JPH0468025A - Aniline polymer, membrane for resolving optical isomer, and its production - Google Patents
Aniline polymer, membrane for resolving optical isomer, and its productionInfo
- Publication number
- JPH0468025A JPH0468025A JP2180641A JP18064190A JPH0468025A JP H0468025 A JPH0468025 A JP H0468025A JP 2180641 A JP2180641 A JP 2180641A JP 18064190 A JP18064190 A JP 18064190A JP H0468025 A JPH0468025 A JP H0468025A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- aniline
- group
- polymer
- 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.)
- Granted
Links
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000003287 optical effect Effects 0.000 title claims abstract description 42
- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 239000012528 membrane Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001448 anilines Chemical class 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 35
- 229910052697 platinum Inorganic materials 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000010408 film Substances 0.000 description 16
- -1 1so-propyl Chemical group 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003115 supporting electrolyte Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 150000003057 platinum Chemical class 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YPGCWEMNNLXISK-UHFFFAOYSA-N alpha-phenylpropionic acid Natural products OC(=O)C(C)C1=CC=CC=C1 YPGCWEMNNLXISK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- YPGCWEMNNLXISK-SSDOTTSWSA-N (R)-hydratropic acid Chemical compound OC(=O)[C@H](C)C1=CC=CC=C1 YPGCWEMNNLXISK-SSDOTTSWSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- IWYDHOAUDWTVEP-ZETCQYMHSA-N (S)-mandelic acid Chemical compound OC(=O)[C@@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-ZETCQYMHSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- GAWAYYRQGQZKCR-UWTATZPHSA-N (2r)-2-chloropropanoic acid Chemical compound C[C@@H](Cl)C(O)=O GAWAYYRQGQZKCR-UWTATZPHSA-N 0.000 description 1
- DIWVBIXQCNRCFE-MRVPVSSYSA-N (2r)-2-methoxy-2-phenylacetic acid Chemical compound CO[C@@H](C(O)=O)C1=CC=CC=C1 DIWVBIXQCNRCFE-MRVPVSSYSA-N 0.000 description 1
- DIWVBIXQCNRCFE-QMMMGPOBSA-N (2s)-2-methoxy-2-phenylacetic acid Chemical compound CO[C@H](C(O)=O)C1=CC=CC=C1 DIWVBIXQCNRCFE-QMMMGPOBSA-N 0.000 description 1
- WHBMMWSBFZVSSR-GSVOUGTGSA-N (R)-3-hydroxybutyric acid Chemical compound C[C@@H](O)CC(O)=O WHBMMWSBFZVSSR-GSVOUGTGSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UWTATZPHSA-N (R)-malic acid Chemical compound OC(=O)[C@H](O)CC(O)=O BJEPYKJPYRNKOW-UWTATZPHSA-N 0.000 description 1
- YPGCWEMNNLXISK-ZETCQYMHSA-N (S)-hydratropic acid Chemical compound OC(=O)[C@@H](C)C1=CC=CC=C1 YPGCWEMNNLXISK-ZETCQYMHSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- DBTWOTKWIVISQR-UHFFFAOYSA-N 2-bromopropan-1-ol Chemical compound CC(Br)CO DBTWOTKWIVISQR-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 1
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 1
- HFUFDXLQDZVBEC-UHFFFAOYSA-N 30-bromotriacontan-1-ol Chemical compound OCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCBr HFUFDXLQDZVBEC-UHFFFAOYSA-N 0.000 description 1
- BXFRPMWPDOIMQR-UHFFFAOYSA-N 30-chlorotriacontan-1-ol Chemical compound OCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCl BXFRPMWPDOIMQR-UHFFFAOYSA-N 0.000 description 1
- SIJLYRDVTMMSIP-UHFFFAOYSA-N 4-Bromo-1-butanol Chemical compound OCCCCBr SIJLYRDVTMMSIP-UHFFFAOYSA-N 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000276426 Poecilia Species 0.000 description 1
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BCUPGIHTCQJCSI-UHFFFAOYSA-N chloromethanol Chemical compound OCCl BCUPGIHTCQJCSI-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940116298 l- malic acid Drugs 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-M mandelate Chemical compound [O-]C(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規なアニリン系重合体、および該重合体を
使用した分割膜、すなわち光学異性体を電気化学的に分
割することが可能な分割膜、更に詳しくいえば、６体と
１体の、或いは３体とＲ体の混合溶液中で膜に電位をか
けることで、どちらか一方の光学異性体のみを選択的に
取り込むことが可能な高分子膜およびその製造方法に関
する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel aniline polymer and a separation membrane using the polymer, that is, a separation membrane capable of electrochemically resolving optical isomers. A split membrane, more specifically, by applying a potential to the membrane in a mixed solution of 6-isomers and 1-isomer, or 3-isomers and R-isomer, it is possible to selectively incorporate only one optical isomer. The present invention relates to a polymer membrane and a method for manufacturing the same.
これまでのアニリン系重合体は、ベンゼン環にハロゲン
やアルキル基、アルコキシ基、あるいはスルホン酸基等
を有するものや、Ｎ位にアルキル基やフェニル基を有す
るものであって、その利用分野も各種導電体、エレクト
ロクロミック素子、−次あるいは二次電池の電極などに
限られていて有機化合物の分離に利用するものはなかっ
た。その一方で、種々の不斉原子を有する有機化合物の
合成において、生じる光学異性体を分離する、或いは光
学異性体の内一方のみを選択的に合成する試みは数多く
なされている。前者では、光学活性体を用いた光学分割
剤を用いる方法、光学活性ポリマーを担体としたカラム
を用いた液体クロマトグラフによるものや不斉選択透過
性を有した透過膜による分離方法が良く知られている。Conventional aniline polymers include those with a halogen, alkyl group, alkoxy group, or sulfonic acid group in the benzene ring, and those with an alkyl group or phenyl group at the N-position, and their applications are diverse. It has been limited to electrical conductors, electrochromic devices, and electrodes for secondary or secondary batteries, and has not been used to separate organic compounds. On the other hand, in the synthesis of organic compounds having various asymmetric atoms, many attempts have been made to separate the resulting optical isomers or to selectively synthesize only one of the optical isomers. For the former, well-known separation methods include an optical resolution agent using an optically active substance, a liquid chromatography method using a column using an optically active polymer as a carrier, and a separation method using a permeable membrane with asymmetric permselectivity. ing.
