JPH04314710A - New polymer having sugar derivative group in side chain and separating agent - Google Patents
New polymer having sugar derivative group in side chain and separating agentInfo
- Publication number
- JPH04314710A JPH04314710A JP3082303A JP8230391A JPH04314710A JP H04314710 A JPH04314710 A JP H04314710A JP 3082303 A JP3082303 A JP 3082303A JP 8230391 A JP8230391 A JP 8230391A JP H04314710 A JPH04314710 A JP H04314710A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- carbon atoms
- meth
- acrylic acid
- 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.)
- Pending
Links
- 235000000346 sugar Nutrition 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 title description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000002252 acyl group Chemical group 0.000 claims abstract description 3
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 abstract description 21
- 230000003287 optical effect Effects 0.000 abstract description 8
- -1 1-12C alkoxycarbonyl Chemical group 0.000 abstract description 6
- 238000012856 packing Methods 0.000 abstract description 2
- 125000003282 alkyl amino group Chemical group 0.000 abstract 1
- 238000000921 elemental analysis Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 2
- DZSGDHNHQAJZCO-UHFFFAOYSA-N 1-isocyanato-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(N=C=O)=C1 DZSGDHNHQAJZCO-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 2
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- AEMOLEFTQBMNLQ-DTEWXJGMSA-N D-Galacturonic acid Natural products O[C@@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-DTEWXJGMSA-N 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-RSVSWTKNSA-N D-altro-hexose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-RSVSWTKNSA-N 0.000 description 1
- SHZGCJCMOBCMKK-SVZMEOIVSA-N D-fucopyranose Chemical compound C[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O SHZGCJCMOBCMKK-SVZMEOIVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- BJHIKXHVCXFQLS-PUFIMZNGSA-N D-psicose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)C(=O)CO BJHIKXHVCXFQLS-PUFIMZNGSA-N 0.000 description 1
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 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
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- SRBFZHDQGSBBOR-OWMBCFKOSA-N L-ribopyranose Chemical compound O[C@H]1COC(O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-OWMBCFKOSA-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
- 239000004793 Polystyrene Substances 0.000 description 1
- 101100184046 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mid1 gene Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IAJILQKETJEXLJ-RSJOWCBRSA-N aldehydo-D-galacturonic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-RSJOWCBRSA-N 0.000 description 1
- GZCGUPFRVQAUEE-ZXXMMSQZSA-N aldehydo-D-idose Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-ZXXMMSQZSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N aldehydo-D-ribose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- GZCGUPFRVQAUEE-KAZBKCHUSA-N aldehydo-D-talose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-KAZBKCHUSA-N 0.000 description 1
- PNNNRSAQSRJVSB-KCDKBNATSA-N aldehydo-L-fucose Chemical compound C[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C=O PNNNRSAQSRJVSB-KCDKBNATSA-N 0.000 description 1
- PYMYPHUHKUWMLA-YUPRTTJUSA-N aldehydo-L-lyxose Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-YUPRTTJUSA-N 0.000 description 1
- PNNNRSAQSRJVSB-BXKVDMCESA-N aldehydo-L-rhamnose Chemical compound C[C@H](O)[C@H](O)[C@@H](O)[C@@H](O)C=O PNNNRSAQSRJVSB-BXKVDMCESA-N 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-WAXACMCWSA-N alpha-D-glucuronic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-WAXACMCWSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N beta-D-galactopyranuronic acid Natural products OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-QZABAPFNSA-N beta-D-glucosamine Chemical compound N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-QZABAPFNSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- BJHIKXHVCXFQLS-UYFOZJQFSA-N keto-D-fructose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、例えば光学分割を行う
機能材料として極めて有用な、新規なポリマーに関する
。詳細には、側鎖に糖誘導体を有するポリアクリル酸又
はメタクリル酸誘導体及びこれを主成分とする分離剤に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymer extremely useful as a functional material for optical resolution, for example. In particular, the present invention relates to polyacrylic acid or methacrylic acid derivatives having sugar derivatives in their side chains, and separation agents containing these as main components.
【０００２】0002
【従来の技術及び発明が解決しようとする課題】これま
で側鎖に光学活性なアミノ酸あるいはアミン化合物を有
するポリメタクリル酸誘導体をシリカゲルなどに固定し
た液体クロマトグラフィーの充填剤が、光学分割の能力
を有している事が知られている（Ｇ． Ｂｌａｓｃｈｋ
ｅ， Ｗ． Ｂｒｏｋｅｒ ａｎｄ Ｗ．Ｆｒａｅｎｋ
ｅｌ， Ａｎｇｅｗ． Ｃｈｅｍ． Ｉｎｔ． Ｅｄ．
Ｅｎｇｌ．， ８３０， ２５， １９８６）。し
かしながら、その分割の対象は限られたものであった。[Prior Art and Problems to be Solved by the Invention] Up until now, liquid chromatography packing materials in which polymethacrylic acid derivatives having optically active amino acids or amine compounds in their side chains have been immobilized on silica gel, etc., have achieved optical resolution. (G. Blaschk)
e, W. Broker and W. Fraenk
el, Angew. Chem. Int. Ed.
