JP2023115690A - Chelate polymer, and production method thereof - Google Patents
Chelate polymer, and production method thereof Download PDFInfo
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- JP2023115690A JP2023115690A JP2022018051A JP2022018051A JP2023115690A JP 2023115690 A JP2023115690 A JP 2023115690A JP 2022018051 A JP2022018051 A JP 2022018051A JP 2022018051 A JP2022018051 A JP 2022018051A JP 2023115690 A JP2023115690 A JP 2023115690A
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- polysaccharide
- heavy metal
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- 239000013522 chelant Substances 0.000 title claims abstract description 135
- 229920000642 polymer Polymers 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 64
- 150000004804 polysaccharides Chemical class 0.000 claims abstract description 43
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 42
- 239000005017 polysaccharide Substances 0.000 claims abstract description 42
- 150000002500 ions Chemical class 0.000 claims abstract description 40
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 39
- 229920001284 acidic polysaccharide Polymers 0.000 claims abstract description 22
- 150000004805 acidic polysaccharides Chemical class 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 125000000962 organic group Chemical group 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 229910001437 manganese ion Inorganic materials 0.000 description 13
- 235000010443 alginic acid Nutrition 0.000 description 12
- 229920000615 alginic acid Polymers 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000783 alginic acid Substances 0.000 description 10
- 229960001126 alginic acid Drugs 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000004781 alginic acids Chemical class 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229920000578 graft copolymer Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- -1 sec-hexyl group Chemical group 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 150000002772 monosaccharides Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VWJBZYCTOTWLQU-UHFFFAOYSA-N O.N(CC(=O)O)CC(=O)O.[Na].[Na] Chemical compound O.N(CC(=O)O)CC(=O)O.[Na].[Na] VWJBZYCTOTWLQU-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical compound [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 3
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical group NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- NARVIWMVBMUEOG-UHFFFAOYSA-N 2-Hydroxy-propylene Natural products CC(O)=C NARVIWMVBMUEOG-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical group OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical group OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-BZINKQHNSA-N D-Guluronic Acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@@H](O)[C@H]1O AEMOLEFTQBMNLQ-BZINKQHNSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N beta-D-galactopyranuronic acid Natural products OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229950007919 egtazic acid Drugs 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical group NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
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- 125000006850 spacer group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
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- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- MMTOZJBMQSASCE-UHFFFAOYSA-N 1,4-dipyridin-2-yl-2,3-bis(pyridin-2-ylmethyl)butane-2,3-diamine Chemical compound C=1C=CC=NC=1CC(C(N)(CC=1N=CC=CC=1)CC=1N=CC=CC=1)(N)CC1=CC=CC=N1 MMTOZJBMQSASCE-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- ZOJIBRUWYLWNRB-UHFFFAOYSA-N 2-(2-ethenoxyethoxymethyl)oxirane Chemical compound C=COCCOCC1CO1 ZOJIBRUWYLWNRB-UHFFFAOYSA-N 0.000 description 1
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- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
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- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
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- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- CPHURRLSZSRQFS-UHFFFAOYSA-N 3-[4-[2-[4-(3-hydroxypropoxy)phenyl]propan-2-yl]phenoxy]propan-1-ol Chemical compound C=1C=C(OCCCO)C=CC=1C(C)(C)C1=CC=C(OCCCO)C=C1 CPHURRLSZSRQFS-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002567 Chondroitin Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920002148 Gellan gum Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CVRXLMUYFMERMJ-UHFFFAOYSA-N N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine Chemical group C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CCN(CC=1N=CC=CC=1)CC1=CC=CC=N1 CVRXLMUYFMERMJ-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical group OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229920002230 Pectic acid Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- PCCNIENXBRUYFK-UHFFFAOYSA-O azanium;cerium(4+);pentanitrate Chemical compound [NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PCCNIENXBRUYFK-UHFFFAOYSA-O 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- DLGJWSVWTWEWBJ-HGGSSLSASA-N chondroitin Chemical compound CC(O)=N[C@@H]1[C@H](O)O[C@H](CO)[C@H](O)[C@@H]1OC1[C@H](O)[C@H](O)C=C(C(O)=O)O1 DLGJWSVWTWEWBJ-HGGSSLSASA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000010492 gellan gum Nutrition 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- 229960002897 heparin Drugs 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Graft Or Block Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
本発明は、キレートポリマー及びその製造方法に関するものである。 TECHNICAL FIELD The present invention relates to a chelate polymer and a method for producing the same.
従来、金属イオンとの間でキレートを形成してこれらを選択的に捕捉するキレート官能基が導入されたキレート樹脂は、金属イオン、特に重金属イオンに対して優れた選択性を有しているため、排水処理等の水処理分野で重金属の除去に用いられてきた。近年、半導体の高集積化やリチウムイオン電池の長寿命化要請に対応して、有機溶媒中の微量重金属イオンの除去についてもニーズが高まってきており、キレート樹脂による有機溶媒の精製が行われている。しかしながら、従来のキレート樹脂はジビニルベンゼン等の架橋剤により高度に架橋されたビーズ状粒子であるため、樹脂内部への重金属イオンの拡散が遅く、処理速度を遅くし、ゆっくりと通液しないと重金属イオンの捕捉効率が低下してしまうといった問題点を有していた。 Conventionally, chelating resins introduced with chelate functional groups that form chelates with metal ions and selectively capture them have excellent selectivity for metal ions, especially heavy metal ions. It has been used to remove heavy metals in the field of water treatment such as wastewater treatment. In recent years, in response to the demand for higher integration of semiconductors and longer life of lithium-ion batteries, the need for removal of trace heavy metal ions in organic solvents has increased. there is However, since conventional chelate resins are bead-like particles that are highly crosslinked with a crosslinking agent such as divinylbenzene, the diffusion of heavy metal ions into the interior of the resin is slow, slowing down the treatment speed and slowing down the flow of heavy metal ions. There is a problem that the ion trapping efficiency is lowered.
上記ビーズ状キレート樹脂の問題点を解決するため、繊維状のキレート樹脂が提案されている（例えば、特許文献１、２参照。）。繊維状のキレート樹脂は比表面積が大きく、表面近傍にキレート官能基が導入されているため重金属イオンの捕捉速度が速く、上記ビーズ状キレート樹脂の欠点を改善できるものであった。しかし、重金属イオンの除去レベルに対する要求は、近年、ますます高くなっており、上記繊維状キレート樹脂を用いても除去レベルを満足できないケースが増えてきている。 In order to solve the problems of the bead-like chelate resin, fibrous chelate resins have been proposed (see, for example, Patent Documents 1 and 2). The fibrous chelate resin has a large specific surface area and a chelate functional group introduced in the vicinity of the surface, so that it captures heavy metal ions at a high rate and can improve the drawbacks of the bead-like chelate resin. However, in recent years, the demand for a removal level of heavy metal ions has become higher and higher, and there are an increasing number of cases where the removal level cannot be satisfied even with the use of the fibrous chelate resin.
本発明は、微量の重金属イオンを迅速に捕捉し、短時間でｐｐｍレベル以下まで重金属イオン量を低減可能なキレートポリマーを提供することを目的とする。 An object of the present invention is to provide a chelate polymer capable of quickly trapping trace amounts of heavy metal ions and reducing the amount of heavy metal ions to the ppm level or less in a short period of time.
本発明者らは、上記課題を解決するべく鋭意検討を行った結果、酸性多糖類もしくは塩基性多糖類に共有結合を介してキレート官能基を導入して得られるキレートポリマーが前記目的を達成し得ることを見出し、本発明を完成するに至った。 The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a chelate polymer obtained by introducing a chelate functional group into an acidic polysaccharide or a basic polysaccharide via a covalent bond has achieved the above-mentioned object. We have found that we can obtain it, and have completed the present invention.
すなわち、本発明の各態様は、以下に示す［１］～［９］である。
［１］ 下記一般式（１）で示される構造を有し、キレート官能基を０．２～５ｍｍｏｌ／ｇ含む、キレートポリマー。
That is, each aspect of the present invention is [1] to [9] shown below.
[1] A chelate polymer having a structure represented by the following general formula (1) and containing 0.2 to 5 mmol/g of a chelate functional group.
