JP5796867B2 - Chelating resin - Google Patents

Chelating resin Download PDF

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JP5796867B2
JP5796867B2 JP2009045325A JP2009045325A JP5796867B2 JP 5796867 B2 JP5796867 B2 JP 5796867B2 JP 2009045325 A JP2009045325 A JP 2009045325A JP 2009045325 A JP2009045325 A JP 2009045325A JP 5796867 B2 JP5796867 B2 JP 5796867B2
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capture
chelate resin
resin
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JP2010194509A (en
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嘉則 井上
嘉則 井上
英之 梁井
英之 梁井
満 齊藤
満 齊藤
重浩 加賀谷
重浩 加賀谷
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Nippon Filcon Co Ltd
Toyama University
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Nippon Filcon Co Ltd
Toyama University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/10—Acylation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Description

本発明は、工場排水、用水、環境水、食品、薬品等の被処理溶液中から重金属元素の除去、回収に用いられるキレート樹脂において、被処理溶液中に多量に存在するアルカリ土類金属類の妨害を受けず、かつ既存のアミノカルボン酸型キレート樹脂で捕捉しにくい金属のオキソ酸類をも含めた重金属元素を高度に捕捉しうるアミノカルボン酸型キレート樹脂及びその製造方法に関するものである。 The present invention relates to a chelate resin used for removal and recovery of heavy metal elements from a solution to be treated such as factory effluent, water for use, environmental water, food, chemicals, etc., in the alkaline earth metals present in a large amount in the solution to be treated. The present invention relates to an aminocarboxylic acid type chelate resin that can highly capture heavy metal elements including metal oxo acids that are not disturbed and that are difficult to capture with existing aminocarboxylic acid type chelate resins, and a method for producing the same.

重金属は高い有害性を示し、土中残留性や生体濃縮性が高いため、工場排水、用水、環境水、食品、薬品等から可能な限り除去する必要がある。また、廃棄された電子機器中には希少金属が大量に含まれており、これらは都市鉱山とも呼ばれる貴重な資源であるため、これらに含まれる有価金属の回収に関する技術開発が進められている。被処理液中から重金属を除去する手法としては、凝集沈殿をはじめとして種々の方法が行われているが、高度な除去・回収法としては、イオン交換樹脂やキレート樹脂を用いた方法が広く用いられてきた。一般に、これらの被処理液中には高濃度の塩類や有機物が含まれており、イオン交換樹脂での重金属除去が困難な場合も多く、キレート樹脂を利用したほうが効率良く除去・回収できるとされている。 Heavy metals are highly harmful and have high soil persistence and bioconcentration. Therefore, they must be removed from factory wastewater, irrigation water, environmental water, food, medicine, etc. as much as possible. In addition, the discarded electronic devices contain a large amount of rare metals, and these are valuable resources called urban mines. Therefore, technological development relating to the recovery of valuable metals contained in these metals has been promoted. Various methods such as agglomeration and precipitation have been used to remove heavy metals from the liquid to be treated, but methods using ion exchange resins and chelate resins are widely used as advanced removal and recovery methods. Has been. In general, these treatment liquids contain high concentrations of salts and organic substances, and it is often difficult to remove heavy metals with ion exchange resins, and it is said that removal and recovery can be performed more efficiently using chelate resins. ing.

キレート樹脂としては、イミノ二酢酸 (ＩＤＡ)、ポリアミン、アミノリン酸、イソチオウロニウム、ジチオカルバミン酸、グルカミン等の官能基が導入されたものが市販されている。この内、汎用性という点からはアミノカルボン酸の一種であるＩＤＡ型のキレート樹脂が多用されている。しかしながら、ＩＤＡは、代表的なキレート剤であるエチレンジアミン四酢酸 (ＥＤＴＡ) に比べ錯体の安定度定数が低く、被処理液中の夾雑イオン濃度が高い場合には、それらの妨害により除去率や回収率が変動しやすい等の問題も生じる。 As the chelating resin, those into which functional groups such as iminodiacetic acid (IDA), polyamine, aminophosphoric acid, isothiouronium, dithiocarbamic acid, glucamine are introduced are commercially available. Among these, from the viewpoint of versatility, an IDA type chelate resin which is a kind of aminocarboxylic acid is frequently used. However, IDA has a lower stability constant of the complex than ethylenediaminetetraacetic acid (EDTA), which is a typical chelating agent, and when the concentration of contaminant ions in the liquid to be treated is high, the removal rate and recovery due to their interference. There are also problems such as rate fluctuations.

キレート性官能基における金属錯体形成のしやすさは、一般に安定度定数 (ｌｏｇＫML) で示される。ポリアミノカルボン酸型キレート剤においては、金属元素にもよるが、エチレンイミンの繰り返し単位が多いほど、あるいはポリエチレンイミン鎖の鎖長が長いほど錯体の安定度定数が大きくなるが、カルシウムの安定度定数はさほど大きくはならない (非特許文献１及び非特許文献２)。つまり、鎖長が長いほど金属の捕捉性が高くなり、カルシウムとの選択性が相対的に改善されるということを意味している。 The ease of forming a metal complex in a chelating functional group is generally indicated by a stability constant (log K ML ). In polyaminocarboxylic acid type chelating agents, although depending on the metal element, the more the repeating unit of ethyleneimine or the longer the chain length of the polyethyleneimine chain, the greater the stability constant of the complex, but the stability constant of calcium. It is not so large (Non-Patent Document 1 and Non-Patent Document 2). That is, it means that the longer the chain length, the higher the metal trapping property, and the relative selectivity with calcium is relatively improved.

ＩＤＡ型キレート樹脂における捕捉性や選択性の低さの問題を解消するため、金属捕捉性や選択性の改善を目指した新たなアミノカルボン酸型キレート樹脂に関するいくつかの開示がある。特許文献1ではα-アミノ-ε-カプロラクタムを出発原料としたニトリロ三酢酸型、特許文献２ではジエチレントリアミンを導入しカルボキシメチル化したジエチレントリアミン-Ｎ、Ｎ、Ｎ´、Ｎ´−四酢酸型、特許文献３ではジエチレントリアミン等を導入しカルボキシメチル化したジエチレントリアミン-Ｎ、Ｎ´、Ｎ"、Ｎ"−四酢酸型、特許文献４では三級アミノ基を有する陰イオン交換樹脂に、高分子量ポリエチレンイミンを導入後にカルボキシメチル化した四級アンモニウム基を有する高分子型のキレート樹脂に関して開示されている。特許文献３においては、旧来のイミノ二酢酸型に比べ鎖長の長いジエチレントリアミン、トリエチレンテトラミン骨格の官能基の導入が記載されている。このように鎖長を長くすることにより錯体の安定度定数は改善されると考えられるが、特許文献３の実施例においては不明な点が多く、その効果も明確に記述されてはいない。また特許文献４は長鎖のポリエチレンイミンをイオン交換樹脂のイオン交換基に結合させたキレート樹脂に関するものであり、特に有機溶媒中での金属捕捉に関するもので、有機溶媒中での官能基の伸長を利用している。また、ポリアミン型キレート樹脂を、さらにカルボキシメチル化したキレート樹脂に関する記載もあるが、実施例によればカルボキシメチル化度が非常に低く、カルボキシメチル基は補助的であり、本質的にはポリアミン型キレート樹脂と同様の効果が得られる。 In order to solve the problem of low capture property and selectivity in the IDA type chelate resin, there are some disclosures regarding a new aminocarboxylic acid type chelate resin aimed at improving metal capture property and selectivity. In Patent Document 1, nitrilotriacetic acid type using α-amino-ε-caprolactam as a starting material, and in Patent Document 2, diethylenetriamine-N, N, N ′, N′-tetraacetic acid type obtained by introducing diethylenetriamine into carboxymethyl, patent In Document 3, diethylenetriamine-N, N ′, N ″, N ″ -tetraacetic acid type carboxymethylated by introducing diethylenetriamine or the like, and in Patent Document 4, high molecular weight polyethyleneimine is added to an anion exchange resin having a tertiary amino group. A polymer-type chelate resin having a quaternary ammonium group carboxymethylated after introduction is disclosed. In Patent Document 3, introduction of a functional group of a diethylenetriamine or triethylenetetramine skeleton having a longer chain length than the conventional iminodiacetic acid type is described. Although it is considered that the stability constant of the complex is improved by increasing the chain length in this way, there are many unclear points in the example of Patent Document 3, and the effect is not clearly described. Patent Document 4 relates to a chelate resin in which a long-chain polyethyleneimine is bound to an ion exchange group of an ion exchange resin, and particularly relates to metal capture in an organic solvent. Is used. Further, there is also a description about a chelate resin obtained by further carboxymethylating a polyamine type chelate resin, but according to the examples, the degree of carboxymethylation is very low, the carboxymethyl group is auxiliary, and essentially the polyamine type chelate resin. The same effect as the chelate resin can be obtained.

一方、キレート樹脂を用いて実際の被処理液中の重金属を捕捉しようとする場合、被処理液中に共存するアルカリ金属による妨害は極端に高濃度の場合を除いてほとんど無視することができるが、マグネシウム、カルシウム、バリウム等のアルカリ土類金属類はキレート樹脂に捕捉されるため重金属の捕捉を妨害する。これらのアルカリ土類金属類は一般的な排水、環境水、金属処理液等の中には高濃度で共存しているため、目的とする重金属の除去率、回収率が大きく変動してしまうことも多い。
なお、厳密には、マグネシウムはアルカリ土類金属には含まれないが、本発明ではマグネシウムも含めてアルカリ土類金属類と表記する。 On the other hand, when trying to capture heavy metals in the actual liquid to be treated using a chelate resin, interference caused by alkali metals coexisting in the liquid to be treated can be almost ignored except in extremely high concentrations. Alkaline earth metals such as magnesium, calcium, and barium are trapped by the chelate resin, thereby preventing the capture of heavy metals. Since these alkaline earth metals coexist in high concentrations in general waste water, environmental water, metal treatment liquids, etc., the removal rate and recovery rate of the intended heavy metal will vary greatly. There are also many.
Strictly speaking, magnesium is not included in alkaline earth metals, but in the present invention, it is expressed as alkaline earth metals including magnesium.

前述のように、ポリエチレンイミンの鎖長を長くした場合には重金属の錯体の安定度定数は大きくなるが、アルカリ土類金属類の錯体の安定度定数が小さくなるわけではないため、アルカリ土類金属類の捕捉特性は大きく変化することはない。つまり，単純に鎖長を長くしても、アルカリ土類金属類の妨害を受けずに重金属を選択的に捕捉可能な、実用面で有効なキレート樹脂を得ることはできない。 As described above, when the chain length of polyethyleneimine is increased, the stability constant of the complex of heavy metal increases, but the stability constant of the complex of alkaline earth metal does not decrease. The capture properties of metals do not change significantly. That is, even if the chain length is simply increased, a practically effective chelate resin capable of selectively capturing heavy metals without being disturbed by alkaline earth metals cannot be obtained.

近年、このような問題に対して、酸性条件下でアルカリ土類金属類の妨害を受けにくい機能を有したキレート樹脂ＮＯＢＩＡＳＣｈｅｌａｔｅ−ＰＡ１ (株式会社日立ハイテクノロジーズ社製) が市販されている。このキレート樹脂は、ジエチレントリアミン-Ｎ、Ｎ´、Ｎ"、Ｎ"-四酢酸型官能基を導入したものであり、特許文献３と同一の官能基構造を有する。このキレート樹脂では、酸性条件下においてアルカリ土類金属類を捕捉することはない (非特許文献３ないし非特許文献５参照)。このアルカリ土類金属類が捕捉されにくい機構に関しては明確化されてはいないが、樹脂中に残存するイミノ基に依存するものとされている。 In recent years, a chelate resin NOBIASChelate-PA1 (manufactured by Hitachi High-Technologies Corporation) having a function that is difficult to be disturbed by alkaline earth metals under acidic conditions is commercially available. This chelate resin has diethylenetriamine-N, N ′, N ″, N ″ -tetraacetic acid type functional groups introduced therein, and has the same functional group structure as Patent Document 3. This chelate resin does not capture alkaline earth metals under acidic conditions (see Non-Patent Document 3 to Non-Patent Document 5). The mechanism by which the alkaline earth metals are difficult to be captured is not clarified, but is dependent on the imino group remaining in the resin.

