JPH0722711B2 - Anion exchange resin and method for producing the same - Google Patents
Anion exchange resin and method for producing the sameInfo
- Publication number
- JPH0722711B2 JPH0722711B2 JP61134530A JP13453086A JPH0722711B2 JP H0722711 B2 JPH0722711 B2 JP H0722711B2 JP 61134530 A JP61134530 A JP 61134530A JP 13453086 A JP13453086 A JP 13453086A JP H0722711 B2 JPH0722711 B2 JP H0722711B2
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- Prior art keywords
- anion exchange
- exchange resin
- copolymer
- group
- amination
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、新規な構造を有する陰イオン交換樹脂および
その製造方法に関するものであり、詳しくは１級アミノ
基から４級アンモニウム基までの陰イオン交換基をクロ
ルメチル化（以下CM化と略記）工程をへることなく容易
に導入することができる製造方法及びそれにより製造さ
れた化学的安定性にすぐれた陰イオン交換樹脂に関する
ものである。Description: TECHNICAL FIELD The present invention relates to an anion exchange resin having a novel structure and a method for producing the same, and more specifically to anions from a primary amino group to a quaternary ammonium group. The present invention relates to a production method in which an ion exchange group can be easily introduced without a chloromethylation (hereinafter referred to as CM) step, and an anion exchange resin produced by the method and having excellent chemical stability.
従来、スチレン単位を有する陰イオン交換樹脂として
は、架橋共重合体の芳香環に、一般式（３）又は（４）
で表わされる官能基を結合したものがよく知られてい
る。Conventionally, as an anion exchange resin having a styrene unit, a general formula (3) or (4) is added to the aromatic ring of the cross-linked copolymer.
It is well known that a functional group represented by is bonded.
このような陰イオン交換樹脂の製造方法として、従来広
く行なわれているのは、架橋ポリスチレンをクロルメチ
ルメチルエーテル（以下CMEと略記）でCM化した後、ア
ミンと反応させてアミノ化する方法である。この方法で
用いられるCME中には、発ガン物質であるビスクロルメ
チルエーテルが不純物として含まれているため、作業環
境の整備、廃液の処理等、厳重な管理の基で、CM化を行
なう必要があつた。また、CM化の触媒として塩化亜鉛等
の重金属を用いると、触媒を分解した後、重金属を回収
せねばならないという問題があつた。 As a method of producing such an anion exchange resin, a method that has been widely performed conventionally is a method of converting crosslinked polystyrene into CM with chloromethyl methyl ether (hereinafter abbreviated as CME), and then reacting with amine to aminate. is there. Since CME used in this method contains bischloromethyl ether, a carcinogen, as an impurity, it is necessary to convert it into CM under strict control such as maintenance of working environment and treatment of waste liquid. I got it. In addition, when a heavy metal such as zinc chloride is used as a catalyst for commercialization, there is a problem that the heavy metal must be recovered after the catalyst is decomposed.
このCM化工程をへることのない陰イオン交換樹脂の製造
方法として、いくつかの方法が試みられている。例え
ば、架橋ポリスチレンとアリルクロライド等を反応し
て、クロルエチル基を導入した後アミノ化する方法が行
なわれているが、十分な交換容量を持つものが得られて
いない。架橋ポリスチレンを、Ｎ−メチル−Ｎ−クロロ
メチルアセトアミドや、Ｎ−メチロイルアセトアミド、
Ｎ−クロロメチルフタルイミド等々のアミノ化試薬によ
り、直接アミノ化する方法も行なわれているが、この方
法では、主に１級アミンしか得られず、３級アミン、４
級アンモニウム基を導入するためには、アミノ化後更に
アルキル化反応を行なう必要があり、工程が長くなる欠
点を有する。モノマーとして、スチレンの代りにクロル
メチルスチレン（以下CMSと略記、別称ビニルベンジル
クロライド）を用いて、架橋剤と共重合した後、得られ
た架橋ポリクロルメチルスチレンをアミノ化する方法も
行なわれているが、CMSを用いる懸濁重合は、分散媒で
ある水相が酸性になる、球状ポリマーを得にくい等、ス
チレンを用いる場合に比べ、重合工程の管理が難しい。Several methods have been attempted as a method for producing an anion exchange resin that does not go through the CM process. For example, a method in which crosslinked polystyrene is reacted with allyl chloride or the like to introduce a chloroethyl group and then amination is carried out, but one having a sufficient exchange capacity has not been obtained. Cross-linked polystyrene is treated with N-methyl-N-chloromethylacetamide, N-methyloylacetamide,
Although a method of directly aminating with an aminating reagent such as N-chloromethylphthalimide has also been carried out, only a primary amine is mainly obtained by this method, and a tertiary amine,
In order to introduce a primary ammonium group, it is necessary to carry out a further alkylation reaction after amination, which has the drawback of lengthening the process. As a monomer, chloromethylstyrene (hereinafter abbreviated as CMS, also called vinylbenzyl chloride) instead of styrene is used, and after copolymerizing with a crosslinking agent, a method of aminating the obtained crosslinked polychloromethylstyrene is also performed. However, suspension polymerization using CMS is more difficult to control the polymerization process than when styrene is used, because the aqueous phase that is the dispersion medium becomes acidic, and it is difficult to obtain spherical polymers.
