JPS63185871A - Manufacture of inorganic layered 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 [Technical Field] The present invention relates to a method for producing an inorganic layered porous material having excellent heat insulation properties.

[Background 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 susceptible to the effects of 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 the above-mentioned 10 Å or less in the case of no 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 thermophysical 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 an inorganic pillar between the layers, and also inserts an amphoteric surfactant between the layers, and then dries the compound and inserts an inorganic pillar between the layers. The gist of this paper is a method for producing inorganic layered porous materials that form fine voids.

Hereinafter, one embodiment of the present invention will be described 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.

As the swelling layered compound, Na-montmorillonite F
+ Ca-montmorillonite, acid clay, 3-octahedral synthetic smectite, Na-hectorite, Li-hectite, Na-teniolite, Li-teniolite, and synthetic mica (Na-fluorine element silicon mica, etc.), but swelling It is not limited to these as long as it is a layered compound.When using a swelling layered compound such as Ca-montmorillonite and acid clay as the main material, it is difficult to swell unless strong shearing force is applied. , it is necessary to knead during swelling.

As the inorganic pillar inserted between the layers of the swellable layered compound, metal alcoholate (hereinafter referred to as [metal alcoholate AJ
At least one of a colloidal inorganic compound and a polymer obtained by hydrolyzing .

As metal alcoholate A, 5t (OR) 4゜A 1
(OR)3. T i (0R)4. Z r (
OR) i and G e (OR) a, etc.
These may be used alone or in combination.

Such metal alcoholate A becomes a polymer having a metal-oxygen bond as the main chain by the hydrolysis, and it becomes a polymer having a metal-oxygen bond as the main chain.
This becomes the inorganic pillar.

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

S 1 (OCzHs)4. S i('0CHs)4*
Ge(OCzHy)4. Ge(OCtHS)a.

Colloidal inorganic compounds are not particularly limited, but include:
A thermally stable oxide or one that expands when heated is preferred. Such compounds include, for example,
SiO2,5bzC)+ , FezO5, A1zO3,
Examples include Ti0t, 5not and ZrO2,
These may be used alone or in combination.

Although the particle size of such a colloidal inorganic compound is not particularly limited in the present invention, it is preferably about 50 to 150 particles.

The above-mentioned inorganic pillars may be inserted as they are between the layers of the swellable layered compound, but the surface of the inorganic pillars is a cationic inorganic compound and a metal alcoholate other than the metal alcoholate A (hereinafter referred to as "metal alcoholate"). B) may be modified and then inserted between the layers.

Cationic inorganic compounds used to modify the surface of inorganic pillars include titanium compounds, zirconium compounds, hafnium compounds, diiron compounds, copper compounds, chromium compounds, nickel compounds, and zinc compounds. , aluminum-based compounds, manganese-based compounds, phosphorus-based compounds, boron-based compounds, and the like. Examples of such cationic inorganic compounds include metal chlorides such as TiCl4, metal oxychlorides such as Z r OCl z, and nitrate compounds, but other compounds may also be used.

Further, as metal alcoholate B used for the same purpose, T i (OR) 4. Z r (OR)-, P
O(OR) 3. A I (OR)3, and B
(OR)3 etc. are mentioned. These may be used alone or in combination.

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

Ti(OC3Ht)n, Zr(OCaHt)a, P
O(OCH3)4, PO(OCzHsLs, B(O
The amphoteric surfactant inserted between the layer 1.1 of the swellable layered compound together with an inorganic pillar such as CHi)4°B(OCzHs)4° or more,
Although various types can be considered, for example, those having the following groups are preferred for this invention.

Cation part: Aliphatic amine type Anion part: At least one selected from the group consisting of carboxyl group, sulfate ester group, sulfone group, and phosphate ester group.

Further, in the present invention, organic pillars other than the amphoteric surfactant described above can also be inserted between the layers 1.1.

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 A+. This compound At, which is the main material, is mixed with a solvent such as water (kneaded if necessary), and as shown in Figure 3, the solvent 4 is impregnated between the layers 1 and 1 to swell it in advance. Water is generally used as the solvent, but other polar solvents such as methanol, DMF, DMSO, etc. may be used alone or in combination.

