JPH0723212B2 - 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 thickening (gelling) when dispersed in a highly polar organic solvent, a method for producing the same, and a thickener.

[0002]

Clay minerals are divided into layered silicate minerals and amorphous minerals, most of which are the former. The layered silicate mineral has a sheet in which SiO ₄ tetrahedra are arranged in a two-dimensional network. Among them, the 2: 1 type layered silicate mineral is a silicate layer having a sandwich type three-layer structure in which two silica tetrahedral layers have a magnesium octahedral layer or an aluminum octahedral layer sandwiched therebetween. It has a structure in which several to several tens layers are laminated. The silicic acid layer of the swelling layered silicate has a negative layer charge, but since the charge is neutralized by the presence of alkali metal cations and alkaline earth metal cations between the layers, the charge as a whole is changed. Is in balance. These swellable layered silicates, smectites and swellable mica, have cation exchange ability, the layers are easily spread, they are dispersed in water to form a sol, and when the concentration is high, a gel is formed to form thixotropy. It has a unique property of showing sex. Utilizing this property, the swellable layered silicate is used for applications such as a mud composition for excavation, a binder for foundry sand, and a water-based viscosity modifier.

Further, the swellable layered silicate is prepared by reacting with various cationic organic or inorganic compounds,
It can be a complex. As an example of such an organic composite, a clay-organic composite in which dimethyl-dioctadecyl-ammonium ion of a quaternary ammonium ion is introduced by cation exchange between smectite layers is industrially produced, It is used as a thickener. However, the organic solvent which can disperse and thicken this is limited to low polar solvents such as toluene and xylene. Also, as a thickener for polar solvents,
Clay-organic composites in which dimethyl-benzyl-octadecyl-ammonium ions are introduced between smectite layers are also known, but they do not have a sufficient thickening effect for highly polar organic solvents.

On the other hand, a thickener for an organic solvent which is made organic by modifying the surface of fine silica with an organic substance is also known, but the thickening effect cannot be obtained unless it is used in a large amount.
Further, since it has a low affinity with a solvent, it has a drawback that part of it precipitates and redispersion becomes difficult after long-term use.

[0005]

The above existing thickeners for organic solvents are difficult to give a sufficient thickening effect to highly polar organic solvents such as alcohols, ketones, ethers and amides. Further, since it has a drawback that it cannot withstand long-term use, it is required to develop a clay-organic composite having a high affinity with a highly polar organic solvent and being usable as a thickener that is stable for a long period of time.

[0006]

[Means for Solving the Problems] As a result of years of intensive research to develop a clay-organic composite useful as a thickener for highly polar organic solvents, the present inventors have found that hydroxypolyoxy as a substituent can be used as a substituent. Introducing a quaternary ammonium ion having an ethylene group between the layers of the swellable layered silicate, swellable layered silicate and alcohols, ethers,
It was found that the affinity with highly polar organic solvents such as ketones and amides was improved, the swellable layered silicate was dispersed in the highly polar solvent, and showed a sufficient thickening effect. The present invention has been made based on this finding.

That is, the present invention provides a compound of the general formula (I) between the layers of the swellable layered silicate.

[0008]

[Chemical 2]

[Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different (CH ₂ CH ₂ O) _n H group (n is 2 or more), an alkyl group having 1 to 30 carbon atoms or hydrogen. Representing an atom, _{1 to} 3 of R _{1 to} R ₄ are (CH ₂ CH ₂ O) _n.
H groups, and at least three of R _{1 to} R ₄ are (CH
₂ CH ₂ O) _n H group or an alkyl group having 1 to 30 carbon atoms], which is a clay-organic complex into which a quaternary ammonium ion is introduced.

The swelling layered silicate is a layered silicate having a cation exchange ability and having a unique property of taking in water between layers and swelling, and smectite-type clay, swelling mica, etc. Are known.

The smectite type clay which can be used in the present invention includes hectorite, saponite, stevensite,
Examples thereof include natural smectite-type clays such as beidellite, montmorillonite, nontronite, and bentonite, chemically synthesized synthetic smectite-type clays, and substitution products, derivatives or mixtures thereof. Examples of the swelling mica that can be used in the present invention include chemically synthesized swelling mica, and examples thereof include synthetic swelling mica having Li ions and Na ions between layers, or a substitution product, derivative or mixture thereof. You can

The cation exchange capacity of the swellable layered silicate used for producing the clay-organic composite of the present invention is not less than 70 milliequivalents per 100 g of clay, particularly preferably 85 to 130 meq. Is. The thickening agent for highly polar organic solvents comprising the clay-organic composite of the present invention is 50
% Or less non-clay impurities may be contained, but the amount of non-clay impurities is preferably 10% or less.