アミノカルボン酸型キレートは広範囲な金属を捕捉するとされているが、ヒ素、モリブデン、バナジウム等のオキソ酸を形成する金属の捕捉能力は低い。また、クロム (三価クロム、クロム（III）) はアミノカルボン酸と強く錯形成をするが、錯形成速度が遅く、流通型での高度捕捉は難しいとされている。 Although aminocarboxylic acid type chelates are said to capture a wide range of metals, the ability to capture oxo acids such as arsenic, molybdenum and vanadium is low. Chromium (trivalent chromium, chromium (III)) forms a strong complex with aminocarboxylic acid, but the complex formation rate is slow, and high-level capture in the flow type is difficult.

特開平５−７１０００号公報JP-A-5-71000 特開２００８−１１５４３９号公報JP 2008-115439 A 特開２００５−２１３４７７号公報JP 2005-213477 A 特開２００５−２１８８３号公報JP 2005-21883 A

株式会社同仁化学研究所カタログ２６版、p.３２０-３２１Dojindo Laboratories catalog 26th edition, p.320-321 L. Ｇ. Sillen、 A. E. Martell、 Stability Constants ofMetal-Ion Complexes、 2nd Ed.、the Chemical Society、 London (1964).L. G. Sillen, A. E. Martell, Stability Constants of Metal-Ion Complexes, 2nd Ed., The Chemical Society, London (1964). Y. Sohrin、S. Urushihara、 S. Nakatsuka、 T.Kono、 E. Hiｇo、 T. Minami、 K. Noriyasu、 S. Umetani、 Anal. Chem. 80 (2008) 6267.Y. Sohrin, S. Urushihara, S. Nakatsuka, T. Kono, E. Higo, T. Minami, K. Noriyasu, S. Umetani, Anal. Chem. 80 (2008) 6267. 山本和子、坂本秀之、米谷明、白崎俊浩、日本海水学会誌 ６１（２００７）２６０.Kazuko Yamamoto, Hideyuki Sakamoto, Akira Yoneya, Toshihiro Shirasaki, Journal of the Japan Society of Seawater 61 (2007) 260. 坂本秀之、山本和子、白崎俊浩、井上嘉則、分析化学 ５５（２００６）１３３.Hideyuki Sakamoto, Kazuko Yamamoto, Toshihiro Shirasaki, Yoshinori Inoue, Analytical Chemistry 55 (2006) 133.

本発明は、上記の問題点を鑑みてなされたもので、工場排水、用水、環境水、食品、薬品等の被処理溶液中に多量に存在するアルカリ土類金属類の妨害を受けずに、被処理溶液中からの重金属除去、及び有価重金属を高度に捕捉することが可能なキレート樹脂と、その製造方法を提供することを目的とする。 The present invention was made in view of the above problems, without being disturbed by alkaline earth metals present in large amounts in the solution to be treated such as factory waste water, irrigation water, environmental water, food, and chemicals. An object of the present invention is to provide a chelate resin capable of removing heavy metals from a solution to be treated and highly capturing valuable heavy metals, and a method for producing the same.

本発明の発明者が鋭意研究を行った結果、至適な分子量 (鎖長) のポリエチレンイミン骨格を有する化合物が導入された高分子担体を、アルカリ性溶液中でハロゲン化酢酸を用いてカルボキシメチル化する際に、反応に供するハロゲン化酢酸の量を調節することで、優れた重金属捕捉性とともに、アルカリ土類金属類が捕捉されにくい機能を有するキレート樹脂を製造できることを見出した。 As a result of intensive studies by the inventors of the present invention, a polymer carrier into which a compound having a polyethyleneimine skeleton having an optimal molecular weight (chain length) has been introduced is carboxymethylated using a halogenated acetic acid in an alkaline solution. In doing so, it was found that by adjusting the amount of halogenated acetic acid to be used in the reaction, a chelate resin having a function of not only easily capturing alkaline earth metals but also having excellent heavy metal scavenging properties can be produced.

本発明において、高分子担体に導入されるキレート性官能基としては、ポリエチレンイミン骨格を有する化合物であり、ハロゲン化酢酸によりカルボキシメチル化される。 In the present invention, the chelating functional group introduced into the polymer carrier is a compound having a polyethyleneimine skeleton and is carboxymethylated with a halogenated acetic acid.

本発明では、反応性官能基を有する高分子担体に、ポリエチレンイミン骨格を有する化合物を導入後、アルカリ条件下でハロゲン化酢酸を用いてカルボキシメチル化を行うが、カルボキシメチル化反応に用いるハロゲン化酢酸の量は、高分子担体に導入されたポリエチレンイミン骨格を有する化合物中の窒素量の１．０〜３．０倍モルである。 In the present invention, after introducing a compound having a polyethyleneimine skeleton into a polymer carrier having a reactive functional group, carboxymethylation is performed using halogenated acetic acid under alkaline conditions. The amount of acetic acid is 1.0 to 3.0 times the amount of nitrogen in the compound having a polyethyleneimine skeleton introduced into the polymer carrier.

また、前記ポリエチレンイミン骨格を有する化合物は、平均分子量が２００ないし６００であるものが用いられる。 In addition, the compound having a polyethyleneimine skeleton having an average molecular weight of 200 to 600 is used.

本発明での高分子担体が有する反応性官能基としては、ハロゲン化アルキル基、エポキシ基、アルデヒド基、ケトン基、アシルクロリド基、酸無水物基等があげられ、アミンと反応する官能基である。 Examples of the reactive functional group possessed by the polymer carrier in the present invention include a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, an acid anhydride group, and the like. is there.

本発明に用いる反応性官能基を有する高分子担体は，グリシジルメタクリレートあるいはハロゲン化アルキルスチレン (クロロメチルスチレン) のようなアミンと反応するエポキシ基やハロゲン化アルキル基を有する反応性モノマーと架橋性モノマーとの共重合体である。 The polymer carrier having a reactive functional group used in the present invention includes a reactive monomer having an epoxy group that reacts with an amine such as glycidyl methacrylate or a halogenated alkylstyrene (chloromethylstyrene) or a halogenated alkyl group, and a crosslinkable monomer. And a copolymer.

本発明は、上記のごとく、１）アミンと反応するハロゲン化アルキル基、エポキシ基、アルデヒド基、ケトン基、アシルクロリド基、酸無水物基等の反応性官能基を有する高分子担体に、２）ポリエチレンイミン骨格を有する化合物を反応させた後、３）ポリエチレンイミン骨格を有する化合物中の窒素量の１．０〜３．０倍モルのハロゲン化酢酸をアルカリ溶液中で反応させてなるキレート樹脂と、その製造方法である。 As described above, the present invention provides a polymer carrier having a reactive functional group such as 1) a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, and an acid anhydride group that reacts with an amine. 1) after reacting a compound having a polyethyleneimine skeleton, 3) a chelate resin obtained by reacting 1.0 to 3.0 moles of halogenated acetic acid in an alkaline solution with a nitrogen amount in the compound having a polyethyleneimine skeleton. And its manufacturing method.

本発明によれば、アルカリ土類金属類の妨害を受けにくい機能を有し、金属のオキソ酸類を含めた重金属を高度に捕捉するキレート樹脂を容易に合成することが可能である。本発明のキレート樹脂は、酸性条件下でアルカリ土類金属類を捕捉しないため、排水や用水等からの重金属除去、海水や河川水等の環境水や金属処理溶液中からの有価金属の回収を効率よく行うことができる。さらには、微量金属の機器分析における妨害元素の除去及び分析対象元素の抽出・濃縮等の前処理用途にも使用することが可能である。 According to the present invention, it is possible to easily synthesize a chelate resin having a function that is not easily disturbed by alkaline earth metals and highly capturing heavy metals including metal oxo acids. Since the chelate resin of the present invention does not capture alkaline earth metals under acidic conditions, it removes heavy metals from wastewater and irrigation water, and recovers valuable metals from environmental water and metal treatment solutions such as seawater and river water. It can be done efficiently. Furthermore, it can also be used for pretreatment applications such as removal of interfering elements in instrumental analysis of trace metals and extraction / concentration of analysis target elements.

