JPH09201539A - Ion exchange resin purification method - Google Patents
Ion exchange resin purification methodInfo
- Publication number
- JPH09201539A JPH09201539A JP8013723A JP1372396A JPH09201539A JP H09201539 A JPH09201539 A JP H09201539A JP 8013723 A JP8013723 A JP 8013723A JP 1372396 A JP1372396 A JP 1372396A JP H09201539 A JPH09201539 A JP H09201539A
- Authority
- JP
- Japan
- Prior art keywords
- water
- exchange resin
- ion exchange
- organic solvent
- ion
- 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.)
- Granted
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyethers (AREA)
Abstract
(57)【要約】
【課題】 イオン交換樹脂中の微量の水溶性不純物を効
率よく除去する。
【解決手段】 イオン交換樹脂を水洗することにより膨
潤させ、次いでこれに水溶性有機溶媒を接触させて膨潤
時の体積の２／３以下に収縮させることにより、内部の
不純物を樹脂外に排出させる。(57) [Abstract] [PROBLEMS] To efficiently remove a trace amount of water-soluble impurities in an ion exchange resin. SOLUTION: The ion exchange resin is swollen by washing with water, and then a water-soluble organic solvent is brought into contact with the ion exchange resin to shrink the volume to 2/3 or less of the volume at the time of swelling, thereby discharging impurities inside the resin. .
Description
【０００１】[0001]
【発明の属する技術分野】本発明はイオン交換樹脂から
水溶性不純物を除去する方法に関するものであり、特に
経口医薬品として用いられるイオン交換樹脂中に、水洗
後に残存している水溶性不純物を効率よく除去する方法
に関するものである。TECHNICAL FIELD The present invention relates to a method for removing water-soluble impurities from ion exchange resins, and particularly to efficiently removing water-soluble impurities remaining after washing with water in ion exchange resins used as oral pharmaceuticals. It concerns the method of removal.
【０００２】[0002]
【従来の技術】イオン交換樹脂が経口投与用の医薬とし
て有用であることは従来から知られている。例えばスチ
レン−ジビニルベンゼン架橋共重合体をスルホン化して
なる陽イオン交換樹脂は、高カリウム血症の治療薬とし
て有効であるとされている。また、陰イオン交換樹脂が
コレステロール低下剤として有効であるとされている。
コレステロール低下剤として用いられている陰イオン交
換樹脂の代表的なものはコレスチラミンであり、このも
のはスチレン−ジビニルベンゼン架橋共重合体をハロア
ルキル化し、これに脂肪族第３級アミンを反応させるこ
とにより製造される。このコレスチラミンは、原料であ
る脂肪族第３級アミンに由来する悪臭があり、且つ１日
の服用量が８〜１６ｇと相当に多量であることが問題と
されており、より好適なイオン交換樹脂が種々検討され
ている。その例としては、陰イオン交換樹脂の官能基と
してイミダゾール塩基を用いたもの（特開昭６０−２０
９５２３号）、ビニルピリジンを用いたもの（特開平２
−２１４７１１号）、ジメチルアミノピリジンを用いた
もの（特開平７−１２６１７４号）などがあり、官能基
以外の構成としてはポリアミド系樹脂（ＥＰ−３８９０
７９）やエポキシ系樹脂（特開昭６０−２０９５２３
号）を用いたもの、更にはシクロデキストリンやポリサ
ッカライドなどの糖類を用いたものなどが検討されてい
る。2. Description of the Related Art It has been conventionally known that an ion exchange resin is useful as a medicine for oral administration. For example, a cation exchange resin obtained by sulfonating a styrene-divinylbenzene cross-linked copolymer is said to be effective as a therapeutic agent for hyperkalemia. Further, anion exchange resins are said to be effective as cholesterol lowering agents.
A typical anion exchange resin used as a cholesterol lowering agent is cholestyramine, which is capable of haloalkylating a styrene-divinylbenzene cross-linked copolymer and reacting it with an aliphatic tertiary amine. Manufactured by. This cholestyramine has an offensive odor derived from an aliphatic tertiary amine as a raw material, and its daily dose is 8-16 g, which is a considerably large amount. Various resins have been studied. As an example thereof, an imidazole base is used as a functional group of an anion exchange resin (JP-A-60-20).
