CN105669984B - Skeleton contains phosphonyl group and the block polymer of ammonium ion and preparation method thereof - Google Patents
Skeleton contains phosphonyl group and the block polymer of ammonium ion and preparation method thereof Download PDFInfo
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- CN105669984B CN105669984B CN201610012928.0A CN201610012928A CN105669984B CN 105669984 B CN105669984 B CN 105669984B CN 201610012928 A CN201610012928 A CN 201610012928A CN 105669984 B CN105669984 B CN 105669984B
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- monomer
- segment
- group
- phosphonyl group
- polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000005499 phosphonyl group Chemical group 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012528 membrane Substances 0.000 claims abstract description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 10
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001728 nano-filtration Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 150000003009 phosphonic acids Chemical class 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 150000004662 dithiols Chemical class 0.000 claims description 7
- 239000012634 fragment Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 238000010612 desalination reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000010 aprotic solvent Substances 0.000 abstract 1
- 239000003205 fragrance Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- KHQWPLUMQKQAMY-UHFFFAOYSA-N benzene-1,2-dicarboxamide piperazine Chemical compound C(C=1C(C(=O)N)=CC=CC1)(=O)N.N1CCNCC1 KHQWPLUMQKQAMY-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical class [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 238000005954 phosphonylation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses skeletons to contain phosphonyl group and the block polymer of ammonium ion and preparation method thereof.Monomer containing phosphonyl group and diphenol monomer are mixed in a certain ratio, the segment containing phosphonyl group of certain molecular weight is prepared；Monomer containing amino and diphenol monomer are mixed in a certain ratio, the segment containing amino of certain molecular weight is prepared, and blocked using how fluorine-substituted monomer, obtains using the polysubstituted fluorided structure of fragrance as the segment containing amino of end group；In the presence of middle highly basic and toluene, in higher boiling aprotic solvent, it is mixed by the segment containing phosphonyl group and by the segment containing amino of end group of fluorine, is heated to certain temperature reaction, obtained dope obtains the polymer containing phosphonyl group and ammonium ion after processing.These novel block polymers show preferable nanofiltration/reverse osmosis desalination performance and proton conduction property, can be applied to water process and Proton Exchange Membrane Fuel Cells field.
Description
Present patent application obtains national young Nsfc Projects（Project number is：51503151）With Tianjin section
Skill supports key special subjects project（Contract number is：12ZCDZSF07000）Subsidy.
Technical field
The invention belongs to technical field of polymer materials, are related to nanofiltration, anti-penetration wastewater disposal membrane material and fuel cell
The preparation field of proton exchange membrane material, more particularly to the structure of the block polymer containing phosphonyl group and ammonium ion and its
Preparation method, be in particular a kind of skeleton containing zwitterionic membrane for water treatment material and proton exchange membrane material and its efficiently
Preparation method.
Background technology
Fuel cell technology has energy security, supply security and the advantages such as environmental-friendly.Proton exchange membrane is fuel electricity
One of the core component in pond, the proton exchange membrane in high-efficiency fuel cell should have the characteristics that：High proton conductivity is low
Electronic conductivity, fuel and oxidant hypotonicity, low water conductibility, oxidation and hydrolytic stability are done, are good under wet condition
Mechanical performance can be used for making film battery assembly device and low cost.Auto industry circle and many scientific research institutions generally make at present
Material is the Nafion membrane produced by DuPont.Although Nafion membrane good, high humility with chemical stability
The advantages that lower high proton conductivity, but there is also low mechanical strengths under low proton conductibility under expensive, low humidity and high temperature
Etc. deadly defects.Seek high proton conductivity and heat safe novel proton exchange membranes material under cheap, low humidity to have become
For one of the research direction of fuel cell sciemtifec and technical sphere forefront.
