JP2838218B2 - Method for producing organic liquid gel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) An organic liquid gel can be used as a gelling fuel or by dissolving an active ingredient such as a fragrance, an insecticide, or a bactericidal component, and used as a deodorant, an insecticide, or a bactericide.

(Prior art) Conventionally, to gel an organic liquid such as alcohol,
A method in which a dehydration condensate of an aromatic aldehyde and a pentavalent or higher polyhydric alcohol is added as a gelling agent;
As disclosed in JP-A-292, a resin obtained by neutralizing a crosslinked synthetic polymer having an anionic substituent with a specific amine and / or quaternary ammonium salt is added as a gelling agent. There is a way.

(Problems to be Solved by the Invention) In the former method, in order to sufficiently dissolve the gelling agent, it is necessary to heat the organic medium to near the boiling point. For this reason, there is a disadvantage that if the perfume or the like to be dissolved is not heat resistant, it cannot be used.

In the latter method, since the resin is swollen in an organic liquid to form a gel, the gel moldability is not sufficient.

(Means for Solving the Problems) Conventionally, alginic acid, pectin or Azotobacter genenergie gum has been used to gel an aqueous solution or aqueous suspension.

We have identified these polysaccharides as specific amines and / or
Alternatively, it has been found that a substance neutralized with a quaternary ammonium salt swells or dissolves in an organic medium, and as a result of earnest study, the present invention which solves the above problems has been completed.

That is, the present invention relates to alginic acid, pectin, Azotobacter vinelandie gum. [Wherein, R ₁ , R ₂ and R ₃ are each selected from hydrogen, alkyl, alkylene, phenyl, benzyl and hydroxyalkyl, and the sum of carbon atoms contained in R ₁ , R ₂ and R ₃ is 6 to 4
8, preferably 9 to 36] and / or [Wherein R ₄ , R ₅ , R ₆ and R ₇ are all hydrogen, alkyl,
Alkylene, phenyl, benzyl or hydroxyalkyl, or R ₄ , R ₅ and R ₆ together with the nitrogen to which they are attached form a pyridinium or picolium ring, and R ₇ is alkyl, alkylene, phenyl, benzyl or hydroxyalkyl And the total number of carbon atoms contained in R ₄ , R ₅ , R ₆ and R ₇ is from 8 to 48. X is a halogen or an anion of an acid], and a substance neutralized with a quaternary ammonium salt (hereinafter, referred to as a neutralized product) is added to an organic medium and mixed (hereinafter, referred to as a mixture); This is gelled by the method used to gel aqueous solutions and suspensions with alginic acid, pectin or Azotobacter vinelandie gum, that is, gelled with divalent or higher polyvalent metal ions or made acidic, And producing an organic liquid gel.

Azotobacter vinerangi gum is Japanese Patent Publication No. 58-3944
It can be manufactured by the method described in Japanese Patent Publication No. Alginic acid may be any of alginic acid and salts such as sodium alginate. Examples of the gellable organic medium include alcohols such as methanol, ethanol, propenol, isopropanol, butanol, ethylene glycol and benzyl alcohol; ketones such as acetone and methyl ethyl ketone; amides such as formamide and dimethylformamide; hexane and heptane Saturated hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene and nitrobenzene; halogenated hydrocarbons such as chloroform, carbon tetrachloride and methylene chloride; tetrahydrofuran;
Ethers such as dioxane and diethyl ether; fats and oils such as olive oil; dimethyl sulfoxide, acetonitrile and the like. Mixtures of two or more of these are also listed as gellable organic media.

Also, a mixture of water and the above organic medium can be gelled. For various organic media, the amount of the neutralized substance added is 0.
1% by weight or more, preferably 0.5 to 50% by weight may be added, and the hardness of the gel can be freely adjusted by the added amount.

Examples of the amine represented by the general formula I include dipropylamine, dibutylamine, triethylamine, hexylamine, diallylamine, triallylamine, and
-Diethylaminopropanol, triethanolamine, trioctylamine, N-methylpiperidinebenzylamine, dibenzylamine, phenylcyclohexylamine and the like.

On the other hand, examples of the quaternary ammonium salt represented by the general formula II include N-benzylpyridinium chloride and N-benzylpyridinium chloride.
Examples thereof include hydroxyethylpyridinium chloride, tetrabutylammonium sulfate, trioctylmethylammonium chloride, benzyltrimethylammonium chloride, and N-lauryl-4-picolium chloride.

Neutralization is possible in any of water, organic medium and water-organic medium. It may be neutralized in an organic medium to be gelled, and then gelled. Neutralization degree is 0.01-1.
A range of 0 is used.

The following metal salts can be used as the divalent or higher polyvalent metal ion used for gelation.

Calcium chloride, calcium nitrate, calcium acetate,
Calcium salts such as calcium benzoate, calcium citrate, calcium lactate, calcium carbonate, calcium biphosphate, calcium hypophosphite, calcium hydrogen phosphate, monobasic calcium phosphate, dibasic calcium phosphate, tertiary calcium phosphate, calcium pyrophosphate, barium chloride, nitric acid Barium salts such as barium, barium acetate, barium carbonate, barium hydrogen phosphate, barium diphosphate, magnesium chloride, magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium stearate, magnesium citrate, magnesium carbonate, primary phosphoric acid Magnesium, magnesium salts such as dibasic magnesium phosphate and tribasic magnesium phosphate, strontium chloride, strontium acetate, strontium citrate, strontium nitrate, charcoal Strontium salts such as strontium, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum sulfate, aluminum stearate, aluminum monophosphate, aluminum phosphate such as aluminum phosphate, tertiary aluminum phosphate, ferric chloride, nitric acid Ferric, ferric acetate, ferric ammonium citrate, iron carbonate, ferric ammonium sulfate, ferric sulfate,
Examples thereof include iron salts such as ferrous lactate, ferrous phosphate, ferric phosphate, and ferric pyrophosphate, and preferably calcium salts such as calcium chloride.

