JP2005290032A - Method for producing hierarchical porous body containing meso pore having long range order - Google Patents
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この発明は無機系および有機無機ハイブリッド多孔質材料の新規な製造方法に関する。この発明の製造方法は、クロマトグラフィー用充填剤、血液分離用多孔質体、吸湿剤用多孔質体、消臭等低分子吸着用多孔質体あるいは酵素担体および触媒担体用多孔質体等の製造に好適に利用される。 The present invention relates to a novel method for producing inorganic and organic-inorganic hybrid porous materials. The production method of the present invention includes the production of a chromatographic filler, a porous material for blood separation, a porous material for a hygroscopic agent, a porous material for low-molecular adsorption such as deodorant, or a porous material for enzyme carrier and catalyst carrier. Is suitably used.
上述したような用途に用いられる多孔質材料としては、従来より、スチレン・ジビニルベンゼン共重合体等の有機ポリマーよりなるものと、シリカゲル等の無機系材料から成るものがよく知られており、一般に、カラム状に充填して用いられる。
有機系の材質で構成されたカラムは、低強度のために耐圧性が低い、溶媒により膨潤・収縮してしまう、加熱殺菌が不可能である等の難点がある。従って、特に高温での操作によって生産性を上げようとする場合、こうした難点がない無機系のもの、特にシリカゲルが、汎用されている。
一般にシリカゲル等の無機質多孔体は、液相反応であるゾル−ゲル法によって作製される。ゾル−ゲル法とは、よく知られているように、加水分解性の官能基を有する無機低分子化合物を出発物質とし、ゾル−ゲル反応、すなわち、加水分解とその後の重合（重縮合）反応により、最終的に無機低分子化合物から酸化物の凝集体や重合体を得る方法一般のことを指す。出発物質となる無機低分子化合物としては、金属アルコキシドが最もよく知られており、このほか、金属塩化物、カルボキシル基やβ−ジケトンのような加水分解性の官能基を持つ金属塩もしくは配位化合物、さらには金属アミン類等が挙げられる。
多孔質材料を各種担体等として利用する場合には、孔の表面に担持されて機能を発現する物質の大きさに依存した、最適の中心細孔径とできるだけ狭い細孔径分布とが必要である。従って、ゾル−ゲル法によって得られる多孔質体についても、ゲル合成時の反応条件を制御することによって、細孔サイズを制御する試みがなされてきた（特許文献１）。
特に、近年多くの研究者によって界面活性剤やブロック共重合体などいわゆる両親媒性物質（より厳密には、両親媒性物質が自己組織化して形成された分子集合体）を鋳型成分として共存させてゾル−ゲル法による多孔質体を合成することにより、ナノメートル領域の細孔構造を高い精度で制御することができると報告されている。
As porous materials used for the above-mentioned applications, those made of organic polymers such as styrene / divinylbenzene copolymer and those made of inorganic materials such as silica gel are well known. Used in a columnar form.
A column made of an organic material has problems such as low pressure resistance due to low strength, swelling / shrinkage with a solvent, and inability to sterilize by heating. Therefore, especially when trying to increase productivity by operating at a high temperature, inorganic materials that do not have such difficulties, particularly silica gel, are widely used.
In general, an inorganic porous material such as silica gel is produced by a sol-gel method which is a liquid phase reaction. As is well known, the sol-gel method is based on an inorganic low molecular weight compound having a hydrolyzable functional group as a starting material, and a sol-gel reaction, that is, hydrolysis and subsequent polymerization (polycondensation) reaction. The general method for finally obtaining an oxide aggregate or polymer from an inorganic low molecular weight compound. Metal alkoxides are the most well-known inorganic low-molecular compounds used as starting materials. In addition, metal salts or coordination with hydrolyzable functional groups such as metal chlorides, carboxyl groups and β-diketones. Examples of the compound include metal amines.
When a porous material is used as various carriers, it is necessary to have an optimum central pore size and a narrowest pore size distribution depending on the size of a substance that is supported on the surface of the pores and exhibits a function. Therefore, an attempt has been made to control the pore size of the porous material obtained by the sol-gel method by controlling the reaction conditions during gel synthesis (Patent Document 1).
In particular, many researchers have recently made so-called amphiphilic substances such as surfactants and block copolymers (more precisely, molecular aggregates formed by self-organization of amphiphilic substances) coexist as template components. It has been reported that the pore structure in the nanometer region can be controlled with high accuracy by synthesizing a porous material by the sol-gel method.
しかし、ゾル−ゲル法で得られる従来の多孔質体は、通常ナノメートル領域の細孔（いわゆるメソ細孔）のみを有し、その形態は多くの場合粉末や薄膜および不規則な粒子状である。塊状材料が得られる場合にも、より大きいスケールの細孔構造（いわゆるマクロ細孔）が同時に系統的に制御されている例は極めて少ない。一例として無定形（結晶のような長距離にわたる周期性を示さない）メソ孔と、鋭い細孔径分布をもつマクロ孔からなる無機系多孔質材料は知られているが、メソ孔の形状と長距離にわたる規則性は制御されていない。メソ孔の秩序を保ちながら、金属塩の共存下で反応溶液を作り、基板の上に膜状に展開した反応溶液の上面から溶媒を蒸発させることによって、金属塩の濃厚相がマクロ孔を形成する例が報告されているが、マクロ孔のサイズや分布は精密に制御されていない。
また、アミド系の共存物質を用いたり、ケイ素アルコキシドからシリカゲルを製造する場合には塩基性触媒のもとでゾル−ゲル反応を行うことにより、平均細孔径を大きくできることが知られているが、これらの材料はせいぜい中心細孔径２０ナノメートル以下の細孔のみを持ち、しかもおもに細孔径の小さい側へ広がった分布を示す。
However, conventional porous bodies obtained by the sol-gel method usually have only nanometer-scale pores (so-called mesopores), and the form is often in the form of powder, thin film and irregular particles. is there. Even when a massive material is obtained, there are very few examples in which pore structures of larger scales (so-called macropores) are controlled systematically. As an example, inorganic porous materials consisting of amorphous (not showing periodicity over long distances like crystals) mesopores and macropores with a sharp pore size distribution are known, but the shape and length of mesopores Regularity over distance is not controlled. While maintaining the order of the mesopores, a concentrated solution of the metal salt forms macropores by creating a reaction solution in the presence of the metal salt and evaporating the solvent from the top surface of the reaction solution developed in the form of a film on the substrate. However, the size and distribution of macropores are not precisely controlled.
In addition, it is known that when an amide-based coexisting substance is used, or when silica gel is produced from silicon alkoxide, the average pore diameter can be increased by performing a sol-gel reaction under a basic catalyst. These materials have at most a pore having a central pore diameter of 20 nanometers or less, and exhibit a distribution that spreads to the smaller pore diameter side.
上述したようなナノメートル領域の細孔（メソ細孔）のみから成る多孔質材料は、一般に、細かく粉砕したり粉砕物を結着させた状態で充填して、フィルターや担体材料等として使用される。すなわち、被処理物質（移動相としてのガスまたは液体）は、粉砕物の充填や結着によって生じる多孔体粒子間の隙間を通ってメソ細孔内に導入されて該多孔質材料の所定の機能が発揮される。しかし、それらの隙間は一般に不規則である上、充分な多孔性を供しないことが多いため所望の効果が得られないことが多い。ナノメートル領域の細孔（メソ細孔）への外部からの目的物質の接触が促進されるような多孔性の集合状態や、そのような条件を満足するマクロ細孔構造をもつ塊状試料を得ようとする場合には、煩雑で長時間を要する成形プロセスが要求される。 Porous materials consisting only of pores (mesopores) in the nanometer range as described above are generally used as filters, carrier materials, etc. after being finely pulverized or packed in a pulverized state. The In other words, the substance to be treated (gas or liquid as the mobile phase) is introduced into the mesopores through the gaps between the porous particles generated by filling and binding of the pulverized material, and a predetermined function of the porous material is obtained. Is demonstrated. However, these gaps are generally irregular and often do not provide sufficient porosity, so the desired effect is often not obtained. Obtaining a massive sample with a porous aggregate state that facilitates contact of the target substance from the outside with pores (mesopores) in the nanometer range and a macropore structure that satisfies such conditions When trying to do so, a complicated and long molding process is required.
