JP5099969B2 - スルホン化ポリホスファゼン、その使用法、及びその調製法 - Google Patents
スルホン化ポリホスファゼン、その使用法、及びその調製法 Download PDFInfo
- Publication number
- JP5099969B2 JP5099969B2 JP2004509736A JP2004509736A JP5099969B2 JP 5099969 B2 JP5099969 B2 JP 5099969B2 JP 2004509736 A JP2004509736 A JP 2004509736A JP 2004509736 A JP2004509736 A JP 2004509736A JP 5099969 B2 JP5099969 B2 JP 5099969B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfonated
- polyphosphazene
- polymer
- group
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920002627 poly(phosphazenes) Polymers 0.000 title claims description 60
- 238000002360 preparation method Methods 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims description 62
- 239000003153 chemical reaction reagent Substances 0.000 claims description 27
- 239000012528 membrane Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- 239000002019 doping agent Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 230000001012 protector Effects 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000005518 polymer electrolyte Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 8
- -1 hydroxyalkyl sulfonic acid Chemical compound 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- JKMFEOPHQBMBSE-UHFFFAOYSA-L disodium;4-hydroxybenzenesulfonate Chemical compound [Na+].[Na+].OC1=CC=C(S([O-])(=O)=O)C=C1.OC1=CC=C(S([O-])(=O)=O)C=C1 JKMFEOPHQBMBSE-UHFFFAOYSA-L 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- VIXPKJNAOIWFMW-UHFFFAOYSA-M dihexadecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC VIXPKJNAOIWFMW-UHFFFAOYSA-M 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000004627 regenerated cellulose Substances 0.000 description 3
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000001769 aryl amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 2
- KQJVAWJYANRCPG-UHFFFAOYSA-M dihexadecyl(dimethyl)azanium 4-hydroxybenzenesulfonate Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC.C1=CC(=CC=C1O)S(=O)(=O)[O-] KQJVAWJYANRCPG-UHFFFAOYSA-M 0.000 description 2
- IRMGVPILCPGYNQ-UHFFFAOYSA-M dimethyl-di(tetradecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCC IRMGVPILCPGYNQ-UHFFFAOYSA-M 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NWYYWIJOWOLJNR-UHFFFAOYSA-N 2-Amino-3-methyl-1-butanol Chemical compound CC(C)C(N)CO NWYYWIJOWOLJNR-UHFFFAOYSA-N 0.000 description 1
- XBTPDFKIHJXUFI-UHFFFAOYSA-N 2-benzyl-N,N-diethyl-3-phenylpropan-1-amine Chemical compound C(C1=CC=CC=C1)C(CN(CC)CC)CC1=CC=CC=C1 XBTPDFKIHJXUFI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-M 4-hydroxybenzenesulfonate Chemical compound OC1=CC=C(S([O-])(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-M 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004947 alkyl aryl amino group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000004475 heteroaralkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- BLXAGSNYHSQSRC-UHFFFAOYSA-M sodium;2-hydroxybenzenesulfonate Chemical compound [Na+].OC1=CC=CC=C1S([O-])(=O)=O BLXAGSNYHSQSRC-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 125000005000 thioaryl group Chemical group 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
Description
酸感受性側基を含む広範囲のポリホスファゼンホモポリマー及びコポリマーの合成を可能にする。
本発明のひとつの見地に従って、スルホン化ポリホスファゼンは、下記の一般式、
に基づき生産され、ここでnは正の整数であり、又ポリマー鎖に沿うRxは同一又は異なる基であり、このような同一又は異なる基はポリマー鎖に沿って反復し、又ここでポリマー鎖に沿って反復する懸垂基の少なくとも1個は下記の構造式M
