CA2379962C - Covalently cross-linked polymers and polymer membranes via sulfinate alkylation - Google Patents
Covalently cross-linked polymers and polymer membranes via sulfinate alkylation Download PDFInfo
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- CA2379962C CA2379962C CA2379962A CA2379962A CA2379962C CA 2379962 C CA2379962 C CA 2379962C CA 2379962 A CA2379962 A CA 2379962A CA 2379962 A CA2379962 A CA 2379962A CA 2379962 C CA2379962 C CA 2379962C
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- Prior art keywords
- polymer
- groups
- polymer blend
- membrane
- cross
- Prior art date
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- Expired - Lifetime
Links
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 32
- 229920005597 polymer membrane Polymers 0.000 title claims abstract description 16
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 title description 12
- 238000005804 alkylation reaction Methods 0.000 title description 4
- 230000029936 alkylation Effects 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 93
- 229920002959 polymer blend Polymers 0.000 claims abstract description 43
- 238000004132 cross linking Methods 0.000 claims abstract description 27
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 238000005341 cation exchange Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- -1 ammonium ions Chemical class 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 101100275854 Arabidopsis thaliana CSI1 gene Proteins 0.000 claims abstract description 4
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 77
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 33
- 229910052645 tectosilicate Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000000975 dye Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 229920006254 polymer film Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical group OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 229910052799 carbon Chemical group 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 229920005601 base polymer Polymers 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 229920002492 poly(sulfone) Polymers 0.000 claims 2
- 229920001955 polyphenylene ether Polymers 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 239000004696 Poly ether ether ketone Substances 0.000 claims 1
- 239000004734 Polyphenylene sulfide Substances 0.000 claims 1
- 229920000491 Polyphenylsulfone Polymers 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000000502 dialysis Methods 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 238000000909 electrodialysis Methods 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims 1
- 239000004745 nonwoven fabric Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000005373 pervaporation Methods 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- 229920001643 poly(ether ketone) Polymers 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 229920002530 polyetherether ketone Polymers 0.000 claims 1
- 229920005649 polyetherethersulfone Polymers 0.000 claims 1
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 1
- 238000001223 reverse osmosis Methods 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 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 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 2
- MBEVSMZJMIQVBG-UHFFFAOYSA-N 2-(hydroxymethyl)guanidine Chemical class NC(N)=NCO MBEVSMZJMIQVBG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101100243951 Caenorhabditis elegans pie-1 gene Proteins 0.000 description 1
- 241000861718 Chloris <Aves> Species 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910001588 amesite Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 201000010549 croup Diseases 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
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Abstract
The invention relates to a covalently cross-linked polymer or polymer membrane consisting of one or more polymers, which can bear the following functional groups (M=Hal (F, Cl, Br, I), OR, NR2; R=alkyl, hydroxyalkyl, aryl; (Me=H, Li, Na, K, Cs, or other metal cations or ammonium ions); a) precursors of cation exchange groups: SO2M and/or POM2 and/or COM b) sulphinate groups SO2Me and which can be covalently cross-linked using the following organic compounds: a) di, tri or oligofunctional haloalkanes or haloaromatics, which have been reacted with sulphinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane (Y=cross-linking bridges, X=Hal (F, Cl, Br, I), OR, Y=(CH2)x-; -arylene-; -(CH2)x-arylene-; CH2arylene-CH2-, x=3-12): polymer-SO2Y-SO2-polymer and/or b) compounds containing the following groups: Hal-(CH2)x-NHR, one side of which (Hal-) has been reacted with sulphinate groups SO2ME and the other side (-NHR) with SO2M groups, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane: polymer-SO2-(CH2)x-NR-SO2-polymer and/or c) compounds containing the following groups: NHR-(CH2)x)-NHR, which have been reacted with sulphinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane: polymer-SO2-NR-(CH2)x-NR-SO2-polymer.
Description
CA 02379962 2002-01-18 .
Covalently cross linked polymers and polymer membranes via sulfinate alkyla ion Description Prior art The author of t .s patent application has developed a new method for prep .ing covalently cross-linked ionomer membranes, whic is based on an alkylation reaction of sulfinate group -containing polymers, polymer blends and polymer (blend) membranes (J. Kerres, W. Cui, W.
Schnurnberger: 'Vernetzung von modifizierten Engineering Thermoplasten", German Patent 196 22 337.7 (Application dated June 4, 1996), carman Patent Office (1997), "Reticulation de Materiaux ThermdpIastiques Industriels Modifies", French Patent F 97 06716 dated May 30, 1997). An advantage of the covalent networ is its resistance to hydrolysis even at higher temperatires. A disadvantage of the ion conductive.
covalently cros -linked polymers and polymer blends described in the above in ention is the formation of a hydrophobic network when al ylating the sulfinate groups during forming the membrane, t is hydrophobic network being partially incompatible wi h the ion conductive polymer (blend) component such =s a sulfonated polmer polymer-S03Me, so that an inhomogeneou- polymer (blend) morphology is generated, which reduces ti e mechanical stability (embrittlement on drying up!) an. also prevents a complete cross-linking due to the partial se.aration of sulfinate phase and sulfonate phase.
Covalently cross linked polymers and polymer membranes via sulfinate alkyla ion Description Prior art The author of t .s patent application has developed a new method for prep .ing covalently cross-linked ionomer membranes, whic is based on an alkylation reaction of sulfinate group -containing polymers, polymer blends and polymer (blend) membranes (J. Kerres, W. Cui, W.
Schnurnberger: 'Vernetzung von modifizierten Engineering Thermoplasten", German Patent 196 22 337.7 (Application dated June 4, 1996), carman Patent Office (1997), "Reticulation de Materiaux ThermdpIastiques Industriels Modifies", French Patent F 97 06716 dated May 30, 1997). An advantage of the covalent networ is its resistance to hydrolysis even at higher temperatires. A disadvantage of the ion conductive.
covalently cros -linked polymers and polymer blends described in the above in ention is the formation of a hydrophobic network when al ylating the sulfinate groups during forming the membrane, t is hydrophobic network being partially incompatible wi h the ion conductive polymer (blend) component such =s a sulfonated polmer polymer-S03Me, so that an inhomogeneou- polymer (blend) morphology is generated, which reduces ti e mechanical stability (embrittlement on drying up!) an. also prevents a complete cross-linking due to the partial se.aration of sulfinate phase and sulfonate phase.
2 Description Thus, the object of the invention is to provide new covalently cross-linked polymers/membranes in which the covalently cross-linked polymer (blend) component is well compatible with the ion conductive polymer (blend) component.
This object is achieved by providing covalently cross-linked polymer or covalently cross-linked polymer membranes comprising one or more polymers which optionally have the following functional groups:
a) precursors of cation exchange groups: SO2M and/or POM2 and/or COM, b) sulfinate groups SO2Me, where M is independently Hal, OR or NR2, Hal is F, Cl, Br or I, R
is independently alkyl, hydroxyalkyl, or aryl, and Me is independently H, Li, Na, K, Cs, another metal cation, or an ammonium ion, where said polymer may be covalently cross-linked by the following organic compounds:
c) difunctional, trifunctional or oligofunctional haloalkanes or haloaromatics, which have been reacted with sulfinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-Y-S02-polymer, where Y is - (CH2)x-; -arylene-; - (CH2)x-arylene-; or -CH2-arylene-CH2-, where x is 3-12;
and/or d) compounds containing the following groups: Hal-(CHAx-NHR, which have been reacted on the Hal- side with sulfinate groups SO2Me and on the -NIR side with SO2M- groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02- (CH2)-NR-S02-polymer;
and/or 2a e) compounds containing the following groups: NHR-(CH2).-NHR, which have been reacted with SO2Me groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-NR- (CH2)x-NR-S02-polymer.
Further the process according to the invention adds to this purpose.
Thereto a polymer solution comprising polymers containing the following functional groups:
= sulfinate groups -S02Me = sulfochloride groups and/or other precursors of cation exchange groups, is prepared.
Additionally, a bifunctional or oligofunctional alkylation cross-linking agent (typically an a,w-dihaloalkane) and optionally a secondary diamine cross-linking agent NHR(CH2)x-NHR is added to the polymer solution. The formation of the covalent cross-linking bridges takes place during formation of the membrane when evaporating the solvent by alkylating the sulfinate groups and optionally by the formation of sulfonamide via reaction of the sulfohalogenide groups present in the polymer with the secondary amino groups of the diamine cross-linking agent. During the acidic and/or basic and/or neutral aqueous after-treatment of the membranes following the membrane formation, the precursors of the cation exchange groupings are hydrolyzed to form cation exchange groups.
