JPS6111667B2 - - Google Patents
Info
- Publication number
- JPS6111667B2 JPS6111667B2 JP58025756A JP2575683A JPS6111667B2 JP S6111667 B2 JPS6111667 B2 JP S6111667B2 JP 58025756 A JP58025756 A JP 58025756A JP 2575683 A JP2575683 A JP 2575683A JP S6111667 B2 JPS6111667 B2 JP S6111667B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polycyclodextrin
- cyclodextrin
- monohalogenoalkyl
- sulfonate
- 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.)
- Expired
Links
- 239000011347 resin Substances 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 description 16
- 229920000858 Cyclodextrin Polymers 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- -1 cyclic oligosaccharide Chemical class 0.000 description 7
- 239000001116 FEMA 4028 Substances 0.000 description 6
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 6
- 229960004853 betadex Drugs 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKTHLFYZKHPYBY-UHFFFAOYSA-M sodium;1-chloroethanesulfonate Chemical compound [Na+].CC(Cl)S([O-])(=O)=O AKTHLFYZKHPYBY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【発明の詳細な説明】
本発明は、新規なイオン交換体、さらに詳しく
いえば、ポリシクロデキストリン樹脂にモノハロ
ゲノアルキルスルホン酸塩を反応させて得られる
包接作用を有する強酸型陽イオン交換体及びその
製造方法に関するものである。Detailed Description of the Invention The present invention relates to a novel ion exchanger, more specifically, a strong acid type cation exchanger having an inclusion effect obtained by reacting a polycyclodextrin resin with a monohalogenoalkyl sulfonate. and its manufacturing method.
シクロデキストリンは、６個以上のグルコース
がα−１・４−結合した環状のオリゴ糖であつ
て、分子内に筒状の空洞を有し、その空洞中に
種々の物質を包み込んで包接化合物を形成しうる
物質である。このような包接化合物形成性を有す
る物質は、その空洞に適合した分子形状と大きさ
を有する物質をその中に取り込んで包接化合物を
形成し、また、被包接物質の種類によつて親和力
の異なる包接化合物を形成する。包接化合物形成
能を有する物質はこのような特性を有し、その特
性を利用して種々の物質の混合物から特定の化合
物又は化合物群の分割あるいは単離などを行うこ
とができる。物質分離などに実用する場合には、
通常、包接化合物形成物質を、例えば架橋高分化
するなどにより不溶性化して、クロマトグラフイ
ー用カラムに充てん使用されている。 Cyclodextrin is a cyclic oligosaccharide in which six or more glucose units are α-1,4-linked, and has a cylindrical cavity within the molecule, which envelops various substances and forms clathrate compounds. It is a substance that can form Substances that have such clathrate-forming properties form clathrates by incorporating into them substances with molecular shapes and sizes that suit the cavity, and depending on the type of clathrate substance, Forms clathrates with different affinities. Substances capable of forming clathrate compounds have such properties, and by utilizing these properties, it is possible to divide or isolate a specific compound or compound group from a mixture of various substances. When used in practical applications such as substance separation,
Generally, the clathrate-forming substance is made insoluble by, for example, cross-linking and polymerization, and then used to fill a column for chromatography.
ところで、シクロデキストリンの包接化合物の
形成は、上記のように、その空洞に包接しうる形
状と大きさの物質に対して効果的に作用するが、
一般に包接形成性を有する樹脂を用いて物質の分
離を行う場合には、分子の大きさと形の類似した
物質の分離は困難であり、ポリシクロデキストリ
ン樹脂の場合も同様な困難性をもつものである。 By the way, the formation of cyclodextrin inclusion compounds effectively acts on substances of a shape and size that can be included in the cavity, as described above.
Generally, when separating substances using resins that have inclusion-forming properties, it is difficult to separate substances with similar molecular sizes and shapes, and polycyclodextrin resins have similar difficulties. It is.
