JPH0551402A - Production of cyclodextrin polymer - Google Patents
Production of cyclodextrin polymerInfo
- Publication number
- JPH0551402A JPH0551402A JP23865891A JP23865891A JPH0551402A JP H0551402 A JPH0551402 A JP H0551402A JP 23865891 A JP23865891 A JP 23865891A JP 23865891 A JP23865891 A JP 23865891A JP H0551402 A JPH0551402 A JP H0551402A
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- JP
- Japan
- Prior art keywords
- cyclodextrin
- polymer
- group
- reaction
- hours
- 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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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、吸着又は分離剤として
利用できるサイクロデキストリンポリマーの製造方法に
関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing a cyclodextrin polymer which can be used as an adsorbing or separating agent.
【０００２】[0002]
【従来の技術】サイクロデキストリンはその環状空洞内
に種々の化合物を包接する性質を有しており、これらの
包接化合物は吸着・分離剤として利用することができ
る。しかしながら、サイクロデキストリンは水に可溶で
あり、更に特定の有機溶媒にも溶解しうるものである。
従って、このようなサイクロデキストリンに種々の系か
ら化合物を包接し、単離することは困難であった。この
ため、サイクロデキストリンを不溶性高分子化合物とし
て用いる方法が提案されている。Cyclodextrins have the property of clathrating various compounds in their annular cavities, and these clathrates can be used as adsorbing / separating agents. However, cyclodextrin is soluble in water and also soluble in a specific organic solvent.
Therefore, it has been difficult to include and isolate compounds from various systems in such cyclodextrins. Therefore, a method of using cyclodextrin as an insoluble polymer compound has been proposed.
【０００３】このように、サイクロデキストリンを高分
子化合物として用いる方法としては、例えば、特開昭54
-61290号及び同54-61291号各公報に記載されている、ク
ロロメチル化ポリスチレンにサイクロデキストリンの誘
導体を反応させたもの、特開昭59-227906号公報に記載
の不溶性高分子物質にサイクロデキストリン誘導体を反
応させた固定化サイクロデキストリンアミノ誘導体、及
び特開昭62-275102号公報に記載のサイクロデキストリ
ンをエピクロルヒドリンで架橋させ高分子化合物とし、
残水酸基を他の官能基に変換したもの等、更に共重合体
の末端官能基に高分子反応でサイクロデキストリンを固
定させたもの等が挙げられる。As described above, as a method of using cyclodextrin as a polymer compound, for example, JP-A-54 is used.
-61290 and 54-61291, chloromethylated polystyrene reacted with cyclodextrin derivative, insoluble polymer substance described in JP-A-59-227906, cyclodextrin An immobilized cyclodextrin amino derivative reacted with a derivative, and a cyclodextrin described in JP-A-62-275102 are crosslinked with epichlorohydrin to form a polymer compound,
Examples thereof include those obtained by converting the residual hydroxyl group into another functional group, and those obtained by further fixing cyclodextrin to the terminal functional group of the copolymer by a polymer reaction.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
方法にてポリマーに高分子反応によりサイクロデキスト
リンを固定化する場合、固定量が極めて少なく、前記の
如きサイクロデキストリンの機能は期待し難く、また、
架橋により得られたものも、水溶性が高く、水溶液中で
の使用は困難である。更にサイクロデキストリンとエピ
クロルヒドリンを反応させた場合は、分子内架橋がおこ
りやすく、その為サイクロデキストリンの本来有する包
接機能をはたさなくなる。However, when cyclodextrin is immobilized on a polymer by a polymer reaction by the above method, the amount of immobilization is extremely small, and the function of cyclodextrin as described above is difficult to expect, and
The product obtained by crosslinking is also highly water-soluble and is difficult to use in an aqueous solution. Furthermore, when cyclodextrin is reacted with epichlorohydrin, intramolecular crosslinking is likely to occur, and thus the inclusion function originally possessed by cyclodextrin is lost.
