JP2005213477A - Chelate resin and method for producing the same - Google Patents
Chelate resin and method for producing the same Download PDFInfo
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- JP2005213477A JP2005213477A JP2004025449A JP2004025449A JP2005213477A JP 2005213477 A JP2005213477 A JP 2005213477A JP 2004025449 A JP2004025449 A JP 2004025449A JP 2004025449 A JP2004025449 A JP 2004025449A JP 2005213477 A JP2005213477 A JP 2005213477A
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- chelate resin
- polyamine
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- iminoethyl
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- 239000013522 chelant Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- -1 poly(iminoethyl) Polymers 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 claims abstract 4
- 238000004132 cross linking Methods 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000001242 acetic acid derivatives Chemical class 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 4
- 230000006675 polyamination Effects 0.000 description 4
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- AXQVKDQRBAXYBP-UHFFFAOYSA-N 2-aminoethanimidic acid Chemical compound NCC=N AXQVKDQRBAXYBP-UHFFFAOYSA-N 0.000 description 1
- DUAWRLXHCUAWMK-UHFFFAOYSA-N 2-iminiopropionate Chemical compound CC(=[NH2+])C([O-])=O DUAWRLXHCUAWMK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BUZRUIZTMOKRPB-UHFFFAOYSA-N carboxycarbamic acid Chemical class OC(=O)NC(O)=O BUZRUIZTMOKRPB-UHFFFAOYSA-N 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical compound [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- ZUKSLMGYYPZZJD-UHFFFAOYSA-N ethenimine Chemical group C=C=N ZUKSLMGYYPZZJD-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- PYHOFAHZHOBVGV-UHFFFAOYSA-N triazane Chemical compound NNN PYHOFAHZHOBVGV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は有害金属、特に銅イオンを効率良く選択、濃縮できるキレート樹脂及びその製造方法に関する。該キレート樹脂は、金属イオンの吸着量が多くかつ、脱着速度が速いので、廃液処理用の他分析用前処理剤，クロマトグラフィ担体等にも用いることが出来る。 The present invention relates to a chelate resin capable of efficiently selecting and concentrating harmful metals, particularly copper ions, and a method for producing the same. Since the chelate resin has a large amount of adsorption of metal ions and has a high desorption rate, it can be used for a pretreatment agent for analysis, a chromatographic carrier and the like for waste liquid treatment.
キレート樹脂とは、2つ以上の官能基を有し,キレート結合により特定のイオンを選択的吸着する。キレート結合にあずかる官能基の組み合わせが（N，O）の場合を例にとると、一般的には、クロロメチル化したスチレンとジビニルベンゼンとの共重合体を処理してイミノジ酢酸型，イミノジプロピオン酸型が作製される。ナトリウムイオン，カルシウムイオン，マグネシウムイオン等が多量に存在し、普通のイオン交換だと実用上使用できない廃水中の重金属の選択除去に用いられる(化学大辞典) (1296の化学商品)。担体に導入する イミノジ酢酸（IDA），イミノプロピオン酸等のイミノジカルボン酸は、金属の選択性も小さく、吸着量が十分でない等の課題がある。従って，従来のイミノジ酢酸（IDA）型は、マトリックスの多い試料中の金属を濃縮する目的としては必ずしもベストではない。
また、銅等とキレ−ト化率の高いアミノトリ酢酸(NTA)，エチレンジアミンテトラ酢酸等は、試薬が高価で実用化できないという問題もあった。
A chelate resin has two or more functional groups and selectively adsorbs specific ions through chelate bonds. For example, when the combination of functional groups involved in a chelate bond is (N, O), generally, a copolymer of chloromethylated styrene and divinylbenzene is treated to give an iminodiacetic acid type or iminodiamine. A propionic acid form is created. Sodium ion, calcium ion, magnesium ion, etc. are present in large quantities, and they are used for selective removal of heavy metals in wastewater that cannot be used practically by ordinary ion exchange (Chemical Dictionary) (1296 chemical products). Iminodicarboxylic acids such as iminodiacetic acid (IDA) and iminopropionic acid to be introduced into the carrier have problems such as low metal selectivity and insufficient adsorption. Therefore, the conventional iminodiacetic acid (IDA) type is not always the best for the purpose of concentrating metals in a sample with a lot of matrix.