Engl. , 830, 25, 1986). However, the scope of this division was limited.
【０００３】0003
【課題を解決するための手段】本発明者らは、不斉源と
して安価で入手の容易な天然の糖誘導体を側鎖に有する
ポリアクリル酸又はメタクリル酸誘導体が、光学分割用
充填剤として優れた不斉識別能力を持つことを見出し、
本発明を完成させた。[Means for Solving the Problems] The present inventors have discovered that polyacrylic acid or methacrylic acid derivatives having an inexpensive and easily available natural sugar derivative in the side chain as an asymmetric source are excellent as fillers for optical resolution. discovered that it has the ability to discriminate asymmetry.
The present invention has been completed.
【０００４】即ち、本発明は、水酸基及びアミノ基の水
素原子の５０％ないし １００％が下記一般式（１）
、（２） 、（３） あるいは（４） で示される基で
置換された糖誘導体を側鎖に持つポリアクリル酸又はメ
タクリル酸誘導体（以下ポリ（メタ）アクリル酸誘導体
と略記する）、及びこれを主成分とするラセミ化合物あ
るいは構造異性体混合物を分離するための分離剤を提供
するものである。That is, in the present invention, 50% to 100% of the hydrogen atoms of the hydroxyl group and the amino group are represented by the following general formula (1).
, (2), (3) or (4) A polyacrylic acid or methacrylic acid derivative (hereinafter abbreviated as poly(meth)acrylic acid derivative) having a sugar derivative substituted with a group represented by the following in its side chain, and this The object of the present invention is to provide a separating agent for separating racemic compounds or structural isomer mixtures having as main components.
【０００５】[0005]
【化３】[Chemical formula 3]
【０００６】〔式中、Ｑ はヘテロ原子を含んでいても
よい芳香族炭化水素基であり、非置換であっても、また
は炭素数１〜１２のアルキル、炭素数１〜１２のアルコ
キシ、炭素数１〜１２のアルキルチオ、シアノ、ハロゲ
ン、炭素数１〜８のアシル、炭素数１〜８のアシルオキ
シ、ヒドロキシ、炭素数１〜１２のアルコキシカルボニ
ル、ニトロ、およびジ（炭素数１〜８のアルキル）アミ
ノからなる群の１つ以上の基によって置換されていても
よい。Ｘ は炭素数１〜４の炭化水素基であり、二重結
合あるいは三重結合を含んでいても良い。〕
Ｑ で示されるヘテロ原子を含んでいてもよい芳香族炭
化水素基を例示するならば、フェニル、ナフチル、フェ
ナントリル、アントラシル、インデニル、インダニル、
フリル、チオニル、ピリル、ベンゾフリル、ベンズチオ
ニル、インジル、ピリジル、ピリミジル、キノリル及び
イソキノリルなどの基が挙げられる。特に好ましいのは
フェニル基、ナフチル基、ピリジル基である。[In the formula, Q is an aromatic hydrocarbon group which may contain a heteroatom, even if unsubstituted, or alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, carbon Alkylthio having 1 to 12 carbon atoms, cyano, halogen, acyl having 1 to 8 carbon atoms, acyloxy having 1 to 8 carbon atoms, hydroxy, alkoxycarbonyl having 1 to 12 carbon atoms, nitro, and di(alkyl having 1 to 8 carbon atoms) ) may be substituted by one or more groups of the group consisting of amino. X is a hydrocarbon group having 1 to 4 carbon atoms, and may contain a double bond or triple bond. ] Examples of the aromatic hydrocarbon group which may contain a heteroatom represented by Q include phenyl, naphthyl, phenanthryl, anthracyl, indenyl, indanyl,
Groups such as furyl, thionyl, pyryl, benzofuryl, benzthionyl, indyl, pyridyl, pyrimidyl, quinolyl and isoquinolyl may be mentioned. Particularly preferred are phenyl, naphthyl, and pyridyl groups.
【０００７】Ｘ で示される炭素数１〜４の炭化水素基
を例示すれば、メチレン、エチレン、エチリデン、エテ
ニレン、エチニレン、１，２ −または１，３ −プロ
ピレン、１，１ −または２，２ −プロピリデンなど
の基である。Examples of the hydrocarbon group represented by X having 1 to 4 carbon atoms include methylene, ethylene, ethylidene, ethenylene, ethynylene, 1,2- or 1,3-propylene, 1,1- or 2,2 - a group such as propylidene.
【０００８】本発明において、特に好ましいポリ（メタ
）アクリル酸誘導体としては、下記一般式（５） で示
される繰り返し単位よりなるものである。In the present invention, particularly preferred poly(meth)acrylic acid derivatives are those consisting of repeating units represented by the following general formula (5).