ＰＳ－Ｘ－Ａ－ＣＬ （１）
（式中、ＰＳは酸性多糖類又は塩基性多糖類を表す。Ｘは－Ｏ－又は－Ｎ（Ｒ）－で示される基を表し、Ｒは水素原子又は炭素数が１～６の炭化水素基を表す。Ａは３個～３０個の炭素原子を有する有機基を表し、ＣＬはキレート官能基を含む炭素数が１～３０の有機基を表す。）
［２］ 下記一般式（２）で示される構造を有する、上記［１］に記載のキレートポリマー。
PS-XA-CL (1)
(In the formula, PS represents an acidic polysaccharide or a basic polysaccharide. X represents a group represented by -O- or -N(R)-, and R is a hydrogen atom or a hydrocarbon having 1 to 6 carbon atoms. A represents an organic group having 3 to 30 carbon atoms, and CL represents an organic group having 1 to 30 carbon atoms containing a chelating functional group.)
[2] The chelate polymer according to [1] above, which has a structure represented by the following general formula (2).
（式中、Ａ、ＣＬは前記と同じ意味を表す。Ｍは水素原子またはアルカリ金属イオンを表し、ｎは１０～１０００の整数を表す。）
［３］ 重量平均分子量が１０，０００～１，０００，０００である、上記［１］又は［２］に記載のキレートポリマー。
［４］ 酸性多糖類および／または塩基性多糖類に、エピハロヒドリンおよび／または２～６個のエポキシ基を有する多官能エポキシ化合物を反応させた後、アミノ基とキレート官能基を有する化合物を反応させる、上記［１］に記載のキレートポリマーの製造方法。
［５］ 下記一般式（３）で示される構造を有し、キレート官能基を０．２～５ｍｍｏｌ／ｇ含む、キレートポリマー。
(Wherein, A and CL have the same meanings as described above. M represents a hydrogen atom or an alkali metal ion, and n represents an integer of 10 to 1000.)
[3] The chelate polymer according to [1] or [2] above, which has a weight average molecular weight of 10,000 to 1,000,000.
[4] Reacting an acidic polysaccharide and/or a basic polysaccharide with an epihalohydrin and/or a polyfunctional epoxy compound having 2 to 6 epoxy groups, and then reacting a compound having an amino group and a chelate functional group. , the method for producing a chelate polymer according to the above [1].
[5] A chelate polymer having a structure represented by the following general formula (3) and containing 0.2 to 5 mmol/g of a chelate functional group.
（式中、ＰＳ、Ｘは前記と同じ意味を表す。Ｂはキレート官能基を含み４～３０個の炭素原子を有するビニルモノマー残基を表し、Ｄはキレート官能基を含まない４～３０個の炭素原子を有するビニルモノマー残基を表し、ｌ、ｍはそれぞれ独立して１０～５００の整数を表す。）
［６］ 下記一般式（４）で示される構造を有する上記［５］に記載のキレートポリマー。
(In the formula, PS and X have the same meanings as above. B represents a vinyl monomer residue containing a chelate functional group and having 4 to 30 carbon atoms, and D represents a 4 to 30 carbon atom residue containing no chelate functional group. represents a vinyl monomer residue having a carbon atom, and l and m each independently represents an integer of 10 to 500.)
[6] The chelate polymer according to [5] above, which has a structure represented by the following general formula (4).
（式中、Ｂ、Ｄ、Ｍ、ｌ、ｍ、ｎは前記と同じ意味を表す。）
［７］ 重量平均分子量が１０，０００～１，０００，０００である、上記［５］又は［６］に記載のキレートポリマー。
［８］ 酸性多糖類および／または塩基性多糖類に、エポキシ基含有ビニルモノマーをグラフト重合させた後、アミノ基とキレート官能基を有する化合物を反応させる、上記［５］に記載のキレートポリマーの製造方法。
［９］ 上記［１］～［３］、［５］～［７］のいずれかに記載のキレートポリマーを重金属イオンを含有する溶液に添加し、該キレートポリマーで重金属イオンを捕捉する、重金属イオンの捕捉方法。
(Wherein, B, D, M, l, m and n have the same meanings as above.)
[7] The chelate polymer according to [5] or [6] above, which has a weight average molecular weight of 10,000 to 1,000,000.
[8] The chelate polymer according to [5] above, wherein an epoxy group-containing vinyl monomer is graft-polymerized with an acidic polysaccharide and/or a basic polysaccharide, and then a compound having an amino group and a chelate functional group is reacted. Production method.
[9] Heavy metal ions, wherein the chelate polymer according to any one of [1] to [3] and [5] to [7] is added to a solution containing heavy metal ions, and the heavy metal ions are captured by the chelate polymer. capture method.
なお、本発明のキレートポリマーによって前記目的が達成される理由に関し、本発明者らは以下のように推察する。 The present inventors speculate as follows regarding the reason why the chelate polymer of the present invention achieves the above object.
すなわち、本発明のキレートポリマーは水溶性もしくは水膨潤性であり、極性の高い有機溶媒に対しても親和性か高く、粉砕も容易で微粒子化可能なため、極性有機溶媒中の微量重金属イオンを短時間で迅速に吸着・除去できる。 That is, the chelate polymer of the present invention is water-soluble or water-swellable, has a high affinity for highly polar organic solvents, and can be easily pulverized into fine particles. Can be quickly adsorbed and removed in a short time.
本発明によれば、微量の重金属イオンを迅速に捕捉し、短時間でｐｐｍレベル以下まで重金属イオン量を低減可能なキレートポリマーを簡便な方法で製造し、提供することが可能となる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce and provide a chelate polymer capable of quickly trapping trace amounts of heavy metal ions and reducing the amount of heavy metal ions to the ppm level or less in a short period of time.
以下、本発明をその好適な実施形態に即して詳細に説明する。 BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments.
本発明の一態様である、第一のキレートポリマーは、前記一般式（１）で示され、酸性多糖類もしくは塩基性多糖類に共有結合を介してキレート官能基を導入して得られる。 The first chelate polymer, which is one aspect of the present invention, is represented by the general formula (1) and is obtained by introducing a chelate functional group into an acidic polysaccharide or a basic polysaccharide via a covalent bond.
ＰＳは酸性多糖類又は塩基性多糖類を示す。酸性多糖類とは、カルボキシル基や硫酸基等の酸性を示す官能基を含有している多糖類を指し、それらの例としては、カルボキシメチルセルロース、ジェランガム、アルギン酸、硫酸化アルギン酸、カラギーナン、キサンタンガム、コンドロイチン硫酸、ヘパリン、ヒアルロン酸、ペクチン酸、アラビアガム、寒天、トラガントガムやそれらの塩が挙げられる。更に、キレート官能基含有量を著しく低下させない範囲で、中性多糖類や他の水溶性ポリマーと混合して用いても差し支えない。また、水や有機溶媒に対する膨潤性を有していれば、架橋構造を導入してもかまわない。これらの酸性多糖類のうち、アルギン酸、硫酸化アルギン酸やそれらの塩が耐酸化性に優れ、機械的強度も高いことから好ましく用いられる。アルギン酸の構成成分であるマンヌロン酸とグルロン酸の比率は任意であり、柔軟なゲルを生成するマンヌロン酸比率の高いアルギン酸、剛直なゲルが得られるグルロン酸比率の高いアルギン酸、いずれも用いることができる。 PS indicates acidic polysaccharides or basic polysaccharides. Acidic polysaccharides refer to polysaccharides containing acidic functional groups such as carboxyl groups and sulfate groups, examples of which include carboxymethylcellulose, gellan gum, alginic acid, sulfated alginic acid, carrageenan, xanthan gum, and chondroitin. Sulfuric acid, heparin, hyaluronic acid, pectic acid, gum arabic, agar, gum tragacanth, and salts thereof. Further, it may be mixed with neutral polysaccharides or other water-soluble polymers to the extent that the chelate functional group content is not significantly lowered. Moreover, a crosslinked structure may be introduced as long as it has swelling properties with respect to water or an organic solvent. Among these acidic polysaccharides, alginic acid, sulfated alginic acid and salts thereof are preferably used because of their excellent oxidation resistance and high mechanical strength. The ratio of mannuronic acid and guluronic acid, which are the constituents of alginic acid, is arbitrary, and either alginic acid with a high mannuronic acid ratio that produces a flexible gel or alginic acid with a high guluronic acid ratio that produces a rigid gel can be used. .
一方、塩基性多糖類とは、アミノ基等の塩基性を示す官能基を含有している多糖類を指し、それらの例としては、キトサンが挙げられる。 On the other hand, basic polysaccharides refer to polysaccharides containing basic functional groups such as amino groups, and examples thereof include chitosan.