本発明者らは、シクロデキストリンの包接作用
を利用し、それを高分子化して得られるポリシク
ロデキストリン樹脂を用いて物質分離を行うに当
り、上記のような分子の大きさ及び形の類似した
化合物をも効果的に分離しうる方法を開発すべ
く、特にポリシクロデキストリン樹脂の改質につ
いて鋭意研究を重ねた結果、ポリシクロデキスト
リン樹脂にスルホアルキル基を導入するとき、包
接作用と陽イオン交換能を併せもつた望ましいポ
リシクロデキストリン系樹脂が得られることを見
出し、本発明をなすに至つた。 The present inventors utilized the inclusion effect of cyclodextrin to perform substance separation using polycyclodextrin resin obtained by polymerizing it. In order to develop a method that can effectively separate even the compounds that are It was discovered that a desirable polycyclodextrin resin having ion exchange ability can be obtained, and the present invention was completed.
すなわち、本発明は、ポリシクロデキストリン
樹脂にモノハロゲノアルキルスルホン酸塩を反応
させることを特徴とする包接作用を有する強酸型
陽イオン交換体の製造方法及びそのような方法で
得られた陽イオン交換体を提供するものである。 That is, the present invention relates to a method for producing a strong acid type cation exchanger having an inclusion action, which is characterized by reacting a polycyclodextrin resin with a monohalogenoalkyl sulfonate, and a method for producing a cation exchanger having an inclusion effect, which is characterized by reacting a polycyclodextrin resin with a monohalogenoalkyl sulfonate; It provides an exchange body.
本発明におけるポリシクロデキストリン樹脂の
形成に用いられるシクロデキストリンは、α−シ
クロデキストリン、β−シクロデキストリ又はγ
−シクロデキストリンのいずれであつてもよく、
また、これらは２種あるいは３種を組み合わせて
用いることもできる。ポリシクロデキストリン樹
脂は、これらのシクロデキストリンを高分子化し
たものであつて、スルホアルキル基導入反応に耐
えるものであればすべて使用できるが、とりわ
け、エピクロルヒドリン又はジエポキシ化合物を
用いて架橋高分子化したポリシクロデキストリン
樹脂が好ましい。そのような架橋高分子化樹脂
は、熱とアルカリに対する耐性が大きいだけでな
く、モノハロゲノアルキルスルホン酸塩と反応す
るための水酸基を多数有するので極めて好適であ
る。 The cyclodextrin used to form the polycyclodextrin resin in the present invention may be α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin.
- may be any of cyclodextrin;
Moreover, these can also be used in combination of two or three types. Any polycyclodextrin resin can be used as long as it is a polymerized cyclodextrin that can withstand the sulfoalkyl group introduction reaction, but in particular, it can be used as a polymerized cyclodextrin resin cross-linked using epichlorohydrin or a diepoxy compound. Polycyclodextrin resins are preferred. Such a crosslinked polymerized resin is extremely suitable because it not only has high resistance to heat and alkali, but also has a large number of hydroxyl groups for reacting with the monohalogenoalkyl sulfonate.
本発明の方法においては、このようなポリシク
ロデキストリン樹脂にモノハロゲノアルキルスル
ホン酸塩を反応させるが、そのようなモノハロゲ
ノアルキルスルホン酸塩としては、低級アルキル
基を含むモノクロロアルキルスルホン酸、モノブ
ロモアルキルスルホン酸、モノヨードアルキルス
ルホン酸のアルカリ金属塩及びアルカリ土類金属
塩類が用いられる。 In the method of the present invention, such a polycyclodextrin resin is reacted with a monohalogenoalkyl sulfonate, and examples of such a monohalogenoalkyl sulfonate include monochloroalkyl sulfonic acid containing a lower alkyl group, monobromo Alkali metal salts and alkaline earth metal salts of alkylsulfonic acids, monoiodoalkylsulfonic acids are used.
この反応に際しては、ポリシクロデキストリン
樹脂をアルカリ性水溶液、例えば水酸化ナトリウ
ム又は水酸化カリウムの20〜50重量％の比較的高
濃度の水溶液に分散させ、この分散液にモノハロ
ゲノアルキルスルホン酸塩が加えられる。この反
応媒体水溶液は強いアルカリ性を有し、固体のポ
リシクロデキストリン樹脂は、アルカリ水溶液中
では膨潤して樹脂の強度が低下するので、望まし
くはポリシクロデキストリン樹脂はビーズ状で反
応に供されるが、粉砕した粉末として用いること
もできる。また、ポリシクロデキストリン樹脂の
分散には、通常、例えば該樹脂の３〜10重量倍の
上記アルカリ性水溶液が好適に用いられる。 In this reaction, the polycyclodextrin resin is dispersed in an alkaline aqueous solution, such as a relatively high concentration aqueous solution of 20 to 50% by weight of sodium hydroxide or potassium hydroxide, and a monohalogenoalkyl sulfonate is added to this dispersion. It will be done. This reaction medium aqueous solution has strong alkalinity, and solid polycyclodextrin resin swells in an alkaline aqueous solution and the strength of the resin decreases, so it is preferable that the polycyclodextrin resin is subjected to the reaction in the form of beads. It can also be used as a ground powder. Further, for dispersing the polycyclodextrin resin, the above-mentioned alkaline aqueous solution is usually suitably used, for example, in an amount of 3 to 10 times the weight of the resin.
