JPH0723210B2 - Clay organic complex - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a clay-organic composite having a function of dispersing in a highly polar organic solvent and increasing the viscosity.

[0002]

2. Description of the Related Art The main clay mineral constituting a smectite type clay, which is a typical swelling clay, is called smectite, and two silica tetrahedral layers sandwich a magnesium octahedral layer or an aluminum octahedral layer. Sandwich type 3
It is a member of a phyllosilicate having a structure in which a silicate layer having a layer structure is laminated several to several tens times.

The smectite silicate layer has a negative layer charge, and the charge is neutralized by the presence of alkali metal cations and alkaline earth metal cations between the layers to balance the charge as a whole. .

Compared with mica having a similar silicate structure, smectite has a smaller layer charge, so that the layers easily spread,
It disperses in water to form a sol, and when the concentration increases, it forms a gel and exhibits thixotropic properties, or has a property of having cation exchange ability. Utilizing this property, smectite-type clay is used for applications such as a mud composition for excavation, a binder for foundry sand, and a water-based viscosity modifier.

Smectite-type clay is prepared by reacting with various cationic organic compounds or inorganic compounds,
A complex can be formed.

Conventionally, as such a composite, for example, a clay organic composite in which a quaternary ammonium compound is used and dimethyl dioctadecyl ammonium ion is introduced between the smectite layers by cation exchange is known. , Used as a thickener for paints.

However, this organic composite has the drawback that the organic solvent that can be dispersed and thickened is limited to low polar solvents such as toluene and xylene.

Clay organic composites in which dimethyl, benzyl, octadecyl, ammonium ions are introduced between the smectite layers by cation exchange are known as thickeners for polar solvents. It has not yet shown a sufficient thickening effect for use as an agent in industrial processes.

Further, there is known a thickener for an organic solvent which is made organophilic by modifying the surface of fine silica with an organic substance, but it is necessary to use a large amount for thickening. Since it has a low affinity with a solvent, it has a drawback that a part thereof is precipitated during long-term use and redispersion becomes difficult.

The above-mentioned existing thickeners for organic solvents are
It is difficult to give a sufficient thickening effect to highly polar organic solvents such as ketones, halogenated hydrocarbons and amides.
It had the drawback of not being able to withstand long-term use.

[0011]

The object of the present invention is to disperse organic solvents which can be dispersed in a highly polar organic solvent for a long period of time and are used in various industrial processes such as paint, plastic product, film and adhesive production. A clay organic complex and a thickener for an organic solvent which have a sufficient thickening effect on a solvent and can give a film formed after molding a good film-forming ability in the production of a plastic film or the like. To provide.

[0012]

Means for Solving the Problems The present inventors have introduced trioctyl-methyl-ammonium ions between the layers of smectite-type clay to obtain smectite-type clay and ketones, halogenated hydrocarbons, amides, etc. The affinity with the highly polar organic solvent is improved, the smectite type clay disperses in the solvent and shows a sufficient effect as a thickener, and when it is dried, a very uniform thin film is formed. After finding out, the present invention was completed.

That is, the first aspect of the present invention is a clay-organic composite having an affinity for a highly polar organic solvent in which trioctylmethylammonium ions are introduced between layers of smectite type clay.

The second aspect of the present invention is a thickening agent for a highly polar organic solvent, which comprises the clay organic composite.

The present invention will be described in detail below. Examples of the smectite clay used in the present invention include hectorite, saponite, stevensite, beidellite, montmorillonite, nontronite, natural smectite clay such as bentonite, chemically synthesized synthetic smectite clay, and substitution products thereof and Examples thereof include derivatives and mixtures thereof.

The cation exchange capacity of the smectite type clay is preferably 70 meq or more per 100 g of clay,
More preferably, it is 85 to 130 meq.

The smectite-type clay used in the present invention has a characteristic that trioctyl-methyl-ammonium-ion reacts only with the smectite-type clay, and thus may contain 50% or less of non-clay impurities. Is preferably 10% or less.

The clay-organic composite of the present invention can be obtained by ion-exchange of the exchangeable cation of smectite type clay and trioctyl methyl ammonium ion.

