JP2002119872A - Anion exchange resin - Google Patents
Anion exchange resinInfo
- Publication number
- JP2002119872A JP2002119872A JP2000312063A JP2000312063A JP2002119872A JP 2002119872 A JP2002119872 A JP 2002119872A JP 2000312063 A JP2000312063 A JP 2000312063A JP 2000312063 A JP2000312063 A JP 2000312063A JP 2002119872 A JP2002119872 A JP 2002119872A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- anion exchange
- group
- ion
- anion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は陰イオン交換樹脂、
特にイオン交換基が塩型であり、かつ金属イオンの含有
量が著るしく少ない陰イオン交換樹脂に関するものであ
る。TECHNICAL FIELD The present invention relates to an anion exchange resin,
In particular, the present invention relates to an anion exchange resin in which the ion exchange group is of a salt type and the content of metal ions is extremely small.
【0002】[0002]
【従来の技術】陰イオン交換樹脂は、陽イオン交換樹脂
と共に、水処理その他の分野で広く用いられている。市
場で入手できる代表的な陰イオン交換樹脂は、モノビニ
ルモノマーとポリビニルモノマーとの架橋共重合体を母
体とし、1級ないし3級アンモニウム基又は第4級アン
モニウム基をイオン交換基とするものである。これらの
陰イオン交換樹脂のなかでも最も大量に消費されている
のは、第4級アンモニウム基をイオン交換基とする強塩
基性陰イオン交換樹脂である。第4級アンモニウム基は
遊離型(OH型)よりも塩型の方が安定なので、この陰
イオン交換樹脂は専ら塩型、特に塩素イオン型として市
場に供給されている。BACKGROUND OF THE INVENTION Anion exchange resins, along with cation exchange resins, are widely used in water treatment and other fields. Typical anion exchange resins available on the market are those having a crosslinked copolymer of a monovinyl monomer and a polyvinyl monomer as a base and having a primary to tertiary ammonium group or a quaternary ammonium group as an ion exchange group. . Among these anion exchange resins, the most widely consumed is a strongly basic anion exchange resin having a quaternary ammonium group as an ion exchange group. Since the quaternary ammonium group is more stable in the salt form than in the free form (OH form), this anion exchange resin is supplied to the market exclusively as the salt form, especially as the chloride ion form.
【0003】第4級アンモニウム基をイオン交換基とす
る陰イオン交換樹脂の最も一般的な製造法では、先ずモ
ノビニルモノマーとポリビニルモノマー、通常はスチレ
ンとジビニルベンゼン、を共重合させて架橋共重合体か
らなる母体を製造する。次いでこれにハロアルキル基を
導入したのち、3級アミン、通常はトリメチルアミン又
はジメチルエタノールアミンを反応させて、母体に第4
級アンモニウム基を導入する。3級アミンの代りにアン
モニア又は1〜2級アミンを反応させると、1〜3級ア
ミノ基を導入することができる。得られた陰イオン交換
樹脂は、ハロアルキル基に由来するハロゲンイオンを対
イオンとする塩型なので、通常は水洗して未反応アミン
などを除去しただけで製品として市場に供給される。In the most common method for producing an anion exchange resin having a quaternary ammonium group as an ion exchange group, first, a monovinyl monomer and a polyvinyl monomer, usually styrene and divinylbenzene are copolymerized to form a crosslinked copolymer. A mother body consisting of Next, after introducing a haloalkyl group into this, a tertiary amine, usually trimethylamine or dimethylethanolamine, is reacted to give the mother a quaternary amine.
A quaternary ammonium group is introduced. When ammonia or a primary or secondary amine is reacted instead of a tertiary amine, a primary or secondary amino group can be introduced. Since the obtained anion exchange resin is a salt type having a halogen ion derived from a haloalkyl group as a counter ion, it is usually supplied to the market as a product only by washing with water to remove unreacted amine and the like.