Next, when using a polymer of metal alcoholate A as the inorganic pillar 21, a solvent such as ethanol or isopropanol is added to metal alcoholate A to dissolve it, and water and a reaction catalyst such as hydrochloric acid (hydrated Decomposition catalyst) is added and mixed to cause a hydrolysis reaction. This hydrolysis reaction is preferably carried out at a temperature of about 70°C, although it is not particularly limited. Further, when the hydrolysis reaction of the inorganic pillar 21 has progressed to a certain extent and the nucleus has grown, metal alcoholate B or a cationic inorganic compound is added to the reaction solution, and these compounds are applied to the surface of the nucleus. If you make an addition reaction,
As shown in FIG. 4(b), a reactant 21' whose surface is positively charged is obtained.

When using a colloidal inorganic compound as the inorganic pillar 21, it may be used as is, or
The metal alcoholate B or the cationic inorganic compound is added to the dispersion of the colloidal inorganic compound, and these compounds are subjected to an addition reaction on the surface of the inorganic pillar 21 in the same manner as in the previous case. Obtain item 21゛.

The above reaction @ff2L' or inorganic pillar 21
is mixed with the swellable layered compound which has been swollen in advance together with the amphoteric surfactant 5, and inserted (intercalated) between the layers 1.1 of the layered compound. The temperature during mixing is not particularly limited in this invention, but is 60°C.
The temperature is preferably around 70°C.

Then, organic pillars such as amphoteric surfactant 5 are added to layer 1,
1 is expanded and held, and at the same time, the inorganic pillar 2
It works to slow down the movement of 1 and keep it between 1° and 1 in this layer. The retained inorganic pillar 21 is thereby
Layers 1.1 are kept spread apart. In addition, when this inorganic pillar 21 is a reactant 21' whose surface is modified, the positive charge on its surface is electrically connected to the negative part on the surface of layer 1, as shown in FIG. It is believed that this bonding makes it possible to maintain the distance between the layers 1 and 1 even further.

After the reaction solution as described above is dehydrated by centrifugation, it is 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,
Firing is performed at 00 to 600°C, preferably 450 to 550°C. By this firing, the inorganic pillar 21 and the reactant 21'
The trace amount of organic matter contained in it and organic pillar 5 are C.
0t = NH, H, O, etc. and removed, and as shown in FIG. 1, a plate-shaped inorganic layered porous body with an inorganic compound 2 inserted between the layers can be obtained.

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.

In the above examples, the inorganic pillar (inorganic pillar) reactant and the amphoteric surfactant were separately inserted between the layers of the swellable layered compound, but these were mixed in advance. It may be inserted between the layers after being placed there.

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

(Example 1) As an inorganic pillar, a 10% by weight aqueous solution of silica sol (Snowtefx OXS, manufactured by Nissan Chemical Industries, Ltd., average particle size 60), which is a colloidal inorganic compound, was used, and in this, a cationic inorganic compound, silica sol, was used. TicI4 (Hani Chemicals■
A 25 wt % aqueous solution of 100% by weight was added thereto and thoroughly mixed, and a reaction was carried out to obtain a reaction solution in which the reactants were dispersed. At this time,
The blending ratio (molar ratio) of silica sol and T i C14 is 5
Converted to iOz and T i Ot, Sin, :TkO,
=10wl.

For this reaction product, an amphoteric surfactant, dimethylcocoalkylbetaine (Nippon Oil Co., Ltd., Nitsusan Anon BF)
) was mixed with a 25% aqueous solution of Na-montmorillonite (Nipia F manufactured by Kunimine Industries), which is a swellable layered compound that had been swollen with water in advance.
It was mixed with a wt % aqueous solution and subjected to insertion reaction at 60° C. for 1.5 hours.

After the reaction, this was centrifuged, oriented into a plate shape with a spatula, dried at room temperature for one day, and then dried with warm air at 60°C. This was placed in an electric furnace and fired at 450°C to a thickness of 1.5
A plate-like inorganic layered porous material sample of m was obtained.

In addition, Na-montmorillonite, SiO□, T'OZ
+The final composition ratio of the amphoteric surfactant is 1:1 in molar ratio.
The ratio was 0:1:2.88.