分散液に添加されるモノハロゲノアルキルスル
ホン酸塩は、スルホアルキル基の所望導入率によ
り、その添加量が選択されるが、通常ポリシクロ
デキストリン樹脂１重量部に対して0.5〜５重量
部の範囲が好適である。しかし、スルホアルキル
基の低い導入率を望むならば0.5重量部以下の量
を添加することもできる。 The amount of the monohalogenoalkyl sulfonate added to the dispersion is selected depending on the desired introduction rate of sulfoalkyl groups, but it is usually in the range of 0.5 to 5 parts by weight per 1 part by weight of the polycyclodextrin resin. is suitable. However, if a low introduction rate of sulfoalkyl groups is desired, it can be added in an amount of 0.5 parts by weight or less.
ポリシクロデキストリン樹脂を分散させたアル
カリ性水溶液に、かきまぜながらモノハロゲノア
ルキルスルホン酸塩を加えたのち、反応液の温度
を、例えば40〜60℃程度のゆるやかな加熱条件に
保つて、かきまぜながら反応させるとき、所定の
スルホアルキル基が導入されたポリシクロデキス
トリン樹脂が容易に得られる。反応温度は、60℃
より高い温度で行うこともできるが、得られる目
的の樹脂が着色する場合があり、また40℃以下で
は、スルホアルキル基の導入率が低下する恐れが
あつて、所定の導入率を達成するのに長時間を要
するので、上記温度範囲が好ましい。反応系のか
きまぜ条件は、あまり激しいと樹脂を粉砕するの
で好ましくなく、通常100〜500rpm程度が好適で
ある。 After adding the monohalogenoalkyl sulfonate to an alkaline aqueous solution in which polycyclodextrin resin is dispersed, while stirring, maintain the temperature of the reaction solution at a gentle heating condition of, for example, 40 to 60°C, and react while stirring. At this time, a polycyclodextrin resin into which a predetermined sulfoalkyl group has been introduced can be easily obtained. Reaction temperature is 60℃
Although it can be carried out at a higher temperature, the desired resin obtained may be colored, and if the temperature is below 40°C, the introduction rate of sulfoalkyl groups may decrease, making it difficult to achieve the specified introduction rate. The above temperature range is preferable since it takes a long time for the reaction to occur. The stirring conditions of the reaction system are not preferable if the stirring conditions are too vigorous because the resin will be crushed, and a stirring condition of about 100 to 500 rpm is usually suitable.
このような条件で反応を行うとき、通常５〜24
時間で反応は完了し、スルホアルキル基をもつた
ポリシクロデキストリン樹脂が得られる。反応生
成物は、次いで分離され、蒸留水でその洗液が中
性になるまで洗浄したのち、アセトン又は低級ア
ルコールで脱水処理し乾燥される。こうして得ら
れたスルホアルキル基を有するポリシクロデキス
トリン系樹脂は、そのスルホン酸基が使用した水
酸化アルカリのアルカリ金属塩の型になつている
が、これを又は上記水洗段階で、例えば希塩酸の
ような希酸で処理することにより容易にＨ型に変
換することができ、強酸型陽イオン交換体として
使用することができる。 When carrying out the reaction under these conditions, it is usually 5 to 24
The reaction is completed within a few hours, and a polycyclodextrin resin having sulfoalkyl groups is obtained. The reaction product is then separated, washed with distilled water until the washings become neutral, and then dehydrated with acetone or lower alcohol and dried. The polycyclodextrin-based resin having a sulfoalkyl group thus obtained has a sulfonic acid group in the form of an alkali metal salt of the alkali hydroxide used, and it can be washed with dilute hydrochloric acid or the like in the water washing step. It can be easily converted to the H type by treatment with a dilute acid, and can be used as a strong acid type cation exchanger.
