EP2212373A2 - Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau - Google Patents
Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eauInfo
- Publication number
- EP2212373A2 EP2212373A2 EP08851293A EP08851293A EP2212373A2 EP 2212373 A2 EP2212373 A2 EP 2212373A2 EP 08851293 A EP08851293 A EP 08851293A EP 08851293 A EP08851293 A EP 08851293A EP 2212373 A2 EP2212373 A2 EP 2212373A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyaniline
- substrate
- acid
- doped
- coated substrate
- 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.)
- Withdrawn
Links
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 136
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 41
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000008199 coating composition Substances 0.000 claims abstract description 16
- 238000000746 purification Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 51
- 239000006185 dispersion Substances 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 150000003573 thiols Chemical class 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 244000005700 microbiome Species 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- 241000700605 Viruses Species 0.000 claims description 3
- 239000002775 capsule Substances 0.000 claims description 3
- 231100001240 inorganic pollutant Toxicity 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 244000045947 parasite Species 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002759 woven fabric Substances 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 11
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 8
- -1 alkyl radicals Chemical class 0.000 description 8
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 150000001448 anilines Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 229920000775 emeraldine polymer Polymers 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- 238000011165 process development Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 101000734334 Arabidopsis thaliana Protein disulfide isomerase-like 1-1 Proteins 0.000 description 1
- 101000609815 Caenorhabditis elegans Protein disulfide-isomerase 1 Proteins 0.000 description 1
- 101000609840 Caenorhabditis elegans Protein disulfide-isomerase 2 Proteins 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 101100278953 Rattus norvegicus Ecel1 gene Proteins 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000011000 absolute method Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 210000001601 blood-air barrier Anatomy 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002851 polycationic polymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
-
- 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
- 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
- B01D71/60—Polyamines
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/02—Polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/91—Bacteria; Microorganisms
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
Definitions
- the invention relates to polyaniline derivatives with organosulfur units and to the use of the polyaniline derivatives in water treatment, for the purification of air, for the production of redox-flow batteries or in electrolysis.
- the invention also relates to a process for the preparation of the novel polyaniline derivatives and substrates coated with the polyaniline derivatives.
- Advanced Oxidation Processes generate OH radicals, which then act oxidatively on the impurities.
- polyaniline produces active oxygen species, such as OH radicals, superoxide radical anions and the like, from the oxygen dissolved in the water and can be electrochemically regenerated.
- ICP intrinsically conductive polymers
- the group of ICP also includes polyaniline (PAni).
- PAni polyaniline
- the synthesis of polyaniline is carried out via free-radical (Min-Jong Chang, Yun-Hsin Liao, Allan S. Myerson, TK Kwei, J. Appl. Pol. Sei., Vol. 62, 1427-1428) or electrochemical polymerization from acidic solution ( BJ Hwang, R. Santhanam, CR Wu, and YW Tsai, J. Solid State Electrochem., 5: 280-286, 2001).
- Polyaniline been used mainly as protection against corrosion, in the electronics (conductive layer in flexible PCB 's and displays), for EMI shielding, or as anti-static component.
- Polyaniline is also described in the literature for water treatment (see for example EP 0 782 970 B1).
- the use of polyaniline can be carried out, for example, as granules and the treatment of the waters in bulk beds.
- Membranes in which a catalytic activity is directly combined with a special barrier structure are of particular interest in process intensification. This can be achieved by embedding a catalyst in the bulk of the membrane material or by immobilization on the outer or inner membrane surface.
- An example of the latter variant is the catalytic detoxification of an aqueous stream (degradation of chlorinated hydrocarbons) by a porous membrane of cellulose acetate with immobilized Fe / Ni nanoparticles (Meyer DE, Wood K., Bachas LG, Bhattacharyya D., Environmental Progress 2004 ; 23: 232-242).
- JP 2003-159596 which describes polyaniline-coated membranes for the destruction of microorganisms by active oxygen.
- the invention was therefore based on the object to eliminate the disadvantages known in the prior art, ie to provide a polyaniline which is readily dispersible and has good adhesion to substrates and is also suitable for water treatment.
- the object is achieved by a polyaniline comprising aniline units and organosulfur units, characterized in that the polyaniline is doped and has a number-average degree of polymerization of from about 5 to about 50
- Also included within the scope of the invention is a process for preparing polyaniline wherein aniline and at least one organosulfur moiety are reacted in an oxidative, acid-catalyzed polymerization reaction to form a polyaniline dehydrate.
- the invention likewise relates to a coated substrate which is coated with the polyaniline according to the invention and to a method for coating the substrate,
- the scope of the invention also includes a coating composition which is suitable for coating the substrate.
- the invention thus also relates to a process for the preparation of the coating composition, the process comprising the steps: a) providing a ground polyaniline according to the invention, b) optionally further grinding the polyaniline, c) producing a dispersion of the ground polyaniline and a dispersant, d) optionally treating the dispersion by energy input, in particular with ultrasound, and e) filtering.