【０００５】従って本発明の目的は、サイクロデキスト
リンユニットの固定量が増大し、その機能性が大巾に向
上したサイクロデキストリンポリマーを提供することに
ある。Therefore, an object of the present invention is to provide a cyclodextrin polymer in which the fixed amount of the cyclodextrin unit is increased and the functionality thereof is greatly improved.
【０００６】また、本発明の別の目的は、特定の高分子
化合物を用いることで水等に不溶であるが酵素により分
解可能であり、この結果分解性ポリマーとして使用しう
るサイクロデキストリンポリマーを提供することにあ
る。Another object of the present invention is to provide a cyclodextrin polymer which is insoluble in water and the like but can be decomposed by an enzyme by using a specific polymer compound, and as a result, can be used as a degradable polymer. To do.
【０００７】[0007]
【課題を解決すべき手段】本発明者等は前記課題に鑑み
て鋭意研究の結果、本発明の上記目的は、サイクロデキ
ストリン（以下、ＣＤと略記する）に下記一般式［Ｉ］
〜［VII］のいずれかで表わされる化合物を反応させる
ことを特徴とするサイクロデキストリンポリマーの製造
方法により達成されることを見出した。DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors in view of the above-mentioned problems, the above-mentioned object of the present invention was found in the following general formula [I]
~ [VII] has been found to be achieved by a method for producing a cyclodextrin polymer, which comprises reacting a compound represented by any one of [VII].
【０００８】[0008]
【化６】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。）[Chemical 6] (In the formula, Y represents a halogen atom or an -OR group, and R represents an alkyl group or a cyclohexyl group.)
【０００９】[0009]
【化７】 る結合手を表わし、Ｙはハロゲン原子又は−ＯＲ基を表
わし、Ｒはアルキル基又はシクロヘキシル基を表わ
す。）[Chemical 7] Represents a bond, Y represents a halogen atom or an —OR group, and R represents an alkyl group or a cyclohexyl group. )
【００１０】[0010]
【化８】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。また、Ｚは
０〜12の整数を表わす。）[Chemical 8] (In the formula, Y represents a halogen atom or an -OR group, R represents an alkyl group or a cyclohexyl group, and Z represents an integer of 0 to 12.)
【００１１】[0011]
【化９】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。）[Chemical 9] (In the formula, Y represents a halogen atom or an -OR group, and R represents an alkyl group or a cyclohexyl group.)
【００１２】[0012]
【化１０】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。）[Chemical 10] (In the formula, Y represents a halogen atom or an -OR group, and R represents an alkyl group or a cyclohexyl group.)
【００１３】以下に本発明を更に詳細に説明する。The present invention will be described in more detail below.
【００１４】本発明において前記一般式［Ｉ］として表
わされる化合物としては具体的には以下の化合物が用い
られる。In the present invention, the following compounds are specifically used as the compound represented by the general formula [I].
【００１５】[0015]
【化１１】 [Chemical 11]
【００１６】上記一般式［Ｉ］〜［VII］の各々におい
て、Ｙで表わされる−ＯＲ基のＲで表わされるアルキル
基として使用できるものとしては、ＣＨ3−，Ｃ2Ｈ
5−，Ｃ3Ｈ7−，Ｃ4Ｈ9−，Ｃ5Ｈ11−、又他にｉ-Ｃ3Ｈ
7−，ｉ-Ｃ4Ｈ9−，ｉ-Ｃ5Ｈ11−，ｔ-Ｃ4Ｈ9−，neo-
Ｃ5Ｈ11−等がある。ハロゲン原子としては、Ｂｒ，Ｃ
ｌ，Ｉ，Ｆ等が使用できる。In each of the above general formulas [I] to [VII], CH 3- , C 2 H can be used as the alkyl group represented by R of the --OR group represented by Y.