The present invention further provides a process for preparing the above-mentioned covalently cross-linked polymers, polymer blends or polymer blend membranes, characterized in that the polymers are dissolved simultaneously or successively in a dipolar aprotic solvent that is N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, dimethylsulfoxide or 2b sulfolane, thereafter the cross-linking agent is added, then the cross-linking agent is homogeneously dispersed in the polymer solution by stirring, thereafter the polymer solution is filtered and then degassed, thereafter the polymer solution is then spread as a thin film on a base , the solvent is then removed by heating to 80 - 130 C and/or by applying low pressure or in a circulating air dryer, the polymer film is then optionally peeled off the base and the polymer film is then cured as follows:
a) in 1-50 weight % aqueous alkali at T = RT - 95 C
b) in completely desalted water at T = RT - 95 C
c) in 1-50 weight % aqueous mineral acid at T = RT - 95 C
d) in completely desalted water at T = RT - 95 C, wherein one or more of the curing steps may optionally be omitted.
The present invention further provides a use of the membranes defined above for producing energy on an electrochemical route.
The present invention further provides a use of the membranes defined above as a component of membrane fuel cells at temperatures of from 0 to 180 C.
The present invention further provides a use of the membranes defined above in electrochemical cells.
The present invention further provides a use of the membranes defined above in secondary batteries.
The present invention further provides a use of the membranes definedabove in electrolytic cells.
The present invention further provides a use of the membranes defined above in a membrane separation process Figure 1 schematically shows the formation of the covalent cross-linking bridges in blends of sulfochlorinated polymer
This object is achieved by providing covalently cross-linked polymer or covalently cross-linked polymer membranes comprising one or more polymers which optionally have the following functional groups:
a) precursors of cation exchange groups: SO2M and/or POM2 and/or COM, b) sulfinate groups SO2Me, where M is independently Hal, OR or NR2, Hal is F, Cl, Br or I, R
is independently alkyl, hydroxyalkyl, or aryl, and Me is independently H, Li, Na, K, Cs, another metal cation, or an ammonium ion, where said polymer may be covalently cross-linked by the following organic compounds:
c) difunctional, trifunctional or oligofunctional haloalkanes or haloaromatics, which have been reacted with sulfinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-Y-S02-polymer, where Y is - (CH2)x-; -arylene-; - (CH2)x-arylene-; or -CH2-arylene-CH2-, where x is 3-12;
and/or d) compounds containing the following groups: Hal-(CHAx-NHR, which have been reacted on the Hal- side with sulfinate groups SO2Me and on the -NIR side with SO2M- groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02- (CH2)-NR-S02-polymer;
and/or 2a e) compounds containing the following groups: NHR-(CH2).-NHR, which have been reacted with SO2Me groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-NR- (CH2)x-NR-S02-polymer.
Further the process according to the invention adds to this purpose.
Thereto a polymer solution comprising polymers containing the following functional groups:
= sulfinate groups -S02Me = sulfochloride groups and/or other precursors of cation exchange groups, is prepared.
Additionally, a bifunctional or oligofunctional alkylation cross-linking agent (typically an a,w-dihaloalkane) and optionally a secondary diamine cross-linking agent NHR(CH2)x-NHR is added to the polymer solution. The formation of the covalent cross-linking bridges takes place during formation of the membrane when evaporating the solvent by alkylating the sulfinate groups and optionally by the formation of sulfonamide via reaction of the sulfohalogenide groups present in the polymer with the secondary amino groups of the diamine cross-linking agent. During the acidic and/or basic and/or neutral aqueous after-treatment of the membranes following the membrane formation, the precursors of the cation exchange groupings are hydrolyzed to form cation exchange groups.
The present invention further provides a process for preparing the above-mentioned covalently cross-linked polymers, polymer blends or polymer blend membranes, characterized in that the polymers are dissolved simultaneously or successively in a dipolar aprotic solvent that is N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, dimethylsulfoxide or 2b sulfolane, thereafter the cross-linking agent is added, then the cross-linking agent is homogeneously dispersed in the polymer solution by stirring, thereafter the polymer solution is filtered and then degassed, thereafter the polymer solution is then spread as a thin film on a base , the solvent is then removed by heating to 80 - 130 C and/or by applying low pressure or in a circulating air dryer, the polymer film is then optionally peeled off the base and the polymer film is then cured as follows:
a) in 1-50 weight % aqueous alkali at T = RT - 95 C
b) in completely desalted water at T = RT - 95 C
c) in 1-50 weight % aqueous mineral acid at T = RT - 95 C
d) in completely desalted water at T = RT - 95 C, wherein one or more of the curing steps may optionally be omitted.
The present invention further provides a use of the membranes defined above for producing energy on an electrochemical route.
The present invention further provides a use of the membranes defined above as a component of membrane fuel cells at temperatures of from 0 to 180 C.
The present invention further provides a use of the membranes defined above in electrochemical cells.
The present invention further provides a use of the membranes defined above in secondary batteries.
The present invention further provides a use of the membranes definedabove in electrolytic cells.
The present invention further provides a use of the membranes defined above in a membrane separation process Figure 1 schematically shows the formation of the covalent cross-linking bridges in blends of sulfochlorinated polymer
3 = =
and suifinated p-lymer, Figure 2 shows the formation of the covalent cross-1 nking bridges in a polymer containing both sulfinate groups and sulfochloride groups.
The composites a.cording to the invention consist of polymers having the folio ing functional groups:
After membrane p eparation, before hydrolysis:
-502M and/or -P0M2 and/or -COM (M = Hal (P, Cl, Br, I), OR, NR2; R I. alkyl, hydroxyalkyl, aryl) = cross-linkin bridges:
a) polymer-S62-Y-502-polymer optionally:
b) polymer-S*2-Y'-NR-S02-polymer c) polymer-S.2-NR-Y1 '-NR-502-polymer After hydrolysis:
= -503M-, -F0212-, -COOM-groupe = above-menti.ned cross-linking bridges The covalently .rose-linking of the aulfinate polymers in a mixture with pr-cursors of cation exchange polymers results in a better mix"ng of blend phases and thus a higher degree of cross-linkin-, so as to achieve a better mechanical stability of th, resultant polymer film compared to covalently cros:-linked polymer (blend) films made from cation exchange polymers and polymeric sulfinates. A further improvement of he mechanical characteristics is achieved by a controlled in orporation of a cross-linking component containing amin. groups, which reacts with the precursors of the cation exch.nge groups, into the polymer network.
A.-lication exa -lea = 4 =
= =
The invention will be illustrated in more detail by two examples as follcws. The weights/volumes of the components used are listed in table 1.
1. Instruction for membrane preparation sulfochlorin.ated PSU Udel (IEC=1.8 meg SO2C1/g) and PSUSO21ji (IEC:=1.95 meg so;Li/g) (for polymer structures see figure 2) are dissolved in N-methylpyrrolidinone (NMP) . Then ci.,o3-diiodobutane is added to the solution of the cross-linking agents. After stirring for 15 minutes the solution is filtered and degp.ssed. A thin film of the polymer solution is knife-coated ontb a glass plate. The glass plate is placed into a vacuum drying oven and the solvent is removed at temperatures of from 80 to 130 C at a low pressure of from 700 up to final y 15 mbar. The film is taken out of the drying oven and cooled: The polymer film is peeled off the glass plate underwater and is hydrolyzed/after-treated at first in 10% hyd.rochloric acid and then in completely desalted water at. temperatures of from 60 to 90 C for 24 h respectively.
2. Used amounts of reactants and characterisation results Table 1: Used amounts of reactants and characterisation results membrane Me PSU-S02C1 PSU-SO2Li cross-lin- TEC swelling Rsr king agent (g) [83 (nil] [me(1/8] [flam]
wz10 10 1 1 0.3 0.2 19.3 337.6 wz13 10 1 0.4 0.12 0.85 18.3 15.2 =
= 5 wz14 . -10 1 0.3 0.09 0.56 8.6 62.6 wz15 10 1 0.2 0.06 0.7 13 -36.14 wz16 10 1* 1* 0.3 0.75 11.7 31_6 * 2 SO2C1 groups per PSU repetitive unit Part 2 of the application Covalently cross-linked composite membranes Prior art The invention on which the present additional is based on relates to a continuation or alternative to the German parent patent application publication No. DE 100 24 575 Al (Kovalent vernetzte Polymere und Polymermembranen via Sulfinatalkylierung).
The products and processes, respectively of this above-mentioned parent application are subjected to the following disadvantages:
For membranes which are prepared by the described processes, moistened gases are still needed for operation in the hydrogen fuel cell. If the gases are not moistened, the membrane dries up and the proton conductivity is decreased to a large extent.
To solve this problem, the present application suggests incorporating tectosilicates and phyllosilicates which are optionally functionalized according to the parent application, particularly into a covalent network.
The parent application only describes the incorporation of polymers into the covalent network. When using functionalized phyllosilicates and/or tectosilicates it was surprisingly found, that the compounds which have low molecular functional groups and are bound to the phyllosilicates and/or tectosilicate are not discharged during employment of the membrane, especially in the case of employment in a hydrogen fuel cell. This allows an increase in the concentration of ion conductive groups within the covalent network without having the usual effect of extremely deteriorating the mechanical characteristics of the membrane (brittlement or strong swelling). In an extreme case it is therefore possible to completely eliminate the use of enclosed ion conductive polymers in the covalent network. Ion conduction then exclusively occurs via silicates having functional groups.