- polyaniline which is doped and has sulfur in the main polymer chain, for water treatment, in particular water purification and / or
- the invention relates to a polyaniline which comprises aniline units and organosulfur units and is characterized in that the polyaniline is doped and has a number-average degree of polymerization of from about 5 to about 50, preferably from about 8 to about 35, more preferably from about 8 to about 30.
- Polyaniline is a conjugated polymer consisting of oxidative and acid-catalyzed coupled aniline monomers.
- Polyaniline may be doped (Emeraldine salt, ES).
- the dopant is the acid anion
- in the basic medium is the base form (Emeraldine base, EB).
- Polyaniline is also a redox-active material: Emeraldine salt can change its color and its conductivity under the influence of different media or a shift in the electrical potential. Undoped polyaniline appears blue, doped polyaniline green, and the reduced forms yellowish.
- the degree of oxidation and the degree of doping, the dopant and the pH of the surrounding medium substantially determine the electrochemical and electrical properties of the polyanion, such as the position of the redox systems and the conductivity.
- oxidation and reduction refer to the oxidation state of the carbon of the polymer chain. This is known as doping the polymer when anions are attached to the nitrogen to form a poly cation. This is an acid-base reaction.
- Emeiaidme Bas Em ⁇ ratdine SsJz
- the doping can be done with any acid.
- Preferred acids are sulfonic acids and acids with bulky substituents. Particularly preferred is alkylbenzenesulfonic acid and, in particular
- Dodecylbenzenesulfonic acid (Ci 2 alkyl benzene).
- the acid should preferably have a pKs ⁇ 5, particularly preferably ⁇ 4, in aqueous solution.
- the degree of doping of the polyanilines according to the invention is usually below 50%, preferably below 35% and in particular at about 25%.
- the degree of doping can be determined by the methods known in the art, for example by titration. This can be done in accordance with DIN 53402 (determination of the acid number).
- the mathematical determination is also possible, the degree of doping resulting from the molar ratio of nitrogen atoms in the polyaniline main chain to the equivalents of the dopant used.
- the polyanilines of the invention are coupled with organosulfur units.
- organosulfur moieties are thiols, and generally all thiols known in the art can be used.
- the thiol polyanilines according to the invention can be represented by the formula PAni-S-R.
- PAni stands for polyaniline
- each of the abovementioned alkyl radicals independently of one another contains 1 to 20 carbon atoms, preferably 1 to 15 and in particular 1 to 12 carbon atoms, may be straight- or branched-chain and optionally substituted by -SO3H, -SCVAlkalikation (especially -S ⁇ 3 ⁇ Na + ), -CO 2 H, -halogen (particularly F, Cl or Br), hydroxy, amino, amino-Ci -2 o alkyl, amino (Ci -2 o-alkyl) 2, -CO 2 -C -20 -Al ky I, -Ci -20- alkyl, -N H-CO-Ci -20 -alkyl, -Si (Ci-3-alkyl) 3 may be mono- or polysubstituted and wherein each of the above-mentioned aryl groups independently may be phenyl or naphthyl, both by -SO 3 H, -SO 3 " Alkalikation (especially
- radicals -S-R are alkylthiols having 1 to 16 carbon atoms or thiobenzene and thionaphthalene. Particularly preferred is dodecanethiol.
- organosulfur moieties for example the said thiols, are linked via their sulfur atom to the terminal end, preferably to the aromatic terminal end, of the polyanil in chain.
- aniline monomer both the unsubstituted aniline and substituted aniline or combinations thereof can be used.
- the aniline derivatives can e.g. Carry substituents with hydrocarbon radicals, e.g. 2-methylaniline, aniline-2-sulphonic acid, aniline-3-sulphonic acid or similar compounds. These copolymers show modified properties e.g. in the redox and solubility behavior.
- the new polyanilines are characterized by a small molecular chain length.
- the reason for this is to be found in the production process of the novel polyanilines wherein aniline and at least one organosulfur unit are reacted in a oxidative, acid-catalyzed polymerization reaction to a polyaniline derivative.
- the organosulfur moiety probably acts as a molecular mass regulator through chain termination. Due to the relatively small degree of polymerization and the resulting short Molecule chain lengths can be relatively easy to disperse the polyanilines according to the invention, resulting in a very fine and homogeneous dispersion, which is ideal as a coating composition.
- Substrates coated with such a coating composition exhibit a more uniform coating with a lower level of coarse particles, for example agglomerates, whereby such a coating on a substrate is consequently stable over an extended period of time. Cracking and chipping of entire coating parts can thus be prevented to a significant degree and the catalytic function of the coated substrate maintained.