The above salt may be directly added to and mixed with the mixture, or may be mixed with the neutralized product and the organic medium at the same time. At this time, by adding a substance having a chelating effect such as sodium tripolyphosphate or sodium citrate, the time until gel formation can be lengthened and the workability can be improved.

Further, an aqueous solution of the above salt or a solution dissolved in a solvent may be added to the mixture or sprayed to form a gel. The mixture can be gelled by dropping the mixture into the above liquid.

The amount of the polyvalent metal ion to be added varies depending on the type and amount of the neutralized product and the type of the medium. If the amount is too small, the gel is too weak.If the amount is too large, all of the neutralized amine or quaternary ammonium is replaced by the polyvalent metal ion and becomes insoluble in the organic liquid, and the gel is formed. And the organic liquid is separated.

Examples of the acid that can be used in the present invention include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as acetic acid, citric acid, and lactic acid. The mixture can be added dropwise to the acid diluent described above or sprayed and gelled. Further, a substance which becomes soluble and becomes acidic such as gluconolactone can be added to the mixture and mixed.

(Function) The present invention is configured as described above, and can gel an organic liquid.

(Example) Example 1 5 g of alginic acid was dispersed in 25 g of water, neutralized with dibutylamine to a degree of neutralization of 0.9, then flowed on a tray, and dried at 60 ° C. in vacuum. This was pulverized, and 1 g of the powder was dispersed and dissolved in 100 ml of methanol. This mixture was dropped into a 0.1 M aqueous solution of calcium chloride, gelled, and quickly separated from the liquid. A spherical gel was obtained.

Example 2 The mixture produced in the same manner as in Example 1 was dropped into 0.1N hydrochloric acid to cause gelation, and a spherical gel was obtained, which was quickly separated from the liquid.

Example 3 In a 100 ml beaker, 2 g of the powder produced in the same manner as in Example 1, 0.1 g of calcium citrate and 0.1 g of sodium tripolyphosphate were added to 80 ml of ethylene glycol and 20 ml of water, and vigorously stirred and mixed. Let stand for minutes. When the beaker was inverted and the contents were removed, a clean beaker-type gel was formed.

Example 4 In a 100 ml beaker, 2 g of the powder produced in the same manner as in Example 1 and 1 g of gluconolactone were added to ethylene glycol 8
0 ml and 20 ml of water were added, mixed vigorously with stirring, and left for 1 hour. When the beaker was inverted and the contents were removed, a clean beaker-type gel was formed.

Example 5 3 g of sodium alginate was added with acetone: benzene ratio
The mixture was dispersed in a mixed solvent of 1: 1 and neutralized by adding 3 g of dibenzylamine. The neutralized product swelled and dissolved in the solvent. This mixture was dropped into a 0.1 M calcium chloride aqueous solution to obtain a spherical gel.

Example 6 50 g of alginic acid was dispersed in 100 g of water, neutralized with tetrabutylammonium sulfate to a degree of neutralization of 0.5, and then drum-dried. 1 g of the obtained powder was dispersed and dissolved in 100 ml of dimethyl sulfoxide. Add this mixture to 0.
It was dropped into 1N hydrochloric acid to obtain a spherical gel.

Example 7 The same operation as in Example 1 was performed except that alginic acid was changed to pectin. A spherical gel was obtained in the same manner as in Example 1.

Example 8 The same operation as in Example 1 was carried out except that alginic acid was changed to Azotobacter vinelandie gum. Example 1
A spherical gel was obtained in the same manner as in 1.

(Effect) Since the present invention is configured as described above, it can be obtained without heating the organic liquid gel. For this reason, fragrances,
When the active ingredients such as insect repellents and antibacterial components are dissolved and used for deodorants, insect repellents, and antibacterial agents, the above active ingredients do not have to be adversely affected by heating.

Also, a gel can be formed in any type. Therefore, a product having excellent design can be manufactured.

Also, by adding excess polyvalent metal ions to the formed gel, the gel can be arbitrarily broken and the organic liquid can be separated.If the gel formation fails, the organic liquid can be recovered without wasting. Available.

Claims (2)

(57) [Claims] Claims: 1. An alginic acid, pectin or Azotobacter vinelandie gum, Wherein R ₁ , R ₂ and R ₃ are each hydrogen, alkyl, alkylene, phenyl, benzyl or hydroxyalkyl, and the total number of carbon atoms contained in R ₁ , R ₂ and R ₃ is 6
~ 36] and / or [Wherein R ₄ , R ₅ , R ₆ and R ₇ are all hydrogen, alkyl,
Alkylene, phenyl, benzyl or hydroxyalkyl, or R ₄ , R ₅ and R ₆ , together with the nitrogen to which they are attached, form a pyridinium or picolium ring;
R ₇ is alkyl, alkylene, phenyl, benzyl or hydroxyalkyl, and the total number of carbon atoms contained in R ₄ , R ₅ , R ₆ and R ₇ is from 8 to 48. X is a halogen or an anion of an acid], and a mixture obtained by adding a substance obtained by neutralization with a quaternary ammonium salt represented by A method for producing an organic liquid gel, which comprises gelling with metal ions. 2. A method for producing an organic liquid gel, characterized in that a substance obtained by adding the substance according to claim 1 to an organic medium which is liquid at room temperature and then mixing the mixture is acidified to form a gel.