JP4756233B2 - Pillarized clay composed of rod-like polysiloxane with ammonium cation on the surface and layered clay mineral, its production method and its use - Google Patents

Description

  The present invention relates to a pillared clay composed of a rod-like polysiloxane having an ammonium cation on the surface and a layered clay mineral, a production method thereof, and a use invention.

  A new clay cross-linked body (pillared clay) is obtained by setting up appropriate pillars (pillars) on the two-dimensional silicate layer of clay minerals and changing the size, type, and number of pores between the layers. It attracts attention as a type of porous material (see Non-Patent Document 1). Compared to the original clay mineral, this material has a large specific surface area and pore volume, and also has improved thermal stability and catalytic activity, so it has been developed in various fields such as catalysts, adsorbents, and ion exchangers. Yes.

  Usually, these pillared clays contain organic ions having various nano sizes (see Non-Patent Documents 2 and 3), inorganic ions (see Non-Patent Documents 4 and 5), sol particles (see Non-Patent Documents 6 and 7), and the like. So far, a variety of pillared clays have been obtained by intercalation. However, although many nanocomposites composed of polymers and clay minerals have been reported so far (see Non-Patent Document 8), examples using polymers as pillaring agents between clay layers have been reported so far. Not. In ordinary polymers, when inserted between clay layers, the stiffness between the layers is widened, or the distance between the clay layers is maintained if there is no bulk to maintain and maintain a sufficient distance between layers. However, there may be no space between the layers.

  There are examples of the synthesis of porous bodies using polymers and clay minerals that have been reported so far. In this synthesis example, nanocomposites composed of polymers and clay minerals were synthesized, and then the polymers were baked. This is due to the removal method (see Non-Patent Document 9). This does not mean that the polymer itself acts as a pillaring agent, but acts as a space after the polymer is removed by baking. That is, no examples using a polymer as a pillaring agent have been reported so far.

  One of the characteristics of a polymer is the ability to form a spatial form on its own. Therefore, the polymer pillared clay is expected to have an interesting property that has never existed before.

Shoji Yamanaka, “Interlayer cross-linking and pore structure design of layered silicates”: “Microporous Crystal”, Editor: Masahiko Shimada, Mitsuo Abe, Yoshio Ono, Hiroo Tominaga, Yoshihiko Morooka, pages: 39-48, (1994/1) M.M. Ogawa and 4 others, “Photochemical hole burning of 1, 4-dihydroxyanthraquinone intercalated in a pillared layered cray minor”, The Journal of Phar. M.M. Ogawa and 3 others, “Oriented microporous film of tetramethylammonium pillar saponite”, Journal of Materials Chemistry, VoL: 4, page: 519-523. S. -R. Lee and four others, “Nanocrystalline solid from form Al2O3 pillared by solid-solid transformation”, Chemistry of Materials, VoL: 15, page 484-484. M.M. Pichowicz and 1 other person, “Stability of Pillared Clays: effect of compaction on the physical chemicals of Al-pillared leys6, Chemistry 26, Chem. S. Yamanaka et al., 4 people, “Preparation and properties of clays pillared with SiO 2 —TiO 2 sol particles”, Bulletin of the Chemical Society, 492: 1925 J. et al. -H. Choy et al., "New CoO-SiO2-sol pillared ass for NOx conversion", Chemistry of Materials, Vol. 14, page: 3823-3828, (2002) “Polymer-Clay Nanocomposites”, edited by T.M. J. et al. Pinnavaia and G.M. W. Beall, John Wiley & Sons, Chichester, (2000) K. A. Carrado et al., “Materials with controlled mesoporosity-derived from synthetic poly- lypyrrolidone-clay composites, 19”, “Mourous and 87”.

