JPS6163521A - Freely swelling synthetic mica - Google Patents

Abstract

PURPOSE:To provide the titled synthetic mica composed of mixed ion of an alkali metal and alkaline earth metal as interlaminar ion, Mg<2+> ion forming octahedron, and Si, O and F, and having a specific composition, and giving an aqueous solution having high viscosity. CONSTITUTION:A freely swelling synthetic mica of formula X1/3-1.5 Y2.0-3.5 Si3.0-4.5O10F1.5-3.0 (wherein X is interlaminar ion consisting of two or more alkali metal and alkaline earth metal; Y is ions forming octahedron, Mg<2+>, or ion obtained by substituting a part of Mg<2+> with Li<+>). The mica gives an aqueous solution having high viscosity, and is useful as a thickener, etc. The specific surface area of the mica can be adjusted freely. The above synthetic mica can be prepared by contacting a synthetic mica of formula M1/3-1Y2-3Si4 O10F2 (wherein M is Li<+> or Na<+>; Y is mg<2+> or ion obtained by substituting a part of Mg<2+> with Li<+>) with an organic cation to obtain an organic inorganic composite, alkalizing a suspension of the complex, and drying the product.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to free-swelling synthetic mica, and more specifically, as a raw material for ceramics, pigments, cosmetics, medicines, adsorbents, catalyst carriers, etc. The present invention relates to useful free-swelling synthetic mica.

``Prior art'' Free-swelling synthetic mica refers to free-swelling properties, that is, water molecules enter the open mica layer, forming many layers of living room water, and this water layer eventually transitions to free water. It is about mica.

Conventionally, such free-swelling synthetic mica contains sodium,
It is obtained by mixing compounds containing lithium, magnesium, silicon, fluorine, etc. in a fixed ratio, melting and cooling the mixture.

As such, for example, lithium hectorite L+h, g2% L1 Si, 0. . F2 (Unexamined Japanese Patent Publication No. 5O-
No. 2698), sodium hectoly1lla3°Mg2. Li, St, O, oF2 (JP-A-5O-269
8), lithium thecoolide LiMg2Li
Si, 01oF2 (JP-A-5O-12400) and sodium tetrasilicic mica Ha11g, 5S
i40. oF2 (Japanese Unexamined Patent Application Publication No. 51-24589), etc. are known as "problems to be solved by the invention". For example, 0 is used in many applications depending on its basic characteristics.

Uses the viscosity of the sol as a thickener, stabilizer, etc.

It is also used as a paint improver by taking advantage of the sol's chicken-tropic properties. In addition, intercalation is used as a material to obtain organic-inorganic composites by incorporating organic matter between the layers.However, in the conventional free-swelling synthetic mica, the interlayer ions are limited to Na or Li. Therefore, its properties were naturally limited.

Therefore, by replacing Na or Li with other ions, we can obtain free-swelling mica that exhibits properties not found in conventional free-swelling 111I compound I&mica, and therefore exhibits unprecedented utility for specific applications. Attempts have been made to try 1) a method of ion-exchanging Na or Li with other ions, and 2) a method of simultaneously mixing and melting ions other than Na or Li, for example, ions or Ha ions, but the former method did not work. In this method, one layer of mica shrinks and aggregates, resulting in limited swelling mica, whereas in the latter method, due to the ionic radius, it may not be located in the living room, or even if it is located in the living room, it will not swell or have limited swelling. Only swollen mica was obtained.

The inventors focused on this point and, as a result of intensive research, succeeded in creating a free III mold synthetic mica that exhibits extremely useful and interesting properties, and the present invention. reached.

That is, 1 the present invention has the following general formula (I):
10' 1.5-3.0CI) (wherein, X is an interlayer ion and represents a mixed ion of two or more types selected from the group consisting of alkali metals and alkaline earth metals, and Y is an octahedral position. It is a free-swelling synthetic mica represented by Mg''t or an ion in which a part of Mg2+ is replaced with Li.

The free-swelling synthetic mica of the present invention preferably has the following formula: % formula %() More preferably, the following formula: x% -1,OY2. o -3,0514010F2
(m). In the above formulas (1) and (2), X and Y represent the meanings defined in the above-mentioned carpenter.

The novel Wg wet type synthetic mica of the present invention has the following ions:
Its structural feature is that it is composed of a mixed ion of two or more types selected from the group consisting of alkali metals and alkaline earth metals.

Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium, preferably lithium, sodium, and potassium; examples of alkaline earth metals include beryllium, magnesium, lesium, strontium, and barium, preferably magnesium and calcium. The ratio of each of the interlayer ions mentioned can be set arbitrarily within a range that does not impede the objective of the present invention, which is to provide a novel swollen synthetic mica, but preferably each ion accounts for 10% to 10% of the total interlayer ions. This amount is 90%.

Specific examples of the synthetic mica of the present invention are listed below, but it goes without saying that the present invention is not limited to these specific examples: Sodium potassium duolite (Ha,K) Ng2Li(Si40.o)F.

Sodium potassium tetrasilicic, mica (Na
, to) Mg2.5 (!lft, O, o) F2 Sodium Lithium Duolite (Na, Li) >1g2Li (Si40,.) F2 Lithium Potassium Duolite (Li, K) Mg,, Li (Si, 01o) F2 Sodium Magnesium Taeniolite (Na, Mg) Kg Li (Si40to)F2
Sodium lithium hectorite (+la, Li) y, Mg 2 H 3/, (s
i40 lO)F2 The synthetic cloud It1 of the present invention is obtained by bringing synthetic mica represented by the following general formula (11) into contact with organic cations to form an organic-inorganic composite, and making the suspension of the composite alkaline to drive out the organic cations. , and then drying the suspension.

M station~12~3si, O□. F. (II)
(In the formula, M represents Li or Na, Y is M
Specific examples of the starting materials represented by the above general formula (n) (representing an ion obtained by replacing a part of Mg2+ or Mg2° with Li) are as follows: Sodium tetrasilicic mica N8Mg2. 5S140toF2 Lithium Taeniolite Li)1g2LiSi, O!
oF2 Sodium Taeniolite NaNg, Li5i
40. oF2 sodium hectorite Na, g to A,,
B Li, 5i40. oF2 lithium~cutolite L duck-g,, qL! +5I40toF2 As the organic cation to form a complex with the synthetic mica represented by the formula (■), any organic cation that can undergo ion exchange with the interlayer ions of the synthetic mica can be used. Specific examples of such substances include non-acid salts of alkylamines, such as hydrochlorides of n-butylamine, n-propylamine, and diethylamine, and non-aS salts of amine alcohols, such as jetanolamine and triethanolamine. salts s@, and inorganic acid salts of amino acids 1 e.g. α
- A method of contacting a synthetic IR mica, which includes hydrochloride of alanine, with an organic cation.

For example, a dipping method, a kneading method, a stirring method, and any known method of reflux calculation can be applied. The contact temperature is not particularly limited, but it is usually carried out at a temperature of 0°C to 100°C. Further, the contact time varies depending on the contact temperature and the concentration of the organic cation, but in any case, a short time is sufficient.

In order to make the suspension of the complex alkaline, it is sufficient to add an alkali metal and alkaline earth metal compound that exhibits alkalinity.The type and amount of the alkali to be added are represented by the formula (I) of the present invention. The chemical composition is selected such that the chemical composition can be formed. In this case, when the amount of alkali is increased, the specific surface area of the product obtained becomes smaller, and conversely, when the amount of alkali is reduced, the specific surface area becomes larger. Therefore, depending on the amount of alkali added, the synthetic mica of the present invention can be made to have a desired specific surface area. Examples of the alkali metal and alkaline earth metal compounds used include their hydroxides and carbonates, such as potassium hydroxide, sodium hydroxide, magnesium hydroxide, sodium carbonate, and lithium carbonate. Further, when making the suspension alkaline, it is effective to use ammonia in combination. The alkaline pH is not particularly limited, but for example, pH 8-14, preferably pH 9-14.
It is 12. The organic cations are driven out by making the suspension of the complex alkaline in this way, but methods for driving them out include, for example, evaporating them from the i-plane while stirring, or evaporating them under reduced pressure with an evaporator. However, it is not limited to these.

If organic cations are expelled and dried in this way, the material will be substantially free of organic matter and one interlayer ion will consist of a combination of two or more ions selected from the group consisting of alkali metals and alkaline earth metals. The free-swelling synthetic mica of the present invention represented by formula (I) is obtained.

"Example" Next, the present invention will be further explained by giving examples and reference examples.
The invention is not limited to these examples.

The specific surface area and viscosity in the Examples were measured by the following methods.

"Specific surface area" After thoroughly drying 1 g of the sample and impregnating it with ethylene glycol monoethyl ether, it was degassed in a desiccator using a vacuum pump, and the amount of equilibrium retention of ethylene glycol monoethyl ether was determined. The specific surface area was calculated from the following formula.

Specific surface area = 3, 5rn'/mg
Using No.1 rotor, 60r, p.