Further, aminotriacetic acid (NTA), ethylenediaminetetraacetic acid and the like, which have a high chelating rate with copper and the like, have a problem that the reagents are expensive and cannot be put into practical use.
本発明者らは，アミノトリ酢酸(NTA)，エチレンジアミンテトラ酢酸等の高価なイミノジカルボン酸等の試薬を用いず、ポリアミン含有ポリマに安価なハロゲン化酢酸を反応させることにより、金属の吸着性が高いキレート樹脂ができることを見出した。 The present inventors do not use expensive reagents such as aminotriacetic acid (NTA) and ethylenediaminetetraacetic acid, but have a high metal adsorptivity by reacting an inexpensive halogenated acetic acid with a polyamine-containing polymer. It was found that a chelate resin can be formed.
本発明は以下の発明に関する。
<１> 架橋担体に導入されるポリアミン含有ポリマにハロゲン化酢酸を反応させてなるキレート樹脂。
<２> 架橋担体に導入されるポリアミン含有ポリマが、下記一般式(1)のポリ（イミノエチル）アミンである<１>記載のキレート樹脂。
<３> 上記一般式(1)のポリ（イミノエチル）アミンが、n=１，2，3であるエチレンジアミン，ジエチレントリアミン，トリエチレンテトラアミンである<２>記載のキレート樹脂。
<４> 架橋担体に導入されるポリアミン含有ポリマが、下記一般式(２)の分岐型ポリ（イミノエチル）アミンである<１>記載のキレート樹脂。
<５> 架橋担体がエポキシまたはハロゲン基含有するもので、ポリ（イミノエチル）アミンにハロゲン化酢酸導入前、または後に、アンモニアによる変性を行うことを特徴とする<１>〜<４>のいずれかに記載のキレート樹脂。
<６> 上記<５>に記載のキレート樹脂の製造法。
The present invention relates to the following inventions.
<1> A chelate resin obtained by reacting a halogenated acetic acid with a polyamine-containing polymer introduced into a crosslinking carrier.
<2> The chelate resin according to <1>, wherein the polyamine-containing polymer introduced into the crosslinking carrier is a poly (iminoethyl) amine represented by the following general formula (1).
<3> The chelate resin according to <2>, wherein the poly (iminoethyl) amine of the general formula (1) is ethylenediamine, diethylenetriamine, or triethylenetetraamine where n = 1,2,3.
<4> The chelate resin according to <1>, wherein the polyamine-containing polymer introduced into the crosslinked carrier is a branched poly (iminoethyl) amine represented by the following general formula (2).
<5> Any one of <1> to <4>, wherein the crosslinking carrier contains an epoxy or a halogen group, and the poly (iminoethyl) amine is modified with ammonia before or after the introduction of halogenated acetic acid. The chelating resin described in 1.
<6> The method for producing a chelate resin according to <5> above.
本発明のキレート樹脂を用いれば、金属の補足量が大きく，特に銅イオンを効率良く選択、濃縮できる。また、本特許記載の製造法に従えば、容易に該キレート樹脂が製造できる。 If the chelate resin of the present invention is used, a large amount of metal is captured, and particularly copper ions can be efficiently selected and concentrated. Further, according to the production method described in this patent, the chelate resin can be easily produced.
以下、本発明の実施形態を詳細に説明する。
本発明は、ポリアミン含有ポリマ(例：式(3))にハロゲン化酢酸を反応させてできるキレート樹脂及びその製造方法に関するものであり、詳しくは、ポリ（イミノエチル）アミン等の担体のポリアミン鎖をハロゲン化酢酸等でカルボキシメチル化し、ポリアミン−ポリカルボン酸型キレート樹脂を合成するものである。該キレート樹脂は、イミノジ酢酸の様な、単一なキレート基を導入したものではないので、以下に示す式(4)〜(6)様な官能基が混在するものである。
Hereinafter, embodiments of the present invention will be described in detail.
The present invention relates to a chelate resin obtained by reacting a halogenated acetic acid with a polyamine-containing polymer (eg, formula (3)) and a method for producing the same. Specifically, a polyamine chain of a carrier such as poly (iminoethyl) amine is used. It carboxymethylates with halogenated acetic acid or the like to synthesize a polyamine-polycarboxylic acid type chelate resin. Since the chelate resin is not the one having a single chelate group introduced like iminodiacetic acid, it has a mixture of functional groups represented by the following formulas (4) to (6).