多糖類に硫酸基が導入された硫酸化多糖類も好適に用いられる。硫酸基は、塩基性塩のみならずＮａＣｌやＣａＣｌ２等の中性塩もイオン交換可能な強酸性陽イオン交換基である。硫酸基の導入位置は、多糖類構造中に含まれる水酸基の部位であり、水酸基の水素が－ＳＯ３Ｈに置換されて導入される。硫酸基の多糖類への含有量は、０．５～５．０ｍｍｏｌ／ｇであることが好ましい。硫酸基含有量が上記範囲であると、キレート官能基含有量が増大し、耐酸化性も向上するため好ましい。 Sulfated polysaccharides in which sulfate groups are introduced into polysaccharides are also preferably used. The sulfate group is a strongly acidic cation exchange group capable of ion-exchanging not only basic salts but also neutral salts such as NaCl and CaCl2 . The introduction position of the sulfate group is the site of the hydroxyl group contained in the polysaccharide structure, and the hydrogen of the hydroxyl group is substituted with —SO 3 H and introduced. The content of sulfate groups in the polysaccharide is preferably 0.5 to 5.0 mmol/g. When the sulfate group content is within the above range, the chelate functional group content is increased and the oxidation resistance is also improved, which is preferable.
Ｘは－Ｏ－又は－Ｎ（Ｒ）－で示される基を表し、Ｒは水素原子又は炭素数が１～６の炭化水素基を表す。炭素数が１～６の炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソブチル基、ｎ－ペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基、イソペンチル基、ネオペンチル基、３－ペンチル基、シクロペンチル基、ｎ－ヘキシル基、イソヘキシル基、ｓｅｃ－ヘキシル基、ｔｅｒｔ－ヘキシル基、ネオヘキシル基、２－メチルペンチル基、３－メチルペンチル基、１，２－ジメチルブチル基、２，２－ジメチルブチル基、１－エチルブチル基、２－エチルブチル基、シクロヘキシル基等が挙げられる。 X represents a group represented by -O- or -N(R)-, and R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of hydrocarbon groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, sec-pentyl group, tert-pentyl group, isopentyl group, neopentyl group, 3-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group , 3-methylpentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, cyclohexyl group and the like.
キレート官能基を含む有機基ＣＬはキレート官能基を含んでいればよく、炭素数が１～３０で炭素、水素の他に酸素や窒素、リン、硫黄等のヘテロ原子を含んでいても良い。キレート官能基とは、複数の配位座を有する配位子を指し、多価金属イオンとの間でキレートを形成できる官能基である。キレート官能基としては、アミノカルボン酸を含むキレート官能基やアミノホスホン酸を含むキレート官能基、ポリアミンを含むキレート官能基が好適に用いられる。アミノカルボン酸を含むキレート官能基の若干の例としては、イミノ二酢酸基、ニトリロ三酢酸基、Ｎ，Ｎ－ビス（２－ヒドロキシエチル）グリシン基、ヒドロキシエチルイミノ二酢酸基、エチレンジアミン三酢酸基、エチレンジアミン四酢酸基、１，２‐ビス（２‐アミノフェノキシ）エタン四酢酸基、１，２－ジアミノシクロヘキサン四酢酸基、ジエチレントリアミン五酢酸基、（２－ヒドロキシエチル）エチレンジアミン三酢酸基、ビス（２－アミノエチル）エチレングリコール四酢酸基、トリエチレントリアミン六酢酸基等が挙げられる。アミノホスホン酸を含むキレート官能基の若干の例としては、アミノメチルホスホン酸基、ニトリロトリス（メチルホスホン酸）等が挙げられる。ポリアミンを含むキレート官能基の若干の例としては、ポリエチレンイミン基、ポリアミドアミンデンドリマー基、テトラキス（２－ピリジルメチル）エチレンジアミン基等が挙げられる。キレート官能基を含む有機基ＣＬとしては、上記キレート官能基のみでも構わないが、キレート官能基にメチル基やエチル基やフェニル基等の炭化水素基や、酢酸エステル等のエステル基、エチルエーテル等のエーテル基、安息香酸アミド等のアミド基、トルエンスルホン酸エステル等のスルホン酸エステル基等が結合していても良い。 The organic group CL containing a chelate functional group only needs to contain a chelate functional group, and has 1 to 30 carbon atoms and may contain oxygen, nitrogen, phosphorus, sulfur and other heteroatoms in addition to carbon and hydrogen. A chelate functional group refers to a ligand having multiple coordination sites and is a functional group capable of forming a chelate with a polyvalent metal ion. As the chelate functional group, a chelate functional group containing aminocarboxylic acid, a chelate functional group containing aminophosphonic acid, and a chelate functional group containing polyamine are preferably used. Some examples of chelating functional groups containing aminocarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, N,N-bis(2-hydroxyethyl)glycine, hydroxyethyliminodiacetic acid, ethylenediaminetriacetic acid. , ethylenediaminetetraacetic acid group, 1,2-bis(2-aminophenoxy)ethanetetraacetic acid group, 1,2-diaminocyclohexanetetraacetic acid group, diethylenetriaminepentaacetic acid group, (2-hydroxyethyl)ethylenediaminetriacetic acid group, bis( 2-aminoethyl)ethylene glycol tetraacetic acid group, triethylenetriamine hexaacetic acid group, and the like. Some examples of chelating functional groups containing aminophosphonic acid include aminomethylphosphonic acid groups, nitrilotris (methylphosphonic acid), and the like. Some examples of chelating functional groups containing polyamines include polyethyleneimine groups, polyamidoamine dendrimer groups, tetrakis(2-pyridylmethyl)ethylenediamine groups, and the like. As the organic group CL containing a chelate functional group, only the above chelate functional group may be used, but the chelate functional group may be a hydrocarbon group such as a methyl group, an ethyl group, a phenyl group, an ester group such as an acetate ester, an ethyl ether, or the like. , an amide group such as benzoic acid amide, a sulfonate group such as toluenesulfonate, and the like may be bonded.
キレートポリマーに含まれるキレート官能基の量は０．２～５ｍｍｏｌ／ｇであり、好ましくは０．５～５ｍｍｏｌ／ｇである。キレート官能基の含有量がこの範囲にあると、重金属イオンが迅速に捕捉でき、重金属イオン捕捉量も十分であるため好ましい。 The amount of chelate functional groups contained in the chelate polymer is 0.2-5 mmol/g, preferably 0.5-5 mmol/g. When the content of the chelate functional group is within this range, heavy metal ions can be rapidly captured and the amount of heavy metal ion captured is sufficient, which is preferable.
キレートポリマーの分子量は、重量平均分子量で好ましくは１０，０００～１，０００，０００、更に好ましくは５０，０００～１，０００，０００である。重量平均分子量がこの範囲にあると、十分な機械的強度が確保でき、加工時の粘性も問題のない範囲に調整できるため好ましい。 The weight average molecular weight of the chelate polymer is preferably 10,000 to 1,000,000, more preferably 50,000 to 1,000,000. When the weight-average molecular weight is within this range, sufficient mechanical strength can be ensured, and the viscosity during processing can be adjusted within a range that poses no problems, which is preferable.
キレート官能基を含む有機基ＣＬはスペーサーである－Ａ－を介して酸性多糖類又は塩基性多糖類に導入される。Ａは３～３０個の炭素原子を有する有機基であり、プロピレン基やブチレン基、フェニレン基といった二価の炭化水素基やそれらの炭化水素基に水酸基等が導入された基が好ましく用いられる。これらスペーサーの若干の例としては、２－ヒドロキシプロピレンや２，２－ビス［４－（ヒドロキシプロピルオキシ）フェニル］プロパン、１，２－ビス（２－ヒドロキシプロピルオキシ）エチル、１，３－ビス（２－ヒドロキシプロピルオキシ）ベンゼンなどが例示される。なお、本発明で用いられる有機基とは、炭素、水素の他に酸素や窒素、リン、硫黄等のヘテロ原子が含まれた基を指すものである。 An organic group CL containing a chelate functional group is introduced into an acidic polysaccharide or a basic polysaccharide via a spacer -A-. A is an organic group having 3 to 30 carbon atoms, and a divalent hydrocarbon group such as a propylene group, a butylene group, a phenylene group, or a group obtained by introducing a hydroxyl group or the like into these hydrocarbon groups is preferably used. Some examples of these spacers are 2-hydroxypropylene, 2,2-bis[4-(hydroxypropyloxy)phenyl]propane, 1,2-bis(2-hydroxypropyloxy)ethyl, 1,3-bis Examples include (2-hydroxypropyloxy)benzene. The organic group used in the present invention refers to a group containing heteroatoms such as oxygen, nitrogen, phosphorus, sulfur, etc., in addition to carbon and hydrogen.