5 -, C 3 H 7 - , C 4 H 9 -, C 5 H 11 -, also other i-C 3 H
7 -, i-C 4 H 9 -, i-C 5 H 11 -, t-C 4 H 9 -, neo-
C 5 H 11- and the like. As the halogen atom, Br, C
l, I, F, etc. can be used.
【００１７】本発明において、ＣＤを上記のような化合
物と反応させてＣＤポリマーを合成するための反応例と
しては以下のようなものが挙げられる。In the present invention, examples of the reaction for synthesizing the CD polymer by reacting CD with the above compound include the following.
【００１８】[0018]
【化１２】 [Chemical formula 12]
【００１９】[0019]
【化１３】 [Chemical 13]
【００２０】[0020]
【化１４】 [Chemical 14]
【００２１】[0021]
【化１５】 [Chemical 15]
【００２２】[0022]
【化１６】 [Chemical 16]
【００２３】[0023]
【化１７】 [Chemical 17]
【００２４】上記反応は具体的には以下のようにして行
なわれる。 （１）脱水ＤＭＦ／脱水ピリジン中にβ−ＣＤを室温で
溶解後窒素気流下０〜５℃に冷却する。その系にＤＭＦ
に溶解したテレフタル酸塩化物を窒素気流下ゆっくりと
滴下する。滴下終了後０〜５℃下で２時間、さらに室温
で２時間、ついで120〜140℃下で６時間反応させる。反
応終了後、溶媒を減圧下留去し、残渣を大量の氷水中に
注ぎよく攪拌する。析出した沈殿物を集めよく水洗し、
乾燥することでポリマーを得る。The above reaction is specifically carried out as follows. (1) β-CD is dissolved in dehydrated DMF / dehydrated pyridine at room temperature and then cooled to 0 to 5 ° C under a nitrogen stream. DMF to the system
The terephthalic acid chloride dissolved in is slowly added dropwise under a nitrogen stream. After completion of the dropping, the reaction is carried out at 0 to 5 ° C for 2 hours, further at room temperature for 2 hours, and then at 120 to 140 ° C for 6 hours. After completion of the reaction, the solvent is distilled off under reduced pressure and the residue is poured into a large amount of ice water and well stirred. The deposited precipitate is collected and washed well with water,
A polymer is obtained by drying.
【００２５】（２）重合反応管中にβ−ＣＤ及びテレフ
タル酸ジメチル、酢酸カルシウム２水和物及び三酸化ア
ンチモンのＤＭＦ溶液を入れ均一溶液とする。混合物を
加熱し、毛管を反応管の底に届くように入れ窒素を流
す。100〜120℃で６時間混合物中のメタノールを留去し
た後、140〜160℃で６時間加熱する。そして減圧にし、
さらに12時間加熱し、反応終了後は窒素気流下で放冷す
る。ＤＭＦ溶液はそのまま大量の水中に入れ再沈殿さ
せ、得られた沈殿物を濾過し、よく水洗した後乾燥する
ことでポリマーを得る。(2) A DMF solution of β-CD, dimethyl terephthalate, calcium acetate dihydrate and antimony trioxide is placed in a polymerization reaction tube to make a uniform solution. The mixture is heated and a capillary is introduced to reach the bottom of the reaction tube and flushed with nitrogen. After distilling off the methanol in the mixture at 100 to 120 ° C for 6 hours, the mixture is heated at 140 to 160 ° C for 6 hours. And decompress,
After heating for another 12 hours, after the reaction is complete, the mixture is allowed to cool under a nitrogen stream. The DMF solution is put in a large amount of water as it is for reprecipitation, and the obtained precipitate is filtered, washed well with water and then dried to obtain a polymer.