- the degree of polymerization of the polyanilines is possible by conventional methods of determination (gel permeation chromatography, GPC), but an exact determination requires a polyaniline standard.
- the degree of polymerization is determined by the molecular weight of MALDI-TOF, which is a so-called absolute method and gives a relatively accurate result.
- the degree of polymerization can also be easily determined by the N / S atomic ratio.
- the polyaniline has an N / S atomic ratio of 5: 1 to 50: 1, more preferably 8: 1 to 35: 1, and most preferably 8: 1 to 30: 1, in the polyaniline backbone.
- the N / S atomic ratio relates exclusively to the nitrogen and sulfur atoms present in the polyaniline main chain, that is to say the backbone of the polymer, so that, when considering the atomic ratio, any nitrogen and / or sulfur atoms present in the side chain are disregarded ,
- sulfonic acid groups which are found for reasons of self-doping and adjustment of the solubility of the polyaniline depending on the route of synthesis in the side chain.
- the N / S atomic ratio can be determined by the methods known in the art, in particular via a CHNS elemental analysis. Possible nitrogen and sulfur atoms in the side chain of the polyaniline (eg sulfonic acids) are also detected in a CHNS elemental analysis and Therefore, taking into account further parameters, such as the ratio of starting materials used, measured values from MALDI-TOF mass spectrometry and, if appropriate, relevant analytical data such as FT-IR, Raman and NMR data, must be excluded.
- the polyaniline comprises an acid group.
- such acid groups are usually in the side chain, that is, for example, attached to the aromatic of the aniline, which self-doping polyanilines are obtained by the acid group. Therefore, in the PAni synthesis preferably aniline-2-sulfonic acid or aniline-3-sulfonic acid is used in addition to aniline as a comonomer. It therefore no longer requires the addition of an acid for doping.
- Self-doping polyanilines are already known in the art and can be prepared, for example, by sulfonation of polyaniline (J.Yue, AJ Epstein, J. Am. Chem.
- a particularly preferred embodiment is provided when an aliphatic thiol is attached to the aromatic terminal end of the polyaniline backbone, the polyaniline has a number average degree of polymerization of from about 5 to about 30, and has sulfonic acid groups on the aniline moieties.
- the polyanilines of the invention are prepared by a process wherein aniline and at least one organosulfur moiety are reacted in an oxidative, acid-catalyzed polymerization reaction to form a polyaniline derivative.
- the polymerization process is particularly preferably a precipitation polymerization. It is in the method according to the invention is preferred if an organosulfur unit, as has already been defined above, is used. Preferably, therefore, the polymerization is carried out in the presence of a thiol HSR, wherein R is as defined above for PAni-SR. Particularly preferred is dodecanethiol (DCT).
- any acid can be used as the acid for the acid-catalyzed reaction.
- the acid should have a pKs ⁇ 5, more preferably ⁇ 4.
- the oxidative acid-catalyzed polymerization reaction process further requires an oxidizing agent, using oxidizing agents known in the art. Examples include hydrogen peroxide, potassium peroxodisulfate, ammonium peroxodisulfate,
- Substrates which can be coated with the polyaniline according to the invention are, for example, an electrode, a packed bed, a membrane
- Preferred substrates are graphite and carbon fiber fabric and stainless steel. Further preferred is, for example, a combination of a membrane as a cathode, for example a
- Hollow fiber membrane as a cathode Preferred support materials are organic polymers, polymer compositions, inorganic materials or composite materials.
- the advantage of the polyanilines according to the invention is that, in contrast to the prior art, they can be applied to both conductive and non-conductive substrates.
- Membrane separations are increasingly becoming key technologies in water treatment.
- the separation and separation efficiency of the membrane is determined by the structure of the barrier layer: water desalination or separation of low molecular weight substances by reverse osmosis or nanofiltration is based on membranes with nonporous barrier layers, whereas membranes with porous layers are used for the separation of macromolecules or colloidal substances by ultrafiltration or microfiltration separating layers be used.
- Typical microfiltration membranes have release effective pores in the range between 0.1 and 1 ⁇ m; Compared to conventional filter materials, these pores are smaller and the inner surfaces are significantly larger.
- Membranes which can be used according to the invention can be classified as follows:
- membrane material organic polymers, inorganic materials (oxides, ceramics, metals), composite materials of various materials; Diaphragm cross-section: isotropic ("symmetrical"), integral anisotropic
- phase separation phase separation
- sol-gel processes thermal degradation, interfacial reaction, stretching, extrusion, nuclear tracking, microfiltration
- Membrane shape flat membrane, hollow fiber or capillary, hollow capsule.
- microfiltration membranes are made of organic polymers such as e.g. non-conductive polysulfone or non-conductive polypropylene.
- the pore size distribution across the membrane cross-section is either isotropic or slightly anisotropic.
