JPH1192132A - Production of organic composite of clay having interlaminar pillar - Google Patents
Production of organic composite of clay having interlaminar pillarInfo
- Publication number
- JPH1192132A JPH1192132A JP9275108A JP27510897A JPH1192132A JP H1192132 A JPH1192132 A JP H1192132A JP 9275108 A JP9275108 A JP 9275108A JP 27510897 A JP27510897 A JP 27510897A JP H1192132 A JPH1192132 A JP H1192132A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- compd
- clay
- guest
- interlaminar
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特定の機能をもつ
有機化合物を層間支柱を有する粘土、いわゆるピラード
クレー（ｐｉｌｌａｒｄ ｃｌａｙ）と複合化して、そ
の機能を保持したまま安定な複合体とする方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of compounding an organic compound having a specific function with a clay having interlayer supports, a so-called pillar clay, to form a stable composite while maintaining its function. Things.
【０００２】[0002]
【従来の技術】有機化合物は、その本来有する機能に基
づき、光機能材料をはじめとして各種材料に広く利用さ
れているが、一般に、耐熱性が低く、また大気中の酸素
により変質されやすいという欠点を有している。このた
め、ゼオライトのような多孔質無機物質中に吸着させた
り、ガラスやプラスチックに封入して安定化することが
行われている。しかし多孔質無機物質に吸着させるに
は、有機化合物を適当な溶媒に溶かし、この溶液を多孔
質無機物質に含浸させ、溶媒を蒸発させるという煩雑な
操作を必要とする。また、溶媒の表面張力のため、微細
な空隙に浸透させて均一に複合化することがむずかしい
上に、必ずしも満足しうる安定化が得られないという欠
点がある。一方、ガラスやプラスチックに封入する場合
は、加熱により変質するのを免れないという欠点があ
り、これまで、実用上十分に満足しうる方法は知られて
いなかった。2. Description of the Related Art Organic compounds are widely used for various materials including optical functional materials based on their inherent functions. However, in general, organic compounds have low heat resistance and are liable to be deteriorated by oxygen in the atmosphere. have. For this reason, stabilization is carried out by adsorbing in a porous inorganic substance such as zeolite or enclosing in glass or plastic. However, the adsorption to the porous inorganic substance requires a complicated operation of dissolving the organic compound in an appropriate solvent, impregnating the solution with the porous inorganic substance, and evaporating the solvent. In addition, due to the surface tension of the solvent, it is difficult to penetrate into fine voids to form a uniform composite, and furthermore, there is a drawback that satisfactory stabilization cannot be obtained. On the other hand, in the case of encapsulation in glass or plastic, there is a disadvantage that it is unavoidable to deteriorate by heating, and there has been no known practically satisfactory method.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、有機化合物
の本来の機能をそこなうことなく、簡単な処理でしかも
十分に安定化された有機化合物の含有割合の高い複合体
を製造する方法を提供することを目的としてなされたも
のである。SUMMARY OF THE INVENTION The present invention provides a method for producing a complex having a high content of an organic compound which is easily stabilized and sufficiently stabilized without deteriorating the original function of the organic compound. It was done for the purpose of doing.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、有機化合
物をゲスト分子とした無機層状化合物との複合体につい
て種々研究を重ねた結果、先に二酸化炭素の超臨界状態
を利用して、有機ゲスト分子を無機層状化合物と複合化
することにより、有機化合物の機能性と無機化合物の安
定性を併有する複合体を製造した。Means for Solving the Problems The present inventors have conducted various studies on a complex with an inorganic layered compound using an organic compound as a guest molecule. By complexing an organic guest molecule with an inorganic layered compound, a complex having both the functionality of an organic compound and the stability of an inorganic compound was produced.