本発明に係るスルホアルキル基の導入されたポ
リシクロデキストリン系樹脂は、シクロデキスト
リンの包接作用を有するだけでなく、強酸型陽イ
オン交換能を有する極めて特異な新規物質であ
る。従つてそれぞれの特性を個々に利用しうるの
みならず、両方の特性を利用して、従来分離が困
難であつた分子の大きさや形の類似した物質の分
離を行うことができるので、イオン交換体、分離
剤及び吸着剤としてさらに広い範囲にわたつて有
利に使用することができる。 The polycyclodextrin-based resin into which a sulfoalkyl group has been introduced according to the present invention is an extremely unique new substance that not only has a cyclodextrin inclusion effect but also has a strong acid type cation exchange ability. Therefore, not only can each property be used individually, but also both properties can be used to separate substances with similar molecular sizes and shapes, which were previously difficult to separate. Furthermore, they can be used advantageously over a wide range of applications as substances, separation agents and adsorbents.
次に実施例により本発明をさらに詳細に説明す
る。 Next, the present invention will be explained in more detail with reference to Examples.
参考例
粉末状のβ−シクロデキストリン25ｇに水12.5
mlを加えて混練し、30％水酸化ナトリウム水溶液
37.5ml及び水素化ホウ素ナトリウム100mgを加え
て均一な溶液とし、50℃に保つて200rpmの速度
でかきまぜつつ7.5mlのエピクロルヒドリンを滴
下し、30分間かきまぜた後、泡を消すために30分
間50℃に保つた。得られたシロツプ状の液体に流
動パラフイン375mlを加えて50℃に保ちつつ
1000rpmで５分間かきまぜて均一に分散させた
後、エピクロルヒドリン25mlを加えて更に２時間
50℃に保つてかきまぜた。得られたビーズをろ過
して分離し、ヘキサン100mlで３回、次いでアセ
トン100mlで３回洗浄した後、洗浄液のPHが中性
になるまで蒸留水で洗浄し、更に蒸留水１に１
日浸して水溶性成分を溶出除去した。これを50％
アセトン水で洗浄した後、300mlのアセトンに１
日浸して脱水し、70℃の温度で１日乾燥させ、更
に真空デシケーター中で五酸化リンにより１日乾
燥させた。かくして得られたポリ−β−シクロデ
キストリンビーズ29ｇをふるいにかけることによ
り50〜200メツシユのビーズが26ｇ得られた。Reference example: 25g of powdered β-cyclodextrin and 12.5g of water
ml and knead, 30% aqueous sodium hydroxide solution
Add 37.5 ml and 100 mg of sodium borohydride to make a homogeneous solution, keep at 50°C, add 7.5 ml of epichlorohydrin dropwise while stirring at 200 rpm, stir for 30 minutes, and then heat at 50°C for 30 minutes to eliminate bubbles. I kept it. Add 375ml of liquid paraffin to the resulting syrupy liquid and keep it at 50℃.
Stir at 1000 rpm for 5 minutes to ensure uniform dispersion, then add 25 ml of epichlorohydrin and stir for another 2 hours.
It was kept at 50℃ and stirred. The obtained beads were separated by filtration, washed 3 times with 100 ml of hexane, then 3 times with 100 ml of acetone, washed with distilled water until the pH of the washing solution became neutral, and further washed with 1 part distilled water to 1 part distilled water.
Water-soluble components were eluted and removed by soaking in the sun. 50% of this
After washing with acetone water, add 1 to 300ml of acetone.
It was dehydrated by soaking in the sun, dried for 1 day at a temperature of 70°C, and further dried for 1 day with phosphorus pentoxide in a vacuum desiccator. By sieving 29 g of the poly-β-cyclodextrin beads thus obtained, 26 g of beads having a mesh size of 50 to 200 were obtained.
