JPS62105908A - Crystalline complex of zirconium phosphate-cyclodextrin and its production - Google Patents
Crystalline complex of zirconium phosphate-cyclodextrin and its productionInfo
- Publication number
- JPS62105908A JPS62105908A JP60243617A JP24361785A JPS62105908A JP S62105908 A JPS62105908 A JP S62105908A JP 60243617 A JP60243617 A JP 60243617A JP 24361785 A JP24361785 A JP 24361785A JP S62105908 A JPS62105908 A JP S62105908A
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- zirconium phosphate
- composite
- crystalline
- zirconium
- 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
- Enzymes And Modification Thereof (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は各種化学反応に対する触媒・固定化人工酸素、
化学薬品特に医薬品、農薬す殺虫剤・除草剤などのマイ
クロカプセル剤、ゲルクロマトグラフィーの充填剤など
として使用される新規なα−リン酸ジルコニウムとシク
ロデキストリン系化合物の結晶質複合体及びその製造法
に関する。[Detailed description of the invention] Industrial application field The present invention relates to catalysts for various chemical reactions, immobilized artificial oxygen,
A novel crystalline complex of α-zirconium phosphate and cyclodextrin compounds used as microcapsules for chemicals, especially pharmaceuticals, agricultural chemicals, insecticides, herbicides, etc., and as a packing material for gel chromatography, and a method for producing the same. Regarding.
従来技術
従来、シクロデキストリン系化合物は、その分子包接能
と触媒能を利用することにより、化学的に不安定な物質
、特に医薬品、殺虫剤、除草剤などを安定化するための
マイクロカプセル化剤、難溶性物質の可溶化剤、カラム
クロマトグラフィ用充填剤などに使用されている。また
酸素モデルとして注目され、特殊な官能基を導入して機
能を高度化し、人工酵素として活用する試みも行われて
いる。Conventional technology Conventionally, cyclodextrin compounds have been used in microencapsulation to stabilize chemically unstable substances, especially pharmaceuticals, pesticides, herbicides, etc., by utilizing their molecular inclusion ability and catalytic ability. It is used as a solubilizing agent for poorly soluble substances, a packing material for column chromatography, etc. It has also attracted attention as an oxygen model, and attempts are being made to introduce special functional groups to improve its functionality and use it as an artificial enzyme.
そして、シクロデキストリンの機能の高度化としては、
従来ゾクロデキス） ＩＪンに官能基の導入または高分
子化することが行われている。As for the advancement of the functions of cyclodextrin,
Conventionally, the introduction of functional groups or polymerization into IJ has been carried out.
本発明者はさきに、化学式Ｚｒ（ＨＰＯ４）２・Ｈ２Ｏ
で示される層状構造を有するα−リン酸ジルコニウムを
モノ−（６−β−アミノエチルアミ７−６−デオキシ）
−β−シクロデキストリンの重炭酸塩の水溶液に浸漬す
ると、転化反応により約２９１の層間距離を持つ結晶質
複合体を開発した（Ｅ本化学会第４８秋季年会講演予稿
集１．２Ｂ１２）。The inventor previously proposed that the chemical formula Zr(HPO4)2.H2O
Mono-(6-β-aminoethylami7-6-deoxy) α-zirconium phosphate having the layered structure shown in
When immersed in an aqueous solution of bicarbonate of -β-cyclodextrin, a crystalline composite with an interlayer distance of about 291 was developed by a conversion reaction (Proceedings of the 48th Autumn Annual Meeting of the Chemical Society of Japan 1.2B12).
しかし、この転化反応の転化率を高めるため、反応溶液
の濃度を上げると、生成する複合体は急激に非晶質化し
、結局この結晶質複合体の生成率は低率に留まっていた
。さ°らに、この複合体はリン酸ジルコニウムの層間内
に取りこまれたシクロデキストリン分子が互に空洞にふ
たをし、しかも機能を発揮するには都合の悪い構造のも
のであった。However, when the concentration of the reaction solution was increased in order to increase the conversion rate of this conversion reaction, the resulting composite rapidly became amorphous, and in the end, the production rate of this crystalline composite remained at a low rate. Furthermore, this complex had a structure in which the cyclodextrin molecules incorporated between the zirconium phosphate layers covered each other's cavities, which was inconvenient for it to function properly.