【００２６】（３），ともＹがハロゲン原子の場
合：β−ＣＤを水に溶解し室温で水酸化ナトリウム水溶
液を加えよく攪拌させる。その系にイソフタル酸塩化物
又はフタル酸塩化物（Ｙ；Ｃｌ）のクロロホルム溶液を
２回に分けて加える。反応液はよく攪拌し、生じた乳濁
液を30分さらに反応させる。この乳濁液を大量のアセト
ン中より再沈殿させる。沈殿物はアセトンで洗浄し、つ
いで水洗を繰り返す。そして再度アセトンで洗浄後、乾
燥することでポリマーを得る。(3) In both cases where Y is a halogen atom: β-CD is dissolved in water, an aqueous sodium hydroxide solution is added at room temperature, and the mixture is stirred well. A solution of isophthalic acid chloride or phthalic acid chloride (Y; Cl) in chloroform is added to the system in two portions. The reaction solution is well stirred, and the resulting emulsion is further reacted for 30 minutes. This emulsion is reprecipitated from a large amount of acetone. The precipitate is washed with acetone and then washed with water repeatedly. Then, the polymer is obtained by washing again with acetone and then drying.
【００２７】，ともＹがエステルの場合：重合反応
管中にβ−ＣＤ及びイソフタル酸ジメチル又はフタル酸
ジメチル（Ｙ；ＯＣＨ3）、酢酸カルシウム２水和物、
さらに三酸化アンチモンのＤＭＦ溶液を入れ均一溶液と
する。この混合溶液を加熱し、毛管を反応管の底へ届く
ように入れ窒素を流す。100〜120℃で６時間混合物中の
メタノールを留去した後、140〜160℃でさらに６時間加
熱する。そして系を減圧にし12時間加熱し、反応終了
後、窒素気流下で放冷する。ＤＭＦ溶液はそのまま大量
の水中へ入れ再沈殿させ、得られた沈殿物は濾過し、よ
く水洗した後乾燥することでポリマーを得る。When Y is an ester: β-CD and dimethyl isophthalate or dimethyl phthalate (Y; OCH 3 ), calcium acetate dihydrate in the polymerization reaction tube,
Furthermore, a DMF solution of antimony trioxide is added to make a uniform solution. The mixed solution is heated, and a capillary is introduced so as to reach the bottom of the reaction tube, and nitrogen is flowed. After distilling off the methanol in the mixture at 100-120 ° C for 6 hours, heat at 140-160 ° C for a further 6 hours. Then, the system is evacuated and heated for 12 hours, and after the reaction is completed, it is allowed to cool under a nitrogen stream. The DMF solution is put into a large amount of water as it is for reprecipitation, and the obtained precipitate is filtered, washed well with water, and dried to obtain a polymer.
【００２８】（４）Ｙがハロゲン原子の場合：脱水ＤＭ
Ｆ／脱水ピリジン中にβ−ＣＤを室温下で溶解後窒素気
流下冷却する。その系に脱水ＤＭＦに溶解したジフェニ
ルメタン−ｐ，ｐ′−カルボン酸塩化物（Ｘ；−ＣＨ2
−，Ｙ；Ｃｌ）をゆっくりと滴下する。滴下終了後０〜
５℃下で２時間、さらに室温で２時間、ついで120〜140
℃下で６時間反応させる。反応終了後、溶媒を減圧下留
去し、残渣を大量の氷水中に注ぎよく攪拌する。析出し
た沈殿物を集め、よく水洗し乾燥することでポリマーを
得る。(4) When Y is a halogen atom: dehydrated DM
F / β-CD was dissolved in dehydrated pyridine at room temperature and then cooled in a nitrogen stream. Diphenylmethane -p dissolved in anhydrous DMF to the system, p'carboxylic acid chlorides (X; -CH 2
-, Y; Cl) is slowly added dropwise. 0 after dropping
2 hours at 5 ℃, 2 hours at room temperature, then 120-140
React at 6 ° C for 6 hours. After completion of the reaction, the solvent is distilled off under reduced pressure, and the residue is poured into a large amount of ice water and well stirred. The deposited precipitates are collected, washed well with water and dried to obtain a polymer.