実施例 １
参考例で得られたポリ−β−シクロデキストリ
ンビーズ５ｇを33％水酸化ナトリウム水溶液30ml
に分散させ、200rpmの速度でかきまぜつつ２−
クロロエタンスルホン酸ナトリウム５ｇを加え60
℃の温度に加温して５時間かきまぜた後、50℃に
15時間保つた。反応生成物を分離し、洗浄水のPH
が中性になるまで蒸留水で洗浄した後、蒸留水
200ml中に１日浸して水溶性成分を除去した。次
いで50％アセトン水で洗浄し、更に100mlのアセ
トンに１日浸して脱水し、真空デシケーター中に
て五酸化リンにより乾燥させた。かくして、スル
ホエチル基を有するポリ−β−シクロデキストリ
ンビーズ5.6ｇがナトリウム塩として得られた。
この５ｇを1Nの塩酸に浸してナトリウムイオン
を水素イオンで置換し、十分に水洗した後、
0.1Nの水酸化ナトリウム水溶液を用いて滴定し
た結果、５ｇ中に1.8×10-3モルのスルホエチル
基を含んでいた。従つて、このポリ−β−シクロ
デキストリンビーズ５ｇはナトリウムイオンにし
て1.8×10-3モル相当の陽イオンを吸着すること
ができ、陽イオン交換体として使用できる。Example 1 5 g of poly-β-cyclodextrin beads obtained in Reference Example were added to 30 ml of 33% sodium hydroxide aqueous solution.
2- while stirring at a speed of 200 rpm.
Add 5g of sodium chloroethanesulfonate and add 60
After heating to a temperature of ℃ and stirring for 5 hours, the temperature was raised to 50℃.
It kept for 15 hours. Separate the reaction products and check the pH of the washing water
Wash with distilled water until it becomes neutral, then add distilled water.
Water-soluble components were removed by soaking in 200ml for one day. Next, it was washed with 50% acetone water, further immersed in 100 ml of acetone for 1 day to dehydrate, and dried with phosphorus pentoxide in a vacuum desiccator. Thus, 5.6 g of poly-β-cyclodextrin beads having sulfoethyl groups were obtained as the sodium salt.
Soak 5g of this in 1N hydrochloric acid to replace sodium ions with hydrogen ions, and rinse thoroughly with water.
As a result of titration using a 0.1N aqueous sodium hydroxide solution, it was found that 1.8×10 -3 mol of sulfoethyl group was contained in 5 g. Therefore, 5 g of the poly-β-cyclodextrin beads can adsorb cations equivalent to 1.8×10 −3 mol of sodium ions and can be used as a cation exchanger.
Claims (1)
リン系樹脂から成る包接作用を有する強酸型陽イ
オン交換体。 ２ ポリシクロデキストリン樹脂にモノハロゲノ
アルキルスルホン酸塩を反応させることを特徴と
する包接作用を有する強酸型陽イオン交換体の製
造方法。 ３ モノハロゲノアルキルスルホン酸がモノクロ
ロ低級アルキルスルホン酸である特許請求の範囲
第２項記載の製造方法。[Scope of Claims] 1. A strong acid-type cation exchanger having an inclusion effect and comprising a polycyclodextrin resin having a sulfoalkyl group. 2. A method for producing a strong acid type cation exchanger having an inclusion effect, which comprises reacting a polycyclodextrin resin with a monohalogenoalkyl sulfonate. 3. The manufacturing method according to claim 2, wherein the monohalogenoalkylsulfonic acid is monochlorolower alkylsulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58025756A JPS59150544A (en) | 1983-02-17 | 1983-02-17 | Strong acid type cation exchange substance having inclusion action and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58025756A JPS59150544A (en) | 1983-02-17 | 1983-02-17 | Strong acid type cation exchange substance having inclusion action and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59150544A JPS59150544A (en) | 1984-08-28 |
| JPS6111667B2 true JPS6111667B2 (en) | 1986-04-04 |
Family
ID=12174674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58025756A Granted JPS59150544A (en) | 1983-02-17 | 1983-02-17 | Strong acid type cation exchange substance having inclusion action and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59150544A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU191101B (en) * | 1983-02-14 | 1987-01-28 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt,Hu | Process for preparing water-soluble cyclodextrin polymers substituted with ionic groups |
| CN106883322A (en) * | 2017-03-08 | 2017-06-23 | 天津大学 | The preparation of polynary cyclodextrin and its application in CE chiral analysis |
-
1983
- 1983-02-17 JP JP58025756A patent/JPS59150544A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59150544A (en) | 1984-08-28 |
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