図１は、実施例1のキレート樹脂Ａと市販ＩＤＡ型樹脂との金属（１０種類）の捕捉特性比較を示す。FIG. 1 shows a comparison of metal (10 types) capture characteristics between the chelate resin A of Example 1 and a commercially available IDA type resin. 図１ａは、銅Ｃｕの捕捉特性比較を示す。FIG. 1a shows a comparison of copper Cu capture characteristics. 図１ｂは、ニッケルＮｉの捕捉特性比較を示す。FIG. 1b shows a comparison of nickel Ni capture characteristics. 図１ｃは、カドミウムＣｄの捕捉特性比較を示す。FIG. 1c shows a comparison of the capture properties of cadmium Cd. 図１ｄは、鉛Ｐｂの捕捉特性比較を示す。FIG. 1d shows a comparison of lead Pb capture characteristics. 図１ｅは、マグネシウムＭｇの捕捉特性比較を示す。FIG. 1e shows a comparison of the trapping properties of magnesium Mg. 図１ｆは、カルシウムＣａの捕捉特性比較を示す。FIG. 1f shows a comparison of calcium Ca capture properties. 図１ｇは、クロムＣｒ（３価）の捕捉特性比較を示す。FIG. 1g shows a comparison of the chromium Cr (trivalent) capture properties. 図１ｈは、モリブデンＭｏの捕捉特性比較を示す。FIG. 1h shows a comparison of the molybdenum Mo capture characteristics. 図１ｉは、バナジウムＶの捕捉特性比較を示す。FIG. 1i shows a comparison of the trapping properties of vanadium V. 図１ｊは、ヒ素Ａｓの捕捉特性比較を示す。FIG. 1j shows a comparison of the arsenic As capture characteristics. 図２は、実施例１のキレート樹脂Ａと市販ポリアミノカルボン酸型キレート樹脂との１０種類の金属の捕捉特性比較を示す。FIG. 2 shows a comparison of the trapping characteristics of 10 types of metals between the chelate resin A of Example 1 and a commercially available polyaminocarboxylic acid type chelate resin. 図２ａは、銅Ｃｕの捕捉特性比較を示す。FIG. 2a shows a comparison of the capture characteristics of copper Cu. 図２ｂは、ニッケルＮｉの捕捉特性比較を示す。FIG. 2b shows a comparison of nickel Ni capture characteristics. 図２ｃは、カドミウムＣｄの捕捉特性比較を示す。FIG. 2c shows a comparison of the capture properties of cadmium Cd. 図２ｄは、鉛Ｐｂの捕捉特性比較を示す。FIG. 2d shows a comparison of lead Pb capture characteristics. 図２ｅは、マグネシウムＭｇの捕捉特性比較を示す。FIG. 2e shows a comparison of the trapping properties of magnesium Mg. 図２ｆは、カルシウムＣａの捕捉特性比較を示す。FIG. 2f shows a comparison of calcium Ca capture properties. 図２ｇは、クロムＣｒ（３価）の捕捉特性比較を示す。FIG. 2g shows a comparison of the chromium Cr (trivalent) capture properties. 図２ｈは、モリブデンＭｏの捕捉特性比較を示す。FIG. 2h shows a comparison of the molybdenum Mo capture characteristics. 図２ｉは、バナジウムＶの捕捉特性比較を示す。FIG. 2 i shows a comparison of the trapping properties of vanadium V. 図２ｊは、ヒ素Ａｓの捕捉特性比較を示す。FIG. 2j shows a comparison of the arsenic As capture characteristics. 図３は、実施例１のキレート樹脂Ａと市販ポリアミノカルボン酸型キレート樹脂との試料通液量と相対捕捉回収率の比較を示す。FIG. 3 shows a comparison of sample flow rate and relative capture recovery rate between the chelate resin A of Example 1 and a commercially available polyaminocarboxylic acid type chelate resin. 図４は、実施例１のキレート樹脂Ａ、実施例２のキレート樹脂Ｂ及び比較例１のキレート樹脂ｆと市販ポリアミノカルボン酸型キレート樹脂における１０種類の金属の捕捉特性比較を示す。FIG. 4 shows a comparison of the trapping characteristics of 10 kinds of metals in the chelate resin A of Example 1, the chelate resin B of Example 2, the chelate resin f of Comparative Example 1 and a commercially available polyaminocarboxylic acid type chelate resin. 図４ａは、銅Ｃｕの捕捉特性比較を示す。FIG. 4a shows the copper Cu capture characteristics comparison. 図４ｂは、ニッケルＮｉの捕捉特性比較を示す。FIG. 4b shows a comparison of nickel Ni capture characteristics. 図４ｃは、カドミウムＣｄの捕捉特性比較を示す。FIG. 4c shows a comparison of the cadmium Cd capture characteristics. 図４ｄは、鉛Ｐｂの捕捉特性比較を示す。FIG. 4d shows a comparison of lead Pb capture characteristics. 図４ｅは、マグネシウムＭｇの捕捉特性比較を示す。FIG. 4e shows a comparison of the Mg Mg trapping properties. 図４ｆは、カルシウムＣａの捕捉特性比較を示す。FIG. 4f shows a comparison of calcium Ca capture properties. 図４ｇは、クロムＣｒ（３価）の捕捉特性比較を示す。FIG. 4g shows a comparison of the chromium Cr (trivalent) capture properties. 図４ｈは、モリブデンＭｏの捕捉特性比較を示す。FIG. 4h shows a comparison of the trapping characteristics of molybdenum Mo. 図４ｉは、バナジウムＶの捕捉特性比較を示す。FIG. 4 i shows a comparison of the capture properties of vanadium V. 図４ｊは、ヒ素Ａｓの捕捉特性比較を示す。FIG. 4j shows a comparison of the arsenic As capture characteristics. 図５は、実施例３のキレート樹脂Ｃ、実施例４のキレート樹脂Ｄ及び比較例２のキレート樹脂ｇと市販ポリアミノカルボン酸型キレート樹脂における１０種類の金属の捕捉特性比較を示す。FIG. 5 shows a comparison of the trapping properties of 10 kinds of metals in the chelate resin C of Example 3, the chelate resin D of Example 4, the chelate resin g of Comparative Example 2, and the commercially available polyaminocarboxylic acid type chelate resin. 図５ａは、銅Ｃｕの捕捉特性比較を示す。FIG. 5a shows a comparison of the capture characteristics of copper Cu. 図５ｂは、ニッケルＮｉの捕捉特性比較を示す。FIG. 5b shows a comparison of nickel Ni capture characteristics. 図５ｃは、カドミウムＣｄの捕捉特性比較を示す。FIG. 5c shows a comparison of the capture properties of cadmium Cd. 図５ｄは、鉛Ｐｂの捕捉特性比較を示す。FIG. 5d shows a comparison of lead Pb capture characteristics. 図５ｅは、マグネシウムＭｇの捕捉特性比較を示す。FIG. 5e shows a comparison of the trapping properties of magnesium Mg. 図５ｆは、カルシウムＣａの捕捉特性比較を示す。FIG. 5f shows a comparison of calcium Ca capture properties. 図５ｇは、クロムＣｒ（３価）の捕捉特性比較を示す。FIG. 5g shows a comparison of the chromium Cr (trivalent) capture properties. 図５ｈは、モリブデンＭｏの捕捉特性比較を示す。FIG. 5h shows a comparison of molybdenum Mo capture characteristics. 図５ｉは、バナジウムＶの捕捉特性比較を示す。FIG. 5 i shows a comparison of the trapping properties of vanadium V. 図５ｊは、ヒ素Ａｓの捕捉特性比較を示す。FIG. 5j shows a comparison of the arsenic As capture characteristics. 図６は、実施例５のキレート樹脂Ｅと市販ポリアミノカルボン酸型キレート樹脂との１０種類の金属の捕捉特性比較を示す。FIG. 6 shows a comparison of the trapping characteristics of 10 types of metals between the chelate resin E of Example 5 and a commercially available polyaminocarboxylic acid type chelate resin. 図６ａは、銅Ｃｕの捕捉特性比較を示す。FIG. 6a shows the copper Cu capture characteristics comparison. 図６ｂは、ニッケルＮｉの捕捉特性比較を示す。FIG. 6b shows a comparison of nickel Ni capture characteristics. 図６ｃは、カドミウムＣｄの捕捉特性比較を示す。FIG. 6c shows a comparison of the capture properties of cadmium Cd. 図６ｄは、鉛Ｐｂの捕捉特性比較を示す。FIG. 6d shows a comparison of lead Pb capture characteristics. 図６ｅは、マグネシウムＭｇの捕捉特性比較を示す。FIG. 6e shows a comparison of the trapping properties of magnesium Mg. 図６ｆは、カルシウムＣａの捕捉特性比較を示す。FIG. 6f shows a comparison of calcium Ca capture properties. 図６ｇは、クロムＣｒ（３価）の捕捉特性比較を示す。FIG. 6g shows a comparison of the chromium Cr (trivalent) capture properties. 図６ｈは、モリブデンＭｏの捕捉特性比較を示す。FIG. 6h shows a comparison of molybdenum Mo capture characteristics. 図６ｉは、バナジウムＶの捕捉特性比較を示す。FIG. 6i shows a comparison of the capture properties of vanadium V. 図６ｊは、ヒ素Ａｓの捕捉特性比較を示す。FIG. 6 j shows a comparison of the arsenic As capture characteristics.

本発明は、上記のように、至適な鎖長を有するポリエチレンイミン骨格を有する化合物を高分子担体に導入後、ハロゲン化酢酸の量を調節してカルボキシメチル化を行うキレート樹脂に関するものである。 The present invention relates to a chelate resin which, as described above, performs carboxymethylation by adjusting the amount of halogenated acetic acid after introducing a compound having a polyethyleneimine skeleton having an optimal chain length into a polymer carrier. .

本発明の製造法において使用されるポリエチレンイミン骨格を有する化合物の製造法は、エチレンイミンの開環重合、塩化エチレンとエチレンジアミンとの重縮合、あるいは２−オキサゾリドンの加熱反応等が挙げられるが、いずれのものも使用することができる。これらポリエチレンイミン骨格を有する化合物は、鎖長の異なる化合物の混合物であるとともに、アミン構造が異なる複数の化合物の混合物である。例えば、化１に示す直鎖状構造の他、化２に示すような分岐構造も存在している。したがって、ポリエチレンイミン骨格を有する化合物に含まれるアミノ基構造は、一級、二級、三級のアミノ基が混在したものである。本発明において使用されるポリエチレンイミン骨格を有する化合物の構造や一級ないし三級アミンの比率はどの様なものであってもよく、本発明ではそれらを総合してポリエチレンイミン骨格の化合物という。 Examples of the method for producing a compound having a polyethyleneimine skeleton used in the production method of the present invention include ring-opening polymerization of ethyleneimine, polycondensation of ethylene chloride and ethylenediamine, or heating reaction of 2-oxazolidone. Can also be used. These compounds having a polyethyleneimine skeleton are a mixture of compounds having different chain lengths and a mixture of a plurality of compounds having different amine structures. For example, in addition to the linear structure shown in Chemical Formula 1, there is a branched structure as shown in Chemical Formula 2. Therefore, the amino group structure contained in the compound having a polyethyleneimine skeleton is a mixture of primary, secondary, and tertiary amino groups. The structure of the compound having a polyethyleneimine skeleton used in the present invention and the ratio of primary to tertiary amines may be any. In the present invention, these are collectively referred to as a compound having a polyethyleneimine skeleton.

本発明の製造方法において、高分子担体に導入されるポリエチレンイミン骨格を有する化合物は、至適な鎖長を有するポリエチレンイミン骨格の化合物であり、その平均分子量は２００ないし６００である。 In the production method of the present invention, the compound having a polyethyleneimine skeleton introduced into the polymer carrier is a polyethyleneimine skeleton compound having an optimum chain length, and the average molecular weight thereof is 200 to 600.

ポリエチレンイミン骨格の鎖長と錯体の安定度定数との関係は前述したように、鎖長が長いほど錯体の安定度定数が高くなることが知られている。鎖長が短い (化１におけるｎが４未満のもの) 場合には、酸性条件下での金属の捕捉能力は低下するとともに、金属のオキソ酸の捕捉能力も低くなる。また、官能基鎖の自由度も低く、迅速な吸脱着ができないため、錯形成速度の遅いクロム(III) に対しては高い捕捉能を示すことができない。一方、鎖長が長い、たとえば平均分子量が６００以上、特に１、０００以上を有するポリエチレンイミン骨格を有する化合物を用いると金属の捕捉特性は改善されるものと考えられるが、高分子担体が多孔質体の場合には，高分子担体の細孔内部まで官能基を高度に導入させることができなくなるという問題が発生する。さらに，高分子鎖同士の絡み合いも発生するため，むやみに鎖長を長くしても官能基の自由度が必ずしも高くなるというわけではない。 As described above, the relationship between the chain length of the polyethyleneimine skeleton and the stability constant of the complex is known to increase as the chain length increases. When the chain length is short (when n in Chemical Formula 1 is less than 4), the ability to capture a metal under acidic conditions decreases, and the ability to capture a metal oxo acid also decreases. In addition, since the degree of freedom of the functional group chain is low and rapid adsorption / desorption cannot be performed, high scavenging ability cannot be exhibited for chromium (III) having a slow complex formation rate. On the other hand, when a compound having a polyethyleneimine skeleton having a long chain length, for example, an average molecular weight of 600 or more, particularly 1,000 or more, is considered to improve the metal trapping property, the polymer support is porous. In the case of a body, there is a problem that it becomes impossible to introduce a functional group to the inside of the pores of the polymer carrier. Furthermore, entanglement between polymer chains also occurs, so even if the chain length is increased unnecessarily, the degree of freedom of the functional group does not necessarily increase.

本発明では、反応性官能基を有する高分子担体にポリエチレンイミン骨格を有する化合物を反応させた後、アルカリ条件下でハロゲン化酢酸を用いてアミノ基及びイミノ基のカルボキシメチル化を行う。ハロゲン化酢酸としては、クロロ酢酸、ブロモ酢酸等が用いられる。 In the present invention, after reacting a polymer carrier having a reactive functional group with a compound having a polyethyleneimine skeleton, carboxymethylation of an amino group and an imino group is carried out using a halogenated acetic acid under alkaline conditions. As the halogenated acetic acid, chloroacetic acid, bromoacetic acid or the like is used.