【０００９】[0009]
【化４】[C4]
【００１０】（式中、Ｙ は水素原子もしくはメチル基
、Ｚ は酸素原子、硫黄原子もしくは２級アミノ基、Ｒ
は炭素数１〜１０の炭化水素基であり、ヘテロ原子を
含んでいても良い。Ａ は水酸基及びアミノ基の水素原
子の５０％ないし １００％が上記一般式（１） 、（
２） 、（３） あるいは（４） で示される基で置換
された糖誘導体、ａ は０又は１、ｂは０又は１、ｎは
重合度を示し２〜１００００ 、好ましくは５〜５００
０の範囲の数である。）
糖誘導体のポリ（メタ）アクリル酸との結合様式として
は、エーテル、チオエーテル、アミド及びエステル等が
有り、糖の結合部位としてはＣ１〜Ｃ６炭素に結合する
官能基のいずれであっても良い。(In the formula, Y is a hydrogen atom or a methyl group, Z is an oxygen atom, a sulfur atom or a secondary amino group, R
is a hydrocarbon group having 1 to 10 carbon atoms, and may contain a hetero atom. A represents the above general formula (1) in which 50% to 100% of the hydrogen atoms of the hydroxyl group and amino group are represented by the above general formula (1), (
2), (3) or (4) A sugar derivative substituted with a group represented by the following, where a is 0 or 1, b is 0 or 1, and n represents the degree of polymerization, from 2 to 10,000, preferably from 5 to 500.
It is a number in the range 0. ) The bonding mode of sugar derivatives with poly(meth)acrylic acid includes ether, thioether, amide, ester, etc., and the bonding site of sugar may be any functional group bonded to C1 to C6 carbon. .
【００１１】本発明によるポリ（メタ）アクリル酸誘導
体の合成法としては、糖を側鎖に持つ（メタ）アクリル
酸モノマーを重合した後、糖の水酸基あるいはアミノ基
に酸クロライドもしくはイソシアネートを反応させる方
法、或いは、糖を側鎖に持つ（メタ）アクリル酸モノマ
ーの糖の水酸基あるいはアミノ基を、酸クロライドもし
くはイソシアネートで反応させた後、重合する方法があ
る。The method for synthesizing poly(meth)acrylic acid derivatives according to the present invention involves polymerizing (meth)acrylic acid monomers having sugars in their side chains, and then reacting acid chloride or isocyanate with the hydroxyl groups or amino groups of the sugars. Alternatively, there is a method in which the hydroxyl group or amino group of the sugar of a (meth)acrylic acid monomer having sugar as a side chain is reacted with acid chloride or isocyanate, and then polymerized.
【００１２】本発明における糖とは、天然糖、天然物変
性糖及び合成糖、また単糖及びオリゴ糖いずれかを問わ
ず、光学活性であればいかなるものでも良い。単糖を例
示すれば、Ｄ−アロース、Ｄ−アルトロース、Ｄ−ガラ
クトース、Ｄ−グルコース、Ｄ−グロース、Ｄ−イドー
ス、Ｄ−マンノース、Ｄ−タロース、Ｄ−アラビノース
、Ｌ−リキソース、Ｄ−リボース、Ｄ−キシロース、Ｄ
−フルクトース、Ｄ−プシコース、Ｌ−ソルボース、Ｄ
−タガレース、Ｄ−グルコサミン、Ｌ−ラムノース、Ｌ
−フコース、Ｄ−フコース、Ｄ−グルクロン酸、Ｄ−ガ
ラクトロン酸、Ｄ−ガラクツロン酸などがある。[0012] The sugar in the present invention may be any optically active sugar, regardless of whether it is a natural sugar, a natural modified sugar, a synthetic sugar, a monosaccharide or an oligosaccharide. Examples of monosaccharides include D-allose, D-altrose, D-galactose, D-glucose, D-gulose, D-idose, D-mannose, D-talose, D-arabinose, L-lyxose, D- Ribose, D-xylose, D
-fructose, D-psicose, L-sorbose, D
-tagarace, D-glucosamine, L-rhamnose, L
-fucose, D-fucose, D-glucuronic acid, D-galactronic acid, D-galacturonic acid, etc.
【００１３】本発明のポリ（メタ）アクリル酸誘導体は
、機能材料として極めて有用な物質であり、特に光学分
割用充填剤として有用なものである。The poly(meth)acrylic acid derivative of the present invention is an extremely useful substance as a functional material, and is particularly useful as a filler for optical resolution.
【００１４】本発明のポリ（メタ）アクリル酸誘導体を
分離剤として、ラセミ化合物や構造異性体の混合物を分
離する目的に使用するには、本発明のポリ（メタ）アク
リル酸誘導体を充填したガスクロマトグラフィー、液体
クロマトグラフィー、薄層クロマトグラフィーなどのク
ロマトグラフィー法を用いるのが一般的であるが、この
他、本発明のポリ（メタ）アクリル誘導体を含む膜を成
形し、これで膜分離を行うこともできる。In order to use the poly(meth)acrylic acid derivative of the present invention as a separating agent for the purpose of separating racemic compounds and mixtures of structural isomers, a gas filled with the poly(meth)acrylic acid derivative of the present invention is used. Although chromatography methods such as chromatography, liquid chromatography, and thin layer chromatography are generally used, it is also possible to form a membrane containing the poly(meth)acrylic derivative of the present invention and use it to perform membrane separation. You can also do this.
