JP5297462B2 - 化学結合クラウンエーテルを有する非イオン性多孔性の小さい固体樹脂 - Google Patents
化学結合クラウンエーテルを有する非イオン性多孔性の小さい固体樹脂 Download PDFInfo
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- JP5297462B2 JP5297462B2 JP2010526426A JP2010526426A JP5297462B2 JP 5297462 B2 JP5297462 B2 JP 5297462B2 JP 2010526426 A JP2010526426 A JP 2010526426A JP 2010526426 A JP2010526426 A JP 2010526426A JP 5297462 B2 JP5297462 B2 JP 5297462B2
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- Prior art keywords
- crown ether
- solution
- resin
- sodium
- porogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000011347 resin Substances 0.000 title claims description 72
- 229920005989 resin Polymers 0.000 title claims description 72
- 150000003983 crown ethers Chemical class 0.000 title claims description 67
- 239000007787 solid Substances 0.000 title claims description 31
- 239000000243 solution Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 26
- 239000003361 porogen Substances 0.000 claims description 23
- 239000011324 bead Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 21
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical group CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229960000878 docusate sodium Drugs 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical group CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000012969 di-tertiary-butyl peroxide Chemical group 0.000 claims 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000008240 homogeneous mixture Substances 0.000 claims 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000001577 simple distillation Methods 0.000 claims 1
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 239000004317 sodium nitrate Substances 0.000 claims 1
- 235000010288 sodium nitrite Nutrition 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 44
- 239000011148 porous material Substances 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- -1 amino crown ethers Chemical class 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000189 neurotoxic Toxicity 0.000 description 1
- 230000002887 neurotoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3263—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. an heterocyclic or heteroaromatic structure
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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Description
ジビニルベンゼン(DVB)、46.75gm
エチルスチレン、27.5gm
4−アクリルアミドベンゾ18−クラウン−6、750mg
イソブタノール(IBA)、44ml
トルエン、81ml
過酸化ベンゾイル(BPO)、1.87gm
脱塩水、525ml
ヒドロキシエチルセルロース(HEC)、3.15gm
リグノスルホン酸ナトリウム、0.525gm
塩化カルシウム、13gm
塩化ナトリウム、184gm