本発明になる陰イオン交換樹脂の官能基〔１〕、〔２〕
と類似した官能基を持つ陰イオン交換樹脂として、（メ
タ）アクリル酸グリシジルエステルの架橋共重合体とア
ミンを反応させて得られる陰イオン交換樹脂が知られて
いる。しかし、この樹脂は、骨格構造にエステル構造を
有するため、加水分解を受けやすい欠点があつた。得に
アルカリには弱く、架橋ポリ（メタ）アクリル酸グリシ
ジルエステルと３級アミンとを反応させて得られる４級
アンモニウム型の強塩基性樹脂は、水溶液中で放置する
と、自己加水分解を起してしまうという大きな欠点があ
つた。Functional groups [1] and [2] of the anion exchange resin according to the present invention
As an anion exchange resin having a functional group similar to that described above, an anion exchange resin obtained by reacting a crosslinked copolymer of glycidyl acrylate (meth) acrylate with an amine is known. However, since this resin has an ester structure in the skeleton structure, it has a drawback that it is susceptible to hydrolysis. In particular, it is weak against alkali, and a quaternary ammonium type strong basic resin obtained by reacting a crosslinked poly (meth) acrylic acid glycidyl ester with a tertiary amine causes self-hydrolysis when left in an aqueous solution. There was a big drawback that it would end up.
このように、現在までに知られている陰イオン交換樹脂
で、化学的安定性にすぐれ、容易に製造可能な陰イオン
交換樹脂は知られていなかつた。As described above, there is no known anion exchange resin which has been known to date and which has excellent chemical stability and can be easily produced.
本発明の目的は、化学的に安定であり、かつ、製造方法
の容易な陰イオン交換樹脂及びその製造方法を提供する
ことである。すなわち、化学的安定性にすぐれた架橋ポ
リスチレンに、CM化工程をへることなく、アミノ基又は
４級アンモニウム基を結合してなる陰イオン交換樹脂及
び該樹脂を製造する方法を提供するものである。An object of the present invention is to provide an anion exchange resin which is chemically stable and easy to produce, and a production method thereof. That is, it is intended to provide an anion exchange resin obtained by bonding an amino group or a quaternary ammonium group to a crosslinked polystyrene having excellent chemical stability without going through a CM formation step, and a method for producing the resin. is there.
本発明の陰イオン交換樹脂はスチレン単位を有する架橋
共重合体の芳香環に下記一般式〔１〕又は〔２〕で表わ
される官能基を結合してなる陰イオン交換樹脂である。The anion exchange resin of the present invention is an anion exchange resin obtained by bonding a functional group represented by the following general formula [1] or [2] to an aromatic ring of a crosslinked copolymer having a styrene unit.
（式中、ｍ、ｎは０〜６の整数、R1、R2、R3は水素、ア
ルキル基又はヒドロキシアルキル基を示す。） その製造方法としては、下記一般式〔３〕で表わされる
グリシジル基を有するスチレン誘導体を架橋剤と共重合
させた後、得られた共重合体のグリシジル基をアンモニ
ア又はアミンと反応させることにより、アミノ基又は４
級アンモニウム基を有する架橋ポリスチレン誘導体とし
ての陰イオン交換樹脂を得る方法による。 (In the formula, m and n are integers of 0 to 6, and R 1 , R 2 and R 3 represent hydrogen, an alkyl group or a hydroxyalkyl group.) The production method thereof is represented by the following general formula [3]. After copolymerizing a styrene derivative having a glycidyl group with a cross-linking agent, the glycidyl group of the resulting copolymer is reacted with ammonia or an amine to give an amino group or 4
By a method of obtaining an anion exchange resin as a crosslinked polystyrene derivative having a primary ammonium group.