  The present invention is intended to develop pillared clay using a polymer compound as a pillar from such a situation. Therefore, as a result of searching for a pillaring agent that can enter a clay layer and maintain a certain distance to form a space between the layers, the present inventors have developed a surface of ammonium on the surface. It came to find the rod-like polysiloxane which has a cation. As a result, it is possible to provide a new type of porous material made of pillared clay consisting of rod-like polysiloxane having ammonium cations on the surface and layered clay mineral, that is, polymer as a pillaring agent, by a simple synthesis method. I found out that I can do it. The present invention has been made based on this finding. Since the synthesized pillared clay has pores between clay layers, it has been clarified that it can be used as various adsorbents including gas adsorption and separation.

  The pillared clay is not only used as an adsorbent, but also has a specific function that enables adsorption of a specific gas or introduction of functional organic molecules due to the ammonium group of the rod-shaped polysiloxane present between the layers. It was revealed that In addition, the material obtained by the present invention uses a rod-like polymer as a pillaring agent, so that the shape of the pore space is unique and never loses its function due to molecular aggregation. It can also be used as a base material for a photofunctional molecule (for example, a molecule whose fluorescence emission is suppressed by aggregation such as a laser dye). It has been revealed that its applicability is extremely excellent in terms of providing new compounds and is highly practical.

  The means for achieving the above aim will be summarized again and derived from the following prior art steps. That is, the present inventors have succeeded in synthesizing a cationic polysiloxane having a rod structure by a sol-gel reaction of an organoalkoxysilane having an amino group. A patent application was filed (Patent Documents 1 and 2). This polysiloxane has a rigid rod structure that builds a hexagonal phase in addition to water solubility and ion exchange properties. These properties led to the idea that this polysiloxane is useful in pillaring between clay layers. That is, it was considered that this polysiloxane can be easily inserted between clay layers due to its water solubility and ion exchange properties, and can be expanded between clay layers due to its rigidity and bulkiness.

Yoshiro Kaneko and 4 others, “Layered polyaminoalkylsiloxane composites having anion exchange properties and production method and use thereof”, Patent Application 2004-046049 Yoshiro Kaneko and three others, “High-order structure laminate made of rod-like polysiloxane having ammonium cation on its surface, its production method and its use”, Patent Application 2004-230030

  Based on the above idea, the present inventors specifically inserted a rod-like polysiloxane having an ammonium cation between layered clay mineral layers having an anionic surface by intercalation or ion exchange reaction. Then, it came to the idea that it would be possible to easily synthesize pillared clay by polymer.

  As a result of earnest research based on the above basic policy, in order to have sufficient space between clay layers, it is necessary that the rod-like polysiloxane has an appropriate interval between the layers, and saponite etc. It has been found that it is optimal to use a clay mineral having a relatively low layer charge density (theoretical exchange capacity: 50 to 100 milliequivalent / 100 g of clay mineral) as a host material.

  From the above, the inventors of the present invention, as a result of diligent investigation based on the idea that a pillared clay composed of a rod-like polysiloxane having an ammonium cation on the surface and a layered clay mineral can be developed. It is a success.

  That is, the present invention has been achieved by taking the solving means described in the following (1) to (4).

(1) First of all, the pillar is a cation of rod-shaped polysiloxane, and the cation of the rod-shaped polysiloxane has a repeating unit represented by (Chemical Formula 1). aminopropyl) siloxane salt, or (rod poly having a repeating unit represented by chemical formula 2) (3- (2-aminoethylamino) propyl) pillars, wherein cations der Rukoto obtained siloxane salt It provides the clay. The structure image and synthesis scheme of pillared clay are shown in FIG. However, the rod-shaped polysiloxane in FIG. 1 is an example of a structure represented by the following (Chemical Formula 1).