発明の目的
本発明は前記従来の結晶質複合体の欠点を解消せんとす
るものであや、その目的は分子包接に適したリン酸ジル
コニウム−シクロデキストリン化合物の結晶質複合体を
提供するにある。OBJECTS OF THE INVENTION The present invention aims to overcome the drawbacks of the conventional crystalline composites, and its purpose is to provide a crystalline composite of zirconium phosphate-cyclodextrin compound suitable for molecular inclusion. .
発明の構成
本発明者は前記目的を達成すべく更に鋭、意研究の結果
、前記欠点の原因は、モノ−（６−β−アミノエチルア
ミノ−６−デオキシ）−β−シクロデキストリンの重炭
酸塩を使用したためであり、これに代え、重層酸分を除
き塩基型にするとその欠点をなくし得られることを究明
し得た。この知見に基いて本発明を完成した。Composition of the Invention In order to achieve the above object, the inventors of the present invention have conducted further intensive research and found that the cause of the above drawback is the bicarbonate of mono-(6-β-aminoethylamino-6-deoxy)-β-cyclodextrin. This was due to the use of a salt, and it was found that replacing this with a base type by removing the layered acid content could eliminate this drawback. The present invention was completed based on this knowledge.
本発明の要旨は・
化学式Ｚｒ（ＨＰＯ４）２・Ｈ２Ｏで示される層状構造
を有するα−リン酸ジルコニウム（以下α−リン酸ジル
コニウムと略記する）と、その層間にモノ−（６−β−
アミノエチルアミノ−６−デオキシ）−β−シクロデキ
ストリンを存在させたものからなり、かつ３５〜３７叉
の範囲内の層間距離を有するものからなるリン酸ジルコ
ニウム−シクロデキストリン系化合物の結晶質複合体に
ある。The gist of the present invention is - α-zirconium phosphate (hereinafter abbreviated as α-zirconium phosphate) having a layered structure represented by the chemical formula Zr(HPO4)2H2O, and a mono-(6-β-
A crystalline composite of a zirconium phosphate-cyclodextrin compound in which aminoethylamino-6-deoxy)-β-cyclodextrin is present and has an interlayer distance within the range of 35 to 37 prongs. It is in.
本発明に使用するシクロデギス） ＩＪｙ系化合物及び
α−リン酸ジルコニウムは共に分子包接能を有する化合
物である。分子包接能とは、原子または分子が結合して
できた三次元または二次元構造の内部に適当な大きさの
空洞がち抄、その中に他の分子を取込んで特定の結晶構
造を形成する性能である。Both the IJy compound and α-zirconium phosphate used in the present invention are compounds having molecular inclusion ability. Molecular inclusion ability is the ability to create a cavity of an appropriate size inside a three-dimensional or two-dimensional structure formed by bonding atoms or molecules, and to incorporate other molecules into the cavity to form a specific crystal structure. It has the ability to
例えば、Ｄ−グルコースの環状重合体であるシクロデキ
ストリンは中央部に直径５〜８Ｘ、深さ８Ｘの円筒状の
空洞を、側鎖に触媒活性のアルコール基を持っており、
包接能と触媒能を兼ね備えている。For example, cyclodextrin, which is a cyclic polymer of D-glucose, has a cylindrical cavity with a diameter of 5 to 8 times and a depth of 8 times in the center, and a catalytically active alcohol group in the side chain.
It has both inclusion and catalytic abilities.
また前記化学式で示したα−リン酸ジルコニウムは層状
構造を有し、包接能を有する。このα−リン酸ジルコニ
ウムの層間にシクロデキストリン系化合物を導入し複合
体とすることにより、層状及び円筒状の２つの包接格子
を有するものとなり、シクロデキストリンの高機能化即
ち反応の屋質特異性や、ゲルｆ過材としての性質を向上
し得られ、また化学薬品９％に医薬品、農薬、殺虫剤、
除草剤などのマイクロカプセル化剤、ゲルクロマトグラ
フィの充填剤として更に酵素モデルとしても有用なもの
となし得たのである。Further, α-zirconium phosphate shown in the above chemical formula has a layered structure and has inclusion ability. By introducing a cyclodextrin-based compound between the layers of this α-zirconium phosphate to form a complex, it has two inclusion lattices, layered and cylindrical. It is obtained by improving the properties as a gel filter material, and also contains 9% of chemicals such as pharmaceuticals, agricultural chemicals, insecticides, etc.