【００１５】本発明のポリ（メタ）アクリル酸誘導体を
分離剤として液体クロマトグラフィー法に応用するには
、その粉体としてカラムに充填する方法が簡便である。
この際、本発明のポリ（メタ）アクリル酸誘導体を粉砕
するか、ビーズ状にすることが好ましく、粒子は多孔質
であってもよい。更に、分離剤の耐圧能力の向上、溶媒
置換による膨潤、収縮の防止、理論段数の向上のために
ポリ（メタ）アクリル酸誘導体を担体に結合あるいは担
持させることも好ましい。[0015] In order to apply the poly(meth)acrylic acid derivative of the present invention as a separation agent to liquid chromatography, it is convenient to fill the powder into a column. At this time, it is preferable to crush the poly(meth)acrylic acid derivative of the present invention or form it into beads, and the particles may be porous. Furthermore, in order to improve the pressure resistance of the separating agent, prevent swelling and shrinkage due to solvent substitution, and increase the number of theoretical plates, it is also preferable to bind or support a poly(meth)acrylic acid derivative on a carrier.
【００１６】粉体として用いる場合の粒子の大きさ及び
担体の大きさは使用するカラムの大きさによって異なる
が、１μｍ 〜１ｍｍであり、好ましくは５μｍ 〜
３００μｍ である。担体は多孔質であることが好まし
く、細孔径は１０Å〜 １００μｍ であり、好ましく
は５０Å〜５００００ Åである。担体に担持させるポ
リ（メタ）アクリル酸誘導体の量は担体に対して１〜
１００重量％、好ましくは５〜５０重量％である。[0016] When used as a powder, the size of the particles and the size of the carrier vary depending on the size of the column used, but are 1 μm to 1 mm, preferably 5 μm to 1 mm.
It is 300 μm. The carrier is preferably porous, with a pore diameter of 10 Å to 100 μm, preferably 50 Å to 50,000 Å. The amount of poly(meth)acrylic acid derivative supported on the carrier is 1 to
100% by weight, preferably 5-50% by weight.
【００１７】ポリ（メタ）アクリル酸誘導体を担体に担
持させる方法は化学的方法でも物理的方法でもよい。物
理的方法としては、ポリ（メタ）アクリル酸誘導体を可
溶性の溶剤に溶解させ、担体と良く混合し、減圧又は加
温下、気流により溶剤を留去させる方法や、ポリ（メタ
）アクリル酸誘導体を可溶性の溶剤に溶解させ、担体と
良く混合した後、ポリ（メタ）アクリル酸誘導体に対し
不溶性の溶剤に分散させることによって可溶性溶剤を拡
散させてしまう方法もある。化学的方法としては、担体
に二重結合を持つ基を導入し、（メタ）アクリル酸誘導
体モノマーを共重合させる方法がある。The method for supporting the poly(meth)acrylic acid derivative on the carrier may be either a chemical method or a physical method. Physical methods include dissolving the poly(meth)acrylic acid derivative in a soluble solvent, mixing well with the carrier, and distilling off the solvent with an air stream under reduced pressure or heating; There is also a method in which the poly(meth)acrylic acid derivative is dissolved in a soluble solvent, thoroughly mixed with a carrier, and then dispersed in a solvent insoluble to the poly(meth)acrylic acid derivative, thereby diffusing the soluble solvent. As a chemical method, there is a method in which a group having a double bond is introduced into a carrier and a (meth)acrylic acid derivative monomer is copolymerized.
【００１８】用いる担体としては多孔質有機担体又は多
孔質無機担体がある。多孔質有機担体としては、ポリス
チレン、ポリアクリルアミド、ポリアクリレート等から
なる高分子物質が挙げられる。多孔質無機担体として適
当なものは、シリカ、アルミナ、ジルコニア、マグネシ
ア、ガラス、カオリン、酸化チタン、ケイ酸塩等である
。これら担体の表面は、ポリ（メタ）アクリル酸誘導体
との親和性を良くするため、（メタ）アクリル酸誘導体
モノマーと反応させるため、また担体自身の表面を改質
するために処理を施したものを用いてもよい。The carrier used may be a porous organic carrier or a porous inorganic carrier. Examples of the porous organic carrier include polymeric substances such as polystyrene, polyacrylamide, and polyacrylate. Suitable porous inorganic carriers include silica, alumina, zirconia, magnesia, glass, kaolin, titanium oxide, silicates, and the like. The surface of these carriers has been treated to improve affinity with poly(meth)acrylic acid derivatives, to react with (meth)acrylic acid derivative monomers, and to modify the surface of the carrier itself. may also be used.
【００１９】本発明のポリ（メタ）アクリル酸誘導体を
分離膜として応用するには、ポリ（メタ）アクリル酸誘
導体単独、あるいは他の基材に複合もしくはコーティン
グし、中空糸あるいはフィルムとして用いる方法がある
。In order to apply the poly(meth)acrylic acid derivative of the present invention as a separation membrane, it is possible to use the poly(meth)acrylic acid derivative alone, or to combine or coat it onto other substrates and use it as a hollow fiber or film. be.