【００２９】Ｙがエステルの場合：重合反応管中にβ−
ＣＤ及びジフェニルメタン−ｐ，ｐ′−カルボン酸メチ
ル（Ｘ；−ＣＨ2−，Ｙ；ＯＣＨ3）、酢酸カルシウム２
水和物、さらに三酸化アンチモンのＤＭＦ溶液を入れ均
一溶液とする。この混合溶液を加熱し、毛管を反応管の
底へ届くように入れ窒素を流す。100〜120℃で６時間混
合物中のメタノールを留去した後、140〜160℃でさらに
６時間加熱する。そして系を減圧にし12時間加熱、反応
終了後窒素気流下で放冷する。ＤＭＦ溶液はそのまま大
量の水中へ入れ再沈殿させ、得られた沈殿物は濾過し、
よく水洗した後乾燥することでポリマーを得る。When Y is an ester: β-in the polymerization reaction tube
CD and diphenylmethane -p, p'-carboxylate (X; -CH 2 -, Y ; OCH 3), calcium acetate 2
Add a hydrate and a solution of antimony trioxide in DMF to make a uniform solution. The mixed solution is heated, and a capillary is introduced so as to reach the bottom of the reaction tube, and nitrogen is flowed. After distilling off the methanol in the mixture at 100-120 ° C for 6 hours, heat at 140-160 ° C for a further 6 hours. Then, the system is evacuated and heated for 12 hours, and after the reaction is completed, it is left to cool under a nitrogen stream. The DMF solution was put into a large amount of water as it was for reprecipitation, and the obtained precipitate was filtered,
A polymer is obtained by thoroughly washing with water and then drying.
【００３０】（５）Ｙがハロゲン原子の場合：アジピ
ン酸塩化物（Ｚ＝４，Ｙ；Ｃｌ）とβ−ＣＤ及びニトロ
ベンゼン／ＤＭＦの混合物を窒素気流下ゆっくり加熱す
る。そして120〜130℃において８時間反応させる。反応
終了後減圧下、ニトロベンゼン、ＤＭＦを留去し、乾固
させる。残留した固体を集め、よく水洗し、さらにメタ
ノールで洗浄し乾燥することでポリマーを得る。(5) When Y is a halogen atom: A mixture of adipic acid chloride (Z = 4, Y; Cl), β-CD and nitrobenzene / DMF is slowly heated under a nitrogen stream. And it is made to react at 120-130 degreeC for 8 hours. After completion of the reaction, nitrobenzene and DMF are distilled off under reduced pressure to dryness. The residual solid is collected, washed thoroughly with water, further washed with methanol and dried to obtain a polymer.
【００３１】Ｙがエステルの場合：重合反応管中にβ−
ＣＤ及びアジピン酸ジメチル（Ｚ＝４，Ｙ；ＯＣ
Ｈ3）、一酸化鉛、ジ−tert−ブチルヒドロキノンのＤ
ＭＦ溶液を入れ均一溶液とする。この混合溶液を加熱
し、毛管を反応管の底へ届くように入れ窒素を流す。15
0〜160℃で４時間加熱後、系をゆっくりと減圧にし、そ
の後減圧状態のまま190〜200℃に上げ、さらに４時間反
応させる。窒素気流下で放冷しＤＭＦ溶液をそのまま大
量の水中へ入れ再沈殿させ、得られた沈殿物は濾過し、
よく水洗した後乾燥することでポリマーを得る。When Y is an ester: β-in the polymerization reaction tube
CD and dimethyl adipate (Z = 4, Y; OC
H 3), lead monoxide, di -tert- butyl hydroquinone D
Add the MF solution to make a uniform solution. The mixed solution is heated, and a capillary is introduced so as to reach the bottom of the reaction tube, and nitrogen is flowed. 15
After heating at 0 to 160 ° C. for 4 hours, the pressure of the system is gradually reduced, and then the pressure is raised to 190 to 200 ° C. and the reaction is continued for another 4 hours. The mixture was allowed to cool under a nitrogen stream, the DMF solution was put into a large amount of water as it was for reprecipitation, and the obtained precipitate was filtered,
A polymer is obtained by thoroughly washing with water and then drying.
