JP2700377B2 - Gelling or solidifying agent for organic liquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an esterification product which gels or solidifies an organic liquid which is liquid at room temperature (when the organic liquid is alcohol, a monohydric alcohol having 4 or more carbon atoms). The gelling or solidifying agent of the present invention is an electric, electronic, magnetic device, machine, automobile, daily necessities, dyes, inks, paints, cosmetics, toiletries, pharmaceuticals, agriculture, fisheries, feed, food, paper, textiles, Leather, resin, polymer,
It can be used in the field of processing rubber and metal.

[0002]

2. Description of the Related Art Heretofore, as a substance having a function of solidifying oils and fats, hydrocarbons or solvents in a gel state, (1) metal soaps of higher fatty acids, 12-hydroxystearic acid, dibenzylidene sorbitol, dibenzylidene xylitol , N-acylamino acid derivatives, (2) dextrin fatty acid esters, acrylic acid polymers and the like are known.

[0003] Among them, the type (1) is one in which the whole is solidified into a gel by mainly dissolving or dispersing it in liquid esters or fats and oils and cooling.
Such a gelling agent has a melting point of 12-hydroxystearic acid: 80 ° C., a melting point of dibenzylidene sorbitol: 16
The melting point is generally high, such as 0 ° C., so that when solidifying so-called organic liquids such as fats and oils, a heating operation is performed in advance to melt the gelling agent itself, or the gelling agent and the fats and oils, for example. Needed to be melted. In addition, this type of gelling agent dissolves in organic solvents such as isoparaffin, hexane, and butanol that are industrially used as a low boiling point solvent, and solidifies only after adding a very large amount of gelling agent. However, it was not suitable for solidifying such an organic solvent.

On the other hand, the gelling agent of the type (2) includes
For example, Acrylic CA manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. is an acrylic acid-based polymer that solidifies most hydrocarbon compounds, but ester compounds, especially higher fatty acids having a large alkyl group chain length. It does not exert the effect of gel-like solidification on fats and oils having a residue.
In addition, while this type (1) melts and solidifies the gelling agent and the object to be gelled, the type (1) absorbs the object to be gelled in the gelling agent and solidifies. Therefore, it was difficult to obtain a uniform gel.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for adding a small amount of organic liquids such as alcohols (monohydric alcohols having 4 or more carbon atoms), esters and hydrocarbons which are liquid at room temperature. It is an object of the present invention to provide a gelling or solidifying agent which forms a uniform, smooth solid, preferably a gel-like solid.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, have found that a gel or solid can be obtained by using a specific esterification product. As a result, the present invention has been completed. That is, the present invention relates to glycerin or a condensate thereof (hereinafter, referred to as glycerin), a linear saturated fatty acid having 2 to 28 carbon atoms (hereinafter, simply referred to as a fatty acid), and 12 to 28 carbon atoms.
An organic liquid consisting of an esterification product with an aliphatic saturated dibasic acid (hereinafter, simply referred to as a dibasic acid)
Is a gelling or solidifying agent.

[0007] As an essential raw material component for producing the esterification product of the present invention, there is glycerin and the like. Among them, the glycerin condensate is an average degree of polymerization of 2 or more, preferably 2 to 10 polyglycerin, diglycerin,
Examples include triglycerin, tetraglycerin, hexaglycerin, decaglycerin and the like, and these can be used alone or as a mixture including glycerin.

Next, the fatty acid, that is, the monobasic acid, is required to be a linear saturated fatty acid having 2 to 28 carbon atoms.
Acetic acid, propionic acid, as specific linear saturated fatty acids,
Caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 10-hydroxystearic acid, 10-ketostearic acid, 12-
Examples thereof include hydroxystearic acid, arachiic acid, hebenic acid, and montanic acid. In the present invention, these may be used alone or in a mixture.