【００２０】[0020]
【実施例】以下に本発明を実施例によって記述するが、
本発明は、これらの実施例に限定されるものではない。[Example] The present invention will be described below by way of example.
The present invention is not limited to these examples.
【００２１】実施例１
ポリグルコシルエチルメタクリレート〔日本精化（株）
製、重合度ｎ＝１９００〕１ｇをピリジン５０ｍｌに入
れ、２時間還流させる。温度を １１５℃に下げた後、
４−ジメチルアミノピリジン０．４２ｇ、さらにｐ−メ
チルベンゾイルクロリド５．２９ｇを加え５５時間反応
させた。これをメタノール１リットル中へ注ぎ込み、生
成した沈澱を濾別し真空乾燥した。Example 1 Polyglucosylethyl methacrylate [Nippon Fine Chemical Co., Ltd.]
(manufactured by Nippon Steel, Inc., polymerization degree n=1900) was added to 50 ml of pyridine, and the mixture was refluxed for 2 hours. After lowering the temperature to 115℃,
0.42 g of 4-dimethylaminopyridine and further 5.29 g of p-methylbenzoyl chloride were added and reacted for 55 hours. This was poured into 1 liter of methanol, and the resulting precipitate was filtered off and dried under vacuum.
【００２２】得られたポリマーの収量は１．８６ｇ（収
率７１．１％）、比旋光度〔α〕５８９ ＝＋３５．８
であった。以下に得られたポリマーの構造式（６） 及
び元素分析値を示す。また、図１には、そのＩＲスペク
トルを示す。尚、ＩＲの測定は日本分光（株）製ＩＲ−
８１０ を使用した。The yield of the obtained polymer was 1.86 g (yield 71.1%), specific optical rotation [α] 589 = +35.8
Met. The structural formula (6) and elemental analysis values of the obtained polymer are shown below. Moreover, FIG. 1 shows its IR spectrum. In addition, the IR measurement was performed using an IR-
810 was used.
【００２３】[0023]
【化５】[C5]
【００２４】
元素分析
実測値 Ｃ ：６８．３５ Ｈ ：
５．７８ Ｎ ： ０．１５ （ｗ
ｔ％） 計算値 Ｃ ：６９．１０
Ｈ ： ５．８０ Ｎ ： ０．００
（ｗｔ％）実施例２
ポリグルコシルエチルメタクリレート〔日本精化（株）
製、重合度ｎ＝１９００〕１ｇをピリジン５０ｍｌに入
れ、２時間還流させる。温度を １００℃に下げた後、
３，５−ジメチルフェニルイソシアネート５．０３ｇを
加え３２時間反応させた。これをメタノール１リットル
中へ注ぎ込み、生成した沈澱を濾別し真空乾燥した。Elemental analysis Actual value C: 68.35 H:
5.78 N: 0.15 (w
t%) Calculated value C: 69.10
H: 5.80 N: 0.00
(wt%) Example 2 Polyglucosylethyl methacrylate [Nippon Fine Chemical Co., Ltd.]
(manufactured by Nippon Steel, Inc., polymerization degree n=1900) was added to 50 ml of pyridine, and the mixture was refluxed for 2 hours. After lowering the temperature to 100℃,
5.03 g of 3,5-dimethylphenylisocyanate was added and reacted for 32 hours. This was poured into 1 liter of methanol, and the resulting precipitate was filtered off and dried under vacuum.
【００２５】得られたポリマーの収量は２．４６ｇ（収
率８１．７％）、比旋光度〔α〕５８９ ＝＋４９．６
であった。以下に得られたポリマーの構造式（７） 及
び元素分析値を示す。また、図２には、そのＩＲスペク
トルを示す。尚、ＩＲの測定は日本分光（株）製ＩＲ−
８１０ を使用した。The yield of the obtained polymer was 2.46 g (yield 81.7%), specific optical rotation [α] 589 = +49.6
Met. The structural formula (7) and elemental analysis values of the obtained polymer are shown below. Moreover, FIG. 2 shows its IR spectrum. In addition, the IR measurement was performed using an IR-
810 was used.
【００２６】[0026]
【化６】[C6]
【００２７】
元素分析
実測値 Ｃ ：６５．２２ Ｈ ：
６．３９ Ｎ ： ６．４７ （ｗ
ｔ％） 計算値 Ｃ ：６５．４９
Ｈ ： ６．６４ Ｎ ： ６．３６
（ｗｔ％）実施例３
実施例２で得られたポリマー１ｇをテトラヒドロフラン
２０ｍｌに溶かした後、シリカゲル（７μｍ）４ｇに浸
漬し、減圧することにより溶剤を留去した。得られた担
体を内径４．６ｍｍ 、長さ２５０ｍｍ のカラムに充
填した。表１に液体クロマトグラフィーとして用いた結
果を示す。Elemental analysis Actual value C: 65.22 H:
6.39 N: 6.47 (w
t%) Calculated value C: 65.49
H: 6.64 N: 6.36
(wt%) Example 3 After 1 g of the polymer obtained in Example 2 was dissolved in 20 ml of tetrahydrofuran, it was immersed in 4 g of silica gel (7 μm), and the solvent was distilled off by reducing the pressure. The obtained carrier was packed into a column having an inner diameter of 4.6 mm and a length of 250 mm. Table 1 shows the results of use in liquid chromatography.
