqueous phase reactions object solution；
(2) organic solvent is selected to match liquefaction phase reaction object solution, so that containing 0.1- in oil phase reaction object solution described in every 100mL
The solute of 3g；
(3) support membrane of supporting layer is cleaned；
(4) it with the support membrane 1-60min of aqueous phase reactions object solution dipping supporting layer, takes out support membrane and removes surface solution, then use
Oily phase reaction object solution dipping support membrane 2-300s carries out interface polymerization reaction；
(5) film is heat-treated 5-120min in a manner of baking oven or heating plate at 25-80 DEG C after the completion of interface polymerization reaction, and
It is soaked in 2-24h in deionized water, obtains the decoloration film.
10. application of the decoloration film according to any one of claims 1 to 5 in product decoloration；
Preferably, the product is the product of food service industry, daily use chemicals industry, chemical industry, environmental protection industry (epi) or textile industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811299757.XA CN109289557A (en) | 2018-11-02 | 2018-11-02 | A kind of decoloration film and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811299757.XA CN109289557A (en) | 2018-11-02 | 2018-11-02 | A kind of decoloration film and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109289557A true CN109289557A (en) | 2019-02-01 |
Family
ID=65145536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811299757.XA Pending CN109289557A (en) | 2018-11-02 | 2018-11-02 | A kind of decoloration film and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109289557A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109925892A (en) * | 2019-04-01 | 2019-06-25 | 东华大学 | A kind of small molecule-modified nanofiber-based composite nanometer filtering film and preparation method thereof |
| CN110339724A (en) * | 2019-06-26 | 2019-10-18 | 四川大学 | One kind having salinity responsiveness composite polyamide membranes and its preparation method and application |
| CN112023726A (en) * | 2020-08-10 | 2020-12-04 | 万华化学集团股份有限公司 | Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof |
| CN112316755A (en) * | 2020-08-14 | 2021-02-05 | 同济大学 | Composite nanofiltration membrane and preparation method thereof |
| CN112535955A (en) * | 2020-11-12 | 2021-03-23 | 中国科学院过程工程研究所 | Decolorizing membrane and preparation method and application thereof |
| CN112755811A (en) * | 2020-12-18 | 2021-05-07 | 中化(宁波)润沃膜科技有限公司 | Acid and alkali resistant composite nanofiltration membrane, and preparation method and application thereof |
| CN112870996A (en) * | 2021-01-11 | 2021-06-01 | 北京工业大学 | Preparation and application of hydrophilic chlorine-resistant polysulfone membrane |
| CN113750800A (en) * | 2021-10-26 | 2021-12-07 | 天津工业大学 | Preparation method of arginine modified composite nanofiltration membrane |
| CN114307687A (en) * | 2021-12-23 | 2022-04-12 | 江苏久膜高科技股份有限公司 | Beer decolorizing membrane and preparation method thereof |
| CN115920655A (en) * | 2022-12-29 | 2023-04-07 | 中国科学院过程工程研究所 | Pollution-resistant and wetting-resistant hydrophilic-hydrophobic composite membrane for membrane distillation and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224393A (en) * | 2007-10-19 | 2008-07-23 | 浙江大学 | Fabricating method of pervaporation membranes by electric field driving polyelectrolyte layer-by-layer self-assembly |
| CN104437110A (en) * | 2014-12-15 | 2015-03-25 | 彭博 | High-flux polyamide composite film |
| CN106422811A (en) * | 2015-08-11 | 2017-02-22 | 贵阳时代沃顿科技有限公司 | Novel polyelectrolyte nanofiltration membrane and preparation method thereof |
| CN107837689A (en) * | 2017-09-25 | 2018-03-27 | 浙江理工大学 | Preparation method of composite nanofiltration membrane with ultrathin separation layer |
| CN108325400A (en) * | 2018-02-09 | 2018-07-27 | 陕西省膜分离技术研究院有限公司 | A kind of preparation method of LBL self-assembly doughnut forward osmosis membrane |
| CN108435002A (en) * | 2018-03-27 | 2018-08-24 | 东华大学 | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified |
-
2018
- 2018-11-02 CN CN201811299757.XA patent/CN109289557A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224393A (en) * | 2007-10-19 | 2008-07-23 | 浙江大学 | Fabricating method of pervaporation membranes by electric field driving polyelectrolyte layer-by-layer self-assembly |
| CN104437110A (en) * | 2014-12-15 | 2015-03-25 | 彭博 | High-flux polyamide composite film |
| CN106422811A (en) * | 2015-08-11 | 2017-02-22 | 贵阳时代沃顿科技有限公司 | Novel polyelectrolyte nanofiltration membrane and preparation method thereof |
| CN107837689A (en) * | 2017-09-25 | 2018-03-27 | 浙江理工大学 | Preparation method of composite nanofiltration membrane with ultrathin separation layer |
| CN108325400A (en) * | 2018-02-09 | 2018-07-27 | 陕西省膜分离技术研究院有限公司 | A kind of preparation method of LBL self-assembly doughnut forward osmosis membrane |
| CN108435002A (en) * | 2018-03-27 | 2018-08-24 | 东华大学 | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified |
Non-Patent Citations (1)