- variants of the phase separation of polymer solutions preferably induced by a non-solvent-induced phase separation (NIPS) or by cooling into an unstable region (TIPS) dominate among the preparation processes.
- NIPS non-solvent-induced phase separation
- TIPS unstable region
- both flat membranes (in spiral wound modules or plate modules) and capillary membranes are common.
- a polyaniline which is doped and contains sulfur in the polyaniline chain is suitable for water treatment and / or air purification, and thus can Purposes are used.
- a polyaniline as described above can be used for water treatment and / or for the purification of air.
- the water treatment and / or the purification of air includes the removal of organic and inorganic pollutants, bacteria, viruses, microorganisms and / or parasites, so both a cleaning, and to a certain extent a sterilization / sterilization of water or air.
- OH radicals active oxygen species
- organic or inorganic pollutants can be oxidized by the OH radicals, for example, and thus rendered harmless.
- anilines of the invention can also be used advantageously in redox-flow batteries and in electrolysis systems.
- a coating composition is also required for the production of a coated substrate, which is why the scope of the invention also includes a process for the preparation of a coating composition, the process comprising the steps:
- Polyaniline like all ICP, is usually insoluble and has no melting point or other softening behavior. For this reason, polyaniline can not be processed like ordinary thermoplastic polymers. Processing therefore takes place via the finest distribution (dispersion) in solvents or dispersants. The starting point for many applications are therefore polyaniline dispersions.
- polyaniline In order to process polyaniline, the polyaniline is dispersed in powder form in solvents.
- the starting point for further processing are the polyaniline dispersions prepared in this way. From such dispersions can
- Layers on a substrate are the better, the smaller the particles and the more homogeneous the distribution of the polyaniline in the dispersant.
- the quality of the layer is determined by the particle size and nature of the layer
- agglomerates in ⁇ m size occur. This may be due to unfavorable polymerization conditions or to the choice of solvent or dispersant or dispersing method.
- the aim should be to produce as homogeneous a dispersion as possible with particle sizes ⁇ 1 ⁇ m.
- the particle size can be determined by a standard method, "Dynamic Laser Light Scattering". The advantages in the production and processing of such a dispersion arise from:
- the polyaniline should be doped. It has proved to be particularly advantageous if the polyaniline after step e.) Of the process according to the invention, the filtration, is re-doped with Alkybenzolsulfonklare. Particularly preferred is dodecylbenzenesulfonic acid (DBS). It may be advantageous, the Coating composition after doping a further energy input, in particular a further ultrasonic treatment to undergo. Possible agglomerates formed in the doping can be redispersed again. By doping the doping level can be adjusted exactly. This is otherwise difficult with the doping, which is present directly after the synthesis. By precisely adjusting the degree of doping, the conductivity of the polyaniline can thus also be adapted to the required conditions.
- DBS dodecylbenzenesulfonic acid
- the coating of a substrate with a coating composition according to the invention is usually carried out by applying the coating composition to the substrate by methods known in the art and then drying the coating. Possible application methods are, for example, dipping, doctoring, spraying, gravure printing, overlaying and stripping, reverse roll and spin coating, painting or application with a roller and the like.
- Such a coated substrate for example a coated membrane
- a purification reactor for the treatment of water and / or for the purification of air.
- the scope of the invention thus also includes a purification reactor, the reactor having a reaction chamber with inlet opening and outlet opening for the medium to be cleaned, at least one, in particular one, two, three or more coated substrates according to the invention, at least one, in particular one, two, three or more counter-electrodes, and optionally at least one, in particular one, two, three or more separating means between the coated substrate (s) and the anode (s).
- An inventive laboratory construction can be seen, for example, Figure 1, wherein the reference electrode is necessary only for the laboratory setup.
- the counter electrode (s) can be used with inexpensive materials such as stainless steel as a carrier material and current collector.
- the electrodes can be designed as flat sheets, perforated sheets, wires, loose beds or stretched metals. The use of carbon fleeces is also possible.
- the electrochemically active substance is the polyaniline derivative. Direct synthesis on the electrodes of monomers is industrially attractive. In addition, care is taken in the process development to apply coatings of the already synthesized polymer on the electrodes. For this purpose, established thick film coating processes are known in which the polyaniline film is possibly cast directly onto metal foils with one or more intermediate layers of a conductive adhesion promoter. The coated films can then work as a sheet, stretched or in thread form as working electrodes. Particularly attractive is the combination of polyaniline with hollow fiber membranes.
- the polyaniline may be present as a layer or doping on or in the polymer.
- the distance between the anode and cathode to avoid short circuits can be made by separators, diaphragms or spacers. Hydrophilic nonwovens or fabrics, such as e.g. from PPS, on. These are used as supporting membranes in reverse osmosis technical use. It is also possible to equip prefabricated electrodes with separator membranes by reprecipitation.