Based on factors above, organic acid is introduced into macromolecular chain by scientists, the organic polymer material of synthesizing new
Material, and it is that sulfonic group is introduced into high molecular skeleton that document report is more at present.Sulfonated polysulfone membrane has certain
The ion of hydrophily, high proton conductivity and selectivity passes through effect.However, since the conductibility of sulfonated polysulfone membrane intermediate ion is
It is to rely on water, when which limits using sulfonated polysulfone as proton exchange membrane, operation temperature cannot be excessively high（100℃）.It is firing
In the application for expecting battery, it has been found that, operation temperature is higher, and advantage is more, and temperature is higher, and the resistance to CO abilities of Pt electrodes are higher, energy
Imitate higher, and compared with low temperature when be heat-treated it is more convenient.Therefore, all have under dry, wet condition conductive new well
Type membrane material has been increasingly becoming the hot spot of research.The composite membrane of benzimidazole family macromolecule and phosphoric acid due to its good heat resistance and
High proton conductivity becomes one of the material system of the current most study of scientists.But this system is maximum to be lacked
Point, which is exactly that phosphoric acid is easy in water, to be lost in, and causes operation very unstable.It is exactly to utilize to overcome the most powerful method of this defect
Covalent bond is introduced into phosphate group the appropriate location in macromolecule.Based on this point, the high-molecular compound containing phosphonyl group
The concern of many scientists is attracted, this kind of high-molecular compound high temperature resistant, antioxygenic property is good, in high temperature and dry, wet condition
Under have good proton-conducting, low water absorbing properties that can reduce the swelling of film.Although phosphonylation polymer is fuel electricity
The very promising candidate material of proton exchange membrane when the high-temperature operation of pond, but there is the high phosphono of high conductance energy due to synthesizing
The polymer of change is relatively difficult, therefore relatively fewer for this kind of polymer material research.
In recent years, amphoteric ion polymer（Not only contain cationic unit in polymer but also contain anionic units）At
For good resistant to pollution material.The polymer of class phosphatide is coated on ultrafiltration membrane, wherein the both sexes functional group units contained can
To improve the flux of film and reduce pollution（Polymer International, 2009, 58(12):1350-1361）.Material
The presence of middle relative charge so that amphoteric ion surface can form the hydration layer of " Free water ", and it is fine so that material has
Biocompatibility and contamination resistance.
Polyether aromatic phosphine（Or thioether）Polymer is due to its chemical stability height, and mechanical performance, heat resistance are good, at film water
Reason and proton or anion-exchange membrane fuel cells field have a wide range of applications.The polyether aromatic phosphine of ammonification（Or thioether）Polymerization
Functional groups amino in object not only can directly be crosslinked to obtain novel cross-linked polymer compound, but also can be converted into bone
The controllable novel high polymer material of the hydrophily of frame cation.Polyether aromatic phosphine containing ammonium ion at present（Or thioether）In film
Application in terms of water process is rarely reported.It is found through being retrieved to existing technical literature, early in nineteen eighty-two Kesting, R. E. are just
Be prepared for the complex reverse osmosis membrane of cellulose acetate and quaternized poly- piperazine phthalamide, have preferable thermal stability and
Chlorine resistance [Report (1982), 49 pp]；Kovacs in 2011, Jason R are prepared for gathering using the method disperseed layer by layer
The reverse osmosis composite membrane of diallyldimethylammonium chloride/4- sulfonate polystyrene/montmorillonite, improves the choosing of reverse osmosis membrane
Selecting property [PMSE Preprints (2011)].
Currently, reverse osmosis, the NF membrane of the marketization are based primarily upon two kinds of macromolecules, cellulose acetate and aromatic polyamides.
However, cellulose acetate film is easily attacked by microorganism, easy shrinkage deformation under high temperature or condition of high voltage, and it is adapted only to relatively narrow acid
Basicity（pH）Range；Aromatic polyamides composite membrane but to being constantly exposed to oxidant such as free chlorine, shows quite weak resistance
Power, therefore pretreated technique is increased, to also increase the cost of clean water treatment.It is new containing ammonium ion or phosphonyl group
Type high molecular polymer not only has a good proton-conducting, but also has higher thermally and chemically stability, especially compared with
There is superpower anti-chlorine performance within the scope of wide pH, therefore show promise as novel reverse osmosis, nanofiltration membrane for water treatment material.