カルボキシメチル化に用いられるハロゲン化酢酸の使用量は、金属の捕捉特性及びアルカリ土類金属類の捕捉特性やそれらによる妨害の度合いに大きく関係する。反応性官能基を有する高分子担体に導入されたポリエチレンイミン骨格を有する化合物中の窒素量の１．０〜３．０倍モル、好ましくは２．０〜２．５倍モルのハロゲン化酢酸を使用してカルボキシメチル化反応を行う。３．０倍モルを超えるハロゲン化酢酸を用いるとカルボキシメチル化の度合いが高くなり、得られるキレート性官能基の金属捕捉力は向上するが、同時にアルカリ土類金属類の捕捉性も増加するため、酸性側からアルカリ土類金属類の捕捉が始まる。つまり、酸性条件下における選択性が低下し、アルカリ土類金属類の妨害により重金属を安定して高度に捕捉することはできなくなることとなる。一方、１．０倍モル未満のハロゲン化酢酸を用いると、カルボキシメチル化の度合いが低くなり、銅等の窒素親和性の高い元素を除き、重金属の捕捉能力は低くなる。また、アルカリ土類金属類の捕捉能力が極端に低くなるため、酸性条件下での重金属とアルカリ土類金属類との相互分離は可能となるが、キレート樹脂としての金属捕捉能力が低く、実際の重金属処理には適用しにくいものとなる。つまり、金属捕捉能力の向上と、アルカリ土類金属類の妨害低減を達成するためには、カルボキシメチル化度の至適範囲がある。 The amount of halogenated acetic acid used for carboxymethylation is greatly related to the metal-capturing properties and the alkaline-earth metal-capturing properties and the degree of interference caused by them. 1.0 to 3.0 times mol, preferably 2.0 to 2.5 times mol of nitrogen halide in the compound having a polyethyleneimine skeleton introduced into a polymer carrier having a reactive functional group Used to carry out a carboxymethylation reaction. When the halogenated acetic acid exceeding 3.0 times mol is used, the degree of carboxymethylation is increased, and the metal scavenging ability of the resulting chelating functional group is improved, but at the same time, the scavenging ability of alkaline earth metals is also increased. The capture of alkaline earth metals starts from the acidic side. That is, the selectivity under acidic conditions is lowered, and heavy metals cannot be stably captured to a high degree due to the interference with alkaline earth metals. On the other hand, when the halogenated acetic acid is used in an amount of less than 1.0-fold mol, the degree of carboxymethylation is reduced, and the ability to capture heavy metals is reduced except for elements having high nitrogen affinity such as copper. In addition, since the ability to capture alkaline earth metals is extremely low, heavy metals and alkaline earth metals can be separated from each other under acidic conditions, but the ability to capture metals as chelating resins is low. It is difficult to apply to the heavy metal treatment. That is, there is an optimum range of the degree of carboxymethylation in order to improve the metal capturing ability and reduce the interference of alkaline earth metals.

本発明において，反応性官能基を有する高分子担体としては，エポキシ基あるいはハロゲン化アルキル基を有する反応性モノマーと架橋性モノマーとの共重合体が選ばれる。エポキシ基を有する反応性モノマーとしては、例えば、グリシジルメタクリレート、グリシジルアクリレート、ビニルベンジルグリシジルエーテル等が挙げられる。ハロゲン化アルキル基を有する反応性モノマーとしては、例えば、クロロメチルスチレン、３−クロロ−２−ヒドロキシプロピルメタクリレート、３−クロロ−2−ヒドロキシプロピルアクリレート、２−クロロエチルメタクリレート、２−クロロエチルアクリレート等が挙げられる。また、これら反応性モノマーと共重合が可能な架橋性モノマーとしては、ジビニルベンゼン，ジビニルナフタレン等の芳香族架橋性モノマー、エチレンジメタクリレート、ジエチレングリコールジメタクリレート、グリセリンジメタクリレート、トリメチロールプロパントリメタクリレート、ネオペンチルグリコールトリメタクリレート等の多官能メタクリレート系モノマー、エチレンジアクリレート、ジエチレングリコールジアクリレート、グリセリンジアクリレート、トリメチロールプロパントリアクリレート、ネオペンチルグリコールトリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート等の多官能アクリレート系モノマー、この他、トリアリルイソシアヌレート、トリメタアリルイソシアヌレート等のシアヌル酸骨格をもつ架橋性モノマー等が挙げられる。これら反応性モノマーと架橋性モノマーとの共重合は公知の懸濁重合法によって行われ、反応性官能基を有する不溶性高分子担体が得られる。必要に応じて、他の重合方法、例えば、塊状重合法により、反応性官能基を有する不溶性高分子担体を得てもよい。 In the present invention, as the polymer carrier having a reactive functional group, a copolymer of a reactive monomer having an epoxy group or a halogenated alkyl group and a crosslinkable monomer is selected. Examples of the reactive monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, vinylbenzyl glycidyl ether, and the like. Examples of the reactive monomer having a halogenated alkyl group include chloromethylstyrene, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 2-chloroethyl methacrylate, and 2-chloroethyl acrylate. Is mentioned. Crosslinkable monomers that can be copolymerized with these reactive monomers include aromatic crosslinkable monomers such as divinylbenzene and divinylnaphthalene, ethylene dimethacrylate, diethylene glycol dimethacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, neodymium. Polyfunctional methacrylate monomers such as pentyl glycol trimethacrylate, polyfunctional acrylates such as ethylene diacrylate, diethylene glycol diacrylate, glycerin diacrylate, trimethylolpropane triacrylate, neopentyl glycol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Other monomers, triallyl isocyanurate, trimethallyl ester Crosslinking monomers with cyanuric acid skeleton such cyanurate and the like. The copolymerization of the reactive monomer and the crosslinkable monomer is performed by a known suspension polymerization method, and an insoluble polymer carrier having a reactive functional group is obtained. If necessary, an insoluble polymer carrier having a reactive functional group may be obtained by another polymerization method, for example, a bulk polymerization method.

高分子担体の形状に関しても特に限定はなく，公知の塊状重合法により得られた樹脂の粉砕による不定形粒子、公知の懸濁重合法により得られた球状粒子であってもよい。高分子担体の物理的構造は非多孔質型又は多孔質型の何れでも採用できる。非多孔質型の高分子担体を用いる場合には，錯体形成に係わる官能基は高分子担体の表層にのみ導入される。この場合、官能基導入量は低くなるが、細孔内部への拡散という要素を無視できるため、吸脱着速度は大きくなる。一方、多孔質担体を用いる場合には、比表面積が大きいため官能基の導入量を高くすることが可能となり、金属捕捉量を向上させることが可能となる。非多孔質型あるいは多孔質型の何れかを選択するかは使用目的に応じて判断すればよいが、一般的な使用条件等を考慮すると多孔質型のほうが好ましい。多孔質型の場合、細孔容積０．３〜２．０ｍＬ／ｇ、平均細孔径４〜５００ｎｍ、比表面積１０〜１０００ｍ２／ｇの範囲のものを採用するのが好ましい。 The shape of the polymer carrier is not particularly limited, and may be irregular particles obtained by pulverization of a resin obtained by a known bulk polymerization method, or spherical particles obtained by a known suspension polymerization method. The physical structure of the polymer carrier can be either a non-porous type or a porous type. When a non-porous type polymer carrier is used, the functional group involved in complex formation is introduced only into the surface layer of the polymer carrier. In this case, the amount of functional groups introduced is low, but the element of diffusion into the pores can be ignored, so the adsorption / desorption rate increases. On the other hand, when a porous carrier is used, since the specific surface area is large, the amount of functional groups introduced can be increased, and the amount of captured metal can be improved. Whether to select the non-porous type or the porous type may be determined according to the purpose of use, but the porous type is more preferable in consideration of general use conditions. In the case of the porous type, those having a pore volume of 0.3 to 2.0 mL / g, an average pore diameter of 4 to 500 nm, and a specific surface area of 10 to 1000 m 2 / g are preferably employed.

高分子担体の材質に関しては特に制限はないが、ハロゲン化アルキル基、エポキシ基、アルデヒド基、ケトン基、アシルクロリド基、酸無水物基等のアミンと反応することが可能な官能基を有する不溶性高分子であればよく、公知の方法により得られる架橋ポリスチレン、架橋ポリメタクリレート、架橋ポリビニルアルコール等を基材とした高分子担体を用いることができる。また、公知の架橋樹脂に二次反応によって、これらのアミンと反応する官能基を導入した高分子担体でもよい。高分子担体の形状に関しても特に規定することはなく、公知の塊状重合法により得られた樹脂の粉砕による不定形粒子、公知の懸濁重合法により得られた球状粒子であってもよい。高分子担体の物理的構造は非多孔質型又は多孔質型の何れでも採用できるが、本発明では使用条件等から多孔質型のほうが好ましい。多孔質型の場合、細孔容積０．３〜２．０ｍＬ／ｇ、平均細孔径４〜５００ｎｍ、比表面積１０〜１０００ｍ２／ｇの範囲のものを採用するのが好ましい。 The material of the polymer carrier is not particularly limited, but is insoluble having functional groups capable of reacting with amines such as halogenated alkyl groups, epoxy groups, aldehyde groups, ketone groups, acyl chloride groups, and acid anhydride groups. A polymer carrier may be used as long as it is a polymer, and a polymer carrier based on crosslinked polystyrene, crosslinked polymethacrylate, crosslinked polyvinyl alcohol or the like obtained by a known method can be used. Moreover, the polymer support | carrier which introduce | transduced the functional group which reacts with these amines by secondary reaction to well-known crosslinked resin may be sufficient. The shape of the polymer carrier is not particularly limited, and may be an irregularly shaped particle obtained by pulverizing a resin obtained by a known bulk polymerization method or a spherical particle obtained by a known suspension polymerization method. The physical structure of the polymer carrier can be either a non-porous type or a porous type, but in the present invention, the porous type is preferred from the conditions of use. In the case of the porous type, those having a pore volume of 0.3 to 2.0 mL / g, an average pore diameter of 4 to 500 nm, and a specific surface area of 10 to 1000 m 2 / g are preferably employed.

本発明のキレート樹脂は、（１）アミンと反応するハロゲン化アルキル基、エポキシ基、アルデヒド基、ケトン基、アシルクロリド基、酸無水物基等の反応性官能基を有する高分子担体を得た後、（２）高分子担体にポリエチレンイミン骨格を有する化合物を反応させて、ついで（３）ポリエチレンイミン骨格を有する化合物中の窒素量の１．０〜３．０倍モルのハロゲン化酢酸をアルカリ溶液中で反応させることにより製造される。 The chelate resin of the present invention provides (1) a polymer carrier having a reactive functional group such as a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, and an acid anhydride group that reacts with an amine. Thereafter, (2) the polymer carrier is reacted with a compound having a polyethyleneimine skeleton, and then (3) a halogenated acetic acid having 1.0 to 3.0 moles of nitrogen in the compound having a polyethyleneimine skeleton is alkalinized. Produced by reacting in solution.

反応性官能基を有する高分子担体とポリエチレンイミン骨格を有する化合物との反応は、公知のとおり、ポリエチレンイミン骨格を有する化合物を、水、アルコール、ジメチルホルムアミド等あるいはそれらの混合溶媒中に溶解した反応溶液中に高分子担体を分散させて、攪拌下、室温〜８０℃で、３〜２４時間の反応によりポリアミノ化を行う。ただし、アルデヒド基やケトン基を有する高分子担体に反応させる場合、シッフ塩基型の結合であるため、ＬｉＢＨ３ＣＮ、ＮａＢＨ３ＣＮ、（ＣＨ３）２ＮＨＢＨ３等を用いた公知の方法により還元を行う。また、アミド構造で導入されたものを還元する必要がある場合には、ＬｉＡｌＨ４、ＢＨ３-ＴＨＦを用いた公知の方法で還元してもよい。 As is well known, a reaction between a polymer carrier having a reactive functional group and a compound having a polyethyleneimine skeleton is a reaction in which a compound having a polyethyleneimine skeleton is dissolved in water, alcohol, dimethylformamide, or a mixed solvent thereof. A polymer carrier is dispersed in a solution, and polyamination is performed by a reaction at room temperature to 80 ° C. for 3 to 24 hours with stirring. However, when reacting with a polymer carrier having an aldehyde group or a ketone group, since it is a Schiff base type bond, it is reduced by a known method using LiBH 3 CN, NaBH 3 CN, (CH 3 ) 2 NHBH 3 or the like. I do. Moreover, when it is necessary to reduce what was introduced with an amide structure, it may be reduced by a known method using LiAlH 4 or BH 3 -THF.