The dibasic acid has 12 to 2 carbon atoms.
8 need to be aliphatically saturated. Unsaturated or esterified products of dibasic acids having less than 12 carbon atoms have reduced gelling ability, and dibasic acids having more than 28 carbon atoms are difficult to obtain as industrial raw materials. Therefore, in the present invention, dodecadicarboxylic acid, tetradecadicarboxylic acid, eicosadicarboxylic acid, docosacosadicarboxylic acid,
Dibasic acids such as tetracosadicarboxylic acid, hexacosadicarboxylic acid, octacosadicarboxylic acid and the like may be used alone or as a mixture. Of these, octacosadicarboxylic acid can be easily obtained from oil seeds such as sesame seeds. It can be separated and is suitable. Linear saturated with 2 to 28 carbon atoms
Ratio of fatty acid and aliphatic saturated dibasic acid having 12 to 28 carbon atoms
Is suitably 1 (mol): 0.1 to 0.5 (mol)
You. Glycerin or a glycerin condensate and the fat
The ratio of transesterification with the total amount of acid is 1 mol of the former.
1 to 5 moles is suitable for this. Perform esterification reaction
The catalyst can be either enzyme or chemical catalyst.
No.

The above-mentioned fatty acid and dibasic acid can be used in an appropriate combination in the present invention. Particularly preferred combination is that when the dibasic acid has less than 20 carbon atoms, the fatty acid has 22 to 22 carbon atoms. When the dibasic acid has 20 carbon atoms, the fatty acid has 18 to 28 carbon atoms, and when the dibasic acid has 28 carbon atoms, the fatty acid has 2 carbon atoms.
28.

In order to obtain the esterification product of the present invention using the above-mentioned raw materials, any of the following methods may be employed. That is, a fatty acid and a dibasic acid are simultaneously subjected to oligoesterification, such as glycerin, or a fatty acid is first esterified with glycerin or the like, and further subjected to an oligoesterification reaction or transesterification reaction with a dibasic acid, or with glycerin or the like. The dibasic acid is first subjected to oligoesterification, which is then esterified with a fatty acid.

The esterification reaction is carried out in the presence or absence of an acid, alkali or metal catalyst, preferably in an organic solvent or / and a gas inert to the reaction at 100 to 240 ° C.
For several hours to 20 hours to remove by-produced water. The transesterification is carried out at 20 to 140 ° C. for several tens to several tens of hours using a catalyst such as a metal alcoholate or a lipase. The progress of the reaction can be evaluated by measuring the acid value in the system or the composition of the acid component in a free state, and the end point of the reaction may be determined based on this. Esterification or transesterification reactants are fatty acids, such as unreacted glycerin,
May contain dibasic acids, other by-product fatty acids,
Since low-molecular-weight glycerides and the like may be mixed, these may be separated and removed if necessary by known methods such as washing with water and alkali deacidification, and, if necessary, subjected to decolorization and deodorization treatment for purification.

The esterification product of the present invention thus obtained is a mixture in which a fatty acid such as glycerin and a dibasic acid are oligoesterified linearly and / or in a network,
The melting point is about 50-80 ° C. The degree of esterification when a glycerin condensate having a high degree of polymerization is used is not necessarily required to be perfect (full ester). For example, in the case of pentaglycerin to decaglycerin, an esterification degree of at least half of these hydroxyl groups is required. You only have to. If the degree of esterification is small, the gelling ability and the solidifying ability for the organic liquid targeted by the present invention are inferior. The hydroxyl value of the esterification product of the present invention can be easily calculated and adjusted from the mixing ratio of the raw materials, that is, the reaction molar equivalent of glycerin and the like, and the reaction molar equivalent of fatty acid and dibasic acid. It can also be controlled by the reaction temperature, reaction time, and whether or not the reaction product is purified.

The esterification product of the present invention can be used alone or as a mixture to gel or solidify an organic liquid. Here, the organic liquid refers to an organic compound that exhibits a liquid at normal temperature, butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, butylene glycol monoethyl ether, 2-ethylhexanol, nonanol, 2-heptylundecanol, Linear or branched, saturated or unsaturated monohydric alcohols having 4 or more carbon atoms such as 2-octyldodecanol, oleyl alcohol, acetic acid, propionic acid, caproic acid, caprylic acid, oleic acid, various isostearic acids Fatty acids such as isopropyl myristate, octyldodecyl myristate, glyceride tri-2-ethylhexanoate, mixed-chain fatty acid glycerides, esters such as ethyl acetate, soybean oil, rapeseed oil, sunflower oil, safflower oil, cottonseed oil, olive oil , Sesame oil, a Two oils, fats and oils and their partial decomposition products of such fish oil, dimethyl ether, diethyl ether, ethers such as petroleum ether, pentane, hexane, heptane, isooctane, paraffin,
Hydrocarbons such as isoparaffin are preferred. In addition, a monohydric alcohol having 3 or less carbon atoms is hard to be solidified by the gelling or solidifying agent of the present invention, and is not suitable as an object. In addition, silicone oil, kerosene, and the like that are liquid at room temperature can also be used.