Thus, the present invention solves the problem of drying up the membrane and of a limitation in the number of ion conductive groups within the membranes to a not marginal extent.
Thus the object of the invention is to provide new covalently cross-linked polymers/membranes displaying proton conductivity even when used with gases which are not moistened or only slightly moistened. Moreover, a further object is to incorporate low molecular functionalized compounds which are coupled to a silicate into the covalent network such that they remain in the membrane for an industrially useful period time.
Further the process according to the invention helps to solve this object.
The present invention further provides a covalently cross-linked composite polymer or covalently cross-linked composite polymer membrane comprising one or more polymers and tectosilicates and/or phyllosilicates, wherein the tectosilicates and/or phyllosilicates present can be functionalized or not functionalised, wherein the polymers are characterized in that they may have the following functional groups:
a) precursors of cation exchange groups: SO2M and/or POM3 and/or COM, 7a b) sulfinate groups SO2Me, where M is independently Hal, OR, or NR2, Hal is F, Cl, Br or I, R
is independently alkyl, hydroxyalkyl or aryl, Me is independently H, Li, Na, K, Cs, another metal cation, or an ammonium ion, said polymers may be covalently cross-linked by the following organic compounds:
C) difunctionial, trifunctional or oligofunctional haloalkanes or haloaromatics which have been reacted with sulfinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-Y-S02-polymer where Y is the cross-linking bridge: -(CH2)õ-; -arylene-;
-(CH2)x-arylene-; or -CH2-arylene-CH2-, where x is 3-12 and/or d) compounds containing the following groups: Hal- (CHAx-NHR, which have been reacted on the Hal- side with sulfinate groups SO2Me and on the -NHR side with SO2M groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02- (CH2) x-NR-S02-polymer;
and/or e) compounds containing the following groups: NHR-(CH2)x-NHR, which have been reacted with SO2Me groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-NR- (CH2) x-NR-S02-polymer .
Description of the invention:
The following text expressively refers to the parent patent application publication No. DE 100 24 575 Al:
=
A mixture in a s itable solvent, preferably an aprotic one, is prepared, whi.h contains polymers and functionalized tectosilicates ad/or phyllosilicates and optionally low molecular compouuds.
The mixture cont ins polymers and the following functional groups;
= sulfinate gr.ups SO2Me (Me is a monovalent or polyvalent metal cation = sulfochlorid- groups and/or other precursors of cation exchange gro ps.
Additionally, a -ifunctional or oligofunctional alkylation cross-linking ag nt (typically an a,m-dihaloalkane) and optionally a sec-ndary diamine cross-linking agent NUR-(Cliz)x-NTIR is ad.ed to the mixture, preferably a polymer solution. The f-rmation of the covalent cross-linking bridges takes place dur'ng the formation of the membrane when evaporating the solvent by alkylating the sulfinate groups and optionally formation of sulfonamide via reaction of the sulfohalide groups present in the polymer with the secondary amino groups of the diamine cross-linking agent.
During the acid'c and/or basic and/or neutral aqueous after-treatment of th. membranes following the formation of the membrane the pr cursors of the ion exchange groupings are hydrolyzed and oxidized to form ion exchange groups, respectively.
Figure 1 schema ically shows the formation of the covalent cross-linking b idges in blends of sulfochlorinated polymer and sulfinated -olymer, Figure 2 shows the formation of the covalent cross-linking bridges in a polymer containing both - sulfinate group= and sulfochloride groups.
The composites a.cording to the invention consist of polymers having the folio ing functional groups:
After membrane p eparation, before hydrolysis:
= S02101 and/or !0M2 and/or CoM (M m Hal (F, Cl, Br, I), OR, Nit, R=alkyl, hydroxyalkyl, aryl) = cross-linkin bridges;
a) polymer-S=2-Y-S02-polymer optionally:
b) polymer-S02-Y'-NR-S02-polymer c) polymer-S=2-NR-Y"-NR-S02-polymer After hydrolysi_:
= -S03M, -1,03M -COOM groups = above-menti.ned cross-linking bridges By covalently c oss-linking the sulfinate polymers mixed with precursors of i.n exchange polymers, especially cation exchange polyms.s, in the presence of functionalized phyllosilicates and/or tectosilicates a better mixing of the blend phases an. thus also a higher degree of cross-linking is achieved, gi,ing raise to a better mechanical stability of the resultant p-lymer film compared to covalently cross-linked polymer blend) films made of cation exchange polymers and polymeric s if mates. By a controlled inclusion of a cross-linking c.mponent having amino groups, which reacts , 25 with the precur.ors of the cation exchange groups, into the polymer network a further improvement of the mechanical characteristics is achieved.
By incorporati functionalized tectosilicates and/or phyllosilicate into the covalent network during the formation of t e membrane, the water retention capability of the membrane i. increased. The functional groups protruding from the surfa.e of the functionalized tectosilicates or =
phyllosilicate, additionally change the membrane characteristics in accordance with their functionality_ Description of the inorganic filler The inorganic active filler is a phyllosilicate based on montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, talc, fluorhectorite, saponite, beidelite, nontronite, stevensite, bentonite, mica, vermiculite, fluorvermiculite, halloysite, fluor containing synthetical talc types or blends of two or more of the above-mentioned phyllosilicates. The phyllosilicate can be delaminated or pillared. Particularly preferred is montmorillonite.
The weight ratio of the phyllosilicate is preferably from 1 to 80 %, more preferably from 2 to 30 % by weight, most preferably from 5 to 20 %-If the functionalized filler, especially zcolites and members of the beidelite series and bentonites, is the only ion-conducting component, its weight ratio is usually in a range of from 5 to 80 wtVs, preferably of from 20 to 70 wt% and especially in a range of from 30 to 60 wt%-.
Description of the functionalized phyllosilicate:
The term "a phyllosilicate" in general means a silicate, in which the SiO4 tetraeders are connected in two-dimensional infinite networks. (The empirical formula for the anion is . The single layers are linked to one another by the cations positioned between them, which are usually Na, K, Mg, Al or/and Ca in the naturally occurring phyllosilicates.
By the term "a delaminated functionalized phyllosilicate" we understand phyllosilicates in which the layer distances are at first increased by reaction with so-called functionalisation agents. The layer thickness of such silicates before delamination is preferably 5 to 100 angstrom, more preferably 5 to 50 and most preferably 8 to 20 angstrom. To increase the layer distances (hydrophobisation) . .
- . -11 =
=
the phyllosilica es are reacted (before production of the composites acco .ing to the invention) with so-called functionalizing Iydrophobisation agents which are often also called onium io s or onium salts.
The cations of -he phyllosilicates are replaced by organic functionalizing hydrophobisation agents whereby the desired layer distances which depend on the kind of the respective functionalizing molecule or polymer which is to be incorporated inio the phyllosilicate can be adjusted by the kind of the org:nic residue.
The exchange of the metal ions or protons can be complete or partial. Prefe red is the complete exchange of metal ions or protons. The = entity of exchangeable metal ions or protons is usually expr ssed as milli equivalent (meq) per 1 g of phyllosilicate tectosilicate and is referred to as ion exchange capaci y.
Preferred are p yllosilicates or tectosilicates having a cation exchange capacity of at least 0,5, preferably 0,8 to 1,3 meq/g.
Suitable organ'c functionalizing hydrophobisation agents are derived from o onium, ammonium, phosphonium and sulfonium ions, which ma carry one or more organic residues.
As suitable fu ctionalizing hydrophobisation agents those of general formul- I and/or II are mentioned:
=
ne Z naz n8 R3. MR2 I IX
-Where the subst'tuents have the following meaning:
'5 R1, R2, R3, R4 -re independently from each other hydrogen, a straight chain, branched, saturated or unsaturated hydrocarbon rad'cal with 1 to 40, preferably 1 to 20 C atoms, optionally carr ing at least one functional group or 2 of the radicals are ii ed with each other, preferably to a heterocyclic re idue having 5 to 10 C atoms, more preferably having one or -re N atoms.
X represents ph.sphorous, nitrogen or carbon, Y represents ox gen or sulfur, n is an integer from 1 to 5, preferably 1 to 3 and Z is an anion.
Suitable functi=nal groups are hydroxyl, nitro or sulfo groups, whereas carboxyl or sulfonic acid groups are especially pref-rred. In the same way sulfochloride and carboxylic aci, chloride groups are especially preferred.
Suitable anion- Z are derived from proton delivering acids, in particular ineral acids, wherein halogens such as chlorine, brom ne, fluorine, iodine, sulfate, sulfonate, phosphate, pho phonate, phosphite and carboxylate, especially acetate are pr ferred. The phyllosilicates used as starting materials are -enerally reacted as a suspension. The preferred susp-nding agent is water, optionally mixed with =
alcohols, especi-lly lower alcohols having 1 to 3 carbon atoms. If the f nctionalizing hydrophobisation agent is not water-soluble, len a solvent is preferred in which said agent is solubl.-,. In such cases, this is especially an aprotic solvent. Further examples for suspending agents are ketones and hyd.ocarbons. Usually a suspending agent miscible with w-ter is preferred. On addition of the hydrophobizing -gent to the phyllosilicate, ion exchange occurs whereby .he phyllosilicate usually precipitates from the solution. he metal salt resulting as a by-product of the ion exchang is preferably water-soluble, so that the hydrophobized poyllosilicate can be separated as a crystalline sol d, for example, by filtration.