反応終了後、水及び有機溶媒で洗浄後、真空乾燥を行う。導入されたポリエチレンイミン骨格を有する化合物中の窒素量は、元素分析装置 (いわゆるＣＨＮ計) で測定する。
ハロゲン化酢酸によるカルボキシメチル化は、公知のとおりアルカリ条件下で反応を行う。この時、使用するハロゲン化酢酸の量は、元素分析装置により得られた窒素量を基に決定する。また、アルカリの濃度に関しては、特に規定はしないが、一般には、０．５〜３ｍｏｌ/Ｌ（モル／リットル）の水酸化ナトリウムあるいは水酸化カリウムを用いる。このようにして得られたキレート樹脂は、水、酸、水の順で洗浄し、目的に応じて対イオン交換を行った後、使用する。 After completion of the reaction, washing with water and an organic solvent is followed by vacuum drying. The amount of nitrogen in the introduced compound having a polyethyleneimine skeleton is measured with an elemental analyzer (so-called CHN meter).
Carboxymethylation with halogenated acetic acid is performed under alkaline conditions as is well known. At this time, the amount of halogenated acetic acid to be used is determined based on the amount of nitrogen obtained by the elemental analyzer. The alkali concentration is not particularly specified, but generally 0.5 to 3 mol / L (mol / liter) sodium hydroxide or potassium hydroxide is used. The chelate resin thus obtained is used after being washed in order of water, acid, and water, and subjected to counterion exchange according to the purpose.

つぎに実施例によって本発明を説明するが、この実施例によって本発明を何ら限定するものではない。 Next, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

キレート樹脂Ａの合成
（１）高分子担体の製造
高分子担体の合成は、公知の懸濁重合法にしたがい行った。グリシジルメタクリレート８０ｇ、エチレンジメタクリレート１２０ｇ、酢酸ブチル２００ｇ及びアゾビスイソブチロニトリル２ｇの混合物を、０．１％ポリビニルアルコール水溶液２，０００ｍＬ（ミリリットル）中に加え、油滴の径が６０μmになるように攪拌した。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、水、メタノール、水の順で洗浄した。次いで、一日風乾後、分級して４５〜９０μmの多孔性架橋重合体粒子８５ｇを得た。 Synthesis of chelate resin A (1) Production of polymer carrier The polymer carrier was synthesized according to a known suspension polymerization method. A mixture of 80 g of glycidyl methacrylate, 120 g of ethylene dimethacrylate, 200 g of butyl acetate and 2 g of azobisisobutyronitrile is added to 2,000 mL (milliliter) of 0.1% polyvinyl alcohol aqueous solution so that the diameter of the oil droplets becomes 60 μm. Was stirred. Thereafter, a polymerization reaction was carried out at 70 ° C. for 6 hours. After the reaction product was cooled, the produced copolymer particles were collected by filtration and washed with water, methanol and water in this order. Subsequently, after air-drying for one day, classification was performed to obtain 85 g of porous crosslinked polymer particles of 45 to 90 μm.

（２）ポリアミノ化反応
イソプロピルアルコール５０ｍＬ、水２００ｍＬに平均分子量６００のポリエチレンイミン(日本触媒社製、商品名：エポミンＳＰ−００６、平均分子量：６００、アミン比：一級３５％、二級３５％、三級３０％) ３５ｇを溶解し、前記(1) で得られた多孔性架橋重合体粒子２０ｇを加え、５０℃で６時間反応させた。反応物を濾過し、水、メタノール、水の順で洗浄した。このポリアミノ化樹脂の窒素量を元素分析装置 (パーキンエルマー社製２４００ Ｓｅｒｉｅｓ II ＣＨＮＳ/Ｏ Ｅｌｅｍｅｎｔａｌ Ａｎａｌｙｚｅｒ) で測定したところ７．８８％−Ｎ／ｇであった。 (2) Polyamination reaction 50 mL of isopropyl alcohol, polyethyleneimine having an average molecular weight of 600 in 200 mL of water (manufactured by Nippon Shokubai Co., Ltd., trade name: Epomin SP-006, average molecular weight: 600, amine ratio: primary 35%, secondary 35%, (Third class 30%) 35 g was dissolved, 20 g of the porous crosslinked polymer particles obtained in the above (1) was added, and the mixture was reacted at 50 ° C. for 6 hours. The reaction was filtered and washed with water, methanol, and water in that order. The amount of nitrogen in this polyaminated resin was measured with an elemental analyzer (2400 Series II CHNS / O Elemental Analyzer manufactured by PerkinElmer Co., Ltd.) and found to be 7.88% -N / g.

（３）カルボキシメチル化
２ＭＮａＯＨ水溶液２００ｍＬにクロロ酢酸ナトリウム３１．５ｇ (導入窒素量の２．４倍モル相当) を溶解し、前記（２） で得られたポリアミノ化樹脂を２０ｇ入れ、４０℃で６時間反応させ、反応物を濾過し、十分に水で洗浄後、メタノールに置換し、乾燥してキレート樹脂Ａを得た。 (3) Dissolve 31.5 g of sodium chloroacetate (corresponding to 2.4 times the mole of introduced nitrogen) in 200 mL of carboxymethylated 2M NaOH aqueous solution, add 20 g of the polyaminated resin obtained in (2) above at 40 ° C. Reaction was performed for 6 hours, the reaction product was filtered, sufficiently washed with water, then replaced with methanol, and dried to obtain chelate resin A.

（４）評価
得られたキレート樹脂Ａを６０℃の真空乾燥機内で３時間乾燥後、２５０ｍｇをとり、下部に孔径２０μｍのフィルタを挿入した注射筒型固相抽出カートリッジに充てんし、さらに上部にも孔径２０μｍのフィルタを挿入した。このカートリッジに、アセトニトリル、純水、３Ｍ硝酸、純水及び０．１Ｍ酢酸アンモニウム緩衝液 (ｐＨ５) の順で、それぞれ１０ｍＬずつ通液して、カートリッジのコンディショニングを行った。その後、０．０５Ｍ酢酸アンモニウム緩衝液 (ｐＨ５) で調整された０．５Ｍ硫酸銅溶液３ｍＬをゆっくり通液し、充てんされたキレート樹脂Ａに銅を吸着させた。その後、純水１０ｍＬ、０．００５Ｍの硝酸５ｍＬの順で洗浄した後、キレート樹脂Ａに吸着捕捉させた銅を３Ｍ硝酸３ｍＬで溶出させ、溶出液を純水で１０ｍＬに定容し、吸光光度計で８０５ｎｍにおける銅の吸光度を測定し、キレート樹脂Ａにおける銅の捕捉量を求めた。その結果、銅の捕捉量は、０．４３ｍｍｏｌＣｕ／ｇであり、十分な捕捉性を示した。 (4) Evaluation After the obtained chelate resin A was dried in a vacuum dryer at 60 ° C. for 3 hours, 250 mg was taken and filled into a syringe-type solid phase extraction cartridge having a filter with a pore size of 20 μm inserted in the lower part, and further in the upper part. Also, a filter having a pore diameter of 20 μm was inserted. The cartridge was conditioned by passing 10 mL each of acetonitrile, pure water, 3M nitric acid, pure water and 0.1M ammonium acetate buffer (pH 5) in this order. Thereafter, 3 mL of 0.5 M copper sulfate solution adjusted with 0.05 M ammonium acetate buffer (pH 5) was slowly passed through to adsorb copper onto the filled chelate resin A. Then, after washing in order of 10 mL of pure water and 5 mL of 0.005 M nitric acid, the copper adsorbed and trapped on the chelate resin A is eluted with 3 mL of 3 M nitric acid, and the eluate is made up to 10 mL with pure water. The absorbance of copper at 805 nm was measured with a total, and the amount of copper trapped in chelate resin A was determined. As a result, the trapped amount of copper was 0.43 mmol Cu / g, indicating a sufficient trapping property.

比較試験１Comparative test 1

金属捕捉特性の評価
実施例１で得られたキレート樹脂Ａを実施例１（４）と同様に固相抽出カートリッジに充てんし、同様のコンディショニングを行った。その後、種々のｐＨに調整した金属イオン混合標準液（銅Ｃｕ、ニッケルＮｉ、カドミウムＣｄ、鉛Ｐｂ、マグネシウムＭｇ、カルシウムＣａ、クロムＣｒ（３価）、モリブデンＭｏ、バナジウムＶ、ヒ素Ａｓの１０種類）を通液し、金属を捕捉させた。捕捉した金属は、前記実施例１（４）と同様に３Ｍ硝酸３ｍＬで溶出させ、ＩＣＰ発光分析装置 (パーキンエルマー社製、Ｏｐｔｉｍａ ３０００ ＤＶ) を用いて溶液中濃度を測定し、捕捉回収率を求めた。比較として、ＩＤＡ型キレート樹脂であるキレックス１００ (商品名、バイオラッドラボラトリーズ社製、交換容量：０．４ｍｅｑ／ｍＬ) を用いて同様の金属の捕捉特性比較試験を行った。結果を図1（図1ａないし図１ｊ）に示す。図1に示すとおり、銅、ニッケル、カドミウム、鉛のような重金属の酸性条件下での捕捉回収率は、ＩＤＡ型に比べ大きく改善されていた。また、キレート樹脂Ａでは、アルカリ土類金属類はｐＨ７以下では全く捕捉されず、アルカリ土類金属類の妨害を受けずに高度に重金属を捕捉回収できることができた。さらに、クロム、モリブデン、バナジウム、ヒ素に関しては、キレート樹脂ＡはすべてのｐＨ範囲で高い捕捉回収率を示した。 Evaluation of metal capture characteristics The chelate resin A obtained in Example 1 was filled into a solid-phase extraction cartridge in the same manner as in Example 1 (4), and the same conditioning was performed. Thereafter, mixed metal ion standard solutions (copper Cu, nickel Ni, cadmium Cd, lead Pb, magnesium Mg, calcium Ca, chromium Cr (trivalent), molybdenum Mo, vanadium V, and arsenic As adjusted to various pHs. ) Was passed to capture the metal. The trapped metal was eluted with 3 mL of 3M nitric acid in the same manner as in Example 1 (4), and the concentration in the solution was measured using an ICP emission analyzer (manufactured by PerkinElmer, Optima 3000 DV) to determine the capture recovery rate. Asked. For comparison, the same metal capture property comparison test was performed using Kilex 100 (trade name, manufactured by Bio-Rad Laboratories, exchange capacity: 0.4 meq / mL), which is an IDA-type chelating resin. The results are shown in FIG. 1 (FIGS. 1a to 1j). As shown in FIG. 1, the capture and recovery rate of heavy metals such as copper, nickel, cadmium and lead under acidic conditions was greatly improved compared to the IDA type. In addition, with the chelate resin A, alkaline earth metals were not captured at pH 7 or lower, and heavy metals could be highly captured and recovered without being disturbed by alkaline earth metals. Furthermore, with respect to chromium, molybdenum, vanadium, and arsenic, the chelating resin A exhibited a high capture recovery rate in the entire pH range.