第一のキレートポリマーのうち、特に好ましいキレートポリマーは下記一般式（２）の構造を有するキレートポリマーである。 A particularly preferred chelate polymer among the first chelate polymers is a chelate polymer having the structure of the following general formula (2).
（式中、Ａ、ＣＬは前記と同じ意味を表す。Ｍは水素原子またはアルカリ金属イオンを表し、ｎは１０～１０００の整数を表す。）
上記キレートポリマーは耐酸化性に優れたアルギン酸またはアルギン酸塩にキレート官能基が共有結合を介して導入されたものであり、過酷な条件下でも重金属イオンを捕捉・除去できる。
(Wherein, A and CL have the same meanings as described above. M represents a hydrogen atom or an alkali metal ion, and n represents an integer of 10 to 1000.)
The chelate polymer is obtained by introducing a chelate functional group into alginic acid or alginate, which has excellent oxidation resistance, through a covalent bond, and is capable of capturing and removing heavy metal ions even under severe conditions.
次に、第一のキレートポリマーの製造方法について説明する。第一の製造方法は、酸性多糖類および／または塩基性多糖類に、エピハロヒドリンおよび／または２～６個のエポキシ基を有する多官能エポキシ化合物を反応させた後、アミノ基とキレート官能基を有する化合物を反応させ、共有結合を介してキレート官能基を酸性多糖類もしくは塩基性多糖類に導入する方法である。最初の反応は、酸性多糖類の水酸基や塩基性多糖類のアミノ基とエピハロヒドリンおよび／または２～６個のエポキシ基を有する多官能エポキシ化合物との反応である。塩基性多糖類のアミノ基とエピハロヒドリンおよび／または２～６個のエポキシ基を有する多官能エポキシ化合物の反応は、特に塩基の添加は必要ではないが、酸性多糖類の水酸基とエピハロヒドリンおよび／または２～６個のエポキシ基を有する多官能エポキシ化合物との反応では、水酸化ナトリウム等の塩基の添加が必要である。塩基の添加量は、酸性多糖類の水酸基１モルに対して０．５～２モルの範囲で添加する。本反応は、溶媒にアルコールや水／アルコール混合溶媒を用いた不均一系で実施してもかまわないが、反応の均一性を確保するためには、酸性多糖類や塩基性多糖類を水に溶解させて反応することが好ましい。多糖類水溶液の濃度に特に制限はないが、０．１～５％がハンドリング性に優れ、生産性も良好であるため好ましい。反応温度については、多糖類の加水分解を抑制するため低温での反応が好ましく、０～２０℃が好ましい。反応時間は反応温度に応じて設定することが好ましく、３時間～２４時間が好ましい。 Next, a method for producing the first chelate polymer will be described. The first production method is to react an acidic polysaccharide and/or a basic polysaccharide with an epihalohydrin and/or a polyfunctional epoxy compound having 2 to 6 epoxy groups, and then react the amino group and the chelate functional group. It is a method of reacting compounds to introduce chelate functional groups into acidic polysaccharides or basic polysaccharides via covalent bonds. The first reaction is the reaction of hydroxyl groups of acidic polysaccharides or amino groups of basic polysaccharides with epihalohydrin and/or polyfunctional epoxy compounds having 2 to 6 epoxy groups. The reaction between the amino group of the basic polysaccharide and epihalohydrin and/or the polyfunctional epoxy compound having 2 to 6 epoxy groups does not particularly require the addition of a base, but the hydroxyl group of the acidic polysaccharide and epihalohydrin and/or 2 Reactions with polyfunctional epoxy compounds having ˜6 epoxy groups require the addition of a base such as sodium hydroxide. The amount of the base to be added is in the range of 0.5 to 2 mol per 1 mol of the hydroxyl group of the acidic polysaccharide. This reaction may be carried out in a heterogeneous system using an alcohol or a water/alcohol mixed solvent as a solvent. It is preferable to dissolve and react. Although the concentration of the polysaccharide aqueous solution is not particularly limited, it is preferably 0.1 to 5% because of excellent handleability and good productivity. As for the reaction temperature, the reaction is preferably carried out at a low temperature, preferably 0 to 20° C., in order to suppress hydrolysis of the polysaccharide. The reaction time is preferably set according to the reaction temperature, preferably 3 to 24 hours.
エピハロヒドリンの若干の例としては、エピクロロヒドリン、エピブロモヒドリン、エピヨードヒドリン、及びこれらの混合物を用いることができる。また、２～６個のエポキシ基を有する多官能エポキシ化合物の若干の例としては、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、レゾルシンジグリシジルエーテル、エチレングリコールジグリシジルエーテル、グリセリントリグリシジルエーテル、１，３－ビス（オキシラン－２－イルメトキシ）－２，２－ビス［（オキシラン－２－イルメトキシ）メチル］プロパン等が挙げられる。 Some examples of epihalohydrins that can be used are epichlorohydrin, epibromohydrin, epiiodohydrin, and mixtures thereof. Some examples of polyfunctional epoxy compounds having 2 to 6 epoxy groups also include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, glycerin triglycidyl ether, 1,3-bis(oxiran-2-ylmethoxy)-2,2-bis[(oxiran-2-ylmethoxy)methyl]propane and the like.
エピハロヒドリンおよび／または２～６個のエポキシ基を有する多官能エポキシ化合物の添加量は、多糖類の単糖ユニット１モルに対し、１～２０モルの範囲で添加すればよい。このような条件で酸性多糖類もしくは塩基性多糖類とエピハロヒドリンおよび／または２～６個のエポキシ基を有する多官能エポキシ化合物を反応させると、該多糖類にクロロメチル基やエポキシ基が導入される。クロロメチル基やエポキシ基が導入された多糖類は、アルコールやアセトンなどの多糖類の貧溶媒に反応溶液を滴下して沈殿させ、回収してもよいし、未反応のエピハロヒドリンや多官能エポキシ化合物を加熱等により除去し、次の反応に用いてもよい。このようにして該多糖類に導入されたクロロメチル基やエポキシ基と、アミノ基とキレート官能基を有する化合物中のアミノ基との反応により、キレート官能基が共有結合を介して該多糖類に導入される。本反応も多糖類の加水分解を抑制するため温和な条件での反応が好ましく、反応温度は４０～８０℃が好ましい。反応時間は反応温度に応じて設定することが好ましく、１～８時間が好ましい。アミノ基とキレート官能基を有する化合物の添加量は、多糖類の単糖ユニット１モルに対し、１～２０モルの範囲で添加すればよい。アミノ基とキレート官能基を有する化合物の具体例としては、イミノ二酢酸、ニトリロ三酢酸、エチレンジアミン四酢酸、Ｎ，Ｎ‐ビス（２‐ヒドロキシエチル）グリシン、１，２‐ジアミノシクロヘキサン四酢酸、ジエチレントリアミン五酢酸、Ｎ‐（２‐ヒドロキシエチル）エチレンジアミン三酢酸、ビス（２‐アミノエチル）エチレングリコール四酢酸、ビス（２‐アミノフェニル）エチレングリコール四酢酸、Ｎ‐（２‐ヒドロキシエチル）イミノ二酢酸、テトラキス（２‐ピリジルメチル）エチレンジアミン、トリエチレンテトラミン六酢酸、ポリエチレンイミン、アミノメチルホスホン酸、アミノエチルホスホン酸、アミノプロピルホスホン酸、ニトリロトリス（メチルホスホン酸）及びそれらの塩が挙げられる。これらのアミノ基を有するキレート化合物は、単独で用いても二種類以上を混合して用いてもかまわない。 The amount of the epihalohydrin and/or the polyfunctional epoxy compound having 2 to 6 epoxy groups to be added may be in the range of 1 to 20 mol per 1 mol of the monosaccharide unit of the polysaccharide. When an acidic polysaccharide or basic polysaccharide is reacted with epihalohydrin and/or a polyfunctional epoxy compound having 2 to 6 epoxy groups under such conditions, a chloromethyl group or an epoxy group is introduced into the polysaccharide. . Polysaccharides into which chloromethyl groups or epoxy groups have been introduced may be precipitated by dropping the reaction solution into a polysaccharide poor solvent such as alcohol or acetone, or may be collected by recovering unreacted epihalohydrin or polyfunctional epoxy compounds. may be removed by heating or the like and used in the next reaction. The reaction between the chloromethyl group and the epoxy group thus introduced into the polysaccharide and the amino group in the compound having an amino group and a chelate functional group causes the chelate functional group to covalently bond to the polysaccharide. be introduced. This reaction is also preferably carried out under mild conditions in order to suppress hydrolysis of the polysaccharide, and the reaction temperature is preferably 40 to 80°C. The reaction time is preferably set according to the reaction temperature, preferably 1 to 8 hours. The compound having an amino group and a chelate functional group may be added in an amount of 1 to 20 mol per 1 mol of the monosaccharide unit of the polysaccharide. Specific examples of compounds having an amino group and a chelate functional group include iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N,N-bis(2-hydroxyethyl)glycine, 1,2-diaminocyclohexanetetraacetic acid, diethylenetriamine. Pentaacetic acid, N-(2-hydroxyethyl)ethylenediaminetriacetic acid, bis(2-aminoethyl)ethyleneglycoltetraacetic acid, bis(2-aminophenyl)ethyleneglycoltetraacetic acid, N-(2-hydroxyethyl)iminodiacetic acid , tetrakis(2-pyridylmethyl)ethylenediamine, triethylenetetraminehexaacetic acid, polyethyleneimine, aminomethylphosphonic acid, aminoethylphosphonic acid, aminopropylphosphonic acid, nitrilotris (methylphosphonic acid) and salts thereof. These amino group-containing chelate compounds may be used alone or in combination of two or more.