The research of high molecular material in polymeric system simultaneously containing phosphonic acids and ammonium root group at home and abroad still belongs to blank,
The combination of the two is expected to develop mechanical performance to play strong hydrogen bonding effect and the selectivity of ammonium root group of phosphonyl group
Excellent, swelling behavior is controllable, equipment with high desalinization and flux or high proton conductivity novel film materials.
Invention content
The present invention is directed to prepare a series of high score that chemical stabilities are high, cheap and easily-available, containing phosphonic acids and ammonium root group
Sub- material is applied in reverse osmosis, nanofiltration and proton exchange membrane field.
The invention discloses a kind of novel skeletons can be used as membrane for water treatment material and proton exchange membrane material to contain phosphine
The block polymer and preparation method thereof of acid and ammonium root group.
The invention discloses a kind of novel skeletons can be used as membrane for water treatment material and proton exchange membrane material to contain phosphine
The block polymer of acid and ammonium root group, shown in structure such as following formula (I)：
x,y=2-500；
m=0,1；n=1,2；
X=F,Cl,Br,I,NO3,HSO3,HSO4Or NaSO4；
Y=oxygen or sulphur；
M=H, first family alkali metal, amine NR1R2R3（R1, R2, R3=H, C1-C3 alkyl）.
The invention discloses the preparation methods that skeleton contains the block polymer of phosphonic acids and ammonium root group, it is characterised in that presses
Following step carries out：
（1）By the monomer containing phosphonyl group and diphenol monomer（Or dithiol monomer）It is mixed in a certain ratio, is added two
Phenol monomer（Or dithiol monomer）The middle highly basic of 1.15-2 times of molal quantity, 160 DEG C after refluxing toluene divides water, high boiling non-
In proton polar solvent improve temperature to 185 DEG C react 12 hours；After being cooled to room temperature, reaction mixture is filtered to remove insoluble
Then filtrate is deposited in isopropanol by object, isopropanol is used in combination to wash 3 times, collects solid, certain molecular weight is obtained after dry
Segment containing phosphonyl group；Fragments molecules amount is 2000-20000；
（2）By the monomer containing amino and diphenol monomer（Or dithiol monomer）It is mixed in a certain ratio, diphenol list is added
Body（Or dithiol monomer）The middle highly basic of 1.15-2 times of molal quantity, 160 DEG C after refluxing toluene divides water, high boiling non-proton
In polar solvent improve temperature to 185 DEG C react 12 hours；Prepare the segment containing amino of certain molecular weight；Fragments molecules amount
For 2000-20000；
（3）It will（2）In be made segment without separation, excessive how fluorine-substituted monomer is added at room temperature, 85 DEG C through hexamethylene
After alkane reflux water-dividing, in high boiling aprotic polar solvent improve temperature to 110 DEG C react 12 hours；It is cooled to room temperature
Afterwards, reaction mixture is filtered to remove insoluble matter, then filtrate is deposited in isopropanol, isopropanol is used in combination to wash 3 times, collected
Solid, obtained after dry certain molecular weight containing amino, using fluorine as the segment of end group；Fragments molecules amount is 2000-
20000；
（4）It will be above-mentioned（1）With（3）Obtained segment oligomer is according to molal quantity 1:1 ratio mixing, high boiling non-
In proton polar solvent, reacted 12 hours under the conditions of 110 DEG C.Reaction solution is slowly poured into deionized water, it is poly- to obtain threadiness
Close object, is then impregnated 5-10 hour under the conditions of 60-80 DEG C, repeatedly 3-5 times, filter, then in 0.5M aqueous sulfuric acids, in
It is impregnated 5-10 hours under the conditions of 60-80 DEG C, repeats 2-3 times, then impregnate 5- in deionized water under the conditions of 60-80 DEG C again
It 10 hours, repeats 3-5 times, filters, dry, vacuum drying obtains the block polymer containing phosphonic acids and ammonium ion（I）（X=
HSO4, m=1；M=H, n=2）；
（5）It will be from step（4）It is obtained（I）N is dissolved in, in N- dimethylacetylamides（A concentration of 20%）, by this solution
It is poured into 0.5 M aqueous slkalis, soaking at room temperature is overnight, and obtained solid is washed with deionized three times again, vacuum dried to obtain
Polymer containing phosphonate and amino（I）；The aqueous slkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide
Caesium, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, amine（NHR1R2R3 ；R1, R2, R3=H or C1-3 alkyl）It is water-soluble
Liquid.