HEC、リグノスルホン酸ナトリウム、CaCl2及び塩化ナトリウムを水に溶解することにより水相を調製し、溶液を80℃まで加熱した(ステップ1)。透明な溶液が形成するまで、45〜50℃で撹拌しながら4−アクリルアミドベンゾ−l8−クラウン−6をIBAに溶解させた(ステップ2)。周囲温度で撹拌しながらBPOをDVB及びエチルスチレンに溶解させ、次いで、混合物をステップ2で調製したクラウンエーテル溶液に添加した。次いで、トルエンをこの溶液に添加し、周囲温度で少なくとも30分混合物を撹拌した。これにより、有機相が形成する。撹拌しながら有機相を水相(ステップ1)に添加し、必要な粒径のビーズを生じるように、撹拌の速度を適切に調整した。次いで、この反応混合物を78〜80℃まで加熱し、撹拌しながら18時間維持した。軟質ビーズ、及び次いで、硬質ビーズを形成した。その後、80〜82℃で少なくとも8時間硬化させた。次いで、ポリマーを濾過して除去し、水で洗浄して付着した化学物質、安定剤等を除去し、洗浄したビーズを過剰な水の中で撹拌してスラリーを形成した。スラリーを加熱し、完全にポロゲン溶媒を蒸留して除去した。反応混合物を室温まで冷却した。樹脂を濾過し、水、メタノール(微量のポロゲン溶媒を除去するために、及び再度水で洗浄した。真空下で過剰な水を濾過して除去し、樹脂を充填した。ここで結合したクラウンエーテルの量は、同じサイズの非多孔性樹脂表面に結合したと思われる量の約500倍と計算される。65gの樹脂中の約3gのクラウンエーテルが、この方法で共有結合することができる。それ故、該樹脂中の細孔表面積は、約1200m2/gとなろう。
Claims (15)
- 懸濁重合による共有結合クラウンエーテルを有する非イオン性多孔性の固体球状ビーズ形樹脂の調製方法であって、
懸濁安定剤及び塩を水に溶解するステップ、及び溶液を加熱して水相を得るステップ、アクリル基官能化クラウンエーテル及びアクリルアミド基官能化クラウンエーテルから選択される少なくとも一種のクラウンエーテルを第1のポロゲン溶媒に溶解して、クラウンエーテル溶液を得るステップ、並びに重合開始剤をモノマー及び/又は架橋剤に溶解して、第2の溶液を得るステップ、前記溶液をクラウンエーテル溶液に添加し、その後、第2のポロゲン溶液を添加して、生成した均一混合物を得て、その後、撹拌して最終的な有機相を得るステップ、攪拌下で有機相を水相に添加して、安定な懸濁液の形態である反応混合物を得るステップ、反応混合物を加熱及び撹拌して、ポリマービーズを得るステップ、ポリマービーズを硬化させるステップを含み、その後、精製して、共有結合クラウンエーテルを有する非イオン性多孔性固体樹脂を得るステップを含む方法。 - 前記懸濁安定剤が、0.2%〜2%の濃度のヒドロキシエチルセルロース(HEC)、ポリビニルアルコール、カルボキシメチルセルロース、及びゼラチンから選択され、当該懸濁安定剤が0.1%〜1%の濃度のリグノスルホン酸ナトリウム、ポリスチレンスルホン酸ナトリウム、ベントナイト、ホウ酸ナトリウム、ナフタレンスルホン酸ナトリウム、ラウリルスルホン酸ナトリウム、ポリ−ジメチルジアリルアンモニウムクロリド、スルホコハク酸ジオクチル、及びドデシルベンゼンスルホン酸ナトリウム塩から選択される更なる懸濁安定剤と組み合わされる、請求項1に記載の方法。
- 前記塩が、5%〜40%の割合の塩化ナトリウム(NaCl)、硫酸ナトリウム(Na2SO4)、硝酸ナトリウム(NaNO3)及び亜硝酸ナトリウム(NaNO2)から選択されるか、又は
モノマーが、スチレン、エチルスチレン、メチルアクリレート、エチルアクリレート、ブチルアクリレート、メチルメタクリレートから選択される、及び/又は架橋剤がジビニルベンゼン(DVB)、及びエチレングリコールジメタクリレート(EGDMA)から選択されるか、又は
前記第1のポロゲン溶媒が、イソブタノール、イソオクタノール、及びアミルアルコールから選択されるか、又は
前記第2のポロゲン溶媒が、トルエン、ベンゼン、キシレン、ヘプタン、及びヘキサンから選択される、請求項1に記載の方法。 - 2つ以上の不混和性モノマーの共重合の前記技法が、全てのモノマーがその中で混和できる、適切な不活性ポロゲン溶媒の選択及び使用を伴うか、又は
前記重合開始剤が、過酸化ベンゾイル、過酸化水素、過酸化ラウリル、アゾイソブチロニトリル、第三級ブチルペルオキシベンゾエート、ジ−第三級ブチルペルオキシド、第三級ブチルヒドロペルオキシド、過硫酸アンモニウム、及び過硫酸カリウムから選択される、請求項1に記載の方法。 - 前記重合開始剤が、モノマーの総重量の0.1%〜5%の割合で使用されるか、又は
前記水溶液が、懸濁安定剤及び塩を水に溶解すること、及び60〜90℃まで加熱することにより形成される、請求項1に記載の方法。 - クラウンエーテル溶液が、45〜50℃で撹拌しながら加熱することにより形成される、請求項1に記載の方法。
- 重合開始剤が、周囲温度で撹拌しながらモノマー及び/又は架橋剤溶液に溶解されるか、又は、
生成した混合物が周囲温度で撹拌される、請求項1に記載の方法。 - 生成した混合物が少なくとも2分〜45分撹拌され、前記混合物を完全に均質にする、請求項1に記載の方法。
- 水相及び有機相を含む反応混合物が、60〜90℃の範囲の温度まで加熱される、請求項1に記載の方法。
- 生成した混合物が、8〜25時間の期間撹拌される、請求項1に記載の方法。
- ポリマービーズが75〜95℃で硬化される、請求項1に記載の方法。
- ポリマービーズが5〜15時間の期間にわたって硬化される、請求項1に記載の方法。
- ポリマービーズの精製ステップが、水で洗浄することによりポリマービーズを濾過して取り除くこと、及び過剰な水の中でビーズを撹拌してスラリーを形成すること、スラリーを加熱してポロゲンを蒸留し、その後、スラリーを冷却するか又は極性溶媒を使用してポリマービーズからポロゲンを抽出すること、ポリマービーズを濾過し、有機溶媒で洗浄し、その後、水で洗浄し、乾燥させることを含む、請求項1に記載の方法。
- ポロゲン溶媒が、単なる蒸留又は真空蒸留により除去されるか、又は抽出が、エタノール、メタノール、アセトン、ジオキサン、及びエーテルから選択される極性溶媒を使用して実施されるか、又は洗浄に使用される有機溶媒が、メタノール及びエタノールアセトンから選択される、請求項13に記載の方法。
- 請求項1〜14のいずれか一項に記載の方法により製造された、25〜1400μmの粒径を有する、共有結合クラウンエーテルによる繰返し使用周期に、より適した非イオン性多孔性の固体球状ビーズ形樹脂。
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WO2013099224A1 (ja) * | 2011-12-27 | 2013-07-04 | 国立大学法人山口大学 | ネットワークポリマー及びポリマーゲル電解質 |
SE537053C2 (sv) * | 2012-08-23 | 2014-12-16 | Helse Stavanger Hf | Förfarande för framställning av monolitkolonner |
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