本発明の目的は、狭い細孔径分布と長距離にわたる規則性および形状を制御したメソ細孔に加えて、精密に制御されたマクロ細孔も併せ持つ無機系および有機無機ハイブリッド系多孔質体を製造することのできる新しい製造方法を提供することにある。特に、反応溶液から溶媒を除去しながら濃縮およびゲル化させたり、ゲルの乾燥に超臨界乾燥法を用いるなどの、煩雑な手法を含まず、密閉条件下における反応溶液のゾル−ゲル転移と常温・常圧下での乾燥および通常の熱処理操作のみによって、狭い細孔径分布と長距離にわたる規則性および形状を制御したメソ細孔に加えて、精密に制御されたマクロ細孔も併せ持つ無機系および有機無機ハイブリッド系多孔質体を製造する方法を提供することである。 The object of the present invention is to produce inorganic and organic-inorganic hybrid porous bodies that have precisely controlled macropores in addition to mesopores with controlled narrow pore size distribution and regularity and shape over long distances. It is to provide a new manufacturing method that can be performed. In particular, it does not involve complicated methods such as concentration and gelation while removing the solvent from the reaction solution, or using a supercritical drying method for drying the gel, and the sol-gel transition of the reaction solution under sealed conditions and room temperature.・ Inorganic and organic materials that have precisely controlled macropores in addition to mesopores with controlled narrow pore size distribution and regularity and shape over long distances by only drying under normal pressure and normal heat treatment. It is providing the method of manufacturing an inorganic hybrid type porous body.
本発明者は、両親媒性物質を鋳型成分として共存させてゾル−ゲル法により無機系多孔質体を製造するに当って、ゾル−ゲル転移と相分離過程が同時に起こるようにし、1)鋳型成分の集合状態を安定化させる成分を共存させる、あるいは2)鋳型成分の集合状態が安定化する溶液組成で好ましい相分離が起こるような加水分解性の官能基を有する無機低分子化合物を選択する、の少なくともひとつの条件を満たすことにより、上記の目的が達成されることを見出した。
かくして、本発明に従えば、下記の各工程を含むことを特徴とする、長距離秩序性ならびに形状および細孔径分布の制御されたメソ細孔に加えて、制御された細孔径分布を有するマクロ細孔を併せ持つ、無機系および有機無機ハイブリッド系多孔質体の製造方法が提供される。
(i) ゾル−ゲル反応触媒成分を含有する水溶液に、鋳型成分として両親媒性物質を溶かして均一溶液を調製する工程、
(ii) 該均一溶液に、両親媒性物質が自己組織化して形成された分子集合体が溶液中で安定化される溶媒組成あるいは添加成分を用いて溶液あるいは分散液を調製する工程、
(iii) 該溶液あるいは分散液に、加水分解性の官能基を有する無機低分子化合物を添加しゾル−ゲル反応を行わせて、溶媒に富む溶媒リッチ相と、ゾル−ゲル反応により前記無機低分子化合物から生成した無機酸化物重合体であって、前記両親媒性物質から成る鋳型成分の表面上に固着した無機酸化物重合体に富む骨格相とから成る、連続した３次元網目構造の湿潤ゲルを形成する工程、
(iv) 該湿潤ゲルを乾燥して前記溶媒リッチ相から溶媒を蒸発除去することによりマクロ細孔を形成する工程、および
(v) 乾燥後のゲルから熱分解または抽出により前記鋳型成分を除去することにより前記骨格相内にメソ細孔を形成する工程。
The present inventor made the sol-gel transition and the phase separation process occur simultaneously in the production of the inorganic porous material by the sol-gel method in the presence of an amphiphile as a template component. Ingredients that stabilize the aggregation state of the components coexist, or 2) Select an inorganic low molecular weight compound having a hydrolyzable functional group that causes favorable phase separation in a solution composition that stabilizes the aggregation state of the template component It has been found that the above object can be achieved by satisfying at least one of the following conditions.
Thus, according to the present invention, in addition to long-range order and controlled mesopores of shape and pore size distribution, the macromolecules having a controlled pore size distribution are characterized by comprising the following steps: A method for producing an inorganic and organic-inorganic hybrid porous body having both pores is provided.
(i) a step of preparing a homogeneous solution by dissolving an amphiphile as a template component in an aqueous solution containing a sol-gel reaction catalyst component;
(ii) preparing a solution or dispersion in the homogeneous solution using a solvent composition or an additive component in which a molecular assembly formed by self-organization of an amphiphile is stabilized in the solution;
(iii) An inorganic low molecular weight compound having a hydrolyzable functional group is added to the solution or dispersion to cause a sol-gel reaction, and the solvent-rich solvent rich phase and the inorganic low molecular weight compound by the sol-gel reaction. Wet of a continuous three-dimensional network structure comprising an inorganic oxide polymer formed from a molecular compound and a skeleton phase rich in an inorganic oxide polymer fixed on the surface of a template component made of the amphiphile Forming a gel;
(iv) forming the macropores by drying the wet gel and evaporating and removing the solvent from the solvent-rich phase; and
(v) A step of forming mesopores in the skeleton phase by removing the template component from the dried gel by thermal decomposition or extraction.
本発明の無機系多孔質体の製造方法の特徴は、適当な添加成分によって安定化せしめられた形状や集合状態を有する両親媒性物質の分子集合体を、鋳型成分として共存させてゾル−ゲル法により無機系多孔質体を製造するに際して、ゾル−ゲル転移と相分離とが同時に起こるように反応条件を調整することにより、後の乾燥工程によりマクロ細孔を形成し得る溶媒リッチ相と、後の熱分解工程により内部にメソ細孔を形成し得る骨格相とから成るゲルを調製する工程を含むことにある。
これに対して、両親媒性物質を鋳型成分として共存させてゾル−ゲル法による多孔体を合成する従来の方法に従えば、既述のように、得られる多孔体はメソ細孔のみを有するものであった。これは、従来の方法においては、鋳型成分の表面で局所的に早期に酸化物重合体が形成されて沈澱し系から分離してしまうからであると考えられる。また分子集合体を安定化させる成分を加えずに作製される、相分離を伴うゾル−ゲル反応による多孔体は、整ったマクロ細孔は有するものの、大きさの揃ったメソ細孔は無定形であり、長距離にわたる秩序や細孔形状の制御がなされたものではなかった。
なお、本発明において用いられる「マクロ細孔」および「メソ細孔」という語は、よく知られたIUPACによる提唱に従って定義されるものとする。すなわち、マクロ細孔とは直径が50ナノメートル（nm）以上の細孔を指称し、また、メソ細孔とは、マクロ細孔とミクロ細孔（直径2ナノメートル以下）との中間、すなわち、直径が2〜50ナノメートルの範囲にある細孔を指称し、本発明によって得られる多孔質体は、一般に、直径が2〜10ナノメートル程度のメソ細孔を中心として狭い細孔分布を有する。
A feature of the method for producing an inorganic porous material of the present invention is that a sol-gel is obtained by coexisting a molecular assembly of an amphiphile having a shape and an aggregation state stabilized by an appropriate additive component as a template component. When producing an inorganic porous material by the method, by adjusting the reaction conditions so that sol-gel transition and phase separation occur simultaneously, a solvent-rich phase capable of forming macropores in a subsequent drying step; The object is to include a step of preparing a gel composed of a skeleton phase capable of forming mesopores therein by a subsequent pyrolysis step.
On the other hand, according to the conventional method of synthesizing a porous body by a sol-gel method in the presence of an amphiphilic substance as a template component, as described above, the obtained porous body has only mesopores. It was a thing. This is considered to be because, in the conventional method, an oxide polymer is locally formed on the surface of the template component at an early stage and precipitates and separates from the system. In addition, a porous body by sol-gel reaction with phase separation, which is produced without adding a component that stabilizes molecular aggregates, has regular macropores, but mesopores with uniform sizes are amorphous. Therefore, the order and the shape of the pores over a long distance were not controlled.
The terms “macropore” and “mesopore” used in the present invention shall be defined according to the well-known proposal by IUPAC. That is, a macropore refers to a pore having a diameter of 50 nanometers (nm) or more, and a mesopore is an intermediate between a macropore and a micropore (diameter of 2 nanometers or less), that is, The porous material obtained by the present invention generally has a narrow pore distribution centering on mesopores having a diameter of about 2 to 10 nanometers. Have.