9523), using vinyl pyridine (Japanese Patent Application Laid-Open No. HEI-2)
No. 214711), a resin using dimethylaminopyridine (JP-A-7-126174) and the like, and a polyamide resin (EP-3890) as a constitution other than a functional group.
79) and epoxy resin (Japanese Patent Laid-Open No. 60-209523).
No.), and further, those using sugars such as cyclodextrin and polysaccharides are being studied.
【０００３】[0003]
【発明が解決しようとする課題】医薬に用いるイオン交
換樹脂は、当然のことながら不純物の少ないものでなけ
ればならない。特に水溶性不純物は体内で樹脂から溶出
し易いので、その含有量は極力低減させる必要がある。
しかし水洗を反復しても、樹脂内部に存在する水溶性不
純物の除去は極めて困難である。この除去の困難性は、
イオン交換樹脂が水中で膨潤し易いほど大きくなる。し
かるに本発明者らの知見によれば、経口医薬として用い
るイオン交換樹脂は、水中で膨潤し易いほど吸着活性が
大きい傾向がある。従って本発明は、水中において大き
な膨潤性を示すイオン交換樹脂からでも、その含有する
水溶性不純物を効率よく除去することのできる方法を提
供せんとするものである。As a matter of course, the ion exchange resin used in medicine must have a small amount of impurities. In particular, since water-soluble impurities are easily eluted from the resin in the body, the content thereof needs to be reduced as much as possible.
However, even if the washing with water is repeated, it is extremely difficult to remove the water-soluble impurities existing inside the resin. The difficulty of this removal is
The larger the ion exchange resin swells in water, the larger it becomes. However, according to the findings of the present inventors, the ion exchange resin used as an oral medicine tends to have a larger adsorption activity as it swells more easily in water. Therefore, the present invention provides a method capable of efficiently removing the water-soluble impurities contained therein even from an ion exchange resin which exhibits a large swelling property in water.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、イオン
交換樹脂を水洗してその含有している不純物を除去する
と共にイオン交換樹脂を膨潤させ、次いで膨潤状態のイ
オン交換樹脂を水溶性有機溶媒と接触させてその体積を
膨潤時の２／３以下に収縮させることにより、水洗後に
樹脂内に残存する水溶性不純物を樹脂外に排出させるこ
とができる。According to the present invention, the ion exchange resin is washed with water to remove impurities contained therein, and the ion exchange resin is swollen, and then the swollen ion exchange resin is treated with a water-soluble organic compound. The water-soluble impurities remaining in the resin after washing with water can be discharged to the outside of the resin by bringing the solvent into contact with the solvent and shrinking the volume thereof to 2/3 or less of the volume when swollen.
【０００５】[0005]
【発明の実施の形態】本発明について更に詳細に説明す
るに、本発明はイオン交換樹脂からの水溶性不純物の除
去に広く適用することができるが、特に経口医薬用のイ
オン交換樹脂の製造に際し、通常の水洗では除去し得な
い微量の水溶性不純物の除去に有利に適用される。BEST MODE FOR CARRYING OUT THE INVENTION To explain the present invention in more detail, the present invention can be widely applied to the removal of water-soluble impurities from ion-exchange resins, but particularly in the production of ion-exchange resins for oral medicine. , And is advantageously applied to the removal of a trace amount of water-soluble impurities that cannot be removed by ordinary water washing.
