JP3535197B2 - Gelling or solidifying agent for alcohol - 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 for solidifying an alcohol which is liquid at room temperature (excluding 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 sundries, dye, ink, paint, cosmetics, toiletry,
It can be used in the fields of pharmaceuticals, agriculture, fisheries, feeds, foods, and processing fields such as paper, textiles, leather, resins, polymers, rubbers and metals.

[0002]

2. Description of the Related Art Conventionally, (1) higher fatty acid metal soap, 12-hydroxystearic acid, dibenzylidene sorbitol, dibenzylidene xylitol, which has a function of solidifying oils and fats, hydrocarbons, solvents and the like into a gel. , N-acyl amino acid derivatives, (2) dextrin fatty acid esters, acrylic acid-based polymers and the like are known.

Of these, the type (1) is one in which the whole is solidified into a gel state by uniformly 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
It has a high melting point such as 0 ° C. and is not suitable for solidifying short-chain alcohols. For example, as an organic solvent such as ethylene glycol, cellosolve, and ethanol, which are industrially widely used as low boiling point solvents, It can be solidified only by dissolving and adding an extremely large amount of a gelling agent or a solidifying agent, which is not suitable for solidifying such an organic solvent.

On the other hand, as the gelling agent of the type (2),
For example, as an acrylic acid-based polymer, there is "Aqualic CA" manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., which solidifies most hydrocarbon compounds, but gels solidification against ester compounds and alcohols. Does not have the effect. Moreover, in contrast to the type (1) of this type, which melts and solidifies the gelling agent and the substance to be gelled, the so-called gelled substance is absorbed in the gelling agent to be solidified. Therefore, it was difficult to obtain a uniform gel-like material.

[0005]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to form an alcohol which is liquid at room temperature (excluding monohydric alcohol having 4 or more carbon atoms) into a uniform, smooth, preferably gel-like solidified product. To provide a solidifying or solidifying agent.

[0006]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the inventors of the present invention have conducted extensive studies, and as a result, a gelled product or solidified product of the alcohol was obtained by using a specific esterification product. The present invention has been completed and the present invention has been completed. That is, the present invention, glycerin or average
Condensate of glycerin having a degree of polymerization of 2 or more (hereinafter, glycerin
Etc.) , a linear saturated fatty acid having 18 to 28 carbon atoms (hereinafter, simply referred to as fatty acid), and an aliphatic saturated dibasic acid having 20 to 28 carbon atoms (hereinafter, simply referred to as dibasic acid) Gelation of a liquid alcohol at room temperature (however, a monohydric alcohol having 4 or more carbon atoms is excluded), which is a product and is composed of a partially esterified product in which more than 1/2 of the hydroxyl groups such as glycerin remain. It is a solidifying agent.

First, glycerin and the like are essential raw material components for producing the esterification product of the present invention. In the present invention, the average degree of polymerization of the glycerin condensate is 2
The polyglycerin having an average degree of polymerization of 5 or more is preferable, and polyglycerin having a mean degree of polymerization of about 10 is more preferable. Specifically, diglycerin, triglycerin,
Pentaglycerin, hexaglycerin, decaglycerin, etc. can be illustrated, and these can be used individually or as a mixture.

Next, it is essential that the fatty acid, that is, the monobasic acid is a linear saturated fatty acid having 18 to 28 carbon atoms. As a specific linear saturated fatty acid, stearic acid, 1
Examples thereof include 0-hydroxystearic acid, 10-ketostearic acid, 12-hydroxystearic acid, arachidic acid, hepnic acid, montanic acid, etc. In the present invention, these may be used alone or in a mixture. . When the fatty acid has less than 18 carbon atoms,
The esterification product hardly solidifies the alcohol targeted by the present invention.

The dibasic acid has 20 to 2 carbon atoms.
It is necessary to have an aliphatic saturation of 8. Unsaturated products and esterification products of dibasic acids having less than 20 carbon atoms have poor 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, octacosadicarboxylic acid may be used alone or in combination, among which octacosadicarboxylic acid. Acids are preferable because they can be easily isolated from oil seeds such as sesame seeds.

The above raw materials can be used in an appropriate combination, and in order to obtain the esterification product of the present invention, any one of the following methods may be adopted. That is, a fatty acid and a dibasic acid such as glycerin are simultaneously subjected to an oligoesterification reaction, or glycerin and the like are first esterified with a fatty acid, and this is further subjected to an oligoesterification reaction or a 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 at 100 to 240 ° C. in the presence or absence of an acid, alkali or metal catalyst, preferably in an organic solvent or / and gas inert to the reaction.
The water produced as a by-product is removed for several hours to 20 hours. The transesterification reaction is carried out at 20 to 140 ° C. for several tens of minutes to several tens of hours using a catalyst such as metal alcoholate or 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 the free state, and the end point of the reaction may be determined by this. Esterification or transesterification reaction products include unreacted glycerin, fatty acids,
Fatty acids that may contain dibasic acids and are by-produced in addition to these,
Since low molecular weight glycerides and the like may be mixed, if necessary, they are separated and removed by a known method such as washing with water and alkaline deoxidation, and if necessary, they are decolorized and deodorized for purification.