（式中、ｍ及びｎは０〜６の整数、Ｒは水素又はアルキ
ル基を示す。） 以下、本発明の構成要素を詳細に説明する。 (In the formula, m and n are integers of 0 to 6, and R represents hydrogen or an alkyl group.) Hereinafter, the constituent elements of the present invention will be described in detail.
本発明で用いられる一般式〔３〕で表わされるグリシジ
ル基を有するスチレン誘導体としてはビニルベンジルグ
リシジルエーテル、メチルビニルベンジルグリシジルエ
ーテル、ビニルフエニルブチルグリシジルエーテル、ビ
ニルベンジルオキシエチルグリシジルエーテル、等々が
あげられる。Examples of the styrene derivative having a glycidyl group represented by the general formula [3] used in the present invention include vinylbenzyl glycidyl ether, methylvinylbenzyl glycidyl ether, vinylphenyl butyl glycidyl ether, vinylbenzyloxyethyl glycidyl ether, and the like. .
架橋剤としては、ジビニルベンゼン、ジビニルトルエ
ン、ジビニルナフタレン、エチレングリコールジメタク
リレート、トリメチロールプロパントリ（メタ）アクリ
レート等々のスチレンと共重合しうる二個以上のビニル
基を有する単量体が用いられる。As the cross-linking agent, a monomer having two or more vinyl groups capable of copolymerizing with styrene, such as divinylbenzene, divinyltoluene, divinylnaphthalene, ethylene glycol dimethacrylate, and trimethylolpropane tri (meth) acrylate is used.
グリシジル基を有するスチレン誘導体と架橋剤との共重
合は、公知の懸濁重合により行なうことができる。すな
わち、分散安定剤を含む水相中に、モノマー相としてグ
リシジル基を有するスチレン誘導体、架橋剤、重合開始
剤及び必要に応じ多孔質化剤を含む有機相を分散させた
後、加熱、重合することによりビーズ状の共重合体を得
ることができる。ここで、分散安定剤としては、ゼラチ
ン、ポリビニルアルコール、カルボキシメチルセルロー
ス等々の高分子化合物や、ケイ酸マグネシウム、硫酸カ
ルシウム等の微粉末無機化合物が0.05〜５％の濃度で用
いられる。重合開始剤としては、過酸化ベンゾイルに代
表される過酸化物、アゾビスイソブチロニトリルに代表
されるアゾ化合物等々が単量体に対し0.01〜10重量％用
いられる。多孔質な架橋共重合体を得るためには、モノ
マー相に多孔質化剤を加える必要がある。多孔質化剤と
しては、ヘプタン、オクタン、デカン、シクロヘキサン
等の（シクロ）アルカン、ヘキサノール、ペンタノー
ル、２−エチルヘキサノール等のアルコール等々、モノ
マーは溶かすが線状ポリマーは溶解しない溶媒（貧溶媒
とも言う）を単独で単量体に対し20〜70％で又はトルエ
ン、ジクロロエタン等の線状ポリマーも溶解する溶媒
（良溶媒とも言う）と共に単量体に対し40〜200％で用
いたり、ポリスチレン等の線状ポリマーを単独で単量体
に対し２〜40％又は良溶媒と共に用いたりする。重合反
応は、主に窒素雰囲気下で、50〜90℃で５〜24時間加熱
することにより行なわれる。The copolymerization of the styrene derivative having a glycidyl group and the crosslinking agent can be carried out by a known suspension polymerization. That is, in a water phase containing a dispersion stabilizer, a styrene derivative having a glycidyl group as a monomer phase, a cross-linking agent, a polymerization initiator, and an organic phase containing a porosifying agent are dispersed, and then heated and polymerized. As a result, a bead-shaped copolymer can be obtained. Here, as the dispersion stabilizer, polymer compounds such as gelatin, polyvinyl alcohol, carboxymethyl cellulose, etc., and fine powder inorganic compounds such as magnesium silicate, calcium sulfate, etc. are used at a concentration of 0.05 to 5%. As the polymerization initiator, a peroxide represented by benzoyl peroxide, an azo compound represented by azobisisobutyronitrile, or the like is used in an amount of 0.01 to 10% by weight based on the monomer. In order to obtain a porous crosslinked copolymer, it is necessary to add a porosifying agent to the monomer phase. Examples of the porosifying agent include (cyclo) alkanes such as heptane, octane, decane, and cyclohexane, alcohols such as hexanol, pentanol, and 2-ethylhexanol. Solvents in which a monomer dissolves but a linear polymer does not dissolve (also a poor solvent) 20% to 70% of the monomer, or 40 to 200% of the monomer together with a solvent (also called a good solvent) that also dissolves linear polymers such as toluene and dichloroethane, polystyrene, etc. The linear polymer of 1) may be used alone in an amount of 2 to 40% with respect to the monomer or with a good solvent. The polymerization reaction is carried out mainly by heating at 50 to 90 ° C. for 5 to 24 hours under a nitrogen atmosphere.