本発明の原理は、背景技術に関連して既述したようなゾル−ゲル法により低分子化合物から酸化物の重合体を生成し得るものとして知られた各種の無機化合物に適用することができるが、本発明の方法が特に好ましく適用されるのは、多孔質体を構成する無機酸化物重合体が、シリカおよび／または有機官能基含有シロキサン重合体の場合である。
本発明に従いシリカやシロキサン重合体から成りメソ細孔とマクロ細孔とを併せ持つ多孔質体を製造するには、ゾル−ゲル反応工程を少なくともその反応初期において酸性領域で行い、且つ、該ゾル−ゲル反応において触媒成分を含有する水の量が反応系中のシリカ1.0ｇ（無水シリカ換算重量として）に対して1.0〜50.0ｇの範囲にあるように反応条件を調整することが必要であり、これによって、ゾル−ゲル転移と相分離が同時に起こり、溶媒リッチ相と骨格相とから成るゲルが生成する。
更に詳述すれば、両親媒性物質を鋳型としてゾル−ゲル反応によりシリカを主成分とする多孔質体を製造する場合、酸性、中性、塩基性いずれの触媒条件においても鋳型成分による大きさの揃ったメソ孔を得ることができることは従来より知られているが、本発明に従い溶媒リッチ相と骨格相に分離したゲルを作製するためには、均質な加水分解およびゲル形成を起こすことが容易な酸性領域での反応が必要である。あるいは反応溶液内部からの均質な反応によって、反応初期に酸性であった液性を徐々に塩基性に変化させて（例えば、反応溶液中に尿素を添加しておき、この尿素が徐々に加水分解してアンモニアを発生するようにする）均質な加水分解とゲル形成を誘起しても良い。すなわち、ゾル−ゲル反応は、加水分解による結合部位（重縮合反応部位：代表的には水酸基）の生成と、該結合部位を介する重縮合反応によるゲル形成とから成るものであるが、酸性領域では加水分解反応が促進されて多くの重縮合反応部位が形成され、この多くの部位を介して均質に重縮合反応（ゲル形成）が起こるものと考えられる。これに対して、ゾル−ゲル反応初期から塩基性であると重縮合反応の方が促進されて不均質なゲル形成が誘起されてしまう。ゾル−ゲル反応の触媒成分としては、塩酸、硝酸、硫酸等の鉱酸および酢酸、クエン酸などの有機酸、またはアンモニア、アミン類などの弱塩基類、水酸化ナトリウム、水酸化カリウム等の強塩基類を挙げることができるが、液性の調整が重要な因子であるのでこれらの物質に限定されない。
The principle of the present invention can be applied to various inorganic compounds known to be capable of producing an oxide polymer from a low molecular weight compound by the sol-gel method as described above in relation to the background art. However, the method of the present invention is particularly preferably applied when the inorganic oxide polymer constituting the porous body is a silica and / or an organic functional group-containing siloxane polymer.
In order to produce a porous body composed of silica or siloxane polymer according to the present invention and having both mesopores and macropores, the sol-gel reaction step is carried out in the acidic region at least in the initial stage of the reaction, and the sol- In the gel reaction, it is necessary to adjust the reaction conditions so that the amount of water containing the catalyst component is in the range of 1.0 to 50.0 g with respect to 1.0 g of silica in the reaction system (as weight of anhydrous silica), Thereby, sol-gel transition and phase separation occur simultaneously, and a gel composed of a solvent-rich phase and a skeleton phase is generated.
More specifically, when a porous material mainly composed of silica is produced by a sol-gel reaction using an amphiphile as a template, the size of the template component depends on any acidic, neutral or basic catalyst conditions. It has been known that a uniform mesopore can be obtained. However, in order to produce a gel separated into a solvent-rich phase and a skeleton phase according to the present invention, homogeneous hydrolysis and gel formation may occur. A reaction in an easy acidic region is necessary. Alternatively, the liquidity that was acidic at the beginning of the reaction is gradually changed to basic by a homogeneous reaction from within the reaction solution (for example, urea is added to the reaction solution, and this urea is gradually hydrolyzed. To generate ammonia) and may induce homogeneous hydrolysis and gel formation. That is, the sol-gel reaction is composed of the formation of a binding site (polycondensation reaction site: typically a hydroxyl group) by hydrolysis and gel formation by a polycondensation reaction via the binding site. Then, the hydrolysis reaction is promoted to form many polycondensation reaction sites, and it is considered that the polycondensation reaction (gel formation) occurs homogeneously through these many sites. On the other hand, if it is basic from the beginning of the sol-gel reaction, the polycondensation reaction is promoted, and inhomogeneous gel formation is induced. The catalyst component of the sol-gel reaction includes mineral acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as acetic acid and citric acid, weak bases such as ammonia and amines, strong acids such as sodium hydroxide and potassium hydroxide. Although bases can be mentioned, since adjustment of liquidity is an important factor, it is not limited to these substances.
また、本発明に従いシリカやシロキサン重合体から成りメソ細孔に加えてマクロ細孔を併せ持つ多孔質体を得るには、ゾル−ゲル反応における水の量も重要な因子であり、反応系中のケイ素原子0.0167モル（無水シリカ換算重量として1.0ｇ）に対して、触媒成分を含む水の量として、1.0〜50.0ｇ、好ましくは2.0〜30.0ｇ、より好ましくは3.0〜20.0ｇとなるようにする。水の量が多すぎると重合度が充分に上がらない重合体が水中に沈澱してしまい均一なゲルができ難くなる。この現象は出発物質の反応性や反応温度に依存するため、その組成範囲や反応条件を一概に述べることは困難であるが、両親媒性物質を鋳型成分として共存させるゾル−ゲル法によるが、メソ細孔しか有しない多孔質体を製造する従来の方法においては、上記のように定義される水の量は、一般に50ｇ以上であり、100ｇ以上とするものも多い。
以上のようにして、本発明においては、ゾル−ゲル転移と相分離とが実質的に同時に起こるようにゾル−ゲル反応工程を調整することにより、溶媒（水）に富む溶媒リッチ相と酸化物重合体に富む骨格相とから成るゲルが生成され、この生成は、沈澱を生じることなく溶液が白濁することによって確認される。この生成物は、粉末や沈殿ではなく一塊の固体として固化するので、その強度を増すために暫く熟成し（必要に応じて僅かに加温する）、これを乾燥および熱分解（または抽出）に供することにより目的の多孔質体が得られる。
In addition, the amount of water in the sol-gel reaction is an important factor for obtaining a porous body composed of silica or siloxane polymer according to the present invention and having macropores in addition to mesopores. The amount of water containing the catalyst component is 1.0 to 50.0 g, preferably 2.0 to 30.0 g, more preferably 3.0 to 20.0 g with respect to 0.0167 mol of silicon atoms (1.0 g in terms of anhydrous silica). . If the amount of water is too large, a polymer whose degree of polymerization does not sufficiently increase will precipitate in water, making it difficult to form a uniform gel. Since this phenomenon depends on the reactivity and reaction temperature of the starting material, it is difficult to describe the composition range and reaction conditions in general, but it is based on the sol-gel method in which an amphiphile coexists as a template component. In a conventional method for producing a porous body having only mesopores, the amount of water defined as described above is generally 50 g or more, and many are 100 g or more.
As described above, in the present invention, the solvent-rich phase and oxide rich in the solvent (water) are prepared by adjusting the sol-gel reaction step so that the sol-gel transition and the phase separation occur substantially simultaneously. A gel consisting of a polymer rich backbone phase is produced, which is confirmed by the cloudiness of the solution without precipitation. The product solidifies as a solid mass rather than a powder or precipitate, so it is aged for a while to increase its strength (warm slightly if necessary), and then dried and pyrolyzed (or extracted) By supplying, the target porous body is obtained.
かくして、本発明の方法に従いメソ細孔とマクロ細孔を併せ持つ無機質多孔質を製造するには、先ず、ゾル−ゲル反応触媒成分を含有する水溶液に鋳型成分として両親媒性物質を溶かして均一溶液を調製する。この均一溶液に、必要に応じて両親媒性物質の分子集合体を安定化させる成分を加えた後、加水分解性の官能基を有する無機低分子化合物を添加してゾル−ゲル反応を行うと、上述したように、溶媒リッチ相と骨格相とに分離したゲルが生成する。
溶媒リッチ相は、マクロ細孔に対応する直径を有する３次元網目状に連続した相であり、このことは、後述のように乾燥によって溶媒を除去した後の構造体を電子顕微鏡によって観察することにより確認できる（図１参照）。
骨格相は、ゾル−ゲル反応により無機低分子化合物から生成した無機酸化物重合体あるいは有機無機ハイブリッド重合体に富み、やはり連続した３次元網目構造の相である。この相は、鋳型成分となる両親媒性物質（厳密には、両親媒性物質が自己組織化して形成された分子集合体）の表面に固着して形成されているものであり、このことは、後に鋳型成分（両親媒性化合物）を除去すると、該骨格相の内部に細孔（メソ細孔）が形成されていることからも確認できる（図２参照）。すなわち、酸化物重合体は、表面に水酸基を有し、この部分が両親媒性物質のプロトン受容部分と強く引力相互作用することによって、鋳型成分が溶液中で形成する自己組織化構造をゲル網目の中に転写することができる。
ゾル−ゲル反応の生成物（ゲル）が固化した後、適当な熟成時間を経た後、乾燥によって溶媒を除去すると、溶媒リッチ相の占めていた空間が連続貫通したマクロ細孔となる。次いで両親媒性物質から成る鋳型成分を熱分解あるいは抽出除去すると、鋳型成分の自己組織化した構造によって形成されたナノメートル領域の大きさの揃った細孔（メソ細孔）が得られる。
Thus, in order to produce an inorganic porous material having both mesopores and macropores according to the method of the present invention, first, an amphiphilic substance is dissolved as a template component in an aqueous solution containing a sol-gel reaction catalyst component, and a uniform solution is obtained. To prepare. When a component that stabilizes the molecular assembly of the amphiphilic substance is added to the homogeneous solution as necessary, an inorganic low-molecular compound having a hydrolyzable functional group is added to perform a sol-gel reaction. As described above, a gel separated into a solvent-rich phase and a skeleton phase is generated.