【０００５】しかしながら、このような方法により得ら
れる複合体は、有機ゲスト化合物の含有割合が低く、そ
の利用分野が制限されるのを免れない。このため、本発
明者らは、有機ゲスト化合物の含有割合の高い有機無機
複合体を得る方法について、さらに研究を重ねた結果、
有機ゲスト化合物の導入用媒体として超臨界状態にある
二酸化炭素を用いるとともに、無機層状化合物として、
層間支柱を有する粘土、いわゆるピラードクレーを用い
ることにより、その有機ゲスト化合物の含有量を著しく
増大しうることを見出し、この知見に基づいて本発明を
なすに至った。[0005] However, the composite obtained by such a method has a low content ratio of the organic guest compound, and it is inevitable that the field of use is restricted. Therefore, the present inventors have further studied on a method of obtaining an organic-inorganic composite having a high content ratio of an organic guest compound, and as a result,
While using carbon dioxide in a supercritical state as a medium for introducing an organic guest compound, as an inorganic layered compound,
It has been found that the content of the organic guest compound can be significantly increased by using a clay having an interlayer support, so-called pillared clay, and the present invention has been accomplished based on this finding.
【０００６】すなわち、本発明は、無機層状化合物の層
間空隙中に有機ゲスト化合物を導入し、有機無機複合体
を形成させるに当り、無機層状化合物として層間支柱を
有する粘土を用い、かつ超臨界状態の二酸化炭素を媒質
として有機ゲスト化合物を導入することを特徴とする有
機無機複合体の製造方法を提供するものである。ここ
で、有機ゲスト化合物とは、無機層状化合物の層間空隙
中に導入される、所定の機能をもった有機化合物のこと
をいう。また、超臨界状態の二酸化炭素とは臨界温度Ｔ
ｃ（３１．７℃）及び臨界圧力Ｐｃ（７．１３ＭＰａ）
以上にある二酸化炭素をいい、これは液体と気体の中間
の性質、すなわち液体に近い密度と溶解性及び気体に近
い粘性、表面張力、拡散性を有している。That is, according to the present invention, when an organic guest compound is introduced into an interlayer gap of an inorganic layered compound to form an organic-inorganic composite, a clay having an interlayer support is used as the inorganic layered compound and a supercritical state is used. A method for producing an organic-inorganic composite, which comprises introducing an organic guest compound using carbon dioxide as a medium. Here, the organic guest compound refers to an organic compound having a predetermined function and introduced into the interlayer gap of the inorganic layered compound. In addition, carbon dioxide in a supercritical state means a critical temperature T
c (31.7 ° C) and critical pressure Pc (7.13 MPa)
The above-mentioned carbon dioxide refers to carbon dioxide, which has a property intermediate between liquid and gas, that is, density and solubility close to liquid and viscosity, surface tension, and diffusivity close to gas.
【０００７】[0007]
【発明の実施の形態】本発明においては、無機層状化合
物として層間支柱を有する粘土を用いることが必要であ
る。このものは、例えばモンモリロナイト、スメクタイ
ト、ヘクトライト、サポナイト、バーミキュライト、タ
ルク、パイロフィライト、ハイデライト、雲母などの層
状粘土の層間陽イオンを支柱となる第四級アンモニウム
イオンやセラミックス酸化物と交換することにより得る
ことができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, it is necessary to use a clay having an interlayer support as an inorganic layered compound. It exchanges interlayer cations of layered clay such as montmorillonite, smectite, hectorite, saponite, vermiculite, talc, pyrophyllite, hyderite, mica, etc. with quaternary ammonium ions and ceramic oxides serving as pillars. Can be obtained.
【０００８】この中で支柱として第四級アンモニウムイ
オンを含むものは、例えばテトラアルキルアンモニウム
塩の水溶液に所定の粘土を浸せきし、必要に応じ５０〜
９０℃の温度に加温しながら１〜１０時間かきまぜたの
ち、十分に水洗し乾燥することにより調製される。[0008] Among them, the pillars containing quaternary ammonium ions are, for example, immersed in a predetermined clay in an aqueous solution of a tetraalkylammonium salt, and if necessary, 50 to 50 cm.
It is prepared by stirring for 1 to 10 hours while heating to a temperature of 90 ° C., thoroughly washing with water and drying.