- Potentiostatic operation with a three-electrode arrangement has been used on a laboratory scale for process development.
- the electrochemical parameters can be determined.
- the potential of a saturated calomel electrode is used.
- a diaphragm separates this reference electrode from the water (or air) to be treated.
- diaphragms tend to become blocked by crystallization or colonization with microbes.
- the transition from potentiostatic to galvanostatic operation is conceivable.
- the control loops are simplified, but greater emphasis is placed on the homogeneous distribution of the electric fields in the reactor design.
- the laboratory structure is sketched in principle.
- the centerpiece is an electrochemical cell with exchangeable electrodes. These allow the use of different coatings and substrates.
- the electrodes are driven by a potentiostat which makes a corresponding polarization of the electrodes.
- a potentiostat which makes a corresponding polarization of the electrodes.
- polyaniline can be used as a coating or constituent of
- the oxidant solution is prepared as follows: 11 g (48 mmol) of ammonium peroxodisulfate (APS) are weighed in and subsequently made up to 30 ml with deionized water. The solution is transferred to a dropping funnel.
- APS ammonium peroxodisulfate
- reaction mixture continues to react for about 5 hours.
- Step 6 Rinse with 1 L of deionized water.
- the filter cake is placed in a beaker after washing and dried to constant weight in a vacuum oven.
- Figure 2 shows polyaniline DCT immediately after synthesis, magnification 100 fold.
- the polymerization product is present as loosely agglomerated particles; larger agglomerates (1 -10 ⁇ m) are easily recognizable, which decay into finer particles ( ⁇ 1 ⁇ m) when the slide is moved mechanically.
- FIG. 3 shows an IR spectrum of the polyaniline DCT base.
- the labeled regions identify the DCT component in the polyaniline.
- the starting material for dispersions is the powder of the non-conductive base form of polyaniline (EB).
- the dispersion prepared in step 1 is hereinafter called PAni-EB-NMP 2.5% (w / v) parent dispersion.
- the mixture is homogenized for at least 30 minutes in an ultrasonic bath at 50 ° C. and filtered through a cellulose filter in order to remove any agglomerates which may have formed during the preparation.
- This dispersion is called PAni-ES-DBS-NMP 2% (w / v) parent dispersion
- the dispersion prepared under 2) can be diluted with other solvents or solvent mixtures as needed to adjust the concentration, the flow or the wetting properties and is then ready for coating or for incorporation into other substances.
- Example 3 Preparation Example, Coating of Steel Sheet:
- a cleaned and degreased film section is placed on the flat support surface, over which a doctor is pulled away.
- the squeegee has a width (inside) of 73 mm; this width determines the width of the coating on the steel sheet.
- the gap width between substrate and doctor blade is 50 ⁇ m.
- the squeegee is placed behind the slider on the substrate; into the interior of the doctor blade is added 1 ml of 1% (w / v) dispersion.
- the doctor blade is subsequently pulled over the steel foil and a thin film of the coating dispersion remains on the substrate.
- the solvent is evaporated at 200 0 C (setting on the hair dryer). After evaporation of the solvent, the remaining solvent residues are evaporated at 120 0 C in a vacuum oven. This gives a green shimmering polyaniline layer with a thickness of about 200-1000 nm.
- a microfiltration membrane made of polypropylene (flat membrane 2EHF, Membrana GmbH) with a nominal pore size (cut-off) of 0.4 microns and a specific surface area of 25 m 2 / g is installed in a filter holder made of Teflon (diameter 47 mm) and using a peristaltic pump flushed through successively with the following solutions (in each case 1 mL / min):
- Stabilizer SLOTONIP 64 (Schlötter), and 1, 5 mL reductor SLOTONIP 66 (Schlötter), made up of 25 mL water (25 0 C), for 20 min.
- the membrane is dried in a vacuum oven at 45 0 C. Characterization is carried out by SEM, nitrogen adsorption (BET), permporometry and measurements of water permeability.
- Example 4.2 Preparation of a conductive membrane doped with conductive carbon black and PAn i by precipitation-agent-induced phase separation
- a solution of 12% by weight of polyethersulfone in a mixture of NMP and triethylene glycol (ratio 2: 1, v / v) is prepared (stirring at 45 ° C. for about 3 hours). Subsequently, 6 wt .-% Leitruß and 10 wt .-% of a 2% PAni dispersion, each based on the total solution added. After 10 min. Dispersing in an ultrasonic bath, the solution is stirred for a further 1 h at 45 0 C. Subsequently, using a doctor blade, a 250 ⁇ m thick film of the polymer solution is produced on a polished glass plate. After a residence time of 30 sec.
- the precipitation takes place in a bath of ultrapure water with a content of 25% by volume of NMP. After a residence time of 1 h in the precipitation bath, the membrane is transferred to a washing bath of ultrapure water, which is exchanged twice at intervals of ⁇ 4 or -16 hours. The membrane thus produced is then treated by solvent exchange (water -> ethanol) and then dried.
- the layer thickness of the membrane is about 200 microns.
- Characterization is carried out by SEM, nitrogen adsorption (BET), permporometry and measurements of water permeability.
- FIG. 4 shows a laboratory reactor for generating OH radicals:
- the sample is dried at 110 ° C. overnight.
- Counter electrode Stainless steel electrode 1 .4301, surface like working electrode
- Reference electrode saturated calomel electrode A Abbssttaanndd A AEb // GUEb :: 2 mm, check for possible short circuits with
- the working electrode is polarized in each case for 2 min (120 s) to - 700 mV against a saturated calomel electrode and the RNO concentration is monitored by means of an inline photometer.
- the RNO signals are shifted for about 1 minute due to the time delay effects between the electrocatalytic chamber and the photometer probe.
- Figure 5 shows the RNO concentration in the pulsed polarization degradation experiment of the polyaniline working electrode.
- the absorption signal at 438 nm pulsates in parallel and reproducibly with the applied polarization.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Water Supply & Treatment (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200710056423 DE102007056423A1 (de) | 2007-11-23 | 2007-11-23 | Herstellung und Verwendung neuer Polyaniline zur Wasserbehandlung |
PCT/EP2008/065909 WO2009065892A2 (fr) | 2007-11-23 | 2008-11-20 | Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2212373A2 true EP2212373A2 (fr) | 2010-08-04 |
Family
ID=40585714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08851293A Withdrawn EP2212373A2 (fr) | 2007-11-23 | 2008-11-20 | Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau |
Country Status (13)
Country | Link |
---|---|
US (1) | US20100307974A1 (fr) |
EP (1) | EP2212373A2 (fr) |
JP (1) | JP2011505441A (fr) |
KR (1) | KR20100089882A (fr) |
CN (1) | CN101910249A (fr) |
AU (1) | AU2008327879A1 (fr) |
BR (1) | BRPI0819821A8 (fr) |
CA (1) | CA2705409A1 (fr) |
DE (1) | DE102007056423A1 (fr) |
MX (1) | MX2010005512A (fr) |
RU (1) | RU2010125616A (fr) |
WO (1) | WO2009065892A2 (fr) |
ZA (1) | ZA201003549B (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109802736A (zh) * | 2019-03-13 | 2019-05-24 | 西安电子科技大学 | 一种频谱感知的方法、装置及计算机存储介质 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100196306A1 (en) * | 2007-09-28 | 2010-08-05 | Auckland Uniservices Limited | Bioactive aniline copolymers |
ES2704645T3 (es) * | 2008-12-11 | 2019-03-19 | Univ California | Membrana de filtración |
CN102044648B (zh) * | 2009-10-16 | 2013-04-10 | 大连融科储能技术发展有限公司 | 聚芳基醚苯并咪唑离子交换膜及其制备和全钒液流电池 |
CN103180027B (zh) * | 2010-10-22 | 2015-11-25 | 皇家飞利浦电子股份有限公司 | 分离氧气的装置和方法 |
BR112015008023B1 (pt) | 2012-10-12 | 2022-03-03 | The Regents Of The University Of California | Processo de aumento de hidrofilicidade e membrana de polianilina submetida ao mesmo |
PT2996799T (pt) | 2013-05-15 | 2021-10-15 | Univ California | Membranas de polianilina formadas por inversão de fase para aplicações de osmose direta |
SG11201608333XA (en) | 2014-04-08 | 2016-11-29 | Univ California | Polyaniline-based chlorine resistant hydrophilic filtration membranes |
CN104312255B (zh) * | 2014-10-29 | 2016-06-01 | 湖北大学 | 一种水性聚丙烯酸掺杂聚苯胺缓蚀剂及其制备方法 |
US10274451B2 (en) * | 2015-02-18 | 2019-04-30 | Santa Clara University | Affordable electrochemical detection of environmental contaminants |
DE102015005732A1 (de) * | 2015-05-07 | 2016-11-10 | Forschungszentrum Jülich GmbH | Kohlenstoffhaltige Membrane für die Wasser- und Gastrennung |
CN104909435B (zh) * | 2015-06-03 | 2017-03-01 | 湖南大学 | 一种氨基乙酸掺杂聚苯胺修饰电极及其制备方法和应用 |
CN106563573B (zh) * | 2015-10-12 | 2019-10-11 | 国电科学技术研究院 | 一种改性聚苯胺湿式静电除尘器阳极模块 |
TWI568491B (zh) | 2015-12-31 | 2017-02-01 | 財團法人工業技術研究院 | 過濾材料 |
RU2641278C1 (ru) * | 2016-10-19 | 2018-01-16 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") | Способ получения водного раствора полианилина |
JP6597678B2 (ja) * | 2017-03-10 | 2019-10-30 | 株式会社豊田中央研究所 | 負極用電解液及びフロー電池 |
WO2019112080A1 (fr) * | 2017-12-05 | 2019-06-13 | 주식회사 파라 | Procédé de préparation d'un composite polyaniline pour l'utilisation antibactérienne et élimination des métaux lourds, dans lequel de l'acide organique et des ions métalliques sont dopés dans un polymère conducteur de polyaniline sous un ordre prédéterminé, et composite polyaniline préparé par l'intermédiaire du même procédé |
CN110639438B (zh) * | 2019-08-16 | 2021-08-20 | 华东理工大学 | 一种聚苯胺中空微球的制备及回收电子垃圾中的贵金属及其再利用的方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5324453A (en) * | 1992-08-07 | 1994-06-28 | Neste Oy | Electrically conducting polyaniline: method for emulsion polymerization |
JP3043981B2 (ja) * | 1995-12-26 | 2000-05-22 | 健一 森田 | 活性酸素発生剤およびそれを用いた活性酸素発生方法 |
DE69611901T2 (de) | 1995-12-26 | 2001-06-21 | Ken-Ichi Morita | Methode zur Erzeugung von aktivem Sauerstoff |
DE69704361T2 (de) * | 1996-05-20 | 2001-09-20 | Dinex A/S, Middelfart | Verfahren und reaktor zur elektrochemischen umwandlung eines materials, z.b. in einer flüssigkeit unlöslichen russpartikeln |
US6429282B1 (en) * | 1996-05-31 | 2002-08-06 | The Regents Of The University Of California | Stable, concentrated solutions of polyaniline using amines as gel inhibitors |
JP3743691B2 (ja) * | 1997-03-25 | 2006-02-08 | 矢崎総業株式会社 | アニリン系重合体、電極材料及び二次電池 |
TW502046B (en) * | 1998-10-22 | 2002-09-11 | Nippon Catalytic Chem Ind | Method for production of water-soluble conducting polyaniline |
DE19916802A1 (de) * | 1999-04-14 | 2001-10-25 | Gerhard Illing | Verbundmembran auf Polyanilinbasis |
US6380346B1 (en) * | 2000-01-18 | 2002-04-30 | Chien-Chung Han | Heterogeneous reaction method for preparing functionalized polyanilines |
JP2003159596A (ja) | 2001-11-28 | 2003-06-03 | Kenichi Morita | 活性汚泥殺菌膜及びその製造方法並びに汚泥処理装置 |
JP4297673B2 (ja) * | 2002-10-17 | 2009-07-15 | 日立マクセル株式会社 | 非水二次電池 |
WO2005035626A1 (fr) * | 2003-10-08 | 2005-04-21 | The Yokohama Rubber Co., Ltd. | Procede permettant de produire une polyaniline conductrice et composition polymere organique |
US7351359B2 (en) * | 2003-10-08 | 2008-04-01 | The Yokohama Rubber Co., Ltd. | Method for producing conductive polyaniline and organic polymer composition |
JP4190511B2 (ja) * | 2004-03-31 | 2008-12-03 | 横浜ゴム株式会社 | 導電性ポリアニリン分散液から形成された色素増感太陽電池の光電変換素子用導電基板並びにその基板を用いた色素増感太陽電池 |
TWI279405B (en) * | 2005-03-08 | 2007-04-21 | Ind Tech Res Inst | Retardant on polymerization of aniline |
DE102005031715A1 (de) * | 2005-07-07 | 2007-01-18 | Illing, Gerhard | Protonenleitfähige Polymerelektrolytmembran auf der Basis von Polyanilin, dotiert mit Polysäuren |
-
2007
- 2007-11-23 DE DE200710056423 patent/DE102007056423A1/de not_active Withdrawn
-
2008
- 2008-11-20 KR KR1020107013832A patent/KR20100089882A/ko not_active Application Discontinuation
- 2008-11-20 MX MX2010005512A patent/MX2010005512A/es unknown
- 2008-11-20 RU RU2010125616/04A patent/RU2010125616A/ru not_active Application Discontinuation
- 2008-11-20 US US12/743,620 patent/US20100307974A1/en not_active Abandoned
- 2008-11-20 EP EP08851293A patent/EP2212373A2/fr not_active Withdrawn
- 2008-11-20 AU AU2008327879A patent/AU2008327879A1/en not_active Abandoned
- 2008-11-20 CA CA 2705409 patent/CA2705409A1/fr not_active Abandoned
- 2008-11-20 JP JP2010534472A patent/JP2011505441A/ja active Pending
- 2008-11-20 CN CN2008801238861A patent/CN101910249A/zh active Pending
- 2008-11-20 BR BRPI0819821A patent/BRPI0819821A8/pt not_active IP Right Cessation
- 2008-11-20 WO PCT/EP2008/065909 patent/WO2009065892A2/fr active Application Filing
-
2010
- 2010-05-19 ZA ZA2010/03549A patent/ZA201003549B/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2009065892A2 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109802736A (zh) * | 2019-03-13 | 2019-05-24 | 西安电子科技大学 | 一种频谱感知的方法、装置及计算机存储介质 |
Also Published As
Publication number | Publication date |
---|---|
CA2705409A1 (fr) | 2009-05-28 |
DE102007056423A1 (de) | 2009-06-04 |
AU2008327879A1 (en) | 2009-05-28 |
KR20100089882A (ko) | 2010-08-12 |