The esterified product of the present invention is added to the above-mentioned organic liquid in an amount of 1 to 10% by weight, preferably 3 to 5% by weight. If the mixture is allowed to stand at room temperature or after cooling to about 5 ° C., a uniform, viscous, smooth gel or solid, or a gel solid can be obtained. It maintains a uniform state in the entire system at room temperature without generating a liquid portion. The gelling or solidifying agent of the present invention may be used alone or as a mixture of the esterification products,
Unless it deviates from the object of the present invention, an appropriate amount of conventionally known waxes such as carnauba wax, candelilla wax, montan wax, microcrystalline wax, paraffin wax and the like, as well as palmitic acid, stearic acid, behenic acid, etc. You may mix | blend the solid fat which consists of glyceride. It may be used in combination with the known gelling agent.

[0016]

EXAMPLES In the following Synthesis Examples and Examples,% is based on weight. Synthesis Example 1 92 g (1.0 mol) of glycerin, 569 g (2.0 mol) of stearic acid, and 171 g (0 mol) of eicosadicarboxylic acid were placed in a four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a water separator. .5 mol), and p was used as a catalyst.
-Toluenesulfonic acid 0.1%, xylene 5% as a refluxing solvent is added, and in a nitrogen gas stream at 180 to 230 ° C,
The esterification reaction was carried out for 10 hours until no decrease in the acid value was observed. After completion of the reaction, the product was washed with water, decolorized with activated carbon, and deodorized by blowing steam to obtain 663 g of an esterification product of the present invention (sample symbol: A). It has an acid value of 2.0, a hydroxyl value of 7.0 and a melting point of 58-6.
It was 0 ° C.

Synthesis Example 2 17 g (0.05 mol) of eicosadicarboxylic acid was added to 75 g (0.1 mol) of decaglycerin having an average degree of polymerization of 10 and 170 g (0.5 mol) of behenic acid. Similarly, an esterification reaction was carried out, followed by purification treatment to obtain 201 g of an esterification product of the present invention (sample symbol: B).
It has an acid value of 0.5, a hydroxyl value of 134 and a melting point of 5
2-57 ° C.

Synthesis Example 3 47 g (0.1 mol) of tricaprylin obtained by esterifying glycerin and caprylic acid by a conventional method, and the method described in Japanese Patent Application No. 5-230734 filed earlier by the present applicant.
That is, 23 g of octacosadicarboxylic acid (0.0 g) obtained by dispersing and dissolving the sesame crude oil precipitate (ori) in ethanol, and cooling to separate the precipitated insoluble matter.
Lipase (Meito Sangyo Co., Ltd.)
Lipase QL) was added in an amount of 1% based on the raw material, and while stirring at 120 ° C., the content of by-produced caprylic acid was analyzed by gas chromatography.
The transesterification was performed for 2 hours. After completion of the reaction, the reaction product was purified in the same manner as in Synthesis Example 1 to obtain 59 g of the esterification product of the present invention (sample symbol: C). This had an acid value of 6.0, a hydroxyl value of 5.0 and a melting point of 58 to 64 ° C.

Synthesis Example 4 (Comparative Synthesis Example 1) Esterification product (sample code: D) was treated in the same manner as in Synthesis Example 1 except that 171 g of eicosadicarboxylic acid was replaced with 59 g (0.5 mol) of succinic acid. And).
It has an acid value of 6.3, a hydroxyl value of 8.5 and a melting point of 5
3-56 ° C.

Example 1 Esterification products obtained in Synthesis Examples 1 to 4 (sample symbols: A to
D) The gelling ability of 12-hydroxystearic acid and carnauba wax on soybean oil was tested. Table 1 shows the results. The test method was as follows. A soybean oil and 3% of each sample were taken in a beaker, heated to 80 ° C. with stirring, melted, left to cool at room temperature for 1 hour, and then obtained gel state Was observed. The evaluation was ◎: hard, uniform and smooth gel-like substance, 物: uniform and smooth gel-like substance, Δ: partially solid-liquid separated, ×: non-solidified.