【0004】[0004]
【発明が解決しようとする課題】母体へのハロアルキル
基の導入法として最も一般的な方法は、塩化亜鉛、塩化
鉄、塩化アルミニウム、塩化錫などのルイス酸の存在下
に、クロロメチルメチルエーテルを母体に反応させて、
母体にクロロメチル基を導入する方法である。従って生
成する陰イオン交換樹脂中には、これらの金属が含まれ
ている。そしてアミンを反応させた後に行われている通
常の水洗では、これらの金属の含有量を十分に低減させ
ることは不可能であり、陰イオン交換樹脂は一般に数百
ppmないし数千ppmもの金属を含有した状態で市場
に供給されている。しかしながら、陰イオン交換樹脂の
用途によっては、使用中に樹脂中の金属が溶出して製品
を汚染することがある。また陰イオン交換樹脂は一般に
遊離型に転換して用いるが、その際に樹脂中に多量の金
属が含有されていると、この金属が流出して環境を汚染
する。従って本発明は、金属含有量の著るしく少ない塩
型の陰イオン交換樹脂を提供しようとするものである。The most common method for introducing a haloalkyl group into a base is to prepare chloromethyl methyl ether in the presence of a Lewis acid such as zinc chloride, iron chloride, aluminum chloride or tin chloride. Let your mother react
This is a method of introducing a chloromethyl group into the parent. Therefore, these metals are contained in the formed anion exchange resin. And it is impossible to sufficiently reduce the content of these metals by ordinary water washing performed after reacting the amine, and the anion exchange resin generally removes several hundred ppm to several thousand ppm of metal. It is supplied to the market in a state where it is contained. However, depending on the use of the anion exchange resin, the metal in the resin may be eluted during use to contaminate the product. In general, an anion exchange resin is used after being converted to a free form. If a large amount of metal is contained in the resin at that time, this metal flows out and pollutes the environment. Accordingly, an object of the present invention is to provide a salt type anion exchange resin having a remarkably small metal content.
【0005】[0005]
【課題を解決するための手段】本発明に係る陰イオン交
換樹脂は、モノビニルモノマーとポリビニルモノマーと
の架橋共重合体を母体とし、1級ないし3級アミノ基又
は第4級アンモニウム基をイオン交換基とするものであ
って、イオン交換基が塩型であり、かつ金属含有量が1
00ppm以下であることを特徴とするものである。The anion exchange resin according to the present invention is based on a crosslinked copolymer of a monovinyl monomer and a polyvinyl monomer as a base, and ion-exchanges a primary to tertiary amino group or a quaternary ammonium group. Wherein the ion-exchange group is of a salt type and has a metal content of 1
It is characterized by being at most 00 ppm.
【0006】[0006]
【発明の実施の形態】本発明に係る陰イオン交換樹脂
は、常法に従って陰イオン交換樹脂を製造し、次いで得
られた陰イオン交換樹脂から含有されている金属を溶出
させることにより製造される。先ずモノビニルモノマー
とポリビニルモノマー、通常はスチレンとジビニルベン
ゼン、とを共重合させて架橋共重合体を製造する。モノ
マー混合物に占めるポリビニルモノマーの比率は、陰イ
オン交換樹脂の用途により異なるが、通常は数%(重
量)である。共重合反応は通常は懸濁重合方式で行われ
るが、製品に要求される形状によっては他の重合方式に
よることもできる。BEST MODE FOR CARRYING OUT THE INVENTION The anion exchange resin according to the present invention is produced by producing an anion exchange resin according to a conventional method, and then eluting a contained metal from the obtained anion exchange resin. . First, a crosslinked copolymer is produced by copolymerizing a monovinyl monomer and a polyvinyl monomer, usually styrene and divinylbenzene. The ratio of the polyvinyl monomer in the monomer mixture varies depending on the use of the anion exchange resin, but is usually several% (weight). The copolymerization reaction is usually performed by a suspension polymerization method, but may be performed by another polymerization method depending on the shape required for a product.