【０００６】本発明は、水で膨潤し且つ水溶性有機溶媒
で収縮する任意のイオン交換樹脂に広く適用することが
できるが、水中での膨潤度の大きいイオン交換樹脂に適
用するのが有利であり、好ましくは水中で５ｍｌ／ｇ以
上、特に９ｍｌ／ｇ以上の膨潤度を有するイオン交換樹
脂に適用される。本発明の適用対象として特に好適なイ
オン交換樹脂の一つは、下記一般式（１）で表わされる
イミダゾール化合物と、下記一般式（２）で表わされる
エピハロヒドリン化合物との共重合体の架橋物である。The present invention can be broadly applied to any ion exchange resin which swells with water and contracts with a water-soluble organic solvent, but is advantageously applied to an ion exchange resin having a large degree of swelling in water. Yes, it is preferably applied to an ion exchange resin having a swelling degree of 5 ml / g or more, particularly 9 ml / g or more in water. One of the ion exchange resins particularly suitable for application of the present invention is a crosslinked product of a copolymer of an imidazole compound represented by the following general formula (1) and an epihalohydrin compound represented by the following general formula (2). is there.
【０００７】[0007]
【化３】 Embedded image
【０００８】（式中、Ｒ1 は水素原子、炭素数１〜１７
のアルキル基又は炭素数６〜８のアリール基を表わし、
Ｒ2 及びＲ3 は、それぞれ独立して、水素原子又は炭素
数１〜３のアルキル基を表わす）(In the formula, R 1 is a hydrogen atom and has 1 to 17 carbon atoms.
Represents an alkyl group or an aryl group having 6 to 8 carbon atoms,
R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)
【０００９】[0009]
【化４】 Embedded image
【００１０】（式中、Ｒ4 は水素原子又はメチル基を表
わし、Ｘは塩素、臭素などのハロゲン原子を表わす）(In the formula, R 4 represents a hydrogen atom or a methyl group, and X represents a halogen atom such as chlorine or bromine.)
【００１１】このイミダゾール塩基を官能基とする陰イ
オン交換樹脂はコレステロール低下剤として公知である
が、本願発明者らの検討によれば、なかでも目開き１８
０μｍの篩を全通する粒度に粉砕したものの水中での膨
潤度が９〜２０ｍｌ／ｇ、特に１２〜２０ｍｌ／ｇのも
のが、コレステロール低下に導く血中胆汁酸濃度の低下
作用が大きい。本発明方法によりこのイオン交換樹脂を
精製すると、溶出してくるイミダゾール塩基を極微量に
まで低減できる。This anion exchange resin having an imidazole base as a functional group is known as a cholesterol lowering agent, but according to the study by the inventors of the present invention, among others, the aperture is 18
Those having a degree of swelling in water of 9 to 20 ml / g, particularly 12 to 20 ml / g, which has been crushed to a particle size that passes through a 0 μm sieve, have a large effect of lowering blood bile acid concentration, which leads to cholesterol lowering. When this ion exchange resin is purified by the method of the present invention, the amount of imidazole base that is eluted can be reduced to an extremely small amount.
【００１２】本発明では、イオン交換樹脂を先ず常法に
より水洗して、水溶性不純物を除去する。水洗は十分に
行ない、表面に付着している不純物など水洗により除去
し易い不純物は、できるだけこの水洗により除去するよ
うにする。通常は水溶性不純物の７５重量％以上を水洗
により除去する。好ましくは水溶性不純物の９０重量％
以上、特に９８重量％以上を水洗により除去するように
する。In the present invention, the ion exchange resin is first washed with water by a conventional method to remove water-soluble impurities. Wash thoroughly with water, and remove impurities such as impurities adhering to the surface that are easily removed by washing with water. Usually, 75% by weight or more of water-soluble impurities are removed by washing with water. Preferably 90% by weight of water-soluble impurities
Above, in particular, 98% by weight or more is removed by washing with water.
【００１３】この水洗により、不純物濃度が低下し且つ
膨潤したイオン交換樹脂は、次いで水溶性有機溶媒と接
触させる。この接触により、水で膨潤したイオン交換樹
脂は収縮するので、内部の水溶性不純物が水と共に樹脂
外に排出される。収縮率が大きいほど内部の水溶性不純
物が多量に外部に排出されるので、通常は膨潤時の体積
の２／３以下に収縮させる。特に１／２以下になるまで
収縮させるのが好ましい。By this washing with water, the swelled ion-exchange resin having a reduced impurity concentration is then brought into contact with a water-soluble organic solvent. By this contact, the ion exchange resin swollen with water contracts, so that the water-soluble impurities inside are discharged out of the resin together with water. The larger the shrinkage rate, the larger the amount of water-soluble impurities in the interior is discharged to the outside. In particular, it is preferable to shrink until it becomes 1/2 or less.