で表示される。このような懸垂基内で、Xは窒素を欠く有機基として定義され、少なくとも3個の炭素原子を含み、又少なくとも1個のSO3 −基で置換される。YおよびZ成分は、窒素を含む又は含まない側基である。ポリマー鎖に沿って反復する1個又はそれ以上の懸垂基は、ここで記載された懸垂基Mである。
本発明の一見地に従って、スルホン化ポリホスファゼンを調製する一つの方法が提供され、ここで一部にスルホン化された修飾試薬がポリホスファゼン基質と反応される。本方法に従って使用される修飾試薬は、ポリホスファゼンバックボーンが置換される懸垂基に望ましい関係する位置で少なくとも1個のSO3 −基を含んでいる。更に将来の懸垂基は、少なくとも3個の炭素原子を含む無窒素結合を経て、SO3 −基をポリマーバックボーンに結合するものでなければならない。
ヒドロキシベンゼンスルホン酸ナトリウム塩脱水物(4.57g,19.7mmol)が水(100mL)に溶解され、苛性ソーダ液(18.6ml、1N)で滴定される。この混合物に水性メタノール内の臭化ジメチルジパルミチルアンモニウム(25.16g,4.4mmole)溶液が加えられる。生成4−ヒドリキシベンゼンスルホン酸ジメチルジパルミチルアンモニウム塩は溶液から沈殿し、真空下で乾燥される。
4−ヒドロキシベンゼンスルホン酸ナトリウム塩脱水物(4.57g,19.7mmole)が水(100mL)に溶解され、NaOH液(19.7mL 1N)で滴定される。生成4−ヒドロキシベンゼンスルホン酸ジナトリウム塩は減圧凍結乾燥される。
4−ヒドロキシベンゼンスルホン酸ナトリウム塩脱水物(4.57g,19.7mmole)が水(100mL)で溶解され、NaOH液(〜19.7mL,1N)で滴定される。生成4−ヒドロキシベンゼンスルホン酸ジナトリウム塩は減圧凍結乾燥された。
4−ヒドロキシベンゼンスルホン酸ナトリウム塩脱水物(4.57g,19.7mmole)が水(100mL)で溶解され、NaOH液(〜19.7mL,1N)で滴定される。臭化ベンジルトリエチルアンモニウム(5.36g,19.7mmole)がこの混合物に加えられた。生成物は減圧凍結乾燥され、白いパウダー状の4−ヒドロキシベンゼンスルホン酸ジベンジルスルホン酸ジベンジルトリエチルアンモニウムを産出する。
本発明の一実施例において、各種の材料科学技術に使用されるものの望ましい性質を有するスルホン化ポリホスファゼンが生産されている。これらの用途のいくつかの限定されない例は、電池用固体高分子電解質、導電ポリマー用多機能ドーパント、界面活性剤、繊維・織物プロテクター、および膜の開発でのこれらの用途を含む。
Claims (12)
- 前記ポリホスファゼンポリマーが約20,000乃至1,000,000の分子量を持つことを特徴とする請求項1記載の膜。
- 燃料電池への使用のための膜であって、前記膜が、
少なくとも1個のスルホン化懸垂基及び5個以下の異なるスルホン化懸垂基を含むポリホスファゼンポリマーを調製する方法であって、前記方法が第四アンモニウム塩の形態で少なくとも1個のスルホン化修飾試薬をポリホスファゼン基質と反応させることを含む方法で調製されるポリホスファゼンポリマーを含むことを特徴とする膜。 - 前記ポリホスファゼンポリマーが約20,000乃至1,000,000の分子量を持つことを特徴とする請求項3記載の膜。
- 少なくとも1個のスルホン化懸垂基及び5個以下の異なるスルホン化懸垂基を含むポリホスファゼンポリマーを調製する方法であって、前記方法が第四アンモニウム塩の形態で少なくとも1個のスルホン化修飾試薬をポリホスファゼン基質と反応させることを含む方法により調製されるポリホスファゼンポリマーを含む電池用固体高分子電解質、導電ポリマー用多機能ドーパント、界面活性剤、繊維・織物プロテクター、及び膜を含むグループから選択されることを特徴とする製品。
- 前記ポリホスファゼンコポリマーが約20,000乃至1,000,000の分子量を持つことを特徴とする請求項7記載の膜。
- 燃料電池への使用のための膜であって、前記膜が、
単一スルホン化懸垂基を含むポリホスファゼンコポリマーを調製する方法であって、前記方法が第四アンモニウム塩の形態で単一スルホン化修飾試薬をポリホスファゼン基質と反応させる方法により調製されるポリホスファゼンコポリマーを含むことを特徴とする膜。 - 前記ポリホスファゼンコポリマーが20,000乃至1,000,000の分子量を持つことを特徴とする請求項9に記載の膜。
- 単一スルホン化懸垂基を含むポリホスファゼンコポリマーを調製する方法であって、前記方法が第四アンモニウム塩の形態で単一スルホン化修飾試薬をポリホスファゼン基質と反応させる方法により調製されるポリホスファゼンコポリマーを含む電池用固体高分子電解質、導電ポリマー用多機能ドーパント、界面活性剤、繊維・織物用プロテクター、及び膜を含むグループから選択されることを特徴とする製品。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US38498102P | 2002-06-03 | 2002-06-03 | |
US60/384,981 | 2002-06-03 | ||
PCT/US2003/017616 WO2003102050A1 (en) | 2002-06-03 | 2003-05-30 | Sulfonated polyphosphazenes, uses thereof, and methods for preparing same |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2005528488A JP2005528488A (ja) | 2005-09-22 |
JP2005528488A5 JP2005528488A5 (ja) | 2006-07-13 |
JP5099969B2 true JP5099969B2 (ja) | 2012-12-19 |
Family
ID=29712118
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004509736A Expired - Fee Related JP5099969B2 (ja) | 2002-06-03 | 2003-05-30 | スルホン化ポリホスファゼン、その使用法、及びその調製法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US7169499B2 (ja) |
EP (1) | EP1551904A4 (ja) |
JP (1) | JP5099969B2 (ja) |
AU (1) | AU2003240532A1 (ja) |
WO (1) | WO2003102050A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7074256B2 (en) * | 2004-05-13 | 2006-07-11 | Battelle Energy Alliance, Llc | Phosphazene membranes for gas separations |
US20060193820A1 (en) * | 2005-02-18 | 2006-08-31 | Andrianov Alexander K | Immunostimulating polyphosphazene compounds |
US8741454B2 (en) * | 2005-03-29 | 2014-06-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | Proton exchange membrane for fuel cell |
US7943675B2 (en) * | 2005-03-29 | 2011-05-17 | Toyota Motor Engineering & Manufacturing North America, Inc. | Electrolytes for fuel cell electrodes |
