JP2646422B2 - Gelling or solidifying agent for organic liquids - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transesterification product which gels or solidifies an organic substance which is liquid at ordinary temperature.
The gelling or solidifying agent of the present invention is an electric, electronic, magnetic device,
Used in machinery, automobiles, daily necessities, dyes, inks, paints, cosmetics, toiletries, pharmaceuticals, agriculture, fisheries, feed, food, and paper, textiles, leather, resins, polymers, rubber, metals, etc. it can.

[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 ethanol that are industrially used as low-boiling solvents, and solidifies only when an extremely large amount of gelling agent is added. 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 example of an acrylic acid polymer, which solidifies most hydrocarbon compounds, but is an ester compound, especially a higher fatty acid 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 alcohols, esters and the like 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 and smooth solid substance, preferably a gel-like solidified substance, by adding a small amount of an organic liquid such as hydrocarbons.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and as a result, it has been found that a gel or solid can be obtained by using a specific transesterification reaction product. And completed the present invention. That is, the present invention relates to a triglyceride having a linear saturated fatty acid having 2 to 28 carbon atoms (hereinafter, simply referred to as fatty acid) as a constituent fatty acid, and an aliphatic saturated dibasic acid having 20 to 28 carbon atoms (hereinafter, simply referred to as dibasic acid). Said transesterification reaction product containing at least a partial transesterification reaction product obtained by subjecting a lower alcohol diester to a transesterification reaction and leaving one of ester bonds between the dibasic acid and the lower alcohol. It is a gelling or solidifying agent for an organic liquid as an active ingredient.

One of the essential raw materials for producing the transesterification product of the present invention is a triglyceride of a specific fatty acid, that is, a triglyceride composed of a linear saturated fatty acid having 2 to 28 carbon atoms. Specific straight-chain saturated fatty acids include acetic acid, propionic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 10-hydroxystearic acid, 10-ketostearic acid and 12-hydroxy. Stearic acid, arachiic acid, behenic acid, montanic acid and the like can be mentioned as examples. In the present invention, these may be used alone or as a mixture of triglycerides.

[0008] Such triglycerides can be obtained by an esterification reaction with glycerin by a conventional method, and those derived from natural products such as soybean oil, rapeseed oil, olive oil, cottonseed oil, linseed oil, castor oil, coconut oil, palm oil, It may be obtained by subjecting fish oil, beef tallow, lard, etc. to a treatment such as hydrogenation and fractionation. Medium-chain saturated fatty acid triglycerides, so-called MCTs, are suitable for the present invention. In addition, unsaturated fatty acids, side chain fatty acids, diglycerides, monoglycerides, and the like as glyceride components may be contained in a small amount.

The lower alcohol diester of dibasic acid, which is another raw material component, has 20 carbon atoms.
-28, preferably 22-28 aliphatic saturated dibasic acids;
It needs to be a diester with a linear or branched alcohol having preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. If the dibasic acid is unsaturated or has 20 carbon atoms
The transesterification product of less than 10% has a 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, dibasic acids such as eicosadicarboxylic acid, docosacosadicarboxylic acid, tetracosadicarboxylic acid, hexacosadicarboxylic acid, and octacosadicarboxylic acid may be used alone or as a mixture. Acids are preferred because they can be easily isolated from oil seeds, including sesame seeds. The dibasic acid is used by diesterifying it with a lower alcohol such as methanol, ethanol, propanol, isopropanol or butanol by a conventional method.

The above-mentioned triglyceride constituent fatty acid and dibasic acid can be used in an appropriate combination in the present invention, and a particularly preferred combination is a triglyceride constituent fatty acid when the dibasic acid has 20 carbon atoms. The carbon number is 18 to 28, and when the dibasic acid has 28 carbon atoms, the constituent fatty acid of triglyceride has 2 to 28 carbon atoms.

In order to obtain the transesterification reaction product of the present invention using the above-mentioned raw materials, any of the following methods may be employed. That is, triglyceride and dibasic acid diester are mixed at a compounding ratio of less than 10 mol, preferably less than 2 mol of triglyceride to 1 mol of dibasic acid diester, as described later, to form a metal such as sodium methoxide and lithium ethoxide. Either a chemical transesterification reaction is carried out using alcoholate as a catalyst or an enzymatic transesterification reaction is carried out using lipase as a catalyst.