The method for producing the clay-organic composite of the present invention is not particularly limited as long as it is a method capable of efficiently exchanging trioctylmethylammonium ion and the exchangeable cation of clay, but for example, Can be done in any way.

As the first step, smectite type clay is dispersed in water. The solid dispersion concentration can be freely set within a concentration range in which the smectite clay can be sufficiently dispersed, but 1 to 5 wt% is preferable. In this case, it is effective to use the smectite-type clay previously freeze-dried in order to easily produce the organoclay composite.

Next, a trioctyl methyl ammonium salt solution is added to this smectite type clay suspension.
In this case, the smectite-type clay suspension may be added to the trioctyl-methyl-ammonium salt solution.

Examples of the trioctyl methyl ammonium salt include salts of trioctyl methyl ammonium ion with anions such as Cl ⁻ , Br ⁻ , OH ⁻ and NO ₃ ⁻ .

The addition amount of trioctyl methyl ammonium salt is preferably such that the cation exchange capacity of smectite and the trioctyl methyl ammonium ion are equivalent, but a smaller amount than this can also be produced. Alternatively, an excess amount may be added to the cation exchange capacity. The amount of trioctyl methyl ammonium ion is 0.5 to 1.5 of the cation exchange capacity of the clay.
It is preferably double amount (milliequivalent conversion), and more preferably 0.8 to 1.2 times.

The reaction proceeds sufficiently at room temperature, but can be arbitrarily set as long as it is at or below the decomposition point of the trioctyl methyl ammonium salt.

Then, the solid-liquid is separated, and the formed organoclay composite is washed with water or hot water to sufficiently remove the by-product electrolyte. This is dried and, if necessary, pulverized to obtain a clay organic composite.

The formation of the clay-organic composite of the present invention can be evaluated by selecting from the following measurement items according to the purpose or by carrying out a combination thereof.

(1) Chemical analysis (2) X-ray diffraction (3) NMR (4) Infrared absorption spectrum (5) Thermobalance, differential thermal analysis (6) Rheology of highly polar solvent system (7) Highly polar organic solvent Medium swelling power (8) Color tone

For example, the formation of the clay-organic composite of the present invention can be easily confirmed by measuring the magnitude of 001 bottom surface reflection by X-ray diffraction. The raw material smectite clay is 10 Å in a dehydrated state and has a bottom spacing of 12 to 16 Å under normal temperature and humidity. However, the clay organic composite of the present invention is formed because the bottom spacing is about 18 Å. Can be confirmed.

To use the clay-organic composite of the present invention,
To prevent adhesion of water, it is dried and dispersed, for example by adding an organic solvent with stirring. The thickener of the present invention is a clay-organic complex in which trioctyl methyl ammonium ion is introduced between the layers of smectite type clay, but the present invention can be achieved even if the content of impurities is up to 50%. The amount is preferably 10% or less.

When used as a thickener, the thickening effect is higher as the amount of the clay-organic composite is more dispersed, as long as the clay-organic composite can be dispersed. The function of the thickener can be easily confirmed by visually observing the viscosity by dispersing it in a highly polar solvent such as ketones, but measuring the rheological properties of the resulting dispersion with a viscometer. You can also know by

The organic solvent used to disperse the above-mentioned clay organic composite preferably has a strong affinity with the clay organic composite, specifically, ketones, halogenated hydrocarbons, amides and the like. It is preferable to select from

[0032]

EXAMPLES The present invention will be described more specifically below with reference to examples. Example 1 having a hectorite composition and a bottom spacing of 12 in air.
20g of synthetic smectite with 5Å and cation exchange capacity of 110 meq / 100g was dispersed in 1000ml of tap water, and 11.1g of trioctyl methyl ammonium chloride containing 80% was dissolved in pure water.
00 ml was added, and the mixture was reacted at room temperature for 2 hours while stirring. Next, the product was subjected to solid-liquid separation, washed to remove by-product salts, dried and pulverized to obtain a clay organic complex.

The clay organic composite thus obtained was subjected to X-ray diffraction measurement, and the bottom spacing calculated from the 001 reflection was 1
It was 8.0Å, confirming the formation of the clay organic composite of the present invention. The obtained clay-organic composite was dispersed in N, N-dimethylformamide to form a transparent dispersion liquid, and showed an affinity for a highly polar solvent.