【００２８】[0028]
【表１】[Table 1]
【００２９】測定条件
移動相 ヘキサン／２−プロパノール＝ １００／０
．１流 速 １．０ｍｌ ／ｍｉｎ
温 度 室温
検 出 ＵＶ（２５４ｎｍ）
なお、測定には日本分光（株）製液体クロマトグラフィ
ー装置（８８０−ＰＵポンプ、８７５−ＵＶ検出器）を
用いた。また表中の容量比（ｋ１’） 、分離係数（α
）は、それぞれ下式により定義される。Measurement conditions Mobile phase Hexane/2-propanol = 100/0
．． Flow rate 1.0 ml/min Temperature Room temperature detection UV (254 nm) A liquid chromatography device manufactured by JASCO Corporation (880-PU pump, 875-UV detector) was used for the measurement. In addition, the capacity ratio (k1') and separation coefficient (α
) are respectively defined by the following formulas.
【００３０】[0030]
【数１】[Math 1]
【００３１】実施例４
脱水したグルコシルエチルメタクリレートモノマー〔日
本精化（株）製〕５０ｇを脱水ジメチルホルムアミド（
以下ＤＭＦと略記する）に溶かし、室温で撹拌しながら
３，５−ジメチルフェニルイソシアネート ２００ｍ
ｌを加え１２時間反応させた。これをメタノール１リッ
トル中へ注ぎ込み、得られた沈澱を濾別して除き、濾液
に水 ５００ｍｌを加え、生成した沈澱を濾別・真空乾
燥した。Example 4 50 g of dehydrated glucosylethyl methacrylate monomer (manufactured by Nippon Fine Chemical Co., Ltd.) was mixed with dehydrated dimethylformamide (
3,5-dimethylphenylisocyanate 200m while stirring at room temperature.
1 was added and reacted for 12 hours. This was poured into 1 liter of methanol, the resulting precipitate was removed by filtration, 500 ml of water was added to the filtrate, and the resulting precipitate was filtered and vacuum dried.
【００３２】以下に得られたモノマーの構造式（８）
および元素分析値を示す。Structural formula (8) of the monomer obtained below
and elemental analysis values.
【００３３】[0033]
【化７】[C7]
【００３４】
元素分析
実測値 Ｃ ：６５．９５ Ｈ ：
６．３５ Ｎ ： ７．５６ （ｗ
ｔ％） 計算値 Ｃ ：６５．４９
Ｈ ： ６．６４ Ｎ ： ６．３６
（ｗｔ％） 得られたモノマー５ｇをＤＭＦ５ｍｌ
中に溶かし、窒素気流下２，２’−アゾビス（２，４
−ジメチルバレロニトリル）〔和光純薬（株）製〕０．
０２ｇを加え温度を室温から １００℃まで徐々に上昇
させ２０時間反応させ、０．０５ｇのカテコールを加え
て反応を停止させた。これをメタノール５００ｍｌ 中
へ注ぎ込み、生成した沈澱を濾別し、真空乾燥した。得
られたポリマーは収量１．８３ｇ（収率３６．６％）、
比旋光度〔α〕５８９ ＝＋３８．３であった。Elemental analysis Actual value C: 65.95 H:
6.35 N: 7.56 (w
t%) Calculated value C: 65.49
H: 6.64 N: 6.36
(wt%) 5 g of the obtained monomer was added to 5 ml of DMF.
2,2'-Azobis(2,4
-dimethylvaleronitrile) [manufactured by Wako Pure Chemical Industries, Ltd.] 0.
The temperature was gradually raised from room temperature to 100°C and the reaction was continued for 20 hours, and the reaction was stopped by adding 0.05 g of catechol. This was poured into 500 ml of methanol, and the resulting precipitate was filtered off and dried under vacuum. The yield of the obtained polymer was 1.83 g (yield 36.6%),
The specific optical rotation [α] was 589 = +38.3.
【００３５】以下に得られたポリマーの構造式（９）
及び元素分析値を示す。また、図３には、そのＩＲスペ
クトルを示す。尚、ＩＲの測定は日本分光（株）製ＩＲ
−８１０ を使用した。Structural formula (9) of the polymer obtained below
and elemental analysis values. Moreover, FIG. 3 shows its IR spectrum. In addition, the IR measurement was performed using an IR manufactured by JASCO Corporation.
-810 was used.