Among them, the transesterification method using lipase is based on the difference in specificity with respect to the position of glyceride.
It is classified into a random type at the 3-position and a selective type at the 1,3-position. In the present invention, a transesterification method using a lipase having selectivity at the 1,3-position is preferable. As this type of selective lipase, those derived from microorganisms are most convenient, and Rhizopus delemar, Mucor-Mehi (Mu)
cor miehei), Aspergillus niger
and lipase derived from Alcaligenes sp., such as lipase QL, manufactured by Meito Sangyo Co., Ltd.

In the transesterification reaction, for example, when a metal alcoholate is used, the raw material is converted to a substantially anhydrous state, and
The mixture may be stirred at about 140 ° C. for about 0.5 to 5 hours, and in the case of using lipase, in the presence or absence of a solvent inert to the reaction in the presence of substantially anhydrous or trace amount of water. The stirring may be preferably performed at 20 to 130 ° C. for about 10 minutes to 100 hours without using any solvent. Since the lipase QL exhibits transesterification activity at a high temperature of about 80 to 130 ° C., it can be used very conveniently in a reaction using a raw material having a high melting point as in the present invention.

The course of the reaction can be evaluated by measuring the content of the lower alcohol ester of the by-produced fatty acid in the reaction system, for example, by gas chromatography, and the end point of the reaction may be determined. . Unreacted raw material components may remain in the transesterification reaction product, and since lower alcohol esters of by-produced fatty acids are mixed with them, they are washed with water, alkali deacidification, solvent separation, vacuum distillation, adsorbent, It is separated and removed by a known method such as a molecular sieve, and if necessary, is subjected to decolorization and deodorization treatment for purification.

The transesterification reaction product of the present invention thus obtained mainly comprises a component obtained by transesterification of the raw material triglyceride and dibasic acid diester at a molar ratio of 1: 1, 1: 2 and 2: 1. The mixture is a mixture having a melting point of about 40 to 90 ° C. containing a linear or / and network-like mono- or oligoesterified component, and an ester bond of one of the dibasic acid diesters. Only the transesterification is performed, and the other is left as a lower alcohol ester, that is, contains at least a partially transesterified component. In order to achieve such a composition, the raw material mixing ratio of the transesterification reaction is set to less than 10 moles, preferably less than 2 moles of triglyceride per mole of diester dibasic acid. The transesterification reaction product that does not contain the partial transesterification reaction component does not easily gel or solidify the organic liquid.

It should be noted that the ester bond between the dibasic acid and the lower alcohol remained in the transesterification product of the present invention was determined by removing the unreacted products and by-products by the above purification treatment. Can be carried out, for example, by hydrolyzing hydrochloric acid, and analyzing the lower alcohol generated in the decomposition product by gas chromatography.

The transesterification product of the present invention can be used alone or as a mixture to gel or solidify an organic liquid. Here, the organic liquid substance refers to an organic compound that exhibits a liquid state at normal temperature, and specific examples are shown below, but the present invention is not limited thereto. First, methanol, ethanol, isopropanol, butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, butylene glycol monoethyl ether, 2-ethylhexanol, nonanol, 2-heptylundecanol, 2-octyldodecanol, oleyl alcohol, ethylene For linear or side chain, saturated or unsaturated alcohols such as glycol, dipropylene glycol and glycerin, and fatty acids such as acetic acid, propionic acid, caproic acid, caprylic acid, oleic acid and various isostearic acids. be able to.

Also, esters such as isopropyl myristate, octyldodecyl myristate, glyceride tri-2-ethylhexanoate, glyceride of mixed medium chain fatty acid and ethyl acetate, soybean oil, rapeseed oil, sunflower oil, safflower oil, cottonseed oil, olive oil , Sesame oil, linseed oil, oils and fats such as fish oil and their partially decomposed products, dimethyl ether, diethyl ether, ethers such as petroleum ether,
Hydrocarbons such as pentane, hexane, heptane, isooctane, paraffin, isoparaffin are preferred. In addition, silicone oil, kerosene, and the like that are liquid at room temperature can also be used.