The solvent-rich phase is a three-dimensional network-like continuous phase having a diameter corresponding to the macropores, which means that the structure after removing the solvent by drying is observed with an electron microscope as described later. (See FIG. 1).
The skeletal phase is rich in an inorganic oxide polymer or an organic-inorganic hybrid polymer formed from an inorganic low-molecular compound by a sol-gel reaction, and is also a continuous three-dimensional network phase. This phase is formed by adhering to the surface of the amphiphilic substance (strictly speaking, a molecular assembly formed by self-organization of the amphiphile) as the template component. When the template component (amphiphilic compound) is removed later, pores (mesopores) are formed in the skeleton phase (see FIG. 2). That is, the oxide polymer has a hydroxyl group on the surface, and this part strongly interacts with the proton-accepting part of the amphiphile to form a self-organized structure formed by the template component in the gel network. Can be transferred to the inside.
After the product (gel) of the sol-gel reaction has solidified, after passing through an appropriate aging time, when the solvent is removed by drying, macropores in which the space occupied by the solvent-rich phase is continuously penetrated are formed. Next, when the template component comprising the amphiphile is pyrolyzed or extracted and removed, pores (mesopores) having a uniform size in the nanometer region formed by the self-organized structure of the template component are obtained.
本発明の方法において鋳型として用いられる両親媒性物質として好ましいのは、四級アンモニウム塩等の親水部と主にアルキル基からなる疎水部とを含むカチオン性界面活性剤もしくは非イオン性界面活性剤から成る界面活性剤、または親水部と疎水部をもつブロック共重合体であり、具体的な例としては、ハロゲン化アルキルアンモニウム、ポリオキシエチレンアルキルエーテル、エチレンオキシド−プロピレンオキシド−エチレンオキシドブロック共重合体などが挙げられるが、これらに限られるものではない。本発明において用いられる両親媒性物質は、界面活性剤や上記のブロック共重合体のように反応溶液に均一に溶解するものが好ましい。また、既述の説明から理解されるように、本発明における両親媒性物質は、鋳型成分としてナノメートル領域の細孔（メソ細孔）の径を整える働きに加えて、マクロ細孔となる溶媒リッチ相を持つ構造を生じさせる共存物質としての働きを兼ね備えた成分である。 Preferred as an amphiphilic substance used as a template in the method of the present invention is a cationic surfactant or a nonionic surfactant containing a hydrophilic part such as a quaternary ammonium salt and a hydrophobic part mainly composed of an alkyl group. Or a block copolymer having a hydrophilic part and a hydrophobic part. Specific examples thereof include alkyl ammonium halides, polyoxyethylene alkyl ethers, ethylene oxide-propylene oxide-ethylene oxide block copolymers, etc. However, it is not limited to these. The amphiphilic substance used in the present invention is preferably one that is uniformly dissolved in the reaction solution, such as a surfactant or the above-mentioned block copolymer. Further, as can be understood from the above description, the amphiphilic substance in the present invention becomes macropores in addition to the function of adjusting the diameter of nanometer region pores (mesopores) as a template component. It is a component that also serves as a coexisting substance that produces a structure having a solvent-rich phase.
本発明の方法において上述の両親媒性物質の分子集合体を安定化させて、形状の整った長距離（典型的に１００ｎｍ以上）にわたるＸ線回折等の手法で検出可能な秩序を発現させ、なおかつその秩序構造が無機系および有機無機ハイブリッド系ゲルの構造中に細孔として転写されるための適切な添加物としては、非プロトン性の有機液体、例えばトリメチルベンゼンやクロロホルムなどが好適であるが、これに限定されるものではない。出発物質として比較的水の多い組成においてマクロ孔を生じる相分離を起こすアルコキシドを用いた場合には、上述の添加物を用いることなく両親媒性物質の分子集合体を安定化させて、形状の整った長距離にわたるＸ線回折当の手法で検出可能な秩序を発現させることもできる。この場合には上述の添加物は、主として細孔径の制御を行うために加えられる。また上述の添加物を両親媒性物質に対して、長距離秩序が得られる適切な濃度範囲を超えて過剰に添加すると、両親媒性物質の分子集合体は再び秩序の低い状態に転化していくが、その際には典型的に直径２０ｎｍ以上の比較的大きいメソ細孔からなるメソ細孔構造が得られる。この構造はメソ構造セル状泡（Mesostructured Cellurar Foam）と呼ばれ、すでに両親媒性物質を含むゾル−ゲル反応によって粉末や沈殿の形状では知られているが、本発明によればこの特徴的な構造も、制御されたマクロ孔を与えるゲル骨格中に転写することが可能である。両親媒性物質の分子集合体を安定化させる添加物の好適な添加量は、両親媒性物質のに対して重量比で、０〜１００％、好ましくは０〜７０％、より好ましくは０〜５０％の範囲である。添加物は通常ゾル−ゲル反応系の溶媒への溶解度が低いため、これを大過剰に加えると、両親媒性物質の分子集合体中へ溶解し切れなかった添加物が反応溶液中に液滴状に分散し、溶液を不均一な状態にし、結果として得られるゲルの多孔構造の中に液滴状の不均一なマクロ孔を形成するため、整ったマクロ孔を有する構造体を得るためには、これを避けることが必要である。 In the method of the present invention, the molecular assembly of the above-mentioned amphiphile is stabilized, and an order that can be detected by a technique such as X-ray diffraction over a long distance (typically 100 nm or more) with a uniform shape is expressed, In addition, suitable additives for transferring the ordered structure as pores in the structure of inorganic and organic-inorganic hybrid gels are preferably aprotic organic liquids such as trimethylbenzene and chloroform. However, the present invention is not limited to this. When using an alkoxide that causes phase separation that produces macropores in a relatively water-rich composition as a starting material, the molecular assembly of the amphiphile is stabilized without using the above-mentioned additives, It is also possible to develop an order that can be detected by a technique such as X-ray diffraction over a long distance. In this case, the above-mentioned additives are added mainly for controlling the pore diameter. In addition, if the above additives are added excessively to the amphiphile beyond the appropriate concentration range where long-range order is obtained, the molecular aggregate of the amphiphile is again converted into a low order state. In that case, however, a mesopore structure consisting of relatively large mesopores typically having a diameter of 20 nm or more is obtained. This structure is called Mesostructured Cellurar Foam, which is already known in the form of powder or precipitate by sol-gel reaction containing amphiphiles. The structure can also be transferred into a gel skeleton that provides controlled macropores. A suitable addition amount of the additive for stabilizing the molecular assembly of the amphiphile is 0 to 100%, preferably 0 to 70%, more preferably 0 to 0 by weight with respect to the amphiphile. The range is 50%. Additives usually have low solubility in the solvent of the sol-gel reaction system, so if they are added in large excess, the additives that could not be completely dissolved in the molecular assembly of the amphiphile will drop into the reaction solution. In order to obtain a structure with well-defined macropores, in order to disperse the solution and make the solution inhomogeneous and to form droplet-like heterogeneous macropores in the resulting gel porous structure It is necessary to avoid this.
また、本発明において用いられる加水分解性の官能基を有する無機低分子化合物としては、背景技術に関連して既述したような金属アルコキシドをはじめとする各種の金属化合物が適用可能であるが、本発明の特に好ましい態様に従い、シリカから成る多孔質体を製造する場合においては、シリカ源としてケイ素アルコキシドの単量体および低分子重合体（オリゴマー）が好適に使用される。また、有機官能基含有シロキサン重合体（有機・無機ハイブリッド）から成る多孔質体を製造する場合には、そのような有機・無機ハイブリッド源として、少なくとも１つのケイ素−炭素結合を含むケイ素アルコキシドの単量体および低分子量重合体、あるいは２つ以上のケイ素原子間を１つ以上の炭素を含む炭化水素鎖あるいはヘテロ原子を含む炭化水素鎖が架橋している構造の化合物（例えばビストリアルコキシシリルアルカン類）を用いることができる。なお、シリカと有機官能基含有シロキサン重合体とを組み合わせて本発明の無機系多孔質体を製造することもできる。 In addition, as the inorganic low molecular weight compound having a hydrolyzable functional group used in the present invention, various metal compounds including metal alkoxide as described above in relation to the background art can be applied. In the case of producing a porous body composed of silica according to a particularly preferred embodiment of the present invention, a silicon alkoxide monomer and a low molecular weight polymer (oligomer) are suitably used as a silica source. In the case of producing a porous body composed of an organic functional group-containing siloxane polymer (organic / inorganic hybrid), a single silicon alkoxide containing at least one silicon-carbon bond is used as such an organic / inorganic hybrid source. Polymers and low molecular weight polymers, or compounds having a structure in which a hydrocarbon chain containing one or more carbons or a hydrocarbon chain containing heteroatoms is bridged between two or more silicon atoms (for example, bistrialkoxysilylalkanes) ) Can be used. The inorganic porous material of the present invention can also be produced by combining silica and an organic functional group-containing siloxane polymer.
以下に本発明の特徴を更に明らかにするため実施例を示すが、本発明はこれらの実施例により限定されるものではない。 Examples are given below to further clarify the features of the present invention, but the present invention is not limited to these Examples.
（実施例１）：
まず両親媒性物質であるエチレンオキシド−プロピレンオキシド−エチレンオキシドブロック共重合体（EO20-PO70-EO20、平均分子量5800、アルドリッチ）1.90ｇを0.1mol/L硝酸水溶液5.76ｇに溶解し、トリメチルベンゼン0.20gを加えた後、得られた均一溶液にビス（トリメトキシシリル）エタン2.15ｇを攪拌下で加えて加水分解反応を行った。この場合、触媒成分を含有する水の量は、シリカ1.0ｇ当たり12.0ｇである。数分攪拌したのち、得られた透明溶液を密閉容器に移し、60℃の恒温漕中に保持したところ約60分後に溶液の白濁に引き続いて固化した。
固化した試料をさらに数時間熟成させ、ついで60℃において溶媒を蒸発させて除去し、そののち100℃／ｈの昇温速度で350℃まで加熱してこの温度で５時間保持した後、室温まで冷却した。これによって、ケイ素原子をエチレン鎖が架橋した構造をもつ有機無機ハイブリッドよりなる多孔質体を得た。
(Example 1):
First, 1.90 g of ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO20-PO70-EO20, average molecular weight 5800, Aldrich), an amphiphilic substance, is dissolved in 5.76 g of 0.1 mol / L nitric acid aqueous solution, and 0.20 g of trimethylbenzene is dissolved. After the addition, 2.15 g of bis (trimethoxysilyl) ethane was added to the obtained homogeneous solution under stirring to conduct a hydrolysis reaction. In this case, the amount of water containing the catalyst component is 12.0 g per 1.0 g of silica. After stirring for several minutes, the obtained transparent solution was transferred to a sealed container and kept in a constant temperature bath at 60 ° C., and after about 60 minutes, the solution solidified following the cloudiness of the solution.
The solidified sample is further aged for several hours, then the solvent is removed by evaporation at 60 ° C., then heated to 350 ° C. at a rate of 100 ° C./h and held at this temperature for 5 hours, then to room temperature. Cooled down. As a result, a porous body made of an organic-inorganic hybrid having a structure in which an ethylene chain was cross-linked with a silicon atom was obtained.
得られた多孔質体中には中心孔径2μｍ（＝2000nm）程度の揃った貫通孔と太さ約1μｍのゲル骨格が３次元網目状に絡み合った構造で存在していることが電子顕微鏡観察（図１）によって確かめられた。そして、その貫通孔の内壁に直径5.5nm付近に分布の中心を持つ細孔が多数存在し、300m2/g以上の比表面積を有していることが、窒素吸着測定によって確かめられた。その細孔分布を図２に示す。この試料の電界放射型走査電子顕微鏡像には、マクロ細孔を形成するゲル骨格の断面に、大きさの均一な２次元六方配列状にならんだメソ細孔が観察された（図３）。さらにこの試料の粉末Ｘ線回折を測定したところ、約9nmに相当する秩序の高い周期配列を示す回折プロファイルが得られた（図４）。このことから、本試料のゲル骨格の内部には、直径約5.5nmのメソ細孔と約3.5nmの厚さのゲルの壁とが交互に長距離（典型的に100nm以上）に渡って配列し、全体の配列は２次元六方対称性を有することがわかった。この結果は上述の電界放射型走査電子顕微鏡像の与える情報と良く整合し、本試料が細孔分布の制御されたマクロ細孔と、長距離秩序をもつ大きさの揃ったメソ孔を併せ持っていることが証明された。 In the obtained porous material, it is observed with an electron microscope that a through-hole having a center hole diameter of about 2 μm (= 2000 nm) and a gel skeleton with a thickness of about 1 μm are intertwined in a three-dimensional network ( This was confirmed by FIG. It was confirmed by nitrogen adsorption measurement that there are many pores having a distribution center near the diameter of 5.5 nm on the inner wall of the through-hole and a specific surface area of 300 m2 / g or more. The pore distribution is shown in FIG. In the field emission scanning electron microscope image of this sample, mesopores aligned in a two-dimensional hexagonal array having a uniform size were observed in the cross section of the gel skeleton forming the macropores (FIG. 3). Further, when the powder X-ray diffraction of this sample was measured, a diffraction profile showing a highly ordered periodic array corresponding to about 9 nm was obtained (FIG. 4). Therefore, mesopores with a diameter of approximately 5.5 nm and gel walls with a thickness of approximately 3.5 nm are alternately arranged over a long distance (typically 100 nm or more) inside the gel skeleton of this sample. The entire array was found to have two-dimensional hexagonal symmetry. This result is in good agreement with the information given by the above-mentioned field emission scanning electron microscope image. This sample has both macropores with controlled pore distribution and mesopores with long-range order and uniform size. Proven to be.
（実施例２）：
まず両親媒性物質であるエチレンオキシド−プロピレンオキシド−エチレンオキシドブロック共重合体（EO20-PO70-EO20、平均分子量5800、アルドリッチ）1.90ｇを0.1mol/L硝酸水溶液5.76ｇに溶解し、トリメチルベンゼン0.25gを加えた後、得られた均一溶液にビス（トリメトキシシリル）エタン2.15ｇを攪拌下で加えて加水分解反応を行った。この場合、触媒成分を含有する水の量は、シリカ1.0ｇ当たり12.0ｇである。数分攪拌したのち、得られた透明溶液を密閉容器に移し、55℃の恒温漕中に保持したところ約50分後に溶液の白濁に引き続いて固化した。
固化した試料をさらに数時間熟成させ、ついで60℃において溶媒を蒸発させて除去し、そののち100℃／ｈの昇温速度で350℃まで加熱してこの温度で５時間保持した後、室温まで冷却した。これによって、ケイ素原子をエチレン鎖が架橋した構造をもつ有機無機ハイブリッドよりなる多孔質体を得た。
(Example 2):
First, 1.90 g of ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO20-PO70-EO20, average molecular weight 5800, Aldrich), an amphiphile, is dissolved in 5.76 g of 0.1 mol / L nitric acid aqueous solution, and 0.25 g of trimethylbenzene is dissolved. After the addition, 2.15 g of bis (trimethoxysilyl) ethane was added to the obtained homogeneous solution under stirring to conduct a hydrolysis reaction. In this case, the amount of water containing the catalyst component is 12.0 g per 1.0 g of silica. After stirring for several minutes, the obtained transparent solution was transferred to a sealed container and kept in a constant temperature bath at 55 ° C., and after about 50 minutes, the solution solidified following the cloudiness of the solution.
The solidified sample is further aged for several hours, then the solvent is removed by evaporation at 60 ° C., then heated to 350 ° C. at a rate of 100 ° C./h and held at this temperature for 5 hours, then to room temperature. Cooled down. As a result, a porous body made of an organic-inorganic hybrid having a structure in which an ethylene chain was cross-linked with a silicon atom was obtained.
得られた多孔質体中には中心孔径0.4μｍ（＝400nm）程度の揃った貫通孔と太さ約0.3μｍのゲル骨格が３次元網目状に絡み合った構造で存在していることが電子顕微鏡および水銀圧入測定によって確かめられた（図５（ａ）（ｂ）および図６）。そして、その貫通孔の内壁に直径5nm付近に分布の中心を持つ細孔が多数存在し、300m2/g以上の比表面積を有していることが、窒素吸着測定によって確かめられた。その細孔分布を図７に示す。
この試料の電界放射型走査電子顕微鏡像には、マクロ細孔を形成するゲル骨格の断面に、大きさの均一な２次元六方配列状に並んだメソ細孔と、大きさは揃っているが破断面内には一見してそれと分かる秩序の認められない構造を持ったメソ孔とが、一定の広さの領域をもって交じり合った状態で観察された（図８）。さらにこの試料の粉末Ｘ線回折を測定したところ、約10nmに相当する秩序の高い周期配列を示す回折プロファイルが得られた（図９）が、既に報告されている３次元六方対称構造のメソ孔をもつ物質の粉末Ｘ線回折との比較により、この試料には２次元六方対称構造と３次元六方対称構造が共存していることが分かった。
このことから、本試料のゲル骨格の内部には、直径約6nmのメソ細孔と約4nmの厚さのゲルの壁とが交互に長距離（典型的に100nm以上）に渡って配列し、全体の配列は２次元六方対称性を有する構造と、同等の細孔径をもつが３次元六方対称性を有する構造とが共存することがわかった。この結果は上述の電界放射型走査電子顕微鏡像の与える情報と良く整合し、本試料が細孔分布の制御されたマクロ細孔と、２種類の異なった長距離秩序をもつ大きさの均一なメソ孔を併せ持っていることが証明された。
In the obtained porous body, an electron microscope shows that a through-hole having a center hole diameter of about 0.4 μm (= 400 nm) and a gel skeleton having a thickness of about 0.3 μm are entangled in a three-dimensional network. And confirmed by mercury intrusion measurement (FIGS. 5A and 5B and FIG. 6). It was confirmed by nitrogen adsorption measurement that the inner wall of the through hole had many pores with a distribution center near 5 nm in diameter and had a specific surface area of 300 m2 / g or more. The pore distribution is shown in FIG.