【００３２】また（５）の反応は、のアジピン酸塩
化物をの化合物にかえることで同様に行なうことがで
きる。The reaction (5) can be carried out in the same manner by replacing the adipic acid chloride of the above with the compound of the above.
【００３３】（６）ｉ）Ｙがハロゲン原子の場合 脱水ＤＭＦ／脱水ピリジン中にβ−ＣＤを室温で溶解後
窒素気流下０〜５℃に冷却する。その系にＤＭＦに溶解
したナフタレン２，３−ジカルボン酸塩化物を窒素気流
下ゆっくりと滴下する。滴下終了後０〜５℃下で２時
間、さらに室温で２時間、ついで120〜140℃下で６時間
反応させる。反応終了後、溶媒を減圧下留去し、残渣を
大量の氷水中に注ぎよく撹拌する。析出した沈殿物を集
めよく水洗し、乾燥することでポリマーを得る。(6) i) When Y is a halogen atom: β-CD is dissolved in dehydrated DMF / dehydrated pyridine at room temperature and then cooled to 0 to 5 ° C under a nitrogen stream. Naphthalene 2,3-dicarboxylic acid chloride dissolved in DMF is slowly added dropwise to the system under a nitrogen stream. After completion of the dropping, the reaction is carried out at 0 to 5 ° C for 2 hours, further at room temperature for 2 hours, and then at 120 to 140 ° C for 6 hours. After completion of the reaction, the solvent is distilled off under reduced pressure and the residue is poured into a large amount of ice water and well stirred. The precipitated precipitate is collected, washed well with water, and dried to obtain a polymer.
【００３４】ii）Ｙがエステルの場合 重合反応管中にβ−ＣＤ及びナフタレン２，３−ジカル
ボン酸メチル、酢酸カルシウム２水和物及び三酸化アン
チモンのＤＭＦ溶液を入れ均一溶液とする混合物を加熱
し、毛管を反応管の底に届くように入れ窒素を流す。10
0〜120℃で６時間混合物中のメタノールを留去した後、
140〜160℃で６時間加熱する。そして減圧にし、さらに
12時間加熱し、反応終了後は窒素気流下で放冷する。Ｄ
ＭＦ溶液はそのまま大量の水中に入れ再沈殿させ、得ら
れた沈殿物を濾過し、よく水洗した後乾燥することでポ
リマーを得る。Ii) When Y is an ester: A mixture of β-CD and methyl naphthalene 2,3-dicarboxylate, calcium acetate dihydrate, and antimony trioxide in DMF is heated into a homogeneous reaction mixture in a polymerization reaction tube. Then, insert the capillary so that it reaches the bottom of the reaction tube and flush with nitrogen. Ten
After distilling off the methanol in the mixture at 0-120 ° C for 6 hours,
Heat at 140-160 ° C for 6 hours. Then decompress, and
After heating for 12 hours, after the reaction is completed, it is left to cool under a nitrogen stream. D
The MF solution is put into a large amount of water as it is for reprecipitation, and the obtained precipitate is filtered, washed well with water and then dried to obtain a polymer.
【００３５】また、ナフタレン２，３−ジカルボン酸塩
化物のかわりにナフタレン２，６−ジカルボン酸塩化
物、ナフタレン１，４−ジカルボン酸塩化物を用いても
同様に反応を行ないポリマーを得ることができる。Even if naphthalene 2,6-dicarboxylic acid chloride or naphthalene 1,4-dicarboxylic acid chloride is used instead of naphthalene 2,3-dicarboxylic acid chloride, the same reaction can be performed to obtain a polymer. it can.