【００１４】水溶性有機溶媒としては、常温で水に対し
１０重量倍以上の溶解度を示すものを用いるのが好まし
く、通常はアセトン、メタノール、エタノール、テトラ
ヒドロフラン、Ｎ，Ｎ−ジメチルホルムアミドなど水と
任意に混じるものが用いられる。水で膨潤したイオン交
換樹脂と水溶性有機溶媒との接触方法は任意であるが、
最も簡単には常温の含水有機溶媒中に水で膨潤したイオ
ン交換樹脂を投入して攪拌すればよい。この際、大量の
水溶性有機溶媒を用いることにより、排出された水で希
釈された後でも水溶性有機溶媒中の水分濃度を低く保つ
方が、一般にイオン交換樹脂の収縮率は大きくなるが、
水分濃度が低過ぎると樹脂中に浸透した含水有機溶媒へ
の水溶性不純物の溶解度が低下して、不純物の抽出が困
難となるおそれがある。従って先ず、水分濃度の比較的
高い含水有機溶媒が形成される様に、水溶性有機溶媒中
に水で膨潤したイオン交換樹脂を投入して適度に収縮さ
せ、次いでこの適度に収縮したイオン交換樹脂を、前回
よりも低い水分濃度の含水有機溶媒が形成される様に有
機溶媒中に投入して更に収縮させるというように、多段
階に収縮させるのが好ましい。また、水溶性有機溶媒で
収縮させたイオン交換樹脂を水中に投入して膨潤させ、
次いで再び水溶性有機溶媒で収縮させてもよい。As the water-soluble organic solvent, it is preferable to use one that exhibits a solubility of 10 times by weight or more in water at room temperature, usually acetone, methanol, ethanol, tetrahydrofuran, N, N-dimethylformamide or any other water. What is mixed in is used. The method of contacting the water-swollen ion exchange resin and the water-soluble organic solvent is arbitrary,
The easiest way is to put the ion-exchange resin swollen with water in a water-containing organic solvent at room temperature and stir it. At this time, by using a large amount of the water-soluble organic solvent, keeping the water concentration in the water-soluble organic solvent low even after being diluted with the discharged water generally increases the shrinkage rate of the ion exchange resin,
If the water concentration is too low, the solubility of the water-soluble impurities in the water-containing organic solvent that has penetrated into the resin may decrease, and it may be difficult to extract the impurities. Therefore, first, an ion-exchange resin swollen with water is put into a water-soluble organic solvent to cause a proper shrinkage so that a water-containing organic solvent having a relatively high water concentration is formed. It is preferable to shrink in a multi-step manner, for example, by pouring into the organic solvent so as to form a water-containing organic solvent having a water concentration lower than the previous time and further shrinking. In addition, the ion-exchange resin contracted with a water-soluble organic solvent is put into water to swell,
Then, it may be contracted again with a water-soluble organic solvent.