ポリアミン含有ポリマは，ハロゲン化酢酸が反応できるものであれば特に限定しないが、液体試料(廃液)等から、キレート樹脂を取り出す等の作業を考えると実用上、架橋担体に、ポリアミンが導入されたものが好ましい。 The polyamine-containing polymer is not particularly limited as long as it can react with halogenated acetic acid. However, in consideration of operations such as taking out a chelate resin from a liquid sample (waste liquid) or the like, in practice, polyamine is introduced into the cross-linked carrier. Those are preferred.
架橋担体としては、多孔性ポリスチレンの誘導体，多孔性ポリエステルその誘導体，多孔性ポリビニルアルコールの誘導体等が挙げられるが、ポリアミン導入が容易に出きる様に、ハロゲン基含有のポリクロロメチルスチレン，エポキシ基含有のポリグリシジルメタクリレート等が好ましい。 Examples of the cross-linking carrier include porous polystyrene derivatives, porous polyester derivatives thereof, porous polyvinyl alcohol derivatives, etc., but halogen group-containing polychloromethylstyrene, epoxy group so that polyamine can be easily introduced. Containing polyglycidyl methacrylate is preferred.
担体の合成方法は、特に限定しないが例えば、クロロメチルスチレン，グリシジルメタクリレート等を特許文献１記載の方法に準じて水性懸濁重合させて行うことができる。なお、クロロメチルスチレン，グリシジルメタクリレート等のアミノ基と反応する基を含有モノマーは、10〜90重量％用いる必要がある。少なすぎると、ポリアミン導入量が少なくなり、金属補足量が減る。多すぎると、架橋担体の強度が弱くなり、廃液等で膨潤し、操作が困難となるとともにポリアミン架橋を生じる。 The method for synthesizing the carrier is not particularly limited, and for example, chloromethylstyrene, glycidyl methacrylate and the like can be subjected to aqueous suspension polymerization according to the method described in Patent Document 1. In addition, it is necessary to use 10 to 90% by weight of a monomer containing a group that reacts with an amino group such as chloromethylstyrene or glycidyl methacrylate. If the amount is too small, the amount of polyamine introduced is reduced and the amount of metal supplement is reduced. When the amount is too large, the strength of the cross-linking carrier becomes weak, and it swells with waste liquid or the like, which makes operation difficult and causes polyamine cross-linking.
ハロゲン基，エポキシ基含有ポリマを合成した場合は、ポリアミノ化後及びハロゲン化酢酸導入後に、ハロゲン基，エポキシ基が残り、試料中のマトリックス(有機物質)と反応してしまう可能性があるので、必要に応じて、ハロゲン化酢酸導入前後に、アンモニア水で、ポリアミノ化変性することが好ましい。 When synthesizing halogen group and epoxy group-containing polymers, after polyamination and introduction of halogenated acetic acid, halogen groups and epoxy groups may remain and react with the matrix (organic substance) in the sample. If necessary, it is preferable to perform polyamination modification with aqueous ammonia before and after the introduction of halogenated acetic acid.
架橋担体に導入するポリアミンとしては、アミン含有ポリマであれば良いが、特に前記一般式(1)に示すエチレンジアミン，ジエチレントリアミン，トリエチレンテトラアミン等，前記一般式(2)に示す分岐ポリ（イミノエチル）アミンが望ましい。ポリ（イミノエチル）アミンは、分子鎖が長いと吸着量は増すが、分子鎖が巻くため、脱着が不充分になり、分離剤やクロマトグラフィや、等の用途では不利となる。 The polyamine introduced into the cross-linking carrier may be an amine-containing polymer, but in particular, the branched poly (iminoethyl) represented by the general formula (2) such as ethylenediamine, diethylenetriamine, triethylenetetraamine, etc. represented by the general formula (1). Amines are desirable. Poly (iminoethyl) amine increases the amount of adsorption when the molecular chain is long. However, since the molecular chain is wound, desorption becomes insufficient, which is disadvantageous for uses such as a separating agent and chromatography.
作製した（イミノエチルアミン）を導入した担体（ポリアミン含有ポリマ）に、ハロゲン化酢酸でカルボキシメチル化することにより、キレート樹脂が作製できる。ハロゲン化酢酸としては、クロロ酢酸，ブロモ酢酸等が挙げられる。 A chelate resin can be produced by carboxymethylating the produced carrier (polyamine-containing polymer) into which (iminoethylamine) has been introduced with halogenated acetic acid. Examples of the halogenated acetic acid include chloroacetic acid and bromoacetic acid.