しかしながらこれらの方法は取扱いが困難、分離に時間
がかかる、コストが高い等の問題点を有している。However, these methods have problems such as being difficult to handle, requiring time for separation, and being expensive.
一方、後者では酵素や不斉原子を有する化合物を触媒と
する、いわゆる不斉合成触媒を用いる方法が良く知られ
ている。しかし、この様な触媒は高価であり、また、反
応後の回収等取扱いが困難である等の問題点を有してい
る。On the other hand, for the latter method, a method using a so-called asymmetric synthesis catalyst using an enzyme or a compound having an asymmetric atom as a catalyst is well known. However, such catalysts are expensive and have problems such as being difficult to handle and recover after the reaction.
本発明は、この様な問題点を解決し、新規なアニリン系
重合体およびそれを使用して電気化学的に光学分割を行
うことが可能な分離膜及びその製造方法を提供すること
を目的としている。The present invention aims to solve these problems and provide a novel aniline polymer, a separation membrane that can perform electrochemical optical resolution using the same, and a method for producing the same. There is.
本発明者は、前記問題点を解決すべく鋭意検討した結果
、アニリンのＮ位に不斉炭素を有する置換基を導入した
アニリン系重合体の膜を利用して、電気化学的光学分割
が可能なことを見いだし、本発明を完成させた。As a result of intensive studies to solve the above problems, the present inventors have discovered that electrochemical optical resolution is possible by using a film of an aniline polymer in which a substituent having an asymmetric carbon is introduced into the N-position of aniline. They discovered this and completed the present invention.
本発明の請求項１の発明は下記−能代（Ｉ）八
（ＣＨ２）１１
／
Ｂ−Ｃ”−Ｃ−Ｏ
（式中、Ａ、Ｂ、Ｄは、それぞれ不斉炭素Ｃ“に結合し
、かつＡ、Ｂ、Ｄは互に同し基でない水素、水酸基、ア
ルキル基、アルケニル基、了り−ル基又はアルコキシ基
を示し、ｍは１〜３０の整数、ｎは８〜５００の整数を
示す）
で表わされるアニリン系重合体である。The invention of claim 1 of the present invention is as follows - Noshiro (I) 8
(CH2)11 / B-C''-C-O (wherein A, B, and D are each bonded to the asymmetric carbon C'', and A, B, and D are hydrogen or hydroxyl groups that are not the same group) , an alkyl group, an alkenyl group, an alkyl group, or an alkoxy group, m is an integer of 1 to 30, and n is an integer of 8 to 500).
請求項２の発明は下記−能代（１）
Ａ （ＣＨ２）ｌＩ
／
Ｂ−Ｃ”−Ｃ−０
（式中、Ａ、Ｂ、Ｄおよびｍ、ｎは前記の意味を有する
）で表わされるアニリン系重合体からなる光学異性体分
割膜である。The invention of claim 2 is an aniline represented by the following - Noshiro (1) A (CH2)lI / B-C"-C-0 (wherein A, B, D, m, and n have the above-mentioned meanings) This is an optical isomer separation membrane made of a polymer.
請求項３の発明は、アニリンのＮ位に、下記−能代（Ｉ
Ｉ）
（ＣＨ２）、ＱＣ−Ｃ” −Ｂ （ＩＩ）ＩＩ
Ｄ
（式中、Ａ、Ｂ、Ｄは、それぞれ不斉炭素Ｃ”に結合し
、かつ、Ａ、Ｂ、Ｄが互に同じ基でない水素、水酸基、
アルキル基、アルケニル基、アリール基又は、アルコキ
シ基を示し、ｍは１〜３０の整数を示す）で表わされる
置換基を有するアニリン誘導体を電気化学的酸化重合に
よりアニリン系重合体を電極上に製膜せしめ、しかるの
ち、アンモニア処理又は電気化学的に脱ドーピングして
なる光学異性体分割膜の製造方法である。The invention of claim 3 provides the following - Noshiro (I) at the N-position of aniline.
I) (CH2), QC-C''-B (II)II D (wherein A, B, and D are each bonded to the asymmetric carbon C'', and A, B, and D are the same group) Hydrogen, hydroxyl group,
An aniline polymer is produced on an electrode by electrochemical oxidation polymerization of an aniline derivative having a substituent represented by an alkyl group, an alkenyl group, an aryl group, or an alkoxy group, and m is an integer from 1 to 30. This is a method for producing an optical isomer separation film, which is formed by forming a film, and then subjecting it to ammonia treatment or electrochemical dedoping.
請求項４の発明は、アニリンのＮ位に、下記−能代（Ｉ
Ｉ）
（ＣＨ２）、ＱＣ−Ｃ” −Ｂ （Ｉ［）
Ｄ
（式中、Ａ、Ｂ、Ｄおよびｍは前記の意味を有する）で
表わされる置換基を有するアニリン誘導体を酸化剤によ
り酸化重合してアニリン系重合体を生成し、得られた該
重合体をアンモニア処理又は電気化学的に脱ドーピング
を施し、しかるのち製膜せしめてなる光学異性体分割膜
の製造方法である。The invention of claim 4 provides the following - Noshiro (I) at the N-position of aniline.
I) (CH2), QC-C''-B (I[)
An aniline derivative having a substituent represented by D (wherein A, B, D and m have the above meanings) is oxidatively polymerized with an oxidizing agent to produce an aniline polymer, and the resulting polymer This is a method for producing an optical isomer separation film, in which a film is subjected to ammonia treatment or electrochemical dedoping, and then a film is formed.
本発明のアニリン系重合体は、置換基に不斉炭素を有す
るアニリン誘導体を酸化重合することによって得られる
。酸化重合の方法としては電気化学的酸化又は酸化剤を
用いる方法が利用できる。The aniline polymer of the present invention can be obtained by oxidative polymerization of an aniline derivative having an asymmetric carbon as a substituent. As a method for oxidative polymerization, electrochemical oxidation or a method using an oxidizing agent can be used.