US20100307974A1 (en) | 2010-12-09 |
BRPI0819821A8 (pt) | 2016-04-26 |
WO2009065892A3 (fr) | 2009-09-24 |
MX2010005512A (es) | 2010-06-03 |
JP2011505441A (ja) | 2011-02-24 |
ZA201003549B (en) | 2011-07-27 |
WO2009065892A2 (fr) | 2009-05-28 |
RU2010125616A (ru) | 2011-12-27 |
CN101910249A (zh) | 2010-12-08 |
BRPI0819821A2 (pt) | 2015-05-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2009065892A2 (fr) | Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau | |
Liu et al. | Scalable conductive polymer membranes for ultrafast organic pollutants removal | |
Homayoonfal et al. | A comparison between blending and surface deposition methods for the preparation of iron oxide/polysulfone nanocomposite membranes | |
Yang et al. | Photocatalytic PVDF ultrafiltration membrane blended with visible-light responsive Fe (III)-TiO2 catalyst: Degradation kinetics, catalytic performance and reusability | |
Obaid et al. | Effective polysulfone-amorphous SiO2 NPs electrospun nanofiber membrane for high flux oil/water separation | |
Khorshidi et al. | Novel nanocomposite polyethersulfone-antimony tin oxide membrane with enhanced thermal, electrical and antifouling properties | |
Kumar et al. | Permeation, antifouling and desalination performance of TiO2 nanotube incorporated PSf/CS blend membranes | |
Bai et al. | Preparation and characterization of poly (vinylidene fluoride) composite membranes blended with nano-crystalline cellulose | |
Daraei et al. | An ultra-antifouling polyethersulfone membrane embedded with cellulose nanocrystals for improved dye and salt removal from water | |
US11787698B2 (en) | Purification and drying of graphene oxide | |
EP2106466B1 (fr) | Fibres nanométriques et mésométriques à particules modifiées procede de produciton et utilisation | |
Du et al. | Advanced photocatalytic performance of novel BiOBr/BiOI/cellulose composites for the removal of organic pollutant | |
Lin et al. | Asymmetrically porous anion exchange membranes with an ultrathin selective layer for rapid acid recovery | |
WO2010085945A1 (fr) | Procédé de production de nanoparticules contenant du métal, enrobées de polymères et articles pouvant être obtenus à partir desdites nanoparticules | |
Samadi Mollayousefi et al. | Preparation, characterization, and performance study of PVDF nanocomposite contained hybrid nanostructure TiO2-POM used as a photocatalytic membrane | |
Imtiaz et al. | Direct ink writing of dehydrofluorinated Poly (Vinylidene Difluoride) for microfiltration membrane fabrication | |
WO2002036661A1 (fr) | Procede de production d'une solution constituee d'un polymere contenant des unites azole recurrentes, solutions produites selon ledit procede et leur utilisation | |
Chandra et al. | Nitrogenated graphene oxide-decorated metal sulfides for better antifouling and dye removal | |
Jia et al. | β-cyclodextrin-based adsorbents integrated with N-doped TiO2 photocatalysts for boosting dye elimination of industrial wastewater | |
Pervez et al. | Tuning the surface functionality of polyethylene glycol-modified graphene oxide/chitosan composite for efficient removal of dye | |
CN112076635B (zh) | 一种导电聚合物分离膜、制备方法以及在染料分离中的用途 | |
DE102012024329B4 (de) | Verfahren zur Herstellung von reduziertem Graphenoxid sowie damit hergestelltes reduziertes Graphenoxid und dessen Verwendung | |
DE112006000253T5 (de) | Benzimidazolsubstituierte Polybenzimidazole als Grundmaterial für die Herstellung von protonenleitenden Membranen | |
Missaoui et al. | Removing organic dye by cellulose acetate nanocomposite membrane ultrafiltration: Effect of bio-nanoparticle size | |
DE102013217840A1 (de) | Kronenether-enthaltende PEM-Elektrode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20100512 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
17Q | First examination report despatched |
Effective date: 20101025 |
|
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SUED-CHEMIE IP GMBH & CO. KG |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20140602 |