JPS6020924A - Production of bead-foam insoluble cyclodextrin polymer - Google Patents
Production of bead-foam insoluble cyclodextrin polymerInfo
- Publication number
- JPS6020924A JPS6020924A JP12818283A JP12818283A JPS6020924A JP S6020924 A JPS6020924 A JP S6020924A JP 12818283 A JP12818283 A JP 12818283A JP 12818283 A JP12818283 A JP 12818283A JP S6020924 A JPS6020924 A JP S6020924A
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- crosslinking agent
- bead
- polymer
- production
- 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
Abstract
Description
【発明の詳細な説明】
本発明は、ビーズ状シクロデキストリンポリマーに関し
、更に詳しくは、シクロデキストリンに架橋剤を反応さ
せることによりビーズ状の不溶性樹脂を製造する方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to bead-shaped cyclodextrin polymers, and more particularly to a method for producing bead-shaped insoluble resins by reacting cyclodextrin with a crosslinking agent.
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り、その分子内に筒
状の空洞を有していて、種々の物仙をその中に取り込む
ことによって包接化合物を形成する。この包接化合物を
形成するためには、被包接吻質の分子の形と大きさがシ
クロデキストリンの空洞に適合しなければならず、適合
の度合により被包接吻質とシクロデキストリンとの間に
働く親和力に差が生じるために、その差を利用すること
によって種々の物質の分離・分割を行うことが可能であ
る。Cyclodextrin has six or more glucose α-1
, 4-linked cyclic oligosaccharide, which has a cylindrical cavity within its molecule, and forms clathrate compounds by incorporating various molecules into it. In order to form this clathrate, the shape and size of the molecule of the encapsulated proboscis must fit into the cavity of the cyclodextrin, and the degree of fit determines the relationship between the encapsulated proboscis and the cyclodextrin. Since there is a difference in the working affinity, it is possible to separate and divide various substances by utilizing this difference.
この分離や分割にはいくつかの方法があるが、とりわけ
、シクロデキストリンを高分子化することによって不溶
性の樹脂とし、それをカラムクロマトグラフィーの充填
剤として利用する方法が有望視されている。There are several methods for this separation and division, but one method that is particularly promising is to polymerize cyclodextrin to make it an insoluble resin and use it as a packing material for column chromatography.
さて、不溶性シクロデキストリン樹脂の製法としては、
例えば、シクロデキストリンにエピクロルヒドリン、ジ
ェポキシ化合物、ジイソシアネ−ト、アクリルアミド誘
導体などを作用させて架橋高分子化する方法が知られて
いる。しかしながら、これらの方法により得られる樹脂
はゲル状であっＣ１水などを吸収して膨潤する欠点を有
しており、カラムなどに利用するためには機械的強度を
高め、かつ、溶媒の流通性を良くする必要があり、その
ためにはビーズ状であることが望まれる。Now, as for the manufacturing method of insoluble cyclodextrin resin,
For example, a method is known in which cyclodextrin is made to react with epichlorohydrin, a jepoxy compound, a diisocyanate, an acrylamide derivative, etc. to form a crosslinked polymer. However, the resins obtained by these methods are gel-like and have the disadvantage of swelling when absorbing C1 water, etc., and in order to be used in columns, etc., it is necessary to increase mechanical strength and solvent flowability. It is necessary to improve the quality of the particles, and for this purpose it is desirable that they be bead-shaped.
ビーズ状のシクロデキストリンポリマーをつくるために
は、アルカリ水溶液中に高濃度で溶解せしめたシクロデ
キストリンを、トルエン、キシレン、メチルイソブチル
ケトンなどの溶媒に分散させ、エピクロルヒドリン、エ
チレングリコールジグリシジルエーテルなどと反応させ
る方法が知られている。しかしながら、これらの方法に
おいては、有機相の溶媒もしくはエマルジョンの安定化
に用いる界面活性剤が生成したビーズ内に取り込まれ、
洗浄によって完全に除去することが困難なため、使用中
に溶出する欠点を有している。In order to make bead-shaped cyclodextrin polymers, cyclodextrin dissolved in a high concentration in an alkaline aqueous solution is dispersed in a solvent such as toluene, xylene, or methyl isobutyl ketone, and then reacted with epichlorohydrin, ethylene glycol diglycidyl ether, etc. There are known ways to do this. However, in these methods, the solvent in the organic phase or the surfactant used to stabilize the emulsion is incorporated into the produced beads;
Since it is difficult to completely remove by washing, it has the disadvantage that it elutes during use.