The ion exchang- is mostly independent from the reaction temperature. T e temperature is preferably above the crystallization point of the medium and below the boiling point thereof. For aqueous systems the temperature is between 0 and 100 C, preferably between 40 and 80 C.
For a cation a - anion exchange polymer alkylammonium ions are preferred, in particular if as a functional group additionally a carboxylic acid chloride or sulfonic acid chloride is pr-sent in the same molecule. The alkylammonium ions can be ob.ained via usual methylation reagents such as methyl iodide. Suitable ammonium ions are omega-aminocarboxyli. acids, especially preferred are omega-aminoarylsulfo ic acids and omega-alkylaminosulfonic acids.
Omega-aminoary sulfonic acids and omega-alkylaminosulfonic acids can be o.tained with usual mineral acids, for example hydrochloric a.id, sulfuric acid or phosphoric acid or by methylation re.gents such as methyl iodide.
Additional prefe red ammonium ions are pyridine and laurylammonium i.ns. After hydrophobizing the layer distance of the phyllosil:cates is in general between 10 and 50 angstrom, prefer=bly 13 and 40 angstrom.
The hydrophobize. and functionalized phyllosilicate is freed of water by dryil g. In general a thus treated phyllosilicate still contains - residual water content of 0-5 weight % of water_ Subsequ=ntly the hydrophobized phyllosilicate can be mixed in form oi a suspension in a suspending agent which is free as much as possible from water with the mentioned polymers and be further processed to obtain a membrane.
An especially p,eferred functionalization of the tectosilicates -ndfor phyllosilicates is, in general, achieved with ma.dified dyes or their precursors, especially with triphenylm-thane dyes. They are represented by the general formula NN.10 -s%R4 .NS,%, 1110 R = alkyl (essecially CH3; CiRO
In the present invention dyes derived from the following basic skeleton are used:
=
=
*
R contains Ci-- C40, and 0-4 N-atoms, and 0-3 S-atoms, R can be charged positively.
S In order to functionalize the phyllosilicate the dye or its reduced precursor is sufficiently stirred in an aprotic solvent (e,g. tetrahydrofuran, DMAc. NM?) together with the silicate in a vessel. After 24 hours the dye and the precursor, respectively, is intercalated into the cavities of the phyllosilicate. The intercalation must be such that the ion conductive croup is located on the surface of the silicate particle.
The following figure schematically shows the process:
R¨..õ
cit;C.A.kt )401. dye 111.111 ptett...S.Seht The thus functionalized phyllosilicates is added as an additive to the polymer solution as described in application publication No. DE 100 24 575 Al. It was found to be especially preferable to use the precursor of the dyes.
Only in the acidic after-treatment the dyes themselves are formed by splitting off water.
=H J
RN
./R 1111 R
=
In the case of the triphenylmethane dyes it was hereby surprisingly found that these dyes support the proton conductivity in the membranes prepared thereby. Whether this is even a water-free proton conductivity cannot be stated with sufficient certainty. If the dyes are not bound to the silicate, thus if they are present in the membrane in a free form, they are discharged from the fuel cell with the reaction water already after a short period of time.
According to the invention the polymer blends containing sulfinate groups of the above-mentioned parent application, most preferably the thermoplatic functionalized polymers (ionomers) are added to the suspension of the hydrophobized phyllosilicates.
This can be done by using an already dissolved form or the polymers are solubilized in the suspension itself.
Preferably the amount of the 17 =
phyllosilicates s of from 1 to 70 weight %, more preferably of from 2 to 40 eight Ps and most preferably of from 5 to 15 weight %.
A further improv-ment with respect to the parent patent application can -e the additional blending of zirconyl chloride (ZrOC12 into the membrane polymer solution and into the cavities of he phyllosilicates and/or tectosilicates. If the after-treat -nt of the membrane is performed in phosphoric acid, hardly soluble zirconium phosphate precipitates in the direct proximity of the silicate grain in the membrane. Z'rconium phosphate shows self-proton conductivity wh.n operating the fuel cell. The proton conductivity aces through the formation of hydrogen phosphates as i termediate steps and is part of the state of the art. A cont,olled inclusion in the direct proximity of a water storing a.ent (silicates) is novel.
1. Etrbodiment for membrane preparation Su1foch1orinate4 PSU Udell (IECa1.8 meg sO2c1/g) and PSUSO2Li (IEC1.95 meg SPiLi/g) (for polymer structures see figure 2) and montmorillo ite functionalized with triphenylmethane dye are dissolved i N-methylpyrrolidinone (Nmp). Then a,ca-diiodobutane as a cross-linking agent is added to the solution. After stirring for 15 minutes the solution is filtered and desassed. A thin film of the polymer solution is knife-coated o o a glass plate. The glass plate is placed into a vacuum ing oven and the solvent is removed at temperatures o from 80 to 130 C at a low pressure of from 700 up to fina ly 15 mbar. The film is taken out of the drying oven an. cooled. The polymer film is peeled off the glass plate un-erwater and is hydrolyzed/after-treated at first in 10% hyd.ochloric acid and then in completely desalted Water a. temperatures of from 60 to 90 C for 24 h, respectively.
2. Embodiment Sulfochlorinated PSU Udell (IBC-1.2 meg S02C1/g) and PSUSO2Li (IBC.1.95 meg SO Li/g) and montmorillonite treated with a,0-aminoalkylsulfoc bride (with sulfochloride groups facing to the outside) are dissolved in N-methylpyrrolidinone (414P).
Then the cross-linking agent a,w-diiodobutane is added to the solution. Af er stirring for 15 minutes the solution is filtered and deg,ssed and processed to a membrane as described in exa pie 1.
This membrane h-s a higher IEC value after curing than a control without the functionalized phyllosilicate.
3. Embodiment Sulfochlorinate. PSU Udele (IBC.1.8 meg SO2C1/g) and PSUSO2Li (IBC-1.95 meg Se2Li/g) (for polymer structures see figure 2) and montmorillo ite treated with zirconyl chloride are dissolved in di ethylsulfoxide (DMSO).
The dissolution takes place in the following order: First montmorillonite K10 is suspended in DMSO and 10 weight t zirconyl chlori.e, based on the total membrane amount, is added. Then the other polymer components are added. Then the cross-linking a:ent m,o-diiodobutane is added to the solution. After stirring for 15 minutes the solution is filtered and de=assed. A thin film of the polymer solution is =
knife-coated onto a glass plate. The glass plate is placed into a vacuum drying oven and the solvent is removed at temperatures of from 80 to 130 C at a low pressure of from 700 up to finally 15 mbar. The film is taken out of the drying oven and cooled. The polymer film is peeled off the glass plate under phosphoric acid and stored in phosphoric acid at a temperature of between 30 and 90 C for about 10 hours and then optionally further hydrolyzed/after-treated in 10% hydrochloric adid and then in completely desalted water at temperatures of from 60 to 90 C for 24 h respectively.
and suifinated p-lymer, Figure 2 shows the formation of the covalent cross-1 nking bridges in a polymer containing both sulfinate groups and sulfochloride groups.
The composites a.cording to the invention consist of polymers having the folio ing functional groups:
After membrane p eparation, before hydrolysis:
-502M and/or -P0M2 and/or -COM (M = Hal (P, Cl, Br, I), OR, NR2; R I. alkyl, hydroxyalkyl, aryl) = cross-linkin bridges:
a) polymer-S62-Y-502-polymer optionally:
b) polymer-S*2-Y'-NR-S02-polymer c) polymer-S.2-NR-Y1 '-NR-502-polymer After hydrolysis:
= -503M-, -F0212-, -COOM-groupe = above-menti.ned cross-linking bridges The covalently .rose-linking of the aulfinate polymers in a mixture with pr-cursors of cation exchange polymers results in a better mix"ng of blend phases and thus a higher degree of cross-linkin-, so as to achieve a better mechanical stability of th, resultant polymer film compared to covalently cros:-linked polymer (blend) films made from cation exchange polymers and polymeric sulfinates. A further improvement of he mechanical characteristics is achieved by a controlled in orporation of a cross-linking component containing amin. groups, which reacts with the precursors of the cation exch.nge groups, into the polymer network.
A.-lication exa -lea = 4 =
= =
The invention will be illustrated in more detail by two examples as follcws. The weights/volumes of the components used are listed in table 1.
1. Instruction for membrane preparation sulfochlorin.ated PSU Udel (IEC=1.8 meg SO2C1/g) and PSUSO21ji (IEC:=1.95 meg so;Li/g) (for polymer structures see figure 2) are dissolved in N-methylpyrrolidinone (NMP) . Then ci.,o3-diiodobutane is added to the solution of the cross-linking agents. After stirring for 15 minutes the solution is filtered and degp.ssed. A thin film of the polymer solution is knife-coated ontb a glass plate. The glass plate is placed into a vacuum drying oven and the solvent is removed at temperatures of from 80 to 130 C at a low pressure of from 700 up to final y 15 mbar. The film is taken out of the drying oven and cooled: The polymer film is peeled off the glass plate underwater and is hydrolyzed/after-treated at first in 10% hyd.rochloric acid and then in completely desalted water at. temperatures of from 60 to 90 C for 24 h respectively.