【００１５】水溶性有機溶媒処理により精製したイオン
交換樹脂は、次いで常法により乾燥して製品のイオン交
換樹脂とすることができる。なお、水溶性有機溶媒処理
に供するイオン交換樹脂の粒径は任意であり、通常は常
法による懸濁重合により得られる粒径数百〜数千μｍの
ものをそのまま用いればよい。なお、本明細書において
イオン交換樹脂の膨潤度は、Ｃｌ型又はＮａ型のイオン
交換樹脂につき、内径１１ｍｍの２５ｍｌメスシリンダ
ーを用いて、２５℃で測定した値である。膨潤度の単位
はｍｌ／ｇ−乾燥樹脂であり、膨潤度の算出に用いるイ
オン交換樹脂の乾燥重量は、５ｍｍＨｇ以下に減圧され
ている減圧乾燥器で１０５℃で４時間乾燥したものにつ
いて測定する。The ion exchange resin purified by the treatment with the water-soluble organic solvent can then be dried by a conventional method to obtain the ion exchange resin of the product. The particle size of the ion-exchange resin used for the treatment with the water-soluble organic solvent is arbitrary, and normally, the particle size of several hundred to several thousand μm obtained by suspension polymerization by a conventional method may be used as it is. In the present specification, the degree of swelling of the ion exchange resin is a value measured at 25 ° C. using a 25 ml graduated cylinder having an inner diameter of 11 mm for the Cl type or Na type ion exchange resin. The unit of the degree of swelling is ml / g-dry resin, and the dry weight of the ion exchange resin used for calculating the degree of swelling is measured for 4 hours at 105 ° C. in a reduced pressure dryer having a reduced pressure of 5 mmHg or less. .
【００１６】また、イオン交換樹脂の水溶性不純物の含
有量は、５０ｍｌ密栓付きガラス瓶に樹脂約１ｇ（乾量
基準）と水４０ｍｌを加え、マグネチックスターラーを
用いて室温で１時間攪拌したのち、上澄み液を０．４５
μｍのフィルターで瀘過し、瀘液を分析して算出する。
新たに合成されたイオン交換樹脂の場合には、水溶性不
純物のうち有機性のものの大部分は、通常は合成に用い
たモノマーがオリゴマー化した構造のものである。Regarding the content of water-soluble impurities in the ion exchange resin, about 1 g of resin (dry weight basis) and 40 ml of water were added to a glass bottle with a 50 ml sealed stopper, and the mixture was stirred at room temperature for 1 hour using a magnetic stirrer. 0.45 of the supernatant
It is filtered with a μm filter, and the filtrate is analyzed and calculated.
In the case of a newly synthesized ion exchange resin, most of the water-soluble impurities, which are organic, usually have a structure in which the monomers used for the synthesis are oligomerized.
【００１７】[0017]
【実施例】次に実施例により本発明をさらに具体的に説
明するが、本発明は以下の実施例に限定されるものでは
ない。 イオン交換樹脂の製造 還流冷却器、温度計及び攪拌機を取付けた四つ口フラス
コに、２−メチルイミダゾール４１．１ｇ（０．５モ
ル）と水６０ｍｌを入れ、均一溶液とした。この溶液を
８０℃に保ち、攪拌下これにエピクロロヒドリン４６．
３ｇ（０．５モル）を１時間かけて滴下した。次いで９
０℃に昇温して１４時間反応を行ない、２−メチルイミ
ダゾールとエピクロロヒドリンとの共重合体を生成させ
た。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. Production of Ion Exchange Resin A 4-necked flask equipped with a reflux condenser, a thermometer and a stirrer was charged with 41.1 g (0.5 mol) of 2-methylimidazole and 60 ml of water to prepare a uniform solution. This solution was kept at 80 ° C. and stirred with epichlorohydrin 46.
3 g (0.5 mol) was added dropwise over 1 hour. Then 9
The temperature was raised to 0 ° C. and the reaction was carried out for 14 hours to form a copolymer of 2-methylimidazole and epichlorohydrin.
【００１８】反応生成液を４７℃に冷却したのち、これ
にエピクロロヒドリン９．３ｇ（０．１モル）を加えて
２時間攪拌した。２７℃に冷却したのち、これに２５％
水酸化ナトリウム水溶液１６ｇ（０．１モル）を加えて
１時間攪拌し、共重合体に部分的にエポキシ基を導入し
た。この反応生成液に、セルロースアセテートブチレー
ト２．５ｇを含む二塩化エタン２５０ｍｌを加え、攪拌
して反応生成液を二塩化エタン中に液滴として分散させ
たのち７０℃に昇温し、２０時間懸濁重合を行なった。After the reaction product solution was cooled to 47 ° C., 9.3 g (0.1 mol) of epichlorohydrin was added thereto and stirred for 2 hours. 25% after cooling to 27 ° C
16 g (0.1 mol) of aqueous sodium hydroxide solution was added and stirred for 1 hour to partially introduce an epoxy group into the copolymer. To this reaction product liquid, 250 ml of ethane dichloride containing 2.5 g of cellulose acetate butyrate was added and stirred to disperse the reaction product liquid in ethane dichloride as droplets, and then the temperature was raised to 70 ° C. for 20 hours. Suspension polymerization was performed.