【０００９】一方、支柱としてセラミックス酸化物を含
むものは、先ず粘土層間中の陽イオンを多核金属水酸化
イオンでイオン交換し、水洗後層間に取り込まれたイオ
ンを加熱脱水して酸化物を形成させることにより調製さ
れる。このようにして、Ａｌ2Ｏ3、Ｇａ2Ｏ3、ＺｒＯ2、
Ｆｅ2Ｏ3、Ｇｒ2Ｏ3、ＴｉＯ2、ＺｒＯ2−Ａｌ2Ｏ3、Ｂ
ｉ2Ｏ3、Ｖ2Ｏ5、Ａｌ2Ｏ3−ＳｉＯ2、ＳｉＯ2などを支
柱として含む層状粘土が得られる。On the other hand, in the case of a column containing a ceramic oxide as a support, first, cations in a clay layer are ion-exchanged with polynuclear metal hydroxide ions, and after washing with water, ions taken in between layers are heated and dehydrated to form an oxide. It is prepared by allowing Thus, Al 2 O 3 , Ga 2 O 3 , ZrO 2 ,
Fe 2 O 3, Gr 2 O 3, TiO 2, ZrO 2 -Al 2 O 3, B
A layered clay containing i 2 O 3 , V 2 O 5 , Al 2 O 3 —SiO 2 , SiO 2, etc. as pillars is obtained.
【００１０】次に、この層状粘土の層間に取り入れられ
る有機ゲスト化合物としては、炭化水素類、アミン類、
アルコール類、ケトン類、アルデヒド類、カルボン酸
類、エーテル類、ニトリル類など広範囲のものが用いら
れるが、特定の機能をもつ有機化合物、例えば４‐フェ
ニルアゾアニリン、ローダミン、スピロピラン、アゾベ
ンゼンのような色素を用いると、その色相を変えること
なく安定性を向上しうるので好ましい。Next, as the organic guest compound to be introduced between the layers of the layered clay, hydrocarbons, amines,
A wide range of compounds such as alcohols, ketones, aldehydes, carboxylic acids, ethers, and nitriles are used, but organic compounds having a specific function, for example, dyes such as 4-phenylazoaniline, rhodamine, spiropyran, and azobenzene Is preferred because the stability can be improved without changing the hue.
【００１１】本発明方法においては、前記の無機層状化
合物と有機ゲスト化合物分子とを、超臨界状態にある二
酸化炭素の存在下で接触させることが必要である。この
二酸化炭素の超臨界状態は、二酸化炭素を温度３５〜５
０℃、圧力１０〜２０ＭＰａ、好ましくは温度４０〜４
５℃、圧力１３〜１７ＭＰａに維持することによりもた
らされる。例えば耐圧密閉容器中に二酸化炭素を導入
し、いったん冷却して二酸化炭素を液化したのち、温度
を徐々に上げて温度４０℃、圧力１４．５ＭＰａに維持
すると超臨界状態になる。このようにして得られる超臨
界状態の二酸化炭素は気体のような流動性と液体に近い
密度、溶解性を有している。In the method of the present invention, it is necessary that the inorganic layer compound and the organic guest compound molecule are brought into contact in the presence of carbon dioxide in a supercritical state. The supercritical state of the carbon dioxide is such that the carbon dioxide is heated to a temperature of 35-5.
0 ° C., pressure 10-20 MPa, preferably temperature 40-4
Maintained at 5 ° C., pressure 13-17 MPa. For example, carbon dioxide is introduced into a pressure-resistant closed vessel, and once cooled to liquefy carbon dioxide, the temperature is gradually increased to maintain a temperature of 40 ° C. and a pressure of 14.5 MPa, thereby bringing the supercritical state. The supercritical carbon dioxide thus obtained has fluidity like a gas, density and solubility close to those of a liquid.