以下に本発明の新規なアニリン系重合体の合成方法を述
べる。The method for synthesizing the novel aniline polymer of the present invention will be described below.
本発明のアニリン系重合体を構成するモノマーは、Ｎ位
に不斉炭素を含む置換基を有するアニリン誘導体であり
、以下の方法で合成することができる。The monomer constituting the aniline polymer of the present invention is an aniline derivative having a substituent containing an asymmetric carbon at the N-position, and can be synthesized by the following method.
すなわち、−能代（Ｉ）
Ｂ−Ｃ” −ＣＯＯＨ（ＩＩＩ）
（式中、Ａ、Ｂ、Ｄは前記の意味を有する）で表わされ
る不斉炭素を有するカルボン酸を、ベンゼン等の溶媒中
で硫酸等を触媒として Ｘ（ＣＨ２）、 −０Ｈ（Ｘは
ハロゲン、ｍは１〜３０の整数を示す）で表わされるア
ルコールとエステル化反応をさせ、−能代（ＩＶ）に示
すエステルを得る。That is, a carboxylic acid having an asymmetric carbon represented by -Noshiro (I) B-C" -COOH (III) (wherein A, B, and D have the above-mentioned meanings) is dissolved in a solvent such as benzene. An esterification reaction is carried out with an alcohol represented by X (CH2) and -0H (X is a halogen and m is an integer from 1 to 30) using sulfuric acid or the like as a catalyst to obtain the ester shown in -Noshiro (IV).
Ｏ
Ｂ−Ｃ” −Ｃ−０−（ＣＨ，）、Ｘ （ＩＶ
）次に、上記−能代（ＴＶ）のエステルをアニリンとエ
ーテル系溶媒中で反応させ、Ｎ位に、前記−能代（ＩＩ
）に示すような不斉炭素を含む置換基を有するアニリン
誘導体を得ることができる。O B-C''-C-0-(CH,),X (IV
) Next, the ester of -Noshiro (TV) was reacted with aniline in an ether solvent, and the -Noshiro (II) was added to the N-position.
) Aniline derivatives having a substituent containing an asymmetric carbon can be obtained.
−能代（ｎ）の中のＡ、Ｂ、Ｄ及びｍは前記の意味を有
し、Ａ、Ｂ、Ｄは具体的には、例えば、以下に示すよう
な基が挙げられ、互に異なっていることが必要である。- A, B, D and m in Noshiro (n) have the above meanings, and specific examples of A, B and D include the following groups, and they are different from each other. It is necessary to be present.
すなわち、水素；水酸基；メチル、エチル、ｎプロピル
、１ｓｏ−プロピル、ｎ−ブチル、１ｓｏ−ブチル、５
ｅｃ−ブチル、ｔｅｒ ｔ−ブチル、ｎ−ペンチル、ｎ
−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｎノニル、
ｎ−デシル、ｎ−ドデシル、ｎ−ヘキサデシル、ｎ−エ
イコシル、ｎ−トコシル等のアルキル基；ビニル、アリ
ル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル等
のアルケニル基；ヘンシル、フェネチルの様なフェニル
置換アルキル基；フェニル、トリル、キシレニル、アニ
リル、ナフチル、アントリル、フェナントリル、ピレニ
ル等のアリール基；メトキシ、エトキシ、プロポキシ等
のアルコキシ基などが本発明でいうアニリン誘導体に適
用される。That is, hydrogen; hydroxyl group; methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 1so-butyl, 5
ec-butyl, tert-butyl, n-pentyl, n
-hexyl, n-heptyl, n-octyl, n-nonyl,
Alkyl groups such as n-decyl, n-dodecyl, n-hexadecyl, n-eicosyl, n-tocosyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl; phenyl-substituted alkyl groups such as hensyl and phenethyl Aryl groups such as phenyl, tolyl, xylenyl, anilyl, naphthyl, anthryl, phenanthryl, and pyrenyl; and alkoxy groups such as methoxy, ethoxy, and propoxy are applicable to the aniline derivatives referred to in the present invention.
なお、−能代（ＩＩＩ）で表わされる不斉炭素を有する
カルボン酸としては、例えば、（Ｓ）−（＋）−マルデ
ル酸、（Ｒ）−（−）−マルデル酸、（Ｒ）−（−）−
α−メトキシフェニル酢酸、（Ｓ）−（＋）−α−メト
キシフェニル酢酸、（Ｒ） −（＋）−２−クロロプロ
ピオン酸、（Ｓ）−（−）−２−クロロプロピオン酸、
（Ｒ）（−）−２−フェニルプロピオン酸、（Ｓ）−（
＋）−２−フェニルプロピオン酸、（Ｒ）−（−）−３
−ヒドロキシ酪酸、（Ｓ）−（、＋）−３−ヒドロキシ
酪酸、Ｄ−乳酸、Ｌ−乳酸、Ｄりんご酸、Ｌ−りんご酸
等が挙げられる。In addition, examples of the carboxylic acid having an asymmetric carbon represented by -Noshiro (III) include (S)-(+)-malderic acid, (R)-(-)-malderic acid, (R)-(- )−
α-methoxyphenylacetic acid, (S)-(+)-α-methoxyphenylacetic acid, (R)-(+)-2-chloropropionic acid, (S)-(-)-2-chloropropionic acid,
(R)(-)-2-phenylpropionic acid, (S)-(
+)-2-phenylpropionic acid, (R)-(-)-3
-hydroxybutyric acid, (S)-(,+)-3-hydroxybutyric acid, D-lactic acid, L-lactic acid, D-malic acid, L-malic acid, and the like.