得られた共重合体のアミノ化に用いられる化合物は、ア
ンモニア、メチルアミン、ジメチルアミン、トリメチル
アミン、エチルアミン、ジエチルアミン、トリエチルア
ミン、エタノールアミン、ジエタノールアミン、トリエ
タノールアミン、ジメチルエタノールアミン、アニリ
ン、エチレンジアミン、ジエチレントリアミン、ポリエ
チレンイミン等々、グリシジル基と反応する、１級アミ
ン、２級アミン、３級アミンであれは、脂肪族系、芳香
族系を問わず、すべてのアミンが使用可能である。The compound used for the amination of the obtained copolymer is ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, aniline, ethylenediamine, diethylenetriamine, As for the primary amine, secondary amine, and tertiary amine that react with glycidyl groups such as polyethyleneimine, all amines can be used regardless of whether they are aliphatic or aromatic.
アミノ化時の溶媒は、使用しなくてもよいが、ジオキサ
ン、エチレンジクロライド、トルエン等の共重合体を膨
潤する溶媒を用いるとアミノ化が容易に進行する。The solvent for the amination may not be used, but if a solvent that swells the copolymer such as dioxane, ethylene dichloride, or toluene is used, the amination will easily proceed.
アミノ化の程度は、アンモニア又はアミンの使用量をコ
ントロールすることにより、コントロールできる。アミ
ノ基をできるだけたくさん入れるためには、共重合体中
のグリシジル基の量の、10〜20倍量のアンモニア又はア
ミンを用いる。The degree of amination can be controlled by controlling the amount of ammonia or amine used. In order to add as many amino groups as possible, 10 to 20 times as much ammonia or amine as the amount of glycidyl groups in the copolymer is used.
アミノ化反応は、20〜90℃で、２〜24時間行なう。The amination reaction is carried out at 20 to 90 ° C for 2 to 24 hours.
アミノ化を終了した樹脂は、グリシジル基の残存をなく
す目的で、１〜10％程度の硫酸を用いて、50〜80℃で１
〜８時間程度加熱して開環反応を行ない、陰イオン交換
樹脂を得る。The resin that has undergone amination is treated with 1 to 10% sulfuric acid at 50 to 80 ° C for the purpose of eliminating the residual glycidyl group.
The ring-opening reaction is carried out by heating for about 8 hours to obtain an anion exchange resin.
以下に、本発明を実施例により更に詳細に説明するが、
本発明はその要旨を超えない限り、以下の実施例に限定
されるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist.
実施例１ A:多孔質架橋ポリビニルベンジルグリシジルエーテルの
合成 撹拌装置と窒素導入管、冷却器及び温度計を取り付けた
500mlの四ツ口フラスコに、分散媒として、ポリビニル
ピロリドン2.5gを含む水275mlを入れ、モノマー相とし
て、ビニルベンジルグリシジルエーテル19g、ジビニル
ベンゼン（純度55％）15.4g、４−メチル−２−ペンタ
ノール28g、オクタン7g、アゾビスイソブチロニトリル
0.7gの混合溶液を分散した。窒素雰囲気下で30分間分散
した後、70℃−24時間重合反応を行なつた。得られた共
重合体ビーズは、過、熱メタノール洗浄後アセトン洗
浄を行ない、60℃で減圧乾燥した。収量は31gであつ
た。Example 1 A: Synthesis of porous cross-linked polyvinyl benzyl glycidyl ether A stirring device, a nitrogen introducing tube, a condenser and a thermometer were attached.