本発明者らは、このような実情に鑑み、ビーズ状シクロ
デキス） ＩＪンポリマーの製法を改良すべく鋭意研究
を重ねた結果、分散媒である有機相として架橋剤そのも
のを用いることにより、前記の欠点を改善できることを
見い出し、これに基づいて本発明を成すに至った。In view of these circumstances, the present inventors have conducted extensive research to improve the method for producing bead-shaped cyclodextrin polymers, and have found that the above drawbacks can be overcome by using the crosslinking agent itself as the organic phase, which is the dispersion medium. The present invention has been accomplished based on this discovery.
すなわち、本発明は、架橋剤によりあらかじめ不溶化し
ない程度に高分子化したシクロデキストリンを有機相と
しての架橋剤中に分散させ３０℃〜８０°Ｃで反応させ
ることにより、ビーズ状シクロデキストリンポリマーを
製造する方法を提供するものである。That is, the present invention produces bead-shaped cyclodextrin polymers by dispersing cyclodextrin, which has been polymerized to such an extent that it does not become insolubilized by a crosslinking agent, in a crosslinking agent as an organic phase and reacting it at 30°C to 80°C. This provides a method to do so.
本発明方法においては、用いるシクロデキストリンはα
−シクロデキストリン、β〜シクロデキストリン、γ−
シクロデキストリンおよびそれらの混合物であって、こ
れらのシフロブキス） ＩＪンをあらかじめ不溶化しな
い程度に高分子化しておく必要がある。高分子化に用い
る架橋剤としては、エピクロルヒドリン、エチレングリ
コールジグリシジルエーテル、１．４−ブタンジオール
ジグリシジルエーテル、１．２．７．８−ジェポキシオ
クタン、エチレングリコールビス（２−クロロエチル）
エールなどが好んで用いられる。この高分子化されたシ
クロデキストリンの分子量は不溶化しない範囲であれば
できるだけ大きい方が望ましく、エピクロルヒドリンを
用いた場合は平均分子散が５０００〜８０００程度とな
る。通常、この高分子化においてｌ・および架橋剤０，
１〜１０重量部の範囲で用いることが望ましく、特に架
橋剤の量は不溶化しない範囲に設定することが必要であ
る。この高分子化反応における温度は３０’Ｃ〜８０℃
が好ましく、特に５０°Ｃ前後が好適である。通常、１
００〜５００ ｒｌ）Ｔｌｌ程度の回転速度でかきまぜ
つつ、架橋剤をゆっくり滴下することによって３０分〜
２時間で終了し、シロップ状の粘性の高い液体が得られ
る。In the method of the present invention, the cyclodextrin used is α
-Cyclodextrin, β~Cyclodextrin, γ-
Cyclodextrins and mixtures thereof, such as cyclodextrins, must be polymerized in advance to such an extent that they do not become insolubilized. Examples of crosslinking agents used for polymerization include epichlorohydrin, ethylene glycol diglycidyl ether, 1.4-butanediol diglycidyl ether, 1.2.7.8-jepoxyoctane, and ethylene glycol bis(2-chloroethyl).
Ale etc. are preferably used. The molecular weight of this polymerized cyclodextrin is preferably as large as possible within a range that does not cause insolubilization, and when epichlorohydrin is used, the average molecular dispersion is about 5,000 to 8,000. Usually, in this polymerization, l. and crosslinking agent 0,
It is desirable to use the crosslinking agent in an amount of 1 to 10 parts by weight, and in particular, it is necessary to set the amount of the crosslinking agent within a range that does not cause insolubilization. The temperature in this polymerization reaction is 30'C to 80°C.
is preferable, particularly around 50°C. Usually 1
00 to 500 rl) While stirring at a rotational speed of approximately Tll, slowly drop the crosslinking agent for 30 minutes to
The process is completed in 2 hours and a syrupy, highly viscous liquid is obtained.
次に、このシロップ状の液体より泡を除き、粘度が高ず
ぎる場合は：１ｌｆｉ ｆｊｔ （０，１〜０４５重邦
：部）の水を加えて有機相に分散しやすい粘度に調製し
た後、シクロデキストリンの１重量部に対して５〜１０
０重量部の架橋剤を加え前記の温度に保ちつつ５００〜
３０００ ｒｐｍの回転速度でかきまぜて反応させる。Next, remove bubbles from this syrupy liquid, and if the viscosity is too high, add 1 lfi fjt (0.1 to 0.45 parts) of water to adjust the viscosity to easily disperse in the organic phase. , 5 to 10 per part by weight of cyclodextrin
500~ while adding 0 parts by weight of crosslinking agent and keeping at the above temperature.