2. Used amounts of reactants and characterisation results Table 1: Used amounts of reactants and characterisation results membrane Me PSU-S02C1 PSU-SO2Li cross-lin- TEC swelling Rsr king agent (g) [83 (nil] [me(1/8] [flam]
wz10 10 1 1 0.3 0.2 19.3 337.6 wz13 10 1 0.4 0.12 0.85 18.3 15.2 =
= 5 wz14 . -10 1 0.3 0.09 0.56 8.6 62.6 wz15 10 1 0.2 0.06 0.7 13 -36.14 wz16 10 1* 1* 0.3 0.75 11.7 31_6 * 2 SO2C1 groups per PSU repetitive unit Part 2 of the application Covalently cross-linked composite membranes Prior art The invention on which the present additional is based on relates to a continuation or alternative to the German parent patent application publication No. DE 100 24 575 Al (Kovalent vernetzte Polymere und Polymermembranen via Sulfinatalkylierung).
The products and processes, respectively of this above-mentioned parent application are subjected to the following disadvantages:
For membranes which are prepared by the described processes, moistened gases are still needed for operation in the hydrogen fuel cell. If the gases are not moistened, the membrane dries up and the proton conductivity is decreased to a large extent.
To solve this problem, the present application suggests incorporating tectosilicates and phyllosilicates which are optionally functionalized according to the parent application, particularly into a covalent network.
The parent application only describes the incorporation of polymers into the covalent network. When using functionalized phyllosilicates and/or tectosilicates it was surprisingly found, that the compounds which have low molecular functional groups and are bound to the phyllosilicates and/or tectosilicate are not discharged during employment of the membrane, especially in the case of employment in a hydrogen fuel cell. This allows an increase in the concentration of ion conductive groups within the covalent network without having the usual effect of extremely deteriorating the mechanical characteristics of the membrane (brittlement or strong swelling). In an extreme case it is therefore possible to completely eliminate the use of enclosed ion conductive polymers in the covalent network. Ion conduction then exclusively occurs via silicates having functional groups.
Thus, the present invention solves the problem of drying up the membrane and of a limitation in the number of ion conductive groups within the membranes to a not marginal extent.
Thus the object of the invention is to provide new covalently cross-linked polymers/membranes displaying proton conductivity even when used with gases which are not moistened or only slightly moistened. Moreover, a further object is to incorporate low molecular functionalized compounds which are coupled to a silicate into the covalent network such that they remain in the membrane for an industrially useful period time.
Further the process according to the invention helps to solve this object.
The present invention further provides a covalently cross-linked composite polymer or covalently cross-linked composite polymer membrane comprising one or more polymers and tectosilicates and/or phyllosilicates, wherein the tectosilicates and/or phyllosilicates present can be functionalized or not functionalised, wherein the polymers are characterized in that they may have the following functional groups:
a) precursors of cation exchange groups: SO2M and/or POM3 and/or COM, 7a b) sulfinate groups SO2Me, where M is independently Hal, OR, or NR2, Hal is F, Cl, Br or I, R
is independently alkyl, hydroxyalkyl or aryl, Me is independently H, Li, Na, K, Cs, another metal cation, or an ammonium ion, said polymers may be covalently cross-linked by the following organic compounds:
C) difunctionial, trifunctional or oligofunctional haloalkanes or haloaromatics which have been reacted with sulfinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-Y-S02-polymer where Y is the cross-linking bridge: -(CH2)õ-; -arylene-;
-(CH2)x-arylene-; or -CH2-arylene-CH2-, where x is 3-12 and/or d) compounds containing the following groups: Hal- (CHAx-NHR, which have been reacted on the Hal- side with sulfinate groups SO2Me and on the -NHR side with SO2M groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02- (CH2) x-NR-S02-polymer;
and/or e) compounds containing the following groups: NHR-(CH2)x-NHR, which have been reacted with SO2Me groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-S02-NR- (CH2) x-NR-S02-polymer .
Description of the invention:
The following text expressively refers to the parent patent application publication No. DE 100 24 575 Al:
=
A mixture in a s itable solvent, preferably an aprotic one, is prepared, whi.h contains polymers and functionalized tectosilicates ad/or phyllosilicates and optionally low molecular compouuds.
The mixture cont ins polymers and the following functional groups;
= sulfinate gr.ups SO2Me (Me is a monovalent or polyvalent metal cation = sulfochlorid- groups and/or other precursors of cation exchange gro ps.
Additionally, a -ifunctional or oligofunctional alkylation cross-linking ag nt (typically an a,m-dihaloalkane) and optionally a sec-ndary diamine cross-linking agent NUR-(Cliz)x-NTIR is ad.ed to the mixture, preferably a polymer solution. The f-rmation of the covalent cross-linking bridges takes place dur'ng the formation of the membrane when evaporating the solvent by alkylating the sulfinate groups and optionally formation of sulfonamide via reaction of the sulfohalide groups present in the polymer with the secondary amino groups of the diamine cross-linking agent.
During the acid'c and/or basic and/or neutral aqueous after-treatment of th. membranes following the formation of the membrane the pr cursors of the ion exchange groupings are hydrolyzed and oxidized to form ion exchange groups, respectively.
Figure 1 schema ically shows the formation of the covalent cross-linking b idges in blends of sulfochlorinated polymer and sulfinated -olymer, Figure 2 shows the formation of the covalent cross-linking bridges in a polymer containing both - sulfinate group= and sulfochloride groups.
The composites a.cording to the invention consist of polymers having the folio ing functional groups:
After membrane p eparation, before hydrolysis:
= S02101 and/or !0M2 and/or CoM (M m Hal (F, Cl, Br, I), OR, Nit, R=alkyl, hydroxyalkyl, aryl) = cross-linkin bridges;
a) polymer-S=2-Y-S02-polymer optionally:
b) polymer-S02-Y'-NR-S02-polymer c) polymer-S=2-NR-Y"-NR-S02-polymer After hydrolysi_:
= -S03M, -1,03M -COOM groups = above-menti.ned cross-linking bridges By covalently c oss-linking the sulfinate polymers mixed with precursors of i.n exchange polymers, especially cation exchange polyms.s, in the presence of functionalized phyllosilicates and/or tectosilicates a better mixing of the blend phases an. thus also a higher degree of cross-linking is achieved, gi,ing raise to a better mechanical stability of the resultant p-lymer film compared to covalently cross-linked polymer blend) films made of cation exchange polymers and polymeric s if mates. By a controlled inclusion of a cross-linking c.mponent having amino groups, which reacts , 25 with the precur.ors of the cation exchange groups, into the polymer network a further improvement of the mechanical characteristics is achieved.
By incorporati functionalized tectosilicates and/or phyllosilicate into the covalent network during the formation of t e membrane, the water retention capability of the membrane i. increased. The functional groups protruding from the surfa.e of the functionalized tectosilicates or =
phyllosilicate, additionally change the membrane characteristics in accordance with their functionality_ Description of the inorganic filler The inorganic active filler is a phyllosilicate based on montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, talc, fluorhectorite, saponite, beidelite, nontronite, stevensite, bentonite, mica, vermiculite, fluorvermiculite, halloysite, fluor containing synthetical talc types or blends of two or more of the above-mentioned phyllosilicates. The phyllosilicate can be delaminated or pillared. Particularly preferred is montmorillonite.
The weight ratio of the phyllosilicate is preferably from 1 to 80 %, more preferably from 2 to 30 % by weight, most preferably from 5 to 20 %-If the functionalized filler, especially zcolites and members of the beidelite series and bentonites, is the only ion-conducting component, its weight ratio is usually in a range of from 5 to 80 wtVs, preferably of from 20 to 70 wt% and especially in a range of from 30 to 60 wt%-.
Description of the functionalized phyllosilicate:
The term "a phyllosilicate" in general means a silicate, in which the SiO4 tetraeders are connected in two-dimensional infinite networks. (The empirical formula for the anion is . The single layers are linked to one another by the cations positioned between them, which are usually Na, K, Mg, Al or/and Ca in the naturally occurring phyllosilicates.
By the term "a delaminated functionalized phyllosilicate" we understand phyllosilicates in which the layer distances are at first increased by reaction with so-called functionalisation agents. The layer thickness of such silicates before delamination is preferably 5 to 100 angstrom, more preferably 5 to 50 and most preferably 8 to 20 angstrom. To increase the layer distances (hydrophobisation) . .
- . -11 =
=
the phyllosilica es are reacted (before production of the composites acco .ing to the invention) with so-called functionalizing Iydrophobisation agents which are often also called onium io s or onium salts.