The alkyl group in the quaternary ammonium ion of the formula (I) has 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl,
Examples thereof include undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and octadecyl, but it is preferable that at least one alkyl group has 10 to 20 carbon atoms.

Hydroxypolyoxyethylene group (CH _{2
N of} CH ₂ O) _n H is preferably 2 to 20, and the number of addition condensations thereof is preferably large. When a plurality of hydroxypolyoxyethylene groups are substituted, the total of these oxyethylene units is 4 to 50, but 10 or more, particularly 15 or more is preferable. To introduce the quaternary ammonium ion of formula (I), a quaternary ammonium salt containing the ion is used, and such a salt is used.
As BR>, for example, Cl ⁻ , Br ⁻ , NO ₃ ⁻ , OH
^-, CH ₃ COO ^- it can be exemplified salts with such anions.

Specific examples of the quaternary ammonium include monohydroxypolyoxyethylenetrialkylammonium chloride, monohydroxypolyoxyethylenetrialkylammonium bromide, monohydroxypolyoxyethylenedialkylammonium chloride and monohydroxypolyoxyethylenedialkylammonium. Acetate, dihydroxypolyoxyethylenedialkylammonium chloride, dihydroxypolyoxyethylenedialkylammonium bromide,
Dihydroxypolyoxyethylenealkylammonium chloride, dihydroxypolyoxyethylenealkylammonium acetate, trihydroxypolyoxyethylenealkylammonium chloride, trihydroxypolyoxyethylenealkylammonium bromide, trihydroxypolyoxyethyleneammonium chloride, trihydroxypolyoxyethyleneammonium acetate, etc. Can be mentioned.

The clay-organic composite of the present invention is obtained by cation exchange between layers, and can be produced, for example, by the following method. As a first step, the swellable layered silicate is dispersed in water. The solid dispersion concentration is usually 1 to 15 w
Although t% is desirable, it can be freely set within a concentration range in which the swelling layered silicate can be sufficiently dispersed. In this case, it is effective to use the swellable layered silicate that has been previously freeze-dried in order to easily produce the clay-organic composite. Then, the quaternary ammonium salt solution described above is added to this swellable layered silicate suspension, or conversely, the swellable layered silicate suspension is added to the above quaternary ammonium salt solution. It is also possible to produce a clay-composite.

The amount of the quaternary ammonium salt added is preferably equivalent to the cation exchange capacity of the swelling silicate as the quaternary ammonium ion, but a smaller amount than this can be used for the production. Further, an excess amount may be added to the cation exchange capacity. The amount thereof is preferably 0.5 to 1.5 times (milliequivalent), particularly preferably 0.8 to 1.2 times the cation exchange capacity of the clay.

The reaction proceeds sufficiently at room temperature, but may be heated. The maximum temperature of heating is governed by the heat resistance of the quaternary ammonium salt used, and can be arbitrarily set as long as it is below its decomposition point. Then, the solid-liquid is separated, and the produced clay-organic complex is washed with water to sufficiently remove the by-product electrolyte. This is dried and, if necessary, crushed to obtain a final product.

When the clay-organic composite of the present invention is used as a thickener, the clay-organic composite is added to an organic solvent and dispersed by stirring or the like. If the amount can be dispersed,
The thicker the amount added, the higher the thickening effect. The organic solvent having a higher polarity such as dimethylformamide, methanol and ethanol is more effectively thickened.

The general properties of the novel clay-organic composite obtained by carrying out the present invention can be evaluated by selecting from the following items according to the purpose or by carrying out a combination thereof. it can. (1) Chemical analysis (2) X-ray diffraction (powder method or oriented method) (3) NMR (4) Infrared absorption spectrum analysis (5) Thermobalance / differential thermal analysis (6) Rheology of highly polar organic solvent system Measurement (7) Color tone (8) Swelling power in highly polar organic solvents

For example, the formation of the clay-organic composite of the present invention can be easily confirmed by measuring the position of 001 bottom surface reflection by X-ray diffraction. For example, when smectite-type clay is used as a raw material, it is 10
Å Under normal temperature and humidity, it has a bottom spacing of 12 to 16Å, but the clay-organic composite of the present invention has a carbon number of an alkyl group in an inter-layer quaternary ammonium ion and a hydroxypolyoxyethylene group. Although it depends on the number of addition condensations, the bottom surface interval is 18 Å or more, which indicates that a clay-organic complex is formed. The function of the thickener can be easily confirmed by visually observing the viscosity by dispersing it in a highly polar solvent such as alcohol, but the rheological property of the resulting dispersion is measured with a viscometer. You can know it.