Stir and react at a rotation speed of 3000 rpm.
架橋剤の量およびかくはん速度は、前記の範囲外でもよ
いが、一般に架橋剤のｂｙが多く、また、か（はん速度
が速いほど生成したビーズの粒子径は小さくなる。また
、この段階で使用する架橋剤は、水溶性ポリマーを製造
する段階で用いたものと異ってもよい。通常は３０分〜
２時間でビーズの生成が始まり、２〜１０時間で完了す
る。The amount of crosslinking agent and stirring speed may be outside the above ranges, but generally the amount of crosslinking agent is large, and The crosslinking agent used may be different from that used in the step of producing the water-soluble polymer.Usually 30 minutes to
Bead formation begins in 2 hours and completes in 2-10 hours.
このようにして得られた生成物をアセトンもしくは低級
アルコールにて数回洗浄し、次いで洗浄水のｐＨが中性
になるまで蒸留水で洗ｎ＋ した後、アセトンもしくは
低級アルコールにより脱水し乾燥することによりビーズ
状のシクロデキストリンポリマーが得られる。ビーズ中
に残留している未反応の架橋剤を除くためには、１０〜
３０％水酸化ナトリウム水溶液中に４０°Ｃ〜６０’Ｇ
で２〜５時間浸した後、前記と同様に洗浄、脱水、乾燥
を行う。The product thus obtained is washed several times with acetone or lower alcohol, then washed with distilled water until the pH of the washing water becomes neutral, and then dehydrated with acetone or lower alcohol and dried. A bead-shaped cyclodextrin polymer is obtained. In order to remove unreacted crosslinking agent remaining in the beads,
40°C to 60'G in 30% aqueous sodium hydroxide solution
After soaking for 2 to 5 hours, washing, dehydration, and drying are performed in the same manner as above.
本発明方法の特徴は、あらかじめ不溶化しない程度に高
分子化したポリマーを調製し、それを大量の架橋剤中に
分散させることによりビーズ状のシクロデキストリンポ
リマーを製造することであり、従来の方法と比較して架
橋剤以外の分散媒を使用しないため、生成したビーズの
精製が簡単であり、かつ不純物を含まないビーズが得ら
れる。A feature of the method of the present invention is that a bead-shaped cyclodextrin polymer is produced by preparing a polymer that has been polymerized in advance to the extent that it does not become insolubilized and dispersing it in a large amount of crosslinking agent. In comparison, since no dispersion medium other than a crosslinking agent is used, the produced beads can be easily purified and beads containing no impurities can be obtained.
次に、実施例により本発明を更に詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
粉末状のβ−シクロデキストリン２ｇに水１ 、’５
ｍｌを加えて混練し、これに４０９６水酸化ナトリウム
水溶液２．５ ｍｌ；及び水素化ホウ素ナトリウム２０
ｍｇを加えて均一な溶液とし、これを５０°Ｃに保って
２０Ｏｒｌ）ｎ〕の速度でかきまぜながらｌ ｍｌのエ
ピクロルヒドリンを約１０分間で滴下し、更に２時間か
きまぜた復水２ｄを加えて泡を除き、得られたシロップ
状の液体に５０ｄのエピクロルヒドリンを加えて５０℃
に保ちつつ２０００ ｒｌ）ｍの回転速度で４時間かき
まぜた。Example 1 2 g of powdered β-cyclodextrin and 1 part of water, '5
2.5 ml of 4096 sodium hydroxide aqueous solution; and 20 ml of sodium borohydride
1 ml of epichlorohydrin was added dropwise over about 10 minutes while stirring at 50°C, and 2 d of condensate stirred for 2 hours was added to form a homogeneous solution. Add 50 d of epichlorohydrin to the resulting syrupy liquid and heat at 50°C.
The mixture was stirred for 4 hours at a rotational speed of 2000 rl) m while maintaining the temperature.
得られたビーズをろ過して分離し、アセトン５９ ｍｌ
づつで３回洗浄し、洗浄液のｐＨが中性になるまで蒸留
水で洗浄し、更に蒸留水中に１日没した後、アセトン１
００ｍ１中に５時間浸して脱水し、真空デシケータ−中
で五酸化リンにより１日乾燥した。The obtained beads were separated by filtration, and 59 ml of acetone was added.