(2) The second is to provide a method for manufacturing a pin color clay as (1) above, wherein. The configuration is as follows. That is, the repeating units, represented Carlo head like poly (3-aminopropyl) siloxane salt in the following (Chemical Formula 1), or repeating units, Carlo head shaped poly represented by the following (Formula 2) (3- (2-aminoethylamino) propyl) adjusting the solution of siloxane salt, the solution, clay minerals: the (theoretical exchange capacity 50-100 meq / clay mineral 100 g) is dispersed mixed suspension, characterized by Rukoto cations and the rod-like polymers of clay and cations by ion exchange reaction.
(Chemical formula 1)
Z ⁻ .NH ₃ ⁺ (CH ₂ ) ₃ SiO _1.5 (wherein Z ⁻ represents a halogen element anion such as a chloride ion or an anion such as a nitrate ion)
(Chemical formula 2)
(Z ⁻ ) ₂ .NH ₃ ⁺ (CH ₂ ) ₂ NH ₂ ⁺ (CH ₂ ) ₃ SiO _1.5 (wherein Z ⁻ represents an anion such as a halogen element anion such as a chloride ion or a nitrate ion) To express)

The pillared clay described before Symbol (1), can also be used as an adsorbent for use in various adsorption and separation. The adsorbent especially It is also possible to use for gas separation. Moreover, as a gas isomer separation, it can be used exclusively for the carbon dioxide immobilization.

Further, said pillared clay according to (1), functional inorganic - can be used as a substrate for an organic complex creation.

  By taking the above solution, the invention of the present application succeeded in synthesizing a pillared clay composed of a rod-like polysiloxane having an ammonium cation on the surface and a layered clay mineral by a simple method called an ion exchange reaction. It is a thing.

  Since the present invention provides a pillared clay using a polymer as a pillaring agent, which has not existed in the past, it has industrial utility in addition to academic interest. Significance is great. In addition, since it is possible to introduce specific gas adsorption and functional organic molecules, it is expected to be used in various fields in the future. In this material, since the clay layer is pillared with a polymer, the pores to be formed are a special one that has never been seen before. It is considered that the pores are independent of the adjacent pores by forming a pillar with a macromolecule grown only in one dimension such as a polymer. Solidification of the dye laser can be expected by dispersing and adsorbing laser dye molecules that lose their optical functionality when aggregated in the pores. Further, it is expected to be used as a carbon dioxide adsorbent by converting the ammonium group on the surface of the rod-shaped polysiloxane inserted between clay layers into an amino group.

  The solution of the present invention is as described above, and will be specifically described below based on examples. However, these examples are shown as an aid for easily understanding the present invention, and are not intended to limit the present invention.

A polymer solution serving as a pillar was prepared by adding 10 ml of distilled water to 0.15 g of poly (3-aminopropyl) siloxane hydrochloride. This solution was added dropwise to a suspension prepared by adding 10 ml of distilled water to 0.15 g of sodium saponite, and the reaction suspension was stirred at room temperature for 2 hours to cause an ion exchange reaction. Separately, it was washed with distilled water and then dried under reduced pressure at room temperature. Characterization was performed by infrared (IR) spectrum, CHN elemental analysis, X-ray diffraction (XRD), and nitrogen adsorption / desorption measurement. From the IR spectrum of the product, absorption of ammonium ion (NH ₃ ⁺ ) in poly (3-aminopropyl) siloxane was observed at 1515 cm ⁻¹ , indicating that the polysiloxane (polymer) was inserted into the product. It was confirmed (FIG. 2). Moreover, when the exchange amount per unit of the rod-shaped polysiloxane taken in between the saponite layers was calculated from CHN elemental analysis, it was 126 milliequivalent / 100 g saponite.