A 500 ml four-necked flask was charged with 275 ml of water containing 2.5 g of polyvinylpyrrolidone as a dispersion medium, and as a monomer phase, 19 g of vinylbenzyl glycidyl ether, 15.4 g of divinylbenzene (purity 55%), 4-methyl-2-pen. 28g Tanol, 7g Octane, Azobisisobutyronitrile
0.7 g of the mixed solution was dispersed. After dispersing for 30 minutes in a nitrogen atmosphere, a polymerization reaction was carried out at 70 ° C for 24 hours. The obtained copolymer beads were washed with excess methanol, hot methanol, and then with acetone, and dried under reduced pressure at 60 ° C. The yield was 31 g.
得られた共重合体ビーズのエポキシ環の含有量を、塩酸
−ジオキサン法により測定したところ、2.5mmol/gであ
つた。The epoxy ring content of the obtained copolymer beads was measured by the hydrochloric acid-dioxane method and found to be 2.5 mmol / g.
B:多孔質架橋ポリビニルベンジルグリシジルエーテルの
アミノ化 撹拌装置、冷却器、温度計を取りつけた三ツ口フラスコ
にＡで得られた共重合体5.0g、ジオキサン50mlを入れ、
アスピレーターを用いて、樹脂から気泡がでなくなるま
で脱気した。その後、ジエタノールアミン25.8gを加
え、撹拌しながら、80℃−24時間アミノ化反応を行なつ
た。アミノ化終了後、樹脂を過し、ジオキサンで洗浄
した後、更にアセトンで洗浄した。B: Amination of porous cross-linked polyvinyl benzyl glycidyl ether 5.0 g of the copolymer obtained in A and 50 ml of dioxane were placed in a three-necked flask equipped with a stirrer, a cooler and a thermometer.
The resin was degassed using an aspirator until the air bubbles disappeared. Thereafter, 25.8 g of diethanolamine was added, and an amination reaction was carried out at 80 ° C. for 24 hours while stirring. After completion of the amination, the resin was filtered, washed with dioxane, and further washed with acetone.
60℃で減圧乾燥した後収量を測定したところ6.2gであつ
た。また、塩酸−ジオキサン法により残存グリシジル基
の定量を行なつたところ、５％であり、反応率は95％で
あることがわかつた。After drying under reduced pressure at 60 ° C., the yield was measured and found to be 6.2 g. Further, when the residual glycidyl group was quantified by the hydrochloric acid-dioxane method, it was found to be 5% and the reaction rate was 95%.
実施例２ A:多孔質架橋ポリビニルベンジルグリシジルエーテルの
合成 撹拌装置と窒素導入管、冷却器及び温度計を取りつけた
四ツ口フラスコに、分散媒として、ポリビニルアルコー
ル1.5gを含む水300mlを入れ、モノマー相として、ビニ
ルベンジルグリシジルエーテル20g、ジビニルベンゼン
（純度56％）20g、ｎ−ヘプタン15g、2,2′−アゾビス
−2,4−ジメチルバレロニトリル0.2gの混合溶液を分散
した。窒素雰囲気下で30分間分散した後、70℃−８時間
重合反応を行なつた。得られた共重合体ビーズは、
過、水洗後、アセトンで洗浄した後、室温で減圧乾燥し
た。収量は32gであつた。Example 2 A: Synthesis of porous cross-linked polyvinyl benzyl glycidyl ether In a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a condenser and a thermometer, 300 ml of water containing 1.5 g of polyvinyl alcohol was placed as a dispersion medium, As a monomer phase, a mixed solution of 20 g of vinylbenzyl glycidyl ether, 20 g of divinylbenzene (purity 56%), 15 g of n-heptane and 0.2 g of 2,2'-azobis-2,4-dimethylvaleronitrile was dispersed. After dispersing for 30 minutes in a nitrogen atmosphere, a polymerization reaction was carried out at 70 ° C. for 8 hours. The obtained copolymer beads are
After washing with water, washing with acetone, and drying under reduced pressure at room temperature. The yield was 32 g.