The cations of -he phyllosilicates are replaced by organic functionalizing hydrophobisation agents whereby the desired layer distances which depend on the kind of the respective functionalizing molecule or polymer which is to be incorporated inio the phyllosilicate can be adjusted by the kind of the org:nic residue.
The exchange of the metal ions or protons can be complete or partial. Prefe red is the complete exchange of metal ions or protons. The = entity of exchangeable metal ions or protons is usually expr ssed as milli equivalent (meq) per 1 g of phyllosilicate tectosilicate and is referred to as ion exchange capaci y.
Preferred are p yllosilicates or tectosilicates having a cation exchange capacity of at least 0,5, preferably 0,8 to 1,3 meq/g.
Suitable organ'c functionalizing hydrophobisation agents are derived from o onium, ammonium, phosphonium and sulfonium ions, which ma carry one or more organic residues.
As suitable fu ctionalizing hydrophobisation agents those of general formul- I and/or II are mentioned:
=
ne Z naz n8 R3. MR2 I IX
-Where the subst'tuents have the following meaning:
'5 R1, R2, R3, R4 -re independently from each other hydrogen, a straight chain, branched, saturated or unsaturated hydrocarbon rad'cal with 1 to 40, preferably 1 to 20 C atoms, optionally carr ing at least one functional group or 2 of the radicals are ii ed with each other, preferably to a heterocyclic re idue having 5 to 10 C atoms, more preferably having one or -re N atoms.
X represents ph.sphorous, nitrogen or carbon, Y represents ox gen or sulfur, n is an integer from 1 to 5, preferably 1 to 3 and Z is an anion.
Suitable functi=nal groups are hydroxyl, nitro or sulfo groups, whereas carboxyl or sulfonic acid groups are especially pref-rred. In the same way sulfochloride and carboxylic aci, chloride groups are especially preferred.
Suitable anion- Z are derived from proton delivering acids, in particular ineral acids, wherein halogens such as chlorine, brom ne, fluorine, iodine, sulfate, sulfonate, phosphate, pho phonate, phosphite and carboxylate, especially acetate are pr ferred. The phyllosilicates used as starting materials are -enerally reacted as a suspension. The preferred susp-nding agent is water, optionally mixed with =
alcohols, especi-lly lower alcohols having 1 to 3 carbon atoms. If the f nctionalizing hydrophobisation agent is not water-soluble, len a solvent is preferred in which said agent is solubl.-,. In such cases, this is especially an aprotic solvent. Further examples for suspending agents are ketones and hyd.ocarbons. Usually a suspending agent miscible with w-ter is preferred. On addition of the hydrophobizing -gent to the phyllosilicate, ion exchange occurs whereby .he phyllosilicate usually precipitates from the solution. he metal salt resulting as a by-product of the ion exchang is preferably water-soluble, so that the hydrophobized poyllosilicate can be separated as a crystalline sol d, for example, by filtration.
The ion exchang- is mostly independent from the reaction temperature. T e temperature is preferably above the crystallization point of the medium and below the boiling point thereof. For aqueous systems the temperature is between 0 and 100 C, preferably between 40 and 80 C.
For a cation a - anion exchange polymer alkylammonium ions are preferred, in particular if as a functional group additionally a carboxylic acid chloride or sulfonic acid chloride is pr-sent in the same molecule. The alkylammonium ions can be ob.ained via usual methylation reagents such as methyl iodide. Suitable ammonium ions are omega-aminocarboxyli. acids, especially preferred are omega-aminoarylsulfo ic acids and omega-alkylaminosulfonic acids.
Omega-aminoary sulfonic acids and omega-alkylaminosulfonic acids can be o.tained with usual mineral acids, for example hydrochloric a.id, sulfuric acid or phosphoric acid or by methylation re.gents such as methyl iodide.
Additional prefe red ammonium ions are pyridine and laurylammonium i.ns. After hydrophobizing the layer distance of the phyllosil:cates is in general between 10 and 50 angstrom, prefer=bly 13 and 40 angstrom.
The hydrophobize. and functionalized phyllosilicate is freed of water by dryil g. In general a thus treated phyllosilicate still contains - residual water content of 0-5 weight % of water_ Subsequ=ntly the hydrophobized phyllosilicate can be mixed in form oi a suspension in a suspending agent which is free as much as possible from water with the mentioned polymers and be further processed to obtain a membrane.
An especially p,eferred functionalization of the tectosilicates -ndfor phyllosilicates is, in general, achieved with ma.dified dyes or their precursors, especially with triphenylm-thane dyes. They are represented by the general formula NN.10 -s%R4 .NS,%, 1110 R = alkyl (essecially CH3; CiRO
In the present invention dyes derived from the following basic skeleton are used:
=
=
*
R contains Ci-- C40, and 0-4 N-atoms, and 0-3 S-atoms, R can be charged positively.
S In order to functionalize the phyllosilicate the dye or its reduced precursor is sufficiently stirred in an aprotic solvent (e,g. tetrahydrofuran, DMAc. NM?) together with the silicate in a vessel. After 24 hours the dye and the precursor, respectively, is intercalated into the cavities of the phyllosilicate. The intercalation must be such that the ion conductive croup is located on the surface of the silicate particle.
The following figure schematically shows the process:
R¨..õ
cit;C.A.kt )401. dye 111.111 ptett...S.Seht The thus functionalized phyllosilicates is added as an additive to the polymer solution as described in application publication No. DE 100 24 575 Al. It was found to be especially preferable to use the precursor of the dyes.
Only in the acidic after-treatment the dyes themselves are formed by splitting off water.
=H J
RN
./R 1111 R
=
In the case of the triphenylmethane dyes it was hereby surprisingly found that these dyes support the proton conductivity in the membranes prepared thereby. Whether this is even a water-free proton conductivity cannot be stated with sufficient certainty. If the dyes are not bound to the silicate, thus if they are present in the membrane in a free form, they are discharged from the fuel cell with the reaction water already after a short period of time.
According to the invention the polymer blends containing sulfinate groups of the above-mentioned parent application, most preferably the thermoplatic functionalized polymers (ionomers) are added to the suspension of the hydrophobized phyllosilicates.
This can be done by using an already dissolved form or the polymers are solubilized in the suspension itself.
Preferably the amount of the 17 =
phyllosilicates s of from 1 to 70 weight %, more preferably of from 2 to 40 eight Ps and most preferably of from 5 to 15 weight %.
A further improv-ment with respect to the parent patent application can -e the additional blending of zirconyl chloride (ZrOC12 into the membrane polymer solution and into the cavities of he phyllosilicates and/or tectosilicates. If the after-treat -nt of the membrane is performed in phosphoric acid, hardly soluble zirconium phosphate precipitates in the direct proximity of the silicate grain in the membrane. Z'rconium phosphate shows self-proton conductivity wh.n operating the fuel cell. The proton conductivity aces through the formation of hydrogen phosphates as i termediate steps and is part of the state of the art. A cont,olled inclusion in the direct proximity of a water storing a.ent (silicates) is novel.
1. Etrbodiment for membrane preparation Su1foch1orinate4 PSU Udell (IECa1.8 meg sO2c1/g) and PSUSO2Li (IEC1.95 meg SPiLi/g) (for polymer structures see figure 2) and montmorillo ite functionalized with triphenylmethane dye are dissolved i N-methylpyrrolidinone (Nmp). Then a,ca-diiodobutane as a cross-linking agent is added to the solution. After stirring for 15 minutes the solution is filtered and desassed. A thin film of the polymer solution is knife-coated o o a glass plate. The glass plate is placed into a vacuum ing oven and the solvent is removed at temperatures o from 80 to 130 C at a low pressure of from 700 up to fina ly 15 mbar. The film is taken out of the drying oven an. cooled. The polymer film is peeled off the glass plate un-erwater and is hydrolyzed/after-treated at first in 10% hyd.ochloric acid and then in completely desalted Water a. temperatures of from 60 to 90 C for 24 h, respectively.
2. Embodiment Sulfochlorinated PSU Udell (IBC-1.2 meg S02C1/g) and PSUSO2Li (IBC.1.95 meg SO Li/g) and montmorillonite treated with a,0-aminoalkylsulfoc bride (with sulfochloride groups facing to the outside) are dissolved in N-methylpyrrolidinone (414P).
Then the cross-linking agent a,w-diiodobutane is added to the solution. Af er stirring for 15 minutes the solution is filtered and deg,ssed and processed to a membrane as described in exa pie 1.
This membrane h-s a higher IEC value after curing than a control without the functionalized phyllosilicate.
3. Embodiment Sulfochlorinate. PSU Udele (IBC.1.8 meg SO2C1/g) and PSUSO2Li (IBC-1.95 meg Se2Li/g) (for polymer structures see figure 2) and montmorillo ite treated with zirconyl chloride are dissolved in di ethylsulfoxide (DMSO).
