JPS62267663A - Packing material for liquid chromatography and its production - Google Patents
Packing material for liquid chromatography and its productionInfo
- Publication number
- JPS62267663A JPS62267663A JP61110624A JP11062486A JPS62267663A JP S62267663 A JPS62267663 A JP S62267663A JP 61110624 A JP61110624 A JP 61110624A JP 11062486 A JP11062486 A JP 11062486A JP S62267663 A JPS62267663 A JP S62267663A
- Authority
- JP
- Japan
- Prior art keywords
- group
- gel
- copolymer
- glycidyl
- ether
- 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
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000012856 packing Methods 0.000 title claims abstract description 25
- 238000004811 liquid chromatography Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 52
- -1 alkylene glycol divinyl ester Chemical class 0.000 claims abstract description 39
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 21
- 230000002209 hydrophobic effect Effects 0.000 abstract description 21
- 238000007142 ring opening reaction Methods 0.000 abstract description 15
- 238000004587 chromatography analysis Methods 0.000 abstract description 13
- 230000004048 modification Effects 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 12
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 11
- 239000003085 diluting agent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 239000013076 target substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000012064 sodium phosphate buffer Substances 0.000 description 3
- ACBFXJILDVSGGU-UHFFFAOYSA-N 2-(2-butoxyethoxymethyl)oxirane Chemical compound CCCCOCCOCC1CO1 ACBFXJILDVSGGU-UHFFFAOYSA-N 0.000 description 2
- HFFOOQRTMDCKIB-UHFFFAOYSA-N 2-(2-phenoxyethoxymethyl)oxirane Chemical compound C1OC1COCCOC1=CC=CC=C1 HFFOOQRTMDCKIB-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000019265 Cytochrome c1 Human genes 0.000 description 2
- 108010007528 Cytochromes c1 Proteins 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 102000036675 Myoglobin Human genes 0.000 description 2
- 108010062374 Myoglobin Proteins 0.000 description 2
- 108010058846 Ovalbumin Proteins 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N alpha-naphthol Natural products C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229940092253 ovalbumin Drugs 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- AZLWQVJVINEILY-UHFFFAOYSA-N 2-(2-dodecoxyethoxy)ethanol Chemical compound CCCCCCCCCCCCOCCOCCO AZLWQVJVINEILY-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- ZXJBWUAALADCRI-UHFFFAOYSA-N 2-(octadecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCCCCCOCC1CO1 ZXJBWUAALADCRI-UHFFFAOYSA-N 0.000 description 1
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- FKMHSNTVILORFA-UHFFFAOYSA-N 2-[2-(2-dodecoxyethoxy)ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCO FKMHSNTVILORFA-UHFFFAOYSA-N 0.000 description 1
- IDHKBOHEOJFNNS-UHFFFAOYSA-N 2-[2-(2-phenoxyethoxy)ethoxy]ethanol Chemical compound OCCOCCOCCOC1=CC=CC=C1 IDHKBOHEOJFNNS-UHFFFAOYSA-N 0.000 description 1
- OOFVRUOEWPNSRH-UHFFFAOYSA-N 2-[2-(2-phenoxyethoxy)ethoxymethyl]oxirane Chemical compound C=1C=CC=CC=1OCCOCCOCC1CO1 OOFVRUOEWPNSRH-UHFFFAOYSA-N 0.000 description 1
- RGRVGOMPHMWMJX-UHFFFAOYSA-N 2-[2-[2-(2-phenoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound OCCOCCOCCOCCOC1=CC=CC=C1 RGRVGOMPHMWMJX-UHFFFAOYSA-N 0.000 description 1
- OJCFEGKCRWEVSN-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCO OJCFEGKCRWEVSN-UHFFFAOYSA-N 0.000 description 1
- ALGGDNFSFCRLCR-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-phenoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCCOCCOCCOC1=CC=CC=C1 ALGGDNFSFCRLCR-UHFFFAOYSA-N 0.000 description 1
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 1
- LDZLXQFDGRCELX-UHFFFAOYSA-N 4-phenylbutan-1-ol Chemical compound OCCCCC1=CC=CC=C1 LDZLXQFDGRCELX-UHFFFAOYSA-N 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 108010038061 Chymotrypsinogen Proteins 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 102000016943 Muramidase Human genes 0.000 description 1
- 108010014251 Muramidase Proteins 0.000 description 1
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 101710163270 Nuclease Proteins 0.000 description 1
- 102000006382 Ribonucleases Human genes 0.000 description 1
- 108010083644 Ribonucleases Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 108010027597 alpha-chymotrypsin Proteins 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 229960002376 chymotrypsin Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical group O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004325 lysozyme Substances 0.000 description 1
- 229960000274 lysozyme Drugs 0.000 description 1
- 235000010335 lysozyme Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- YYELLDKEOUKVIQ-UHFFFAOYSA-N octaethyleneglycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCO YYELLDKEOUKVIQ-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は液体クロマトグラフィー、特に疎水性クロマト
グラフィーに利用することのできるクロマトグラフィー
用充填剤及び該クロマトグラフィー用充填剤の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a chromatography packing material that can be used in liquid chromatography, particularly hydrophobic chromatography, and a method for producing the chromatography packing material.
従来の技術
クロマトグラフィーの技術として疎水性クロマトグラフ
ィーは、例えば蛋白質、核酸、酵緊等の生体高分子の有
する疎水的性質を利用して充填剤との疎水性相互作用に
よシ分離精製を行なうものであるが、疎水性クロマトグ
ラフィー用充填剤に望まれる性質としては、非特異的吸
着が少ないこと、高い多孔性を有すること、化学的に安
定で一城、塩濃度、温度の広範な条件下で十分安定であ
シ体積変化がないこと、十分な機械的強度と安定性を有
し流動特性が良いこと、生物学的汚染に４えること、な
どがあげられる。Conventional technology Hydrophobic chromatography is a chromatography technique that utilizes the hydrophobic properties of biopolymers such as proteins, nucleic acids, and enzymes to perform separation and purification through hydrophobic interactions with packing materials. However, the desirable properties of a hydrophobic chromatography packing material include low nonspecific adsorption, high porosity, chemical stability, and compatibility with a wide range of salt concentration and temperature conditions. The characteristics include that it is sufficiently stable under low temperatures and does not undergo any volume change, that it has sufficient mechanical strength and stability, that it has good flow characteristics, and that it is resistant to biological contamination.
従来よυ疎水性クロマトグラフィー用充填剤の基材とし
て用いられているセルロース、デキストラン、ポリアク
リルアミド、アガロース等は、硬さが不足した所謂ソフ
）ゲルであるため流動特性が悪く、分離特性が良くない
という重大な欠点を有し、また寿命も短い。Cellulose, dextran, polyacrylamide, agarose, etc., which have traditionally been used as base materials for hydrophobic chromatography packing materials, are so-called soft gels that lack hardness, so they have poor flow properties and poor separation properties. It has the serious disadvantage of not having a large capacity, and also has a short lifespan.
更に、近年用いられているシリカビーズは、硬さの点で
は満足できるものの、アルカリ性条件下では使用できな
いため、分離条件や溶出・洗浄の条件の選択に大きな制
約が加わるという問題点を有していた。Furthermore, although the silica beads that have been used in recent years are satisfactory in terms of hardness, they cannot be used under alkaline conditions, which poses the problem of placing significant restrictions on the selection of separation conditions and elution/washing conditions. Ta.
発明が解決しようとする問題点
本発明の目的は、前記従来のクロマトグラフィー用充填
基剤の欠点を克服し、疎水性クロマトグラフィー用充填
剤として望まれる前述した諸性質を千金に具有する液体
クロマトグラフィー用充填剤及びその製造方法を提供す
ることにある。Problems to be Solved by the Invention It is an object of the present invention to overcome the drawbacks of the conventional packing base for chromatography and to provide a liquid chromatography material that has all the above-mentioned properties desired as a hydrophobic packing base for chromatography. An object of the present invention is to provide a filler for graphics and a method for producing the same.
問題点を解決するための手段
本発明によって上記目的を達成し得る液体クロマトグラ
フィー用充填剤及びその製造方法が提供される。Means for Solving the Problems The present invention provides a packing material for liquid chromatography that can achieve the above objects and a method for producing the same.
即ち、本発明は、（Ａ）グリシジルモノビニルエステル
ｔｉはグリシジルモノビニルエーテル及び（Ｂ）アルキ
レングリコールジビニルエステルヲ主成分とし、前記（
Ａ）成分が（Ｂ）成分で架橋されたゲル状共重合体（以
下、本発明に係るゲル状共重合体という）の前記（Ａ）
成分に基づくエポキシ基に、または該エポキシ基が水に
より開環変性されて生成するヒドロキシル基にグリシジ
ル基を有する化合物を結合させて得られる変性ケ゛ル状
共重合体（以下、本発明に係る変性ゲル状共重合体とい
う）の前記グリシジル基に、一般式（１）
％式％（）
（式中、Ｒはメチル基、１ｓｏ−プロピル基、ｔｅｒｔ
−７’チル基、シクロヘキシル基、フェニル基、〇−９
ｍ−またはｐ−トリル基、３，４−または３，５−キシ
リル基、１−または２−ナフチル基を表わし、ｔは０ま
たは１を表わし，ｍまたはｎは各々０″！ｉたは１〜１
７の整数を表わす）で表わされる原子団が結合されてい
る多孔性の共重合体から成ることを特徴とする液体クロ
マトグラフィー用充填剤に関する。That is, in the present invention, (A) glycidyl monovinyl ester ti is mainly composed of glycidyl monovinyl ether and (B) alkylene glycol divinyl ester, and the above (
The above (A) of a gel copolymer in which component A) is crosslinked with component (B) (hereinafter referred to as the gel copolymer according to the present invention)
A modified gel copolymer obtained by bonding a compound having a glycidyl group to the epoxy group based on the component or to the hydroxyl group generated by ring-opening modification of the epoxy group with water (hereinafter referred to as the modified gel according to the present invention). The glycidyl group of the general formula (1) % formula % () (in the formula, R is a methyl group, 1so-propyl group, tert
-7'thyl group, cyclohexyl group, phenyl group, 〇-9
m- or p-tolyl group, 3,4- or 3,5-xylyl group, 1- or 2-naphthyl group, t represents 0 or 1, m or n is each 0''!i or 1 ~1
The present invention relates to a packing material for liquid chromatography characterized by being made of a porous copolymer to which atomic groups represented by (representing an integer of 7) are bonded.
また、本発明は、本発明に係るケ゛ル状共重合体の前記
エポキシ基に、または本発明に係る変性デル状共重合体
の前記グリシジル基に、一般式（ＩＩ）Ｈ（ｏＣＨ２Ｃ
Ｈ２）ｍＯ（ＣＨ２）ｎＲ（■）（式中、Ｒ，ｍ及びｎ
は各々前記の意味を有する）で表わされる水酸化化、金
物を作用させるか、または本発明に係るゲル状共重合体
の前記エポキシ基が、または本発明に係る変性ゲル状共
重合体の前記グリシジル基が水によシ開環変性されて生
成するヒドロキシル基に、一般式（ＩＩＩ）（式中、Ｒ
，ｍ及びｎは各々前記の意味を有する）で表わされるエ
ポキシ基を有するエーテル化合物を作用させ、多孔性の
共重合体を得ることを特徴とする液体クロマトグラフィ
ー用充填剤の製造方法に関する。Furthermore, the present invention provides a method for adding the general formula (II) H(oCH2C
H2)mO(CH2)nR(■) (wherein R, m and n
each has the above-mentioned meaning), or the epoxy group of the gel-like copolymer according to the present invention is hydroxylated, or the epoxy group of the modified gel-like copolymer according to the present invention is The hydroxyl group produced by ring-opening modification of the glycidyl group with water is combined with the general formula (III) (wherein R
.
以下、本発明の液体クロマトグラフィー用充填剤及びそ
の製造方法について説明する。Hereinafter, the packing material for liquid chromatography of the present invention and the method for producing the same will be explained.
本発明に係るゲル状共重合体は、特開昭に〇−１０４２
５６号公報等に記載されているように、例えば、（Ａ）
グリシジルモノビニルエステルまたはグリシジルモノビ
ニルニーテルト（Ｂ）アルキレングリコールジビニルエ
ステルとを水不溶性の有機希釈剤の存在下で水性懸濁重
合せしめて多孔性のゲルを得ることにより調製すること
ができる。The gel-like copolymer according to the present invention is disclosed in Japanese Patent Application Laid-open No. 0-1042.
As described in Publication No. 56 etc., for example, (A)
It can be prepared by aqueous suspension polymerization of glycidyl monovinyl ester or glycidyl monovinyl nitrate (B) alkylene glycol divinyl ester in the presence of a water-insoluble organic diluent to obtain a porous gel.
前記（Ａ）成分及び（Ｂ）成分は水に難溶性であるため
水性懸濁重合方式によって共重合させることができ、水
性懸濁重合は簡単な水中油型懸濁方式で行なうことがで
きる。共重合は有機希釈剤の存在下に行なわれ、この有
機希釈剤の存在に起因して、（Ｂ） ノアルキレンクリ
コールノビニルエステル成分が主な架橋成分として作用
し、（５）のグリシゾルモノヒニルエステルマタハクリ
シジルモノビニルエーテル成分中のエポキシ基の大部分
は開環することなくそのまま生成共重合体中に残留せし
めると共に、生成する多孔性ゲルの孔径調整にも役立つ
。Since the components (A) and (B) are sparingly soluble in water, they can be copolymerized by an aqueous suspension polymerization method, and the aqueous suspension polymerization can be carried out by a simple oil-in-water suspension method. Copolymerization is carried out in the presence of an organic diluent, and due to the presence of this organic diluent, the (B) noalkylene glycol novinyl ester component acts as the main crosslinking component, and the glycisol of (5) Most of the epoxy groups in the monovinyl ester matahacrycidyl monovinyl ether component remain in the resulting copolymer without ring opening, and are also useful for adjusting the pore size of the resulting porous gel.
前記（Ａ）成分としては、炭素数３〜１２のモノビニル
カルボン酸のグリシツルエステルまたは炭素数３〜１２
のモノビニルアルコールのグリシジルエーテルが用いら
れる。これらのうち炭素数の少ないものが特に好ましく
用いられ、その例の中にはメタクリル酸グリシジル、ア
クリル酸グリシジル、アリルグリシジルエーテル等が含
まれる。The component (A) is a glycytyl ester of monovinylcarboxylic acid having 3 to 12 carbon atoms or 3 to 12 carbon atoms.
Glycidyl ether of monovinyl alcohol is used. Among these, those having a small number of carbon atoms are particularly preferably used, and examples thereof include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and the like.
一方架橋成分として働く（Ｂ）成分としては、炭素数２
または３のアルキレングリコールまたはそのポリアルキ
レングリコールとアクリル酸もしくはメタクリル酸との
エステルが好ましく用いられる。On the other hand, the component (B) that acts as a crosslinking component has 2 carbon atoms.
or 3 alkylene glycol or an ester of the polyalkylene glycol and acrylic acid or methacrylic acid is preferably used.
例としてエチレングリコールジアクリレート、エチレン
グリコールジメタクリレート、プロピレングリコールジ
アクリレート、プロピレングリコールジアクリレートの
如きアルキレングリコールジビニルエステル及びポリエ
チレングリコールジメタクリレート、ポリプロピレング
リコールジメタクリレートの如きポリアルキレングリコ
ールジビニルエステルがあげられる。Examples include alkylene glycol divinyl esters such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol diacrylate, and polyalkylene glycol divinyl esters such as polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate.
（Ａ）成分対（Ｂ）成分の割合は、前者１０〜９０モル
チに対し後者９０〜１０モルチとする。好ましくは囚成
分４０〜８０モルチ、（Ｂ）成分６０〜２０モル係であ
る。（Ａ）成分の半量以下をコモノマー、例えばメチル
メタクリレート、メチルアクリレート、酢酸ビニルの如
き低級のビニルエステルで置きかえることができる。（
Ａ）成分の割合が大きい程もちろん共重合体中のエポキ
シ基の含有量は増大する。The ratio of component (A) to component (B) is 10 to 90 mole for the former and 90 to 10 mole for the latter. Preferably, the amount of the active ingredient is 40 to 80 mol and the component (B) is 60 to 20 mol. Up to half of component (A) can be replaced by comonomers such as methyl methacrylate, methyl acrylate, lower vinyl esters such as vinyl acetate. (
Of course, the greater the proportion of component A), the greater the content of epoxy groups in the copolymer.
（Ｂ）成分の割合が大きい程共重合体の架橋度は犬とな
り、従って網目構造が密で膨潤度が小さく硬くなる。上
記両成分の割合の範囲外では所期の特徴と特性を充分に
みたすゲル状共重合が得られない。The higher the proportion of component (B), the higher the degree of crosslinking of the copolymer, and therefore the denser the network structure, the lower the degree of swelling, and the harder the copolymer becomes. If the ratio of both components is outside the above range, it will not be possible to obtain a gel-like copolymer that fully satisfies the desired characteristics and properties.
用いられる有機希釈剤は、重合反応に不活性で、水に不
溶乃至難溶性であるが原料モノマーを溶解するものであ
ればよい。使用量は、モノマー成分と有機希釈剤との合
量に基づき、少くとも３０容量チとし、好ましくは４０
〜８０容量係である。The organic diluent used may be one that is inert to the polymerization reaction, insoluble or sparingly soluble in water, but capable of dissolving the raw material monomer. The amount used is at least 30 by volume, preferably 40 by volume, based on the total amount of monomer components and organic diluent.
~80 capacity.
使用量が多い程重合過程におけるエポキシ基の開環が抑
制される。一般的にいって、使用（Ａ）成分の仕込量中
の含有エポキシ基の６０〜９５チ程度を容易に生成重合
体中に残留せしめることができる。The larger the amount used, the more suppressed is the ring opening of the epoxy group during the polymerization process. Generally speaking, about 60 to 95 of the epoxy groups contained in the amount of component (A) used can easily remain in the produced polymer.
残余は重合過程で加水分解されまた一部は架橋に費され
るものと思われる。It is believed that the remainder is hydrolyzed during the polymerization process and a portion is used for crosslinking.
以上の如く、生成ケ゛ル中のエポキシ基の含量は、（Ａ
）成分の使用量即ちω）成分に対する割合またはコモノ
マーによる部分的代替によって、そしてまた有機希釈剤
の使用量によって調節することができるが、生成重合体
中にエポキシ酸素量として表わして１重量％以上存在せ
しめるようにすることが好ましく、最高約１０重量％で
ある。As mentioned above, the content of epoxy groups in the produced cell is (A
) The amount used of component ω) can be adjusted by proportion to component or partial substitution by comonomers and also by the amount of organic diluent used, but not less than 1% by weight expressed as amount of epoxy oxygen in the resulting polymer. Preferably, it is present, up to about 10% by weight.
前述したように、水性懸濁重合時における有機希釈剤の
使用はまた、生成多孔性ゲルの孔径調節にも役立つ。生
成ゲルに対し膨潤性の小さい有機希釈剤を使用すると、
重合過程で懸濁粒子内に相分離が起り、その結果孔径の
大きいゲル所謂巨大有孔構造を有するゲルを得ることが
できる。これに対し、膨潤性の大きい希釈剤を使用する
と、重合過程で生成物が膨潤状態で重合が進行するから
、相分離は起り難く、膨潤によって形成された比較的小
さい孔径の重合体が得られる。膨潤性の大小は、有機希
釈剤の溶解ノにラメ−ターに基づいて知ることができる
。本発明において好適に用いうる有機希釈剤の例として
、生成ゲルに対する膨潤性の大きいものの順にあげれば
、シクロヘキサノン、クロロベンゼン、ベンゼン、トル
エン、ｎ−７’口ピルアセテート、ｎ−ブチルアセテー
ト、ｎ−オクタン等である。As mentioned above, the use of organic diluents during aqueous suspension polymerization also helps control the pore size of the resulting porous gel. When an organic diluent with low swelling property is used for the resulting gel,
Phase separation occurs within the suspended particles during the polymerization process, and as a result, a gel with a large pore size, a so-called giant pore structure, can be obtained. On the other hand, when a highly swelling diluent is used, the polymerization proceeds with the product in a swollen state during the polymerization process, making it difficult for phase separation to occur and resulting in a polymer with relatively small pores formed by swelling. . The degree of swelling can be determined based on the solubility of the organic diluent. Examples of organic diluents that can be suitably used in the present invention include cyclohexanone, chlorobenzene, benzene, toluene, n-7'-pyroacetate, n-butyl acetate, and n-octane, in descending order of swelling properties for the resulting gel. etc.
水性懸濁重合は、遊離基発生触媒の存在下にそれ自体は
公知の常法に従って行なうことができる。The aqueous suspension polymerization can be carried out in the presence of a free-radical generating catalyst according to conventional methods known per se.
水相の量は有機相の量に基づきほぼ同容量またはそれ以
上とし、特に制約はないが約１０倍容量１での量で用い
られる。The amount of the aqueous phase is approximately the same volume or more based on the amount of the organic phase, and is used in an amount of about 10 times the volume, although there is no particular restriction.
また、本発明に係る変性ゲル状共重合体を得るには、先
ず、本発明に係るゲル状共重合体の（Ａ）成分に基づく
エポキシ基を、酸またはアルカリの存在下で水により処
理して開環変性し、生成するヒドロキシル基に、グリシ
ジル基を有する化合物を作用させてグリシツル基を導入
すればよい。Furthermore, in order to obtain the modified gel copolymer according to the present invention, first, the epoxy group based on component (A) of the gel copolymer according to the present invention is treated with water in the presence of an acid or an alkali. A glycidyl group may be introduced by allowing a compound having a glycidyl group to act on the hydroxyl group produced by ring-opening modification.
水による開環変性は、例えば酸の存在下で行われる場合
には硫酸または塩酸を触媒として水中でこれらの共重合
体を７０℃〜１００℃に約２時間加熱することによ）行
われる。酸の濃度は０．１規定〜０，５規定が好ましい
。開環変性はほぼ定量的に行われる。Ring-opening modification with water is carried out, for example, when carried out in the presence of an acid, by heating these copolymers in water at 70° C. to 100° C. for about 2 hours using sulfuric acid or hydrochloric acid as a catalyst. The concentration of acid is preferably 0.1N to 0.5N. Ring-opening modification is performed almost quantitatively.
グリシジル基を有する化合物としては、エピクロロヒド
リン、エピブロモヒドリンなどのエピハロヒドリン類；
エチレングリコールノブリシジルエーテル、１．４−ブ
タンジオールジグリシジルエーテル、ポリエチレングリ
コールジグリシジルエーテルなどのジグリシノルエーテ
ル類；１，３ブタジエンジエポキサイド、１，７−オク
タジニンジエポキサイドなどのアルキルジエンジュポキ
サイド類などがあげられる。Examples of compounds having a glycidyl group include epihalohydrins such as epichlorohydrin and epibromohydrin;
Diglycinol ethers such as ethylene glycol nobricidyl ether, 1,4-butanediol diglycidyl ether, and polyethylene glycol diglycidyl ether; alkyl diene diepoxides such as 1,3 butadiene diepoxide and 1,7-octazidine diepoxide Includes sides.
グリシジル基を導入するては、例えば開環変性されたゲ
ル状共重合体に水酸化ナトリウムまたは炭酸カリウム等
の無機塩基の水溶液中でエピクロロヒドリンを反応させ
るか、または親水性共重合体に水素化ホウ素ナトリウム
を含む水酸化ナトリウムまたは炭酸カリウム等の無機塩
基の水溶液中で、エチレングリフールまたは１．４−ブ
タンジオールジグリシジルエーテル、またはポリエチレ
ングリコールジグリシジルエーテルと反応させるなどし
て行われる。用いられるポリエチレングリコールジグリ
シジルエーテルの繰返し単位−Ｃ２Ｈ４０−の繰返し数
が１〜１０のものを用いるのが好ましい。To introduce a glycidyl group, for example, a ring-opening modified gel copolymer is reacted with epichlorohydrin in an aqueous solution of an inorganic base such as sodium hydroxide or potassium carbonate, or a hydrophilic copolymer is reacted with epichlorohydrin. This is carried out by reacting with ethylene glyfur, 1,4-butanediol diglycidyl ether, or polyethylene glycol diglycidyl ether in an aqueous solution of an inorganic base such as sodium hydroxide or potassium carbonate containing sodium borohydride. It is preferable to use polyethylene glycol diglycidyl ether having a repeating unit -C2H40- of 1 to 10.
次いで、本発明に係るゲル状共重合体のエポキシ基また
は本発明に係る変性ケ゛ル状共重合体のグリシジル基に
、前記一般式（１）で表わされる原子団を導入する方法
について説明する。Next, a method for introducing the atomic group represented by the general formula (1) into the epoxy group of the gel-like copolymer according to the present invention or the glycidyl group of the modified gel-like copolymer according to the present invention will be explained.
ｉ）一般式（ＩＩ）で表わされる水酸化化合物を作用さ
せる方法。i) A method of acting with a hydroxide compound represented by general formula (II).
本発明に係るケ゛ル状共重合体のエポキシ基または本発
明に係る変性ゲル状共重合体のグリシジル基に、一般式
（ＩＩ）で表わされる水酸化化合物を作用させるに際し
ては、溶媒の存在下で行なうことができるが、一般式（
ＩＩ）で表わされる水酸化化合物が反応条件下で液体の
場合は特に溶媒を用いないでもよい。溶媒としては、水
が通常用いられるが、その他ｎ−へキサン、へ／ゼン、
キシレンナどの炭化水素類；テトラヒドロフラン、ノオ
キサンなどのエーテル類；クロロホルム、クロロベンゼ
ンなどの塩素化炭化水素類；アセトンやメチノｔ。When the hydroxide compound represented by the general formula (II) is allowed to act on the epoxy group of the cell-like copolymer according to the present invention or the glycidyl group of the modified gel-like copolymer according to the present invention, in the presence of a solvent. can be done, but the general formula (
When the hydroxide compound represented by II) is liquid under the reaction conditions, no solvent may be used. Water is usually used as a solvent, but other solvents such as n-hexane, he/zene,
Hydrocarbons such as xylenna; ethers such as tetrahydrofuran and nooxane; chlorinated hydrocarbons such as chloroform and chlorobenzene; acetone and methinot.
インブチルケト／などのケトン類などの他、ノメチルホ
ルムアミド、ジメチルスルオキサイドなども用いられ、
またこれらは単一で・も混合溶媒系でも良い。また、特
に触媒は用いないでもよいが水酸化ナトリウム、水酸化
カリウム、炭酸カリウム、炭酸水素ナトリウムなどのア
ルカリまたはアルカリ土類金属の水酸化物または炭酸塩
などを用いることができる。In addition to ketones such as inbutyl keto/, nomethylformamide and dimethyl sulfoxide are also used.
Further, these may be used alone or in a mixed solvent system. Although no catalyst may be used, hydroxides or carbonates of alkali or alkaline earth metals such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium hydrogen carbonate may be used.
一般式（ＩＩ）で表わされる水酸化化合物としては、メ
タノール、エタノール、ｉｓｏ −７’ロバノール、ｎ
−ブタノール、ｔｅｒｔ−ブタノール、ｎ−ヘキサノー
ル、ｎ−オクタツール、ｎ−デカノール、ｎ−ドデカノ
ール、ｎ−オクタデカノール、シクロヘキサノール等の
アルキルアルコール類；ベンジルアルコール、フェネチ
ルアルコール、４−フェニルブタノール等のアラルキル
アルコール類；フェノール、ｏ−ｍ−またはｐ−クンゾ
ール、３，４−または３．５−キシレノール等のフェノ
ール類；１−または２−ナフトール、エチレングリコー
ルモノメチルエーテル、エチレングリコールモノ−ｎ−
ブチルエーテル、エチレングリコールモノ−ｎ−ヘキシ
ルエーテル、エチレンクリコールモノ−ｎ−ドデシルエ
ーテル、ジエチレングリコールモノメチルエーテル、ジ
エチレングリコールモノ−ｎ−ブチルエーテル、ジエチ
レンクリコールモノ−ｎ−ヘキシルエーテル、ジエチレ
ングリコールモノ−ｎ−ドデシルエーテル、トリエチレ
ングリコールモノメチルモノメチルエーテル、トリエチ
レングリコールモノ−ｎ−ブチルエーテル、トリエチレ
ングリコールモノ−ｎ−ドデシルエーテル、テトラエチ
レングリコールモノ−ｎ−）’ｆシルエーテル、ヘキサ
エチレンクリコールモノ−ｎ−ドデシルエーテル、オク
タエチレングリコールモノ−ｎ−ドデシルエーテル等の
アルキルエーテル類；エチレングリコールモノベンジル
エーテル′等のアラルキルエーテル類；エチレングリコ
ールモノフェニルエーテル、ジエチレングリコールモノ
フェニルエーテル、トリエチレンクリコールモノフェニ
ルエーテル、テトラエチレングリコールモノフェニルエ
ーテル、４ンタエチレンクリコールモノフエニルエーテ
ル等のフェニルエーテル類等があげられる。Examples of the hydroxide compound represented by the general formula (II) include methanol, ethanol, iso-7' lovanol, n
- Alkyl alcohols such as butanol, tert-butanol, n-hexanol, n-octatool, n-decanol, n-dodecanol, n-octadecanol, cyclohexanol; benzyl alcohol, phenethyl alcohol, 4-phenylbutanol, etc. Aralkyl alcohols; phenols such as phenol, om- or p-cunzol, 3,4- or 3,5-xylenol; 1- or 2-naphthol, ethylene glycol monomethyl ether, ethylene glycol mono-n-
Butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol mono-n-dodecyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-dodecyl ether, Triethylene glycol monomethyl monomethyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol mono-n-dodecyl ether, tetraethylene glycol mono-n-)'fyl ether, hexaethylene glycol mono-n-dodecyl ether, Alkyl ethers such as octaethylene glycol mono-n-dodecyl ether; aralkyl ethers such as ethylene glycol monobenzyl ether; ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether; Examples include phenyl ethers such as phenyl ether and 4-tentaethylene glycol monophenyl ether.
反応条件てついては必ずしも制限はないが、一般に次の
ような条件を選択して反応を行なうのが好ましい。The reaction conditions are not necessarily limited, but it is generally preferable to select the following conditions to carry out the reaction.
本発明に係るゲル状共重合体または本発明に係る変性ゲ
ル状共重合体の重量（、）と一般式（ＩＩ）で表わされ
る水酸化化合物の重量（ｂ）の比：ａ ： ｂ＝＝１
： ０．３〜１０、より好ましくは、
ａ：ｂ＝１：０．３〜３、
反応温度二〇〜１５０℃、より好ましくは室温〜１００
℃、
反応時間：１〜６０時間、よシ好ましくは１〜３０時間
、
反応圧カニ常圧〜１０ａｔｍ、より好ましくは常已反応
後の後処理についても特別な要件はなく、戸別、洗浄等
通常行なわれている方法にて適宜実施される。Ratio of the weight (,) of the gel copolymer according to the present invention or the modified gel copolymer according to the present invention to the weight (b) of the hydroxide compound represented by general formula (II): a: b== 1
: 0.3-10, more preferably a:b=1:0.3-3, reaction temperature 20-150°C, more preferably room temperature-100°C
°C, reaction time: 1 to 60 hours, preferably 1 to 30 hours, reaction pressure normal pressure to 10 atm, more preferably normal. There are no special requirements for post-treatment after the reaction, and it can be carried out door-to-door, washing, etc. This will be carried out as appropriate using the methods currently in use.
１１）一般式（１）で表わされるエポキシ基を有するエ
ーテル化合物を作用させる方法。11) A method of acting with an ether compound having an epoxy group represented by general formula (1).
本発明に係るゲル状共重合体のエポキシ基は、前述の如
く水によシ容易に開環変性してヒドロキシル基を生成す
るが、本発明に係る変性ゲル状共重合体のグリシジル基
もまた同様の操作によシ容易に開環変性してヒドロキシ
ル基を生成することができる。As mentioned above, the epoxy group of the gel-like copolymer according to the present invention is easily ring-opened and modified with water to generate a hydroxyl group, but the glycidyl group of the modified gel-like copolymer according to the present invention also A hydroxyl group can be easily generated by ring-opening modification using a similar operation.
水により開環変性した本発明に係るゲル状共重合体のヒ
ドロキシル基または本発明に係る変性ゲル状共重合体の
ヒドロキシル基に一般式（ＩＩＩ）で表わされるエポキ
シ基を有するエーテル化合物を作用させるに際しては、
１）と同様の反応条件下で行なうことができる。一般式
（’Ｉ）で表わされるエポキシ基を有するエーテル化合
物としては、メチルグリシジルエーテル、ｎ−ブチルグ
リシジルエーテル、２−エチルへキシルグリシジルエー
テル、ｎ−オクチルグリシジルエーテル、ｎ−ドデシル
グリシジルエーテル、Ｕ−オクタデシルグリシジルエー
テル、エチレンクリコール−ｎ−ブチルグリシジルエー
テル、インタエチレングリコール−ｎ−ブチルグリシジ
ルエーテル、ペンタデカエチレンゲリコール−Ｕ−ドデ
シルグリシジルエーテル等ノアルキルエーテル類：ヘン
ジルグリシジルエーテル等のアラルキルエーテル類：フ
ェニルグリシジルエーテル、エチレンクリコールフェニ
ルクリシジルエーテル、ジエチレングリコールフェニル
クリシジルエーテル、トリエチレングリコールフェニル
グリシジルエーテル、テトラエチレングリコールフェニ
ルグリシジルエーテル、ペンタエチレンクリコールフェ
ニルクリシジルエーテル、ヘキサエチレングリコールフ
ェニルグリシジルエーテル、オクタエチレングリコール
フェニルクリシジルエーテル、ペンタデカエチレングリ
コールフェニルグリシジルエーテル等のアリールエーテ
ル類等があげられる。An ether compound having an epoxy group represented by general formula (III) is applied to the hydroxyl group of the gel-like copolymer according to the present invention that has been ring-opened and modified with water or the hydroxyl group of the modified gel-like copolymer according to the present invention. In this case,
It can be carried out under the same reaction conditions as in 1). Examples of the ether compound having an epoxy group represented by the general formula ('I) include methyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, n-octyl glycidyl ether, n-dodecyl glycidyl ether, U- Noalkyl ethers such as octadecyl glycidyl ether, ethylene glycol n-butyl glycidyl ether, interethylene glycol n-butyl glycidyl ether, pentadecaethylene gelicol U-dodecyl glycidyl ether; aralkyl ethers such as henzyl glycidyl ether : Phenyl glycidyl ether, ethylene glycol phenyl glycidyl ether, diethylene glycol phenyl glycidyl ether, triethylene glycol phenyl glycidyl ether, tetraethylene glycol phenyl glycidyl ether, pentaethylene glycol phenyl glycidyl ether, hexaethylene glycol phenyl glycidyl ether, octa Examples include aryl ethers such as ethylene glycol phenyl glycidyl ether and pentadecaethylene glycol phenyl glycidyl ether.
