JPS62278174A - Manufacture of inorganic layer porous body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Technical Field] The present invention relates to a method for producing an inorganic layered porous body with excellent heat insulation properties.

[Foreground technology]

As a layered compound having voids, there is an intercalation material in which a different substance such as hydroxide is inserted between the layers of a swellable layered compound (for example, Japanese Patent Application Laid-Open No. 54-588
4 and JP-A-54-16386).

However, since this material has a small interlayer distance of 10 Å or less, it is easily affected by adsorbed water, and it cannot be said to be very good in terms of heat insulation.

In contrast, we used a mixture of smectite minerals and water-soluble polymer compounds as microporous clay materials.
In addition, intercalation of cationic oxide or polymeric silica has been proposed in JP-A-60-1318.
78, JP 60-137812, JP 60-137813, JP 60-155526
No. 60-166217, etc. According to these methods, the interlayer distance can be increased from 10 Å or less in the case of the above-mentioned intercalation material to about 30. However, in the layered porous body formed by this method, even if the interlayer distance can be increased to about 30 people as described above, moisture is likely to be adsorbed within the pores. It is unavoidable that a thermal short circuit will occur, and no improvement in thermal properties can be expected.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing an inorganic layered porous body having relatively large voids between layers and having an excellent heat insulating effect.

[Disclosure of the invention]

In order to achieve the above object, the present invention swells a swellable layered compound, inserts at least one of an inorganic pillar and an organic pillar between the layers, and dries the compound to form fine voids between the layers. A method for producing an inorganic layered porous body, wherein swelling of the swellable layered compound and insertion of at least one of the inorganic pillars and organic pillars into the interlayer are carried out in an autoclave. The gist of this paper is a method for producing an inorganic layered porous material characterized by the following.

Hereinafter, embodiments of the present invention will be explained in detail with reference to the accompanying drawings.

As shown in FIG. 1, which schematically shows the structure, the inorganic layered porous material A obtained by the method for producing an inorganic layered porous material of the present invention has an inorganic compound 2 inserted between the layers 1.1 of the inorganic layered compound. Fixed. Therefore, the gap 3 between the layers is maintained between 30 and 600 people.

Examples of the swelling layered compound include Na-montmorillonite,
Examples include Ca-montmorillonite, acid clay, 3-octahedral synthetic smectite, Na-hectolite, Li-hectite, Na-teniolite, Li-teniolite, and synthetic mica (Na-fluorotetrasilicon mica). It is not limited to these as long as it is a compound.

As the inorganic pillar inserted between the layers of the swellable layered compound, metal alcoholade (hereinafter referred to as "metal alcoholade A") is used.
At least one of a colloidal inorganic compound and a polymer obtained by hydrolyzing .

As metal alcoholade A, S i (OR) 4
, Al (OR) 1 , and Qe (OR) 4 , and these may be used alone or in combination. Such a metal alcoholade becomes a polymer having a metal-oxygen bond as its main chain through the hydrolysis, which becomes the inorganic pillar.

Examples of the above-mentioned metal alcolade A include:
The following compounds are available, but other compounds can also be used.

Si (OCz Hs)4. Si (OCHs
)4.

Ge (QC3H?) 4. Ge (OCz Hs
) The 4° colloidal inorganic compound is not particularly limited, but thermally stable oxides and compounds that expand when heated are preferred. Examples of such compounds include SiOz, Sbz○5. Fe z Q 2
+ Al z O3, T I Ot and Zr
Examples include O2, and these may be used alone or in combination. In the present invention, the particle size of such a colloidal inorganic compound is also not particularly limited, but is 50 to 50.
It is preferable that the grain size is about 150 people.

The above-mentioned inorganic pillars may be inserted between the layers of the swellable layered compound as they are, but the surface of the inorganic pillars may be mixed with a cationic inorganic compound and a metal alcoholade different from the metal alcoholade A (hereinafter referred to as "metal alcoholade"). BJ) may be modified and then inserted between the layers.

Cationic inorganic compounds used to modify the surface of the inorganic pillars include titanium compounds, zirconium compounds, and hafnium compounds.

Examples include iron-based compounds, copper-based compounds, chromium-based compounds, nickel-based compounds, zinc-based compounds, aluminum-based compounds, manganese-based compounds, phosphorus-based compounds, boron-based compounds, and the like. Such cationic inorganic compounds include T
Examples include metal chlorides such as iC1a, metal oxychlorides such as ZrOCl2, and nitrate compounds, but other materials may also be used.

In addition, metal alcoholades B used for the same purpose include Tt (OR), Zr (OR)4゜PO(
OR)2, B(OR)3, and the like. These may be used alone or in combination.