Wash with distilled water until the pH of the washing solution becomes neutral, and after soaking in distilled water for one day, wash with acetone 1
00ml for 5 hours to dehydrate, and dried in a vacuum desiccator with phosphorus pentoxide for 1 day.
このようにしてビーズ状β−シクロデキストリンポリマ
ーの２０〜２００メツシユの粒子径のものが２．９ｇ得
られた。In this way, 2.9 g of bead-shaped β-cyclodextrin polymer having a particle size of 20 to 200 mesh was obtained.
実施例２
粉末状のβ−シクロデキストリン２夕に水１．５ｍｌを
加えて混練し、これに４０％水酸化ナトリウム水溶液２
．５ ｍｌおよび水素化ホウ素す） ＩＪウム２ｏＩｎ
９を加えて均一な溶液とし、これを５０℃に保って２０
Ｏｒｐｍの速度でかきまぜながら１．５ｍｌの１，４−
ブタンジオールジグリシジルエーテルを約１０分間で滴
下し、更に２時間かきまぜたのち水２ｍｌを加えてシロ
ップ状の溶液とした。これに１，４−ブタンジオールジ
グリシジルエーテル５ｏ１ｎｌを加えて５０’Ｃに保ち
つつ２００Ｏｒｐｍの回転速度で４時間かきまぜた。Example 2 1.5 ml of water was added to powdered β-cyclodextrin and kneaded, and 40% aqueous sodium hydroxide solution was added to this mixture.
．． 5 ml and boron hydride) IJium2oIn
9 to make a homogeneous solution, keep this at 50℃ and incubate for 20
While stirring at the speed of orpm, add 1.5 ml of 1,4-
Butanediol diglycidyl ether was added dropwise over about 10 minutes, and after further stirring for 2 hours, 2 ml of water was added to form a syrup-like solution. To this was added 501 nl of 1,4-butanediol diglycidyl ether, and the mixture was stirred at a rotational speed of 200 rpm for 4 hours while maintaining the temperature at 50'C.
得られたビーズをろ過して分離し、アセトン５Ｑｍｌづ
つで３回洗浄し、洗浄液のｐＨが中性になるまで蒸留水
で洗浄し、更に蒸留水中に１日没した後、アセトン１０
０ｍ１中に５時間浸して脱水し、真空デシケータ−で五
酸化リンにより１日乾燥した。このようにして２０〜２
００メツシユのビーズ状β−シクロデキストリンポリマ
ー１．９９が得られた。The obtained beads were separated by filtration, washed three times with 5 Qml of acetone each time, washed with distilled water until the pH of the washing solution became neutral, and then submerged in distilled water for one day.
The sample was immersed in 0ml water for 5 hours to dehydrate, and dried in a vacuum desiccator with phosphorus pentoxide for 1 day. In this way 20-2
A beaded β-cyclodextrin polymer of 0.00 mesh was obtained.
特許出願人 工業技術院長 川 口１ 裕 部２１１Patent applicant: Director of the Agency of Industrial Science and Technology Kawaguchi 1 Hiroshi Department 211
Claims (1)
化したシフロブキス）ＩＪンを架橋剤中に分散させて反
応させ不溶性高分子化させることを特徴とするビーズ状
シクロデキストリンポリマーの製法。 ２ 架橋剤がエピクロルヒドリンおよびジェポキシ化合
物である特許請求の範囲第１項記載の製法[Scope of Claims] 1. A method for producing a bead-shaped cyclodextrin polymer, which comprises dispersing Cyfrobukis IJ, which has been polymerized to the extent that it will not become insolubilized, in a cross-linking agent and reacting with it to make it into an insoluble polymer. . 2. The manufacturing method according to claim 1, wherein the crosslinking agent is epichlorohydrin and a jepoxy compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12818283A JPS6020924A (en) | 1983-07-14 | 1983-07-14 | Production of bead-foam insoluble cyclodextrin polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12818283A JPS6020924A (en) | 1983-07-14 | 1983-07-14 | Production of bead-foam insoluble cyclodextrin polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6020924A true JPS6020924A (en) | 1985-02-02 |
| JPS6312490B2 JPS6312490B2 (en) | 1988-03-19 |
Family
ID=14978457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12818283A Granted JPS6020924A (en) | 1983-07-14 | 1983-07-14 | Production of bead-foam insoluble cyclodextrin polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6020924A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61283601A (en) * | 1985-06-10 | 1986-12-13 | Nippon Junyaku Kk | Production of polycyclodextrin bead |
| JP2006143953A (en) * | 2004-11-24 | 2006-06-08 | Aomori Prefecture | Method for producing beaded cyclodextrin polymer |
| JP2008246287A (en) * | 2007-03-29 | 2008-10-16 | Aomori Prefecture | Method for removing surfactant |