【００１２】超臨界状態の二酸化炭素が有機ゲスト化合
物分子と接触すると、有機ゲスト化合物分子は、超臨界
二酸化炭素に溶解する。そして、超臨界二酸化炭素が、
その低い粘性、小さい表面張力、高い拡散性により、無
機層状化合物の層間支柱を有する微細な空隙のすみずみ
まで浸透するに伴い、これらの有機ゲスト化合物分子も
それらの空隙に運ばれる。有機ゲスト化合物分子が空隙
のすみずみにまで行き渡った後に、圧力を低下させる
と、超臨界二酸化炭素の密度が低下し、それに伴い有機
ゲスト化合物分子の溶解度が低下し、有機ゲスト化合物
分子は空隙の各部に一様に析出し、吸着される。このよ
うにして吸着された有機ゲスト化合物分子は空隙表面に
強く保持される。When the supercritical carbon dioxide contacts the organic guest compound molecule, the organic guest compound molecule dissolves in the supercritical carbon dioxide. And supercritical carbon dioxide
Due to their low viscosity, low surface tension, and high diffusivity, these organic guest compound molecules are also carried into the voids as they penetrate through the fine voids having interlayer struts of the inorganic layered compound. When the pressure is reduced after the organic guest compound molecules have spread to all corners of the void, the density of the supercritical carbon dioxide decreases, and the solubility of the organic guest compound molecules decreases accordingly, and the organic guest compound molecules Precipitates uniformly on each part and is adsorbed. The organic guest compound molecules thus adsorbed are strongly held on the surface of the void.
【００１３】本発明方法における無機層状化合物と有機
ゲスト化合物分子との使用割合は、無機層状化合物の種
類やそれに取り入れられる有機ゲスト化合物分子の種類
に左右されるが、通常は無機層状化合物１００重量部当
り、有機ゲスト化合物分子１〜５重量部の範囲内であ
る。また、無機層状化合物と有機ゲスト化合物分子との
接触時間は少なくとも１時間、通常６〜２４時間の範囲
内である。The proportion of the inorganic layered compound and the organic guest compound used in the method of the present invention depends on the type of the inorganic layered compound and the type of the organic guest compound incorporated therein, but usually 100 parts by weight of the inorganic layered compound. Per 1 to 5 parts by weight of the organic guest compound molecule. The contact time between the inorganic layered compound and the organic guest compound molecule is at least 1 hour, usually in the range of 6 to 24 hours.
【００１４】[0014]
【発明の効果】本発明方法によると、従来の有機溶媒に
有機ゲスト化合物を溶解し、無機担体に含浸させたの
ち、有機溶媒を除去して複合体を製造する場合に比べ、
有機ゲスト化合物がより均一に分散し、強固に結合し、
安定性の良好な複合体を、しかも機能の低下を伴うこと
なく短時間で製造することができる。また、層間支柱を
有する粘土を用いるため、非常に多量の有機ゲスト化合
物を含有した複合体を得ることができる。According to the method of the present invention, an organic guest compound is dissolved in a conventional organic solvent and impregnated into an inorganic carrier, and then the organic solvent is removed to produce a composite.
Organic guest compounds are more evenly dispersed and tightly bound,
A composite having good stability can be produced in a short time without deteriorating the function. Further, since a clay having an interlayer support is used, a composite containing an extremely large amount of an organic guest compound can be obtained.
【００１５】[0015]
【実施例】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 described in more detail by way of examples.
【００１６】実施例 モンモリロナイト５００ｍｇを濃度５ｍｇ／ｍｌの塩化
テトラメチルアンモニウム溶液１００ｍｌに懸濁させ、
７０℃で３時間撹拌した。ろ過後、硝酸銀試験で塩化物
イオンが検出されなくなるまで純水で繰り返し洗浄し、
次いで１日室温で真空乾燥して、モンモリロナイトの層
間に支柱を導入した。EXAMPLE 500 mg of montmorillonite was suspended in 100 ml of a tetramethylammonium chloride solution having a concentration of 5 mg / ml.
Stirred at 70 ° C. for 3 hours. After filtration, wash repeatedly with pure water until chloride ions are no longer detected in the silver nitrate test,
Then, it was vacuum-dried at room temperature for one day, and columns were introduced between the layers of montmorillonite.