[0022]

The clay-organic composite of the present invention has an affinity for a highly polar organic solvent and further exhibits a dispersing and thickening effect when the oxygen or terminal proton of the hydroxypolyoxyethylene group and the highly polar organic solvent are present. It is considered that since the protons or oxygen are hydrogen-bonded to each other, the solvent molecules spread the swelling layered silicate layers and separate the laminated silicate layers. It is presumed that the separated silicate layers form a gel structure by irregularly bonding to each other due to the negative charges remaining on the layer surfaces and the positive charges on the end surfaces.

[0023]

EFFECTS OF THE INVENTION The clay-organic composite of the present invention is different from the conventional clay-organic composites in that it is limited to use in a low-polarity solvent, and is highly polar alcohols, ketones, ethers, It can be used as a thickener by dispersing it in an organic solvent such as amides or a solvent containing them.

The clay-organic composite of the present invention has an affinity for a highly polar organic solvent, is easily dispersed, and exhibits an excellent thickening effect even when added in a small amount. Therefore, it is necessary to adjust the viscosity of the highly polar solvent. It can be used as a viscosity modifier, dispersant, emulsifier, binder, etc. in various products and industrial processes such as cosmetics, pharmaceuticals, sanitizers, adhesives, paints, dye materials, various plastic products, textile industry, etc. It is useful. Furthermore, since this clay-organic composite contains a hydroxypolyoxyethylene group, it is an antistatic agent for plastics and fibers, a bactericide,
It can be used as a dyeing aid, a leveling agent, a coupling agent, etc., and is useful. Further, by utilizing the layer space, it can be utilized as an organic substance storage agent, a sustained release agent, a catalyst, a separating agent, an adsorbent, a resin stabilizer, a polymerization initiator, a carrier and a filler, which is useful.

[0025]

The present invention will be described in more detail with reference to examples. Example 1 having a composition of hectorite, which is a type of smectite,
The bottom space is 12.5Å in air, and the cation exchange capacity is 1
20 g of synthetic smectite which is 10 meq / 100 g
Is dispersed in 1000 ml of tap water to give a quaternary ammonium salt represented by the following formula.

[0026]

[Chemical 3]

300 ml of a solution in which 21.4 g of a product containing 95% of was dissolved was added to the above synthetic smectite suspension, and the mixture was reacted for 2 hours at room temperature with stirring. The product was subjected to solid-liquid separation, washed to remove by-product salts, dried and pulverized to obtain the product of the present invention.

According to the X-ray diffraction measurement of the product,
The bottom spacing calculated from one reflection was 21Å, confirming the formation of the clay-organic composite of the present invention. The product of the present invention was completely dispersed in N, N-dimethylformamide to form a transparent dispersion liquid, and showed an affinity for a highly polar organic solvent.

Example 2 The product of the present invention obtained in Example 1 was dispersed in ethanol at various concentrations, and a rotational viscometer (B-type viscometer manufactured by Tokyo Keiki Co., Ltd.) was used.
Was used to measure the apparent viscosity at 6 revolutions / minute (shear rate 5.58 s ⁻¹ ), and a good thickening effect was shown. The results are shown in Table 1. The dispersion is a transparent white color,
It had thixotropy.

[0030]

[Table 1]

Example 3 The product of the present invention obtained in Example 1 was dispersed in methanol at various concentrations, and the apparent viscosity at 6 revolutions / minute (shear rate 5.58 s ^-1 ) was obtained using the above-mentioned rotational viscometer. When it was measured, as shown in Table 2, it showed an extremely good thickening effect, and the dispersion liquid was white with a transparent feeling and showed thixotropic property.

[0032]

[Table 2]

Example 4 The product of the present invention obtained in Example 1 was dispersed in N, N-dimethylformamide at various concentrations, and 6 revolutions / minute (shear rate of 5.58 s using the above-mentioned rotational viscometer). ^When the apparent viscosity in ( ^-1 ) was measured, it showed a very good thickening effect as shown in Table 3, and the dispersion was completely transparent and showed thixotropy.

[0034]

[Table 3]

Example 5 Instead of the quaternary ammonium salt used in Example 1, a product 2 containing 65% of a quaternary ammonium salt represented by the following formula:
Clay-in the same manner as in Example 1 except that 0.9 g was used.
An organic complex was produced.

[0036]

[Chemical 4]

The obtained clay-organic composite was dispersed in N, N-dimethylformamide at various concentrations, and 6 revolutions / minute (shear rate 5.58) was obtained using the above-mentioned rotational viscometer.
When the apparent viscosity at s ^-1 ) was measured, as shown in Table 4, a very good thickening effect was shown, and the dispersion liquid was transparent white and showed thixotropy.

[0038]

[Table 4]

Example 6 Instead of the quaternary ammonium salt in Example 1, 100% quaternary ammonium salt represented by the following formula: 1
Clay-in the same manner as in Example 1 except that 2.2 g was used.
An organic complex was produced.