JP2007042600A (ja) * | 2005-06-30 | 2007-02-15 | Sanyo Electric Co Ltd | 燃料電池 |
US7723463B2 (en) * | 2006-04-12 | 2010-05-25 | Battelle Energy Alliance, Llc | Polyphosphazine-based polymer materials |
US8163439B2 (en) | 2008-06-03 | 2012-04-24 | The University Of Akron | Electrolyte membranes and methods of use |
US8124414B2 (en) * | 2009-11-05 | 2012-02-28 | Battelle Energy Alliance, Llc | Taggants, method for forming a taggant, and a method for detecting an object |
JP5582573B2 (ja) * | 2010-11-09 | 2014-09-03 | 日本電気株式会社 | 二次電池およびそれに用いる二次電池用電解液 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6015670B2 (ja) * | 1982-11-15 | 1985-04-20 | 森六商事株式会社 | 植物培地調整方法 |
GB2185035B (en) * | 1986-01-07 | 1989-11-08 | Sumitomo Chemical Co | Process for preparing 1,4-diaminoanthraquinone-2,3-disubstituted compound |
JPH0816159B2 (ja) * | 1986-12-26 | 1996-02-21 | 大塚化学株式会社 | スルホン基を有するオリゴエチレンオキシポリホスフアゼン及びその製法 |
JPS63186737A (ja) * | 1987-01-29 | 1988-08-02 | Teijin Ltd | 陰イオン固定型の高分子固体電解質 |
JP3181902B2 (ja) * | 1989-01-20 | 2001-07-03 | 大塚化学株式会社 | ポリホスフアゼン系電解質及びその用途 |
JPH02223158A (ja) * | 1989-02-22 | 1990-09-05 | Otsuka Chem Co Ltd | 全固体型電池 |
US5548060A (en) * | 1994-08-08 | 1996-08-20 | Penn State Research Foundation, Inc. | Sulfonation of polyphosphazenes |
JPH10510090A (ja) * | 1994-12-01 | 1998-09-29 | ダナセル エイピィーエス | イオン伝導性ポリマー |
US6365294B1 (en) * | 1999-04-30 | 2002-04-02 | The Administrators Of The Tulane Educational Fund | Sulfonated polyphosphazenes for proton-exchange membrane fuel cells |
US6759157B1 (en) * | 1999-06-11 | 2004-07-06 | The Penn State Research Foundation | Proton conducting polymer membranes |
US6602630B1 (en) * | 2000-03-14 | 2003-08-05 | The Electrosynthesis Company, Inc. | Membrane electrode assemblies for electrochemical cells |
JP3389553B2 (ja) * | 2000-05-01 | 2003-03-24 | 大塚化学株式会社 | フェノキシホスファゼン系化合物の改質方法、難燃性樹脂組成物及び難燃性樹脂成形体 |
WO2001094450A2 (en) * | 2000-06-02 | 2001-12-13 | Sri International | Polymer membrane composition |
-
2003
- 2003-05-30 AU AU2003240532A patent/AU2003240532A1/en not_active Abandoned
- 2003-05-30 US US10/449,230 patent/US7169499B2/en not_active Expired - Fee Related
- 2003-05-30 EP EP03731544A patent/EP1551904A4/en not_active Withdrawn
- 2003-05-30 JP JP2004509736A patent/JP5099969B2/ja not_active Expired - Fee Related
- 2003-05-30 WO PCT/US2003/017616 patent/WO2003102050A1/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
US20040033406A1 (en) | 2004-02-19 |
JP2005528488A (ja) | 2005-09-22 |
EP1551904A1 (en) | 2005-07-13 |
WO2003102050A1 (en) | 2003-12-11 |
EP1551904A4 (en) | 2006-04-05 |
AU2003240532A1 (en) | 2003-12-19 |
US7169499B2 (en) | 2007-01-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102492841B1 (ko) | 신규 중합체 및 이의 제조 방법 | |
KR102048070B1 (ko) | 화학적으로 개질된 음이온 교환막 및 그 제조 방법 | |
ES2237145T3 (es) | Modificacion de polimeros ingenieriles con grupos basicos n y con grupos de intercambio ionico en la cadena lateral. | |
US7132496B2 (en) | Step-by-step alkylation of polymeric amines | |
JP5099969B2 (ja) | スルホン化ポリホスファゼン、その使用法、及びその調製法 | |
Rusanov et al. | Proton-conducting polymers and membranes carrying phosphonic acid groups | |
US20040225153A1 (en) | Synthesis of polyphosphazenes with sulfonimide side groups | |
Hacıvelioğlu et al. | Azole substituted polyphosphazenes as nonhumidified proton conducting membranes | |