The dissolution takes place in the following order: First montmorillonite K10 is suspended in DMSO and 10 weight t zirconyl chlori.e, based on the total membrane amount, is added. Then the other polymer components are added. Then the cross-linking a:ent m,o-diiodobutane is added to the solution. After stirring for 15 minutes the solution is filtered and de=assed. A thin film of the polymer solution is =
knife-coated onto a glass plate. The glass plate is placed into a vacuum drying oven and the solvent is removed at temperatures of from 80 to 130 C at a low pressure of from 700 up to finally 15 mbar. The film is taken out of the drying oven and cooled. The polymer film is peeled off the glass plate under phosphoric acid and stored in phosphoric acid at a temperature of between 30 and 90 C for about 10 hours and then optionally further hydrolyzed/after-treated in 10% hydrochloric adid and then in completely desalted water at temperatures of from 60 to 90 C for 24 h respectively.
Claims (32)
1. Covalently cross-linked polymer or covalently cross-linked polymer membrane comprising one or more polymers and tectosilicates and/or phyllosilicates, wherein the tectosilicates and/or phyllosilicates present can be functionalized or not functionalised, wherein the polymers are characterized in that they have the following functional groups:
a) precursors of cation exchange groups: SO2M and/or POM2 and/or COM, b) sulfinate groups SO2Me, where M is independently Hal, OR or NR2, Hal is F, Cl, Br or I, R
is independently alkyl, hydroxyalkyl, or aryl, and Me is independently H, Li, Na, K, Cs, another metal cation, or an ammonium ion, where said polymer is covalently cross-linked by the following organic compounds:
c) difunctional, trifunctional or oligofunctional haloalkanes or haloaromatics, which have been reacted with sulfinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-SO2-Y-SO2-polymer, where Y is -(CH2)x-; -arylene-; -(CH2)x-arylene-; or -CH2-arylene-CH2-, where x is 3-12;
and/or d) compounds containing the following groups: Hal-(CH2)x-NHR, which have been reacted on the Hal- side with sulfinate groups SO2Me and on the -NHR side with SO2M- groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-SO2-(CH2).-NR-SO2-polymer;
and/or e) compounds containing the following groups: NHR-(CH2)x-NHR, which have been reacted with SO2Me groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-SO2-NR- (CH2) x-NR-SO2-polymer .
a) precursors of cation exchange groups: SO2M and/or POM2 and/or COM, b) sulfinate groups SO2Me, where M is independently Hal, OR or NR2, Hal is F, Cl, Br or I, R
is independently alkyl, hydroxyalkyl, or aryl, and Me is independently H, Li, Na, K, Cs, another metal cation, or an ammonium ion, where said polymer is covalently cross-linked by the following organic compounds:
c) difunctional, trifunctional or oligofunctional haloalkanes or haloaromatics, which have been reacted with sulfinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-SO2-Y-SO2-polymer, where Y is -(CH2)x-; -arylene-; -(CH2)x-arylene-; or -CH2-arylene-CH2-, where x is 3-12;
and/or d) compounds containing the following groups: Hal-(CH2)x-NHR, which have been reacted on the Hal- side with sulfinate groups SO2Me and on the -NHR side with SO2M- groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-SO2-(CH2).-NR-SO2-polymer;
and/or e) compounds containing the following groups: NHR-(CH2)x-NHR, which have been reacted with SO2Me groups, whereby the following cross-linking bridges are present in the polymer/polymer blend/polymer membrane: polymer-SO2-NR- (CH2) x-NR-SO2-polymer .
2. Covalently cross-linked polymer blend or polymer blend membrane according to claim 1, characterized in that the tectosilicates and/or phyllosilicates are functionalized with a reagent of general formula I and/or II:
wherein:
R1, R2, R3, R4 are independently from each other hydrogen, a straight chain, branched, saturated or unsaturated hydrocarbon radical with 1 to 40 carbon atoms, optionally substituted with at least one functional group, or two of R1, R2, R3 and R4 are linked with each other forming a heterocyclic residue, X represents phosphorous, nitrogen or carbon, Y represents oxygen or sulfur, n is an integer from 1 to 5, and Z is an anion.
wherein:
R1, R2, R3, R4 are independently from each other hydrogen, a straight chain, branched, saturated or unsaturated hydrocarbon radical with 1 to 40 carbon atoms, optionally substituted with at least one functional group, or two of R1, R2, R3 and R4 are linked with each other forming a heterocyclic residue, X represents phosphorous, nitrogen or carbon, Y represents oxygen or sulfur, n is an integer from 1 to 5, and Z is an anion.
3. Covalently cross-linked polymer blend or polymer blend membrane according to claim 2, wherein the straight chain, branched, saturated or unsaturated hydrocarbon radical has 1 to 20 carbon atoms.
4. Covalently cross-linked polymer blend or polymer blend membrane according to claim 2 or 3, wherein the straight chain, branched, saturated or unsaturated hydrocarbon is substituted with at least one functional group.
5. Covalently cross-linked polymer blend or polymer blend membrane according to claim 2 or 3, wherein two of R1, R2, R3 and R4, are linked together to form a heterocyclic residue.
6. Covalently cross-linked polymer blend or polymer blend membrane according to claim 5, wherein the heterocyclic residue has 5 to 10 carbon atoms.
7.
Covalently cross-linked polymer blend or polymer blend membrane according to claim 5 or 6, wherein the heterocyclic residue has one or more nitrogen atoms.
Covalently cross-linked polymer blend or polymer blend membrane according to claim 5 or 6, wherein the heterocyclic residue has one or more nitrogen atoms.
8. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 2 to 7, wherein n is 1 to 3.
9. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 2 to 8, characterized in that the reagent with the general formula I and/or II comprises one or more functional groups selected from hydroxyl groups, nitro groups, sulfo groups, carboxylic acid groups or sulfonic acid groups, sulfochloride groups, carbonic acid chloride groups, or any combination thereof, and wherein the anion Z is derived from a proton delivering acid.
10. Covalently cross-linked polymer blend or polymer blend membrane according to claim 9, wherein the proton delivering acid is a mineral acid.
11. Covalently cross-linked polymer blend or polymer blend membrane according to claim 9, wherein the anion Z is chlorine, bromine, fluorine, iodine, sulfate, sulfonate, phosphate, phosphonate, phosphite or carboxylate.
12. Covalently cross-linked polymer blend or polymer blend membrane according to claim 1, characterized in that the tectosilicates and/or phyllosilicates are functionalized with triphenylmethane dyes.
13. Covalently cross-linked polymer blend or polymer blend membrane according to claim 1, characterized in that the membrane contains triphenylmethane dyes.
14. Covalently cross-linked polymer blend or polymer blend membrane according to claim 1 or 12 characterized in that the tectosilicates and/or phyllosilicates are functionalized with triphenylmethane dyes according to the following formula or their precursor wherein R contains C1-020 carbon atoms, 0-4 nitrogen atoms, and 0-3 sulfur atoms, and wherein R optionally has a positive charge.
15. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 1 to 14, characterized in that it is composed of the following polymers:
a) a polymer with at least SO2M groups b) a polymer with at least SO2Me groups.
a) a polymer with at least SO2M groups b) a polymer with at least SO2Me groups.
16. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 1 to 15, characterized in that it consists of a polymer comprising the following groups:
SO2M groups and SO2Me groups.
SO2M groups and SO2Me groups.
17. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 1 to 16, characterized in that the base polymer having the functional groups or the base polymers having the functional groups is selected from the group consisting of polyether sulfones, polysulfones, polyphenylsulfones, polyether ether sulfones, polyether ketones, polyether ether ketones, polyphenylene ether, polydiphenylphenylene ether, polyphenylene sulfide or copolymers containing at least one of these components.
18. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 1 to 17, characterized in that the following are used as base polymers: polysulfones, polyphenylene ether or other polymers which can be lithiated.
19. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 1 to 18, characterized in that the following are used as cross-linking agents: Hal-(CH2).-Hal or Hal-CH2-phenylene-CH2-Hal (x = 3-12, Hal = F, Cl, Br, I).
20. Covalently cross-linked polymer blend or polymer blend membrane according to any one of claims 1 to 19, characterized in that the SO2M groups and/or POM2 groups and/or COM groups of the polymer/polymer (blend) membrane are hydrolyzed to cation exchange groups SO2Me and/or PO3Me2 and/or COOMe (Me = H, Li, Na, K, Cs or other metal cations or ammonium ions) by one or more of the following curing steps:
a) in 1-50 weight % aqueous alkali at T = RT - 95 °C, b) in completely desalted water at T = RT - 95 °C, c) in 1-50 weight % aqueous mineral acid at T = RT - 95 °C, and d) in completely desalted water at T = RT - 95 °C.
a) in 1-50 weight % aqueous alkali at T = RT - 95 °C, b) in completely desalted water at T = RT - 95 °C, c) in 1-50 weight % aqueous mineral acid at T = RT - 95 °C, and d) in completely desalted water at T = RT - 95 °C.
21. Process for preparing covalently cross-linked polymers, polymer blends or polymer blend membranes according to any one of claims 1 to 20, characterized in that the polymers are dissolved simultaneously or successively in a dipolar aprotic solvent that is N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, dimethylsulfoxide or sulfolane, thereafter the cross-linking agent is added, then the cross-linking agent is homogeneously dispersed in the polymer solution by stirring, thereafter the polymer solution is filtered and then degassed, thereafter the polymer solution is then spread as a thin film on a base, the solvent is then removed by heating to 80 - 130 °C and/or by applying low pressure or in a circulating air dryer, wherein the tectosilicates and/or phyllosilicates are added to the polymer solution prior to the addition of the cross-linking agent.