【００１７】この層間支柱を有するモンモリロナイトと
４‐フェニルアゾアニリン粉末を高圧容器中に分離して
置き、この容器を冷却しながら二酸化炭素ガスを導入し
いったん二酸化炭素を液化させた。次に温度を徐々に上
昇させて、二酸化炭素を温度４０℃、圧力１４．５ＭＰ
ａの超臨界状態とした。この状態を１、６、１２時間保
った後、圧力を徐々に下げて、二酸化酸素を揮発・除去
した。残った層間支柱を有するモンモリロナイトをｎ‐
ヘキサンで数回洗浄して試料を得た。この試料中の窒素
量、有機炭素量をＴＮ−ＴＯＣ分析装置で求めた。これ
より計算した超臨界二酸化炭素処理による窒素の増加量
（ΔＮ）及び有機炭素の増加量（ΔＣ）を表１に示す。
表１にはそれらの比（ΔＮ／ΔＣ）も合わせ示した。超
臨界二酸化炭素処理による窒素の増加量は１時間では少
ないが、６時間以降では明らかな増大が認められる。Δ
Ｎ／ΔＣ比は各処理時間で０．２５、０．２３、０．２
０と、４‐フェニルアゾアニリン中のＮ／Ｃ比（０．２
５）とほぼ等しい。すなわち超臨界二酸化炭素で処理す
ることにより、４‐フェニルアゾアニリンが化学変化す
ることなく、モンモリロナイトに吸収されたことが分か
る。これに対応して、試料の色が灰色から赤褐色に変化
した。The montmorillonite having the interlayer support and the powder of 4-phenylazoaniline were separated and placed in a high-pressure vessel, and carbon dioxide gas was introduced into the vessel while cooling the vessel to once liquefy the carbon dioxide. Next, the temperature was gradually increased, and carbon dioxide was heated to a temperature of 40 ° C. and a pressure of 14.5 MPa.
a was set to the supercritical state. After maintaining this state for 1, 6, and 12 hours, the pressure was gradually lowered to volatilize and remove oxygen dioxide. The montmorillonite having the remaining interlayer strut is n-
A sample was obtained by washing several times with hexane. The amount of nitrogen and the amount of organic carbon in this sample were determined with a TN-TOC analyzer. Table 1 shows the calculated increase in nitrogen (ΔN) and increase in organic carbon (ΔC) due to the supercritical carbon dioxide treatment.
Table 1 also shows their ratio (ΔN / ΔC). The amount of increase in nitrogen by the supercritical carbon dioxide treatment is small in one hour, but a clear increase is observed after 6 hours. Δ
The N / ΔC ratio was 0.25, 0.23, 0.2 for each treatment time.
0 and the N / C ratio in 4-phenylazoaniline (0.2
It is almost equal to 5). That is, it can be seen that by treatment with supercritical carbon dioxide, 4-phenylazoaniline was absorbed by montmorillonite without any chemical change. Correspondingly, the color of the sample changed from gray to reddish brown.