The transesterification product of the present invention is used in an amount of 0.1 to 10% by weight, preferably 0.1 to 10% by weight, based on the organic liquid.
Add 5 to 3% by weight, if necessary, heat to about 80 ° C and melt, then stir gently, cool at room temperature or cool to about 5 ° C and let stand to obtain a uniform and viscous A certain smooth gel or solid, or gel solid is obtained. It maintains a uniform state throughout the system without generating liquid parts at temperatures below about 40 ° C.

The gelling or solidifying agent of the present invention may be used alone or as a mixture of the above-mentioned transesterification reaction products. However, unless it deviates from the object of the present invention, a suitable amount of conventionally known waxes such as Carnauba wax, candelilla wax, montan wax, microcrystalline wax, paraffin wax and the like, as well as solid fats composed of glycerides such as palmitic acid, stearic acid and behenic acid may be blended. It may be used in combination with the known gelling agent.

[0021]

EXAMPLES In the following Synthesis Examples and Examples,% is based on weight. Synthesis Example 1 In a flask equipped with a stirrer and a thermometer, medium-chain saturated fatty acid triglyceride (trade name: OD, manufactured by Nisshin Oil Co., Ltd.)
O, constituent fatty acids are caprylic acid 75%, capric acid 25
%) 49.4 g (0.1 mol) and the method described in Japanese Patent Application No. 5-230734 previously filed by the present applicant, that is, a precipitate (ori) of sesame crude oil is dispersed and dissolved in ethanol, 49. A dimethyl ester of octacosadicarboxylic acid obtained by separating insolubles precipitated upon cooling.
6 g (0.1 mol) of a raw material, 1% of a lipase derived from Alcaligenes sp. (Manufactured by Meito Sangyo Co., Ltd., Lipase QL) was added, and 90 g of the lipase was added.
The content of the by-produced fatty acid methyl ester was analyzed by gas chromatography while stirring at ℃, and transesterification was carried out for 72 hours until the increase was not observed.
After completion of the reaction, the transesterification reaction product is purified by silica gel column chromatography and vacuum distillation, and the transesterification reaction product of the present invention (sample symbol: A) 8
2.5 g were obtained. It has an acid value of 4.7 and a hydroxyl value of 4.7.
3.4, melting point: 57-64 ° C.

The transesterification product is dissolved in a large amount of tetrahydrofuran and subjected to high-performance liquid chromatography using a column packed with a polystyrene / divinylbenzene polymer gel (PL-gel, manufactured by Polymer Laboratories). The components were subjected to transesterification at a molar ratio of 1: 1, 1: 2 and 2: 1 by molar ratio between the medium-chain saturated fatty acid triglyceride and octacosadicarboxylic acid dimethyl ester when the composition was quantified and the composition was quantified. However, the ratio was about 2: 3: 2, and these three components accounted for 83% of the whole. The remaining components were considered to be those in which both raw materials repeated the transesterification reaction. Further, the transesterification product was hydrolyzed with 1N-hydrochloric acid by a conventional method, and the decomposed product was subjected to gas chromatography to detect methanol. This confirmed that methyl ester remained in the transesterification product.

Synthesis Example 2 Behenic acid triglyceride 1 synthesized by ester in a conventional manner
14 g (0.1 mol) and 37 g (0.1 mol) of dimethyl ester of eicosadicarboxylic acid were subjected to transesterification in the same manner as in Synthesis Example 1, and the reaction product was subjected to silica gel column chromatography to remove impurities (unreacted). The raw material and by-products) were separated and removed to obtain 92.4 g of the transesterification reaction product of the present invention (sample symbol: B). It has an acid value of 3.2, a hydroxyl value of 2.9 and a melting point of 57 to 61 ° C.
Met.

Synthesis Example 3 In Synthesis Example 1, 1% of lipase was replaced with 0.5% of sodium methoxide, and the mixture was reduced under reduced pressure at 80 ° C. for 30 minutes.
A chemical random transesterification reaction was performed, and the reaction product was similarly purified to obtain 79.8 g of a transesterification reaction product of the present invention (sample symbol: C). This had an acid value of 0.7, a hydroxyl value of 1.8 and a melting point of 58 to 64 ° C.