Examples of the above-mentioned metal alcoholade B include:
The following compounds are available, but other compounds can also be used.

Ti (OC3H7)a, Zr (OC3Hq
)4, PO(OCHi)4. PO(OCz Hs)4゜B(○CI(:l) 4', B(OCz Hs)
) a.

Further, in this invention, in addition to the above-mentioned inorganic pillars, at least one of a water-soluble polymer compound and a quaternary ammonium salt is inserted as an organic pillar between the layers 1 and 1 of the swellable layered compound. You can also do it.

Various water-soluble polymer compounds can be considered, such as polyvinyl alcohol.

Polyethylene glycol, polyethylene glycol, polyethylene oxide, methylcellulose carboxymethylcellulose, polyacrylic acid.

Preferred examples include sodium polyacrylate and polyvinylpyrrolidone.

Moreover, various kinds of quaternary ammonium salts can be considered, but among them, those having groups such as octadecyl group, hexadecyl group, tetradecyl group, and dodecyl group are preferable. Examples of such quaternary ammonium salts include the following compounds, which help the insertion of the inorganic pillars by expanding the space between the layers, are vaporized by firing and leave voids between the layers, and have the ability to Other materials may also be used as long as they are compatible.

Octadecyltrimethylammonium salt, dioctadecyldimethylammonium salt, hexadecyltrimethylammonium salt, dioctadecyldimethylammonium salt, tetradecyltrimethylammonium salt, dioctadecyldimethylammonium salt.

Next, a method for producing an inorganic layered porous body according to the present invention will be explained in detail based on drawings schematically showing one embodiment thereof.

Substances such as swellable clay minerals, as shown in Figure 2,
It is made up of a collection of swellable layered compounds A1. Compound A, which is the main material, is mixed with a solvent such as water (kneaded if necessary) and treated in an autoclave, and as shown in Figure 3, solvent 4 is included between layers 1 and 1. to swell.

Water is generally used as the solvent, but other polar solvents such as methanol, DMF, DMSO, etc. may be used alone or in combination.

When using a swellable layered compound such as Ca-montmorillonite and acid clay as the main material, it is not possible to swell it sufficiently just by mixing it as in the past, and strong shearing force must be applied. It was necessary to knead the mixture when it swelled. On the other hand, in this invention, swelling is performed in an autoclave, so even if the swelling layered compound is difficult to swell, such as the Ca-montmorillonite or acid clay, it can be kneaded for swelling. This eliminates the need for uniform swelling.

Although the temperature conditions of the autoclave are not particularly limited in the present invention, 1) it is preferably within the range of 0 to 200°C, and more preferably within the range of 120 to 150°C. Further, the pressure conditions of the autoclave are not particularly limited since this swelling reaction and the insertion reaction described below are submerged reactions.

Next, at least the inorganic pillars 2' are added to the swollen solution of the swellable layered compound A2 and mixed uniformly, and then the mixed solution is put into the autoclave again to undergo an insertion reaction. The temperature conditions of the autoclave may be the same as the temperature conditions of the autoclave during the previous swelling.

When using a polymer of metal alcoholade A as the inorganic pillar 2', dissolve the metal alcoholade A in a solvent such as ethanol or isopropanol, and add water and a reaction catalyst such as hydrochloric acid (hydrolysis) to the polymer. A catalyst) is added, mixed, and subjected to a hydrolysis reaction to obtain inorganic pillars 2'. This hydrolysis reaction is preferably carried out at a temperature of about 70°C, although it is not particularly limited. When a colloidal inorganic compound is used as the inorganic pillar 2', a dispersion of the colloidal inorganic compound may be used.

The inorganic pillar 2' as described above may be used as it is, but it is preferable to react it with metal alcoholade B or a cationic inorganic compound and modify its surface with these compounds before use. This is because the surface of the inorganic pillar 2' whose surface has been modified with metal alcoholade B or a cationic inorganic compound is positively charged as shown in Figure 5, which increases its swelling property. This is because it is thought that it is possible to electrically couple with the negative portion of the surface of the layer 1 of the layered compound, thereby keeping the space between the layers 1.1 expanded.

In addition, when inserting the above-mentioned inorganic pillar 2' between the layers 1 and 1 of the swellable layered compound and causing the reaction, an organic pillar 5 is also inserted between the layers 1 and 1, as shown in FIG. You may also do so. This is because the organic pillar 5 inserted between the layers 1 and 1 pushes and holds the gap between the layers 1 and 1, and at the same time slows down the movement of the inorganic pillar 2'. This is because it serves to further widen the layer spacing. The timing of insertion of the organic pillar 5 between the layers 1.1 is not particularly limited in the present invention, and even if the organic pillar 5 is mixed with the inorganic pillar 2' after swelling of the swellable layered compound and inserted, In this invention, the inorganic pillars 2' and the organic pillars 5 are inserted in an autoclave as described above. , it becomes possible to perform the insertion reaction uniformly. In addition, the inserted inorganic pillars 2' grow between the layers 1.1 of the swellable layered compound, thereby further expanding the space between the layers.