It has been made useful as a microencapsulating agent for herbicides, a packing material for gel chromatography, and even as an enzyme model.
この複合体は前記シクロデキストリンの水溶液中にα−
リン酸ジルコニウム粉末を一定時間浸漬保持することに
より製造し得られる。This complex is present in the aqueous solution of cyclodextrin.
It can be produced by soaking and holding zirconium phosphate powder for a certain period of time.
例えばα−リン酸ジルコニウム粉末１７に対し、１ミリ
モル以上の前記７クロデキストリンを含む水溶液を混合
し、２０〜６０℃で２時間以上保持することにより製造
し得られる。この場合、複合体を高収率で得るためには
、α−リン酸シルコニ゛ウム粉末１７に対し、前記シク
ロデキストリンを２ミリモル以上とし、水溶液ａＷを１
〜１００ｍＭ程度にすることが好ましい。For example, it can be produced by mixing α-zirconium phosphate powder 17 with an aqueous solution containing 1 mmol or more of the 7 clodextrin and holding the mixture at 20 to 60° C. for 2 hours or more. In this case, in order to obtain the complex in high yield, the cyclodextrin should be 2 mmol or more based on the α-silconium phosphate powder 17, and the aqueous solution aW should be 1 mmol or more.
It is preferable to set the amount to about 100 mM.
また、使用する前記シクロデキストリンは、粗反応物を
ＣＭ−セルローズカラムで分別し、稀アンモニア水及び
純水を用いて溶解→濃縮を数度繰返すことにより、十分
純度を高めたものを使用することが好ましい。In addition, the cyclodextrin to be used should be sufficiently purified by fractionating the crude reaction product with a CM-cellulose column and repeating the process of dissolving and concentrating several times using dilute ammonia water and pure water. is preferred.
得られた複合体を液より分離し、水洗後、３０〜４０℃
で１２〜２４時間乾燥すると、リン酸ジルコニウム−シ
クロデキストリン系化合物の結晶質複合体が得られる。The resulting composite was separated from the liquid, washed with water, and then heated to 30-40°C.
When dried for 12 to 24 hours, a crystalline composite of zirconium phosphate-cyclodextrin compound is obtained.
この結晶質複合体はα−リン酸ジルコニウムの層間にシ
クロデキストリン化合物層が取込まれたミクロ複合構造
を有し、その層間距離が複合前の７．４１ （無水状態
）からシクロデキストリン化合物の２分子層の厚さに相
当する２７．６〜２９．６ Ｘだけ増大している。This crystalline composite has a microcomposite structure in which a cyclodextrin compound layer is incorporated between layers of α-zirconium phosphate, and the interlayer distance varies from 7.41 (anhydrous state) before composite to 2 of the cyclodextrin compound. It increases by 27.6-29.6X, which corresponds to the thickness of the molecular layer.
この２分子層の厚さから考えると、この層間に取りこま
れたシクロデキストリン分子は、その空洞の中心軸がリ
ン酸ジルコニウム層に平行または平行に近い向きになる
ように配列して２分子層を形成していることが分かる。Considering the thickness of this bilayer, the cyclodextrin molecules incorporated between the layers are arranged so that the central axis of the cavity is parallel or nearly parallel to the zirconium phosphate layer. It can be seen that it forms
従って、層間は他のゲスト分子を包接し易い構造となっ
ている。Therefore, the structure between the layers makes it easy to include other guest molecules.
発明の効果
本発明の複合体は、前記のような構造となっているため
、
（１） これを触媒として用いた場合、従来のものは
その溶解性のために、生成分の分離が容易でなかっだが
、結晶質で触媒部分がＩＭ定され不溶化されているため
、生成物の分離が容易で、連続反応を行うことができ、
また層状格子と組合っているため、反応に対する選択性
も高いので、触媒または人工酵素として優れたものとな
る。Effects of the Invention Since the composite of the present invention has the above-mentioned structure, (1) When it is used as a catalyst, due to its solubility, it is difficult to separate the products of the conventional catalyst; However, since it is crystalline and the catalyst part is IM determined and insolubilized, the product can be easily separated and continuous reactions can be carried out.