[0021]

[Table 1]

From Table 1, it can be seen that the esterification products of the present invention (sample symbols: A to C) are homogeneously added to soybean oil in spite of adding a smaller amount than conventional gelling agents and waxes. It was found that a highly gelled solid was formed.
Further, when these were stored at ordinary temperature for one month, it was confirmed that those to which the esterification product of the present invention was added maintained a uniform state and were stable. Although 12-hydroxystearic acid solidifies soybean oil, the solid was hard and had a very ragged feel, and once crushed, the original solid was not regenerated. On the other hand, the esterification product of the present invention was extremely smooth and viscous, and easily returned to the original gel state even when crushed. Sample D was inferior in gelling ability.

Example 2 The ability of the esterification product (sample number: A) obtained in Synthesis Example 1 to gel or solidify various organic liquids was examined in the same manner as in Example 1. Table 2 shows the results. The evaluation code is based on the same reference as in the first embodiment. From Table 2, it can be seen that the esterification product of the present invention has a solidifying ability in a small amount with respect to various liquids, and the solid has a uniform and smooth viscous property. It turned out to be effective.

[0024]

[Table 2]

Example 3 Various esterification products (sample symbols: 1 to 12) were synthesized according to the method of Synthesis Example 1, and 3% was added to glyceryl triisooctanoate to examine the gelling or solidifying ability. Table 3 shows the results. The evaluation code is based on the same reference as in the first embodiment. Table 3 reveals that a preferred gelling or solidifying agent can be prepared by appropriately combining fatty acids, dibasic acids and polyhydric alcohols. Further, polyglycerin could be sufficiently solidified by esterifying at least half of the hydroxyl groups.

[0026]

[Table 3] Note 1) The carbon number is indicated by C value. For example, fatty acid C
22 is hebenic acid and C20 of dibasic acid is eicosadicarboxylic acid. 2) Same as sample symbol A. 3) Same as sample symbol B. 4) Same as sample symbol C. 5) Same as sample symbol D. 6) TMP: trimethylolpropane 7) PE: pentaerythritol

[0027]

According to the present invention, an esterified product of glycerin or a condensate thereof, a linear saturated fatty acid having 2 to 28 carbon atoms, and an aliphatic saturated dibasic acid having 12 to 28 carbon atoms is obtained. It is obtained and is uniform and smooth only by adding a small amount of it to esters, oils and fats, hydrocarbons, polar and non-polar organic solvents, etc. (alcohols are monohydric alcohols having 4 or more carbon atoms) which are liquid at room temperature. To form a viscous and stable gelled or solidified product. Therefore, the esterification product of the present invention can be used as a gelling or solidifying agent of an organic liquid having a lower melting point than that of the conventional one, and having an excellent gelling ability. It can be effectively used as a treating agent, a lubricant, a release agent, an adhesive, a binder, a sealing agent, a lubricant, a coating agent, a coating agent, a volatile component controlling agent, and the like.

Claims (5)

(57) [Claims] 1. A glycerin or glycerin condensate having an average degree of polymerization of 2 to 10 and a linear saturated fatty acid having 2 to 28 carbon atoms.
Aliphatic saturated dibasic acid having 12 to 28 carbon atoms per mole
0.1 to 0.5 mol, the glycerin or the same condensation
Gelation or solidification of an organic liquid composed of an esterified product having a molar ratio of the total amount of the product and the fatty acid of 1: 1 to 5 (however, when the organic liquid is an alcohol, a monohydric alcohol having 4 or more carbon atoms) Agent. 2. The gelling or solidifying agent according to claim 1, wherein when the aliphatic saturated dibasic acid has less than 20 carbon atoms, the linear saturated fatty acid has 22 to 28 carbon atoms. 3. The gelling or solidifying agent according to claim 1, wherein when the aliphatic saturated dibasic acid has 20 carbon atoms, the linear saturated fatty acid has 18 to 28 carbon atoms. 4. The gelling or solidifying agent according to claim 1, wherein when the aliphatic saturated dibasic acid has 28 carbon atoms, the linear saturated fatty acid has 2 to 28 carbon atoms. 5. The organic liquid (where the monohydric alcohol having 4 or more carbon atoms when the organic liquid is alcohol) is an alcohol, fatty acid, ester, ether or hydrocarbon which is liquid at room temperature. Or the gelling or solidifying agent according to 4.