US7763702B2 (en) | Synthesis of polyphosphazenes with sulfonimide side groups | |
RU2276160C1 (ru) | Бензимидазолзамещенные полибензимидазолы - исходный материал для изготовления протонпроводящих мембран | |
WO2022186261A1 (ja) | ポリマー及びその製造方法、分離膜、電解質膜、燃料電池、水電解、並びに電解技術 | |
CN116615488A (zh) | 新型基于聚芴的交联共聚物及制备其的方法和使用其的碱性燃料电池用阴离子交换膜 | |
JP2015212386A (ja) | スルフィナートアルキル化を介した共有結合架橋ポリマーおよびポリマー膜 | |
KR102490321B1 (ko) | 화학적 개질을 통해 얻어진 음이온 전도성 이오노머를 이용한 이온교환막의 제조 방법 및 이에 의해 제조된 이온교환막 | |
KR20190026133A (ko) | 아민화된 폴리스티렌에틸렌부틸렌스틸렌 공중합체를 포함하는 연료전지용 음이온교환막 및 이의 제조방법 | |
KR20190024311A (ko) | 폴리에테르에테르케톤 기반의 복합막, 이의 제조방법 및 이를 포함하는 연료전지용 음이온 교환막 | |
JP2012229423A (ja) | 燃料電池用のプロトン交換膜 | |
KR101546370B1 (ko) | 높은 이온전도성을 보이는 술폰산화 멀티블록형 고분자 및 이를 포함하는 전기화학 시스템 | |
KR102702634B1 (ko) | 신규 폴리플루오렌계 가교 공중합체 및 그 제조방법, 이를 이용한 알칼리 연료전지용 음이온교환막 | |
US20240262961A1 (en) | New phosphonated non-fluorinated and partially fluorinated aryl polymers from sulfonated aryl polymers and new polymeric perfluorophosphonic acids from perfluorosulfonic acids, their process of preparation and use in electromembrane applications | |
KR20220088308A (ko) | 신규 폴리플루오렌계 가교 공중합체 및 그 제조방법, 이를 이용한 알칼리 연료전지용 음이온교환막 | |
US20240317951A1 (en) | Novel polyfluorene-based cross-linked copolymer, method for producing same, and anion exchange membrane for alkaline fuel cell using same | |
KR101812274B1 (ko) | 과불소화 연결제를 사용하지 않는 고이온성 술폰산화 멀티블록형 고분자의 제조방법, 이를 포함하는 전기화학 시스템 | |
CN117321094A (zh) | 新型膦酰化氟代弹性体(pfkm)、膦酰化全氟弹性体(pffkm)、其制备方法及其在电学膜应用中的用途 | |
EP4416201A1 (en) | Aryl-ether-free polyaromatic polymers with branched structures for anion exchange membranes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060529 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060529 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090217 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090303 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20090602 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20090609 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20090703 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20090710 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20090731 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20090807 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090902 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100914 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20101213 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20101220 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20110113 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20110120 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20110214 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20110221 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120110 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20120409 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20120416 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20120508 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20120515 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20120608 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20120615 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120706 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120828 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120925 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151005 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |