JP2017181512A - Filler for column - Google Patents
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- Publication number
- JP2017181512A JP2017181512A JP2017091353A JP2017091353A JP2017181512A JP 2017181512 A JP2017181512 A JP 2017181512A JP 2017091353 A JP2017091353 A JP 2017091353A JP 2017091353 A JP2017091353 A JP 2017091353A JP 2017181512 A JP2017181512 A JP 2017181512A
- Authority
- JP
- Japan
- Prior art keywords
- porous polymer
- particle size
- polymer particles
- particles
- peak
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000945 filler Substances 0.000 title abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 316
- 229920000642 polymer Polymers 0.000 claims abstract description 93
- 238000012856 packing Methods 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 230000002902 bimodal effect Effects 0.000 claims description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 8
- 238000011049 filling Methods 0.000 abstract description 7
- 230000014509 gene expression Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 61
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- -1 alkyl vinyl ethers Chemical class 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 239000000839 emulsion Substances 0.000 description 17
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012736 aqueous medium Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 3
- 239000011146 organic particle Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 2
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- BJQFWAQRPATHTR-UHFFFAOYSA-N 1,2-dichloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1Cl BJQFWAQRPATHTR-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- LIFHMKCDDVTICL-UHFFFAOYSA-N 6-(chloromethyl)phenanthridine Chemical compound C1=CC=C2C(CCl)=NC3=CC=CC=C3C2=C1 LIFHMKCDDVTICL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Images
Abstract
Description
本発明は、カラム用充填材に関する。 The present invention relates to a column packing material.
分離、分取及び分析カラム用充填剤には多孔質シリカ又は多孔質ポリマーの粒子が使用される。これらは、必要に応じて官能基を有し、特定の物質の分離、分取又は分析に用いられてきた。有機粒子を多孔質ポリマー粒子として使用する場合、合成に用いるモノマーの種類（スチレン、ジビニルベンゼン、アクリル系樹脂、アガロース等）によって多様な特性が得られる点が長所である。有機粒子及びその製造法は、例えば、特許文献１〜４等に記載されている。また、アフィニティー精製用等の充填材には、殆ど有機粒子が用いられている。 Porous silica or porous polymer particles are used as fillers for separation, preparative and analytical columns. These have functional groups as required, and have been used for separation, fractionation or analysis of specific substances. When organic particles are used as porous polymer particles, the advantage is that various characteristics can be obtained depending on the types of monomers used in the synthesis (styrene, divinylbenzene, acrylic resin, agarose, etc.). The organic particles and the production method thereof are described in, for example, Patent Documents 1 to 4 and the like. In addition, organic particles are mostly used for fillers for affinity purification and the like.
このような多孔質ポリマー粒子を合成する方法として、懸濁重合法、ＳＰＧ膜乳化法又はシード重合法が用いられている。シード重合によって多孔質ポリマー粒子を合成する場合、粒径の単分散化及び小径化により、得られた多孔質ポリマー粒子を充填材として使用した際のカラムの理論段数が向上することが知られている（例えば、非特許文献１）。一方、粒子の粒度分布が単分散である場合において、粒子充填が不十分であると、理論段数の低下、分析ピークのテーリング発生等の問題があった。粒子充填が不十分になる可能性については、論文（例えば、非特許文献２）にて議論されている。 As a method for synthesizing such porous polymer particles, a suspension polymerization method, an SPG membrane emulsification method or a seed polymerization method is used. When synthesizing porous polymer particles by seed polymerization, it is known that the number of theoretical plates of the column improves when the obtained porous polymer particles are used as a filler by monodispersing and reducing the particle size. (For example, Non-Patent Document 1). On the other hand, when the particle size distribution of the particles is monodisperse, if the particle packing is insufficient, there are problems such as a decrease in the number of theoretical plates and occurrence of tailing of analysis peaks. The possibility of insufficient particle packing is discussed in a paper (for example, Non-Patent Document 2).
上記非特許文献２には、単分散粒子は最密充填以外にも種々の結晶構造で充填される可能性があるため、単分散粒子のみを用いて充填するよりも、粒径にばらつきがある方が密に充填されることが記載されている。また、単分散粒子を充填する際に充填欠陥が発生すると、その部分で欠陥に依存した結晶格子構造を形成するため、新規に結晶格子境界面が発生し易くなり、充填が疎になる問題が発生する。上記の観点から、理論段数の向上及び分析ピークのテーリング発生の抑制のためには、単分散粒子を使用する場合においても、その特性を損なうことなく、充填を最適化することが必要である。 In Non-Patent Document 2, the monodisperse particles may be filled with various crystal structures in addition to the close-packing, so that there is a variation in the particle size as compared with filling using only monodisperse particles. It is described that the direction is more closely packed. In addition, when a filling defect occurs when filling the monodisperse particles, a crystal lattice structure depending on the defect is formed at that portion, so that a new crystal lattice boundary surface is easily generated and the filling becomes sparse. Occur. From the above viewpoint, in order to improve the number of theoretical plates and to suppress the occurrence of tailing of analysis peaks, it is necessary to optimize the packing without impairing the characteristics even when using monodisperse particles.
本発明は、粒子充填性が改善され、高い理論段数を示し、かつ分析ピークのテーリング発生を十分に抑制することができるカラム用充填材を提供するものである。 The present invention provides a packing material for a column that has improved particle packing properties, exhibits a high number of theoretical plates, and can sufficiently suppress the occurrence of tailing of analysis peaks.
本発明は、多孔質ポリマー粒子を含有するカラム用充填材であって、多孔質ポリマー粒子の粒度分布が多峰性であり、各峰に含まれる多孔質ポリマー粒子が、多孔質ポリマー粒子全量に対してそれぞれ１０質量％以上であり、かつ各峰における半値幅及び極大粒径が、下記式（１）で表される要件を満たすカラム用充填材を提供する。
Ａ＜０．１１７７×Ｂ …（１）
［式中、Ａは半値幅を示し、Ｂは極大粒径を示す。］
The present invention is a column packing material containing porous polymer particles, the particle size distribution of the porous polymer particles is multimodal, and the porous polymer particles contained in each peak are in the total amount of the porous polymer particles. In contrast, the present invention provides a packing material for a column that is 10% by mass or more and satisfies the requirements represented by the following formula (1) in which the full width at half maximum and the maximum particle size at each peak.
A <0.1177 × B (1)
[In formula, A shows a half value width and B shows a maximum particle size. ]
なお、本明細書では、多峰性とは、粒度分布において極大粒径が２つ以上存在することをいう。 In this specification, multimodality means that there are two or more maximum particle sizes in the particle size distribution.
上記各峰における極大粒径と上記各峰のうち最も個数比が大きい峰の極大粒径との差は、上記各峰のうち最も個数比が大きい峰の極大粒径の値の１／５以上であると好ましい。これにより、カラムの理論段数をより効率良く向上させることができる。
また、上記各峰における、粒子の分散性を示すＣＶ値（Coefficient of Variation）が、それぞれ５％以下であると好ましい。
The difference between the maximum particle size of each peak and the maximum particle size of the peak having the largest number ratio among the peaks is equal to or more than 1/5 of the maximum particle diameter value of the peak having the largest number ratio among the peaks. Is preferable. Thereby, the theoretical plate number of a column can be improved more efficiently.
Further, it is preferable that the CV value (Coefficient of Variation) indicating the dispersibility of the particles at each peak is 5% or less.
また、上記多孔質ポリマー粒子が、スチレン−ジビニルベンゼンを含むと好ましい。これにより、耐酸及び耐アルカリ性を付与することができ、多孔質ポリマー粒子の表面官能基化が容易となる。
さらに、上記粒度分布が二峰性であると好ましい。二峰性とは、粒度分布において極大粒径が２つであることをいう。また、上記多孔質ポリマー粒子が、２種類のブレンドからなるカラム用充填材とすると好ましい。
また、上記多孔質ポリマー粒子が、シード重合により合成されたものであると好ましい。シード重合で粒子を合成すると、本発明の多孔質ポリマー粒子に適した単分散性の粒子が得られやすい。
The porous polymer particles preferably contain styrene-divinylbenzene. Thereby, acid resistance and alkali resistance can be imparted, and the surface functionalization of the porous polymer particles becomes easy.
Furthermore, the particle size distribution is preferably bimodal. Bimodality means that there are two maximum particle sizes in the particle size distribution. Moreover, it is preferable that the porous polymer particles be a column packing material composed of two kinds of blends.
The porous polymer particles are preferably synthesized by seed polymerization. When particles are synthesized by seed polymerization, monodisperse particles suitable for the porous polymer particles of the present invention can be easily obtained.
本発明のカラム用充填材を用いることにより、単分散粒子の充填が改善され、単分散粒子の特性を損なわずにカラムの理論段数を向上させることが可能となり、かつ分析ピークのテーリング発生を十分に抑制することができる。 By using the column packing material of the present invention, the packing of monodisperse particles is improved, the number of theoretical plates of the column can be improved without impairing the properties of the monodisperse particles, and the occurrence of tailing of analysis peaks is sufficient. Can be suppressed.
以下、本発明の実施の形態について詳細に説明するが、本発明は以下の実施形態に限定されるものではない。また本明細書において「〜」は、その前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示すものとする。また本明細書において、「（メタ）アクリレート」とは、「アクリレート」及びそれに対応する「メタクリレート」を意味する。「（メタ）アクリル酸」等の他の類似の表現においても同様である。 Hereinafter, although an embodiment of the present invention is described in detail, the present invention is not limited to the following embodiment. In addition, in this specification, “to” indicates a range including numerical values described before and after that as a minimum value and a maximum value, respectively. In this specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. The same applies to other similar expressions such as “(meth) acrylic acid”.
（多孔質ポリマー粒子）
本実施形態に係るカラム用充填材における多孔質ポリマー粒子は、例えば、シード重合法によって得ることができる。具体的には、シード粒子をモノマー、多孔化剤（多孔質剤）及び水性媒体を含む乳化液中で膨潤させた後、モノマーを重合させることにより得ることができる。
(Porous polymer particles)
The porous polymer particles in the column packing material according to the present embodiment can be obtained by, for example, a seed polymerization method. Specifically, the seed particles can be obtained by swelling the seed particles in an emulsion containing a monomer, a porous agent (porous agent) and an aqueous medium, and then polymerizing the monomer.
（シード粒子）
シード粒子としては、特に限定されないが、例えば、アクリル系粒子、スチレン系粒子等のビニル系樹脂粒子が挙げられる。
(Seed particles)
The seed particles are not particularly limited, and examples thereof include vinyl resin particles such as acrylic particles and styrene particles.
アクリル系粒子は、（メタ）アクリル系単量体の重合により得ることができる。（メタ）アクリル系単量体としては、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｔｅｒｔ−ブチル、アクリル酸ドデシル、アクリル酸ステアリル、アクリル酸２−エチルヘキシル、アクリル酸テトラヒドロフルフリル、ジエチルアミノエチルアクリレート、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｔｅｒｔ−ブチル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、ジエチルアミノエチルメタクリレート等が挙げられる。これら単量体は、単独で使用してもよく、２種以上併用してもよい。ここで、（メタ）アクリル系とは、アクリル系、メタクリル系、及びそれらの混合物を意味する。 Acrylic particles can be obtained by polymerization of (meth) acrylic monomers. Examples of (meth) acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, dodecyl acrylate, stearyl acrylate, 2-acrylic acid 2- Ethylhexyl, tetrahydrofurfuryl acrylate, diethylaminoethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, methacryl Examples include dodecyl acid, 2-ethylhexyl methacrylate, stearyl methacrylate, and diethylaminoethyl methacrylate. These monomers may be used alone or in combination of two or more. Here, (meth) acrylic means acrylic, methacrylic, and mixtures thereof.
アクリル系粒子は、（メタ）アクリル系単量体と、他の単量体との共重合により得られる粒子であってもよい。他の単量体としては、例えば、エチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等の（メタ）アクリル酸のグリコールエステル類；メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル類；酢酸ビニル、酪酸ビニル等のビニルエステル類；Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド等のＮ−アルキル置換（メタ）アクリルアミド類；アクリロニトリル、メタクリロニトリル等のニトリル類；ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリアクリレート等の多官能性単量体；スチレン、ｐ−メチルスチレン、ｐ−クロロスチレン、クロロメチルスチレン、α−メチルスチレン等のスチレン系単量体が挙げられる。これら他の単量体は、単独で使用してもよく、２種以上併用してもよい。 The acrylic particles may be particles obtained by copolymerization of a (meth) acrylic monomer and another monomer. Examples of other monomers include glycol esters of (meth) acrylic acid such as ethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate , Vinyl esters such as vinyl butyrate; N-alkyl substituted (meth) acrylamides such as N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide and N-ethylmethacrylamide; nitriles such as acrylonitrile and methacrylonitrile Polyfunctional monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane triacrylate; styrene, p-methylstyrene, p-chlorostyrene, chloromethyls Ren, styrenic monomers such as α- methyl styrene. These other monomers may be used alone or in combination of two or more.
スチレン系粒子は、例えば、スチレン、ｐ−メチルスチレン、ｐ−クロロスチレン、クロロメチルスチレン、α−メチルスチレン等のスチレン系単量体の重合により得られる粒子である。これらスチレン系単量体は、単独で使用してもよく、２種以上併用してもよい。 Styrenic particles are particles obtained by polymerization of styrene monomers such as styrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene, and α-methylstyrene. These styrene monomers may be used alone or in combination of two or more.
スチレン系粒子は、スチレン系単量体と、他の単量体との共重合により得られる粒子であってもよい。他の単量体としては、例えば、エチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等の（メタ）アクリル酸のグリコールエステル類；メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル類；酢酸ビニル、酪酸ビニル等のビニルエステル類、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド等のＮ−アルキル置換（メタ）アクリルアミド類；アクリロニトリル、メタクリロニトリル等のニトリル類；ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリアクリレート等の多官能性単量体；アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｔｅｒｔ−ブチル、アクリル酸ドデシル、アクリル酸ステアリル、アクリル酸２−エチルヘキシル、アクリル酸テトラヒドロフルフリル、ジエチルアミノエチルアクリレート、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｔｅｒｔ−ブチル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、ジエチルアミノエチルメタクリレート等の（メタ）アクリル系単量体が挙げられる。これら他の単量体は、単独で使用してもよく、２種以上併用してもよい。 The styrenic particles may be particles obtained by copolymerization of a styrenic monomer and another monomer. Examples of other monomers include glycol esters of (meth) acrylic acid such as ethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate , Vinyl esters such as vinyl butyrate, N-alkyl substituted (meth) acrylamides such as N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide and N-ethylmethacrylamide; nitriles such as acrylonitrile and methacrylonitrile Polyfunctional monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane triacrylate; acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate , Isobutyl acrylate, tert-butyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate , (Meth) acrylic monomers such as n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, diethylaminoethyl methacrylate, etc. Is mentioned. These other monomers may be used alone or in combination of two or more.
シード粒子は、上記の単量体を用いて、乳化重合法、ソープフリー乳化重合法、分散重合法等の公知の方法で合成することができる。 The seed particles can be synthesized by a known method such as an emulsion polymerization method, a soap-free emulsion polymerization method, or a dispersion polymerization method using the above-described monomer.
シード粒子の重量平均分子量（Ｍｗ）は、大きくなるとモノマーの吸収能力が低下したり、吸収させるモノマーと相分離して力学強度が低下し易くなり、小さくなると粒径が均一になり難くなる。そのため、シード粒子のＭｗは、５００００以下にすることが好ましく、３００００以下にすることがより好ましい。また、シード粒子のＭｗは、３０００以上が好ましく、５０００以上がより好ましい。なお、本明細書で規定するＭｗとは、ゲルパーミエイションクロマトグラフィー法（ＧＰＣ）により標準ポリスチレンによる検量線を用いて測定した値である。 When the weight average molecular weight (Mw) of the seed particles increases, the absorption capacity of the monomer decreases, or the mechanical strength tends to decrease due to phase separation with the monomer to be absorbed, and when the seed particles decrease, the particle diameter becomes difficult to be uniform. Therefore, the Mw of the seed particles is preferably 50000 or less, and more preferably 30000 or less. Moreover, 3000 or more are preferable and, as for Mw of a seed particle, 5000 or more are more preferable. In addition, Mw prescribed | regulated by this specification is the value measured using the analytical curve by a standard polystyrene by the gel permeation chromatography method (GPC).
シード粒子の平均粒径は、得られる多孔質ポリマー粒子の設計粒径に応じて調整することができる。シード粒子の平均粒径が大きくなるとモノマーの吸収に時間がかかり、平均粒径が小さくなると粒径が不均一になり真球性も低下し易くなる。シード粒子の平均粒径は多孔質ポリマー粒子の１／１０〜１とすることが好ましく、１／７〜１とすることがより好ましく、１／５〜１とすることがさらに好ましい。 The average particle size of the seed particles can be adjusted according to the design particle size of the obtained porous polymer particles. When the average particle size of the seed particles increases, it takes time to absorb the monomer, and when the average particle size decreases, the particle size becomes non-uniform and the sphericity tends to decrease. The average particle size of the seed particles is preferably 1/10 to 1 of the porous polymer particles, more preferably 1/7 to 1, and further preferably 1/5 to 1.
シード粒子の粒径（直径）の分散性を示す変動係数であるＣＶ（Coefficient of Variation）値は、大きくなると得られる多孔質ポリマー粒子の均一性が低下し易くなることから、５％以下にすることが好ましく、４％以下にすることがより好ましく、３％以下にすることがさらに好ましい。 The CV (Coefficient of Variation) value, which is a coefficient of variation indicating the dispersibility of the particle size (diameter) of the seed particles, is reduced to 5% or less because the uniformity of the obtained porous polymer particles tends to decrease as the particle size increases. It is preferably 4% or less, more preferably 3% or less.
シード粒子の平均粒径及び粒径のＣＶ値は、走査型電子顕微鏡（ＳＥＭ）で、対象となるシード粒子を１００個観察して粒径を測定することにより算出することができ、また、マイクロトラック粒度分析計（日機装株式会社製）のような粒子径・粒度分布測定装置を用いて測定される粒径から算出することも可能である。なお、ＣＶ値は、下記の式で表されるものである。
ＣＶ（％）＝（σ／Ｄ）×１００
σ：標準偏差、Ｄ：平均粒径
このＣＶ値が小さいほどより単分散であることを示す。一般的にＣＶ値が１０％以下になると単分散性が高いとされており、上記の５％以下はきわめて高い単分散性であることを示す。
The average particle size and the CV value of the particle size of the seed particles can be calculated by observing 100 target particle particles with a scanning electron microscope (SEM) and measuring the particle size. It is also possible to calculate from the particle size measured using a particle size / particle size distribution measuring device such as a truck particle size analyzer (manufactured by Nikkiso Co., Ltd.). The CV value is expressed by the following formula.
CV (%) = (σ / D) × 100
σ: Standard deviation, D: Average particle diameter The smaller this CV value, the more monodispersed. Generally, when the CV value is 10% or less, it is considered that the monodispersity is high, and the above 5% or less indicates extremely high monodispersity.
（モノマー）
乳化液に用いられるモノマーとして、例えば、以下の多官能性モノマー、単官能性モノマー等が挙げられる。
(monomer)
Examples of the monomer used in the emulsion include the following polyfunctional monomers and monofunctional monomers.
多官能性モノマーとしては、例えば、ジビニルベンゼン、ジビニルビフェニル、ジビニルナフタレン等のジビニル化合物；（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、（ポリ）テトラメチレングリコールジ（メタ）アクリレート等の（ポリ）アルキレングリコール系ジ（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、１，１，１−トリスヒドロキシメチルエタントリ（メタ）アクリレート、１，１，１−トリスヒドロキシメチルプロパントリアクリレート等の３官能以上の（メタ）アクリレート；エトキシ化ビスフェノールＡ系ジ（メタ）アクリレート、プロポキシ化エトキシ化ビスフェノールＡ系ジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、１，１，１−トリスヒドロキシメチルエタンジ（メタ）アクリレート、エトキシ化シクロヘキサンジメタノールジ（メタ）アクリレート等のジ（メタ）アクリレート；ジアリルフタレート及びその異性体；トリアリルイソシアヌレート及びその誘導体などが挙げられる。これらモノマーの中でも、新中村化学工業株式会社製のＮＫエステル（Ａ−ＴＭＰＴ−６Ｐ０、Ａ−ＴＭＰＴ−３Ｅ０、Ａ−ＴＭＭ−３ＬＭＮ、Ａ−ＧＬＹシリーズ、Ａ−９３００、ＡＤ−ＴＭＰ、ＡＤ−ＴＭＰ−４ＣＬ、ＡＴＭ−４Ｅ、Ａ−ＤＰＨ）等が、商業的に入手可能である。これらの多官能性モノマーは、単独で使用してもよく、２種以上を併用してもよい。上記のなかでも耐酸性及び耐アルカリ性の観点よりジビニルベンゼンを使用することが好ましい。 Examples of multifunctional monomers include divinyl compounds such as divinylbenzene, divinylbiphenyl, divinylnaphthalene; (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and (poly) tetramethylene glycol. (Poly) alkylene glycol-based di (meth) acrylates such as di (meth) acrylate; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri ( (Meth) trifunctional or higher (meth) such as (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane triacrylate Acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meta ) Acrylate, di (meth) acrylate such as ethoxylated cyclohexanedimethanol di (meth) acrylate; diallyl phthalate and isomers thereof; triallyl isocyanurate and derivatives thereof. Among these monomers, NK ester (A-TMPT-6P0, A-TMPT-3E0, A-TMM-3LMN, A-GLY series, A-9300, AD-TMP, AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd. -4CL, ATM-4E, A-DPH) and the like are commercially available. These polyfunctional monomers may be used alone or in combination of two or more. Among these, divinylbenzene is preferably used from the viewpoint of acid resistance and alkali resistance.
単官能性モノマーとしては、例えば、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｏ−エチルスチレン、ｍ−エチルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｐ−クロロスチレン、３，４−ジクロロスチレン等のスチレン及びその誘導体；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ヘキシル、アクリル酸２−エチルヘキシル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸２−クロロエチル、アクリル酸フェニル、α−クロロアクリル酸メチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ヘキシル、メタクリル酸２−エチルヘキシル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸ラウリル、メタクリル酸ステアリル等の（メタ）アクリル酸エステル；酢酸ビニル、プロピオン酸ビニル、安息香酸ビニル、酪酸ビニル等のビニルエステル；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドン等のＮ−ビニル化合物；フッ化ビニル、フッ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、アクリル酸トリフルオロエチル、アクリル酸テトラフルオロプロピル等の含フッ素化モノマー；ブタジエン、イソプレン等の共役ジエンなどが挙げられる。これらは単独で使用してもよく、２種以上を併用してもよい。上記の中でも耐酸性及び耐アルカリ性を有するスチレンを使用することが好ましい。 Examples of the monofunctional monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4- Dimethyl styrene, pn-butyl styrene, pt-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl Styrene such as styrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and derivatives thereof; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid Isobutyl, hexyl acrylate, 2-ethylhexyl acrylate, acrylic acid n-o Chill, dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacryl (Meth) acrylic acid esters such as isobutyl acid, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate; vinyl acetate, vinyl propionate, vinyl benzoate, Vinyl esters such as vinyl butyrate; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; vinyl fluoride, vinylidene fluoride, tetrafluoroe Ren, hexafluoropropylene, trifluoroethyl acrylate, fluorine-containing monomers such as acrylic acid tetrafluoropropyl; butadiene, and the like conjugated dienes isoprene and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use styrene having acid resistance and alkali resistance.
乳化液に用いられるモノマーとしては、スチレン及びジビニルベンゼンを含むことが好ましい。 It is preferable that styrene and divinylbenzene are contained as a monomer used for the emulsion.
（多孔質剤）
多孔質剤（多孔化剤）としては、例えば、シード重合時に相分離剤として作用し、粒子の多孔質化を促進する有機溶媒である脂肪族又は芳香族の炭化水素類、エステル類、ケトン類、エーテル類、アルコール類が挙げられる。具体的には、トルエン、キシレン、ジエチルベンゼン、シクロヘキサン、オクタン、酢酸ブチル、フタル酸ジブチル、メチルエチルケトン、ジブチルエーテル、１−ヘキサノール、２−オクタノール、デカノール、ラウリルアルコール、シクロヘキサノール等が挙げられ、これらを単独で、又は２種以上を混合して用いることができる。
(Porous agent)
Examples of the porous agent (porosifying agent) include aliphatic or aromatic hydrocarbons, esters, and ketones that are organic solvents that act as a phase separation agent during seed polymerization and promote particle porosity. , Ethers and alcohols. Specific examples include toluene, xylene, diethylbenzene, cyclohexane, octane, butyl acetate, dibutyl phthalate, methyl ethyl ketone, dibutyl ether, 1-hexanol, 2-octanol, decanol, lauryl alcohol, cyclohexanol and the like. Or a mixture of two or more.
多孔質剤は、モノマー１００質量％に対して０〜２００質量％使用できる。多孔質剤の量によって、得られるポリマー粒子の空孔率をコントロールできる。さらに多孔質剤の種類によって、孔の大きさ及び形状をコントロールすることができる。 The porous agent can be used in an amount of 0 to 200% by mass with respect to 100% by mass of the monomer. The porosity of the polymer particles obtained can be controlled by the amount of the porous agent. Further, the size and shape of the pores can be controlled by the kind of the porous agent.
（水性媒体）
水性媒体としては、水、又は水と水溶性溶媒（例えば、低級アルコール）との混合媒体が挙げられる。水性媒体には、界面活性剤が含まれている。界面活性剤としては、アニオン系、カチオン系、ノニオン系及び両性イオン系の界面活性剤のうち、いずれも用いることができる。
(Aqueous medium)
Examples of the aqueous medium include water or a mixed medium of water and a water-soluble solvent (for example, a lower alcohol). The aqueous medium contains a surfactant. As the surfactant, any of anionic, cationic, nonionic and zwitterionic surfactants can be used.
アニオン系界面活性剤としては、例えば、オレイン酸ナトリウム、ヒマシ油カリ等の脂肪酸油、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム等のアルキル硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルカンスルホン酸塩、ジオクチルスルホコハク酸ナトリウム等のジアルキルスルホコハク酸塩、アルケルニルコハク酸塩（ジカリウム塩）、アルキルリン酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシエチレンラウリルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキル硫酸エステル塩などが挙げられる。 Examples of the anionic surfactant include fatty acid oils such as sodium oleate and castor oil potassium, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfone. Acid salts, alkane sulfonates, dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate, alkenyl succinates (dipotassium salts), alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkylphenyl ether sulfates Examples thereof include salts, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl sulfate salts.
カチオン系界面活性剤としては、例えば、ラウリルアミンアセテート、ステアリルアミンアセテート等のアルキルアミン塩、ラウリルトリメチルアンモニウムクロライド等の第四級アンモニウム塩などが挙げられる。 Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
ノニオン系界面活性剤としては、例えば、ポリエチレングリコールアルキルエーテル類、ポリエチレングリコールアルキルアリールエーテル類、ポリエチレングリコールエステル類、ポリエチレングリコールソルビタンエステル類、ポリアルキレングリコールアルキルアミン又はアミド類等の炭化水素系ノニオン界面活性剤、シリコーンのポリエチレンオキサイド付加物類、ポリプロピレンオキサイド付加物類等のポリエーテル変性シリコーン系ノニオン界面活性剤、パーフルオロアルキルグリコール類等のフッ素系ノニオン界面活性剤などが挙げられる。 Nonionic surfactants include, for example, hydrocarbon nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, or amides. Agents, polyether-modified silicone-based nonionic surfactants such as silicone polyethylene oxide adducts and polypropylene oxide adducts, and fluorine-based nonionic surfactants such as perfluoroalkyl glycols.
両性イオン系界面活性剤としては、例えば、ラウリルジメチルアミンオキサイド等の炭化水素界面活性剤、リン酸エステル系界面活性剤及び亜リン酸エステル系界面活性剤が挙げられる。 Examples of zwitterionic surfactants include hydrocarbon surfactants such as lauryl dimethylamine oxide, phosphate ester surfactants, and phosphite ester surfactants.
界面活性剤は、１種を単独で又は２種以上を組み合わせて用いてもよい。上記界面活性剤の中でも、モノマーの重合時の分散安定性の観点から、アニオン系界面活性剤が好ましい。 One surfactant may be used alone, or two or more surfactants may be used in combination. Among the above surfactants, an anionic surfactant is preferable from the viewpoint of dispersion stability during polymerization of the monomer.
シード重合法は、公知の方法を参考にして行うことができる。以下にシード重合法の一般的な方法を説明するが、この方法に限定されるものではない。 The seed polymerization method can be performed with reference to a known method. A general method of the seed polymerization method will be described below, but is not limited to this method.
まず、モノマー、多孔化剤（多孔質剤）及び水性媒体を含む乳化液に、シード粒子を添加する。シード粒子は、乳化液に直接添加してもよく、シード粒子を水性分散体（水性媒体）に分散させた形態で添加してもよい。 First, seed particles are added to an emulsion containing a monomer, a porous agent (porous agent) and an aqueous medium. The seed particles may be added directly to the emulsion or may be added in a form in which the seed particles are dispersed in an aqueous dispersion (aqueous medium).
シード重合に用いられる乳化液は、公知の方法により作製できる。例えば、モノマーを水性媒体に添加して、ホモジナイザー、超音波処理機、ナノマイザー等の微細乳化機により水性媒体に分散させることで、乳化液を得ることができる。乳化液は、必要に応じて重合開始剤を含んでいてもよい。重合開始剤は、モノマーに予め混合させた後、水性媒体中に分散させてもよいし、重合開始剤とモノマーとを別々に水性媒体に分散させたものを混合してもよい。得られた乳化液中のモノマー液滴の粒径は、シード粒子の粒径よりも小さいほうが、モノマーがシード粒子に効率よく吸収される。 The emulsion used for seed polymerization can be prepared by a known method. For example, an emulsion can be obtained by adding a monomer to an aqueous medium and dispersing the monomer in an aqueous medium using a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer. The emulsion may contain a polymerization initiator as necessary. The polymerization initiator may be mixed in advance with the monomer and then dispersed in an aqueous medium, or a mixture of a polymerization initiator and a monomer separately dispersed in an aqueous medium may be mixed. When the particle size of the monomer droplets in the obtained emulsion is smaller than the particle size of the seed particles, the monomer is efficiently absorbed by the seed particles.
必要に応じて添加される重合開始剤としては、例えば、過酸化ベンゾイル、過酸化ラウロイル、オルソクロロ過酸化ベンゾイル、オルソメトキシ過酸化ベンゾイル、３，５，５−トリメチルヘキサノイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、ジ−ｔｅｒｔ−ブチルパーオキサイド等の有機過酸化物；２，２’−アゾビスイソブチロニトリル、１，１’−アゾビスシクロヘキサンカルボニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系化合物が挙げられる。重合開始剤は、モノマー１００質量部に対して、０．１〜７．０質量部の範囲で使用するとよい。 Examples of the polymerization initiator added as necessary include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butyl peroxide. Organic peroxides such as oxy-2-ethylhexanoate and di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2,2 ′ -Azo compounds such as azobis (2,4-dimethylvaleronitrile). The polymerization initiator may be used in the range of 0.1 to 7.0 parts by mass with respect to 100 parts by mass of the monomer.
シード粒子を乳化液へ添加した後、シード粒子にモノマーを吸収させて膨潤させる。この吸収は、通常、シード粒子を添加した後の乳化液を、室温（２５℃）で１〜２４時間攪拌することで行うことができる。また、乳化液を３０〜５０℃程度に加温することによりモノマーの吸収を促進することができる。 After the seed particles are added to the emulsion, the seed particles are allowed to absorb the monomer and swell. This absorption can be normally performed by stirring the emulsion after adding seed particles at room temperature (25 ° C.) for 1 to 24 hours. Moreover, absorption of a monomer can be accelerated | stimulated by heating an emulsion to about 30-50 degreeC.
シード粒子は、モノマーを吸収することにより膨潤する。シード粒子に対するモノマーの混合比率が小さくなると、モノマーのシード重合により作製される多孔質ポリマー粒子の粒径の増加が小さくなり、多孔質ポリマー粒子の生産性が低下する傾向にある。一方、モノマーの混合比率が大きくなるとシード粒子に吸収されないで、水性媒体中でモノマーが独自に懸濁重合してしまい、目的とする粒径以外の粒子が生成することがある。なお、モノマーの吸収の終了は、光学顕微鏡を用いてシード粒子を観察して粒径の拡大を確認することにより判定できる。 The seed particles swell by absorbing the monomer. When the mixing ratio of the monomer to the seed particles is reduced, the increase in the particle size of the porous polymer particles produced by the seed polymerization of the monomer is reduced, and the productivity of the porous polymer particles tends to be reduced. On the other hand, when the mixing ratio of the monomer is increased, the monomer may not be absorbed by the seed particles, and the monomer may be uniquely suspension-polymerized in the aqueous medium, and particles other than the target particle size may be generated. The completion of monomer absorption can be determined by observing seed particles using an optical microscope and confirming the increase in particle size.
次に、シード粒子に吸収させたモノマーを重合させる。重合温度は、モノマー及び重合開始剤の種類に応じて、適宜選択することができる。重合温度は、２５〜１１０℃が好ましく、５０〜１００℃がより好ましい。重合反応は、シード粒子が十分に膨潤し、モノマー及び任意に重合開始剤が完全に吸収された後に、昇温して行うのが好ましい。 Next, the monomer absorbed in the seed particles is polymerized. The polymerization temperature can be appropriately selected according to the types of the monomer and the polymerization initiator. The polymerization temperature is preferably 25 to 110 ° C, more preferably 50 to 100 ° C. The polymerization reaction is preferably carried out at an elevated temperature after the seed particles are sufficiently swollen and the monomer and optionally the polymerization initiator are completely absorbed.
上記重合工程において、シード粒子の分散安定性を向上させるために、乳化液に高分子分散安定剤を添加してもよい。高分子分散安定剤としては、例えば、ポリビニルアルコール、ポリカルボン酸、セルロース類（ヒドロキシエチルセルロース、カルボキシメチルセルロース等）、ポリビニルピロリドン等が挙げられ、トリポリリン酸ナトリウム等の無機系水溶性高分子化合物も併用することができる。これらのうち、ポリビニルアルコール又はポリビニルピロリドンが好ましい。高分子分散安定剤の添加量は、モノマー１００質量部に対して１〜１０質量部が好ましい。 In the polymerization step, a polymer dispersion stabilizer may be added to the emulsion in order to improve the dispersion stability of the seed particles. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinyl pyrrolidone, and the like, and an inorganic water-soluble polymer compound such as sodium tripolyphosphate is also used in combination. be able to. Of these, polyvinyl alcohol or polyvinyl pyrrolidone is preferred. The addition amount of the polymer dispersion stabilizer is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the monomer.
水中でモノマーが単独に乳化重合することによって粒子が発生することを抑えるために、亜硝酸塩類、亜硫酸塩類、ハイドロキノン類、アスコルビン酸類、水溶性ビタミンＢ類、クエン酸、ポリフェノール類等の水溶性の重合禁止剤を乳化液に用いてもよい。 In order to suppress the generation of particles by emulsion polymerization of monomers alone in water, water-soluble nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, polyphenols, etc. A polymerization inhibitor may be used in the emulsion.
上述の方法により、シード粒子にモノマーを重合させることによって、多孔質ポリマー粒子を得ることができる。 Porous polymer particles can be obtained by polymerizing the seed particles with a monomer by the above-described method.
多孔質ポリマー粒子の粒度分布が多峰性であるカラム用充填材の製造方法として、例えば、シード重合によって得られる多孔質ポリマー粒子を混合する方法を用いることができる。具体的には、シード重合を複数の条件で行うことで、粒径の異なる多孔質ポリマー粒子を得、得られた多孔質ポリマー粒子を混合することによって、粒度分布に２つ以上の極大粒径を有する多孔質ポリマー粒子を得ることができる。上記の方法の他に、２つ以上の異なる粒径を有するシード粒子を使用し、同時にシード重合することによって、異なる粒径を有する多孔質ポリマー粒子を予め混合された状態で得ることもできる。また、シード重合時にシード粒子を添加するタイミングを複数回に分割し、シード粒子の粒径の増加率を変えることによって、異なる粒径を有する多孔質ポリマー粒子を予め混合された状態で得ることもできる。 As a method for producing a packing material for a column having a multimodal particle size distribution of the porous polymer particles, for example, a method of mixing porous polymer particles obtained by seed polymerization can be used. Specifically, by performing seed polymerization under a plurality of conditions, porous polymer particles having different particle diameters are obtained, and by mixing the obtained porous polymer particles, two or more maximum particle diameters in the particle size distribution are obtained. Porous polymer particles having can be obtained. In addition to the above-mentioned method, porous polymer particles having different particle diameters can be obtained in a premixed state by using seed particles having two or more different particle diameters and simultaneously performing seed polymerization. Also, by dividing the timing of adding seed particles during seed polymerization into multiple times and changing the rate of increase in seed particle size, porous polymer particles having different particle sizes can be obtained in a premixed state. it can.
本実施形態における多孔質ポリマー粒子は、粒度分布において各峰に含まれる多孔質ポリマー粒子が、多孔質ポリマー粒子の全量に対してそれぞれ１０質量％以上である。シード重合を行った後で粒径の異なる多孔質ポリマー粒子を混合することにより粒度分布が多峰性である多孔質ポリマー粒子を得る場合には、混合する各粒径を有する多孔質ポリマー粒子の質量を、多孔質ポリマー粒子の全量に対してそれぞれ１０質量％以上とすることによって、このようなカラム用充填材を得ることができる。 In the porous polymer particles in the present embodiment, the porous polymer particles contained in each peak in the particle size distribution are each 10% by mass or more based on the total amount of the porous polymer particles. When porous polymer particles having a multi-modal particle size distribution are obtained by mixing porous polymer particles having different particle diameters after seed polymerization, the porous polymer particles having respective particle diameters to be mixed are obtained. By setting the mass to 10% by mass or more with respect to the total amount of the porous polymer particles, such a column packing material can be obtained.
また、本実施形態における多孔質ポリマー粒子は、上記各峰における半値幅及び極大粒径が、下記式（１）で表される要件を満たす。
Ａ＜０．１１７７×Ｂ …（１）
［式中、Ａは半値幅を示し、Ｂは極大粒径を示す。］
Moreover, the porous polymer particle in this embodiment satisfy | fills the requirement represented by following formula (1) in the half value width and maximum particle size in each said peak.
A <0.1177 × B (1)
[In formula, A shows a half value width and B shows a maximum particle size. ]
カラム用充填材が、粒度分布が多峰性である多孔質ポリマー粒子を含有することにより、カラム中での粒子の充填が改善され、カラムの理論段数を向上させることができる。粒度分布における粒径の極大値数、すなわち峰の数は特に制限はないが、精密に理論段数を制御する観点から、５つ以下であることが好ましく、２つであることがより好ましい。 When the column packing material contains porous polymer particles having a multimodal particle size distribution, the packing of the particles in the column can be improved, and the number of theoretical plates of the column can be improved. The maximum value of the particle size in the particle size distribution, that is, the number of peaks is not particularly limited, but is preferably 5 or less, more preferably 2 from the viewpoint of precisely controlling the number of theoretical plates.
また、効果的にカラムの理論段数を向上させる目的から、各峰における極大粒径と各峰のうち最も個数比が大きい峰の極大粒径との差は、各峰のうち最も個数比が大きい峰の極大粒径の値の１／５以上であることが望ましく、５以下であることが好ましい。 Also, for the purpose of effectively increasing the number of theoretical plates of the column, the difference between the maximum particle size at each peak and the maximum particle size of the peak with the largest number ratio among the peaks is the largest number ratio among the peaks. It is preferably 1/5 or more of the value of the peak maximum particle size, and preferably 5 or less.
カラム用充填材に含有される多孔質ポリマー粒子全体の平均粒径は、好ましくは５０μｍ以下、より好ましくは１０μｍ以下、さらに好ましくは７．０μｍ以下、特に好ましくは５．０μｍ以下である。また、多孔質ポリマー粒子の平均粒径は、好ましくは１．０μｍ以上、より好ましくは１．７５μｍ以上であり、さらに好ましくは２．０μｍ以上、特に好ましくは２．５μｍ以上である。平均粒径が小さくなると、カラム充填後のカラム圧が増加する可能性がある。 The average particle size of the entire porous polymer particles contained in the column packing material is preferably 50 μm or less, more preferably 10 μm or less, still more preferably 7.0 μm or less, and particularly preferably 5.0 μm or less. The average particle size of the porous polymer particles is preferably 1.0 μm or more, more preferably 1.75 μm or more, still more preferably 2.0 μm or more, and particularly preferably 2.5 μm or more. When the average particle size is reduced, the column pressure after column filling may increase.
カラム充填後のカラム圧を低減する目的で、粒度分布の各峰における粒径のＣＶ値は、それぞれ５％以下であることが好ましい。同様の観点から、各峰における粒径のＣＶ値は、より好ましくは４％以下、さらに好ましくは３％以下である。 For the purpose of reducing the column pressure after column filling, the CV value of the particle size at each peak of the particle size distribution is preferably 5% or less. From the same viewpoint, the CV value of the particle diameter at each peak is more preferably 4% or less, and further preferably 3% or less.
図１は、本実施形態に係るカラム用充填材に含有される多孔質ポリマー粒子の粒度分布を示す概念図である。グラフの横軸は粒径を、縦軸は頻度（％）を示す。峰とは図１においてそれぞれＥｎで示される山状の各領域を指す。峰Ｅｎが粒度分布中に複数存在することを、粒度分布が多峰性であるといい、特に峰Ｅｎが粒度分布中に２つ存在することを、粒度分布が二峰性であるという。各峰はそれぞれ１つの極大粒径を有する。半値幅とは、各峰において頻度が極大頻度Ｄｎの１／２であるときの峰の幅であり、図１中のＡｎで表される。各峰における極大粒径とは、各峰において頻度が最大である粒径であり、図１中のＢｎで表される。各峰のうち最も個数比が大きい峰の極大粒径とは、例えば、図１中、Ｅ１が各峰のうち最も個数比の大きい峰であるとき、Ｂ１で表される。また、このとき、各峰の極大粒径と各峰のうち個数比が最も大きい峰の極大粒径との差とは、Ｅ１以外の各峰Ｅｎの極大粒径Ｂｎと、Ｂ１との差であり、図１中、Ｃｎで示される。例えばＣ１はＢ２とＢ１との差である。 FIG. 1 is a conceptual diagram showing the particle size distribution of porous polymer particles contained in the column packing material according to the present embodiment. The horizontal axis of the graph indicates the particle size, and the vertical axis indicates the frequency (%). The peaks refer to mountain shape of each area indicated respectively by E n in FIG. That peaks E n is more present in the particle size distribution, called the particle size distribution is multimodal, that is particularly Mine E n there are two in the particle size distribution, that the particle size distribution is bimodal . Each peak has one maximum particle size. The half-value width, frequency in each crest is the width of the peaks when a half of the maximum frequency Dn, represented by A n in FIG. The maximum particle size at each peak is a particle size having the highest frequency at each peak, and is represented by Bn in FIG. The peaks of the pole large particle size most number ratio is large among the peaks, for example, in FIG. 1, when E 1 is larger peaks of the most number ratio among the peaks, represented by B 1. At this time, the difference between the largest pole large particle size peaks are number ratio among the peaks of the pole large particle size and Kakumine has a very large size B n of each peaks E n other than E 1, B 1 And is indicated by C n in FIG. For example, C 1 is the difference between B 2 and B 1 .
多孔質ポリマー粒子の粒度分布の、各峰におけるモード径（極大粒径）、半値幅、粒径のＣＶ値、各峰に含まれる粒子の個数、及び平均粒径は、以下の測定法により求めることができる。まず、粒子を超音波分散装置により水に分散させ、１質量％の粒子を含む分散液を調製する。次に、湿式フロー式粒子径・形状分析装置（マルバーン社製のＦＰＩＡ−３０００）を用いて、上記分散液中の粒子約１０万個について、ガラスセル中を流れる懸濁液中の粒子画像をＣＣＤで高速撮像し、個々の粒子画像をリアルタイムに解析する。これにより、各峰におけるモード径（極大粒径）、半値幅、粒径のＣＶ値、各峰に含まれる粒子の数、及び平均粒径を算出することができる。さらに、各峰に含まれる多孔質ポリマー粒子の体積比から各峰に含まれる多孔質ポリマー粒子の質量比を求めることができる。 The mode diameter (maximum particle diameter), half-value width, CV value of the particle diameter, the number of particles contained in each peak, and the average particle diameter of the particle size distribution of the porous polymer particles are determined by the following measurement methods. be able to. First, particles are dispersed in water using an ultrasonic dispersion device to prepare a dispersion containing 1% by mass of particles. Next, using a wet flow type particle size / shape analyzer (FPIA-3000 manufactured by Malvern), about 100,000 particles in the dispersion liquid, a particle image in the suspension flowing in the glass cell is obtained. High-speed imaging is performed with a CCD, and individual particle images are analyzed in real time. Thereby, the mode diameter (maximum particle diameter), the half value width, the CV value of the particle diameter, the number of particles included in each peak, and the average particle diameter can be calculated. Furthermore, the mass ratio of the porous polymer particles contained in each peak can be determined from the volume ratio of the porous polymer particles contained in each peak.
本実施形態における多孔質ポリマー粒子は、表面積が約５０ｍ２／ｇ以上の粒子であることが好ましく、実用性から約８０ｍ２／ｇ以上であることが好ましく、３００ｍ２／ｇ以上であることがさらに好ましい。表面積が小さいと、分析及び分離に悪影響を及ぼすため、好ましくない。 The porous polymer particles in the present embodiment are preferably particles having a surface area of about 50 m 2 / g or more, preferably about 80 m 2 / g or more, and 300 m 2 / g or more in terms of practicality. Further preferred. A small surface area is undesirable because it adversely affects analysis and separation.
多孔質ポリマー粒子の平均細孔直径に関しては、３０〜１０００Åの平均細孔直径を有することが好ましい。この範囲より小さい場合、細孔に入れない物質が増えてくるため好ましくなく、この範囲より大きい場合、表面積が小さくなる。これらは上記の多孔質剤により調整可能である。多孔質ポリマー粒子の表面積及び平均細孔直径は、例えば、自動比表面積計／細孔分布測定装置（日本ベル社製）によって測定することができる。 Regarding the average pore diameter of the porous polymer particles, it is preferable to have an average pore diameter of 30 to 1000 mm. If it is smaller than this range, the number of substances that cannot enter the pores increases, which is not preferable. These can be adjusted by the above porous agent. The surface area and average pore diameter of the porous polymer particles can be measured by, for example, an automatic specific surface area meter / pore distribution measuring device (manufactured by Nippon Bell Co., Ltd.).
以上のようにして製造された多孔質ポリマー粒子は、適宜官能基を付与した後、分離、分取、分析又は精製用充填剤として使用することができる。特に液体クロマトグラフィー用充填剤に好適に用いることができる。 The porous polymer particles produced as described above can be used as a filler for separation, fractionation, analysis or purification after appropriately imparting a functional group. In particular, it can be suitably used for a packing material for liquid chromatography.
以下、本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
（シード粒子１の合成）
５００ｍＬの三口フラスコに、スチレン（ＳＴ）４０ｇ、オクタンチオール（ＯＣＴ）４ｇ、ペルオキソ二硫酸カリウム（ＫＰＳ）１．９８ｇ及び水４００ｇを一括して仕込み、７０℃のウォーターバスで加熱しながら、攪拌機を用いて約８時間攪拌をして、シード粒子１を形成させた。
(Synthesis of seed particles 1)
A 500 mL three-necked flask is charged with 40 g of styrene (ST), 4 g of octanethiol (OCT), 1.98 g of potassium peroxodisulfate (KPS), and 400 g of water, and heated with a water bath at 70 ° C. while stirring. The resulting mixture was stirred for about 8 hours to form seed particles 1.
（シード粒子２の合成）
５００ｍＬの三口フラスコに、スチレン（ＳＴ）４０ｇ、オクタンチオール（ＯＣＴ）４ｇ、過酸化ベンゾイル（ＢＰＯ）２ｇ及び水３４０ｇを一括して仕込み、超音波ホモジナイザーで乳化後、シード粒子１を固形分換算で０．４ｇ投入し、８時間攪拌し、シード粒子１を膨潤させた。続いて、８０℃に昇温し、約８時間攪拌をして、平均粒径３μｍのシード粒子を形成させた。
(Synthesis of seed particles 2)
A 500 mL three-necked flask is charged with 40 g of styrene (ST), 4 g of octanethiol (OCT), 2 g of benzoyl peroxide (BPO), and 340 g of water. 0.4 g was added and stirred for 8 hours to swell seed particles 1. Subsequently, the temperature was raised to 80 ° C., and the mixture was stirred for about 8 hours to form seed particles having an average particle diameter of 3 μm.
さらに、５００ｍＬの三口フラスコに、スチレン（ＳＴ）４０ｇ、オクタンチオール（ＯＣＴ）４ｇ、過酸化ベンゾイル（ＢＰＯ）２ｇ及び水３４０ｇを一括して仕込み、超音波ホモジナイザーで乳化後、上記で得られた平均粒径３μｍのシード粒子を固形分換算で０．４ｇ投入し、２０時間攪拌し、シード粒子を膨潤させた。続いて、乳化液を８０℃に昇温し、約８時間攪拌をして、シード粒子２を形成させた。 Further, 40 g of styrene (ST), 4 g of octanethiol (OCT), 2 g of benzoyl peroxide (BPO) and 340 g of water were charged all at once into a 500 mL three-necked flask, emulsified with an ultrasonic homogenizer, and the average obtained above. 0.4 g of seed particles having a particle size of 3 μm was added in terms of solid content and stirred for 20 hours to swell the seed particles. Subsequently, the emulsion was heated to 80 ° C. and stirred for about 8 hours to form seed particles 2.
合成したシード粒子１及びシード粒子２をそれぞれＳＥＭにより観察し、粒径（平均粒径）及び粒径ＣＶ値を算出した。また、これらの粒子の重量平均分子量（Ｍｗ）を測定した。その結果を表１に示す。 The synthesized seed particles 1 and seed particles 2 were observed by SEM, and the particle size (average particle size) and the particle size CV value were calculated. Further, the weight average molecular weight (Mw) of these particles was measured. The results are shown in Table 1.
（多孔質ポリマー粒子１の合成）
重合開始剤として過酸化ベンゾイル１ｇ、モノマーとしてスチレン１０ｇ及びジビニルベンゼン２．５ｇ、並びに多孔質剤としてトルエン３．７５ｇ及びジエチルベンゼン３．７５ｇを、溶媒（イオン交換水９２．２質量％、エタノール７．５質量％、及び界面活性剤としてエマールＴＤ（ラウリル硫酸トリエタノールアミン、花王株式会社製）０．３質量％を混合したもの）３４０ｇに分散し、ホモジナイザーと超音波照射で１０分間処理し、乳化を行い、乳化液を得た。得られた乳化液にシード粒子１を固形分換算で０．４７ｇ添加した後、２０時間膨潤を行った。その後、８０℃に昇温し、８時間重合を行った。重合終了後、得られた粒子を水及びメタノールで洗浄した。
(Synthesis of porous polymer particle 1)
1 g of benzoyl peroxide as a polymerization initiator, 10 g of styrene and 2.5 g of divinylbenzene as monomers, 3.75 g of toluene and 3.75 g of diethylbenzene as a porous agent, a solvent (92.2% by mass of ion-exchanged water, 7. Disperse in 5% by mass and 340 g of Emar TD (mixed with 0.3% by mass of triethanolamine lauryl sulfate, Kao Co., Ltd.) as a surfactant), treated with a homogenizer and ultrasonic irradiation for 10 minutes, and emulsified To obtain an emulsion. After 0.47 g of seed particles 1 in terms of solid content was added to the obtained emulsion, swelling was performed for 20 hours. Then, it heated up at 80 degreeC and superposition | polymerization was performed for 8 hours. After completion of the polymerization, the obtained particles were washed with water and methanol.
最後に、得られた粒子に濃硫酸を用いてスルホン化を行った。具体的には、得られた粒子１０ｇに対し、ジクロロエタン５７ｇ及び９７質量％硫酸９２ｇを加え、１１０℃で４時間反応を行い、スルホン酸基を導入した多孔質ポリマー粒子１を合成した。 Finally, the resulting particles were sulfonated using concentrated sulfuric acid. Specifically, 57 g of dichloroethane and 92 g of 97% by mass sulfuric acid were added to 10 g of the obtained particles and reacted at 110 ° C. for 4 hours to synthesize porous polymer particles 1 into which sulfonic acid groups had been introduced.
（多孔質ポリマー粒子２の合成）
シード粒子１の量を０．１０ｇに変更した以外は多孔質ポリマー粒子１の合成と同様にして多孔質ポリマー粒子２を合成した。
(Synthesis of porous polymer particle 2)
Porous polymer particle 2 was synthesized in the same manner as the synthesis of porous polymer particle 1 except that the amount of seed particle 1 was changed to 0.10 g.
（多孔質ポリマー粒子３の合成）
シード粒子１の量を０．０７ｇに変更した以外は多孔質ポリマー粒子１の合成と同様にして多孔質ポリマー粒子３を合成した。
(Synthesis of porous polymer particle 3)
Porous polymer particles 3 were synthesized in the same manner as the synthesis of the porous polymer particles 1 except that the amount of the seed particles 1 was changed to 0.07 g.
（多孔質ポリマー粒子４の合成）
シード粒子１の量を０．０５ｇに変更した以外は多孔質ポリマー粒子１の合成と同様にして多孔質ポリマー粒子４を合成した。
(Synthesis of porous polymer particles 4)
Porous polymer particles 4 were synthesized in the same manner as the synthesis of porous polymer particles 1 except that the amount of seed particles 1 was changed to 0.05 g.
（多孔質ポリマー粒子５の合成）
シード粒子１の量を０．０３ｇに変更した以外は多孔質ポリマー粒子１の合成と同様にして多孔質ポリマー粒子５を合成した。
(Synthesis of porous polymer particles 5)
Porous polymer particles 5 were synthesized in the same manner as the synthesis of porous polymer particles 1 except that the amount of seed particles 1 was changed to 0.03 g.
（多孔質ポリマー粒子６の合成）
重合開始剤として過酸化ベンゾイル１ｇ、モノマーとしてスチレン１０ｇ及びジビニルベンゼン２．５ｇ、並びに多孔質剤としてトルエン３．７５ｇ及びジエチルベンゼン３．７５ｇを、溶媒（イオン交換水９２．２質量％、エタノール７．５質量％、及び界面活性剤としてエマールＴＤ０．３質量％）３４０ｇに分散し、リン酸三カルシウム１０質量％水溶液１００ｇを添加し、ホモミキサーで３０分間攪拌した。その後、８０℃に昇温し、８時間懸濁重合を行った。得られた粒子を水及びメタノールで洗浄後、メッシュ分級を行い、粒子を作製した。得られた粒子に対し多孔質ポリマー粒子１と同様にスルホン化を行い、多孔質ポリマー粒子６を作製した。
(Synthesis of porous polymer particles 6)
1 g of benzoyl peroxide as a polymerization initiator, 10 g of styrene and 2.5 g of divinylbenzene as monomers, 3.75 g of toluene and 3.75 g of diethylbenzene as a porous agent, a solvent (92.2% by mass of ion-exchanged water, 7. 5% by mass and 340 g of Emar TD as a surfactant) were dispersed in 340 g, 100 g of a 10% by mass aqueous solution of tricalcium phosphate was added, and the mixture was stirred with a homomixer for 30 minutes. Thereafter, the temperature was raised to 80 ° C., and suspension polymerization was performed for 8 hours. The obtained particles were washed with water and methanol, and then subjected to mesh classification to produce particles. The resulting particles were sulfonated in the same manner as the porous polymer particles 1 to prepare porous polymer particles 6.
上記の方法で得られた多孔質ポリマー粒子１〜６のモード粒径（極大粒径）と粒径ＣＶ値を測定した。具体的には、湿式フロー式粒子径・形状分析装置ＦＰＩＡ−３０００（マルバーン社製）を用いて、ガラスセル中を流れる懸濁液中の粒子画像をＣＣＤで高速撮像し、個々の粒子画像をリアルタイムに解析することで、１０万個の粒子の粒度分布及び粒子形状を評価し、モード粒径（極大粒径）及び粒径ＣＶ値を測定した。その結果を表２に示す。なお、粒度分布は、個数基準の頻度分布として評価した。 The mode particle size (maximum particle size) and particle size CV value of the porous polymer particles 1 to 6 obtained by the above method were measured. Specifically, using a wet flow type particle size / shape analyzer FPIA-3000 (manufactured by Malvern), a particle image in a suspension flowing in a glass cell is imaged at high speed with a CCD, and individual particle images are captured. By analyzing in real time, the particle size distribution and particle shape of 100,000 particles were evaluated, and the mode particle size (maximum particle size) and particle size CV value were measured. The results are shown in Table 2. The particle size distribution was evaluated as a number-based frequency distribution.
上記の方法で得られた多孔質ポリマー粒子１〜５を、表３及び４に示す混合量（質量％）で混合し、粒度分布において２つ以上の極大粒径を有する、すなわち多峰性である多孔質ポリマー粒子を得た（実施例１〜９）。また、上記の方法で得られた多孔質ポリマー粒子１〜６のうち、表４に示す粒子を単独で用いて、比較例１〜５の多孔質ポリマー粒子とした。実施例及び比較例の多孔質ポリマー粒子について、再度、上記同様の方法で粒径測定を行い、多孔質ポリマー粒子全量の平均粒径を測定した。また、各峰における半値幅及び粒径ＣＶ値を算出した。その結果を表３に示す。半値幅の単位はμｍである。各例において、混合した１〜６の多孔質ポリマー粒子のうち、個数の一番多い粒子を●で示した。また、各峰における半値幅及び極大粒径が下記式（１）で表される要件を満たし、かつ各峰の粒径ＣＶ値が５％以下である場合、（○）で示し、それ以外の場合、（×）で示した。
Ａ＜０．１１７７×Ｂ …（１）
［式中、Ａは半値幅を示し、Ｂは極大粒径を示す。］
The porous polymer particles 1 to 5 obtained by the above method are mixed in the mixing amount (% by mass) shown in Tables 3 and 4, and have two or more maximum particle sizes in the particle size distribution, that is, multimodal. Some porous polymer particles were obtained (Examples 1-9). Moreover, it was set as the porous polymer particle of Comparative Examples 1-5 using the particle | grains shown in Table 4 independently among the porous polymer particles 1-6 obtained by said method. With respect to the porous polymer particles of Examples and Comparative Examples, the particle size was measured again by the same method as described above, and the average particle size of the total amount of the porous polymer particles was measured. Moreover, the half value width and particle size CV value in each peak were calculated. The results are shown in Table 3. The unit of the half width is μm. In each example, among the mixed 1 to 6 porous polymer particles, the most numerous particles are indicated by ●. In addition, when the full width at half maximum and the maximum particle size at each peak satisfy the requirement represented by the following formula (1) and the particle size CV value at each peak is 5% or less, (◯) indicates, The case is indicated by (x).
A <0.1177 × B (1)
[In formula, A shows a half value width and B shows a maximum particle size. ]
（ピーク対称度、理論段数）
実施例及び比較例で得られた多孔質ポリマー粒子の混合物を、直径７．８ｍｍ、長さ１５０ｍｍのステンレスカラムに、充填溶媒０．１質量％リン酸、スラリー濃度５０％、充填圧１５ＭＰａ、充填時間３０分の条件で充填した。充填したカラムを用い、溶離液０．１質量％リン酸水溶液、カラム温度２５℃、流速０．５ｍｌ/ｍｉｎ、サンプル３．５質量％ギ酸、サンプル量２μＬ、検出器ＵＶ２１０ｎｍの測定条件で、クロマト特性を測定した。クロマト測定により、解析ソフトを用いて理論段数を求め粒子特性の指標とした。また、ギ酸のピーク対称度を測定し、１以上１．２未満を良好、１．２以上をテーリング、１未満をリーディングと判定した。
(Peak symmetry, number of theoretical plates)
The mixture of the porous polymer particles obtained in the examples and comparative examples was packed in a stainless steel column having a diameter of 7.8 mm and a length of 150 mm, 0.1% by mass phosphoric acid, slurry concentration 50%, packing pressure 15 MPa, and packing. Filled for 30 minutes. Using a packed column, chromatographed under the measurement conditions of eluent 0.1% by mass phosphoric acid aqueous solution, column temperature 25 ° C., flow rate 0.5 ml / min, sample 3.5% by mass formic acid, sample amount 2 μL, detector UV 210 nm. Characteristics were measured. The number of theoretical plates was determined by chromatographic measurement using analysis software and used as an index of particle characteristics. Moreover, the peak symmetry degree of formic acid was measured, and 1 or more and less than 1.2 was judged good, 1.2 or more was judged as tailing, and less than 1 was judged as reading.
実験結果を表３及び４に示す。２つ以上の極大粒径を有する多孔質ポリマー粒子を充填したカラムにおいて、理論段数は、用いた多孔質ポリマー粒子全体の平均粒径が小さい程向上した。また、シード重合で合成した単一粒径粒子を単独で用いる場合より、粒度分布が多峰性である多孔質ポリマー粒子を用いた場合の方が高い理論段数を示すことが分かった。また、シード重合で合成した多孔質ポリマー粒子をカラム用充填材として用いると、従来の懸濁重合にて合成した粒子を用いた場合よりも理論段数が向上することが分かった。実施例で合成した粒子は分級が不要であるため、従来の懸濁重合で合成した場合より、コストを大幅に低減できると考えられる。 The experimental results are shown in Tables 3 and 4. In a column packed with porous polymer particles having two or more maximum particle sizes, the number of theoretical plates was improved as the average particle size of the whole porous polymer particles used was smaller. In addition, it was found that the number of theoretical plates is higher when the porous polymer particles having a multi-modal particle size distribution are used than when the single particle size particles synthesized by seed polymerization are used alone. Further, it was found that the use of porous polymer particles synthesized by seed polymerization as a column packing material improves the number of theoretical plates as compared with the case of using particles synthesized by conventional suspension polymerization. Since the particles synthesized in the examples do not need to be classified, it is considered that the cost can be greatly reduced as compared with the case of synthesis by conventional suspension polymerization.
以上のように、本実施形態の多孔質ポリマー粒子をカラム用充填材として使用することにより、従来品よりもカラムの理論段数をさらに向上させることができた。 As described above, by using the porous polymer particles of this embodiment as a column packing material, the number of theoretical columns of the column can be further improved as compared with the conventional product.
Claims (6)
多孔質ポリマー粒子の平均粒径が７．０μｍ以下であり、多孔質ポリマー粒子の粒度分布が多峰性であり、各峰に含まれる多孔質ポリマー粒子が、多孔質ポリマー粒子全量に対してそれぞれ１０質量％以上であり、かつ各峰における半値幅及び極大粒径が、式（１）で表される要件を満たす、カラム用充填材。
Ａ＜０．１１７７×Ｂ …（１）
［式中、Ａは半値幅を示し、Ｂは極大粒径を示す。］ A packing material for a column containing porous polymer particles,
The average particle size of the porous polymer particles is 7.0 μm or less, the particle size distribution of the porous polymer particles is multimodal, and the porous polymer particles contained in each peak are respectively in the total amount of the porous polymer particles. A packing material for a column that is 10% by mass or more, and that the full width at half maximum and the maximum particle size at each peak satisfy the requirement represented by the formula (1).
A <0.1177 × B (1)
[In formula, A shows a half value width and B shows a maximum particle size. ]
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