また、前記カルボン酸とエステル化反応に用いるハロゲ
ン化アルコールとしては、例えば、クロロメタノール、
フロモメタノール、２−クロロエタノール、２−ブロモ
エタノール、３−クロロプロパツール、３−ブロモプロ
パツール、４−クロロ−１−ブタノール、４−ブロモー
１−ブタノール、１０−クロロ−１−デカンアルコール
、１０−フロモー１−デカンアルコール、２０−クロロ
１−エイサノール、２０−フロモー１−エイサノール、
３０−クロロ−１−トリアコンタノール、３０−ブロモ
−１−トリアコンタノール等が挙げられる。Further, examples of the halogenated alcohol used in the esterification reaction with the carboxylic acid include chloromethanol,
Fromomethanol, 2-chloroethanol, 2-bromoethanol, 3-chloropropanol, 3-bromopropanol, 4-chloro-1-butanol, 4-bromo-1-butanol, 10-chloro-1-decane alcohol, 10-fromo-1-decane alcohol, 20-chloro-1-eisanol, 20-fromo-1-eisanol,
Examples include 30-chloro-1-triacontanol and 30-bromo-1-triacontanol.
本発明の前記−能代（１）で示される新規なアニリン系
重合体は、上記に示したアニリン誘導体を下記のごとき
酸化重合することにより、得ることができる。The novel aniline polymer represented by Noshiro (1) of the present invention can be obtained by subjecting the above-mentioned aniline derivative to oxidative polymerization as described below.
本発明の酸化重合法の一つである電気化学的酸化重合は
陽極酸化であり、通常、電圧は１００ｍＶ〜５０Ｖの範
囲で、例えば定電位電解法、定電流法、定電圧法など（
以下、電解重合法という）が用いられる。重合は、水、
有機溶媒又はこれらの混合物中で行うことができる。ま
たモノマーと共存する支持電解質としては、塩酸、硫酸
、ホウフッ化水素酸、過塩素酸、硝酸、ベンゼンスルホ
ン酸、Ｐ−）ルエンスルホン酸、等のプロトン酸を用い
る。或いは、該プロトン酸の塩を用いてもよい。Electrochemical oxidative polymerization, which is one of the oxidative polymerization methods of the present invention, is anodic oxidation, and the voltage is usually in the range of 100 mV to 50 V, such as constant potential electrolysis method, constant current method, constant voltage method, etc.
(hereinafter referred to as electrolytic polymerization method) is used. Polymerization involves water,
It can be carried out in organic solvents or mixtures thereof. Further, as a supporting electrolyte coexisting with the monomer, a protonic acid such as hydrochloric acid, sulfuric acid, fluoroboric acid, perchloric acid, nitric acid, benzenesulfonic acid, P-)luenesulfonic acid, etc. is used. Alternatively, a salt of the protonic acid may be used.
電解液のｐＨは３以下が好ましい。ｐＨ３以上では重合
体の収率が低い。また電解液には溶存酸素が存在しない
方が好ましく、電解反応も窒素やアルゴンなど不活性ガ
スのもとで行うことが好ましい。The pH of the electrolytic solution is preferably 3 or less. At pH 3 or higher, the yield of the polymer is low. Further, it is preferable that dissolved oxygen does not exist in the electrolytic solution, and it is preferable that the electrolytic reaction is also carried out under an inert gas such as nitrogen or argon.
これは電解液中の溶存酸素は重合反応の進行を抑え、高
分子量の重合体を得ることを困難にするためである。電
解重合に用いる電極としては特に制限はなく、例えば、
白金、金、銅、ニッケル、クロム等の金属や、グラッシ
ーカーボン、グラファイト等の炭素電極、ネサガラス、
ＩＴＯガラス（酸化インジウム）などの金属酸化物との
複合電極など種々の電極を用いることが可能である。This is because dissolved oxygen in the electrolyte suppresses the progress of the polymerization reaction, making it difficult to obtain a high molecular weight polymer. There are no particular restrictions on the electrodes used for electrolytic polymerization, for example,
Metals such as platinum, gold, copper, nickel, and chromium, carbon electrodes such as glassy carbon and graphite, Nesa glass,
Various electrodes can be used, such as a composite electrode with a metal oxide such as ITO glass (indium oxide).
酸化剤を用いる方法としては、モノマーの酸性水溶液ま
たは有機溶媒の溶液を作り、これに酸化剤を加えて２時
間〜１００時間重合を行う。酸化剤としては、過硫酸ア
ンモニウム、過硫酸カリウムや過硫酸ナトリウム等の過
硫酸塩、過マンガン酸カリウム等の過マンガン酸塩、メ
タ過ヨウ素酸ナトリウム等のメタ過ヨウ素酸塩、過酸化
水素、塩化第二鉄等が用いられる。重合温度は特に制限
はないが、−２０°Ｃ−１００°Ｃが好ましい。As a method using an oxidizing agent, an acidic aqueous solution or an organic solvent solution of the monomer is prepared, the oxidizing agent is added thereto, and polymerization is carried out for 2 to 100 hours. Oxidizing agents include ammonium persulfate, persulfates such as potassium persulfate and sodium persulfate, permanganates such as potassium permanganate, metaperiodates such as sodium metaperiodate, hydrogen peroxide, and chloride. Ferric iron etc. are used. The polymerization temperature is not particularly limited, but -20°C to 100°C is preferred.
重合体を得る方法としては、電気化学的酸化重合の方が
、重合体が膜として電極上に生成するので、本発明に用
いるのに有利である。As a method for obtaining the polymer, electrochemical oxidative polymerization is more advantageous for use in the present invention because the polymer is formed as a film on the electrode.
電気化学的酸化重合及び酸化剤による酸化重合のどちら
の方法でも、得られた本発明によるアニリン系重合体は
反応に用いたプロトン酸や酸化剤によってドープされて
いる。本発明においてこれらのドーパントは膜への光学
異性体の取り込みを阻害するので、本発明によるアニリ
ン系重合体を光学異性体分割膜として使用する場合は、
アンモニア水に浸すとか、アンモニアガスに曝すごとき
アンモニア処理、又は飽和カロメル電極に対して、ＯＶ
以下の電位をアニリン系重合体にかけて電気化学的に脱
ドープするなどの方法でドーパントを取り除くことが必
要である。これらのアンモニア処理と電気化学的な脱ド
ープの方法は単独でも併用してもかまわない。In both electrochemical oxidative polymerization and oxidative polymerization using an oxidizing agent, the obtained aniline polymer according to the present invention is doped with the protic acid and oxidizing agent used in the reaction. In the present invention, these dopants inhibit the incorporation of optical isomers into the membrane, so when using the aniline polymer according to the present invention as an optical isomer separation membrane,
OV
It is necessary to remove the dopant by a method such as electrochemical dedoping by applying the following potential to the aniline polymer. These ammonia treatment and electrochemical dedoping methods may be used alone or in combination.