Example 2 The clay-organic composite obtained in Example 1 was dispersed in acetone at various concentrations shown in Table 1, and a dispersion was measured using a rotary viscometer (B-type viscometer manufactured by Tokyo Keiki Co., Ltd.). The apparent viscosity at rotations / minute (shear rate 5.58 s ^-1 ) was measured. The results are shown in Table 1.

[0035]

[Table 1]

As is apparent from Table 1, the obtained clay-organic composite exhibits a good thickening effect, the dispersion is white,
It had thixotropy.

Example 3 The clay-organic composite obtained in Example 1 was dispersed in methyl ethyl ketone at various concentrations, and the above-mentioned rotary viscometer was used.
The apparent viscosity at 6 revolutions / minute was measured. The results are shown in Table 2.
Shown in.

[0038]

[Table 2]

As is clear from Table 2, the obtained clay-organic composite showed a very good thickening effect, the dispersion was white and had thixotropic properties.

Example 4 The clay-organic composite obtained in Example 1 was dispersed in carbon tetrachloride at various concentrations and the rotation viscometer was used to make 6 revolutions / rotation.
The apparent viscosity in minutes was measured. The results are shown in Table 3.

[0041]

[Table 3]

As is clear from Table 3, the obtained clay-organic composite showed a very good thickening effect, the dispersion was white and had thixotropy.

Comparative Example 1 In place of the trioctyl methyl ammonium salt used in Example 1, a dimethyl dioctadecyl ammonium salt (trade name: Arcard 2HT, Lion Akzo Co., Ltd.) 1
A clay organic composite was produced in the same manner as in Example 1 except that 2.4 g was used.

The obtained clay-organic composite was added to acetone and methyl ethyl ketone, but neither dispersed nor separated from the solvent and precipitated, and the apparent viscosity could not be measured.

[0045]

The clay-organic composite and thickener of the present invention are
Since the organic molecules between layers have a high affinity for solvent molecules, the solvent molecules spread the layers and separate the laminated silicate layers, so the conventional thickener for organic solvents consisting of clay-organic composites is low. Unlike the limited use in polar solvents, sufficient dispersing action and thickening effect for organic solvents such as highly polar ketones, halogenated hydrocarbons and amides or solvents containing them Indicates.

The thickener for an organic solvent of the present invention has an affinity for a highly polar organic solvent, and the separated silicate layers of the clay organic complex are bonded to each other by the layer charge on the layer surface and the positive charge on the end surface. Therefore, it forms a gel, easily disperses, and shows a superior thickening effect with the addition of a small amount, so it is necessary to adjust the viscosity of a highly polar solvent.
It is extremely useful because it can be used as a viscosity modifier in various products and industrial processes such as cosmetics, sanitizers, paints, adhesives, dye materials, various plastic products, and textile industry.

Further, since it contains trioctylmethylammonium ion between the layers, it can be used as an antistatic agent for plastics and fibers, a filler, an antibacterial agent, a bactericidal agent, etc., and is useful.

Further, the thickener of the present invention is easily dispersed in a highly polar solvent and forms a film after drying.
Alternatively, it is useful as an additive and a film forming agent in the production of plastic films.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiro Onodera 7-13-6 Sakuragaoka, Aoba-ku, Sendai-shi, Miyagi Prefecture (72) Inventor Takahiro Sekimoto 254 27, 72, Tago, Miyagino-ku, Sendai-shi, Miyagi Invention Toshikazu Fujisaki 1-2-7 Hayashidori Minami, Hoei-shi, Niigata (72) Inventor Yutaro Ishida 4- 16-7 Shiba, Kawaguchi-shi, Saitama (72) Inventor Hiroshi Saiki 2074 Ota-ku, Urawa-shi, Saitama No. 2 Corp. Toyotomi Room 203 Examiner Koji Amemiya (56) References JP-A-63-294936 (JP, A)

Claims (2)

[Claims] 1. A clay-organic composite having an affinity for a highly polar organic solvent in which trioctylmethylammonium ions are introduced between layers of smectite-type clay. 2. A thickener for a highly polar organic solvent, which comprises the clay-organic composite according to claim 1.