【００１８】また、図１に得られた試料のＸ線回折パタ
ーンを示した。２θ＝６．３°付近の回折線は、層状構
造を持つ粘土鉱物であるモンモリロナイトの層間距離に
対応する。図１から超臨界二酸化炭素による処理の時間
が１時間では２θ＝６．３°付近の回折線が処理前とあ
まり変わらないのに対して、６、１２時間処理したもの
は、この回折線が明らかに低角側にシフトしていること
がわかる。すなわち、超臨界二酸化炭素処理によりモン
モリロナイトの層間距離が増大している。また図２には
超臨界二酸化炭素処理の前後における、モンモリロナイ
トの窒素吸着等温線を示す。処理前の試料は５０〜７０
ｍｌ／ｇ程度の細孔容積を持っているのに対して、処理
後の試料の細孔容積は１０ｍｌ／ｇ以下である。Ｘ線回
折で層間距離が増大しているにもかかわらず、層間の空
隙を示す細孔容積が大きく減少していることは、４‐フ
ェニルアゾアニリンが層間支柱を有するモンモリロナイ
トの層間に挿入されたことを示している。すなわち、超
臨界二酸化炭素を用いた処理により、４‐フェニルアゾ
アニリンとモンモリロナイトからなる有機無機複合体が
得られたことが分かる。FIG. 1 shows an X-ray diffraction pattern of the obtained sample. The diffraction line near 2θ = 6.3 ° corresponds to the interlayer distance of montmorillonite which is a clay mineral having a layered structure. From FIG. 1, the diffraction line near 2θ = 6.3 ° is not so different from that before the treatment when the processing time with supercritical carbon dioxide is 1 hour, whereas the diffraction line after 6 or 12 hours is It can be seen that it is clearly shifted to the lower angle side. That is, the interlayer distance of the montmorillonite is increased by the supercritical carbon dioxide treatment. FIG. 2 shows nitrogen adsorption isotherms of montmorillonite before and after the supercritical carbon dioxide treatment. 50-70 samples before treatment
While the sample has a pore volume of about ml / g, the sample after treatment has a pore volume of 10 ml / g or less. The large decrease in the pore volume, which indicates the voids between the layers, despite the increase in the interlayer distance in X-ray diffraction indicates that 4-phenylazoaniline was inserted between the layers of montmorillonite having interlayer supports. It is shown that. That is, it is understood that an organic-inorganic composite composed of 4-phenylazoaniline and montmorillonite was obtained by the treatment using supercritical carbon dioxide.
【００１９】なお、反応時間１２時間の超臨界二酸化炭
素処理における媒質中の４‐フェニルアゾアニリン濃度
を、処理前後の４‐フェニルアゾアニリンの重量減少と
反応容器の容積から求めたところ、０．３３ｍｇ／ｍｌ
であった。これは、反応容器中の４‐フェニルアゾアニ
リン濃度の上限値であると考えられる。The concentration of 4-phenylazoaniline in the medium in the supercritical carbon dioxide treatment for a reaction time of 12 hours was determined from the weight loss of 4-phenylazoaniline before and after the treatment and the volume of the reaction vessel. 33mg / ml
Met. This is considered to be the upper limit of the concentration of 4-phenylazoaniline in the reaction vessel.
【００２０】比較例１ ４‐フェニルアゾアニリンをエタノール又はアセトンに
濃度が１ｍｇ／ｍｌとなるように懸濁し、溶解したもの
５０ｍｌに、実施例で用いた層間支柱を有するモンモリ
ロナイト１００ｍｇを加え、４０℃で１２時間撹拌し、
ろ過後、ｎ‐ヘキサンで数回洗浄した。この溶液処理に
よる窒素及び有機炭素の増大量をＴＮ−ＴＯＣ分析装置
で求めた結果を表１に示す。Comparative Example 1 4-Phenylazoaniline was suspended in ethanol or acetone to a concentration of 1 mg / ml and dissolved in 50 ml, and 100 mg of montmorillonite having an interlayer support used in the example was added. And stir for 12 hours,
After filtration, it was washed several times with n-hexane. Table 1 shows the results obtained by using a TN-TOC analyzer to determine the increased amounts of nitrogen and organic carbon due to this solution treatment.
【００２１】表１よりメタノールやアセトンを使用した
場合には、処理による窒素や有機炭素の増加量はごくわ
ずかである。そして、この表１の結果は、媒質中の４‐
フェニルアゾアニリンの濃度が超臨界二酸化炭素処理の
場合よりも高いことを考えると、溶液処理による有機ゲ
スト化合物分子のモンモリロナイトへの挿入反応が遅い
か、又は一部しか進行しないことを示している。According to Table 1, when methanol or acetone is used, the amount of increase of nitrogen and organic carbon by the treatment is very small. The results in Table 1 show that 4-
Considering that the concentration of phenylazoaniline is higher than that in the case of the supercritical carbon dioxide treatment, it indicates that the insertion reaction of the organic guest compound molecule into the montmorillonite by the solution treatment is slow or progresses only partially.