The field emission scanning electron microscope image of this sample has the same size as the mesopores arranged in a two-dimensional hexagonal array with a uniform size on the cross section of the gel skeleton forming the macropores. Mesopores having a structure with no order that can be seen at first glance were observed in the fractured surface in a state where they intersected with a certain area (Fig. 8). Further, when X-ray powder diffraction of this sample was measured, a diffraction profile showing a highly ordered periodic array corresponding to about 10 nm was obtained (FIG. 9). By comparison with the powder X-ray diffraction of the substance having the above, it was found that the two-dimensional hexagonal symmetric structure and the three-dimensional hexagonal symmetric structure coexist in this sample.
From this, inside the gel skeleton of this sample, mesopores with a diameter of about 6 nm and gel walls with a thickness of about 4 nm are alternately arranged over a long distance (typically 100 nm or more), It was found that the entire arrangement coexists with a structure having two-dimensional hexagonal symmetry and a structure having the same pore diameter but having three-dimensional hexagonal symmetry. This result is in good agreement with the information given by the above-mentioned field emission scanning electron microscope image. This sample is a macropore with a controlled pore distribution and a uniform size with two different long-range orders. Proven to have a mesopore.
（実施例３）：
まず両親媒性物質であるエチレンオキシド−プロピレンオキシド−エチレンオキシドブロック共重合体（EO20-PO70-EO20、平均分子量5800、アルドリッチ）1.90ｇを0.1mol/L硝酸水溶液5.76ｇに溶解し、トリメチルベンゼン0.25gを加えた後、得られた均一溶液にビス（トリメトキシシリル）エタン2.15ｇを攪拌下で加えて加水分解反応を行った。この場合、触媒成分を含有する水の量は、シリカ1.0ｇ当たり12.0ｇである。数分攪拌したのち、得られた透明溶液を密閉容器に移し、35℃の恒温漕中に保持したところ約70分後に溶液の白濁に引き続いて固化した。
固化した試料をさらに数時間熟成させ、ついで60℃において溶媒を蒸発させて除去し、そののち100℃／ｈの昇温速度で350℃まで加熱してこの温度で５時間保持した後、室温まで冷却した。これによって、ケイ素原子をエチレン鎖が架橋した構造をもつ有機無機ハイブリッドよりなる多孔質体を得た。
得られた多孔質体中には中心孔径0.1μｍ（＝100nm）程度の揃った貫通孔と太さ約0.1μｍのゲル骨格が３次元網目状に絡み合った構造で存在していることが電子顕微鏡および水銀圧入測定によって確かめられた。そして、その貫通孔の内壁に直径5.5nm付近に分布の中心を持つ細孔が多数存在し、300m2/g以上の比表面積を有していることが、窒素吸着測定によって確かめられた。その細孔分布を図１０に示す。このゲルには実施例２で述べたのと同様なメソ孔が存在することが同様な方法で、確かめられた。したがって反応温度を変えることにより、細孔径分布の狭いマクロ孔の直径と気孔率だけを変化させて、メソ孔は同様の構造をもつ、多孔質体を作製することができた。
(Example 3):
First, 1.90 g of ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO20-PO70-EO20, average molecular weight 5800, Aldrich), an amphiphile, is dissolved in 5.76 g of 0.1 mol / L nitric acid aqueous solution, and 0.25 g of trimethylbenzene is dissolved. After the addition, 2.15 g of bis (trimethoxysilyl) ethane was added to the obtained homogeneous solution under stirring to conduct a hydrolysis reaction. In this case, the amount of water containing the catalyst component is 12.0 g per 1.0 g of silica. After stirring for several minutes, the resulting clear solution was transferred to a sealed container and kept in a constant temperature bath at 35 ° C., and after about 70 minutes, the solution solidified following the cloudiness of the solution.
The solidified sample is further aged for several hours, then the solvent is removed by evaporation at 60 ° C., then heated to 350 ° C. at a rate of 100 ° C./h and held at this temperature for 5 hours, then to room temperature. Cooled down. As a result, a porous body made of an organic-inorganic hybrid having a structure in which an ethylene chain was cross-linked with a silicon atom was obtained.
In the obtained porous material, an electron microscope shows that a through-hole having a central pore diameter of about 0.1 μm (= 100 nm) and a gel skeleton having a thickness of about 0.1 μm are entangled in a three-dimensional network. And confirmed by mercury intrusion measurements. It was confirmed by nitrogen adsorption measurement that there are many pores having a distribution center near the diameter of 5.5 nm on the inner wall of the through-hole and a specific surface area of 300 m2 / g or more. The pore distribution is shown in FIG. It was confirmed in a similar manner that this gel had mesopores similar to those described in Example 2. Therefore, by changing the reaction temperature, only the diameter and porosity of the macropores having a narrow pore size distribution were changed, and a porous body having mesopores having the same structure could be produced.
（実施例４（比較例））：ｎｏＴＭＢ
まず両親媒性物質であるエチレンオキシド−プロピレンオキシド−エチレンオキシドブロック共重合体（EO20-PO70-EO20、平均分子量5800、アルドリッチ）1.90ｇを0.1mol/L硝酸水溶液5.76ｇに溶解し、両親媒性物質の分子集合体を安定させる役割を持つ添加物を加えることなく、ビス（トリメトキシシリル）エタン2.15ｇを攪拌下で加えて加水分解反応を行った。この場合、触媒成分を含有する水の量は、シリカ1.0ｇ当たり12.0ｇである。数分攪拌したのち、得られた透明溶液を密閉容器に移し、60℃の恒温漕中に保持したところ約60分後に溶液の透明度は特に変化することなく固化した。
固化した試料をさらに数時間熟成させ、ついで60℃において溶媒を蒸発させて除去し、そののち100℃／ｈの昇温速度で350℃まで加熱してこの温度で５時間保持した後、室温まで冷却した。これによって、ケイ素原子をエチレン鎖が架橋した構造をもつ有機無機ハイブリッドよりなる多孔質体を得た。
得られた多孔質体中には電子顕微鏡で確認できる100nm以上の不均一構造は存在しなかった。しかしゲル骨格中には直径5nm付近に分布の中心を持つ細孔が多数存在し、300m2/g以上の比表面積を有していることが、窒素吸着測定によって確かめられた。その細孔分布を図１１に示す。この試料の粉末Ｘ線回折を測定したところ、約9nmに相当する他の試料に比べて秩序の低い構造に対応する回折プロファイルが得られた（図１２）。
このことから、トリメチルベンゼンを用いずに作製した本試料の内部には、直径約5nmのメソ細孔と約4nmの厚さのゲルの壁とが、長距離秩序をもたない無定形状態で分布していることがわかった。
(Example 4 (comparative example)): noTMB
First, 1.90 g of amphiphilic substance ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO20-PO70-EO20, average molecular weight 5800, Aldrich) was dissolved in 5.76 g of 0.1 mol / L nitric acid aqueous solution. Without adding an additive having the role of stabilizing the molecular assembly, 2.15 g of bis (trimethoxysilyl) ethane was added with stirring to conduct a hydrolysis reaction. In this case, the amount of water containing the catalyst component is 12.0 g per 1.0 g of silica. After stirring for several minutes, the obtained transparent solution was transferred to a sealed container and kept in a constant temperature bath at 60 ° C., and after about 60 minutes, the transparency of the solution solidified without any particular change.
The solidified sample is further aged for several hours, then the solvent is removed by evaporation at 60 ° C., then heated to 350 ° C. at a rate of 100 ° C./h and held at this temperature for 5 hours, then to room temperature. Cooled down. As a result, a porous body made of an organic-inorganic hybrid having a structure in which an ethylene chain was cross-linked with a silicon atom was obtained.
There was no heterogeneous structure of 100 nm or more that could be confirmed with an electron microscope in the obtained porous material. However, it was confirmed by nitrogen adsorption measurement that the gel skeleton had many pores with a distribution center around 5 nm in diameter and had a specific surface area of 300 m2 / g or more. The pore distribution is shown in FIG. When the powder X-ray diffraction of this sample was measured, a diffraction profile corresponding to a structure with lower order than other samples corresponding to about 9 nm was obtained (FIG. 12).
Therefore, inside this sample prepared without using trimethylbenzene, mesopores with a diameter of about 5 nm and gel walls with a thickness of about 4 nm are in an amorphous state without long-range order. It was found that it was distributed.