【0007】得られた架橋共重合体には、イオン交換基
を導入する前段階として、先ずハロアルキル基を導入す
る。通常は共重合体を乾燥したのち、ベンゼン、トルエ
ン、二塩化エタンなどの架橋共重合体を膨潤させること
のできる溶媒中で、触媒の存在下にクロロメチルメチル
エーテルを反応させ、架橋共重合体にクロロメチル基を
導入する。触媒としては塩化亜鉛、塩化鉄、塩化アルミ
ニウム、塩化錫などのルイス酸が用いられる。ハロアル
キル基が導入された架橋共重合体は、水洗して残留して
いるクロロメチルメチルエーテルや触媒などを除去した
のち、アンモニア又はアミンを反応させて、ハロアルキ
ル基のハロゲン原子とアンモニア又はアミンの窒素原子
とを置換させる。通常はトリメチルアミン又はジメチル
エタノールアミンを反応させ、第4級アンモニウム基を
有する強塩基性陰イオン交換樹脂とする。A haloalkyl group is first introduced into the obtained crosslinked copolymer as a step prior to introducing an ion exchange group. Usually, after drying the copolymer, chloromethyl methyl ether is reacted in the presence of a catalyst in a solvent capable of swelling the cross-linked copolymer such as benzene, toluene, and ethane dichloride, and the cross-linked copolymer is reacted. To introduce a chloromethyl group. As the catalyst, a Lewis acid such as zinc chloride, iron chloride, aluminum chloride, and tin chloride is used. The haloalkyl group-introduced cross-linked copolymer is washed with water to remove residual chloromethyl methyl ether and catalyst, and then reacted with ammonia or an amine to react the halogen atom of the haloalkyl group with the nitrogen of the ammonia or amine. Replace with atom. Usually, trimethylamine or dimethylethanolamine is reacted to obtain a strongly basic anion exchange resin having a quaternary ammonium group.
【0008】この陰イオン交換樹脂中には、触媒由来の
金属が数百〜数千ppm含まれており、水洗するだけで
はその含有量はあまり低下しない。また、一般にゲル型
樹脂よりもポーラス型樹脂、特に乾燥状態における比表
面積が5m2/g以上の高比表面積の樹脂の方が、金属
含有量が多い傾向がある。[0008] The anion exchange resin contains several hundred to several thousand ppm of a metal derived from a catalyst, and its content does not decrease so much only by washing with water. Generally, a porous resin, particularly a resin having a high specific surface area of 5 m 2 / g or more in a dry state, tends to have a higher metal content than a gel resin.
【0009】本発明では、この多量の金属を含有する陰
イオン交換樹脂を酸水溶液で洗浄することにより、その
金属含有量を100ppm以下まで低下させる。酸水溶
液としては通常は塩酸を用いるが、硫酸などを用いても
よい。洗浄は陰イオン交換樹脂をカラムに充填し、これ
に酸水溶液を常温で通液するだけでよい。酸水溶液とし
ては通常は5N以下、好ましくは1〜2Nのものを用い
る。通液速度は0.1〜5hr-1程度が好ましい。通液
量は通常は1BV(BED VOLUME)以上であ
り、具体的には陰イオン交換樹脂の金属含有量をどこま
で低減させるかにより決定すればよい。通液量を増すこ
とにより金属含有量を10ppm以下にすることは容易
であり、所望ならば金属含有量を5ppm以下とか3p
pm以下とかの極微量にまで低減させることもできる。
酸水溶液の通液により所望のレベルにまで金属含有量を
低下させたならば、引続き酸水溶液を純水に切替えて通
液し、残留している酸を除去して製品の陰イオン交換樹
脂とする。なお、酸水溶液で洗浄する代りに、苛性ソー
ダ水溶液などのアルカリ性水溶液で洗浄しても金属含有
量を低減させることはできるが、樹脂が遊離型となるの
で塩型に再転換しなければならず、操作上不利である。In the present invention, the metal content of the anion exchange resin containing a large amount of metal is reduced to 100 ppm or less by washing with an aqueous acid solution. Usually, hydrochloric acid is used as the acid aqueous solution, but sulfuric acid or the like may be used. For washing, it is only necessary to fill the column with an anion exchange resin and pass an acid aqueous solution through the column at room temperature. As the aqueous acid solution, an aqueous solution of 5 N or less, preferably 1 to 2 N is used. The liquid passing speed is preferably about 0.1 to 5 hr -1 . The flow rate is usually 1 BV (BED VOLUME) or more, and more specifically, may be determined depending on how much the metal content of the anion exchange resin is reduced. It is easy to reduce the metal content to 10 ppm or less by increasing the flow rate.
pm or less.