次に、本発明の一態様である、第二のキレートポリマーについて説明する。第二のキレートポリマーは、一般式（３）で表される。 Next, the second chelate polymer, which is one aspect of the present invention, will be described. The second chelate polymer is represented by general formula (3).
（式中、ＰＳ、Ｘは前記と同じ意味を表す。Ｂはキレート官能基を含み４～３０個の炭素原子を有するビニルモノマー残基を表し、Ｄはキレート官能基を含まない４～３０個の炭素原子を有するビニルモノマー残基を表し、ｌ、ｍはそれぞれ独立して１０～５００の整数を表す。）
第二のキレートポリマーにおいて、キレート官能基はグラフトポリマー鎖中に導入され、共有結合を介して酸性多糖類もしくは塩基性多糖類と結合している。キレート官能基は前記第一のキレートポリマーと同じものが挙げられる。一般式（３）中のＢで示されるキレート官能基を有するビニルモノマー残基としては、グリシジルメタクリレート等のエポキシ基を有するビニルモノマー残基中のエポキシ基とアミノ基とキレート官能基を有する化合物中のアミノ基との反応生成物等が例示される。また、一般式（３）中のＤで示されるキレート官能基を含まない４～３０個の炭素原子を有するビニルモノマー残基としては、グリシジルメタクリレート等のエポキシ基を有するビニルモノマー残基中のエポキシ基がそのまま残存するビニルモノマー残基や、加水分解して開環したビニルモノマー残基のみならず、エポキシ基を有していないビニルモノマー残基が例示される。
(In the formula, PS and X have the same meanings as above. B represents a vinyl monomer residue containing a chelate functional group and having 4 to 30 carbon atoms, and D represents a 4 to 30 carbon atom residue containing no chelate functional group. represents a vinyl monomer residue having a carbon atom, and l and m each independently represent an integer of 10 to 500.)
In the second chelate polymer, chelate functional groups are introduced into the graft polymer chain and linked to the acidic or basic polysaccharide via covalent bonds. The same chelate functional groups as those of the first chelate polymer can be mentioned. As the vinyl monomer residue having a chelate functional group represented by B in the general formula (3), a compound having an epoxy group, an amino group, and a chelate functional group in a vinyl monomer residue having an epoxy group such as glycidyl methacrylate is exemplified by a reaction product with an amino group of As the vinyl monomer residue having 4 to 30 carbon atoms and not containing a chelate functional group represented by D in the general formula (3), epoxy in vinyl monomer residues having an epoxy group such as glycidyl methacrylate Examples include not only vinyl monomer residues in which the group remains as it is, vinyl monomer residues that have been hydrolyzed and ring-opened, but also vinyl monomer residues that do not have an epoxy group.
キレートポリマーに含まれるキレート官能基の量は０．２～５ｍｍｏｌ／ｇであり、好ましくは０．５～５ｍｍｏｌ／ｇである。キレート官能基の含有量がこの範囲にあると、重金属イオンが迅速に捕捉でき、重金属イオン捕捉量も十分であるため好ましい。 The amount of chelate functional groups contained in the chelate polymer is 0.2-5 mmol/g, preferably 0.5-5 mmol/g. When the content of the chelate functional group is within this range, heavy metal ions can be rapidly captured and the amount of heavy metal ion captured is sufficient, which is preferable.
キレートポリマーの分子量は、重量平均分子量で好ましくは１０，０００～１，０００，０００、更に好ましくは５０，０００～１，０００，０００である。重量平均分子量がこの範囲にあると、十分な機械的強度が確保でき、加工時の粘性も問題のない範囲に調整できるため好ましい。 The weight average molecular weight of the chelate polymer is preferably 10,000 to 1,000,000, more preferably 50,000 to 1,000,000. When the weight-average molecular weight is within this range, sufficient mechanical strength can be ensured, and the viscosity during processing can be adjusted within a range that poses no problems, which is preferable.
本発明の第二のキレートポリマーのうち、特に好ましいキレートポリマーは下記一般式（４）の構造を有するキレートポリマーである。 A particularly preferred chelate polymer among the second chelate polymers of the present invention is a chelate polymer having the structure of the following general formula (4).
（式中、Ｂ、Ｄ、Ｍ、ｌ、ｍ、ｎは前記と同じ意味を表す。）
上記キレートポリマーは、耐酸化性に優れたアルギン酸またはアルギン酸塩にキレート官能基を有するポリマーがグラフトした構造を有しており、分子運動性の高いグラフト鎖にキレート官能基が導入されているため重金属イオンの吸着速度が速く、微量の重金属イオンを迅速に捕捉・除去することができる。
(Wherein, B, D, M, l, m and n have the same meanings as above.)
The above chelate polymer has a structure in which a polymer having a chelate functional group is grafted onto alginic acid or alginate, which has excellent oxidation resistance. The adsorption speed of ions is high, and trace amounts of heavy metal ions can be rapidly captured and removed.
第二のキレートポリマーの製造方法は、酸性多糖類および／または塩基性多糖類に、エポキシ基を含有するビニルモノマーをグラフト重合させた後、アミノ基とキレート官能基を有する化合物を反応させ、共有結合を介してキレート官能基を酸性多糖類および／または塩基性多糖類に導入する方法である。エポキシ基を含有するビニルモノマーとしては、グリシジルメタクリレート、グリシジルアクリレート、１－ビニル‐３，４‐エポキシシクロヘキサン、アリルグリシジルエーテル、ビニロキシエチルグリシジルエーテルやそれらの混合物が挙げられる。なお、上記エポキシ基を含有するビニルモノマーに加えて、エポキシ基を含有しないビニルモノマーを混合して用いても差し支えない。エポキシ基を含有しないビニルモノマーとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等の（メタ）アクリル酸エステル；（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸、安息香酸ビニル等のビニルカルボン酸やその塩；ビニルスルホン酸、スチレンスルホン酸等のビニルスルホン酸やその塩；スチレン、ビニルトルエン、ビニルピリジン、ビニルナフタレン等の芳香族ビニル化合物；ブタジエン、イソプレン、クロロプレン等のジエン類；塩化ビニル、塩化ビニリデン、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等のハロゲン化ビニル；エチレン、プロピレン、ブテン、へキセン等のα‐オレフィン等が挙げられる。 A second method for producing a chelate polymer comprises graft-polymerizing a vinyl monomer containing an epoxy group to an acidic polysaccharide and/or a basic polysaccharide, and then reacting an amino group with a compound having a chelate functional group to obtain a covalent A method of introducing chelate functional groups into acidic polysaccharides and/or basic polysaccharides through bonding. Vinyl monomers containing epoxy groups include glycidyl methacrylate, glycidyl acrylate, 1-vinyl-3,4-epoxycyclohexane, allyl glycidyl ether, vinyloxyethyl glycidyl ether and mixtures thereof. In addition to the vinyl monomer containing the epoxy group, a vinyl monomer containing no epoxy group may be mixed and used. Vinyl monomers containing no epoxy group include (meth)acrylic acid esters such as methyl (meth)acrylate and ethyl (meth)acrylate; (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, and vinyl benzoate. vinyl carboxylic acids such as vinyl sulfonic acid and salts thereof; vinyl sulfonic acids such as vinyl sulfonic acid and styrene sulfonic acid and salts thereof; aromatic vinyl compounds such as styrene, vinyl toluene, vinyl pyridine and vinyl naphthalene; dienes such as butadiene, isoprene and chloroprene vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and tetrafluoroethylene; and α-olefins such as ethylene, propylene, butene and hexene.