【００３６】[0036]
【化８】[Chemical formula 8]
【００３７】
元素分析
実測値 Ｃ ：６５．２０ Ｈ ：
６．４５ Ｎ ： ６．７１ （ｗ
ｔ％） 計算値 Ｃ ：６５．４９
Ｈ ： ６．６４ Ｎ ： ６．３６
（ｗｔ％）実施例５
実施例４で得られたポリマー１ｇをアセトン／テトラヒ
ドロフラン／Ｎ，Ｎ −ジメチルアセトアミド＝５／５
／２（容量比）溶液２０ｍｌに溶かした後、シリカゲル
（７μｍ）４ｇに浸漬し、減圧することにより溶剤を留
去した。得られた担体を内径４．６ｍｍ 、長さ２５０
ｍｍ のカラムに充填した。表２に液体クロマトグラフ
ィーとして用いた結果を示す。Elemental analysis Actual value C: 65.20 H:
6.45 N: 6.71 (w
t%) Calculated value C: 65.49
H: 6.64 N: 6.36
(wt%) Example 5 1 g of the polymer obtained in Example 4 was mixed with acetone/tetrahydrofuran/N,N-dimethylacetamide=5/5.
After dissolving in 20 ml of /2 (volume ratio) solution, the mixture was immersed in 4 g of silica gel (7 μm), and the solvent was distilled off under reduced pressure. The obtained carrier had an inner diameter of 4.6 mm and a length of 250 mm.
Packed into a mm column. Table 2 shows the results of use in liquid chromatography.
【００３８】[0038]
【表２】[Table 2]
【００３９】測定条件
移動相 ヘキサン／２−プロパノール＝ １００／０
．１流 速 １．０ｍｌ ／ｍｉｎ
温 度 室温
検 出 ＵＶ（２５４ｎｍ）
なお、測定には日本分光（株）製液体クロマトグラフィ
ー装置（８８０−ＰＵポンプ、８７５−ＵＶ検出器）を
用いた。Measurement conditions Mobile phase Hexane/2-propanol = 100/0
．． Flow rate 1.0 ml/min Temperature Room temperature detection UV (254 nm) A liquid chromatography device manufactured by JASCO Corporation (880-PU pump, 875-UV detector) was used for the measurement.
【００４０】実施例６
シリカゲル（７μｍ）１０ｇを乾燥トルエン中に入れ撹
拌しながらメタクリル酸トリメトキシシリルプロピルエ
ステル１０ｍｌを加え、８０℃で２時間反応させる。得
られたシリカゲルをトルエン、ヘキサンで洗浄して真空
乾燥させた。下記元素分析より固定量は、０．０３７ｍ
ｍｏｌ ／ｇであった。Example 6 10 g of silica gel (7 μm) was placed in dry toluene, 10 ml of trimethoxysilylpropyl methacrylate was added with stirring, and the mixture was reacted at 80° C. for 2 hours. The obtained silica gel was washed with toluene and hexane and dried under vacuum. From the elemental analysis below, the fixed amount is 0.037m
It was mol/g.
【００４１】以下に得られたシリカゲル誘導体の元素分
析値を示す。
元素分析
実測値 Ｃ ： ０．４４ Ｈ ：
０．０８ Ｎ ： ０．００ （ｗ
ｔ％） 得られたシリカゲル誘導体４．５ ｇ及び実
施例４の構造式（８） で示されるモノマー１３．５ｇ
を乾燥ＤＭＦ１３．５ｍｌに溶かす。これに窒素気流下
２，２’−アゾビス（２，４−ジメチルバレロニトリル
）〔和光純薬（株）製〕０．０５ｇを乾燥ＤＭＦ１ｍｌ
中に溶かして注入し、温度を室温から １００℃まで徐
々に上げ１５時間後、カテコール０．１ ｇをＤＭＦ１
ｍｌに溶かして注入して反応を停止させた。得られたシ
リカゲルを濾別し、ＤＭＦ、アセトン、エタノールで洗
浄し真空乾燥した。下記元素分析よりポリマーの固定量
は、２６．４ｍｇ／ｇであった。The elemental analysis values of the obtained silica gel derivative are shown below. Elemental analysis Actual value C: 0.44 H:
0.08 N: 0.00 (w
t%) 4.5 g of the obtained silica gel derivative and 13.5 g of the monomer represented by the structural formula (8) of Example 4
Dissolve in 13.5 ml of dry DMF. To this, under a nitrogen stream, 0.05 g of 2,2'-azobis(2,4-dimethylvaleronitrile) [manufactured by Wako Pure Chemical Industries, Ltd.] was added to 1 ml of dry DMF.
After 15 hours, 0.1 g of catechol was poured into DMF1.
The reaction was stopped by dissolving the solution in 1 ml and injecting it. The obtained silica gel was filtered, washed with DMF, acetone, and ethanol, and dried under vacuum. According to the elemental analysis described below, the amount of polymer immobilized was 26.4 mg/g.
【００４２】以下に得られたシリカゲル誘導体の元素分
析値を示す。
元素分析
実測値 Ｃ ： ２．１６ Ｈ ：
０．２４ Ｎ ： ０．１４ （ｗ
ｔ％）The elemental analysis values of the obtained silica gel derivative are shown below. Elemental analysis Actual value C: 2.16 H:
0.24 N: 0.14 (w
t%)
【図１】実施例１で得られたポリマーのＩＲスペクトル
である。FIG. 1 is an IR spectrum of the polymer obtained in Example 1.
【図２】実施例２で得られたポリマーのＩＲスペクトル
である。FIG. 2 is an IR spectrum of the polymer obtained in Example 2.