Preparation method of the present invention, middle highly basic therein are sodium carbonate, potassium carbonate or cesium carbonate.
Preparation method of the present invention, higher boiling aprotic polar solvent therein are dimethyl sulfoxide, N, N- dimethyl
Acetamide, N,N-dimethylformamide or N-Methyl pyrrolidone.
After the present invention further discloses the block polymer film forming that skeleton contains phosphonic acids and ammonium root group, have preferable
Nanofiltration, reverse osmosis and proton conduction property, can be widely applied to substance separation, water softening, pure water prepare and proton
The fields such as exchange film fuel battery.
Description of the drawings：
Fig. 1 skeletons contain the structure of the block polymer of phosphonic acids and ammonium root group.
Specific implementation mode：
For purposes of simplicity and clarity, the hereafter appropriate description that known technology is omitted, in case those are unnecessary
Details influences the description to the technical program.Below in conjunction with example, the present invention is described further.It is raw materials used not have such as
Special explanation, by commercially available.
Inherent viscosity is measured using Ubbelohde viscosimetry, and test temperature is 25 DEG C, and solvent is the NMP containing 0.05M lithium bromides
Solution.
One, the preparation of polymer
1, the preparation of phosphonic acids segment P
It, will be double under nitrogen atmosphere（4- fluorophenyls）（3- phosphonic acids disodium salt phenyl）Phosphine oxide（PBFPPO）, 4,4 '-'-biphenyl diphenols
（BP）And Anhydrous potassium carbonate（11.5mmol）Be added to equipped with water knockout drum, serpentine condenser, blender and gas-guide tube 100.0
In the straight three-necked flasks of mL, 40.0 mL n,N-dimethylacetamide are then added thereto（DMAc）With 20.0 mL toluene.Heating
To 160 DEG C, toluene is exhausted by water knockout drum after 12 h of reflux band water at such a temperature, 185 DEG C is risen to and continues at such a temperature
12h is reacted, the viscous solution of brown is obtained.Filtering, filtrate fall in isopropanol, collect solid, and isopropanol is used in combination to wash 3
It is secondary, obtain the segment containing phosphonyl group after dry.
2, the preparation of amino fragment A
It, will be double under nitrogen atmosphere（4- fluorophenyls）（3- aminophenyls）Phosphine oxide（ABFPPO）, 4,4 '-'-biphenyl diphenols（BP）With
Anhydrous potassium carbonate（11.5mmol）It is added to 100.0 mL straight three equipped with water knockout drum, serpentine condenser, blender and gas-guide tube
In mouth flask, 40.0 mL n,N-dimethylacetamide are then added thereto（DMAc）With 20.0 mL toluene.It is warming up to 160
DEG C, toluene is exhausted by water knockout drum after 12 h of reflux band water at such a temperature, 185 DEG C is risen to and the reaction was continued at such a temperature
12h obtains the viscous solution of brown.
Excessive decafluorobiphenyl is added without separation in segment obtained above at room temperature（DFBP）Monomer, 85 DEG C through hexamethylene
After alkane reflux water-dividing, improve temperature to 110 DEG C react 12 hours；After being cooled to room temperature, reaction mixture is filtered to remove insoluble
Then filtrate is deposited in isopropanol by object, isopropanol is used in combination to wash 3 times, collects solid, certain molecular weight is obtained after dry
It is containing amino, using fluorine as the segment of end group；
3, the preparation of block polymer
Embodiment 1-10：
By phosphonic acids segment P and amino fragment A according to mole ratio 1:1 mixing, under the conditions of nitrogen protection, in 110 DEG C of temperature
Degree is lower to react 12h, obtains the viscous solution of brown.Reaction solution is slowly poured into deionized water, obtains fibrous polymer, so
Impregnate 10 hours, be repeated 5 times under the conditions of 60-80 DEG C afterwards, filter, then in 0.5M aqueous sulfuric acids, under the conditions of 60-80 DEG C
It impregnates 10 hours, is repeated 3 times, then impregnates 10 hours, be repeated 5 times, mistake in deionized water under the conditions of 60-80 DEG C again
Filter is dried, and vacuum drying obtains the block polymer containing phosphonyl group and ammonium ion（I）.