(Examples 2 to 23) Table 1 (a), (
A plate-like inorganic layered porous material sample was obtained using the component system shown in b).

(Comparative Example 1) Colloidal silica (average particle size: 130 particles, 20% aqueous solution) was used as the colloidal inorganic compound, and Na-montmorillonite (Nipia F manufactured by Kunimine Kogyo ■) was used as the swelling layered compound. was mixed with a water-soluble polymer compound, polyethylene oxide (Alcox E75, manufactured by Meisei Kagaku ■, average molecular weight 1.5 million to 2.2 million) and water at 70° C. for 40 minutes. This mixture was oriented into a plate shape with a spatula, dried, and then fired at 400°C for 2 hours to obtain a plate-shaped 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 moldings. They are also shown in Table 1 (al, (b)).The porosity can be obtained by the following formula.The specific surface area is determined by the BET method in the nitrogen adsorption method, and the average interlayer distance (pore distribution) is determined by the BET method in the nitrogen adsorption method. The CI method in the nitrogen adsorption method was used to obtain the samples.The nitrogen adsorption device used was Autosorb 6 manufactured by Quantachrome.The heat conduction measurement was performed using a heat conduction measurement device using the xenon flash method.

〔Effect of the invention〕

Since the manufacturing method of the inorganic layered porous material of the present invention is configured as described above, the layer spacing is maintained at 30 to 600 in more than 40% of the total by the inorganic compound, and the porosity is 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]

Figure 1 is a schematic side view of an inorganic layered porous material, Figure 2 is a schematic side view of a swellable layered compound, Figure 3 is an explanatory diagram illustrating the state leading to swelling, and Figure 4 (a) is An explanatory diagram illustrating an inorganic pillar formed by hydrolyzing a colloidal inorganic compound or metal alcoholate A. FIG. 4(b) is an explanatory diagram illustrating a reactant whose surface is modified as an inorganic pillar. Figure (al is an explanatory diagram illustrating the state in which the inorganic pillars of Figure 4 (al) and the amphoteric surfactant are inserted between the layers of the swellable layered compound, Figure 5 (b) is the reaction of Figure 4 (b) It is an explanatory diagram explaining a state in which a substance and an amphoteric surfactant are inserted between layers of a swellable layered compound. A... Inorganic layered porous body A,... Swellable inorganic layered compound 1... Layer 2 ... Inorganic compound 3 ... Voids 5 ... Amphoteric surfactant 21.21" ... Inorganic pillar agent Patent attorney Takehiko Matsumoto @1 Figure 2 Figure 3 Figure 4 (a)

Claims (9)

[Claims] (1) Inorganic layered porous structure in which a swellable layered compound is swollen, inorganic pillars are inserted between the layers, an amphoteric surfactant is also inserted between the layers, and fine voids are formed between the layers by drying. How the body is made. (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 material 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 alcoholate. (4) The colloidal inorganic compound is SiO_2, Sb_2
O_3, Fe_2O_3, Al_2O_3, TiO_3
, SnO_2, and ZrO_2, and the metal alcoholate to be the hydrolyzate is Si(OR)_4, Al(OR)_3, Ti
(OR)_4, Zr(OR)_4, and Ge(OR
The method for producing an inorganic layered porous material according to claim 3, which is at least one selected from the group consisting of )_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 alcoholate. 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 alcoholate used for modification is Ti(OR)_4, Zr(OR)_4
, PO(OR)_3, Al(OR)_3, and B(
The method for producing an inorganic layered porous material according to claim 5, which is at least one selected from the group consisting of OR)_3. (7) The cationic part of the amphoteric surfactant is an aliphatic amine type, and the anionic part is a carboxyl group, a sulfuric ester group,
7. The method for producing an inorganic layered porous material according to any one of claims 1 to 6, wherein the material is at least one selected from the group consisting of a sulfone group and a phosphate ester group. (8) After drying, the first claim further includes firing.
7. A method for producing an inorganic layered porous material according to any one of Items 7 to 7. (9) Claim 1 in which the void is 30 to 600 Å
A method for producing an inorganic layered porous material according to any one of Items 1 to 8.