If the metal content is reduced to a desired level by passing the acid aqueous solution, the acid aqueous solution is subsequently switched to pure water and passed through, the remaining acid is removed, and the product is anion exchange resin. I do. In addition, instead of washing with an aqueous acid solution, the metal content can be reduced by washing with an alkaline aqueous solution such as an aqueous caustic soda solution, but since the resin is free, it must be converted back to a salt form. Operationally disadvantageous.
【0010】[0010]
【実施例】以下に実施例により本発明を更に具体的に説
明する。 実施例1 スチレンと工業用ジビニルベンゼンとを懸濁重合させ
て、ポーラス型の架橋共重合体を得た(平均粒径680
μm、比表面積40m2/g、ジビニルベンゼン含有量
6重量%)。この架橋共重合体100gをガラス製フラ
スコに入れ、クロロメチルメチルエーテル315mLを
加えて、室温で1時間撹拌して膨潤させた。これに塩化
亜鉛51gを添加し、室温で30分間撹拌したのち2時
間かけて50℃まで昇温させ、この温度で8時間保持し
てクロロメチル化反応を行わせた。フラスコを室温まで
冷却したのち純水500mLを4時間かけて添加し、触
媒を失活させると共に未反応のクロロメチルメチルエー
テルを分解した。濾過してクロロメチル化された共重合
体を回収し、よく水洗した。The present invention will be described more specifically with reference to the following examples. Example 1 Styrene and industrial divinylbenzene were subjected to suspension polymerization to obtain a porous crosslinked copolymer (average particle size: 680).
μm, specific surface area 40 m 2 / g, divinylbenzene content 6% by weight). 100 g of the crosslinked copolymer was placed in a glass flask, 315 mL of chloromethyl methyl ether was added, and the mixture was stirred at room temperature for 1 hour to swell. To this, 51 g of zinc chloride was added, and the mixture was stirred at room temperature for 30 minutes, heated to 50 ° C. over 2 hours, and kept at this temperature for 8 hours to perform a chloromethylation reaction. After cooling the flask to room temperature, 500 mL of pure water was added over 4 hours to deactivate the catalyst and decompose unreacted chloromethyl methyl ether. The chloromethylated copolymer was recovered by filtration and washed well with water.
【0011】このクロロメチル化された架橋共重合体1
00g、トルエン230mL及び純水380mLをガラ
ス製フラスコに入れ、50℃で1時間撹拌して膨潤させ
たのち放冷した。次いでトリメチルアミンの30%水溶
液226mLを加え、2時間かけて50℃まで昇温さ
せ、この温度で8時間保持してアミノ化反応を行わせ
た。蒸留してトルエンを留去し、架橋共重合体にトリメ
チルアンモニウムメチル基が結合した陰イオン交換樹脂
を取得した。The chloromethylated crosslinked copolymer 1
00 g, 230 mL of toluene and 380 mL of pure water were placed in a glass flask, stirred at 50 ° C. for 1 hour to swell, and then allowed to cool. Next, 226 mL of a 30% aqueous solution of trimethylamine was added, the temperature was raised to 50 ° C. over 2 hours, and the temperature was maintained at this temperature for 8 hours to perform an amination reaction. The toluene was distilled off by distillation to obtain an anion exchange resin in which a trimethylammonium methyl group was bonded to the crosslinked copolymer.