| Title |
|---|
| 陕西省纺织工业总公司: "《陕西纺织科学技术志》", 30 September 1995, 陕西科学技术出版社 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109925892A (en) * | 2019-04-01 | 2019-06-25 | 东华大学 | A kind of small molecule-modified nanofiber-based composite nanometer filtering film and preparation method thereof |
| CN110339724A (en) * | 2019-06-26 | 2019-10-18 | 四川大学 | One kind having salinity responsiveness composite polyamide membranes and its preparation method and application |
| CN110339724B (en) * | 2019-06-26 | 2021-08-03 | 四川大学 | Composite polyamide membrane with salt concentration responsiveness and preparation method and application thereof |
| CN112023726B (en) * | 2020-08-10 | 2022-07-12 | 万华化学集团股份有限公司 | Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof |
| CN112023726A (en) * | 2020-08-10 | 2020-12-04 | 万华化学集团股份有限公司 | Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof |
| CN112316755A (en) * | 2020-08-14 | 2021-02-05 | 同济大学 | Composite nanofiltration membrane and preparation method thereof |
| CN112535955A (en) * | 2020-11-12 | 2021-03-23 | 中国科学院过程工程研究所 | Decolorizing membrane and preparation method and application thereof |
| CN112755811A (en) * | 2020-12-18 | 2021-05-07 | 中化(宁波)润沃膜科技有限公司 | Acid and alkali resistant composite nanofiltration membrane, and preparation method and application thereof |
| CN112870996A (en) * | 2021-01-11 | 2021-06-01 | 北京工业大学 | Preparation and application of hydrophilic chlorine-resistant polysulfone membrane |
| CN112870996B (en) * | 2021-01-11 | 2022-11-29 | 北京工业大学 | Preparation and application of hydrophilic chlorine-resistant polysulfone membrane |
| CN113750800A (en) * | 2021-10-26 | 2021-12-07 | 天津工业大学 | Preparation method of arginine modified composite nanofiltration membrane |
| CN114307687A (en) * | 2021-12-23 | 2022-04-12 | 江苏久膜高科技股份有限公司 | Beer decolorizing membrane and preparation method thereof |
| CN114307687B (en) * | 2021-12-23 | 2022-11-22 | 江苏久膜高科技股份有限公司 | Beer decolorizing membrane and preparation method thereof |
| CN115920655A (en) * | 2022-12-29 | 2023-04-07 | 中国科学院过程工程研究所 | Pollution-resistant and wetting-resistant hydrophilic-hydrophobic composite membrane for membrane distillation and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109289557A (en) | A kind of decoloration film and its preparation method and application | |
| Abdullah et al. | Membranes and membrane processes: fundamentals | |
| CN110314559A (en) | A kind of preparation method of interfacial polymerization composite membrane | |
| CN106731841B (en) | A kind of supermolecule composite nanometer filtering film and its preparation method and application | |
| Wang et al. | In-situ synthesis of PA/PVDF composite hollow fiber membranes with an outer selective structure for efficient fractionation of low-molecular-weight dyes-salts | |
| CN108435002A (en) | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified | |
| CN112808021B (en) | Method for preparing reverse osmosis membrane by adopting novel water phase system | |
| CN104474925A (en) | Preparation method of composite high-water-flux polyamide reverse-osmosis membrane | |
| CN102114391A (en) | Method for preparing polyisophthaloyl metaphenylene diamide nanofiltration membrane | |
| CN107029558A (en) | A kind of chlorine resistance composite nanometer filtering film and preparation method thereof | |
| CN112535955B (en) | Decolorizing membrane and preparation method and application thereof | |
| CN1034991C (en) | Preparation of sulfonated polyary-ether-sulfone nanometer filter film | |
| Joshi et al. | Tight ultrafiltration and loose nanofiltration membranes by concentration polarization-driven fast layer-by-layer self-assembly for fractionation of dye/salt | |
| CN109865501B (en) | Preparation method of composite membrane for adsorbing and removing organic dye in water | |
| CN110339724A (en) | One kind having salinity responsiveness composite polyamide membranes and its preparation method and application | |
| CN112717721A (en) | Acid-resistant composite nanofiltration membrane and preparation method thereof | |
| CN109224888A (en) | A kind of graphene oxide framework modified polyamide reverse osmose membrane and its application | |
| Wang et al. | Fabrication of anti-fouling polyester nanofiltration membrane for dye desalination | |
| CN109692579A (en) | Reverse osmosis membrane and its preparation method and application | |
| CN107486029A (en) | A kind of preparation method of pole low-pressure reverse osmosis membrane | |
| CN104801209B (en) | Ultralow-pressure nanofiltration membrane prepared from imidazole sulfonate grafted polyether sulfone and preparation method thereof | |
| CN114432896A (en) | Preparation method of nanofiltration membrane | |
| CN115282794B (en) | Pollution-resistant seawater desalination reverse osmosis membrane and preparation method thereof | |
| CN108211794B (en) | High-selectivity hollow fiber desalting membrane and preparation method thereof | |
| CN103143271A (en) | Reverse osmosis complex membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190201 |