【００１９】温度計、冷却管及び攪拌機を取付けた四つ
口フラスコに、上記で得られたイオン交換樹脂と水１５
００ｍｌを入れ、徐々に加熱して二塩化エタンを水と一
緒に留出させた。液温が１００℃に達した時に加熱を中
止した。冷却後瀘過して粒径４５〜１０００μｍのイオ
ン交換樹脂９３．２ｇ（乾量基準）を回収した。瀘液量
は９００ｍｌであった。In a four-necked flask equipped with a thermometer, a cooling tube and a stirrer, the ion exchange resin obtained above and water 15
00 ml was added and gradually heated to distill ethane dichloride together with water. The heating was stopped when the liquid temperature reached 100 ° C. After cooling, the solution was filtered and 93.2 g (dry basis) of ion exchange resin having a particle size of 45 to 1000 μm was recovered. The amount of filtrate was 900 ml.
【００２０】イオン交換樹脂の水溶性有機溶媒による精
製 上記で得られた樹脂４６ｇ（乾量基準）に水４５０ｍｌ
を加えて、室温で１時間攪拌したのち瀘過した。樹脂は
１４．５ｍｌ／ｇに膨潤していた。このイオン交換樹脂
の水溶性不純物の含有量は１．０ｍｇ／ｇであった。こ
の樹脂に、水とアセトンとの比がほぼ１：１（容量比）
となる様にアセトンを加え、室温で１時間攪拌したのち
瀘過した。樹脂の水溶性不純物の含有量は０．２ｍｇ／
ｇで、その体積は８．０ｍｌ／ｇ、すなわち水膨潤時の
５５％に収縮していた。次いで、この樹脂に水とアセト
ンとの比がほぼ１：４（容量比）となる様にアセトンを
加えて同じく室温で１時間攪拌したのち瀘過した。樹脂
は６．０ｍｌ／ｇ、すなわち水膨潤時の４１％に収縮し
ていた。また、このイオン交換樹脂の水溶性不純物の含
有量は０．０１ｍｇ／ｇ以下（検出限界以下）であっ
た。Purification of ion-exchange resin with water-soluble organic solvent 450 g of water was added to 46 g (dry basis) of the resin obtained above.
Was added, and the mixture was stirred at room temperature for 1 hour and then filtered. The resin was swollen to 14.5 ml / g. The content of water-soluble impurities in this ion exchange resin was 1.0 mg / g. The resin has a water to acetone ratio of approximately 1: 1 (volume ratio).
Acetone was added so that the mixture became as follows, and the mixture was stirred at room temperature for 1 hour and then filtered. The content of water-soluble impurities in the resin is 0.2 mg /
In g, the volume was 8.0 ml / g, that is, it contracted to 55% of that when swollen in water. Then, acetone was added to this resin so that the ratio of water to acetone was about 1: 4 (volume ratio), and the mixture was stirred at room temperature for 1 hour and then filtered. The resin had shrunk to 6.0 ml / g, that is, 41% when swollen in water. The content of water-soluble impurities in this ion exchange resin was 0.01 mg / g or less (below the detection limit).