【0012】この樹脂をガラスカラムに充填し、2N−
塩酸20BVを5.7時間かけて室温で通液し、含有さ
れている金属を溶出させたのち水洗した。この陰イオン
交換樹脂約1gを秤量して石英三角フラスコに入れ、こ
れに濃硫酸9g、濃硝酸約13mL及び30%過酸化水
素水約1.5mLを加え、加熱して樹脂を湿式分解し
た。次いで分解物に純水を加えて50mLとし、ICP
で亜鉛の含有量を測定した。樹脂の亜鉛含有量は1pp
m(乾量基準)であった。なお、2N−塩酸で洗浄する
前の樹脂中の亜鉛含有量は1290ppmであった。This resin is filled in a glass column, and 2N-
20 BV of hydrochloric acid was passed through at room temperature for 5.7 hours to elute the contained metal, followed by washing with water. About 1 g of this anion exchange resin was weighed and placed in a quartz Erlenmeyer flask, to which 9 g of concentrated sulfuric acid, about 13 mL of concentrated nitric acid and about 1.5 mL of 30% hydrogen peroxide solution were added, and the resin was wet-decomposed by heating. Then, pure water was added to the decomposed product to make 50 mL, and ICP
Was used to measure the zinc content. Resin zinc content is 1pp
m (dry basis). The zinc content in the resin before washing with 2N-hydrochloric acid was 1290 ppm.
【0013】実施例2 実施例1において、クロルメチル化反応の触媒として塩
化亜鉛51gの代りに塩化第2鉄60gを用いた以外
は、実施例1と全く同様にして架橋共重合体にトリメチ
ルアンモニウムメチル基が結合した陰イオン交換樹脂を
得た。この樹脂の鉄含有量は964ppmであった。ま
たこの樹脂を実施例1と全く同様にして2N−塩酸で洗
浄したものの鉄含有量は1ppm以下であった。Example 2 A cross-linked copolymer was prepared in the same manner as in Example 1 except that 60 g of ferric chloride was used instead of 51 g of zinc chloride as a catalyst for the chloromethylation reaction. An anion exchange resin with attached groups was obtained. The iron content of this resin was 964 ppm. The resin was washed with 2N hydrochloric acid in exactly the same manner as in Example 1, but the iron content was 1 ppm or less.
フロントページの続き (72)発明者 舘 正雄 北九州市八幡西区黒崎城石1番1号 三菱 化学株式会社黒崎事業所内 Fターム(参考) 4J100 AB02P AB16Q CA04 CA23 CA31 GC04 HA27 HA31 JA16Continued on the front page (72) Inventor Masao Tate 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu-shi F-term in the Kurosaki Plant of Mitsubishi Chemical Corporation (reference) 4J100 AB02P AB16Q CA04 CA23 CA31 GC04 HA27 HA31 JA16
Claims (6)
ーとの架橋共重合体を母体とし、1級ないし3級アミノ
基又は第4級アンモニウム基をイオン交換基とする陰イ
オン交換樹脂であって、イオン交換基が塩型であり、か
つ金属含有量が100ppm以下であることを特徴とす
る陰イオン交換樹脂。1. An anion exchange resin comprising a crosslinked copolymer of a monovinyl monomer and a polyvinyl monomer as a base and a primary to tertiary amino group or a quaternary ammonium group as an ion exchange group. Is a salt type and has a metal content of 100 ppm or less.
を特徴とする請求項1記載の陰イオン交換樹脂。2. The anion exchange resin according to claim 1, wherein the metal content is 10 ppm or less.
特徴とする請求項1記載の陰イオン交換樹脂。3. The anion exchange resin according to claim 1, wherein the metal content is 5 ppm or less.
あることを特徴とする請求項1ないし3のいずれかに記
載の陰イオン交換樹脂。4. The anion exchange resin according to claim 1, wherein a counter ion of the ion exchange group is a chloride ion.
又は2−ヒドロキシエチル基である)で表される第4級
アンモニウム基であることを特徴とする請求項1ないし
4のいずれかに記載の陰イオン交換樹脂。5. An ion-exchange group represented by the formula (1): 5. A quaternary ammonium group represented by the formula: wherein R 1 and R 2 are methyl groups and R 3 is a methyl group or a 2-hydroxyethyl group. The anion exchange resin according to any one of the above.