Embodiment 11-13：Polymer（I-1-M）（M=Li,Na,K）Preparation
It takes（I-1）2 restrain the DMAc solution at 20%（w/v）, this solution is poured into 0.5 M aqueous slkalis, soaking at room temperature
Overnight, obtained solid is washed with deionized three times again, vacuum dried to obtain I-1-M.
Two, reverse osmosis membrane performance is tested：
Test condition：25 DEG C, 2000 ppm sodium chloride solutions, 40.0 mL min of flow velocity-1, 400 psi of pressure, test
Time is 24 h, and the effective area of wherein membrane cisterna test is about 21.22 cm2。
Embodiment 14-15
0.750 g of polymer is taken to be dissolved in 10.0 mL DMAC, after 0.45 μm of filter filtering, by polymer
Solution is cast at leisure on horizontal, clean glass plate (10.0 × 10.0 cm).Gradually heating is done under a nitrogen atmosphere
It is dry, 60 DEG C of 12 h of drying are first risen to, 90 DEG C of 12 h of drying are then risen to, finally rise to 120 DEG C of 12 h of drying.Again in vacuum
Under the conditions of, dry 8 h at a temperature of 120 DEG C.After being cooled to room temperature, by film glass plate immersion boil 24 h in deionized water, after will
Film strips down to obtain diaphragm transparent, that flexibility is good from glass plate, tests desalination rate and water flux.
Three, nanofiltration performance test
Test condition：The water inlet of NF membrane evaluating apparatus is simulated seawater, is configured with magnesium chloride and pure water, a concentration of 2000
ppm (mgL-1), survey film pressure is 70 psi（About 0.48 MPa）, 40 mLmin of water flow-1, experimental temperature is 25 DEG C, test
Time be 24 h, wherein membrane cisterna test effective area be about 21.22 cm2。
Embodiment 16
With reference to the film-forming method of embodiment 14, diaphragm is made using polymer I-5, carries out the test of nanofiltration performance, test
As a result：MgCl2Rejection：88%, 9.1 mL d of water flux-1。
Four, proton conduction property is tested
Test condition：25 DEG C, relative humidity 100%.
Embodiment 17
It takes polymer I-5 to be dissolved in DMAc, the solution of a concentration of 5wt% is made, filtering after driving bubble away, is poured onto clean
Glass plate on, it is then dry 48 small in the vacuum drying chamber of 120 DEG C of constant temperature dry 24 hours under 25 DEG C of normal pressures of constant temperature
When, obtain plate membrane.0.0086 S/cm of proton conductivity.
After the preferred embodiment of detailed description, it is familiar with this skilled worker and is clearly understood that, it is above-mentioned not departing from
Various change and modification can be carried out under claim and spirit, it is all according to the technical essence of the invention to above example institute
Any simple modification, equivalent change and modification of work belong to the range of technical solution of the present invention.
Claims (5)
1. skeleton contains the block polymer of phosphonic acids and ammonium root group, structure such as following formula（I）It is shown：
x,y=2-500；
m=0,1；n=1,2；
X=F,Cl,Br,I,NO3,HSO3,HSO4Or NaSO4；
Y=oxygen or sulphur；
M=H, first family alkali metal, amine NR1R2R3, wherein R1, R2, R3=H, C1-C3 alkyl.