【００２１】イオン交換樹脂の水洗による精製 上記のイオン交換樹脂の製造で得られた樹脂４６ｇ（乾
量基準）に水４５０ｍｌを加えて室温で１時間攪拌した
のち瀘過した。この水洗操作を更に４回反復した。得ら
れたイオン交換樹脂の水溶性不純物の含有量は０．７ｍ
ｇ／ｇであった。なお、水溶性不純物の含有量は、２−
メチルイミダゾール換算の量であり、瀘液の２１０ｎｍ
の吸光度を測定し、既知濃度の２−メチルイミダゾール
水溶液の２１０ｎｍの吸光度に基づいてその濃度を算出
した。Purification of Ion Exchange Resin by Washing with Water 450 ml of water was added to 46 g (dry basis) of the resin obtained in the production of the above ion exchange resin, and the mixture was stirred at room temperature for 1 hour and then filtered. This water washing operation was repeated four more times. The content of water-soluble impurities in the obtained ion exchange resin is 0.7 m
g / g. The content of water-soluble impurities is 2-
The amount is equivalent to methyl imidazole, and the filtrate is 210 nm.
Was measured, and the concentration was calculated based on the absorbance at 210 nm of a 2-methylimidazole aqueous solution having a known concentration.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池田 芳哉 神奈川県横浜市青葉区鴨志田町1000番地 三菱化学株式会社横浜総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiya Ikeda 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Institute
Claims (7)
するイオン交換樹脂から水溶性の不純物を除去する方法
であって、イオン交換樹脂を水洗してその含有している
不純物を除去すると共にイオン交換樹脂を膨潤させ、次
いで膨潤状態のイオン交換樹脂を水溶性有機溶媒と接触
させてその体積を膨潤時の２／３以下に収縮させること
により、水洗後に樹脂内に残存する水溶性不純物を樹脂
外に排出させることを特徴とするイオン交換樹脂の精製
法。1. A method for removing water-soluble impurities from an ion-exchange resin that swells in water and shrinks in a water-soluble organic solvent, which comprises washing the ion-exchange resin with water to remove impurities contained therein. At the same time, the ion-exchange resin is swollen, and then the swollen ion-exchange resin is brought into contact with a water-soluble organic solvent to shrink the volume to 2/3 or less of that at the time of swelling, so that water-soluble impurities remaining in the resin after washing with water. A method for purifying an ion exchange resin, characterized in that the hydrogen is discharged out of the resin.
るイオン交換樹脂を水溶性有機溶媒との接触に供するこ
とを特徴とする請求項１記載のイオン交換樹脂の精製
法。2. The method for purifying an ion exchange resin according to claim 1, wherein the ion exchange resin which swells to 5 ml / g-dry resin or more with water is brought into contact with a water-soluble organic solvent.
溶性有機溶媒との接触により、その体積を膨潤時の１／
２以下に収縮させることを特徴とする請求項１又は２記
載のイオン交換樹脂の精製法。3. An ion exchange resin swollen with water is contacted with a water-soluble organic solvent to reduce its volume to 1 /
The method for purifying an ion exchange resin according to claim 1 or 2, wherein the method is contracted to 2 or less.
性有機溶媒との接触を、イオン交換樹脂を先ず比較的多
量の水を含む含水有機溶媒と接触させて収縮させ、次い
でより少い量の水を含む含水有機溶媒と接触させて更に
収縮させる少くとも２段階の接触により行なうことを特
徴とする請求項１ないし３のいずれかに記載のイオン交
換樹脂の精製法。4. The contact between the water-swelling ion-exchange resin and the water-soluble organic solvent is first caused to contract by contacting the ion-exchange resin with a water-containing organic solvent containing a relatively large amount of water, and then less. The method for purifying an ion exchange resin according to any one of claims 1 to 3, wherein the method is carried out by contacting with a water-containing organic solvent containing a certain amount of water and further contracting in at least two stages.
純物の大部分を除去したのち、水溶性有機溶媒との接触
に供することを特徴とする請求項１ないし４のいずれか
に記載のイオン交換樹脂の精製法。5. The ion exchange according to claim 1, wherein most of the water-soluble impurities in the ion exchange resin are removed by washing with water, and then the ion exchange resin is brought into contact with a water-soluble organic solvent. Resin purification method.