こうして得られた本発明のアニリン系重合体は、電気化
学的酸化重合で合成された場合電極上に生成するのでそ
のまま光学異性体分割膜として本発明に用いることが可
能であるが、電極から剥離して膜単独で用いることも可
能である。また、酸化剤を用いて重合した場合、電気化
学的酸化重合に用いる電極上にキャスト等の手法で製膜
するか、あるいは適当な基板上で製膜し、膜単独で用い
るかする。When the aniline polymer of the present invention thus obtained is synthesized by electrochemical oxidative polymerization, it is produced on the electrode, so it can be used as it is as an optical isomer separation film in the present invention, but it cannot be peeled off from the electrode. It is also possible to use the membrane alone. Further, when polymerization is performed using an oxidizing agent, a film is formed by a method such as casting on an electrode used for electrochemical oxidative polymerization, or a film is formed on a suitable substrate and used alone.
こうして得られた光学異性体分割膜に、前記の白金、金
、銅等電解重合に用いる電極を対極として、光学異性体
の混合溶液中で飽和カロメル電極または銀／塩化銀電極
に対し０．１〜１０■の電位をかけると、アニリンの置
換基の不斉炭素と同じ対称性の光学異性体のみが膜中に
取り込まれ、異なる対称性の光学異性体は溶液中に残る
。同し対称性の光学異性体を取り込んだ膜に、取り込み
時と逆の電位をかければ、取り込んだ異性体を放出する
。かくして光学異性体の混合溶液から、同一対称性の光
学異性体のみを容易に分離することができる。The optical isomer separation membrane obtained in this way is placed in a mixed solution of optical isomers using the electrode used for electrolytic polymerization of platinum, gold, copper, etc. as a counter electrode, and the saturated calomel electrode or the silver/silver chloride electrode is 0.1 When a potential of ~10 μ is applied, only the optical isomer with the same symmetry as the asymmetric carbon of the aniline substituent is incorporated into the membrane, while the optical isomer with a different symmetry remains in the solution. If a potential opposite to that at the time of uptake is applied to a membrane that has incorporated optical isomers with the same symmetry, the incorporated isomers will be released. In this way, only optical isomers having the same symmetry can be easily separated from a mixed solution of optical isomers.
〈実施例〉
実施例１゜
（Ｓ）−（＋）−マンデル酸と２−ブロモエタノールを
反応させエステル化し、しかる移譲エステルにアニリン
を反応させて（Ｓ）−マンデル酸アニリノエチルモノマ
ーからなるアニリン誘導体を合成した。電解液はこのモ
ノマー０．１ｍｏｆｆ／／２、塩酸２ＩＩｌｏＲ／ｌの
水溶液とし白金を電極として、飽和カロメル電極に対し
０．８ Ｖの電位で２時間、窒素雰囲気下で電解重合を
行った。陽極側の白金電極上に緑色の下式（Ｖ）で表わ
される繰返し単位を有する本発明のアニリン系重合体が
生成した。<Example> Example 1゜(S)-(+)-mandelic acid and 2-bromoethanol are reacted and esterified, and the transferred ester is reacted with aniline to obtain an (S)-anilinoethyl mandelate monomer. Aniline derivatives were synthesized. The electrolytic solution was an aqueous solution containing 0.1 moff//2 of this monomer and 2IIloR/l of hydrochloric acid, and electrolytic polymerization was carried out in a nitrogen atmosphere for 2 hours at a potential of 0.8 V with respect to a saturated calomel electrode using platinum as an electrode. A green aniline polymer of the present invention having a repeating unit represented by the following formula (V) was produced on the platinum electrode on the anode side.
得られた重合体の固を粘度（３０°Ｃにおける、濃度０
．５ｇ／ｄｆＮ−メチル−２−ヒロリドン溶液）は０．
２６ｄｆｆｉ／ｇであった。これを、先ず−０，５Ｖの
電位で２０分間脱ドープを行い、さらに１ｍｏｆ／／２
のアンモニア水に３時間浸し脱ドープを完了し本発明に
よる光学異性体分割膜を作成した。The solidity of the obtained polymer is determined by the viscosity (concentration 0 at 30°C)
．． 5g/dfN-methyl-2-hyrolidone solution) is 0.
It was 26dffi/g. This was first dedoped at a potential of -0.5V for 20 minutes, and then 1mof//2
The film was immersed in aqueous ammonia for 3 hours to complete dedoping, and an optical isomer separation membrane according to the present invention was prepared.
脱ドープしたこの重合物の膜で被われた白金電極に、（
Ｓ）−（＋）−及び（Ｒ） −（−） −Ｌよつ（７）
ウ−１０−スルホン酸アンモニウムヲ０．１ｍｏｌｌｉ
ずつ含む水溶液中で飽和カロメル電極に対し０．５■の
電位を１０分かけ白金電極上の重合体膜に（Ｓ）−（＋
）−Ｌようのう−１０−スルホン酸アンモニウムを取り
込んだ。塩化アンモニウムを支持電解質とした水溶液に
この白金電極を移し、飽和カロメル電極に対し−０，５
Ｖの電位を１０分かけ取り込まれた（Ｓ）−（＋）−Ｌ
ようのう−１０−スルホン酸を脱ドープした。脱ドープ
後の溶液の比旋光度は〔α：ｌ ｚｏＤ＝＋２１’で（
Ｓ） −（＋）体のみが分離されたことが確認でき光学
異性体の分離が容易にできた。A platinum electrode covered with a film of this dedoped polymer was coated with (
S) −(+)− and (R) −(−) −Lyotsu (7)
Ammonium ur-10-sulfonate 0.1 molli
By applying a potential of 0.5 μ to a saturated calomel electrode for 10 minutes in an aqueous solution containing
)-L-10-ammonium sulfonate was incorporated. This platinum electrode was transferred to an aqueous solution with ammonium chloride as a supporting electrolyte, and the temperature was -0.5 with respect to the saturated calomel electrode.