比較試験２Comparative test 2

金属の捕捉特性の評価
実施例１で得られたキレート樹脂Ａと、ジエチレントリアミン骨格のポリアミノカルボン酸基を有する市販キレート樹脂カートリッジＮＯＢＩＡＳＣｈｅｌａｔｅ-ＰＡ１ (株式会社日立ハイテクノロジーズ社製、金属捕捉量：０．２５ｍｍｏｌ−Ｃｕ/ｇ、以下では単にＰＡ１と略記することがある。)とをそれぞれ実施例１（４）と同様に固相抽出カートリッジに充てんし、両者の金属捕捉特性（試料ｐＨと捕捉回収率との関係）を実験し、比較した。充てん量はともに２５０ｍｇとした。銅Ｃｕ、ニッケルＮｉ、カドミウムＣｄ、鉛Ｐｂ、マグネシウムＭｇ、カルシウムＣａ、クロムＣｒ（III、３価）、モリブデンＭｏ、バナジウムＶ、ヒ素Ａｓの１０種類の結果を図２（図２ａないし図２ｊ）に示す。図２に示すとおり、銅、ニッケル、カドミウム、鉛に関しては本質的に大きな差はみられず、同等の金属捕捉性能を示した。アルカリ土類金属類の捕捉に関しては、キレート樹脂ＡのほうがｐＨ７付近まで捕捉せず、ＰＡ１よりも広いｐＨ範囲でアルカリ土類金属類の妨害を受けずに重金属を捕捉・回収できることが判明した。また、他の重金属に比べアミノカルボン酸型キレート樹脂における錯形成速度が非常に遅いとされるクロム(III) においては、キレート樹脂Ａのほうが、より低いｐＨから高度に捕捉された。このことは、官能基鎖長が長くなったことによる錯体の安定度定数の向上、並びに錯体形成に係わる官能基の自由度の増加が大きく寄与しているものと判断される。モリブデン及びバナジウムの捕捉に関しても、アルカリ側での捕捉性の向上が観察された。さらに、ヒ素に関しては、全ｐＨ範囲において２倍以上の捕捉回収率が得られた。以上の通り、本発明のキレート樹脂は、市販キレート樹脂に比べ、アルカリ土類金属類の妨害を受け難く、広いｐＨで重金属を高度に捕捉・回収でき、さらには、従来のキレート樹脂では捕捉しにくい、クロムや金属オキソ酸等の捕捉特性を改善できることが判明した。 Evaluation of metal capture properties Chelate resin A obtained in Example 1 and commercially available chelate resin cartridge NOBIASChelate-PA1 having a polyaminocarboxylic acid group of diethylenetriamine skeleton (manufactured by Hitachi High-Technologies Corporation, metal capture amount: 0.25 mmol) -Cu / g, which may be simply abbreviated as PA1 below), is packed in a solid phase extraction cartridge in the same manner as in Example 1 (4), and the metal capture characteristics (sample pH, capture recovery rate, and The relationship was tested and compared. The filling amount was 250 mg for both. Results of 10 types of copper Cu, nickel Ni, cadmium Cd, lead Pb, magnesium Mg, calcium Ca, chromium Cr (III, trivalent), molybdenum Mo, vanadium V, and arsenic As are shown in FIG. 2 (FIGS. 2a to 2j). Shown in As shown in FIG. 2, there was essentially no difference regarding copper, nickel, cadmium, and lead, and the same metal capture performance was shown. Regarding the capture of alkaline earth metals, it was found that the chelate resin A does not capture up to around pH 7, and can capture and recover heavy metals in the pH range wider than PA1 without being disturbed by alkaline earth metals. Further, in chromium (III), which is considered to have a very slow complex formation rate in the aminocarboxylic acid type chelate resin as compared with other heavy metals, the chelate resin A was more highly captured from a lower pH. This is considered to be largely attributable to the improvement in the stability constant of the complex due to the increase in the functional group chain length and the increase in the degree of freedom of the functional group involved in complex formation. Regarding the capture of molybdenum and vanadium, an improvement in the trapping property on the alkali side was observed. Furthermore, with regard to arsenic, a capture recovery rate of 2 times or more was obtained in the entire pH range. As described above, the chelate resin of the present invention is less susceptible to alkaline earth metal interference than commercially available chelate resins, and can capture and recover heavy metals at a high pH and can be captured with a conventional chelate resin. It has been found that it is difficult to improve the trapping properties of chromium, metal oxoacids and the like.

比較試験３Comparative test 3

試料通液量の評価
比較試験２と同じく２つの固相抽出カートリッジに実施例１で得られたキレート樹脂ＡとＰＡ１をそれぞれ２５０ｍｇ充てんし、試料通液量と捕捉回収率の関係を調べた。測定対象元素は、カドミウム、バナジウム、モリブデンとした。試料中の金属量は、一定重量（１０μｇ）として純水で希釈後、比較試験1に準じてｐＨ５．５に調整して、１０ｍＬ、１００ｍＬ、５００ｍＬ及び１，０００ｍＬの４種類の試料を作製した。この４種類の試料をそれぞれ固相抽出カートリッジに通液して金属を捕捉し、捕捉した金属を３Ｍ硝酸で溶出後、ＩＣＰ発光分光分析装置で捕捉された金属量を測定した。試料通液量が１０ｍＬの場合の捕捉回収量 (両カートリッジ共ほぼ１００％の捕捉回収率) を１００としたときの相対捕捉回収量を相対捕捉回収率として算出した。その結果を図３に示す。カドミウムに関しては両者の差はほとんどなく、２５０ｍｇの充てん剤で約１，０００ｍＬまで通液できた。しかし、バナジウム及びモリブデンに関しては、大きな差がみられ、ＰＡ１では捕捉回収率の大きな低下が観察されたが、実施例1のキレート樹脂Ａでは５００ｍＬまでは大きな減少はみられなかった。試料溶液のｐＨ５．５は、前記比較試験２の結果から明白なように、両カートリッジともほぼ１００％回収する条件である。この差は、キレート性官能基の鎖長の影響、つまり本発明のキレート性官能基の鎖長が長いことによる錯体の安定度定数の向上、並びに、スペーサ的効果による自由度の向上により、金属捕捉性能が改善されている。 Evaluation of sample flow rate As in Comparative Test 2, two solid-phase extraction cartridges were filled with 250 mg of the chelate resin A and PA1 obtained in Example 1, respectively, and the relationship between the sample flow rate and the capture recovery rate was examined. The elements to be measured were cadmium, vanadium, and molybdenum. The amount of metal in the sample was diluted with pure water as a constant weight (10 μg), then adjusted to pH 5.5 according to Comparative Test 1, and four types of samples of 10 mL, 100 mL, 500 mL, and 1,000 mL were prepared. . The four types of samples were each passed through a solid-phase extraction cartridge to capture the metal. The captured metal was eluted with 3M nitric acid, and the amount of the metal captured by the ICP emission spectroscopic analyzer was measured. The relative capture recovery rate was calculated as the relative capture recovery rate when the capture recovery rate (capture recovery rate of approximately 100% for both cartridges) when the sample flow rate was 10 mL was taken as 100. The result is shown in FIG. Regarding cadmium, there was almost no difference between the two, and it was possible to pass up to about 1,000 mL with 250 mg of filler. However, with regard to vanadium and molybdenum, a large difference was observed, and a large decrease in capture recovery rate was observed with PA1, but with Chelate resin A of Example 1, no significant decrease was observed up to 500 mL. The pH 5.5 of the sample solution is a condition that both cartridges are recovered almost 100%, as is apparent from the result of the comparative test 2. This difference is due to the influence of the chain length of the chelating functional group, that is, the stability constant of the complex due to the long chain length of the chelating functional group of the present invention, and the freedom due to the spacer effect. Acquisition performance has been improved.

キレート樹脂Ｂの合成
キレート樹脂Ｂを実施例１と同様な方法により合成した。すなわち、イソプロピルアルコール５０ｍＬ、水２００ｍＬに平均分子量３００のポリエチレンイミン（日本触媒社製、商品名；エポミンＳＰ−００３、平均分子量：３００、アミン比：一級４５％、二級３５％、三級２０％) ３５ｇを溶解し、実施例1（１）で得られた多孔性架橋重合体粒子２０ｇを加え、５０℃で６時間反応させた。反応物を濾過し、水、メタノール、水の順で洗浄し、ポリアミノ化樹脂を得た。このポリアミノ化樹脂の窒素量は７．３１％-Ｎ/ｇであった。このポリアミノ化樹脂２０ｇを、１Ｍ ＮａＯＨ水溶液２００ｍＬにクロロ酢酸ナトリウム２９．０ｇ (導入窒素量の２．４倍モル相当) を溶解した液に加え、４０℃で６時間反応させ、反応物を濾過し、十分に水で洗浄後、メタノールに置換し、乾燥してキレート樹脂Ｂを得た。このキレート樹脂Ｂの銅の捕捉量は、０．４０ｍｍｏｌ Ｃｕ／ｇであった。 Synthesis of chelate resin B Chelate resin B was synthesized in the same manner as in Example 1. In other words, polyethyleneimine having an average molecular weight of 300 in 50 mL of isopropyl alcohol and 200 mL of water (manufactured by Nippon Shokubai Co., Ltd., trade name: Epomin SP-003, average molecular weight: 300, amine ratio: 45% primary, 35% secondary, 20% tertiary) 35 g was dissolved, 20 g of the porous crosslinked polymer particles obtained in Example 1 (1) was added, and the mixture was reacted at 50 ° C. for 6 hours. The reaction product was filtered and washed with water, methanol, and water in this order to obtain a polyaminated resin. The amount of nitrogen of this polyaminated resin was 7.31% -N / g. 20 g of this polyaminated resin was added to a solution obtained by dissolving 29.0 g of sodium chloroacetate (corresponding to 2.4 times the mole of introduced nitrogen) in 200 mL of 1M NaOH aqueous solution, reacted at 40 ° C. for 6 hours, and the reaction product was filtered. After sufficiently washing with water, it was replaced with methanol and dried to obtain a chelate resin B. The amount of copper trapped in this chelate resin B was 0.40 mmol Cu / g.

比較例１Comparative Example 1

キレート樹脂fの合成
イソプロピルアルコール５０ｍＬ、水２００ｍＬにエチレンジアミン (和光純薬社製、試薬特級) ３５ｇを溶解し、実施例１（１）で得られた多孔性架橋重合体粒子２０ｇを加え、５０℃で６時間反応させた。反応物を濾過し、水、メタノール、水の順で洗浄した。このポリアミノ化樹脂の窒素量は６．９１％−Ｎ／ｇであった。ついで、このポリアミノ化樹脂２０ｇを１ＭＮａＯＨ水溶液２００ｍＬにクロロ酢酸ナトリウム２７．５ｇ (導入窒素量の２．４倍モル相当) を溶解した液に添加し、４０℃で６時間反応させ、反応物を濾過し、十分に水で洗浄後、メタノールに置換し、乾燥してキレート樹脂ｆを得た。銅の捕捉量は、０．４１ｍｍｏｌ Ｃｕ／ｇであった。 Synthesis of chelate resin f 35 g of ethylenediamine (manufactured by Wako Pure Chemicals, special grade of reagent) was dissolved in 50 mL of isopropyl alcohol and 200 mL of water, and 20 g of the porous cross-linked polymer particles obtained in Example 1 (1) were added thereto. For 6 hours. The reaction was filtered and washed with water, methanol, and water in that order. The amount of nitrogen of this polyaminated resin was 6.91% -N / g. Next, 20 g of this polyaminated resin was added to a solution of 27.5 g of sodium chloroacetate (corresponding to 2.4 times the amount of introduced nitrogen) in 200 mL of 1 M NaOH aqueous solution, reacted at 40 ° C. for 6 hours, and the reaction product was filtered. Then, after sufficiently washing with water, it was replaced with methanol and dried to obtain a chelate resin f. The amount of copper trapped was 0.41 mmol Cu / g.