されるイミダゾール化合物と、一般式（２）で表わされ
るエピハロヒドリン化合物との共重合体の架橋物である
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
イオン交換樹脂の精製法。 【化１】 （式中、Ｒ1 は水素原子、炭素数１〜１７のアルキル基
又は炭素数６〜８のアリール基を表わし、Ｒ2 及びＲ3
は、それぞれ独立して、水素原子又は炭素数１〜３のア
ルキル基を示す） 【化２】 （式中、Ｒ4 は水素原子又はメチル基を表わし、Ｘは塩
素、臭素などのハロゲン原子を表わす）6. The ion exchange resin is a crosslinked product of a copolymer of an imidazole compound represented by the general formula (1) and an epihalohydrin compound represented by the general formula (2). 6. The method for purifying an ion exchange resin according to any one of 5 to 5. Embedded image (In the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms or an aryl group having 6 to 8 carbon atoms, and R 2 and R 3
Are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) (In the formula, R 4 represents a hydrogen atom or a methyl group, and X represents a halogen atom such as chlorine or bromine.)
ル、エタノール、テトラヒドロフラン、Ｎ，Ｎ−ジメチ
ルホルムアミドから選ばれたものであることを特徴とす
る請求項１ないし６のいずれかに記載のイオン交換樹脂
の精製法。7. The ion exchange according to claim 1, wherein the water-soluble organic solvent is selected from acetone, methanol, ethanol, tetrahydrofuran and N, N-dimethylformamide. Resin purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01372396A JP3994210B2 (en) | 1996-01-30 | 1996-01-30 | Purification method of ion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01372396A JP3994210B2 (en) | 1996-01-30 | 1996-01-30 | Purification method of ion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09201539A true JPH09201539A (en) | 1997-08-05 |
| JP3994210B2 JP3994210B2 (en) | 2007-10-17 |
Family
ID=11841177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01372396A Expired - Lifetime JP3994210B2 (en) | 1996-01-30 | 1996-01-30 | Purification method of ion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3994210B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011088070A (en) * | 2009-10-22 | 2011-05-06 | Kurita Water Ind Ltd | Ultrapure water production method and apparatus for ion exchange resin purifier |
| KR20120039524A (en) | 2009-06-30 | 2012-04-25 | 쿠리타 고교 가부시키가이샤 | Ion-exchange device, process and equipment for producing same, and method and device for forming ion-exchange resin layer |
| WO2012133769A1 (en) * | 2011-03-31 | 2012-10-04 | 日本ゼオン株式会社 | Polyether compound and electrolyte composition |
-
1996
- 1996-01-30 JP JP01372396A patent/JP3994210B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120039524A (en) | 2009-06-30 | 2012-04-25 | 쿠리타 고교 가부시키가이샤 | Ion-exchange device, process and equipment for producing same, and method and device for forming ion-exchange resin layer |
| CN103342404A (en) * | 2009-06-30 | 2013-10-09 | 栗田工业株式会社 | Ion-exchange device, process for producing same and equipment, and method for forming layer of ion-exchange resin and device thereof |
| CN103342404B (en) * | 2009-06-30 | 2015-01-28 | 栗田工业株式会社 | Ion-exchange device, process for producing same and equipment, and method for forming layer of ion-exchange resin and device thereof |
| KR20160073428A (en) | 2009-06-30 | 2016-06-24 | 쿠리타 고교 가부시키가이샤 | Ion-exchange device, process and equipment for producing same, and method and device for forming ion-exchange resin layer |
| JP2011088070A (en) * | 2009-10-22 | 2011-05-06 | Kurita Water Ind Ltd | Ultrapure water production method and apparatus for ion exchange resin purifier |
| WO2012133769A1 (en) * | 2011-03-31 | 2012-10-04 | 日本ゼオン株式会社 | Polyether compound and electrolyte composition |
| JP5720773B2 (en) * | 2011-03-31 | 2015-05-20 | 日本ゼオン株式会社 | Polyether compound and electrolyte composition |
| US9469612B2 (en) | 2011-03-31 | 2016-10-18 | Zeon Corporation | Polyether compound and electrolyte composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3994210B2 (en) | 2007-10-17 |
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