グラフト重合に用いられる開始剤は、レドックス触媒系が好ましく用いられる。具体的には、酸化剤として過酸化水素、過酸化ベンゾイル、クメンヒドロパーオキシド等が、還元剤として二価鉄塩、二酸化チオ尿素、亜硫酸塩、ヒドラジンなどが用いられる。好ましい開始剤としては、硝酸アンモニウムセリウムや硫酸第一鉄アンモニウム／過酸化水素／二酸化チオ尿素等が挙げられる。 A redox catalyst system is preferably used as an initiator for graft polymerization. Specifically, hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, and the like are used as oxidizing agents, and divalent iron salts, thiourea dioxide, sulfites, hydrazine, and the like are used as reducing agents. Preferred initiators include ammonium cerium nitrate and ferrous ammonium sulfate/hydrogen peroxide/thiourea dioxide.
グラフト重合は、酸性多糖類もしくは塩基性多糖類を水や有機溶媒に溶解または分散させた状態でビニルモノマーを添加し、更に開始剤を添加して行う。酸性多糖類もしくは塩基性多糖類の濃度に特に制限はないが、多糖類が溶解している場合０．１～５重量％が、分散している場合３～２０重量％が好ましい濃度である。上記濃度であれば、重合が進行しても撹拌状態を継続でき、均一なグラフト重合を行うことができるため好ましい。ビニルモノマーの初期濃度は、３～３０重量％が好ましい。上記濃度であれば、重合発熱のコントロールも容易で、重合をコントロールしやすいため好ましい。重合温度や重合時間にも特に制限はなく、０～５０℃で１～２４時間重合すればよい。 Graft polymerization is carried out by adding a vinyl monomer to a state in which an acidic polysaccharide or a basic polysaccharide is dissolved or dispersed in water or an organic solvent, and then adding an initiator. Although the concentration of the acidic polysaccharide or basic polysaccharide is not particularly limited, the preferable concentration is 0.1 to 5% by weight when the polysaccharide is dissolved, and 3 to 20% by weight when the polysaccharide is dispersed. The above concentration is preferable because the stirring state can be continued even if the polymerization progresses, and uniform graft polymerization can be performed. The initial concentration of the vinyl monomer is preferably 3-30% by weight. The above concentration is preferable because it facilitates control of polymerization heat generation and facilitates control of polymerization. Polymerization temperature and polymerization time are not particularly limited, and polymerization may be carried out at 0 to 50° C. for 1 to 24 hours.
重合終了後、未反応モノマーを除去・精製してグラフトポリマーを単離する。単離方法としては、加熱により残存モノマーや溶媒を除去しグラフトポリマーを単離する方法や、モノマーは溶解するがグラフトポリマーは溶解しない溶媒中に重合生成物を滴下し、グラフトポリマーを析出させて回収する方法などが挙げられる。 After completion of the polymerization, unreacted monomers are removed and purified to isolate the graft polymer. As an isolation method, the residual monomer and solvent are removed by heating to isolate the graft polymer, or the polymerization product is dropped into a solvent that dissolves the monomer but not the graft polymer to precipitate the graft polymer. Methods of collection, etc. are mentioned.
得られたグラフトポリマーは溶媒中に溶解もしくは分散させ、アミノ基とキレート官能基を有する化合物を添加し、グラフトポリマー中のエポキシ基と反応させる。反応条件は、第一のキレートポリマーの製造方法における、多糖類に導入されたクロロメチル基やエポキシ基とアミノ基とキレート官能基を有する化合物中のアミノ基との反応条件と同様の条件を選択すればよい。 The obtained graft polymer is dissolved or dispersed in a solvent, a compound having an amino group and a chelate functional group is added, and reacted with the epoxy group in the graft polymer. The reaction conditions are selected to be the same conditions as those for the reaction between the chloromethyl group or epoxy group introduced into the polysaccharide and the amino group in the compound having a chelate functional group in the first method for producing a chelate polymer. do it.
得られたキレートポリマーは、溶媒に溶解した溶液や分散液の状態で保存してもよいが、固体として単離して保存してもよい。固体として単離する方法としては、反応後の溶液もしくは分散液を加熱して溶媒を除去し単離する方法や、溶液もしくは分散液をキレートポリマーの貧溶媒であるアルコールやアセトン等に滴下し、ポリマーを沈殿させて単離する方法等が挙げられる。 The resulting chelate polymer may be stored in the form of a solution or dispersion dissolved in a solvent, or may be isolated and stored as a solid. As a method of isolating as a solid, a method of heating the solution or dispersion after the reaction to remove the solvent and isolating it, or a method of dropping the solution or dispersion into alcohol, acetone, etc., which is a poor solvent for the chelate polymer, A method of precipitating and isolating the polymer and the like can be mentioned.
キレートポリマーを重金属イオンを含有する溶液に添加し、該キレートポリマーで重金属イオンを捕捉することができる。 A chelating polymer can be added to a solution containing heavy metal ions to trap heavy metal ions with the chelating polymer.
以下に、本発明を更に詳細に実施例に基づき説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
（実施例１）
＜第一のキレートポリマーの製造＞
(Example 1)
<Production of first chelate polymer>
純水５０ｍｌにアルギン酸ナトリウム（青島聚大洋藻業集団有限公司製、重量平均分子量１，３００，０００）０．５０ｇ（単糖ユニットとして２．５ｍｍｏｌ）を撹拌下少量ずつ添加し、粘調な均一溶液を作製した。次いで、水酸化ナトリウム（東京化成製）０．１０ｇ（２．５ｍｍｏｌ）を添加、溶解させた後、エピクロロヒドリン（東京化成製）３．１０ｇ（５０ｍｍｏｌ）を添加し、２０℃で６時間反応させた。反応後の溶液をエタノール２Ｌに滴下して沈殿を生成させ、沈殿物をろ過により回収し、更にエタノールで洗浄した後、減圧乾燥して単離した。単離収量は０．４３ｇで、水に易溶であった。上記反応生成物を０．３０ｇ秤量し、純水１００ｍｌに溶解させた。次いで、イミノ二酢酸二ナトリウム一水塩（富士フィルム和光純薬製）８．４ｇ（４３ｍｍｏｌ）を添加、溶解させ、８０℃にて２時間反応させた。反応後の水溶液は限外ろ過膜（日本ポール製、分画分子量１０００）により精製し、過剰量のイミノ二酢酸を除去した。精製後の水溶液をアセトン中に滴下することでポリマーを沈殿させ、濾過、回収し減圧乾燥して単離した。単離収量は０．３３ｇ、水に可溶で、水系ＧＰＣを用いて測定した重量平均分子量は３７０，０００であった。窒素含有量は２．２重量％であり、窒素含有量から算出したイミノ二酢酸基含有量は１．６ｍｍｏｌ／ｇであった。 To 50 ml of pure water, 0.50 g of sodium alginate (manufactured by Qingdao Jutaiyo Algae Group Co., Ltd., weight-average molecular weight: 1,300,000) (2.5 mmol as a monosaccharide unit) was added little by little while stirring to give a viscous and uniform mixture. A solution was prepared. Then, after adding and dissolving 0.10 g (2.5 mmol) of sodium hydroxide (manufactured by Tokyo Kasei), 3.10 g (50 mmol) of epichlorohydrin (manufactured by Tokyo Kasei) was added, and the mixture was heated at 20° C. for 6 hours. reacted. The solution after the reaction was added dropwise to 2 L of ethanol to generate a precipitate, which was collected by filtration, washed with ethanol, and dried under reduced pressure for isolation. The isolated yield was 0.43 g, and it was readily soluble in water. 0.30 g of the above reaction product was weighed and dissolved in 100 ml of pure water. Then, 8.4 g (43 mmol) of iminodiacetic acid disodium monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, dissolved, and reacted at 80° C. for 2 hours. The aqueous solution after the reaction was purified with an ultrafiltration membrane (Nippon Pole, molecular weight cut off: 1000) to remove excess iminodiacetic acid. The polymer was precipitated by dropping the purified aqueous solution into acetone, filtered, collected and dried under reduced pressure to isolate. The isolated yield was 0.33 g, it was soluble in water, and the weight average molecular weight measured using aqueous GPC was 370,000. The nitrogen content was 2.2% by weight, and the iminodiacetic acid group content calculated from the nitrogen content was 1.6 mmol/g.