Furthermore, since it is combined with a layered lattice, it has high selectivity for reactions, making it an excellent catalyst or artificial enzyme.
（２）７クロデキストリン系化合物単体では、薬剤の溶
出が比較的速く、薬効の持続性が劣るが、本発明の複合
体では、薬剤はα−リン酸ジルコニウム層間のシンクロ
デキストリン系化合物部分に固定されるので、薬剤が例
えば土壌中の湿潤部に直接接触しないため、その溶出が
抑えられる結果、薬効が長期に亘って持続され、マイク
ロカプセル剤として優れたものとなる。(2) In the case of a single 7-clodextrin compound, the drug elutes relatively quickly and has poor drug efficacy, but in the composite of the present invention, the drug is fixed in the synchrodextrin compound portion between the α-zirconium phosphate layers. As a result, the drug does not come into direct contact with, for example, moist areas in the soil, so its elution is suppressed, and as a result, the drug's efficacy is sustained over a long period of time, making it an excellent microcapsule.
（３）本発明の複合体はα−リン酸ジルコニウム層によ
る分離効果が加わるため、分離能が向上し、クロマトグ
ラフィー充填剤としても優れたものとなる等の優れた効
果を奏し得られる。(3) Since the complex of the present invention has an additional separation effect due to the α-zirconium phosphate layer, it can exhibit excellent effects such as improved separation ability and is also excellent as a chromatography packing material.
実施例１
α−リン酸ジルコニウムＺｒ（ＨＰＯ４ｈｌｈＯＯ，０
５２とモノ−（６−β−アミノエチルアミ、／ ５−
デオキシ）−β−シクロデキストリン（以下ｃＤｅｎと
略記する） ６２．５ ｍＷ水溶液４１Ｒｔとを混合し
、２５℃で１４日間振盪した。同相を遠心分離後、水洗
し、４０℃で乾燥して複合体を得た。Example 1 α-zirconium phosphate Zr (HPO4hlhOO,0
52 and mono-(6-β-aminoethylamide, /5-
Deoxy)-β-cyclodextrin (hereinafter abbreviated as cDen) 62.5 mW aqueous solution 41Rt was mixed and shaken at 25° C. for 14 days. The same phase was centrifuged, washed with water, and dried at 40°C to obtain a composite.
この複合体中のＣＤｅｎと水の含量は、無機４［１モル
当りそれぞれ０．３６８モル、 ５．３ ％ ル”ｔ’
あった。The content of CDen and water in this complex is 0.368 mol, respectively, 5.3% per mol of inorganic 4[t'
there were.
またそのＸ線回折図形は第１図Ａの通りであり、層間距
離３５．６１の結晶質複合体へ転換したことを示してい
る。更に有機層の構造のモデル計算によると、この複合
体は、ＣＤｅｎ分子の空洞中心軸がリン酸ジルコニウム
層にほぼ平行に２分子層配列した構造をとっている。Moreover, its X-ray diffraction pattern is as shown in FIG. 1A, indicating that it has been transformed into a crystalline composite with an interlayer distance of 35.61. Furthermore, according to a model calculation of the structure of the organic layer, this composite has a structure in which the central axis of the CDen molecule cavity is arranged in two molecular layers almost parallel to the zirconium phosphate layer.
なお、第１図Ｂは、α−リン酸ジルコニウム１２当り、
０．１１ ミリ％Ａ＋７）ｃＤｅｎを含む１．３８ ｍ
Ｍ浴溶液用いて作った結晶質複合体のＸ線回折図形であ
る。In addition, FIG. 1B shows that per 12 α-zirconium phosphate,
1.38 m containing 0.11 mm%A+7)cDen
This is an X-ray diffraction pattern of a crystalline composite made using M bath solution.