ーとを共重合させて架橋共重合体を生成させる共重合工
程、得られた架橋共重合体にルイス酸の存在下にハロア
ルキル基を導入するハロアルキル化工程、ハロアルキル
基の導入された架橋共重合体にアミンを反応させてハロ
ゲンイオン型の陰イオン交換樹脂を生成させるイオン交
換基導入工程、及び得られた陰イオン交換樹脂を酸水溶
液で洗浄して含有している金属を除去する酸洗浄工程、
の各工程を経ることを特徴とする請求項1ないし5のい
ずれかに記載の陰イオン交換樹脂の製造方法。6. A copolymerization step of copolymerizing a monovinyl monomer and a polyvinyl monomer to form a crosslinked copolymer, a haloalkylation step of introducing a haloalkyl group into the obtained crosslinked copolymer in the presence of a Lewis acid, An ion-exchange group-introducing step of reacting an amine with the cross-linked copolymer into which the haloalkyl group has been introduced to form a halide-type anion-exchange resin, and containing the resulting anion-exchange resin by washing with an aqueous acid solution. Acid washing step to remove the metal
The method for producing an anion exchange resin according to any one of claims 1 to 5, wherein
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JP2000312063A JP3982166B2 (en) | 2000-10-12 | 2000-10-12 | Anion exchange resin |
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JP2000312063A JP3982166B2 (en) | 2000-10-12 | 2000-10-12 | Anion exchange resin |
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JP3982166B2 JP3982166B2 (en) | 2007-09-26 |
Family
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007297456A (en) * | 2006-04-28 | 2007-11-15 | Osaka Prefecture Univ | Modification method of crosslinked organic polymer |
JP2007297455A (en) * | 2006-04-28 | 2007-11-15 | Osaka Prefecture Univ | Modification method of crosslinked organic polymer |
JP2009112944A (en) * | 2007-11-06 | 2009-05-28 | Kurita Water Ind Ltd | Ultrapure water production method and apparatus, and washing method and apparatus for electronic component members |
JP2012157864A (en) * | 2007-04-19 | 2012-08-23 | Kurita Water Ind Ltd | Method for producing anion exchange resin, anion exchange resin, mixed bed resin, and method for producing ultra-pure water for cleaning electronic component/material |
CN109641206A (en) * | 2016-08-30 | 2019-04-16 | 罗门哈斯公司 | Low sodium resin |
JP2020517276A (en) * | 2017-04-28 | 2020-06-18 | ダウ グローバル テクノロジーズ エルエルシー | Treatment of sugar solution |
-
2000
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007297456A (en) * | 2006-04-28 | 2007-11-15 | Osaka Prefecture Univ | Modification method of crosslinked organic polymer |
JP2007297455A (en) * | 2006-04-28 | 2007-11-15 | Osaka Prefecture Univ | Modification method of crosslinked organic polymer |
JP2012157864A (en) * | 2007-04-19 | 2012-08-23 | Kurita Water Ind Ltd | Method for producing anion exchange resin, anion exchange resin, mixed bed resin, and method for producing ultra-pure water for cleaning electronic component/material |
JP2009112944A (en) * | 2007-11-06 | 2009-05-28 | Kurita Water Ind Ltd | Ultrapure water production method and apparatus, and washing method and apparatus for electronic component members |
CN109641206A (en) * | 2016-08-30 | 2019-04-16 | 罗门哈斯公司 | Low sodium resin |
JP2019531370A (en) * | 2016-08-30 | 2019-10-31 | ローム アンド ハース カンパニーRohm And Haas Company | Low sodium resin |
JP2020517276A (en) * | 2017-04-28 | 2020-06-18 | ダウ グローバル テクノロジーズ エルエルシー | Treatment of sugar solution |
JP7032435B2 (en) | 2017-04-28 | 2022-03-08 | ダウ グローバル テクノロジーズ エルエルシー | Treatment of sugar solution |
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