(S)-(+)-L taken in the potential of V over 10 minutes
Yono-10-sulfonic acid was dedoped. The specific optical rotation of the solution after dedoping is [α:l zoD=+21' (
It was confirmed that only the S) -(+) form was separated, and the optical isomers could be easily separated.
実施例２゜
実施例１で用いたアニリン誘導体からなる千ツマ−２ｇ
をクロロホルム乙こ溶かし、酸化剤として塩化第二鉄を
２ｇ加えて１２時間室温で攪拌した。Example 2゜2g of aniline derivative used in Example 1
was dissolved in chloroform, 2 g of ferric chloride was added as an oxidizing agent, and the mixture was stirred at room temperature for 12 hours.
この溶液をメタノール中に往くと暗緑色の本発明のアニ
リン系重合体が２ｇ得られた。これをｌｌ１ｏｒ！／４
２のアンモニア水中で４時間撹拌し脱１” −プ処理を
行った。脱ドープされた重合体をクロロホルムに熔解し
、キャスト法で白金電極上に本発明による光学異性体分
割膜を作製した。When this solution was poured into methanol, 2 g of a dark green aniline polymer of the present invention was obtained. This is ll1or! /4
The dedoped polymer was stirred for 4 hours in ammonia water (No. 2) to perform de-1''-doping treatment. The dedoped polymer was dissolved in chloroform, and an optical isomer separation membrane according to the present invention was prepared on a platinum electrode by a casting method.
この重合物の膜で被われた白金電極に、（Ｓ）（＋）−
及び（Ｒ）−（−）−Ｌようのう一１０スルホン酸アン
モニウムを０．１ｍｏｆｆｉ／Ｉ！、ｆつ含む水溶液中
で飽和カロメル電極に対し、０，５Ｖの電位を３０分か
け白金電極上の重合体膜に（Ｓ）−（＋）−Ｌようのう
−１０−スルホン酸アンモニウムを取り込んだ。塩化ア
ンモニウムを支持電解質とした水溶液にこの白金電極を
移し、飽和カロメル電極に対し−０，５Ｖの電位を３０
分かけ取り込まれた（Ｓ）−（＋）−Ｌようのう−１０
−スルホン酸を脱ドープした。脱ドープ後の溶液の比旋
光度は〔α）２０Ｄ−＋２１°で（Ｓ）−（＋）体のみ
が分離されたことが確認できた。したがって、光学異性
体の分離が容易に行えた。(S)(+)-
and (R)-(-)-L-10 ammonium sulfonate at 0.1 moffi/I! In an aqueous solution containing F, a potential of 0.5 V was applied to the saturated calomel electrode for 30 minutes to incorporate (S)-(+)-L-10-ammonium sulfonate into the polymer film on the platinum electrode. is. This platinum electrode was transferred to an aqueous solution using ammonium chloride as a supporting electrolyte, and a potential of -0.5 V was applied to the saturated calomel electrode at 30
(S)-(+)-L Yonou-10 taken in minutes
- Dedoped with sulfonic acid. The specific optical rotation of the solution after dedoping was [α)20D−+21°, and it was confirmed that only the (S)−(+) isomer was separated. Therefore, separation of optical isomers could be easily performed.
実施例３６
（Ｓ）−（＋）−マンデル酸と２−ブロモプロパツール
の反応生成物にアニリンを反応させて（Ｓ）−マンデル
酸アニリノプロピルモノマーからなるアニリン誘導体を
合成した。電解液はこのモノマー０．１ｍｏｆ／１．、
塩酸２ｍｏｆ／４２の水溶液とし、白金を電極として、
飽和カロメル電極に対し０．８Ｖの電位で２時間、窒素
雰囲気下で電解重合を行った。陽極側の白金電極上に緑
色の本発明によるアニリン系重合体が生成した。得られ
た重合体の固有粘度（前記の意味を有する）は、０．２
３ ｄ １７ｇであった。これを、先ず一〇、 ５ Ｖ
の電位で２０分間脱ドープを行い、さらに１ｍｏｆ／ｉ
のアンモニア水に３時間浸し脱ドープを完了し本発明に
よる光学異性体分割膜を作製した。Example 36 A reaction product of (S)-(+)-mandelic acid and 2-bromopropanol was reacted with aniline to synthesize an aniline derivative consisting of anilinopropyl (S)-mandelate monomer. The electrolyte contains 0.1 mof of this monomer/1. ,
Using an aqueous solution of 2mof/42 hydrochloric acid and using platinum as an electrode,
Electrolytic polymerization was performed in a nitrogen atmosphere for 2 hours at a potential of 0.8 V with respect to a saturated calomel electrode. A green aniline polymer according to the present invention was formed on the platinum electrode on the anode side. The intrinsic viscosity (as defined above) of the obtained polymer is 0.2
3d 17g. First, apply this to 10, 5 V.
Dedoping was carried out for 20 minutes at a potential of 1 mof/i
The film was immersed in aqueous ammonia for 3 hours to complete dedoping, thereby producing an optical isomer separation membrane according to the present invention.
脱ドープしたこの重合物の膜で被われた白金電極に、、
（Ｓ）−（＋）−及び（Ｒ） −（−） −Ｌようのう
−１０−スルホン酸アンモニウムを０．１ｍｏＥ／ｉ−
ずつ含む水溶液中で飽和カロメル電極に対し０．５Ｖの
電位を３０分かけ白金電極上の重合体膜に（Ｓ）−（＋
）−Ｌようのう−１０−スルホン酸アンモニウムを取り
込んだ。塩化アンモニウムを支持電解質とした水溶液に
この白金電極を移し、飽和カロメル電極に対し−０，５
■の電位を３０分かけ取り込まれた（Ｓ）−（＋）−Ｌ
ようのう−１０−スルホン酸を脱ドープした。溶液の比
旋光度は〔α） ”Ｄ −＋２１°で（Ｓ）−（＋）体
のみが分離されたことが確認できた。このことより、光
学異性体の分離がきわめて容易に行えた。A platinum electrode covered with a film of this dedoped polymer,
(S)-(+)- and (R)-(-)-L-10-ammonium sulfonate at 0.1 moE/i-
A potential of 0.5 V is applied to a saturated calomel electrode for 30 minutes in an aqueous solution containing (S)-(+
)-L-10-ammonium sulfonate was incorporated. This platinum electrode was transferred to an aqueous solution with ammonium chloride as a supporting electrolyte, and the temperature was -0.5 with respect to the saturated calomel electrode.