Synthetic Example 4 (Comparative Synthetic Example 1) In Synthetic Example 1, 109 g (0.5 mol) of triglyceride (trade name: triacetin, manufactured by Wako Pure Chemical Industries, Ltd.) using acetic acid as a raw material and tetradeca 142 g (0.5 mol) of methyl ester of dicarboxylic acid (trade name: tetradecandioic acid, manufactured by Nikko Kyoishi Co., Ltd.)
And subjected to a transesterification reaction in the same manner, followed by purification treatment, and a transesterification reaction product (sample symbol: D)
182 g were obtained. It has an acid value: 4.9 and a hydroxyl value:
It was 5.0 and liquid at normal temperature.

Example 1 The transesterification products (sample symbols: A to D) obtained in Synthesis Examples 1 to 4, 12-hydroxystearic acid and carnauba wax were tested for their ability to gel to soybean oil.
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. Evaluation: ◎: Hard,
Uniform and smooth gel, ○: uniform and smooth gel, Δ: partially solid-liquid separated, ×: non-solidified.

[0027]

[Table 1]

From Table 1, it can be seen that the transesterification products of the present invention (sample symbols: A to C) were added to soybean oil in a smaller amount than conventional gelling agents and waxes. It was found to form a uniform gelled solid. 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. In addition, 1
Although 2-hydroxystearic acid solidifies soybean oil, the solid is hard and has a very rough feel, and once crushed, the original solid was not regenerated. On the other hand, the transesterification reaction 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 Transesterification reaction product obtained in Synthesis Example 1 (sample code:
The gelling or solidifying ability of various organic liquids of A) 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,
The transesterification product of the present invention has a solidifying ability in a small amount with respect to various liquid substances, and the solid substance has a uniform, smooth and viscous property, and this property is suitable for a wide range of polar substances. It turned out to be effective.

[0030]

[Table 2]

Example 3 According to the method of Synthesis Example 1, various transesterification products (sample symbols: 1 to 11) were synthesized, and 3% was added to rapeseed oil 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 preferable gelling or solidifying agent can be prepared by appropriately combining the types of the constituent fatty acids and the dibasic acids of triglycerides.

[0032]

[Table 3] Note 1) The carbon number is indicated by C value. For example, fatty acid C
22 is hebenic acid and C28 of dibasic acid is octacosadicarboxylic acid. 2) Same as sample symbol A. 3) Same as sample symbol B. 4) Same as sample symbol D. 5) High erucic acid rape seed oil (Miyoshi Oil & Fat Co., Ltd.)
): Fatty acid composition: palmitic acid (4.7%), stearic acid (74.6%), arachiic acid (5.0%), behenic acid (15.7%)

[0033]

According to the present invention, the transesterification of a triglyceride containing a linear saturated fatty acid having 2 to 28 carbon atoms as a constituent fatty acid and a lower alcohol diester of an aliphatic saturated dibasic acid having 20 to 28 carbon atoms. A gelation comprising, as an active ingredient, a transesterification reaction product containing at least a partial transesterification reaction product which is a reaction product and at least one of ester bonds between the aliphatic saturated dibasic acid and the lower alcohol is left. Alternatively, a solidifying agent is obtained, and it is added to a small amount of esters, fats and oils, hydrocarbons, polar and non-polar organic solvents, etc., which are liquid at room temperature, and is uniform, smooth, viscous, and stable. Or a solidified product. Therefore, the transesterification reaction product of the present invention can be used as a gelling or solidifying agent for an organic liquid material having a lower melting point than the conventional one and having an excellent gelling ability. , Oil treatment agents, lubricants,
It can be effectively used as a release agent, adhesive, binder, sealing agent, lubricant, coating agent, coating agent, volatile component regulator, and the like.

Claims (5)

(57) [Claims] 1. A and triglyceride 9 moles to 0.3 mole of a constituent fatty linear saturated fatty acid having 2 to 28 carbon atoms,
1 mole of lower alcohol diester of aliphatic saturated dibasic acid having 20 to 28 carbon atoms and metal alcoholate or lipase
The transesterification reaction product containing at least a partial transesterification reaction product obtained by subjecting one of the ester bonds of the aliphatic saturated dibasic acid and the lower alcohol to a transesterification reaction obtained by using And a gelling or solidifying agent for an organic liquid material. 2. The gelling or solidifying agent according to claim 1, wherein the lower alcohol is a linear or branched alcohol having 1 to 4 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 gelling or solidifying agent according to claim 1, wherein the organic liquid is alcohol, fatty acid, ester, ether or hydrocarbon which is liquid at room temperature.