22. The process of claim 21, wherein the polymer film is peeled off the base after solvent removal.
23. The process of claim 21 or 22, further comprising curing the polymer film by one or more of the following curing steps:
a) in 1-50 weight % aqueous alkali at T = RT - 95 °C, b) in completely desalted water at T = RT - 95 °C, c) in 1-50 weight % aqueous mineral acid at T = RT - 95 °C, and d) in completely desalted water at T = RT - 95 °C.
a) in 1-50 weight % aqueous alkali at T = RT - 95 °C, b) in completely desalted water at T = RT - 95 °C, c) in 1-50 weight % aqueous mineral acid at T = RT - 95 °C, and d) in completely desalted water at T = RT - 95 °C.
24. The process of any one of claims 21 to 23, wherein said base is a glass plate, metal plate, woven fabric, non-woven fabric or other.
25. Use of the membrane defined in any one of claims 1 to 20 for producing energy on an electrochemical route.
26. Use of the membrane defined in any one of claims 1 to 20 as a component of membrane fuel cells at temperatures of from 0 to 180 °C.
27. The use according to claim 26, wherein said fuel cells are H2 or direct methanol fuel cells.
28. Use of the membrane defined in any one of claims 1 to 20 in electrochemical cells.
29. Use of the membrane defined in any one of claims 1 to 20 in secondary batteries.
30. Use of the membrane defined in any one of claims 1 to 20 in electrolytic cells.
31. Use of the membrane defined in any one of claims 1 to 20 in a membrane separation process.
32. The use according to claim 31, wherein said separation process is gas separation, pervaporation, perstraction, reverse osmosis, electrodialysis or diffusion dialysis.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10024575.7 | 2000-05-19 | ||
| DE10024575A DE10024575A1 (en) | 2000-11-02 | 2000-05-19 | Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane |
| DE10054233A DE10054233A1 (en) | 2000-05-19 | 2000-11-02 | Covalently cross-linked composite membranes |
| DE10054233.6 | 2000-11-02 | ||
| PCT/EP2001/005826 WO2002000773A2 (en) | 2000-05-19 | 2001-05-21 | Polymers and polymer membranes covalently cross-linked by sulphinate alkylation |
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| Publication Number | Publication Date |
|---|---|
| CA2379962A1 CA2379962A1 (en) | 2002-01-03 |
| CA2379962C true CA2379962C (en) | 2016-10-18 |
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| CA2379962A Expired - Lifetime CA2379962C (en) | 2000-05-19 | 2001-05-21 | Covalently cross-linked polymers and polymer membranes via sulfinate alkylation |
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| Country | Link |
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| EP (1) | EP1290069A2 (en) |
| JP (1) | JP2004502008A (en) |
| CN (1) | CN100354344C (en) |
| AU (2) | AU784360B2 (en) |
| BR (1) | BR0106652A (en) |
| CA (1) | CA2379962C (en) |
| DE (1) | DE10054233A1 (en) |
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| WO (1) | WO2002000773A2 (en) |
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| DE10024575A1 (en) * | 2000-11-02 | 2001-11-22 | Univ Stuttgart | Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane |
| WO2003050169A2 (en) * | 2001-05-21 | 2003-06-19 | Haering Thomas | Covalently cross-linked composite membranes |
| KR100403754B1 (en) * | 2001-06-19 | 2003-10-30 | 송민규 | Composite Polymeric Electrolyte Membrane, Preparation Method Thereof and Fuel Cell Containing the Same |
| DE10209784A1 (en) * | 2001-09-01 | 2003-12-04 | Univ Stuttgart Inst Fuer Chemi | Oligomers and polymers containing sulfinate groups and process for their preparation |
| AU2003229264A1 (en) | 2002-02-28 | 2003-09-09 | Universitat Stuttgart | Oligomers and polymers containing sulfinate groups, and methods for producing the same |
| DE10391005D2 (en) * | 2002-02-28 | 2005-04-14 | Thomas Haering | Layer structures and methods for their production |
| JP4827044B2 (en) * | 2002-02-28 | 2011-11-30 | ウニヴェルズィテート シュトゥットガルト | Oligomer and polymer containing sulfinate group, and method for producing the same |
| KR100486728B1 (en) | 2002-12-12 | 2005-05-03 | 삼성에스디아이 주식회사 | Nanocomposite electrolyte membrane and fuel cell employing the same |
| WO2005090480A1 (en) * | 2004-03-23 | 2005-09-29 | Mitsubishi Gas Chemical Co., Inc. | Solid polyelectrolyte, solid-polymer gel film, solid polyelectrolyte film, and fuel cell |
| JP6016019B2 (en) * | 2012-10-30 | 2016-10-26 | 独立行政法人国立高等専門学校機構 | ELECTROLYTE MEMBRANE FOR FUEL CELL, METHOD FOR PRODUCING ELECTROLYTE MEMBRANE FOR FUEL CELL, AND FUEL CELL |
| CN108258170B (en) * | 2017-12-05 | 2021-07-16 | 宜宾天原集团股份有限公司 | Preparation method of polyether-ether-ketone-based lithium battery diaphragm |
| CN109659601B (en) * | 2018-12-12 | 2021-09-28 | 南京师范大学 | Application of polyacid/high-molecular polymer hybrid nanowire material as solid electrolyte |
| HUE055324T2 (en) | 2019-07-31 | 2021-11-29 | Innolith Tech Ag | So2-based electrolyte for rechargeable battery cell and rechargeable battery cell comprising the same |
| CN115646223B (en) * | 2022-10-19 | 2023-06-27 | 安徽省海徽化工有限公司 | Pollution-resistant polyethersulfone ultrafiltration membrane |
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| EP0574791B1 (en) * | 1992-06-13 | 1999-12-22 | Aventis Research & Technologies GmbH & Co. KG | Polymer electrolyte membrane and process for its manufacture |
| FR2695131B1 (en) * | 1992-09-01 | 1994-09-30 | Alsthom Cge Alcatel | Solid proton conducting polymer electrolyte. |
| DE19622337C1 (en) * | 1996-06-04 | 1998-03-12 | Dlr Deutsche Forschungsanstalt | Networking of modified engineering thermoplastics |
| JP4859264B2 (en) * | 1997-12-01 | 2012-01-25 | アセップ・インク | Perfluorinated sulfone salts and their use as ionic conducting materials |
| WO1999040025A1 (en) * | 1998-02-03 | 1999-08-12 | Acep Inc. | Novel materials useful as electrolytic solutes |
| DE19836514A1 (en) * | 1998-08-12 | 2000-02-17 | Univ Stuttgart | Modification of engineering polymers with N-basic groups and ion exchange groups in the side chain gives membranes of good thermal and mechanical stability useful for fuel cells, diffusion dialysis, electrodialysis, and reverse osmosis |
| AU764333B2 (en) * | 1998-09-11 | 2003-08-14 | Victrex Manufacturing Limited | Ion-exchange polymers |
| DE19919708A1 (en) * | 1999-04-30 | 2001-03-01 | Univ Stuttgart | Gradual alkylation of polymeric amines |
| DE10024576A1 (en) * | 2000-05-19 | 2001-11-22 | Univ Stuttgart | Covalently and ionically crosslinked polymer preparation, for use as electrochemical and separating membranes, comprises crosslinking acid-, sulfinate- and amine-functional polymers |
-
2000
- 2000-11-02 DE DE10054233A patent/DE10054233A1/en not_active Withdrawn
-
2001
- 2001-05-21 BR BR0106652-8A patent/BR0106652A/en not_active IP Right Cessation
- 2001-05-21 IL IL14772601A patent/IL147726A0/en unknown
- 2001-05-21 AU AU93695/01A patent/AU784360B2/en not_active Ceased
- 2001-05-21 WO PCT/EP2001/005826 patent/WO2002000773A2/en active Application Filing
- 2001-05-21 CN CNB018018637A patent/CN100354344C/en not_active Expired - Fee Related
- 2001-05-21 JP JP2002505894A patent/JP2004502008A/en active Pending
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| Publication number | Publication date |
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| DE10054233A1 (en) | 2002-05-08 |
| AU2006202592A1 (en) | 2006-07-13 |
| CA2379962A1 (en) | 2002-01-03 |
| WO2002000773A9 (en) | 2003-02-13 |
| WO2002000773A3 (en) | 2002-07-18 |
| CN100354344C (en) | 2007-12-12 |
| BR0106652A (en) | 2002-04-09 |
| AU9369501A (en) | 2002-01-08 |
| WO2002000773A2 (en) | 2002-01-03 |
| AU784360B2 (en) | 2006-03-16 |
| EP1290069A2 (en) | 2003-03-12 |
| CN1440438A (en) | 2003-09-03 |
| JP2004502008A (en) | 2004-01-22 |
| IL147726A0 (en) | 2002-08-14 |
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