B:多孔質架橋ポリビニルベンジルグリシジルエーテルの
アミノ化 撹拌装置、冷却器、温度計を取りつけた三ツ口フラスコ
にＡで得られた共重合体5.0g、ジオキサン50ml、ジエチ
アミン15gを加え、撹拌しながら、80℃−８時間反応を
行なつた。アミノ化反応終了後、樹脂を過し、ジオキ
サン、水で洗浄した。次いで、残存するエポキシ環をな
くすため、次の開環反応を行なつた。B: Amination of porous cross-linked polyvinyl benzyl glycidyl ether To a three-necked flask equipped with a stirrer, a condenser and a thermometer, 5.0 g of the copolymer obtained in A, 50 ml of dioxane and 15 g of diethylamine were added, and the mixture was stirred at 80 The reaction was carried out at -8 hours. After completion of the amination reaction, the resin was filtered and washed with dioxane and water. Then, in order to eliminate the remaining epoxy ring, the following ring opening reaction was carried out.
アミノ化終了した樹脂を希硫酸と接触させ硫酸塩とした
後、10％硫酸50mlを加え、60℃−５時間加熱した。得ら
れた樹脂は、水洗後希水酸化ナトリウムにより再生し、
十分に水洗を行なつた。このようにして得られた弱塩基
性陰イオン交換樹脂の交換容量（塩酸吸着容量）を測定
したところ、1.6meq/gであつた。The resin after amination was brought into contact with diluted sulfuric acid to form a sulfate, 50 ml of 10% sulfuric acid was added, and the mixture was heated at 60 ° C. for 5 hours. The resulting resin is washed with water and regenerated with diluted sodium hydroxide,
It was washed thoroughly with water. When the exchange capacity (hydrochloric acid adsorption capacity) of the weakly basic anion exchange resin thus obtained was measured, it was 1.6 meq / g.
実施例３ 多孔質架橋ポリビニルベンジルグリシジルエーテルのア
ミノ化； 実施例２・Ａで得られた共重合体ビーズ5.0gを、30％ト
リメチルアミン40mlと30℃−４時間、50℃−４時間で反
応させた。反応操作は、実施例２・Ｂと同様にして行な
つた。Example 3 Amination of Porous Crosslinked Polyvinyl benzyl glycidyl ether; 5.0 g of the copolymer beads obtained in Example 2A were reacted with 40 ml of 30% trimethylamine at 30 ° C for 4 hours and 50 ° C for 4 hours. It was The reaction operation was performed in the same manner as in Example 2B.
得られた４級アンモニウム型強塩基性陰イオン交換樹脂
の中性塩分解能を測定したところ、1.3meq/gであつた。The neutral salt decomposing ability of the obtained quaternary ammonium type strongly basic anion exchange resin was measured and found to be 1.3 meq / g.
実施例４ 多孔質架橋ポリビニルベンジルグリシジルエーテルのア
ミノ化； 実施例２・Ａで得られた共重合体ビーズ5.0gを、28％ア
ンモニア水30mlと30℃−４時間、60℃−４時間で反応さ
せた。反応操作は、実施例２・Ｂと同様にして行なつ
た。Example 4 Amination of porous cross-linked polyvinyl benzyl glycidyl ether; 5.0 g of the copolymer beads obtained in Example 2A were reacted with 30 ml of 28% ammonia water at 30 ° C for 4 hours and 60 ° C for 4 hours. Let The reaction operation was performed in the same manner as in Example 2B.
得られた弱塩基性陰イオン交換樹脂の交換容量（塩酸吸
着容量）を測定したところ、1.2meq/gであつた。The exchange capacity (hydrochloric acid adsorption capacity) of the obtained weakly basic anion exchange resin was measured and found to be 1.2 meq / g.
実施例５ A:架橋ポリビニルベンジルグリシジルエーテルの合成 モノマー相として、ビニルベンジルグリシジルエーテル
10g、ジビニルベンゼン（純度56％）2.5g、トルエン6.2
g、2,2′−アゾビス−2,4−ジメチルバレロニトリル0.1
gの混合溶液を用い0.5％ポリビニルアルコール水100ml
を用いた以外は実施例２・Ａと同様に重合を行なつた。
得られた共重合体ビーズは過、水洗、アセトン洗浄
後、ジオキサンと接触させ、アセトンとジオキサンの置
換を行なつた。Example 5 A: Synthesis of crosslinked polyvinylbenzyl glycidyl ether As a monomer phase, vinylbenzyl glycidyl ether was used.
