JP2016065134A - ジグリコールアミド酸型配位子を有するビニルモノマー - Google Patents
ジグリコールアミド酸型配位子を有するビニルモノマー Download PDFInfo
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- JP2016065134A JP2016065134A JP2014194203A JP2014194203A JP2016065134A JP 2016065134 A JP2016065134 A JP 2016065134A JP 2014194203 A JP2014194203 A JP 2014194203A JP 2014194203 A JP2014194203 A JP 2014194203A JP 2016065134 A JP2016065134 A JP 2016065134A
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- vinyl monomer
- rare earth
- substituent
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- 239000000178 monomer Substances 0.000 title claims abstract description 61
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 48
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 47
- 239000003446 ligand Substances 0.000 title claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 125000001424 substituent group Chemical group 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- CNDWHJQEGZZDTQ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetamide Chemical compound NC(=O)COCC(N)=O CNDWHJQEGZZDTQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000000962 organic group Chemical group 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003926 acrylamides Chemical class 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 30
- 238000010559 graft polymerization reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
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- 230000005855 radiation Effects 0.000 description 10
- 125000000732 arylene group Chemical group 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 8
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- 150000002500 ions Chemical class 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
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- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000005251 gamma ray Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
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- 239000004745 nonwoven fabric Substances 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 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 1
- WBZVQGYKIVWFGQ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetic acid Chemical compound NC(=O)COCC(O)=O WBZVQGYKIVWFGQ-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
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- 238000012690 ionic polymerization Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron(III) chloride Substances Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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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
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/26—Nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
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- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
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- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
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- C07C235/16—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
希土類元素イオンの分離・回収方法として、抽出剤等を用いる溶媒抽出法(液−液抽出法)やイオン交換樹脂等を用いるカラム抽出法(固−液抽出法)等が知られている。ここで、溶媒抽出法とは、分離対象の金属元素を含む水溶液からなる水相と、特定の金属元素を抽出する抽出剤及びそれを希釈するための有機溶媒からなる有機相を接触させることで、特定の金属元素を抽出剤に抽出させることで分離する方法である。