＜重金属イオンの捕捉能評価＞
キレートポリマーの重金属イオン捕捉能を評価するため、以下の測定を行った。上記キレートポリマー０．１ｇを純水２０ｍｌに溶解させ、マンガン酸リチウム（自社で試作、以下ＬＭＯと略す）１．９ｇを加え、スラリーを調製した。得られたスラリーをエバポレーターで濃縮後、８０℃で減圧乾燥して水を除去し、キレートポリマーとＬＭＯの混合物を得た。上記混合物から１．０ｇを分取し、テフロン（登録商標）容器に入れ１２０℃で４時間減圧乾燥した後、密封した。密封したテフロン（登録商標）容器をグローブボックス中で開封し、電解液（キシダ化学製、エチレンカーボネート：ジメチルカーボネート＝１：２の混合溶媒にＬｉＰＦ６を１モル／Ｌ溶解させた溶液）１５ｍｌを添加した後、再度密封し、８５℃で４時間加熱した。加熱終了後、グローブボックス中でテフロン（登録商標）容器を開封し、シリンジフィルターを用いてろ過し、濾過液を採取した。得られた濾過液を酸分解し、ＩＣＰ－ＭＳでマンガンイオンを定量したところ、マンガンイオンの濃度は１ｐｐｍ未満であり、加熱によりＬＭＯから溶出したマンガンイオンがキレートポリマーで捕捉されていることが確認できた。
<Evaluation of ability to trap heavy metal ions>
In order to evaluate the ability of the chelate polymer to trap heavy metal ions, the following measurements were performed. 0.1 g of the above chelate polymer was dissolved in 20 ml of pure water, and 1.9 g of lithium manganate (prototype produced by our company, hereinafter abbreviated as LMO) was added to prepare a slurry. The obtained slurry was concentrated by an evaporator and then dried under reduced pressure at 80° C. to remove water to obtain a mixture of chelate polymer and LMO. A 1.0 g portion was taken from the above mixture, placed in a Teflon (registered trademark) container, dried under reduced pressure at 120° C. for 4 hours, and then sealed. The sealed Teflon (registered trademark) container was opened in a glove box, and 15 ml of electrolytic solution (manufactured by Kishida Chemical Co., Ltd., a solution in which 1 mol/L of LiPF6 was dissolved in a mixed solvent of ethylene carbonate:dimethyl carbonate = 1:2) was added. After that, it was sealed again and heated at 85° C. for 4 hours. After completion of heating, the Teflon (registered trademark) container was opened in the glove box, filtered using a syringe filter, and the filtrate was collected. The obtained filtrate was subjected to acid decomposition, and manganese ions were quantified by ICP-MS. The concentration of manganese ions was less than 1 ppm, confirming that the manganese ions eluted from the LMO due to heating were captured by the chelate polymer. did it.
（実施例２）
＜第二のキレートポリマーの製造＞
(Example 2)
<Production of second chelate polymer>
純水１５０ｍｌに水素イオン形アルギン酸（株式会社キミカ製、キミカアシッドＧ）２．２５ｇ（単糖ユニットとして１２．７ｍｍｏｌ）を撹拌下少量ずつ添加し、白色分散液を作製した。次いで、メタクリル酸グリシジル（東京化成製）４．８６ｇ（３４．２ｍｍｏｌ）を添加、均一分散させた後、硝酸アンモニウムセリウム（ＩＶ）（アルドリッチ製）０．１６ｇ（０．３ｍｍｏｌ）を添加し、５５℃で５時間重合させた。重合後の溶液をメタノール２Ｌに滴下して沈殿を生成させ、沈殿物をろ過により回収し、更にメタノールで洗浄した後、減圧乾燥して単離した。単離収量は７．１５ｇで、収率は１００重量％であった。このようにして得られたグラフトポリマー２．２５ｇをジオキサン／水（４／６）混合溶媒４０ｍｌに分散させ、イミノ二酢酸二ナトリウム一水塩（富士フィルム和光純薬製）１６．８ｇ（８６ｍｍｏｌ）を添加後８０℃に昇温し、６時間反応させた。反応終了後、エバポレートでジオキサンを除去し、純水を加え２５０ｍｌにメスアップしｐＨを３に調整した後、室温で４８時間撹拌した。反応終了時、ポリマーは水に不溶となったため、濾過によりポリマーを回収し、水、メタノールの順に洗浄して減圧乾燥した。収量は３．１ｇ、窒素含有量より算出したキレート官能基含有量は２．２ｍｍｏｌ／ｇであった。反応前後のＩＲスペクトルを比較すると、イミノ二酢酸二ナトリウムとの反応により、１２６０ｃｍ－１のエポキシ基の吸収は減少し、１６００ｃｍ－１のイミノ二酢酸二ナトリウム由来のカルボニ吸収が増加していたことから、反応の進行を確認した。 To 150 ml of pure water, 2.25 g of hydrogen ion alginic acid (Kimika Acid G, manufactured by Kimika Co., Ltd.) (12.7 mmol as a monosaccharide unit) was added little by little with stirring to prepare a white dispersion. Then, 4.86 g (34.2 mmol) of glycidyl methacrylate (manufactured by Tokyo Kasei) was added and uniformly dispersed, and then 0.16 g (0.3 mmol) of ammonium cerium (IV) nitrate (manufactured by Aldrich) was added and the temperature was maintained at 55°C. for 5 hours. The solution after polymerization was added dropwise to 2 L of methanol to generate a precipitate, which was collected by filtration, washed with methanol, and dried under reduced pressure for isolation. The isolated yield was 7.15 g, a yield of 100% by weight. 2.25 g of the graft polymer thus obtained was dispersed in 40 ml of a mixed solvent of dioxane/water (4/6), and 16.8 g (86 mmol) of iminodiacetic acid disodium monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dispersed. was added, the temperature was raised to 80° C., and the reaction was allowed to proceed for 6 hours. After completion of the reaction, dioxane was removed by evaporation, pure water was added to make up the volume to 250 ml, and the pH was adjusted to 3, followed by stirring at room temperature for 48 hours. At the end of the reaction, the polymer became insoluble in water, so the polymer was collected by filtration, washed with water and methanol in that order, and dried under reduced pressure. The yield was 3.1 g, and the chelate functional group content calculated from the nitrogen content was 2.2 mmol/g. Comparing the IR spectra before and after the reaction, the reaction with disodium iminodiacetate reduced the absorption of the epoxy group at 1260 cm-1 and increased the absorption of the carbonic acid derived from disodium iminodiacetate at 1600 cm-1. to confirm the progress of the reaction.
＜重金属イオンの捕捉能評価＞
実施例１で製造したキレートポリマー０．１ｇに代えて、実施例２で製造したキレートポリマー粉砕品（Ｄ５０＝２．９μｍ）０．１ｇと実施例１と同様の方法で重金属イオン捕捉能を評価した。濾過液中のマンガンイオンの濃度は１ｐｐｍ未満であり、加熱によりＬＭＯから溶出したマンガンイオンがキレートポリマーで捕捉されていることが確認できた。
<Evaluation of ability to trap heavy metal ions>
Instead of 0.1 g of the chelate polymer produced in Example 1, 0.1 g of the pulverized chelate polymer (D50 = 2.9 μm) produced in Example 2 was used, and the heavy metal ion trapping ability was evaluated in the same manner as in Example 1. did. The concentration of manganese ions in the filtrate was less than 1 ppm, and it was confirmed that the manganese ions eluted from the LMO due to heating were captured by the chelate polymer.