2. skeleton described in claim 1 contains the preparation method of the block polymer of phosphonic acids and ammonium root group, it is characterised in that press
Following step carries out：
（1）Monomer containing phosphonyl group and diphenol monomer or dithiol monomer are mixed in a certain ratio, diphenol monomer is added
Or the middle highly basic of 1.15-2 times of dithiol monomer molar number, 160 DEG C after refluxing toluene divides water, in high boiling aprotonic polar
In solvent improve temperature to 185 DEG C react 12 hours；After being cooled to room temperature, reaction mixture is filtered to remove insoluble matter, then
Filtrate is deposited in isopropanol, solid is collected, the segment containing phosphonyl group of certain molecular weight is obtained after dry；Segment point
Son amount is 2000-20000；
（2）Monomer containing amino and diphenol monomer or dithiol monomer are mixed in a certain ratio, diphenol monomer or two is added
The middle highly basic of 1.15-2 times of thiophenol monomer molar number, 160 DEG C after refluxing toluene divides water, in high boiling aprotic polar solvent
Middle raising temperature to 185 DEG C react 12 hours；Prepare the segment containing amino of certain molecular weight；Fragments molecules amount is 2000-
20000；
（3）It will（2）In segment is made without separation, be added excessive how fluorine-substituted monomer at room temperature, 85 DEG C are returned through hexamethylene
After flow point water, in high boiling aprotic polar solvent improve temperature to 110 DEG C react 12 hours；It, will after being cooled to room temperature
Reaction mixture is filtered to remove insoluble matter, and then filtrate is deposited in isopropanol, collects solid, certain molecule is obtained after dry
Amount containing amino, using fluorine as the segment of end group；Fragments molecules amount is 2000-20000；
（4）It will be above-mentioned（1）With（3）Obtained segment oligomer is according to molal quantity 1:1 ratio mixing, high boiling non-proton
In polar solvent, reacted 12 hours under the conditions of 110 DEG C；
Reaction solution is slowly poured into deionized water, fibrous polymer is obtained, it is small that 5-10 is then impregnated under the conditions of 60-80 DEG C
When, it repeats 3-5 times, filtering, then impregnated 5-10 hours in 0.5M aqueous sulfuric acids, under the conditions of 60-80 DEG C, repeats 2-3 times,
Then it impregnates 5-10 hours, repeats 3-5 times in deionized water under the conditions of 60-80 DEG C again, filter, dry, vacuum drying,
Obtain the block polymer containing phosphonic acids and ammonium ion（I）,X=HSO4, m=1；M=H, n=2；
（5）It will be from step（4）It is obtained（I）It is dissolved in N, in N- dimethylacetylamides, a concentration of 20%, this solution is poured into
In 0.5 M aqueous slkalis, soaking at room temperature is overnight, and obtained solid is washed with deionized three times again, vacuum dried to be contained
The polymer of phosphonate and amino（I）；The aqueous slkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, carbon
Sour lithium, sodium carbonate, potassium carbonate, cesium carbonate, amine NHR1R2R3；The aqueous solution of R1, R2, R3=H or C1-3 alkyl.
3. the preparation method described in claim 2, middle highly basic therein is sodium carbonate, potassium carbonate or cesium carbonate.
4. the preparation method described in claim 2, higher boiling aprotic polar solvent therein is dimethyl sulfoxide, N, N- dimethyl
Acetamide, N,N-dimethylformamide or N-Methyl pyrrolidone.
5. preparing nanofiltration, reverse osmosis after the block polymer film forming that skeleton described in claim 1 contains phosphonic acids and ammonium root group
Application in terms of membrane for water treatment and in terms of Proton Exchange Membrane Fuel Cells.
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| CN102643421A (en) * | 2012-04-23 | 2012-08-22 | 天津师范大学 | Novel polymer containing phosphonate group and preparation method and application of novel polymer |
| CN103497324A (en) * | 2013-09-29 | 2014-01-08 | 天津师范大学 | Cation-contained high-molecular polyaryl (thio) ether phosphine oxide polymers and preparation method thereof |
| CN105001424A (en) * | 2015-07-06 | 2015-10-28 | 天津师范大学 | Block polymer with skeleton containing phosphonyl and sulfo groups and preparation method thereof |
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| CN103497324A (en) * | 2013-09-29 | 2014-01-08 | 天津师范大学 | Cation-contained high-molecular polyaryl (thio) ether phosphine oxide polymers and preparation method thereof |
| CN105001424A (en) * | 2015-07-06 | 2015-10-28 | 天津师范大学 | Block polymer with skeleton containing phosphonyl and sulfo groups and preparation method thereof |
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