比較試験４Comparative test 4

金属の捕捉特性の評価
実施例１で得られたキレート樹脂Ａ、実施例２で得られたキレート樹脂Ｂ、比較例１で得られたキレート樹脂ｆ、及びＰＡ１を用いて、試料ｐＨと捕捉回収率との関係を調べた。評価方法は前記比較試験１にしたがって行った。銅Ｃｕ、ニッケルＮｉ、カドミウムＣｄ、鉛Ｐｂ、マグネシウムＭｇ、カルシウムＣａ、クロムＣｒ（III、３価）、モリブデンＭｏ、バナジウムＶ、ヒ素Ａｓの１０種類の結果を図４（図４ａないし図４ｊ）に示す。図４に示すとおり、銅に関してはすべてのキレート樹脂で良好な結果が得られた。ニッケル、カドミウム、鉛に関しては、比較例1のキレート樹脂ｆでは酸性条件下での捕捉回収率が低かったが、キレート樹脂Ａ及びキレート樹脂Ｂは良好な捕捉特性を示した。アルカリ土類金属類の捕捉に関しては、キレート樹脂Ａ及びキレート樹脂ＢではｐＨ７付近まで捕捉せず、比較例１で得られたキレート樹脂ｆ及びＰＡ１よりも広いｐＨ範囲でアルカリ土類金属類の妨害を受けずに重金属を捕捉・回収できることができることが判明した。また、クロム(III) は、キレート樹脂Ａ及びキレート樹脂Ｂでは低いｐＨから高度に捕捉することができた。モリブデン及びバナジウムの捕捉に関しては、キレート樹脂Ａ及びキレート樹脂Ｂでアルカリ側での捕捉性の向上が観察された。さらに、ヒ素に関しては、キレート樹脂Ａ及びキレート樹脂Ｂでは全ｐＨ範囲において比較例１のキレート樹脂ｆよりも２倍以上の捕捉回収率であった。 Evaluation of metal capture properties Sample pH and capture recovery using chelate resin A obtained in Example 1, chelate resin B obtained in Example 2, chelate resin f obtained in Comparative Example 1, and PA1 The relationship with rate was examined. The evaluation method was performed according to the comparative test 1. Results of 10 types of copper Cu, nickel Ni, cadmium Cd, lead Pb, magnesium Mg, calcium Ca, chromium Cr (III, trivalent), molybdenum Mo, vanadium V, and arsenic As are shown in FIG. 4 (FIGS. 4a to 4j). Shown in As shown in FIG. 4, with respect to copper, good results were obtained with all chelate resins. Regarding nickel, cadmium, and lead, the chelate resin f of Comparative Example 1 had a low capture recovery rate under acidic conditions, but chelate resin A and chelate resin B showed good capture properties. Regarding the capture of alkaline earth metals, chelate resin A and chelate resin B do not capture up to around pH 7, and interference of alkaline earth metals in a wider pH range than chelate resin f and PA1 obtained in Comparative Example 1 It has been found that heavy metals can be captured and recovered without being subjected to any damage. Chromium (III) could be highly captured from the low pH by the chelate resin A and the chelate resin B. Regarding the capture of molybdenum and vanadium, the chelating resin A and chelating resin B were observed to improve the capturing ability on the alkali side. Furthermore, with respect to arsenic, the chelate resin A and the chelate resin B had a capture recovery rate twice or more that of the chelate resin f of Comparative Example 1 over the entire pH range.

キレート樹脂Ｃの合成
（１）ポリアミノ化樹脂の合成
実施例1と同様の方法でポリアミノ化樹脂を合成した。グリシジルメタクリレート９０ｇ、エチレンジメタクリレート２１０ｇを用いて４５〜９０μｍの多孔性架橋重合体粒子の高分子担体１２５ｇを得た。ついで、イソプロピルアルコール３００ｍＬ、水１２００ｍＬにポリエチレンイミン３００ (日本触媒社製、商品名：エポミンＳＰ−００３) ２５０ｇを溶解し、これに得られた高分子担体１２５ｇを加え、５０℃で６時間反応させた。反応物を濾過し、水、メタノール、水の順で洗浄してポリアミノ化樹脂を得た。このポリアミノ化樹脂の窒素量は５．９１％−Ｎ/ｇであった。 Synthesis of chelate resin C (1) Synthesis of polyaminated resin
A polyaminated resin was synthesized in the same manner as in Example 1. Using 90 g of glycidyl methacrylate and 210 g of ethylene dimethacrylate, 125 g of a polymer carrier of porous crosslinked polymer particles of 45 to 90 μm was obtained. Next, 250 g of polyethyleneimine 300 (product name: Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd.) is dissolved in 300 mL of isopropyl alcohol and 1200 mL of water, and 125 g of the resulting polymer carrier is added thereto and reacted at 50 ° C. for 6 hours. It was. The reaction product was filtered and washed with water, methanol and water in this order to obtain a polyaminated resin. The amount of nitrogen of this polyaminated resin was 5.91% -N / g.

（２)カルボキシメチル化
１Ｍ ＮａＯＨ水溶液２００ｍＬにクロロ酢酸ナトリウム２０ｇ (導入窒素量の２．０倍モル相当) を溶解し、前記（１) で得られたポリアミノ化樹脂２０ｇを入れ、４０℃で６時間反応させ、反応物を濾過し、十分に水で洗浄後、メタノールに置換し、乾燥してキレート樹脂Ｃを得た。このキレート樹脂Ｃの銅の捕捉量は、０．３３ｍｍｏｌ Ｃｕ／ｇであった。 (2) Dissolve 20 g of sodium chloroacetate (corresponding to 2.0 times the mole of introduced nitrogen) in 200 mL of carboxymethylated 1M NaOH aqueous solution, add 20 g of the polyaminated resin obtained in (1) above, and add 6 g at 40 ° C. After reacting for a period of time, the reaction product was filtered, sufficiently washed with water, then replaced with methanol, and dried to obtain a chelate resin C. The amount of copper trapped by this chelate resin C was 0.33 mmol Cu / g.

キレート樹脂Ｄの合成
実施例３（１）で得られたポリアミノ化樹脂２０ｇとクロロ酢酸ナトリウム１０ｇ (導入窒素量の１．０倍モル相当) とを実施例３と同様に反応させて、ポリアミノカルボン酸型キレート樹脂Ｄを製造した。このキレート樹脂Ｄの銅の捕捉量は、０．３１ｍｍｏｌ Ｃｕ／ｇであった。 Synthesis of chelate resin D 20 g of the polyaminated resin obtained in Example 3 (1) and 10 g of sodium chloroacetate (corresponding to 1.0 times the mole of introduced nitrogen) were reacted in the same manner as in Example 3 to obtain polyaminocarboxylic acid. An acid-type chelate resin D was produced. The amount of copper captured by this chelate resin D was 0.31 mmol Cu / g.

比較例２Comparative Example 2

キレート樹脂ｇの合成
実施例３（１）で得られたポリアミノ化樹脂２０ｇとクロロ酢酸ナトリウム３５ｇ (導入窒素量の３．５倍モル相当) とを実施例３と同様に反応させて、ポリアミノカルボン酸型キレート樹脂ｇを製造した。このキレート樹脂ｇの銅の捕捉量は、０．３２mmol Ｃｕ／ｇであった。 Synthesis of chelate resin g 20 g of the polyaminated resin obtained in Example 3 (1) and 35 g of sodium chloroacetate (corresponding to 3.5 times mole of introduced nitrogen amount) were reacted in the same manner as in Example 3 to obtain polyaminocarboxylic acid. Acid type chelate resin g was produced. The amount of copper trapped by the chelate resin g was 0.32 mmol Cu / g.

比較試験５Comparative test 5

金属の捕捉特性の評価
比較試験１にしたがい、４種のキレート樹脂Ｃ、Ｄ、ｇ及びＰＡ１を用いて金属の捕捉特性の比較を行った。銅Ｃｕ、ニッケルＮｉ、カドミウムＣｄ、鉛Ｐｂ、マグネシウムＭｇ、カルシウムＣａ、クロムＣｒ（III、３価）、モリブデンＭｏ、バナジウムＶ、ヒ素Ａｓの１０種類の金属の補足特性の結果を図５（図５ａないし図５ｊ）に示す。窒素親和性の高い銅に関しては、すべての樹脂で良好な捕捉特性を示した。ニッケル、カドミウム及び鉛の酸性側での捕捉特性は、キレート樹脂Ｄ＜ＰＡ１＝キレート樹脂Ｃ＜キレート樹脂ｇの順（＝は、ほぼ同程度であることを示す。以下同じ）で増加し、カルボキシメチル化度の高いキレート樹脂のほうが良好な結果となった。アルカリ土類金属類が捕捉されるかどうかに関しては、ＰＡ１＝キレート樹脂ｇ＜キレート樹脂Ｄ＝キレート樹脂Ｃの順で捕捉されにくいが、カルボキシメチル化度が低いほうがアルカリ土類金属類を捕捉せず、高いｐＨまでアルカリ土類金属類が捕捉されなかった。クロム(III) の捕捉に関しては、ＰＡ１＜キレート樹脂Ｄ＜キレート樹脂ｇ＝キレート樹脂Ｃの順で大きくなり、モリブデン及びバナジウムのアルカリ側での捕捉に関しては、ＰＡ１＜キレート樹脂Ｄ＜キレート樹脂ｇ＜キレート樹脂Ｃの順であった。また、ヒ素の捕捉に関しては、ＰＡ１＜キレート樹脂ｇ＜キレート樹脂Ｃ＜キレート樹脂Ｄの順であった。これらの結果から、金属捕捉特性とアルカリ土類金属類が捕捉されにくい特性とのバランスが取れたキレート樹脂を得るにはカルボキシメチル化度の至適範囲が存在することが明白となった。 According to the comparative evaluation test 1 of metal capture characteristics, metal capture characteristics were compared using four types of chelate resins C, D, g, and PA1. FIG. 5 shows the results of the supplemental characteristics of 10 kinds of metals such as copper Cu, nickel Ni, cadmium Cd, lead Pb, magnesium Mg, calcium Ca, chromium Cr (III, trivalent), molybdenum Mo, vanadium V, and arsenic As. 5a to 5j). With respect to copper having a high nitrogen affinity, all the resins showed good capturing properties. The capturing properties on the acidic side of nickel, cadmium and lead increase in the order of chelate resin D <PA1 = chelate resin C <chelate resin g (= indicates approximately the same level, hereinafter the same), A chelating resin having a higher degree of methylation gave better results. Regarding whether alkaline earth metals are captured, it is difficult to capture in the order of PA1 = chelate resin g <chelate resin D = chelate resin C, but the lower the degree of carboxymethylation, the more alkaline earth metals can be captured. In addition, alkaline earth metals were not trapped up to a high pH. Regarding the capture of chromium (III), PA1 <chelate resin D <chelate resin g = chelate resin C increases in this order, and for capture of molybdenum and vanadium on the alkali side, PA1 <chelate resin D <chelate resin g < It was the order of chelating resin C. Regarding the capture of arsenic, the order was PA1 <chelate resin g <chelate resin C <chelate resin D. From these results, it became clear that there is an optimum range of the degree of carboxymethylation in order to obtain a chelate resin having a balance between the metal trapping properties and the properties in which alkaline earth metals are not easily trapped.