希土類元素イオンの吸着には、カルボキシル基を含むジグリコールアミド酸(DGAA)の骨格(>N−CO−CH2−O−CH2−COOH、−NH−CO−CH2−O−CH2−COOH)が多座配位子として有効であることが知られており、その骨格を有する抽出剤による溶媒抽出法や粒状吸着材によるカラム抽出法が研究されている。溶媒抽出法では、例えば、特定の化学式で表されるジグリコールアミド酸が抽出剤として溶解した溶液を用いて希土類元素を抽出する技術が提案されている(例えば、特許文献1参照)。また、カラム抽出法では、例えば、特定のジグリコールアミド型配位子をシリカゲル表面に導入した吸着材を用いてカラム吸着により希土類元素を分離する技術が提案されている(例えば、非特許文献1参照)。
〔1〕下記一般式(1)で表されるジグリコールアミド酸型配位子を有するビニルモノマー。
〔2〕(メタ)アクリル酸化合物、(メタ)アクリルアミド化合物、スチレン化合物及びビニルアミド(イミド)化合物からなる群から選択される少なくとも1種の化合物である前記〔1〕に記載のビニルモノマー。
〔3〕希土類元素の吸着分離材の製造に用いられる前記〔1〕又は〔2〕に記載のビニルモノマー。
〔4〕前記〔1〕又は〔2〕に記載のビニルモノマーを含有する(共)重合体。
〔5〕希土類元素の吸着分離材として用いる前記〔4〕に記載の(共)重合体。
本発明のビニルモノマーは、下記一般式(1)で表されるジグリコールアミド酸型配位子を有するビニルモノマー(以下、単に「本発明のビニルモノマーともいう」)である。
R1は、水素原子又は炭素数1〜2のアルキル基であることが好ましく、本発明のビニルモノマーの疎水化を避けるという観点から、R1は水素原子又はメチル基であることが特に好ましい。
置換基を有していてもよい2価の有機基としては、直鎖、分岐鎖又は環状のいずれであってもよく、例えば、置換基を有していてもよいアルキレン基、置換基を有していてもよいアリーレン基、−O−、−C(=O)−、−NH−又はこれらが組み合わされた基等が挙げられる。
置換基を有していてもよいアリーレン基のアリーレン基としては、o−フェニレン基、m−フェニレン基、p−フェニレン基等が挙げられる。
前記アリーレン基の置換基としては、例えば、メチル基、エチル基等のアルキル基が挙げられる。
これらの置換基は、アルキレン基及びアリーレン基の基において任意の位置に結合していてよく、同一若しくは相異なって複数個が結合していてもよい。
置換基を有していてもよい2価の有機基としては、直鎖、分岐鎖又は環状のいずれであってもよく、例えば、置換基を有していてもよいアルキレン基、置換基を有していてもよいアリーレン基、−O−、−C(=O)−、−NH−又はこれらが組み合わされた基等が挙げられる。
置換基を有していてもよいアリーレン基のアリーレン基としては、o−フェニレン基、m−フェニレン基、p−フェニレン基等が挙げられる。
置換基は、アルキレン基及びアリーレン基等の基において任意の位置に結合していてよく、同一若しくは相異なって複数個が結合していてもよい。
R2における炭素数1〜3のアルキル基としては、メチル基、エチル基、(イソ)プロピル基が挙げられる。
R2における炭素数1〜2のアシル基としては、例えば、アセチル基等が挙げられる。
R2におけるアルデヒド基としては、例えば、ホルミル基を挙げることができる。
R2における炭素数1〜3のアルキレン基としては、メチレン基、エチレン基、プロピレン基が挙げられる。
本発明のビニルモノマーは、少なくとも1つ以上の1、2級アミンを有するビニルモノマーとジグリコール酸との縮合反応により製造することができる。活性化した酸成分として酸無水物の無水ジグリコール酸を用いる。また、対称酸無水物を用いれば、酸の半分はアミンと反応しない利点もある。
縮合反応について、DGAAを有するスチレンモノマー(DGAAスチレンモノマー)を製造する場合を例に説明する。
得られた反応液を濾過し、濾液を濃縮、ヘキサン、ヘプタン等の有機溶媒を加え晶折させる。析出した結晶を濾取して、ヘプタン洗浄、乾燥を行うことによって、DGAAスチレンモノマーが得られる。
吸着分離材としては、特に限定されないが、例えば、ラジカル重合またはイオン重合による単独重合体と共重合体が挙げられ、既存の形状の担体基材に、本発明のビニルモノマーを使用したグラフト重合によりグラフト鎖を形成させて吸着分離材を製造することが好ましい。
γ線源としては、コバルト、セシウム、ストロンチウムなどが挙げられる。コバルトのγ線源は、透過深度が大きいため、電子線を用いる場合に比べて被照射体の厚みを厚くすることができるので、長尺物をロール状にしてバッチ法で照射する方法において好適に使用することができる。
放射線の照射線量は一般的に10〜500kGy、好ましくは15〜200kGyである。
また、放射線照射は、通常、室温(10〜40℃)で行うが、生成ラジカルの減衰を抑制するため、必要に応じて不活性ガス(例えば、窒素、アルゴンなど)中で行うことができる。
重量グラフト率(wt%)=(グラフト重合後の基材の重量−グラフト重合前の基材の重量)/(グラフト重合前の基材の重量)×100
希土類元素の吸着分離材として用いる場合、当該(共)重合体は粒子状の形態で用いることができる。
重量グラフト率は以下の式により求めた。
重量グラフト率(wt%)=(グラフト重合後の基材の重量−グラフト重合前の基材の重量)/(グラフト重合前の基材の重量)×100
DGAA導入反応前後の基材の質量変化をWとし、以下の式により求めた。
DGAA導入量(mmol/g)=(W(mg)/反応基質の分子量(mg/mmol))/反応後の基材質量(g)
<DGAA−ビニルモノマーの合成>
反応液を濾過し、濾液をそのままシリカゲルカラムに通液し、THFを溶離液として流し、溶出したフラクションを濃縮した。得られた濃縮液にトルエンを加えて晶析させ、析出した結晶を濾取した。得られた結晶をトルエンで洗浄した後、乾燥を行うことによって、DGAA−メタクリレート11.24g(収率45.7%)を得た。
<吸着分離材の作製>
高分子基材としてビニロン不織布を用い、モノマー溶液として合成例1で得られたDGAA−メタクリレートの50wt%水溶液を使用した。モノマー溶液の溶存酸素を除去するため、窒素ガスで1時間バブリングした。
高分子基材に電子線を90kGy照射し、照射後の高分子基材を速やかにモノマー溶液に浸漬させた。高分子基材とモノマー溶液を50℃で15分間反応させ、高分子基材にグラフト鎖を導入した。次いで、純水で十分洗浄した後、40℃で1時間以上で乾燥させ、吸着分離材を得た。
重量グラフト率は136wt%であり、DGAAの導入量は2.35mmol/gであった。
<希土類元素の吸着試験>
希土類元素としてジスプロシウムの塩化物塩とネオジムの塩化物塩、ベースメタルとして銅、鉄(III)及び亜鉛の塩化物塩をそれぞれ1mMになるように蒸留水に溶解し、塩酸でpHを1、2に調整したものを吸着試験水溶液とした。
吸着試験水溶液に作製例1で作製した吸着分離材を加え、振とうしながら約25℃で1日間吸着試験を行った。
吸着試験後、溶液を採取し、0.20μmのメンブレンフィルターで濾過し、ICP発光分析装置(島津製作所製「ICPE−9000」)により水溶液中の金属イオン濃度を測定し、マスバランスから金属イオンの吸着量を算出した。
結果を、図1に示す。
Claims (5)
- (メタ)アクリル酸化合物、(メタ)アクリルアミド化合物、スチレン化合物及びビニルアミド(イミド)化合物からなる群から選択される少なくとも1種の化合物である請求項1に記載のビニルモノマー。
- 希土類元素の吸着分離材の製造に用いられる請求項1又は請求項2に記載のビニルモノマー。
- 請求項1又は請求項2に記載のビニルモノマーを含有する(共)重合体。
- 希土類元素の吸着分離材として用いる請求項4に記載の(共)重合体。
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