L, measured at 25°C.

"Swelling test" Synthetic mica powder was ground in a mortar and placed on a holder, water was added to it using a dropper, and the swelling property was determined based on the X-ray diffraction peak in the wet state. (001) If a clear peak appears around 2θ=5.6° to 8.8° from the (001) diffraction line, it is considered “limited swelling”, and the baseline below 2θ=9° rises gently, and 2θ= 2°～9
A sample in which no clear peak appeared in 6 was defined as "free lIl wettability".

Example 1 Sodium tetrasilicic mica (Na to g2.5S
i, 010F2) l Add n-butylamine hydrochloric acid solution (n-butylamine 100 mJL to concentrated hydrochloric acid 10
Add 0m sentence and add 4.8 parts of distilled water to this solution) 3
00m was added, and the mixture was stirred for 1 hour using a stirrer. Then, 15 mJL of 10% KOH aqueous solution was added, and the mixture was stirred day and night. Next, n-butylamine was forcibly distilled off under reduced pressure while heating in a constant temperature bath at 80°C. The thus obtained suspension was concentrated to an appropriate concentration of about 5 to 20%, and then dried at 150°C to obtain 1 synthetic mica powder. When the swelling properties of this powder were examined using X-rays, it was found that it was free-swelling synthetic mica.

Example 2 Sodium potassium taeniolite was obtained in the same manner as in Example 1 except that sodium taeniolite was used instead of sodium tetrasilicic mica.

When this product was subjected to X-ray diffraction, the results shown in FIG. 1 were obtained. This X-ray diffraction chart is a measurement chart of 2θ=2@~50° by wide-angle X-ray diffraction (reflection) method. 14 constant was performed at 30 KV and 18 mA, and the slit system was D, S = 1°, S, S = 1', R, S = 0.2 mm.
It was used. The measurement conditions are 25° C. and 65% RH.

The amount of components in the above product was measured. The results are shown in the table below. Na, Li and Mg were measured using a flame photometer, and E was used for Mg.
DTA titration method, Si was determined using dehydrated gravimetric absorption method combined method.
was determined by the alizarin combination method.

Unit W/W% From the above results, a chemical formula expressed by the following formula is derived.

(Na0.53KO-80)Lll, 08'g2.37
Si3.70010'2.22 The above chemical formula was determined by a method based on the total number of positive charges.

The swelling property of this product powder was examined by X-rays, and it was found to be free-swelling synthetic mica. The X-ray diffraction chart is shown in FIG.

Example 3 Sodium potassium taeniolite was obtained in the same manner as in Example 2 except that 5 m of 10% KOH aqueous solution was added. Similarly, it was confirmed by an X-ray diffraction chart that it was a free-swelling synthetic mica.

The viscosity and specific surface area of the products obtained in Example 2 and Example 3 were measured. The results were as shown in the table below. For comparison, measured values for conventional free-swelling synthetic mica are also shown.

"Effects of the Invention" The free-swelling synthetic mica of the present invention is a completely new synthetic A matrix, and has a high viscosity in aqueous solution, so it is less effective in applications that utilize the viscosity of liquids such as thickeners. demonstrate.

Furthermore, the free-swelling synthetic mica of the present invention can have a desired specific surface area. Therefore, by so-called intercalation, it is possible to obtain various organic/inorganic composites in which the amount, type, coordination direction, etc. of organic substances are controlled when incorporating organic substances between P#, but this is not possible with conventional synthesis. Since it has properties that mica does not have, its contribution to X is extremely large.

[Brief explanation of the drawing]

The 11th Δ is the xMA diffraction diagram of the synthetic mica obtained in Example 942. Figure 2 is an x11 diffraction diagram in a wet state.
θ indicates the angle of incidence.

Claims (3)

[Claims] (1) The following formula I: X_1_/_3_~_1_. _5Y_2_. ＿0＿〜＿
3__. _5Si_3_. ＿0＿～＿４＿． _5O_1_
0F_1_. ＿５＿～＿３＿． ＿0(I) (in the formula, X
is an interlayer ion and represents a mixed ion of two or more types selected from the group consisting of alkali metals and alkaline earth metals, Y is an ion at an octahedral position, and Mg^2^+
Alternatively, it represents an ion in which a part of Mg^2^+ is replaced with Li^+. ) A free-swelling synthetic mica characterized by: (2) The synthetic mica according to claim 1, wherein X is a mixed ion of sodium and potassium. (3) The synthetic mica according to claim 1, wherein X is a mixed ion of sodium and lithium.