（実施例５）：ＳＩＬＩＣＡ
まず両親媒性物質であるエチレンオキシド−プロピレンオキシド−エチレンオキシドブロック共重合体（EO20-PO70-EO20、平均分子量5800、アルドリッチ）4.00ｇを1.0mol/L硝酸水溶液10.0ｇに溶解し、トリメチルベンゼン0.85gを加えた後、得られた均一溶液にテトラメトキシシラン5.15ｇを攪拌下で加えて加水分解反応を行った。この場合、触媒成分を含有する水の量は、シリカ1.0ｇ当たり5.0ｇである。数分攪拌したのち、得られた透明溶液を密閉容器に移し、40℃の恒温漕中に保持したところ約120分後に溶液の白濁に引き続いて固化した。
固化した試料をさらに数時間熟成させ、ついで60℃において溶媒を蒸発させて除去し、そののち100℃／ｈの昇温速度で600℃まで加熱してこの温度で５時間保持した後、室温まで冷却した。これによって、純粋なシリカよりなる多孔質体を得た。
Example 5: SILICA
First, 4.00 g of ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO20-PO70-EO20, average molecular weight 5800, Aldrich), which is an amphiphile, is dissolved in 10.0 g of 1.0 mol / L nitric acid aqueous solution, and 0.85 g of trimethylbenzene is dissolved. After the addition, 5.15 g of tetramethoxysilane was added to the obtained uniform solution under stirring to conduct a hydrolysis reaction. In this case, the amount of water containing the catalyst component is 5.0 g per 1.0 g of silica. After stirring for several minutes, the resulting clear solution was transferred to a sealed container and kept in a constant temperature bath at 40 ° C., and after about 120 minutes, the solution solidified following the cloudiness of the solution.
The solidified sample is further aged for several hours, then the solvent is removed by evaporation at 60 ° C., then heated to 600 ° C. at a rate of 100 ° C./h and held at this temperature for 5 hours, then to room temperature. Cooled down. As a result, a porous body made of pure silica was obtained.
得られた多孔質体中には中心孔径2μｍ（＝2000nm）程度の揃った貫通孔と太さ約1μｍのゲル骨格が３次元網目状に絡み合った構造で存在していることが電子顕微鏡観察（図１３）によって確かめられた。そして、その貫通孔の内壁に直径6.5nm付近に分布の中心を持つ細孔が多数存在し、300m2/g以上の比表面積を有していることが、窒素吸着測定によって確かめられた。その細孔分布を図１４に示す。この試料の電界放射型走査電子顕微鏡像には、マクロ細孔を形成するゲル骨格の断面に、大きさの均一な２次元六方配列状にならんだメソ細孔が観察された（図１５）。さらにこの試料の粉末Ｘ線回折を測定したところ、約10nmに相当する秩序の高い周期配列を示す回折プロファイルが得られた（図１６）。このことから、本試料のゲル骨格の内部には、直径約6.5nmのメソ細孔と約3.5nmの厚さのゲルの壁とが交互に長距離（典型的に100nm以上）に渡って配列し、全体の配列は２次元六方対称性を有することがわかった。この結果は上述の電界放射型走査電子顕微鏡像の与える情報と良く整合し、本試料が細孔分布の制御されたマクロ細孔と、長距離秩序をもつ大きさの揃ったメソ孔を併せ持っていることが証明された。 In the obtained porous material, it is observed with an electron microscope that a through-hole having a center hole diameter of about 2 μm (= 2000 nm) and a gel skeleton with a thickness of about 1 μm are intertwined in a three-dimensional network ( It was confirmed by FIG. It was confirmed by nitrogen adsorption measurement that there are many pores having a distribution center around 6.5 nm in diameter on the inner wall of the through-hole and having a specific surface area of 300 m2 / g or more. The pore distribution is shown in FIG. In the field emission scanning electron microscope image of this sample, mesopores aligned in a two-dimensional hexagonal array of uniform size were observed in the cross section of the gel skeleton forming the macropores (FIG. 15). Furthermore, when powder X-ray diffraction of this sample was measured, a diffraction profile showing a highly ordered periodic array corresponding to about 10 nm was obtained (FIG. 16). Therefore, mesopores with a diameter of about 6.5 nm and gel walls with a thickness of about 3.5 nm are alternately arranged over a long distance (typically 100 nm or more) inside the gel skeleton of this sample. The entire array was found to have two-dimensional hexagonal symmetry. This result is in good agreement with the information given by the above-mentioned field emission scanning electron microscope image. This sample has both macropores with controlled pore distribution and mesopores with long-range order and uniform size. Proven to be.
（実施例６）
加水分解の際に加えるトリメチルベンゼンの量を0.45g、0.65gおよび0.90gに変化させたほかは実施例５と同様にして反応溶液を調製し、ゲル化、熟成、乾燥、熱処理を行って、純粋なシリカよりなる多孔質体を得た。
得られた多孔質体中にはいずれのトリメチルベンゼン添加量においても中心孔径2μｍ（＝2000nm）程度の揃った貫通孔と太さ約1μｍのゲル骨格が３次元網目状に絡み合った構造で存在していることが電子顕微鏡観察（図１７）によって確かめられた。そして、その貫通孔の内壁に、トリメチルベンゼン添加量が0.45g,0.65gおよび0.90gの場合直径それぞれ 5, 5.5, および 7nm付近に分布の中心を持つ細孔が多数存在し、いずれも300m2/g以上の比表面積を有していることが、窒素吸着測定によって確かめられた。
これに対してトリメチルベンゼンをまったく加えない場合は、細孔径は4nmであった。これらの試料の細孔分布を図１８に示す。トリメチルベンゼン添加量が0.65gである試料の電界放射型走査電子顕微鏡像には、マクロ細孔を形成するゲル骨格の断面に、大きさの均一な２次元六方配列状にならんだメソ細孔が観察された（図１９）。さらにこの試料の粉末Ｘ線回折を測定したところ、約9nmに相当する秩序の高い周期配列を示す回折プロファイルが得られた（図２０）。このことから、本試料のゲル骨格の内部には、直径約5.5nmのメソ細孔と約3.5nmの厚さのゲルの壁とが交互に長距離（典型的に100nm以上）に渡って配列し、全体の配列は２次元六方対称性を有することがわかった。
この結果は上述の電界放射型走査電子顕微鏡像の与える情報と良く整合し、本試料が細孔分布の制御されたマクロ細孔と、長距離秩序をもつ大きさの揃ったメソ孔を併せ持っていることが証明された。トリメチルベンゼンを加えない場合には粉末Ｘ線回折プロファイルは幅広く、窒素吸着法によるデータも併せて、他の試料に比べて細孔径の分布も広いことがわかった。
(Example 6)
A reaction solution was prepared in the same manner as in Example 5 except that the amount of trimethylbenzene added during hydrolysis was changed to 0.45 g, 0.65 g and 0.90 g, and gelation, aging, drying and heat treatment were performed. A porous body made of pure silica was obtained.
The obtained porous material has a structure in which a through-hole having a central pore diameter of about 2 μm (= 2000 nm) and a gel skeleton with a thickness of about 1 μm are intertwined in a three-dimensional network regardless of the amount of trimethylbenzene added. This was confirmed by electron microscope observation (FIG. 17). And on the inner wall of the through-hole, when the trimethylbenzene addition amount is 0.45g, 0.65g and 0.90g, there are many pores with distribution centers around the diameters of 5, 5.5 and 7nm, respectively, all 300m2 / It was confirmed by nitrogen adsorption measurement that it had a specific surface area of g or more.
On the other hand, when no trimethylbenzene was added, the pore diameter was 4 nm. The pore distribution of these samples is shown in FIG. In the field emission scanning electron microscope image of the sample with a trimethylbenzene addition amount of 0.65 g, mesopores aligned in a two-dimensional hexagonal array of uniform size on the cross section of the gel skeleton forming the macropores. Observed (FIG. 19). Furthermore, when powder X-ray diffraction of this sample was measured, a diffraction profile showing a highly ordered periodic array corresponding to about 9 nm was obtained (FIG. 20). Therefore, mesopores with a diameter of approximately 5.5 nm and gel walls with a thickness of approximately 3.5 nm are alternately arranged over a long distance (typically 100 nm or more) inside the gel skeleton of this sample. The entire array was found to have two-dimensional hexagonal symmetry.
This result is in good agreement with the information given by the above-mentioned field emission scanning electron microscope image. This sample has both macropores with controlled pore distribution and mesopores with long-range order and uniform size. Proven to be. When trimethylbenzene was not added, the powder X-ray diffraction profile was wide, and it was found that the pore size distribution was wider than that of other samples, including the data obtained by the nitrogen adsorption method.