発明の効果
本発明により提供される液体クロマトグラフィー用充填
剤は、本発明に係るゲル状共重合体のエポキシ基または
本発明に係る変性ゲル状共重合体のグリシジル基に結合
した原子団の疎水的性質が、例えば蛋白質、核酸、酵素
等の分離精製を非常に有効ならしめるものであることが
確かめられたが、更に本発明に係るゲル状共重合体また
は本発明に係る変性ゲル状共重合体のもたらす親水的性
質は例えば蛋白質等と接触する際の疎水的非特異的吸着
を抑え、またその有孔構造は目的物質の分離精製に有利
に作用しうろことが明らかである。更に本発明により提
供される液体クロマトグラフィー・用充填剤は、架橋度
の高い合成高分子物質であるため、物理的化学的、生物
学的に非常に安定なものであり、特に疎水性クロマトグ
ラフィーで通常行なわれる塩濃度が大きく変化する条件
下でも膨潤収縮が小さく、良好な分離性能を維持するこ
とができ、また広いＰＨ域でも充分安定であるため、目
的物質の分離、精製や充填剤の洗浄等使用条件の選択に
非常に有利である等は大きな利点となる。Effects of the Invention The liquid chromatography packing material provided by the present invention has a hydrophobic atomic group bonded to the epoxy group of the gel copolymer according to the present invention or the glycidyl group of the modified gel copolymer according to the present invention. It has been confirmed that the gel-like copolymer according to the present invention or the modified gel-like copolymer according to the present invention It is clear that the hydrophilic properties brought about by the coalescence suppress hydrophobic non-specific adsorption when coming into contact with, for example, proteins, and that the porous structure has an advantageous effect on the separation and purification of the target substance. Furthermore, since the packing material for liquid chromatography provided by the present invention is a synthetic polymer substance with a high degree of crosslinking, it is extremely stable physically, chemically, and biologically, and is particularly suitable for hydrophobic chromatography. Swelling and shrinkage are small and good separation performance can be maintained even under conditions where the salt concentration changes greatly, which is usually done in the laboratory.It is also sufficiently stable over a wide pH range, making it suitable for separation and purification of target substances and for packing materials. It is a great advantage that it is very convenient for selecting usage conditions such as cleaning.
これらの性質は特に高速液体クロマトグラフィー用の充
填剤及び工業的分離精製プロセス用の充填剤としては欠
くべからざるものであり、本発明により提供される液体
クロ”マドグラフィー用充填剤の効果は非常に大きい。These properties are indispensable especially as a packing material for high-performance liquid chromatography and a packing material for industrial separation and purification processes, and the effects of the packing material for liquid chromatography provided by the present invention are extremely high. big.
本発明によシ提供される液体クロマトグラフィー用充填
剤は、前述の如く疎水性クロマトグラフィー用の充填剤
として有用なものである。The packing material for liquid chromatography provided by the present invention is useful as a packing material for hydrophobic chromatography, as described above.
実施例
以下に、本発明のクロマトグラフィー用充填剤の製造法
について代表的な例を示し、更に具体的に説明する。但
しこれらは説明のための単なる例示であって、本発明は
これらに何ら制限されないことはいうまでもない。EXAMPLES Below, typical examples of the method for producing the packing material for chromatography of the present invention will be shown and explained in more detail. However, these are merely examples for explanation, and it goes without saying that the present invention is not limited thereto.
実施例１
グリシジルメタクリレートとエチレングリコールジメタ
クリレートから得られたエポキシ基含有ゲル状共重合体
０．５Ｎに、フェノール０．５．９及び１０チ水酸化ナ
トリウム水溶液１．０．９を加え、６０℃に加熱して振
盪下で５時間反応させた。次いで、ゲルを戸数し大量の
水で洗い乾燥させた。Example 1 To 0.5N of an epoxy group-containing gel copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate, 0.5.9% of phenol and 1.0.9% of an aqueous solution of 10-thiosodium hydroxide were added, and the mixture was heated at 60°C. The mixture was heated to a temperature of 100.degree. C. and reacted for 5 hours under shaking. Next, the gel was washed with a large amount of water and dried.
こうして得られたゲルを三臭化ホウ素で分解し、遊離し
たフェノールを分析することＫより乾燥ゲル１ｇ当りフ
ェニル基を約１ミリモル担持させていることが確められ
た。また、このゲルのプロトンの核磁気共鳴ス４クトル
を重水素化ジメチルスルホキシド（ＤＭＳＯ−α６）懸
濁下で測定したところ、δ＝６．９５（二重線、３Ｈ）
及びδ＝ ７．２７ （三重線、２Ｈ）にフェニル基に
結合した水素の存在が確められた。The thus obtained gel was decomposed with boron tribromide and the liberated phenol was analyzed. From K, it was confirmed that about 1 mmol of phenyl groups were supported per 1 g of dry gel. In addition, when the nuclear magnetic resonance spectrum of protons of this gel was measured in suspension in deuterated dimethyl sulfoxide (DMSO-α6), δ = 6.95 (double line, 3H).
The presence of hydrogen bonded to the phenyl group was confirmed at and δ = 7.27 (triple line, 2H).
実施例２〜１６
実施例１のゲル状共重合体を第１表に示した一般式（Ｉ
Ｉ）で表わされる水酸化化合物と実施例１と同様の操作
によシ反応させた。その結果を第１表に示した。Examples 2 to 16 The gel copolymer of Example 1 had the general formula (I
A reaction was carried out in the same manner as in Example 1 with the hydroxide compound represented by I). The results are shown in Table 1.
実施例１７
グリシ・ゾルメタクリレートとエチレングリコールジメ
タクリレートから得られた共重合体を水により浦環変性
し、更にエビクロロヒドリンでグリシジル基を導入した
ゲル（エポキシ基：乾燥ゲル１ｆｌ当り０．５ミリモル
）１．０＃に、フェノール０．５ｇ及び１モル水酸化ナ
トリウム水溶液３．０ｇを加え、室温で振盪下、８時間
反応させた。次いで、ゲルを戸数し大量の水で洗い乾燥
させた。こうして得られたゲルは乾燥ゲルＩＩ当りフェ
ニル基を０．３５ ミＩＪモル担持させていることが確
められた。このケ゛ルの疎水的指数は１，１８であった
。Example 17 A gel in which a copolymer obtained from glyci-sol methacrylate and ethylene glycol dimethacrylate was ura-ring modified with water and glycidyl groups were introduced with shrimp chlorohydrin (epoxy group: 0.5 per 1 fl of dry gel) 0.5 g of phenol and 3.0 g of a 1 molar aqueous sodium hydroxide solution were added to 1.0 # (mmol), and the mixture was reacted at room temperature for 8 hours with shaking. Next, the gel was washed with a large amount of water and dried. It was confirmed that the gel thus obtained carried 0.35 mmol of phenyl groups per dry gel II. The hydrophobic index of this cell was 1.18.
実施例１８
グリシジルメタクリレートとエチレングリコール・ジメ
タクリレートから得られた共重合体を水によシ開環変性
し、更にエチレングリコールジグリシジルエーテルでグ
リシジル基を導入したゲル（エポキシ基：乾燥ゲルＩＩ
当り０．３５ミリモル）をｎ−ブタノールと実施例１７
と同様の操作により反応させ、疎水的指数１．０５のケ
゛ルを得た。Example 18 A gel obtained by ring-opening modification of a copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate with water, and further introducing glycidyl groups with ethylene glycol diglycidyl ether (epoxy group: Dry Gel II)
n-butanol and Example 17
The reaction was carried out in the same manner as above to obtain a gel with a hydrophobic index of 1.05.
実施例１９
グリシジルメタクリレートとエチレングリコールジメタ
クリレートから得られた共重合体を水によシ開環変性し
、更に１，４−ブタンジオールジグリシジルエーテルで
グリシツル基を導入したゲル（エポキシ基：乾燥ゲル１
ｇ当り０．２５ミリモル）をフェノールと実施例１７と
同様の操作を行なって反応させることによシ、乾燥ゲル
ＩＩ当りフェニル基を０．２ ミＩＪモル担持するデル
を得た。このゲルの疎水的指数は１．４５であった。Example 19 A gel obtained by ring-opening modification of a copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate with water, and further introducing glycidyl groups with 1,4-butanediol diglycidyl ether (epoxy group: dry gel) 1
By reacting phenol with phenol in the same manner as in Example 17, a gel carrying 0.2 mmol of phenyl group per dry gel II was obtained. The hydrophobic index of this gel was 1.45.