ハロゲン化酢酸は、すべてのアミンに導入する必要はなく、反応状態により、前記式(4)〜(6)等のキレート基が混在する。完全にカルボキシメチル化ができなくともイミノエチレン鎖のスペーサとなり，銅との親和性がアップし、銅の補足量をます。また、酸性下では、プロトネ-ションで排除効果が起き、金属イオン，脱着を容易にすることになる。 Halogenated acetic acid does not need to be introduced into all amines, and chelate groups such as the above formulas (4) to (6) are mixed depending on the reaction state. Even if it cannot be completely carboxymethylated, it becomes a spacer of the iminoethylene chain, increasing its affinity with copper, and supplementing copper. In addition, under acidic conditions, the elimination effect occurs in the protonation, which facilitates metal ions and desorption.
以下実施例により本発明を説明する。
実施例1
The following examples illustrate the invention.
Example 1
(a)架橋担体の製造
グリシジルメタクリレート100ｇ、テトラメチロールメタントリメタクリレート100ｇ、酢酸ブチル１８０ｇ、イソアミルアルコール１２０ｇ及びアゾビスイソブチロニトリル０．７ｇの混合物にイオン交換水１０００ml、1%ポリビニルアルコール水溶液200mlを加え、攪拌しながら水酸化ナトリウム水溶液を用いてpH７〜８に調整した。その後、７０℃で６時間重合反応を行った。反応物を冷却した後、生成した共重合体粒子を濾取し、メタノール及び水で順次洗浄した。次いで、一日風乾し、さらに８０℃の真空乾燥機に入れて６時間乾燥した。乾燥粒子を分級して40〜50μｍの多孔性架橋重合体粒子30ｇを得た。
(b)ポリアミノ化反応
メタノール20g，イオン交換水80gにジエチレンテトラアミン15gを溶解し、(1)で得られた重合体粒子(架橋担体)10ｇを加え、60℃で5時間反応させた。反応物を濾過し、イオン交換水で洗浄した。この反応物をさらに、0.28%アンモニア水溶液100mlに入れ、30℃で5時間反応させ、残存エポキシ基をアミノ開環した。その後、イオン交換水で洗浄して、ポリアミノ化担体(ポリアミン)を得た。
(c)カルボキシメチル化
1M NaOH水溶液100mlにクロロ酢酸ナトリウム14gを溶解し、(b)で得られたポリアミノ化担体(ポリアミン)を全量入れ、40℃で5時間反応させ、反応物を濾過しイオン交換水、メタノールで洗浄し、キレート樹脂を得た。
(d)評価
カートリッジに、作製したキレート樹脂0.25gを充填し、アセトニトリル，10mM硝酸，0.05M酢酸アンモニウム，イオン交換水でコンディショニング後、0.5 M硫酸銅4 mL負荷し、余剰分の硫酸銅を10mM硝酸，イオン交換水で洗い、1 M硝酸6 mLで溶出し、吸光光度計で銅補足量を測定(測定波長：805 nm，参照セル：水)した。補足量は、250μmol/gであった。
実施例２
(a) Manufacture of a cross-linking carrier A mixture of 100 g of glycidyl methacrylate, 100 g of tetramethylolmethane trimethacrylate, 180 g of butyl acetate, 120 g of isoamyl alcohol and 0.7 g of azobisisobutyronitrile was mixed with 1000 ml of ion-exchanged water and 200 ml of 1% aqueous polyvinyl alcohol solution. In addition, the pH was adjusted to 7-8 using an aqueous sodium hydroxide solution with stirring. Thereafter, a polymerization reaction was carried out at 70 ° C. for 6 hours. After cooling the reaction product, the produced copolymer particles were collected by filtration and washed successively with methanol and water. Subsequently, it was air-dried for one day and further put into a vacuum dryer at 80 ° C. for 6 hours. The dried particles were classified to obtain 30 g of porous crosslinked polymer particles of 40 to 50 μm.