【００２２】[0022]
【表１】 [Table 1]
【００２３】比較例２ 層間支柱を有するモンモリロナイトの代りに、単に熱処
理したモンモリロナイトを用いて、実施例１と同様に、
超臨界二酸化炭素による処理を１時間行った。得られた
処理試料中の窒素濃度をＴＮ−ＴＯＣで分析した結果、
０．０４ｍｇ／ｇ（０．２９×１０-4ｍｏｌ／ｇ）であ
った。このことより、層間支柱を有するモンモリロナイ
トを用いることにより、４‐フェニルアゾアニリンの吸
収量は４倍以上増大することが分かる。COMPARATIVE EXAMPLE 2 Instead of montmorillonite having an interlayer support, a heat-treated montmorillonite was used in the same manner as in Example 1.
The treatment with supercritical carbon dioxide was performed for one hour. As a result of analyzing the nitrogen concentration in the obtained processed sample by TN-TOC,
It was 0.04 mg / g (0.29 × 10 −4 mol / g). From this, it can be seen that the use of montmorillonite having an interlayer support increases the absorption of 4-phenylazoaniline by a factor of four or more.
【図１】 実施例で得た超臨界処理したモンモリロナイ
トのＸ線回折パターン。FIG. 1 is an X-ray diffraction pattern of montmorillonite subjected to supercritical treatment obtained in an example.
【図２】 超臨界二酸化炭素処理の前後における窒素吸
着等温線。FIG. 2 is a nitrogen adsorption isotherm before and after supercritical carbon dioxide treatment.
Claims (2)
ト化合物を導入し、有機無機複合体を形成させるに当
り、無機層状化合物として層間支柱を有する粘土を用
い、かつ超臨界状態の二酸化炭素を媒質として有機ゲス
ト化合物を導入することを特徴とする有機無機複合体の
製造方法。Claims: 1. An organic guest compound is introduced into an interlayer void of an inorganic layered compound to form an organic-inorganic composite, wherein a clay having an interlayer support is used as the inorganic layered compound, and carbon dioxide in a supercritical state is used. A method for producing an organic-inorganic composite, comprising introducing an organic guest compound as a medium.
ニウムイオンが支柱として層間に導入されたものである
請求項１記載の有機無機複合体の製造方法。2. The method for producing an organic-inorganic composite according to claim 1, wherein the clay having an interlayer support has quaternary ammonium ions introduced between the layers as a support.
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|---|---|---|---|
| JP27510897A JP3393362B2 (en) | 1997-09-22 | 1997-09-22 | Method for producing organic compound-clay composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27510897A JP3393362B2 (en) | 1997-09-22 | 1997-09-22 | Method for producing organic compound-clay composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1192132A true JPH1192132A (en) | 1999-04-06 |
| JP3393362B2 JP3393362B2 (en) | 2003-04-07 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100428635B1 (en) * | 2000-05-09 | 2004-04-30 | 주식회사 엘지화학 | Method for preparing organoclay nanocomposites using super critical fluid |
| EP1484357A1 (en) * | 2003-06-06 | 2004-12-08 | Université de Liège | Process to prepare biodegradable polyester foams, polyester foams obtained thereby, their use, and process to modify nanofillers |
| JP2014111531A (en) * | 2007-11-13 | 2014-06-19 | Tomoegawa Paper Co Ltd | Clay thin film and method for producing the same |
-
1997
- 1997-09-22 JP JP27510897A patent/JP3393362B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100428635B1 (en) * | 2000-05-09 | 2004-04-30 | 주식회사 엘지화학 | Method for preparing organoclay nanocomposites using super critical fluid |
| EP1484357A1 (en) * | 2003-06-06 | 2004-12-08 | Université de Liège | Process to prepare biodegradable polyester foams, polyester foams obtained thereby, their use, and process to modify nanofillers |
| WO2004108805A1 (en) * | 2003-06-06 | 2004-12-16 | Universite De Liege | Method for modifying nanocharges and applications thereof |
| JP2014111531A (en) * | 2007-11-13 | 2014-06-19 | Tomoegawa Paper Co Ltd | Clay thin film and method for producing the same |
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|---|---|
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