図面は本発明の結晶質複合体のＸ線回折図形であり、Ａ
は実施例１で得られた結晶質複合体、Ｂはα−リン酸ジ
ルコニウムとｃＤｅｎの景を変えた結晶質複合体の場合
を示す。
特許出願人 科学技術庁無機材質研究所長後 藤
優
゛ −
手 続 補 正 書
昭和６１年２ Ｊ１２１ｔｌ
ｌ 事件の表示
昭和６０年特許願第２４３６１７号
３ 補正をする者
事件との関係 特許出願人
昭和６１年１月２８ト］
５ 補正の対象The drawing is an X-ray diffraction pattern of the crystalline composite of the present invention, and A
1 shows the case of the crystalline composite obtained in Example 1, and B shows the case of a crystalline composite obtained by changing the appearance of α-zirconium phosphate and cDen. Patent applicant Goto, director of the Institute for Inorganic Materials, Science and Technology Agency
U゛ - Procedures Amendment Book 1986 2 J121tl Indication of the case 1985 Patent Application No. 243617 3 Person making the amendment Relationship with the case Patent applicant January 28, 1988] 5 Subject of amendment
Claims (1)
層状構造を有するα−リン酸ジルコニウムと、その層間
にモノ−（６−β−アミノエチルアミノ−６−デオキシ
）−β−シクロデキストリンを存在させたものからなり
、かつ３５〜３７Åの範囲内の層間距離を有するものか
らなるリン酸ジルコニウム−シクロデキストリン系化合
物の結晶質複合体。 ２）化学式Ｚｒ（ＨＰＯ＿４）＿２・Ｈ２＿Ｏで示され
る層状構造を有するα−リン酸ジルコニウム粉末を、モ
ノ−（６−β−アミノエチルアミノ−６−デオキシ）−
β−シクロデキストリンの水溶液中に浸漬することを特
徴とするリン酸ジルコニウム−シクロデキストリン系化
合物の結晶質複合体の製造法。[Claims] 1) α-zirconium phosphate having a layered structure represented by the chemical formula Zr(HPO_4)2.H_2O, and mono-(6-β-aminoethylamino-6-deoxy)-β between the layers. - A crystalline composite of a zirconium phosphate-cyclodextrin compound in the presence of cyclodextrin and having an interlayer distance in the range of 35 to 37 Å. 2) α-zirconium phosphate powder having a layered structure represented by the chemical formula Zr(HPO_4)_2・H2_O is converted into mono-(6-β-aminoethylamino-6-deoxy)-
A method for producing a crystalline composite of a zirconium phosphate-cyclodextrin compound, which comprises immersing it in an aqueous solution of β-cyclodextrin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60243617A JPS62105908A (en) | 1985-10-30 | 1985-10-30 | Crystalline complex of zirconium phosphate-cyclodextrin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60243617A JPS62105908A (en) | 1985-10-30 | 1985-10-30 | Crystalline complex of zirconium phosphate-cyclodextrin and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62105908A true JPS62105908A (en) | 1987-05-16 |
| JPH0154283B2 JPH0154283B2 (en) | 1989-11-17 |
Family
ID=17106482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60243617A Granted JPS62105908A (en) | 1985-10-30 | 1985-10-30 | Crystalline complex of zirconium phosphate-cyclodextrin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62105908A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01103908A (en) * | 1987-10-15 | 1989-04-21 | Res Dev Corp Of Japan | Interlayer separatable layer body |
| CN113831597A (en) * | 2021-10-15 | 2021-12-24 | 武汉工程大学 | Bio-based macromolecule modified nano zirconium phosphate flame retardant and fireproof coating prepared by using same |
| WO2023060571A1 (en) * | 2021-10-15 | 2023-04-20 | 武汉工程大学 | Bio-based macromolecule modified nano zirconium phosphate flame retardant and fire-proof coating prepared by using same |
-
1985
- 1985-10-30 JP JP60243617A patent/JPS62105908A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01103908A (en) * | 1987-10-15 | 1989-04-21 | Res Dev Corp Of Japan | Interlayer separatable layer body |
| JPH0572326B2 (en) * | 1987-10-15 | 1993-10-12 | Shingijutsu Kaihatsu Jigyodan | |
| CN113831597A (en) * | 2021-10-15 | 2021-12-24 | 武汉工程大学 | Bio-based macromolecule modified nano zirconium phosphate flame retardant and fireproof coating prepared by using same |
| WO2023060571A1 (en) * | 2021-10-15 | 2023-04-20 | 武汉工程大学 | Bio-based macromolecule modified nano zirconium phosphate flame retardant and fire-proof coating prepared by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0154283B2 (en) | 1989-11-17 |
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