The reaction solution as described above is taken out of the autoclave, centrifuged to dehydrate it, and then oriented into a plate shape using a spatula or the like. After drying this plate material by hot air drying at a temperature of about 60'C, it is further dried at a temperature of 300-600'C.
, preferably at 450 to 550°C. This firing removes trace amounts of organic matter contained in the inorganic pillar 2' and organic pillars 5, etc.
The inorganic layered porous material is removed by changing into H2O, etc., and as shown in FIG. 1, it is possible to obtain a plate-shaped inorganic layered porous material in which the inorganic compound 2 is inserted between the layers.

The inorganic layered porous material thus obtained has a layer spacing of 30 to 600 in more than 40% of the total, and has excellent heat insulation properties in the direction of arrow B in FIG.

Next, examples of the present invention will be described together with comparative examples.

(Example 1) A 0.8% by weight aqueous solution of Na-montmorillonite (Nipia F, Kunimine Industries) was used as the main material, a swellable layered compound.
'C, treated for 30 minutes to swell.

Next, the inorganic pillar silica sol (Nissan Chemical Industry ■
A 20% aqueous solution of Snote Nox
1 polymerization degree 500 (manufactured by Hani Chemical Co., Ltd. (hereinafter referred to as rPVAJ)) was added to the swollen Na-montmorillonite and thoroughly stirred at a temperature of 60°C to prepare a mixed solution. The resulting mixed solution was placed in an autoclave and treated at 120'C for 1 hour to cause an intercalation reaction.

After the reaction, this was centrifuged, oriented into a plate shape with a spatula, and 6
It was dried with hot air at a temperature of 0°C. This was placed in an electric furnace and fired at 450°C to obtain a plate-like inorganic layered porous material sample with a thickness of 1.5 mm.

The blending ratio of Na-montmorillonite and silica sol is 1:10 in molar ratio, Na-montmorillonite and PV
The blending ratio of A was 1:1 by weight. (Example 2) As the inorganic pillar, Si which is metal alcoholade A
(OC2H5) a was hydrolyzed and polymerized under a hydrochloric acid catalyst, and then its surface was coated with TiCl4 (Hani Chemicals 9
A plate-like inorganic layered porous material sample was obtained in the same manner as in Example 1, except that a sample modified by treatment with a 4 mol aqueous solution of KIKU CORPORATION was used.

The final composition ratio of the obtained inorganic layered porous material is a molar ratio of N
a-Montmorillonite: SiO□ :Ti0Z=1:1
The ratio was 0:1.

(Example 3) Octadecyltrimethylammonium chloride (NOF ■), which is a quaternary ammonium salt, was used as an organic pillar.
A plate-shaped inorganic layered porous material sample was obtained in the same manner as in Example 1, except that a 23% by weight aqueous solution of Nisosane cation AB) was used.

(Example 4) As an organic pillar, octadecyltrimethylammonium chloride (NOF@
A plate-like inorganic layered porous material sample was obtained in the same manner as in Example 2, except that a 23% by weight aqueous solution of Nisosane cation AB) was used.

(Example 5) A plate-shaped inorganic layered porous material sample was obtained in the same manner as in Example 1, except that synthetic mica (Daimonai HG manufactured by Topy Industries, Ltd.) was used as the swelling layered compound.

(Comparative Example 1) Colloidal silica (average particle size 130, 20% aqueous solution) was used as a colloidal inorganic compound, and Na-montmorillonite (Nivia F manufactured by Kunimine Kogyo ■) was used as a swelling layered compound. was mixed with polyethylene oxide, a water-soluble polymer compound (Alcox E75° manufactured by Meisei Kagaku@, average molecular weight 1.5 million to 2.2 million), and water at 70° C. for 40 minutes under normal pressure. This mixture was oriented into a plate shape using a spatula, dried, and heated at 400°C.
Firing was performed for 2 hours to obtain a plate-like inorganic layered porous material sample.

The blending ratio of Na-montmorillonite, water, colloidal silica, and polyethylene oxide is 1:1 by weight.
The ratio was 0:3:0.1.