10g, divinylbenzene (purity 56%) 2.5g, toluene 6.2
g, 2,2'-azobis-2,4-dimethylvaleronitrile 0.1
100 ml of 0.5% polyvinyl alcohol water using a mixed solution of g
Polymerization was carried out in the same manner as in Example 2 · A except that was used.
The obtained copolymer beads were washed with water, washed with water, and washed with acetone, and then contacted with dioxane to replace acetone with dioxane.
B:架橋ポリビニルベンジルグリシジルエーテルのアミノ
化 Ａで得られたジオキサンを含む共重合体ビーズ10gを、
ジエチルアミン15gと反応した。反応操作は、実施例２
・Ｂと同様にして行なつた。B: Amination of cross-linked polyvinyl benzyl glycidyl ether 10 g of dioxane-containing copolymer beads obtained in A,
Reacted with 15 g of diethylamine. The reaction procedure is described in Example 2.
・ Same as B.
得られた弱塩基性陰イオン交換樹脂の交換容量（塩酸吸
着容量）を測定したところ3.2meq/gであつた。The exchange capacity (hydrochloric acid adsorption capacity) of the obtained weakly basic anion exchange resin was measured and found to be 3.2 meq / g.
本発明によれば、化学的に安定な新規陰イオン交換樹脂
を容易に製造することができる。According to the present invention, a chemically stable new anion exchange resin can be easily produced.
Claims (2)
て、該共重合体の芳香環に、下記一般式〔１〕又は
〔２〕で表わされる官能基を結合してなる陰イオン交換
樹脂 （前記一般式中、ｍ及びｎは０〜６の整数、R1、R2、R3
は水素、アルキル基、又はヒドロキシアルキル基を示
す。）1. A crosslinked copolymer having a styrene unit, wherein an anion exchange resin having a functional group represented by the following general formula [1] or [2] bonded to an aromatic ring of the copolymer. (In the general formula, m and n are integers of 0 to 6, R 1 , R 2 and R 3
Represents hydrogen, an alkyl group, or a hydroxyalkyl group. )
基を有するスチレン誘導体を二個以上のビニル基を有す
る単量体と共重合させた後、得られた共重合体のグリシ
ジル基を、アンモニア又はアミンと反応させることを特
徴とする陰イオン交換樹脂の製造方法。 （式中、ｍ及びｎは０〜６の整数、Ｒは水素又はアルキ
ル基を示す。）2. A styrene derivative having a glycidyl group represented by the following general formula [3] is copolymerized with a monomer having two or more vinyl groups, and the glycidyl group of the obtained copolymer is A method for producing an anion exchange resin, which comprises reacting with ammonia or amine. (In the formula, m and n are integers of 0 to 6, and R represents hydrogen or an alkyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61134530A JPH0722711B2 (en) | 1986-06-10 | 1986-06-10 | Anion exchange resin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61134530A JPH0722711B2 (en) | 1986-06-10 | 1986-06-10 | Anion exchange resin and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62289238A JPS62289238A (en) | 1987-12-16 |
| JPH0722711B2 true JPH0722711B2 (en) | 1995-03-15 |
Family
ID=15130471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61134530A Expired - Lifetime JPH0722711B2 (en) | 1986-06-10 | 1986-06-10 | Anion exchange resin and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0722711B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2735693B2 (en) * | 1990-12-17 | 1998-04-02 | 株式会社トクヤマ | Anion exchanger |
| DE69522483T2 (en) * | 1994-03-01 | 2002-04-25 | Mitsubishi Chem Corp | Method of demineralizing water or an aqueous liquid |
| US20210237034A1 (en) * | 2018-08-31 | 2021-08-05 | Showa Denko K.K. | Packing material for ion chromatography and production method therefor |
| CN112546873A (en) * | 2020-12-31 | 2021-03-26 | 山东天维膜技术有限公司 | Bipolar membrane and preparation method thereof |
-
1986
- 1986-06-10 JP JP61134530A patent/JPH0722711B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62289238A (en) | 1987-12-16 |
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