実施例２０
グリシジルメタクリレートとエチレングリコール・ジメ
タクリレートから得られた共重合体を水により開環変性
したゲル１．５ｇに、フェニルグリシジルエーテル０．
５Ｆ、１モル水酸化ナトリウム２．５ｇ及び水１．５Ｉ
を加え、４０℃に加熱して攪拌下、４．５時間反応させ
た。次いで、ゲルを戸数し大量の水で洗い乾燥させた。Example 20 To 1.5 g of a gel prepared by ring-opening modification of a copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate with water, 0.0 g of phenyl glycidyl ether was added.
5F, 2.5g 1M sodium hydroxide and 1.5I water
was added, heated to 40°C, and reacted for 4.5 hours with stirring. Next, the gel was washed with a large amount of water and dried.
こうして得られたゲルは乾燥ゲルＩＩ当りフェニル基を
０５０ミリモル担持させていることが確められた。この
ｒルの疎水的指数は０．９２であった。It was confirmed that the gel thus obtained carried 050 mmol of phenyl groups per dry gel II. The hydrophobic index of this molecule was 0.92.
実施例２１
グリシジルメタクリレートとエチレングリコールジメタ
クリレートから得られた共重合体を水により開環変性し
たケ０ルをｎ−ブチルグリシジルエーテルと実施例２０
と同様の操作により反応させ、疎水的指数１．２５のゲ
ルを得た。Example 21 Example 20 A copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate was ring-opened and modified with water, and n-butyl glycidyl ether was used.
The reaction was carried out in the same manner as above to obtain a gel with a hydrophobic index of 1.25.
実施例２２
グリシジルメタクリレートとエチレングリコールジメタ
クリレートから得られた共重合体を水により開環変性し
たゲルをトリエチレングリコールフェニルグリシジルエ
ーテルと実施例２０と同様の操作を行なって反応させ、
乾燥ゲル１ｇ当ジフェニル基を０．３５ ミリモル担持
するゲルを得た。Example 22 A gel obtained by ring-opening modification of a copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate with water was reacted with triethylene glycol phenyl glycidyl ether in the same manner as in Example 20,
A gel carrying 0.35 mmol of diphenyl groups per gram of dry gel was obtained.
このゲルの疎水的指数は１．２１であった。The hydrophobic index of this gel was 1.21.
実施例２３
グリシツルメタクリレートとエチレングリコールジメタ
クリレートから得られた共重合体を水にヨシ開環変性し
たゲルを被ンタエチレングＩＪ コール−ｎ−ブチルグ
リシジルエーテルと実施例２０と同様の操作によって反
応させ、疎水的指数１，１２のゲルを得た。Example 23 A gel prepared by ring-opening modification of a copolymer obtained from glycitol methacrylate and ethylene glycol dimethacrylate in water was reacted with ethylene glycol-n-butyl glycidyl ether in the same manner as in Example 20, A gel with a hydrophobic index of 1.12 was obtained.
実施例２４
グリシジルメタクリレートとエチレングリコールジメタ
クリレートから得られた共重合体を水により開環変性し
、更にテ゛トラエチレングリコールゾグリシジルエーテ
ルでグリシジル基を導入しｋものを更に再び水によシ開
環変性したゲルを７エ二、ルグリシジルエーテルと実施
例２０と同様の操作により反応させ、乾燥ゲル１ｇ当ジ
フェニル基を０．２５ ミリモル担持するゲルを得た。Example 24 A copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate was ring-opened and modified with water, a glycidyl group was introduced with tetraethylene glycol zoglycidyl ether, and the copolymer was ring-opened again with water. The modified gel was reacted with 7enyl glycidyl ether in the same manner as in Example 20 to obtain a gel supporting 0.25 mmol of diphenyl groups per gram of dry gel.
このゲルの疎水的指数は１．４２であった。The hydrophobic index of this gel was 1.42.
実施例２５
グリシジルメタクリレートとエチレングリコールジメタ
クリレートから得られた共重合体を水により開環変性し
、更に１，４−ブタンジオールジグリシジルエーテルで
グリシジル基を導入したものを更に再び水によシ開環変
性したゲルをｎ−ブチルグリシジルエーテルと実施例２
０と同様の操作により反応させて、疎水的指数１．３９
のゲルを得た。Example 25 A copolymer obtained from glycidyl methacrylate and ethylene glycol dimethacrylate was ring-opened and modified with water, and a glycidyl group was introduced with 1,4-butanediol diglycidyl ether, which was further cleaved with water. Example 2: Ring-modified gel with n-butyl glycidyl ether
0, the hydrophobic index was 1.39.
gel was obtained.
試験例１
実施例１９で得たゲルを７．５φ×５０１のステンレス
製カラムに充填し、高速液体クロマトグラフ装置を用い
て■チトクロームＣ１■ミオグロビン、■リボヌクレア
ーゼＡ１■卵白アルブミン、■リゾチーム、■α−キモ
トリプシン、■α−キモトリプシノーダンＡの混合物を
分析したところ、図のようなりロマトダラムが得られた
。Test Example 1 The gel obtained in Example 19 was packed into a 7.5φ x 501 stainless steel column, and using a high-performance liquid chromatography device, ■cytochrome C1 ■ myoglobin, ■ ribonuclease A1 ■ ovalbumin, ■ lysozyme, ■ α When a mixture of -chymotrypsin and α-chymotrypsinodan A was analyzed, romatodalum was obtained as shown in the figure.
溶離液■：０．０２モルトリス塩酸緩衝液（ｐＨ７，４
）〃 ■；溶離液［有］＋３モル硫酸アンモニウムリニ
アグラジェント 溶離液■→溶離液■（６０分）検出器
： 紫外分光光度計２８０ ｎｍ試験例２
実施例２０で得たゲルを８φＸ７５＋ｍｓのステンレス
製カラムに充填し、高速液体クロマトグラフ装置を用い
て２モル硫酸アンモニウムを含む０．１モルリン酸ナト
リウム緩衝液［ｐＨ７，０、溶離液０〕を用いて第２表
に示す目的物質を吸着させ、次いで硫酸アンモニウムを
含まない０．１モルリン酸ナトリウム緩衝液（ｐｉ（７
，０、溶離液◎〕を用いて溶離を行なうことによシ目的
物質の回収率を求め念ところ、第２表のような結果を得
た。Eluent ■: 0.02M Tris-HCl buffer (pH 7.4
)〃 ■; Eluent [with] + 3 molar ammonium sulfate linear gradient Eluent ■ → Eluent ■ (60 minutes) Detector: Ultraviolet spectrophotometer 280 nm Test Example 2 The gel obtained in Example 20 was measured using an 8φX75+ms stainless steel The target substance shown in Table 2 was adsorbed using a 0.1 molar sodium phosphate buffer containing 2 molar ammonium sulfate [pH 7.0, eluent 0] using a high-performance liquid chromatography device. Ammonium sulfate-free 0.1 molar sodium phosphate buffer (pi(7
.