【図３】実施例４で得られたポリマーのＩＲスペクトル
である。FIG. 3 is an IR spectrum of the polymer obtained in Example 4.
Claims (3)
％ないし １００％が下記一般式（１） 、（２） 、
（３） あるいは（４） で示される基で置換された糖
誘導体を側鎖に持つポリアクリル酸又はメタクリル酸誘
導体。 【化１】 〔式中、Ｑ はヘテロ原子を含んでいてもよい芳香族炭
化水素基であり、非置換であっても、または炭素数１〜
１２のアルキル、炭素数１〜１２のアルコキシ、炭素数
１〜１２のアルキルチオ、シアノ、ハロゲン、炭素数１
〜８のアシル、炭素数１〜８のアシルオキシ、ヒドロキ
シ、炭素数１〜１２のアルコキシカルボニル、ニトロ、
およびジ（炭素数１〜８のアルキル）アミノからなる群
の１つ以上の基によって置換されていてもよい。Ｘ は
炭素数１〜４の炭化水素基であり、二重結合あるいは三
重結合を含んでいても良い。〕Claim 1: 50 hydrogen atoms of hydroxyl group and amino group
% to 100% is the following general formula (1), (2),
(3) Or (4) A polyacrylic acid or methacrylic acid derivative having a sugar derivative substituted with the group shown in the following in its side chain. [Formula 1] [In the formula, Q is an aromatic hydrocarbon group which may contain a hetero atom, even if it is unsubstituted, or has 1 to 1 carbon atoms.
12 alkyl, alkoxy having 1 to 12 carbon atoms, alkylthio having 1 to 12 carbon atoms, cyano, halogen, 1 carbon number
-8 acyl, C1-8 acyloxy, hydroxy, C1-12 alkoxycarbonyl, nitro,
and di(C1-C8 alkyl)amino. X is a hydrocarbon group having 1 to 4 carbon atoms, and may contain a double bond or triple bond. ]
し単位よりなるポリアクリル酸又はメタクリル酸誘導体
。 【化２】 （式中、Ｙ は水素原子もしくはメチル基、Ｚ は酸素
原子、硫黄原子もしくは２級アミノ基、Ｒ は炭素数１
〜１０の炭化水素基であり、ヘテロ原子を含んでいても
良い。 Ａ は請求項１記載の糖誘導体、ａ は０又は１、ｂ
は０又は１、ｎは重合度を示し２〜１００００ の範囲
の数である。）2. A polyacrylic acid or methacrylic acid derivative comprising a repeating unit represented by the following general formula (5). [Formula 2] (wherein, Y is a hydrogen atom or a methyl group, Z is an oxygen atom, a sulfur atom, or a secondary amino group, and R is a carbon number of 1
~10 hydrocarbon groups and may contain heteroatoms. A is the sugar derivative according to claim 1, a is 0 or 1, b
is 0 or 1, and n indicates the degree of polymerization and is a number in the range of 2 to 10,000. )
又はメタクリル酸誘導体を主成分とするラセミ化合物あ
るいは構造異性体混合物を分離するための分離剤。3. A separating agent for separating a racemic compound or a mixture of structural isomers containing the polyacrylic acid or methacrylic acid derivative according to claim 1 or 2 as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3082303A JPH04314710A (en) | 1991-04-15 | 1991-04-15 | New polymer having sugar derivative group in side chain and separating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3082303A JPH04314710A (en) | 1991-04-15 | 1991-04-15 | New polymer having sugar derivative group in side chain and separating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04314710A true JPH04314710A (en) | 1992-11-05 |
Family
ID=13770787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3082303A Pending JPH04314710A (en) | 1991-04-15 | 1991-04-15 | New polymer having sugar derivative group in side chain and separating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04314710A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995000463A1 (en) * | 1993-06-22 | 1995-01-05 | Daicel Chemical Industries, Ltd. | Optical isomer separating agent and process for producing the same |
| US5693768A (en) * | 1994-02-15 | 1997-12-02 | Ciba Vision Corporation | Unsaturated carbohydrate derivatives polymers thereof and their use |
| CN110658264A (en) * | 2018-06-28 | 2020-01-07 | 成都中医药大学 | Quality detection method of nine-process sealwort |
-
1991
- 1991-04-15 JP JP3082303A patent/JPH04314710A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995000463A1 (en) * | 1993-06-22 | 1995-01-05 | Daicel Chemical Industries, Ltd. | Optical isomer separating agent and process for producing the same |
| US5587467A (en) * | 1993-06-22 | 1996-12-24 | Daicel Chemical Industries, Ltd. | Separating agent for optical isomers and process for producing the same |
| US5693768A (en) * | 1994-02-15 | 1997-12-02 | Ciba Vision Corporation | Unsaturated carbohydrate derivatives polymers thereof and their use |
| US5856416A (en) * | 1994-02-15 | 1999-01-05 | Ciba Vision Corporation | Unsaturated carbohydrate derivatives polymers thereof and their use |
| CN110658264A (en) * | 2018-06-28 | 2020-01-07 | 成都中医药大学 | Quality detection method of nine-process sealwort |
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