| JP2011213743A (en) * | 2010-03-31 | 2011-10-27 | Aomori Prefectural Industrial Technology Research Center | Granular cyclodextrin polymer and manufacturing method therefor |
| CN103756260A (en) * | 2014-01-23 | 2014-04-30 | 苏州大学 | Biomass modified thermosetting resin and preparation method thereof |
| US9505850B2 (en) | 2012-05-30 | 2016-11-29 | National University Corporation Kumamoto University | Endotoxin adsorbent |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10113385C1 (en) * | 2001-03-16 | 2002-08-29 | Schott Glas | Fresnels |
| ES2310948B2 (en) | 2005-02-25 | 2009-09-16 | Universidade De Santiago De Compostela | PROCEDURE FOR OBTAINING HYDROGELS OF CYCLODEXTRINES WITH GLICIDILETERS, THE COMPOSITIONS OBTAINED AND THEIR APPLICATIONS. |
-
1983
- 1983-07-14 JP JP12818283A patent/JPS6020924A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61283601A (en) * | 1985-06-10 | 1986-12-13 | Nippon Junyaku Kk | Production of polycyclodextrin bead |
| JP2006143953A (en) * | 2004-11-24 | 2006-06-08 | Aomori Prefecture | Method for producing beaded cyclodextrin polymer |
| JP2008246287A (en) * | 2007-03-29 | 2008-10-16 | Aomori Prefecture | Method for removing surfactant |
| JP2011213743A (en) * | 2010-03-31 | 2011-10-27 | Aomori Prefectural Industrial Technology Research Center | Granular cyclodextrin polymer and manufacturing method therefor |
| US9505850B2 (en) | 2012-05-30 | 2016-11-29 | National University Corporation Kumamoto University | Endotoxin adsorbent |
| US10155217B2 (en) | 2012-05-30 | 2018-12-18 | National University Corporation Kumamoto | Endotoxin adsorbent |
| CN103756260A (en) * | 2014-01-23 | 2014-04-30 | 苏州大学 | Biomass modified thermosetting resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6312490B2 (en) | 1988-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3277025A (en) | Anion-exchanger from crosslinked polyhydroxy materials | |
| JPS6317904A (en) | Production of crosslinked porous polyvinyl alcohol particle | |
| US3208994A (en) | Process for preparing hydrophilic copolymerization and product obtained thereby | |
| US4175183A (en) | Hydroxyalkylated cross-linked regenerated cellulose and method of preparation thereof | |
| US4076930A (en) | Polysaccharide polyols | |
| EP0521970B1 (en) | Water-insoluble cyclodextrin polymerizates and process for producing them | |
| US4152170A (en) | Cross-linked pullulan | |
| US10836834B2 (en) | Separating agent for optical isomer | |
| JPS5820962B2 (en) | Production method of cyclodextrin-polyvinyl alcohol polymer | |
| WO1998041546A1 (en) | Hydrogel beads from chitosan | |
| US5360899A (en) | Cyclodextrin polymers and process for their preparation | |
| JPH04166764A (en) | Packing agent for liquid chromatography and preparation thereof | |
| AU2008224044A1 (en) | Imprinted polymers | |
| CN106279442A (en) | The preparation method of a kind of ion liquid functionalization cellulose and cellulose and application | |
| JPS6020924A (en) | Production of bead-foam insoluble cyclodextrin polymer | |
| CS195162B1 (en) | Method of preparing amphoteric ion exchangers | |
| JPH0320706B2 (en) | ||
| CN102352004A (en) | Chloromethylated polyetheretherketone (PEEK) and synthetic method thereof | |
| US8053543B2 (en) | Filler for optical isomer separation | |
| CA1094550A (en) | Ionic pullulan gels and production thereof | |
| JPH07216002A (en) | Production of cyclodextrin derivative, and cyclodextrin derivative | |
| US2862894A (en) | Preparation of anion-exchange resins containing weakly basic and strongly basic functional groups | |
| JPS6011961B2 (en) | Manufacturing method of polycyclodextrin beads | |
| CN111138668A (en) | Cyclodextrin modified macroporous adsorption resin and preparation method thereof | |
| JPH0446961B2 (en) |