【００３６】本発明において用いられるＣＤとしては、
例えばα−ＣＤ、β−ＣＤ及びγ−ＣＤが挙げられる。As the CD used in the present invention,
Examples include α-CD, β-CD and γ-CD.
【００３７】上記の如く得られる本発明のＣＤポリマー
は水又は特定の有機溶媒に不溶である一方、特定の酵素
により分解可能であり、分解性ポリマーとして使用する
こともできる。The CD polymer of the present invention obtained as described above is insoluble in water or a specific organic solvent, but can be decomposed by a specific enzyme, and can be used as a degradable polymer.
【００３８】表１に分解性を示すデータを記す。Data showing the degradability are shown in Table 1.
【００３９】[0039]
【表１】 但し、上記結果は、各々のＣＤポリマーを10cm×10cm
（厚み：約50μm）のフィルム状にし、これを土中に埋
め、一定期間ごとにその状態を調べて得られたものであ
る。[Table 1] However, the above results show that each CD polymer is 10 cm x 10 cm.
It was obtained by making a film (thickness: about 50 μm), burying this in soil, and examining the condition at regular intervals.
【００４０】[0040]
【発明の効果】本発明により、ＣＤを架橋高分子内に固
定することでポリマー中におけるＣＤユニットの固定量
は増加し、確実にＣＤユニットが存在するためその機能
性は大いに期待出来る。またＣＤがほとんど分子内架橋
をしないため不溶性高分子となり、水溶液中で使用で
き、その包接作用を利用して分離・吸着剤となり得る。INDUSTRIAL APPLICABILITY According to the present invention, by immobilizing CD in a crosslinked polymer, the amount of CD units fixed in the polymer is increased, and since CD units are surely present, its functionality can be expected greatly. Further, since CD hardly undergoes intramolecular cross-linking, it becomes an insoluble polymer, can be used in an aqueous solution, and can be used as a separation / adsorbent by utilizing its inclusion effect.
【００４１】さらにエステル結合を含むことで特定の酵
素によって分解出来、ＣＤ自体が酵素分解されるので分
解性ポリマーとして使用出来る。Further, by containing an ester bond, it can be decomposed by a specific enzyme, and CD itself is enzymatically decomposed, so that it can be used as a degradable polymer.
Claims (5)
［Ｉ］で表わされる化合物を反応させることを特徴とす
るサイクロデキストリンポリマーの製造方法。 【化１】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。）1. A method for producing a cyclodextrin polymer, which comprises reacting cyclodextrin with a compound represented by the following general formula [I]. [Chemical 1] (In the formula, Y represents a halogen atom or an -OR group, and R represents an alkyl group or a cyclohexyl group.)
I］で表わされる化合物を反応させることを特徴とする
サイクロデキストリンポリマーの製造方法。 【化２】 る結合手を表わし、Ｙはハロゲン原子又は−ＯＲ基を表
わし、Ｒはアルキル基又はシクロヘキシル基を表わ
す。）2. A cyclodextrin having the following general formula [I
[I] A method for producing a cyclodextrin polymer, which comprises reacting a compound represented by the formula [I]. [Chemical 2] Represents a bond, Y represents a halogen atom or an —OR group, and R represents an alkyl group or a cyclohexyl group. )
I］で表わされる化合物を反応させることを特徴とする
サイクロデキストリンポリマーの製造方法。 【化３】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。また、Ｚは
０〜12の整数を表わす。）3. A cyclodextrin having the following general formula [II
[I] A method for producing a cyclodextrin polymer, which comprises reacting a compound represented by the formula [I]. [Chemical 3] (In the formula, Y represents a halogen atom or an -OR group, R represents an alkyl group or a cyclohexyl group, and Z represents an integer of 0 to 12.)