（実施例７）：ＢＴＭＭ
まず両親媒性物質であるエチレンオキシド−プロピレンオキシド−エチレンオキシドブロック共重合体（EO20-PO70-EO20、平均分子量5800、アルドリッチ）0.90gを0.1mol/L硝酸水溶液15.18g（試料Ａ）あるいは30.36g（試料Ｂ）に溶解し、両親媒性物質の分子集合体を安定させる役割を持つ添加物を加えることなく、ビス（トリメトキシシリル）メタン1.873ｇを攪拌下で加えて加水分解反応を行った。この場合、触媒成分を含有する水の量は、シリカ1.0ｇ当たり17ｇおよび34gである。数分攪拌したのち、得られた透明溶液を密閉容器に移し、60℃の恒温漕中に保持したところ約120分後に溶液の白濁に引き続いて固化した。
固化した試料をさらに数時間熟成させ、ついで60℃において溶媒を蒸発させて除去し、そののち100℃／ｈの昇温速度で350℃まで加熱してこの温度で５時間保持した後、室温まで冷却した。これによって、ケイ素原子をエチレン鎖が架橋した構造をもつ有機無機ハイブリッドよりなる多孔質体を得た。
Example 7: BTMM
First, amphiphilic ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO20-PO70-EO20, average molecular weight 5800, Aldrich) 0.90g 0.1mol / L nitric acid aqueous solution 15.18g (sample A) or 30.36g (sample) The hydrolysis reaction was carried out by adding 1.873 g of bis (trimethoxysilyl) methane under stirring without adding an additive that dissolves in B) and stabilizes the molecular assembly of the amphiphile. In this case, the amount of water containing the catalyst component is 17 g and 34 g per 1.0 g of silica. After stirring for several minutes, the obtained transparent solution was transferred to a sealed container and kept in a constant temperature bath at 60 ° C., and after about 120 minutes, the solution solidified following the cloudiness of the solution.
The solidified sample is further aged for several hours, then the solvent is removed by evaporation at 60 ° C., then heated to 350 ° C. at a rate of 100 ° C./h and held at this temperature for 5 hours, then to room temperature. Cooled down. As a result, a porous body made of an organic-inorganic hybrid having a structure in which an ethylene chain was cross-linked with a silicon atom was obtained.
得られた多孔質体中には、試料Ａでは中心孔径1μｍ程度の揃った貫通孔と太さ約0.8μｍのゲル骨格が、試料Ｂでは中心孔径4μｍ（＝4000nm）程度の揃った貫通孔と太さ約3μｍのゲル骨格が、３次元網目状に絡み合った構造で存在していることが水銀圧入測定（図２１）によって確かめられた。そして、その貫通孔の内壁に、試料Ａでは直径5nm付近に、試料Ｂでは直径6nm付近に、それぞれ分布の中心を持つ細孔が多数存在し、300m2/g以上の比表面積を有していることが、窒素吸着測定によって確かめられた。その細孔分布を第図２２に示す。これらの試料の電界放射型走査電子顕微鏡像には、マクロ細孔を形成するゲル骨格の断面に、大きさの均一な２次元六方配列状にならんだメソ細孔が観察された（４図２３、２４）。さらにこの試料の粉末Ｘ線回折を測定したところ、試料Ａでは約9nm、試料Ｂでは10nmに、それぞれ相当する秩序の高い周期配列を示す回折プロファイルが得られた（図２５）。このことから、本試料のゲル骨格の内部には、試料Ａでは直径約5nmのメソ細孔と約4nmの厚さのゲルの壁とが、試料BＢは直径約6nmのメソ細孔と約4nmの厚さのゲルの壁とが、交互に長距離（典型的に100nm以上）に渡って配列し、全体の配列は２次元六方対称性を有することがわかった。この結果は上述の電界放射型走査電子顕微鏡像の与える情報と良く整合し、本試料が細孔分布の制御されたマクロ細孔と、長距離秩序をもつ大きさの揃ったメソ孔を併せ持っていることが証明された。ビス（トリメトキシシリル）メタンの場合には、実施例６までの反応系とは異なり、両親媒性物質の分子集合体を安定化させる成分を添加しなくても、長距離秩序を持つ大きさの揃ったメソ孔をもつマクロ多孔体を合成することができる。
In the obtained porous body, the sample A has a uniform through hole with a center hole diameter of about 1 μm and a gel skeleton with a thickness of about 0.8 μm, and the sample B has a through hole with a center hole diameter of about 4 μm (= 4000 nm). It was confirmed by mercury intrusion measurement (FIG. 21) that a gel skeleton having a thickness of about 3 μm exists in a structure intertwined in a three-dimensional network. On the inner wall of the through hole, there are a large number of pores having distribution centers in the vicinity of the diameter of 5 nm in the sample A and in the vicinity of 6 nm in the sample B, and have a specific surface area of 300
以上のように本発明によれば、所望の細孔分布に制御された多孔質体を製造することができる。しかも本発明によって得られる多孔質体は、マクロ細孔とメソ細孔との二重気孔構造の多孔質体であることから、筒内に粒子を充填してなる充填型カラムの充填剤としてのみならず、それ自体でカラムとなる一体型カラムとしても適用可能である。 As described above, according to the present invention, a porous body controlled to have a desired pore distribution can be produced. Moreover, since the porous body obtained by the present invention is a porous body having a double pore structure of macropores and mesopores, it can only be used as a packing for a packed column in which particles are packed in a cylinder. In addition, the present invention can also be applied as an integrated column that itself becomes a column.
Claims (3)
(i) ゾル−ゲル反応触媒成分を含有する水溶液に、鋳型成分として両親媒性物質を溶かし、必要に応じて両親媒性物質の分子集合体を安定化させる添加成分を加えて、均一溶液を調製する工程、
(ii) 該均一溶液に、加水分解性の官能基を有する無機低分子化合物を添加しゾル−ゲル反応を行わせて、溶媒に富む溶媒リッチ相と、ゾル−ゲル反応により前記無機低分子化合物から生成した無機酸化物重合体であって、前記両親媒性物質から成る鋳型成分の表面上に固着した無機酸化物重合体に富む骨格相とから成る、連続した３次元網目構造のゲルを形成する工程、
(iii) 該ゲルを乾燥して前記溶媒リッチ相から溶媒を蒸発除去することによりマクロ細孔を形成する工程、および
(iv) 乾燥後のゲルから熱分解または抽出により前記鋳型成分を除去することにより前記骨格相内にメソ細孔を形成する工程、
を含むことを特徴とする方法。 A method for producing an inorganic porous body having macropores in addition to mesopores,
(i) In an aqueous solution containing a sol-gel reaction catalyst component, an amphiphile is dissolved as a template component, and if necessary, an additional component that stabilizes the molecular assembly of the amphiphile is added to obtain a uniform solution. The step of preparing,
(ii) An inorganic low molecular weight compound having a hydrolyzable functional group is added to the homogeneous solution to cause a sol-gel reaction, and a solvent-rich solvent-rich phase and the inorganic low molecular weight compound by a sol-gel reaction. A continuous three-dimensional network structure gel formed from an inorganic oxide polymer produced from the above and comprising a skeleton phase rich in inorganic oxide polymer fixed on the surface of the template component composed of the amphiphilic substance. The process of
(iii) forming the macropores by drying the gel and evaporating and removing the solvent from the solvent-rich phase; and
(iv) forming mesopores in the skeletal phase by removing the template component from the dried gel by thermal decomposition or extraction;
A method comprising the steps of:
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| JP2005290033A (en) * | 2004-03-31 | 2005-10-20 | Kazuki Nakanishi | Method for producing organic-inorganic hybrid-based porous body |
| WO2007010949A1 (en) * | 2005-07-19 | 2007-01-25 | Dynax Corporation | Method for producing alkylsiloxane aerogel, alkylsiloxane aerogel, apparatus for producing same, and method for manufacturing panel containing same |
| KR100746345B1 (en) | 2006-07-26 | 2007-08-03 | 한국과학기술원 | Method for synthesizing the mesoporous silicate having a macropores and its application to adsorbent of vocs |
| JP2009265047A (en) * | 2008-04-30 | 2009-11-12 | Kyoto Univ | Solid-liquid contact device and separation medium by hierarchical porous body containing mesopore having long-range order |
| JP2010518239A (en) * | 2007-02-14 | 2010-05-27 | ユニベルシテ ピエール エ マリー キュリー | Hybrid material and manufacturing method thereof |
| US7741069B2 (en) | 2005-12-27 | 2010-06-22 | Canon Kabushiki Kaisha | Mesoporous material having dendritic skeleton containing immobilized glucose dehydrogenase |
| WO2014034588A1 (en) | 2012-08-27 | 2014-03-06 | 信和化工株式会社 | Porous silica powder |
| JP2016500044A (en) * | 2012-10-01 | 2016-01-07 | ダウ グローバル テクノロジーズ エルエルシー | Compositions and processes for mesoporous silica with large pores with narrow diameter distribution |
| JP2018134624A (en) * | 2017-02-21 | 2018-08-30 | 株式会社 京都モノテック | Monolith filter and solid separation apparatus utilizing the same and manufacturing method for monolith filter |
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