The porosity, interlayer distance, density, and thermal conductivity of the plate-like inorganic layered porous material samples obtained in these Examples and Comparative Examples were measured, and the results were compared to the two comparative examples of gypsum board and sand molding. It is also shown in Table 1. Note that the porosity is obtained by the following formula. The specific surface area is BE in the nitrogen adsorption method.
The average interlayer distance (pore distribution) was obtained using the CI method in the nitrogen adsorption method, respectively. The nitrogen adsorption device used was Autosorb 6 manufactured by Quantachrome. The thermal conductivity measurement was performed using a thermal conductivity measuring device using the xenon flash method.

[Effects of the Invention] Since the method for producing an inorganic layered porous material of the present invention is configured as described above, the inorganic compound maintains the interlayer spacing of 30 to 600% in more than 40% of the total, resulting in a low porosity. 40%
As described above, it is possible to reliably obtain an inorganic layered porous body that has low thermal conductivity and has excellent heat insulating properties that are useful for heat insulating materials and the like.

[Brief explanation of the drawing]

FIG. 1 is a schematic side view of an inorganic layered porous material, FIG. 2 is a schematic side view of a swellable layered compound, and FIG. 3 is an explanatory diagram illustrating the state leading to swelling of the swellable layered compound in an autoclave. Fig. 4 is an explanatory diagram illustrating the state in which the inorganic pillar is inserted between the layers in an autoclave, and Fig. 5 is an explanatory diagram illustrating the state in which the surface of the inorganic pillar is modified with at least one of a cationic inorganic compound and metal alcoholade B. FIG. 6 is an explanatory diagram illustrating a state in which the inorganic pillars and organic pillars of FIG. 5 are mixed and inserted between layers of a swellable layered compound. A...Inorganic layered porous material A,...Swellable inorganic layered compound l...Layer 2...Inorganic compound 2'...Inorganic pillar 3...Void 5...Organic pillar agent
Patent Attorney Takehiko Matsumoto Figure 1 Figure 2

Claims (10)

[Claims] (1) An inorganic layered porous material in which a swellable layered compound is swollen, at least one of an inorganic pillar and an organic pillar is inserted between the layers, and then dried to form fine voids between the layers. A method for producing an inorganic layered porous body, characterized in that swelling of the swellable layered compound and insertion of at least an inorganic pillar of an inorganic pillar and an organic pillar between the layers are both carried out in an autoclave. (2) The swelling layered compound is Na-montmorillonite,
Ca-montmorillonite, acid clay, 3-octahedral synthetic smectite, Na-hectorite, Li-hectite, Na-teniolite, Li-teniolite, and
The method for producing an inorganic layered porous material according to claim 1, which is at least one selected from the group consisting of synthetic mica. (3) The method for producing an inorganic layered porous body according to claim 1 or 2, wherein the inorganic pillar is at least one of a colloidal inorganic compound and a hydrolyzate of a metal alcoholade. (4) The colloidal inorganic compound is SiO_2, Sb_2
O_3, Fe_2O_3, Al_2O_3, TiO_2
, and ZrO_2, and the metal alcoholade to be the hydrolyzate is S
i(OR)_4, Al(OR)_3, and Ge(O
The method for producing an inorganic layered porous material according to claim 3, which is at least one member selected from the group consisting of R)_4. (5) The inorganic layered porous structure according to any one of claims 1 to 4, wherein the inorganic pillar has a surface modified with at least one of a cationic inorganic compound and a metal alcoholade. How the body is made. (6) The cationic inorganic compound is a titanium-based compound, a zirconium-based compound, a hafnium-based compound, an iron-based compound,
Copper compounds, chromium compounds, nickel compounds, zinc compounds, aluminum compounds, manganese compounds,
At least one selected from the group consisting of phosphorus-based compounds and boron-based compounds, and the metal alcoholade used for modification is Ti(OR)_4, Zr(OR)_4
, PO(OR)_3, and B(OR)_3. The method for producing an inorganic layered porous material according to claim 5. (7) The method for producing an inorganic layered porous material according to any one of claims 1 to 6, wherein the organic pillar is at least one of a water-soluble polymer compound and a quaternary ammonium salt. (8) The water-soluble polymer compound is polyvinyl alcohol,
At least one selected from the group consisting of polyethylene glycol, polyethylene oxide, methylcellulose, carboxymethylcellulose, polyacrylic acid, sodium polyacrylate, and polyvinylpyrrolidone, and the quaternary ammonium salt is an octadecyl group, a hexadecyl group, 8. The method for producing an inorganic layered porous material according to claim 7, which has at least one group selected from the group consisting of a tetradecyl group and a dodecyl group. (9) After drying, the first claim further includes firing.
A method for producing an inorganic layered porous material according to any one of Items 1 to 8. (10) The method for producing an inorganic layered porous material according to any one of claims 1 to 9, wherein the voids are 30 to 600 Å.