V］で表わされる化合物を反応させることを特徴とする
サイクロデキストリンポリマーの製造方法。 【化４】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。）4. A cyclodextrin having the following general formula [I
V] is reacted with a compound for producing a cyclodextrin polymer. [Chemical 4] (In the formula, Y represents a halogen atom or an -OR group, and R represents an alkyl group or a cyclohexyl group.)
［Ｖ］、一般式［VI］又は一般式［VII］で表わされる
化合物を反応させることを特徴とするサイクロデキスト
リンポリマーの製造方法。 【化５】 （式中、Ｙはハロゲン原子又は−ＯＲ基を表わし、Ｒは
アルキル基又はシクロヘキシル基を表わす。）5. A method for producing a cyclodextrin polymer, which comprises reacting cyclodextrin with a compound represented by the following general formula [V], general formula [VI] or general formula [VII]. [Chemical 5] (In the formula, Y represents a halogen atom or an -OR group, and R represents an alkyl group or a cyclohexyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3238658A JP3010602B2 (en) | 1991-08-26 | 1991-08-26 | Method for producing cyclodextrin polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3238658A JP3010602B2 (en) | 1991-08-26 | 1991-08-26 | Method for producing cyclodextrin polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0551402A true JPH0551402A (en) | 1993-03-02 |
| JP3010602B2 JP3010602B2 (en) | 2000-02-21 |
Family
ID=17033405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3238658A Expired - Lifetime JP3010602B2 (en) | 1991-08-26 | 1991-08-26 | Method for producing cyclodextrin polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3010602B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011102346A1 (en) * | 2010-02-16 | 2011-08-25 | 株式会社ネオス | Agent and method for selectively anchoring halogenated aromatic compound contained in medium |
| JP2012077109A (en) * | 2010-09-30 | 2012-04-19 | Neos Co Ltd | Method of cleaning cyclodextrin-condensation polymer |
| JP2012229359A (en) * | 2011-04-27 | 2012-11-22 | Neos Co Ltd | Method for producing cyclodextrin polymer and method for selectively adsorbing and removing halogenated aromatic compound contained in medium by using the same |
| JP2012229360A (en) * | 2011-04-27 | 2012-11-22 | Neos Co Ltd | Method for selectively adsorbing and removing halogenated aromatic compound contained in medium using silica-containing cyclodextrin polymer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5911053B2 (en) * | 2011-12-28 | 2016-04-27 | 株式会社ネオス | Radioactive iodine removal material and radioactive iodine removal method |
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1991
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011102346A1 (en) * | 2010-02-16 | 2011-08-25 | 株式会社ネオス | Agent and method for selectively anchoring halogenated aromatic compound contained in medium |
| CN102762294A (en) * | 2010-02-16 | 2012-10-31 | 株式会社尼欧斯 | Selective fixative and selective fixation method for halogenated aromatic compounds contained in media |
| JP5532359B2 (en) * | 2010-02-16 | 2014-06-25 | 株式会社ネオス | Selective fixing agent and selective fixing method of halogenated aromatic compound contained in medium |
| KR101437252B1 (en) * | 2010-02-16 | 2014-09-02 | 네오스 컴파니 리미티드 | Agent and method for selectively anchoring halogenated aromatic compound contained in medium |
| JP2012077109A (en) * | 2010-09-30 | 2012-04-19 | Neos Co Ltd | Method of cleaning cyclodextrin-condensation polymer |
| JP2012229359A (en) * | 2011-04-27 | 2012-11-22 | Neos Co Ltd | Method for producing cyclodextrin polymer and method for selectively adsorbing and removing halogenated aromatic compound contained in medium by using the same |
| JP2012229360A (en) * | 2011-04-27 | 2012-11-22 | Neos Co Ltd | Method for selectively adsorbing and removing halogenated aromatic compound contained in medium using silica-containing cyclodextrin polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3010602B2 (en) | 2000-02-21 |
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