（実施例３）
＜第一のキレートポリマーの製造＞
(Example 3)
<Production of first chelate polymer>
純水５０ｍｌとエタノール５０ｍｌの混合溶媒にキトサン（アルドリッチ製、重量平均分子量３５０，０００）５．０ｇ（単糖ユニットとして２２ｍｍｏｌ）を撹拌下少量ずつ添加し、分散液を作製した。次いで、エピクロロヒドリン（東京化成製）１０．０ｇ（１６４ｍｍｏｌ）を添加し、加熱して還流下２時間反応させた。反応後、分散液をエタノール２Ｌに滴下、撹拌した後、沈殿物をろ過により回収し、更にエタノールで洗浄し、減圧乾燥した。単離収量は６．２ｇであった。上記反応生成物を０．８ｇ秤量し、純水１００ｍｌに分散させた。次いで、イミノ二酢酸二ナトリウム一水塩（富士フィルム和光純薬製）１６．８ｇ（８６ｍｍｏｌ）を添加し、８０℃にて６時間反応させた。反応後の分散液をろ過し、純水で洗浄後、減圧乾燥して単離した。単離収量は０．９ｇ、水に不溶、窒素含有量は６．１重量％であり、窒素含有量から算出したイミノ二酢酸基含有量は４．４ｍｍｏｌ／ｇであった。 To a mixed solvent of 50 ml of pure water and 50 ml of ethanol, 5.0 g of chitosan (manufactured by Aldrich, weight average molecular weight: 350,000) (22 mmol as a monosaccharide unit) was added little by little with stirring to prepare a dispersion. Then, 10.0 g (164 mmol) of epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, heated and reacted under reflux for 2 hours. After the reaction, the dispersion was added dropwise to 2 L of ethanol and stirred, and then the precipitate was collected by filtration, washed with ethanol, and dried under reduced pressure. Isolated yield was 6.2 g. 0.8 g of the above reaction product was weighed and dispersed in 100 ml of pure water. Then, 16.8 g (86 mmol) of iminodiacetic acid disodium monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and reacted at 80° C. for 6 hours. After the reaction, the dispersion was filtered, washed with pure water, and dried under reduced pressure for isolation. The isolated yield was 0.9 g, insoluble in water, the nitrogen content was 6.1% by weight, and the iminodiacetic acid group content calculated from the nitrogen content was 4.4 mmol/g.
＜重金属イオンの捕捉能評価＞
実施例１で製造したキレートポリマー０．１ｇに代えて、実施例３で製造したキレートポリマー粉砕品（Ｄ５０＝３．６μｍ）０．１ｇとアルギン酸ナトリウム（青島聚大洋藻業集団有限公司製、重量平均分子量１，３００，０００）０．１ｇを用いたこと、ＬＭＯ添加量を１．９ｇから１．８ｇに変更したことを除いて、実施例１と同様の方法で重金属イオン捕捉能を評価した。濾過液中のマンガンイオンの濃度は１ｐｐｍ未満であり、加熱によりＬＭＯから溶出したマンガンイオンがキレートポリマーで捕捉されていることが確認できた。
<Evaluation of ability to trap heavy metal ions>
Instead of 0.1 g of the chelate polymer produced in Example 1, 0.1 g of the chelate polymer pulverized product (D50 = 3.6 μm) produced in Example 3 and sodium alginate (manufactured by Qingdao Judao Algae Group Co., Ltd., weight: Heavy metal ion scavenging ability was evaluated in the same manner as in Example 1, except that 0.1 g of an average molecular weight of 1,300,000) was used and the amount of LMO added was changed from 1.9 g to 1.8 g. . The concentration of manganese ions in the filtrate was less than 1 ppm, and it was confirmed that the manganese ions eluted from the LMO due to heating were captured by the chelate polymer.
（実施例４）
＜第一のキレートポリマーの製造＞
(Example 4)
<Production of first chelate polymer>
エピクロロヒドリンに代えて、エチレングリコールジグリシジルエーテル（東京化成製）２８．６ｇ（１６４ｍｍｏｌ）を用いたことを除いて、実施例３と同様の操作反応を行った。得られたエポキシ修飾キトサンの収量は８．０ｇであった。上記エポキシ修飾キトサン０．８ｇを用いて、実施例３と同様の操作でイミノ二酢酸ナトリウムと反応させた。単離収量は０．９ｇ、水に不溶で、窒素含有量は２．８重量％であり、窒素含有量から算出したイミノ二酢酸基含有量は２．２ｍｍｏｌ／ｇであった。元素分析で求めた窒素含有量は２．８質量％、窒素含有量から算出したキレート官能基含有量は２．０ｍｍｏｌ／ｇで、水に不溶であった。 A reaction was carried out in the same manner as in Example 3, except that 28.6 g (164 mmol) of ethylene glycol diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of epichlorohydrin. The yield of epoxy-modified chitosan obtained was 8.0 g. 0.8 g of the above epoxy-modified chitosan was reacted with sodium iminodiacetate in the same manner as in Example 3. The isolated yield was 0.9 g, insoluble in water, the nitrogen content was 2.8% by weight, and the iminodiacetic acid group content calculated from the nitrogen content was 2.2 mmol/g. The nitrogen content determined by elemental analysis was 2.8% by mass, the chelate functional group content calculated from the nitrogen content was 2.0 mmol/g, and was insoluble in water.
＜重金属イオンの捕捉能評価＞
実施例３で製造したキレートポリマー粉砕品に代えて、実施例４で製造したキレートポリマー粉砕品（Ｄ５０＝５．６μｍ）０．１ｇを用いたことを除いて、実施例３と同様の方法で重金属イオン捕捉能を評価した。濾過液中のマンガンイオンの濃度は３ｐｐｍであり、加熱によりＬＭＯから溶出したマンガンイオンがキレートポリマーで捕捉されていることが確認できた。
<Evaluation of ability to trap heavy metal ions>
In the same manner as in Example 3, except that 0.1 g of the chelate polymer pulverized product (D50 = 5.6 μm) produced in Example 4 was used instead of the chelate polymer pulverized product produced in Example 3. Heavy metal ion trapping ability was evaluated. The concentration of manganese ions in the filtrate was 3 ppm, and it was confirmed that the manganese ions eluted from the LMO by heating were captured by the chelate polymer.
（比較例１）
＜重金属イオンの捕捉能評価＞
キレートポリマーを用いず、ＬＭＯのみで実施例１と同様の条件でマンガンイオンの溶出挙動を評価した。濾過液中のマンガンイオンの濃度は１５ｐｐｍであり、実施例より高い値を示した。
(Comparative example 1)
<Evaluation of ability to trap heavy metal ions>
The elution behavior of manganese ions was evaluated under the same conditions as in Example 1 using only LMO without using the chelate polymer. The concentration of manganese ions in the filtrate was 15 ppm, which was higher than that of the example.
（比較例２）
＜重金属イオンの捕捉能評価＞
実施例１で製造したキレートポリマーに代えて、アルギン酸ナトリウム（青島聚大洋藻業集団有限公司製、重量平均分子量１，３００，０００）０．１ｇを用いたことを除いて、実施例１と同様の方法でマンガンイオンの溶出挙動を評価した。濾過液中のマンガンイオンの濃度は１４ｐｐｍであり、実施例より高い値を示した。
(Comparative example 2)
<Evaluation of ability to trap heavy metal ions>
Same as in Example 1, except that 0.1 g of sodium alginate (manufactured by Qingdao Juudao Algae Group Co., Ltd., weight average molecular weight: 1,300,000) was used instead of the chelate polymer produced in Example 1. We evaluated the dissolution behavior of manganese ions by the method of The concentration of manganese ions in the filtrate was 14 ppm, which was higher than that of the example.
以上説明したように、本発明によれば、微量の重金属イオンを迅速に捕捉し、短時間でｐｐｍレベル以下まで重金属イオン量を低減可能なキレートポリマーを提供することが可能となる。 As described above, according to the present invention, it is possible to provide a chelate polymer capable of rapidly trapping trace amounts of heavy metal ions and reducing the amount of heavy metal ions to the ppm level or less in a short period of time.
Claims (9)
ＰＳ－Ｘ－Ａ－ＣＬ （１）
（式中、ＰＳは酸性多糖類又は塩基性多糖類を表す。Ｘは－Ｏ－又は－Ｎ（Ｒ）－で示される基を表し、Ｒは水素原子又は炭素数が１～６の炭化水素基を表す。Ａは３個～３０個の炭素原子を有する有機基を表し、ＣＬはキレート官能基を含む炭素数が１～３０の有機基を表す。） A chelate polymer having a structure represented by the following general formula (1) and containing 0.2 to 5 mmol/g of a chelate functional group.
PS-XA-CL (1)
(In the formula, PS represents an acidic polysaccharide or a basic polysaccharide. X represents a group represented by -O- or -N(R)-, and R is a hydrogen atom or a hydrocarbon having 1 to 6 carbon atoms. A represents an organic group having 3 to 30 carbon atoms, and CL represents an organic group having 1 to 30 carbon atoms containing a chelating functional group.)
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