第２表
試験例３
試験例２において、溶離液■の代シに１．５モル硫酸ア
ンモニウムを含む０．１モルリン酸ナトリウム緩衝液（
ｐ）１７．０）を用いて第３表に示す目的物質を吸着さ
せ、次いで溶離液０を用いて溶離さゼたものについて酵
素活性を求めたところ、第３表のような結果を得た。Table 2 Test Example 3 In Test Example 2, a 0.1 molar sodium phosphate buffer containing 1.5 molar ammonium sulfate (
When the target substances shown in Table 3 were adsorbed using 17.0) and the enzyme activity of the eluted substances was determined using eluent 0, the results shown in Table 3 were obtained. .
第３表Table 3
図は本発明による充填剤を用いた高速液体クロマトグラ
フィーのクロマトグラムである。
図中■はチトクロームＣ１■はミオグロビン、■はり？
ヌクレアーゼＡ１■卵白アルブミン、■リゾチール、■
α−キモトリプシン、■α−キモトリプシノーゲンＡの
各ピークを示す。The figure is a chromatogram of high performance liquid chromatography using the packing material according to the present invention. In the figure, ■ is cytochrome C1, ■ is myoglobin, and ■ is the girder?
Nuclease A1 ■ Ovalbumin, ■ Lysothyl, ■
The peaks of α-chymotrypsin and α-chymotrypsinogen A are shown.
Claims (2)
シジルモノビニルエーテル及び（Ｂ）アルキレングリコ
ールジビニルエステルを主成分とし、前記（Ａ）成分が
（Ｂ）成分で架橋されたゲル状共重合体の前記（Ａ）成
分に基づくエポキシ基に、または該エポキシ基が水によ
り開環変性されて生成するヒドロキシル基にグリシジル
基を有する化合物を結合させて得られる変性ゲル状共重
合体の前記グリシジル基に、一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒはメチル基、ｉｓｏ−プロピル基、ｔｅｒｔ
−ブチル基、シクロヘキシル基、フェニル基、ｏ−，ｍ
−またはｐ−トリル基、３，４−または３，５−キシリ
ル基、１−または２−ナフチル基を表わし、ｌは０また
は１を表わし、ｍまたはｎは各々０または１〜１７の整
数を表わす） で表わされる原子団が結合されている多孔性の共重合体
から成ることを特徴とする液体クロマトグラフィー用充
填剤。(1) The above (A) of a gel-like copolymer mainly composed of (A) glycidyl monovinyl ester or glycidyl monovinyl ether and (B) alkylene glycol divinyl ester, and in which the above (A) component is crosslinked with the (B) component. The general formula ( I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a methyl group, iso-propyl group, tert
-butyl group, cyclohexyl group, phenyl group, o-, m
- or p-tolyl group, 3,4- or 3,5-xylyl group, 1- or 2-naphthyl group, l represents 0 or 1, m or n each represents 0 or an integer from 1 to 17. A packing material for liquid chromatography, characterized in that it is made of a porous copolymer to which atomic groups represented by the following formula are bonded.
シジルモノビニルエーテル及び（Ｂ）アルキレングリコ
ールジビニルエステルを主成分とし、前記（Ａ）成分が
（Ｂ）成分で架橋されたゲル状共重合体の前記（Ａ）成
分に基づくエポキシ基に、または該エポキシ基が水によ
り開環変性されて生成するヒドロキシル基にグリシジル
基を有する化合物を結合させて得られる変性ゲル状共重
合体の前記グリシジル基に、一般式（II） Ｈ（ＯＣＨ＿２ＣＨ＿２）＿ｍＯ（ＣＨ＿２）＿ｎＲ（
II）（式中、Ｒはメチル基、ｉｓｏ−プロピル基、ｔｅ
ｒｔ−ブチル基、シクロヘキシル基、フェニル基、ｏ−
，ｍ−またはｐ−トリル基、３，４−または３，５−キ
シリル基、１−または２−ナフチル基を表わし、ｍまた
はｎは各々０または１〜１７の整数を表わす） で表わされる水酸化化合物を作用させるか、または前記
ゲル状共重合体のエポキシ基が、または前記変性ゲル状
共重合体のグリシジル基が水により開環変性されて生成
するヒドロキシル基に一般式（III） ▲数式、化学式、表等があります▼（III） （式中、Ｒ、ｍ及びｎは各々前記の意味を有する）で表
わされるエポキシ基を有するエーテル化合物を作用させ
、多孔性の共重合体を得ることを特徴とする液体クロマ
トグラフィー用充填剤の製造方法。(2) (A) of a gel-like copolymer containing (A) glycidyl monovinyl ester or glycidyl monovinyl ether and (B) alkylene glycol divinyl ester as the main components, and in which the (A) component is crosslinked with the (B) component. The general formula ( II) H(OCH_2CH_2)_mO(CH_2)_nR(
II) (wherein R is a methyl group, iso-propyl group, te
rt-butyl group, cyclohexyl group, phenyl group, o-
, m- or p-tolyl group, 3,4- or 3,5-xylyl group, 1- or 2-naphthyl group, m or n each represents 0 or an integer from 1 to 17) General formula (III) ▲ Formula , chemical formulas, tables, etc. ▼ (III) Obtaining a porous copolymer by reacting with an ether compound having an epoxy group represented by (in the formula, R, m, and n each have the above meanings) A method for producing a packing material for liquid chromatography, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61110624A JPS62267663A (en) | 1986-05-16 | 1986-05-16 | Packing material for liquid chromatography and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61110624A JPS62267663A (en) | 1986-05-16 | 1986-05-16 | Packing material for liquid chromatography and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62267663A true JPS62267663A (en) | 1987-11-20 |
Family
ID=14540498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61110624A Pending JPS62267663A (en) | 1986-05-16 | 1986-05-16 | Packing material for liquid chromatography and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62267663A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995002820A1 (en) * | 1993-07-16 | 1995-01-26 | Merck Patent Gmbh | Stationary phases for use in hydrophobic interaction chromatography |
| DE10005681B4 (en) * | 2000-02-07 | 2005-06-16 | Atc Dr. Mann E.K. | Method and device for the decontamination of metal-containing waters |
| US7205361B2 (en) * | 2001-09-28 | 2007-04-17 | Showa Denko K.K. | Particulate hydrophobic polymer, production process therefor and column for reversed-phase high-performance liquid chromatography |
| WO2013187512A1 (en) * | 2012-06-15 | 2013-12-19 | 旭化成メディカル株式会社 | Alkali-resistant ion exchange temperature-responsive adsorbent, and method for producing same |
-
1986
- 1986-05-16 JP JP61110624A patent/JPS62267663A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995002820A1 (en) * | 1993-07-16 | 1995-01-26 | Merck Patent Gmbh | Stationary phases for use in hydrophobic interaction chromatography |
| JPH09500210A (en) * | 1993-07-16 | 1997-01-07 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Separation agent for hydrophobic chromatography |
| DE10005681B4 (en) * | 2000-02-07 | 2005-06-16 | Atc Dr. Mann E.K. | Method and device for the decontamination of metal-containing waters |
| US7205361B2 (en) * | 2001-09-28 | 2007-04-17 | Showa Denko K.K. | Particulate hydrophobic polymer, production process therefor and column for reversed-phase high-performance liquid chromatography |
| WO2013187512A1 (en) * | 2012-06-15 | 2013-12-19 | 旭化成メディカル株式会社 | Alkali-resistant ion exchange temperature-responsive adsorbent, and method for producing same |
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