(S)-(+)-L was incorporated by applying the potential of ■ for 30 minutes.
Yono-10-sulfonic acid was dedoped. It was confirmed that only the (S)-(+) isomer was separated at a specific optical rotation of the solution of [α)"D - +21°. From this, it was possible to separate the optical isomers very easily.
実施例４゜
実施例３で用いた本発明のアニリン系重合体を白金電極
より剥離し、クロロホルムに熔解後ガラス基板上にキャ
ストして薄膜を作製した。基板より剥離後、該薄膜に再
び白金電極をつけて実施例３と同様（Ｓ）−（＋）−及
び（Ｒ）−（−）しょうのう−１０−スルホン酸アンモ
ニウムを０．１ｍｏｆｆｉ／ｊ２ずつ含む水溶液中で飽
和カロメル電極に対し０．５ Ｖの電位を３０分かけ電
極上の薄膜に（Ｓ）−（＋）−Ｌようのう−１０−スル
ホン酸アンモニウムを取り込んだ。塩化アンモニウムを
支持電解質とした水溶液にこの白金電極を移し、飽和カ
ロメル電極に対し一〇、５■の電位を３０分かけ取り込
まれた（Ｓ） （十）−Ｌようのう１０−スルホン
酸を脱ドープした。脱ドープ後の溶液の比旋光度は〔α
） ”、 ＝＋２１°で（Ｓ）−（十〕体のみが分離さ
れたことが確認でき、光学異性体の分離が容易であった
。Example 4 The aniline polymer of the present invention used in Example 3 was peeled off from the platinum electrode, dissolved in chloroform, and cast onto a glass substrate to produce a thin film. After peeling off from the substrate, a platinum electrode was attached to the thin film again, and as in Example 3, (S)-(+)- and (R)-(-) ammonium sulfonate-10-sulfonate was added at 0.1 moffi/j2. (S)-(+)-L-10-ammonium sulfonate was incorporated into the thin film on the electrode by applying a potential of 0.5 V to the saturated calomel electrode for 30 minutes in an aqueous solution containing the same amount. This platinum electrode was transferred to an aqueous solution with ammonium chloride as a supporting electrolyte, and a potential of 10.5 μm was applied to the saturated calomel electrode for 30 minutes to collect (S) (10)-L 10-sulfonic acid. Dedoped. The specific optical rotation of the solution after dedoping is [α
)”, it was confirmed that only the (S)-(dec) isomer was separated at =+21°, indicating that the optical isomers were easily separated.
実施例５゜
（Ｒ）−（−）−２−フェニルプロピオン酸と２−ブロ
モエタノールの反応生成物にアニリンを反応させて（Ｒ
）−２−フェニルプロピオン酸アニリノエチルモノマー
からなるアニリン誘導体を合成した。電解液はこのモノ
マー０．１ ｍｏｌｔ ／ Ｉ！、塩酸２１Ｉｌｏｌ／
ｌの水溶液とし白金を電極として、飽和カロメル電極に
対し０．８■の電位で４時間、窒素雰囲気下で電解重合
を行った。陽極側の白金電極上に緑色の上式（Ｖｌ）で
表わされる繰返し単位を有する本発明のアニリン系重合
体が生成した。Example 5 A reaction product of (R)-(-)-2-phenylpropionic acid and 2-bromoethanol was reacted with aniline to form (R)
Aniline derivatives consisting of anilinoethyl )-2-phenylpropionate monomer were synthesized. The electrolyte contains this monomer at 0.1 mol/I! , hydrochloric acid 21Ilol/
Electrolytic polymerization was carried out using a platinum electrode as an aqueous solution in a nitrogen atmosphere for 4 hours at a potential of 0.8 square meters with respect to a saturated calomel electrode. A green aniline polymer of the present invention having a repeating unit represented by the above formula (Vl) was produced on the platinum electrode on the anode side.
得られた重合体の固有粘度（前記の意味を有する）は、
０．２５ｄｆｆ／ｇであった。これを、先ず−０，５■
の電位で２０分間脱ドープを行い、さらに１ｍｏｆｆ／
ｆのアンモニア水に３時間浸し脱ドープを完了し本発明
による光学異性体分割膜を作製した。The intrinsic viscosity (with the meaning given above) of the obtained polymer is:
It was 0.25 dff/g. First, -0,5■
Dedoping was carried out for 20 minutes at a potential of
The film was immersed in aqueous ammonia (f) for 3 hours to complete dedoping, thereby producing an optical isomer separation membrane according to the present invention.
脱ドープしたこの重合物の膜で被われた白金電極に、（
Ｓ）−（＋）−及び（Ｒ） −（−） −りようのう−
１０−スルホン酸アンモニウムを０．１ｍｏｂ／４２ず
つ含む水溶液中で飽和カロメル電極に対し０．５Ｖの電
位を１０分かけ白金電極上の重合体膜に（Ｒ） −（−
）−Ｌようのう−１０−スルホン酸アンモニウムを取り
込んだ。塩化アンモニウムを支持電解質とした水溶液に
この白金電極を移し、飽和カロメル電極に対し−０，５
■の電位を１０分かけ取り込まれた（Ｒ）−（−）−Ｌ
ようのう−１０−スルホン酸を脱ドープした。脱ドープ
後の溶液の比旋光度は〔α） ”Ｄ ＝−２１°で（Ｒ
）−（−）体のみが分離されたことが確認でき光学異性
体の分離が容易に出来た。A platinum electrode covered with a film of this dedoped polymer was coated with (
S) -(+)- and (R) -(-) -Riyou-
(R) -(-
)-L-10-ammonium sulfonate was incorporated. This platinum electrode was transferred to an aqueous solution with ammonium chloride as a supporting electrolyte, and the temperature was -0.5 with respect to the saturated calomel electrode.