  From the powder XRD measurement, the diffraction pattern of the pillared clay as a product was different from the diffraction pattern of sodium saponite and poly (3-aminopropyl) siloxane hydrochloride as raw materials. It was found to be a nano-order intercalated material, ie a nanocomposite (FIG. 3). Further, since the d value of the diffraction peak with the lowest angle of 2θ was 1.80 nm, the interlayer distance was calculated as 0.84 nm considering that the thickness of one saponite layer was 0.96 nm. The

  The ion exchange capacity of the sodium-type saponite used this time is 92 milliequivalents / 100 grams of clay mineral (see Non-Patent Document 10). If the exchange capacity exceeds 100 mm, the polysiloxane is densely inserted between the clay layers, so that a sufficient space cannot be obtained. Further, neither smectite (ion exchange capacity 60 to 100) and vermiculite (ion exchange capacity 100 to 150), which are clay minerals exhibiting normal ion exchange properties, have an exchange capacity of 50 mm or less. For these reasons, the clay mineral that can be used in carrying out the present invention is a clay mineral that can carry out a clay mineral having an ion exchange capacity of 50 to 100 milliequivalents / a value of about 100 grams of clay mineral. As mentioned. However, this value is a value as a rough standard, and in fact, clay minerals outside this range may be used, and the present invention includes such a case.

J. et al. Bujdak and 3 others, “Aggregation and decomposition of a pseudoisyanine dyed in dispersed of layered silicates”, Journal of Colloid and Interface4, 49

The nitrogen adsorption / desorption isotherm is shown in FIG. The adsorption of the product pillared clay represents an isotherm of type I (Langmuir type), indicating the formation of micropores. Some macropores are present, which may be attributed to nitrogen adsorption on the external surface of pillared clay. When the specific surface area and pore volume of the pillared clay were calculated by the t-plot method, they were 370 m ² / g and 0.149 cm ³ / g, respectively. This is because a porous material is formed from a raw material having a dense structure; sodium saponite (BET specific surface area; 26 m ² / g) and poly (3-aminopropyl) siloxane hydrochloride (BET specific surface area; 5 m ² / g). It shows that. When the pore diameter of the pillared clay was calculated by the t-plot method, it was 0.92 nm, and this value almost coincided with the interlayer distance (0.84 nm) derived from the XRD measurement.

In the synthesis of pillared clay, an ion exchange reaction with poly (3-aminopropyl) siloxane hydrochloride was performed using lithium-type teniolite having a relatively high layer charge density instead of sodium-type saponite. A polymer solution serving as a pillar was prepared by adding 10 ml of distilled water to 0.15 g of poly (3-aminopropyl) siloxane hydrochloride. This solution was added dropwise to a suspension prepared by adding 10 ml of distilled water to 0.15 g of lithium teniolite, and the reaction suspension was stirred at room temperature for 2 hours to cause an ion exchange reaction. Separately, it was washed with distilled water and then dried under reduced pressure at room temperature. Although a composite having a sufficient bottom surface spacing was obtained (calculated as about 1.83 nm by XRD measurement), sufficient pore space could not be obtained (BET specific surface area; 53 m ² / g) . Because the layer charge density is high, the distance between charges on the surface of the teniolite is close, and it is considered that poly (3-aminopropyl) siloxane is inserted densely (
Exchange capacity: 140mm equivalent / 100g of teniolite).

On the other hand, instead of poly (3-aminopropyl) siloxane hydrochloride, polyallylamine hydrochloride (average molecular weight; 70,000), which is a normal organic cationic polymer, is used to conduct an ion exchange reaction with sodium saponite. went. A polymer solution serving as a pillar was prepared by adding 10 ml of distilled water to 0.15 g of polyallylamine hydrochloride. This solution was added dropwise to a suspension prepared by adding 10 ml of distilled water to 0.15 g of sodium saponite, and the reaction suspension was stirred at room temperature for 2 hours to cause an ion exchange reaction. Separately, it was washed with distilled water and then dried under reduced pressure at room temperature. Although this was also complexed (confirmed by CHN analysis and IR measurement), a sufficient bottom space was not obtained (calculated to be about 1.54 nm by XRD measurement), and pore space could not be obtained ( BET specific surface area; 52 m ² / g).