(b) Polyamination reaction 15 g of diethylenetetraamine was dissolved in 20 g of methanol and 80 g of ion-exchanged water, and 10 g of the polymer particles (crosslinked carrier) obtained in (1) were added and reacted at 60 ° C. for 5 hours. The reaction was filtered and washed with ion exchange water. This reaction product was further added to 100 ml of 0.28% aqueous ammonia solution and reacted at 30 ° C. for 5 hours to open the remaining epoxy group with amino ring. Thereafter, it was washed with ion-exchanged water to obtain a polyaminated carrier (polyamine).
(c) Carboxymethylation
Dissolve 14 g of sodium chloroacetate in 100 ml of 1M NaOH aqueous solution, add the whole amount of polyaminated carrier (polyamine) obtained in (b), react at 40 ° C for 5 hours, filter the reaction product, wash with ion-exchanged water and methanol Thus, a chelate resin was obtained.
(d) Evaluation The cartridge was filled with 0.25 g of the prepared chelate resin, conditioned with acetonitrile, 10 mM nitric acid, 0.05 M ammonium acetate and ion-exchanged water, loaded with 4 mL of 0.5 M copper sulfate, and 10 mM of excess copper sulfate. It was washed with nitric acid and ion-exchanged water, eluted with 6 mL of 1 M nitric acid, and the amount of copper supplemented was measured with an absorptiometer (measurement wavelength: 805 nm, reference cell: water). The supplemental amount was 250 μmol / g.
Example 2
(a)架橋担体の製造
クロロメチルスチレン100ｇ、ジビニルベンゼン100ｇ、酢酸ブチル１８０ｇ、トルエン１２０ｇ及びアゾビスイソブチロニトリル０．７ｇの混合物にイオン交換水１０００ml、1%ポリビニルアルコール水溶液200mlを加え、攪拌しながら水酸化ナトリウム水溶液を用いてpH７〜８に調整した。その後、７０℃で６時間重合反応を行った。反応物を冷却した後、生成した共重合体粒子を濾取し、メタノール及び水で順次洗浄した。次いで、一日風乾し、さらに８０℃の真空乾燥機に入れて６時間乾燥した。乾燥粒子を分級して40〜50μｍの多孔性架橋重合体粒子30ｇを得た。
(b)ポリアミノ化反応
メタノール20g，イオン交換水80gにテトラエチレンジアミン15gを溶解し、(1)で得られた重合体粒子(架橋担体)10ｇを加え、60℃で5時間反応させた。反応物を濾過し、イオン交換水で洗浄した。この反応物をさらに、0.28%アンモニア水溶液100mlに入れ、30℃で5時間反応させ、残存エポキシ基をアミノ開環した。その後、反応物を濾過し、イオン交換水で洗浄して、ポリアミノ化担体(ポリアミン)樹脂を得た。
(c)カルボキシメチル化
1M NaOH水溶液100mlにクロロ酢酸ナトリウム14gを溶解し、(b)で得られたポリアミノ化担体(ポリアミン)樹脂を全量入れ、40℃で5時間反応させ、反応物を濾過しイオン交換水、メタノールで洗浄して、キレート樹脂を得た。
(d)評価
実施例1(d)の評価方法に従い、銅補足量を求めたところ、180μmol/gであった。
比較例１
(a) Production of cross-linked carrier To a mixture of 100 g of chloromethylstyrene, 100 g of divinylbenzene, 180 g of butyl acetate, 120 g of toluene and 0.7 g of azobisisobutyronitrile, add 1000 ml of ion-exchanged water and 200 ml of 1% polyvinyl alcohol aqueous solution, and stir. The pH was adjusted to 7 to 8 using an aqueous sodium hydroxide solution. Thereafter, a polymerization reaction was carried out at 70 ° C. for 6 hours. After cooling the reaction product, the produced copolymer particles were collected by filtration and washed successively with methanol and water. Subsequently, it was air-dried for one day and further put into a vacuum dryer at 80 ° C. for 6 hours. The dried particles were classified to obtain 30 g of porous crosslinked polymer particles of 40 to 50 μm.
(b) Polyamination reaction 15 g of tetraethylenediamine was dissolved in 20 g of methanol and 80 g of ion-exchanged water, and 10 g of the polymer particles (crosslinked carrier) obtained in (1) were added and reacted at 60 ° C. for 5 hours. The reaction was filtered and washed with ion exchange water. This reaction product was further added to 100 ml of 0.28% aqueous ammonia solution and reacted at 30 ° C. for 5 hours to open the remaining epoxy group with amino ring. Thereafter, the reaction product was filtered and washed with ion exchange water to obtain a polyaminated carrier (polyamine) resin.