(R)-(-)-L was incorporated by applying the potential of ■ for 10 minutes.
Yono-10-sulfonic acid was dedoped. The specific optical rotation of the solution after dedoping is [α)”D = −21° and (R
It was confirmed that only the )-(-) form was separated, and the optical isomers could be easily separated.
本発明によるアニリン系重合体からなる膜を光学異性体
分割膜として使用する場合、光学異性体を電気化学的に
分割できる膜であるため、取扱いが楽であり、光学異性
体の分離が容易にできるので、非常に有用である。When the membrane made of the aniline polymer according to the present invention is used as an optical isomer separation membrane, since the membrane can electrochemically separate optical isomers, it is easy to handle and the separation of optical isomers is easy. It is very useful because it can be done.
特許出願人 株式会社 巴川製紙所Patent applicant: Tomogawa Paper Mills Co., Ltd.
Claims (4)
し、かつＡ，Ｂ，Ｄは互に同じ基でない水素、水酸基、
アルキル基、アルケニル基、アリール基又はアルコキシ
基を示し、ｍは１〜３０の整数、ｎは８〜５００の整数
を示す） で表わされることを特徴とするアニリン系重合体。(1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A, B, and D are each bonded to the asymmetric carbon C^*, and A, B, and D are hydrogen and hydroxyl groups that are not the same group,
An aniline polymer represented by the following formula: an alkyl group, an alkenyl group, an aryl group, or an alkoxy group, m is an integer of 1 to 30, and n is an integer of 8 to 500.
し、かつＡ，Ｂ，Ｄは互に同じ基でない水素、水酸基、
アルキル基、アルケニル基、アリール基又はアルコキシ
基を示し、ｍは１〜３０の整数、ｎは８〜５００の整数
を示す） で表わされるアニリン系重合体からなることを特徴とす
る光学異性体分割膜。(2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A, B, and D are each bonded to the asymmetric carbon C^*, and A, B, and D are hydrogen and hydroxyl groups that are not the same group,
(representing an alkyl group, an alkenyl group, an aryl group, or an alkoxy group, m is an integer of 1 to 30, and n is an integer of 8 to 500). film.
学式、表等があります▼（II） （式中、Ａ，Ｂ，Ｄは、それぞれ不斉炭素Ｃ＾＊に結合
し、かつ、Ａ，Ｂ，Ｄが互に同じ基でない水素、水酸基
、アルキル基、アルケニル基、アリール基又はアルコキ
シ基を示し、ｍは１〜３０の整数を示す）で表わされる
置換基を有するアニリン誘導体を電気化学的酸化重合に
よりアニリン系重合体を電極上に製膜せしめ、しかるの
ちアンモニア処理又は電気化学的に脱ドーピングするこ
とを特徴とする光学異性体分割膜の製造方法。(3) At the N-position of aniline, there is the following general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, A, B, and D each bond to the asymmetric carbon C^*, and an aniline derivative having a substituent represented by A, B, and D each representing a hydrogen, hydroxyl group, alkyl group, alkenyl group, aryl group, or alkoxy group that are not the same group, and m represents an integer of 1 to 30. A method for producing an optical isomer separation membrane, which comprises forming an aniline polymer film on an electrode by electrochemical oxidative polymerization, and then subjecting it to ammonia treatment or electrochemical dedoping.
学式、表等があります▼（II） （式中、Ａ，Ｂ，Ｄは、それぞれ不斉炭素Ｃ＾＊に結合
し、かつ、Ａ，Ｂ，Ｄが互に同じ基でない水素、水酸基
、アルキル基、アルケニル基、アリール基又はアルコキ
シ基を示し、ｍは１〜３０の整数を示す）で表わされる
置換基を有するアニリン誘導体を酸化剤により酸化重合
してアニリン系重合体を生成し、得られた該重合体をア
ンモニア処理又は電気化学的に脱ドーピングすることを
特徴とする光学異性体分割膜の製造方法。(4) At the N-position of aniline, there is the following general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, A, B, D are each bonded to the asymmetric carbon C^*, and an aniline derivative having a substituent represented by A, B, and D each representing a hydrogen, hydroxyl group, alkyl group, alkenyl group, aryl group, or alkoxy group that are not the same group, and m represents an integer of 1 to 30. A method for producing an optical isomer separation membrane, which comprises oxidatively polymerizing with an oxidizing agent to produce an aniline polymer, and subjecting the obtained polymer to ammonia treatment or electrochemical dedoping.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2180641A JP2913325B2 (en) | 1990-07-10 | 1990-07-10 | Aniline-based polymer, optical isomer splitting membrane using the same, and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2180641A JP2913325B2 (en) | 1990-07-10 | 1990-07-10 | Aniline-based polymer, optical isomer splitting membrane using the same, and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0468025A true JPH0468025A (en) | 1992-03-03 |
| JP2913325B2 JP2913325B2 (en) | 1999-06-28 |
Family
ID=16086747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2180641A Expired - Fee Related JP2913325B2 (en) | 1990-07-10 | 1990-07-10 | Aniline-based polymer, optical isomer splitting membrane using the same, and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2913325B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004096873A1 (en) * | 1993-08-31 | 2004-11-11 | Eizo Oikawa | Optically active acetylene polymer, film thereof, and optical resolution with the same |
| CN113699544A (en) * | 2021-08-30 | 2021-11-26 | 袁芳 | Method and device for promoting esterification reaction |
-
1990
- 1990-07-10 JP JP2180641A patent/JP2913325B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004096873A1 (en) * | 1993-08-31 | 2004-11-11 | Eizo Oikawa | Optically active acetylene polymer, film thereof, and optical resolution with the same |
| CN113699544A (en) * | 2021-08-30 | 2021-11-26 | 袁芳 | Method and device for promoting esterification reaction |
| CN113699544B (en) * | 2021-08-30 | 2023-11-21 | 袁芳 | Method and device for promoting esterification reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2913325B2 (en) | 1999-06-28 |
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