  The present invention has been derived and clarified as a result of accumulating many experiments other than the synthesis examples of the examples shown above. The invention is not limited to the disclosed embodiments. Through numerous experiments, the important points in the present invention are the rigidity and bulkiness of rod-like poly (3-aminopropyl) siloxane hydrochloride, and the relatively low layer charge density of sodium-type saponite, that is, moderately separated The distance between charges is extremely important and can be said to have been successful as a result of their interaction.

  As described in the column of the effect of the invention, the significance of the present invention is exceptional. That is, the present invention provides a pillared clay using a polymer as a pillaring agent, which has not existed so far, and can be used industrially, and has great significance. In addition, since it exhibits a specific gas adsorption property and can introduce functional organic molecules, it is expected to be used in various fields in the future. In this material, since the clay layer is pillared with a polymer, the pores to be formed are a special one that has never been seen before. It is considered that the pores are independent of the adjacent pores by forming a pillar with a macromolecule grown only in one dimension such as a polymer. Solidification of the dye laser can be expected by dispersing and adsorbing laser dye molecules that lose their optical functionality when aggregated in the pores. Moreover, utilization as a carbon dioxide adsorbent can be expected by converting the ammonium group on the surface of the rod-shaped polysiloxane inserted between clay layers into an amino group.

The figure showing the synthesis | combination of pillared clay. Infrared absorption spectrum of pillared clay. X-ray diffraction profile of (a) pillared clay, (b) sodium saponite, (c) rod-like poly (3-aminopropyl) siloxane hydrochloride. Nitrogen adsorption / desorption isotherm of pillared clay, sodium-type saponite, rod-like poly (3-aminopropyl) siloxane hydrochloride.

Claims (2)

Pillarized clay with pillars between clay layers and pores formed between clay layers, wherein the pillars are cations of rod-shaped polysiloxane ,
The cation of the rod-shaped polysiloxane is a rod-shaped poly (3-aminopropyl) siloxane salt having a repeating unit represented by the following (Chemical Formula 1) or a repeating unit represented by the following (Chemical Formula 2). rod poly (3- (2-aminoethylamino) propyl) pillared clay, wherein the cation der Rukoto obtained siloxane salt having.
(Chemical formula 1)
Z ⁻ .NH ₃ ⁺ (CH ₂ ) ₃ SiO _1.5 (wherein Z ⁻ represents a halogen element anion such as a chloride ion or an anion such as a nitrate ion)
(Chemical formula 2)
(Z ⁻ ) ₂ .NH ₃ ⁺ (CH ₂ ) ₂ NH ₂ ⁺ (CH ₂ ) ₃ SiO _1.5 (wherein Z ⁻ represents a halogen element anion such as a chloride ion or an anion such as a nitrate ion) To express) The method for producing pillared clay according to claim 1, wherein the repeating unit is a rod-shaped poly (3-aminopropyl) siloxane salt represented by the following (chemical formula 1) or the repeating unit is the following ( A solution in which the rod-shaped poly (3- (2-aminoethylamino) propyl) siloxane salt represented by the chemical formula 2) was dissolved was prepared, and this solution was added to a clay mineral (theoretical exchange capacity: 50 to 100 milliequivalent / A method for producing pillared clay , comprising mixing a clay mineral (100 g) in a dispersed suspension, and subjecting the cation of the clay and the cation of the rod-shaped polymer to an ion exchange reaction.
(Chemical formula 1)
Z ⁻ .NH ₃ ⁺ (CH ₂ ) ₃ SiO _1.5 (wherein Z ⁻ represents a halogen element anion such as a chloride ion or an anion such as a nitrate ion)
(Chemical formula 2)
(Z ⁻ ) ₂ .NH ₃ ⁺ (CH ₂ ) ₂ NH ₂ ⁺ (CH ₂ ) ₃ SiO _1.5 (wherein Z ⁻ represents a halogen element anion such as a chloride ion or an anion such as a nitrate ion) To express)

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