(c) Carboxymethylation
Dissolve 14 g of sodium chloroacetate in 100 ml of 1M NaOH aqueous solution, add the whole amount of polyaminated carrier (polyamine) resin obtained in (b), react at 40 ° C for 5 hours, filter the reaction product with ion-exchanged water and methanol. Washing gave a chelate resin.
(d) Evaluation According to the evaluation method of Example 1 (d), the amount of copper supplement was determined and found to be 180 μmol / g.
Comparative Example 1
実施例1(a)で作製した担体10gを、イミノジ酢酸ナトリウム6gを0.5M水酸化ナトリウム水溶液100mlに入れ、60℃で5時間反応した。反応物を濾過しイオン交換水で洗浄した。この反応物をさらに、0.01N硫酸水溶液100mlに入れ、40℃で5時間反応させ、残存エポキシ基を開環した。その後、反応物を濾過し、イオン交換水で洗浄して、イミノジ酢酸型キレート樹脂を得た。実施例1(d)の評価方法に従い、銅補足量を求めたところ、80μmol/gであった。 10 g of the carrier prepared in Example 1 (a) was placed in 100 ml of 0.5 M aqueous sodium hydroxide solution and 6 g of sodium iminodiacetate, and reacted at 60 ° C. for 5 hours. The reaction was filtered and washed with ion exchange water. This reaction product was further placed in 100 ml of 0.01N aqueous sulfuric acid solution and reacted at 40 ° C. for 5 hours to open the remaining epoxy groups. Thereafter, the reaction product was filtered and washed with ion-exchanged water to obtain an iminodiacetic acid type chelate resin. According to the evaluation method of Example 1 (d), the amount of copper supplement was determined to be 80 μmol / g.
以上のように、実施例１及び２の銅補足量は、比較例１の銅補足量よりも高いことがわかった。
As described above, it was found that the copper supplements of Examples 1 and 2 were higher than the copper supplement of Comparative Example 1.
Claims (6)
A method for producing the chelate resin according to claim 5.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010098257A1 (en) * | 2009-02-27 | 2010-09-02 | 日本フイルコン株式会社 | Chelating resin |
| WO2010122954A1 (en) | 2009-04-23 | 2010-10-28 | 日本フイルコン株式会社 | Metal adsorbent containing chelating polymer |
| JP2010254841A (en) * | 2009-04-27 | 2010-11-11 | Nippon Filcon Co Ltd | Metal-adsorptive sintered porous body and method for producing the same |
| WO2013111891A1 (en) | 2012-01-27 | 2013-08-01 | 日本フイルコン株式会社 | Polymer adsorbent |
| WO2013121863A1 (en) | 2012-02-14 | 2013-08-22 | 日本フイルコン株式会社 | Metal-adsorbing gel and adsorbent supporting metal-adsorbing gel |
| JP2013194339A (en) * | 2012-03-21 | 2013-09-30 | Chubu Kiresuto Kk | Chelate-forming fiber, method for producing the same, metal ion capturing method using the fiber and metal chelate fiber |
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| JPS54135890A (en) * | 1978-03-24 | 1979-10-22 | Sumitomo Chem Co Ltd | Preparation of chelate resin |
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| JPS54135890A (en) * | 1978-03-24 | 1979-10-22 | Sumitomo Chem Co Ltd | Preparation of chelate resin |
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| JP2010194509A (en) * | 2009-02-27 | 2010-09-09 | Nippon Filcon Co Ltd | Chelate resin |
| US20150065617A1 (en) * | 2009-04-23 | 2015-03-05 | Nippon Filcon Co., Limited | Adsorbent containing chelating polymer |
| JP2010253359A (en) * | 2009-04-23 | 2010-11-11 | Nippon Filcon Co Ltd | Metal adsorbent containing chelating polymer compound |
| US20120132852A1 (en) * | 2009-04-23 | 2012-05-31 | Yoshinori Inoue | Metal adsorbent containing chelating polymer |
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| WO2013111891A1 (en) | 2012-01-27 | 2013-08-01 | 日本フイルコン株式会社 | Polymer adsorbent |
| WO2013121863A1 (en) | 2012-02-14 | 2013-08-22 | 日本フイルコン株式会社 | Metal-adsorbing gel and adsorbent supporting metal-adsorbing gel |
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