[0040]

[Chemical 5]

The apparent viscosity of the obtained clay-organic composite was dispersed in N, N-dimethylformamide at various concentrations, and 6 rotations / minute (shear rate 5.58 s ^-1 using the above-mentioned rotational viscometer). When the apparent viscosity in () was measured, as shown in Table 5, it showed a very good thickening effect, and the dispersion was transparent and showed thixotropy.

[0042]

[Table 5]

Example 7 In place of the quaternary ammonium salt in Example 1, 100% quaternary ammonium salt represented by the following formula: 1
Clay-in the same manner as in Example 1 except that 9.9 g was used.
An organic complex was produced.

[0044]

[Chemical 6]

The obtained clay-organic composite was dispersed in N, N-dimethylformamide at various concentrations, and 6 revolutions / minute (shear rate 5.58) was obtained using the above-mentioned rotational viscometer.
When the apparent viscosity at s ^-1 ) was measured, as shown in Table 6, an extremely good thickening effect was shown, and the dispersion liquid was transparent white and showed thixotropic property.

[0046]

[Table 6]

Example 8 A mixture of talc and a finely ground product of sodium silicofluoride was mixed, and 8
Swellable synthetic mica 20.5 obtained by heat treatment at 00 ° C
A product of the present invention was obtained in the same manner as in Example 1 except that g was used instead of synthetic smectite. The product of the present invention is N, N-
It was completely dispersed in dimethylformamide to form a nearly transparent dispersion liquid, which showed an affinity for highly polar organic solvents.

Example 9 The product of the present invention obtained in Example 8 was dispersed in ethanol at various concentrations, and the apparent viscosity at 6 revolutions / minute (shear rate 5.58 s ^-1 ) was obtained using the above-mentioned rotational viscometer. When it was measured, as shown in Table 7, it showed an extremely good thickening effect, and the dispersion liquid was almost transparent white and showed thixotropic property.

[0049]

[Table 7]

Example 10 The product of the present invention obtained in Example 8 was dispersed in methanol at various concentrations, and the apparent viscosity at 6 revolutions / minute (shear rate 5.58 s ^-1 ) was obtained using the above-mentioned rotational viscometer. When it was measured, as shown in Table 8, it showed a very good thickening effect, and the dispersion liquid was white with almost transparent feeling and showed thixotropic property.

[0051]

[Table 8]

Example 11 The clay-organic composite obtained in Example 1 was dispersed in ethanol and N, N-dimethylformamide to prepare dispersions, which were stored by leaving them in a closed container. . As a result, the dispersion did not precipitate even after one year, and maintained a stable gel structure.

Comparative Example 1 Example 1 was repeated except that 12.4 g of a dimethyl-dioctadecyl-ammonium salt (trade name: Arcade 2HT, Lion Akzo strain) was used in place of the quaternary ammonium salt used in Example 1. A clay-organic composite was produced in the same manner as in. This clay-organic composite was dispersed in ethanol and methanol, but it precipitated and the apparent viscosity could not be measured.

Comparative Example 2 A complex of naturally-occurring hectorite and dimethyl-benzyl-octadecyl-ammonium ion (Benton 27, NEL Industries Inc.) was dispersed in ethanol and precipitated to give 2 The apparent viscosity could not be measured because the layers were separated.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takahiro Sekimoto 275-272 Inventor Toshikazu Fujisaki 1-2-7 Hayatominami, Toyoei City, Niigata Prefecture (72) Inventor Motoyuki Ikegami 669-2 Furumachidori Nibancho, Niigata City Niigata Prefecture Daia Palace 306 (72) Inventor Yutaro Ishida 4-16-7 Shiba, Kawaguchi City Saitama Examiner Koji Amamiya (56) References JP-A-61- 286213 (JP, A)

Claims (4)

[Claims] 1. A compound of the general formula (I): between the layers of the swellable layered silicate. [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different (CH ₂ CH ₂ O) _n H group (n is 2 or more), and have 1 to 1 carbon atoms.
30 represents an alkyl group or a hydrogen atom, _{1 to} 3 of R _{1 to} R ₄ are (CH ₂ CH ₂ O) _n H groups, and at least 3 of R _{1 to} R ₄ are (CH ₂ CH ₂ O) _n H
A group or an alkyl group having 1 to 30 carbon atoms], which is a clay-organic complex into which a quaternary ammonium ion is introduced. 2. The clay-organic composite according to claim 1, which has an affinity for a highly polar organic solvent. 3. A quaternary ammonium salt having ammonium ion of formula (I) according to claim 1 is added to the swellable layered silicate by 0.5 to 1.5 of the cation exchange capacity of the clay.
A method for producing a clay-organic composite, which comprises reacting a double amount (equivalent to milliequivalent). 4. A thickener for a highly polar organic solvent, which comprises the clay-organic composite according to claim 1.