キレート樹脂Ｅの合成
クロロメチルスチレン３０ｇ、ジビニルベンゼン７０ｇ、トルエン１５０ｇ及びアゾビスイソブチロニトリル２ｇの混合物を、０．１％ポリビニルアルコール水溶液２、０００ｍＬ中に加え、油滴の径が６０μmになるように攪拌し、７０℃で６時間重合反応を行った。反応物を冷却した後、生成した共重合体を濾取し、水、メタノール、水の順で洗浄した。ついで、一日風乾後、分級して４５〜９０μmの多孔性架橋重合体粒子３５ｇを得た。イソプロピルアルコール４０ｍＬ、水１６０ｍＬにポリエチレンイミン３００ (日本触媒社製、エポミンＳＰ−００３) ３５ｇを溶解し、これに得られた多孔性架橋重合体粒子２０ｇを加え、５０℃で６時間反応させた。反応物を濾過し、水、メタノール、水の順で洗浄してポリアミノ化樹脂を得た。このポリアミノ化樹脂の窒素量は６．８１%−Ｎ／ｇであった。ついで、１Ｍ ＮａＯＨ水溶液２００ｍＬにクロロ酢酸ナトリウム２０．５ｇ (導入窒素量の１．８倍モル相当) を溶解し、得られたポリアミノ化樹脂の全量を入れ、４０℃で６時間反応させ、反応物を濾過し、十分に水で洗浄後、メタノールに置換し、乾燥してキレート樹脂Ｅを得た。このキレート樹脂Ｅの銅の捕捉量は、０．３９ｍｍｏｌＣｕ／ｇであった。 Synthesis of chelate resin E A mixture of 30 g of chloromethylstyrene, 70 g of divinylbenzene, 150 g of toluene and 2 g of azobisisobutyronitrile is added to 2,000 mL of 0.1% polyvinyl alcohol aqueous solution, so that the diameter of the oil droplet is 60 μm. The polymerization reaction was carried out at 70 ° C. for 6 hours. After the reaction product was cooled, the produced copolymer was collected by filtration and washed with water, methanol and water in this order. Then, after air drying for one day, classification was performed to obtain 35 g of porous crosslinked polymer particles having a size of 45 to 90 μm. 35 g of polyethyleneimine 300 (Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd.) was dissolved in 40 mL of isopropyl alcohol and 160 mL of water, and 20 g of the resulting porous cross-linked polymer particles were added thereto and reacted at 50 ° C. for 6 hours. The reaction product was filtered and washed with water, methanol and water in this order to obtain a polyaminated resin. The amount of nitrogen in this polyaminated resin was 6.81% -N / g. Next, 20.5 g of sodium chloroacetate (equivalent to 1.8 times mol of introduced nitrogen) was dissolved in 200 mL of 1M NaOH aqueous solution, and the total amount of the resulting polyaminated resin was added and reacted at 40 ° C. for 6 hours. Was filtered, washed thoroughly with water, replaced with methanol, and dried to obtain chelate resin E. The amount of copper captured by this chelate resin E was 0.39 mmol Cu / g.

比較試験６Comparative test 6

金属捕捉特性の評価
実施例５のキレート樹脂Ｅを用いて、比較試験1にしたがい、ＰＡ１と比較して金属捕捉特性を評価した。銅Ｃｕ、ニッケルＮｉ、カドミウムＣｄ、鉛Ｐｂ、マグネシウムＭｇ、カルシウムＣａ、クロムＣｒ（III、３価）、モリブデンＭｏ、バナジウムＶ、ヒ素Ａｓの１０種類の結果を図６（図６ａないし図６ｊ）に示す。図６に示すとおり、銅、ニッケル、カドミウム、鉛に関しては本質的に大きな差はみられず、同等の金属捕捉性能を示した。アルカリ土類金属類の捕捉に関しては、キレート樹脂Ｅのほうが広いｐＨ範囲でアルカリ土類金属類の妨害を受けずに重金属を捕捉・回収できることができることが判明した。また、クロム(III) においては、キレート樹脂Ｅのほうが、より低いｐＨから高度に捕捉された。モリブデン及びバナジウムの捕捉に関しても、アルカリ側での捕捉性の向上が観察された。さらに、ヒ素に関しては、全ｐＨ範囲において２倍以上の捕捉回収率が得られた。 Evaluation of metal trapping characteristics Using chelate resin E of Example 5, the metal trapping characteristics were evaluated in comparison with PA1 in accordance with Comparative Test 1. Results of 10 types of copper Cu, nickel Ni, cadmium Cd, lead Pb, magnesium Mg, calcium Ca, chromium Cr (III, trivalent), molybdenum Mo, vanadium V, and arsenic As are shown in FIG. 6 (FIGS. 6a to 6j). Shown in As shown in FIG. 6, there was essentially no significant difference regarding copper, nickel, cadmium, and lead, and equivalent metal capture performance was exhibited. Regarding the capture of alkaline earth metals, it has been found that the chelate resin E can capture and recover heavy metals in the wider pH range without being disturbed by alkaline earth metals. In addition, in chromium (III), the chelate resin E was more highly captured from a lower pH. Regarding the capture of molybdenum and vanadium, an improvement in the trapping property on the alkali side was observed. Furthermore, with regard to arsenic, a capture recovery rate of 2 times or more was obtained in the entire pH range.

本発明のキレート樹脂は、酸性条件下ではアルカリ土類金属類を捕捉しないため、排水や用水等からの重金属除去、海水や河川水等の環境水や金属処理溶液中からの有価金属の回収を効率よく行うことができる。さらには、微量金属の機器分析における妨害元素の除去及び分析対象元素の抽出・濃縮等の前処理用途にも使用することが可能である。 Since the chelate resin of the present invention does not capture alkaline earth metals under acidic conditions, it removes heavy metals from wastewater and irrigation water, and recovers valuable metals from environmental water and metal treatment solutions such as seawater and river water. It can be done efficiently. Furthermore, it can also be used for pretreatment applications such as removal of interfering elements in instrumental analysis of trace metals and extraction / concentration of analysis target elements.

●：図１（図1ａないし図１ｊ）における実施例1のキレート樹脂Ａの回収率を示す。
□：図１（図1ａないし図１ｊ）における市販ＩＤＡ型樹脂の回収率を示す。
●：図２（図２ａないし図２ｊ）における実施例1のキレート樹脂Ａの回収率を示す。
□：図２（図２ａないし図２ｊ）における比較対象のＮＯＢＩＡＳＣｈｅｌａｔｅ-ＰＡ１の回収率を示す。
元素記号-Ａ：図３における実施例１のキレート樹脂Ａの相対回収率を示す。
元素記号-Ｒ：図３における比較対象のＮＯＢＩＡＳ Ｃｈｅｌａｔｅ-ＰＡ１の相対回収 率を示す。
◆：図４（図４ａないし図４ｊ）における実施例１のキレート樹脂Ａの回収率を示す。
●：図４（図４ａないし図４ｊ）における実施例２の型キレート樹脂Ｂの回収率を示す。
△：図４（図４ａないし図４ｊ）における比較例１のキレート樹脂ｆの回収率を示す。
□：図４（図４ａないし図４ｊ）における比較対象のＮＯＢＩＡＳＣｈｅｌａｔｅ-ＰＡ１の回収率を示す。
●：図５（図５ａないし図５ｊ）における実施例３のキレート樹脂Ｃの回収率を示す。
△：図５（図５ａないし図５ｊ）における実施例４のキレート樹脂Ｄの回収率を示す。
○：図５（図５ａないし図５ｊ）における比較例２のキレート樹脂ｇの回収率を示す。
□：図５（図５ａないし図５ｊ）における比較対象のＮＯＢＩＡＳＣｈｅｌａｔｅ-ＰＡ１の回収率を示す。
●：図６（図６ａないし図６ｊ）における実施例５のキレート樹脂Ｅの回収率を示す。
□：図６（図６ａないし図６ｊ）における比較対象のＮＯＢＩＡＳＣｈｅｌａｔｅ-ＰＡ１の回収率を示す。 ●: Shows the recovery rate of chelate resin A of Example 1 in FIG. 1 (FIGS. 1a to 1j).
□: Shows the recovery rate of commercially available IDA resin in FIG. 1 (FIGS. 1a to 1j).
●: Shows the recovery rate of chelate resin A of Example 1 in FIG. 2 (FIGS. 2a to 2j).
□: shows the recovery rate of NOBIASChelate-PA1 to be compared in FIG. 2 (FIGS. 2a to 2j).
Element symbol -A: shows the relative recovery of the chelate resin A of Example 1 in FIG.
Element symbol -R: shows the relative recovery of NOBIAS Chelate-PA1 as a comparison target in FIG.
♦: Shows the recovery rate of the chelate resin A of Example 1 in FIG. 4 (FIGS. 4a to 4j).
(Circle): The recovery rate of the type | mold chelate resin B of Example 2 in FIG. 4 (FIG. 4 a thru | or FIG. 4 j) is shown.
(Triangle | delta): The recovery rate of the chelate resin f of the comparative example 1 in FIG. 4 (FIG. 4 a thru | or 4 j) is shown.
□: Indicates the recovery rate of NOBIASChelate-PA1 to be compared in FIG. 4 (FIGS. 4a to 4j).
●: Shows the recovery rate of the chelate resin C of Example 3 in FIG. 5 (FIGS. 5a to 5j).
(Triangle | delta): The recovery rate of the chelate resin D of Example 4 in FIG. 5 (FIG. 5 a thru | or FIG. 5 j) is shown.
○: The recovery rate of the chelate resin g of Comparative Example 2 in FIG. 5 (FIGS. 5a to 5j).
□: Shows the recovery rate of NOBIASChelate-PA1 to be compared in FIG. 5 (FIGS. 5a to 5j).
●: Shows the recovery rate of the chelate resin E of Example 5 in FIG. 6 (FIGS. 6a to 6j).
□: Indicates the recovery rate of NOBIASChelate-PA1 to be compared in FIG. 6 (FIGS. 6a to 6j).

Claims (2)

エポキシ基あるいはハロゲン化アルキル基を有する反応性モノマーと架橋性モノマーとの共重合体よりなる群より選ばれる共重合体の反応性官能基を有する高分子担体にポリエチレンイミン骨格を有する平均分子量が２００ないし６００の化合物を導入後、高分子担体に導入されたポリエチレンイミン骨格を有する化合物の窒素量の１．０〜３．０倍モルのハロゲン化酢酸を用いて部分カルボキシメチル化してなる重金属元素の除去、回収に用いられ、アルカリ土類金属類の妨害を受けにくいキレート樹脂。 The average molecular weight having a polyethyleneimine skeleton is 200 on a polymer carrier having a reactive functional group of a copolymer selected from the group consisting of a copolymer of a reactive monomer having an epoxy group or a halogenated alkyl group and a crosslinkable monomer. Of a heavy metal element obtained by partial carboxymethylation using 1.0 to 3.0 moles of halogenated acetic acid after introduction of a compound of 600 to 600 and then a nitrogen amount of a compound having a polyethyleneimine skeleton introduced into a polymer carrier . A chelating resin that is used for removal and recovery and is not easily disturbed by alkaline earth metals. エポキシ基あるいはハロゲン化アルキル基を有する反応性モノマーと架橋性モノマーとの共重合体よりなる群より選ばれる共重合体の反応性官能基を有する高分子担体にポリエチレンイミン骨格を有する平均分子量が２００ないし６００の化合物を反応させ、ついで高分子担体に導入されたポリエチレンイミン骨格を有する化合物の窒素量の１．０〜３．０倍モルのハロゲン化酢酸を用いて部分カルボキシメチル化することを特徴とする重金属元素の除去、回収に用いられ、アルカリ土類金属類の妨害を受けにくいキレート樹脂の製造方法。 The average molecular weight having a polyethyleneimine skeleton is 200 on a polymer carrier having a reactive functional group of a copolymer selected from the group consisting of a copolymer of a reactive monomer having an epoxy group or a halogenated alkyl group and a crosslinkable monomer. Or 600 compounds are reacted, and then partially carboxymethylated using halogenated acetic acid in an amount of 1.0 to 3.0 times the nitrogen amount of the compound having a polyethyleneimine skeleton introduced into the polymer carrier. A method for producing a chelate resin, which is used for removing and recovering heavy metal elements and is not easily disturbed by alkaline earth metals.
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