The thus-obtained esterification product of the present invention is a mixture of a fatty acid and a dibasic acid such as glycerin, which are linearly and / or network-like oligoesterified,
The melting point is about 50-80 ° C. In addition, it is essential that the residual hydroxyl groups of the esterification product remain in excess of half of the hydroxyl groups of the starting material such as glycerin. When the residual hydroxyl group is less than half, the compatibility with the alcohol targeted by the present invention is poor, and a uniform and smooth gel-like solid is not obtained. The hydroxyl value of the esterification product of the present invention can be easily calculated and adjusted from the mixing ratio of raw materials, that is, the reaction molar equivalents of glycerin and the like and the reaction molar equivalents of fatty acid and dibasic acid. It can also be adjusted depending on the reaction temperature, the reaction time, and the presence or absence of purification of the reaction product.

The esterification product of the present invention can be used as a gelling agent or a solidifying agent for alcohols (excluding monohydric alcohols having 4 or more carbon atoms) which are liquid at room temperature, either alone or in combination. Examples of the alcohol targeted by the present invention include monohydric alcohols having 3 or less carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, and ethylene glycol monomethyl ether, as well as ethylene glycol, diethylene glycol, propylene glycol, and diethylene glycol. Propylene glycol, 1,3-
Butanediol, 1,4-butanediol, glyceryl monoacetate, glycerin, triglycerin, hexaglycerin, decaglycerin, and other polyhydric alcohols, monoethanolamine, dipropanolamine, triethanolamine, and other nitrogen-containing alcohols, and at room temperature Examples thereof include liquid fluorinated alcohols. A monohydric alcohol having 4 or more carbon atoms is not suitable as an object because it hardly solidifies by the gelling or solidifying agent of the present invention.

The esterification product of the present invention is added to the above alcohol in an amount of 3 to 15% by weight, preferably 5 to 7% by weight, and if necessary, heated to about 80 ° C. to melt and then gently stirred. At room temperature or by cooling to about 5 ° C. and allowing to stand, a uniform and viscous smooth gelled product or solidified product or gelled solidified product can be obtained. This product does not generate a liquid part at room temperature and the whole system maintains a uniform state. The gelling or solidifying agent of the present invention may be the esterification product alone or in a mixture thereof,
Unless deviating from the object of the present invention, further suitable amounts 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 and behenic acid. You may mix solid fats consisting of glycerides such as. Moreover, you may use together with the said well-known gelling agent.

[0015]

EXAMPLES In the following synthesis examples and examples,% is based on weight. Synthesis Example 1 75 g (0.1 mol) of decaglycerin, 85 g (0.3 mol) of stearic acid and 17 g of eicosadicarboxylic acid were placed in a four-necked flask equipped with a stirrer, a thermometer, a gas blowing tube and a water separator. (0.05 mol), p-toluenesulfonic acid 0.1% as a catalyst and xylene 5% as a reflux solvent were added, and the mixture was heated to 180-230 in a nitrogen gas stream.
The esterification reaction was carried out at 0 ° C. for 10 hours until no decrease in acid value was observed. After the completion of the reaction, the product was washed with water, decolorized with activated carbon, and deodorized by blowing steam to obtain 138 g of the esterified product of the present invention (sample code: A).
This product has an acid value of 0.4, a hydroxyl value of 264, a melting point of 6
It was 2-67 degreeC.

Synthesis Example 2 Decaglycerin 75 g (0.1 mol) and behenic acid 37 g
17 g (0.0 mol) of eicosadicarboxylic acid
5 mol) was added and the esterification reaction was carried out in the same manner as in Synthesis Example 1, followed by purification treatment to obtain 101 g of the esterification product of the present invention (designated as sample code: B). This product has an acid value of 0.
6, the hydroxyl value was 409 and the melting point was 66 to 69 ° C.

Synthesis Example 3 39 g (0.1 mol) of pentaglycerin and 8 of montanic acid
5 g (0.2 mol) was esterified by a conventional method to obtain a partially esterified product. On the other hand, the method described in Japanese Patent Application No. 5-230734 previously filed by the present applicant, that is, the sesame crude oil precipitate (oli) is dispersed and dissolved in ethanol and cooled to separate the insoluble matter that precipitates. 28 g (0.06 mol) of octacosadicarboxylic acid obtained by the above was added to the partial esterified product, and lipase (manufactured by Meito Sangyo Co., Ltd.,
Lipase QL) was added to the starting material in an amount of 1%, and the content of montanic acid by-produced was analyzed by gas chromatography while stirring at 120 ° C.
The transesterification reaction was carried out for 0 hours. After the completion of the reaction, the product was purified in the same manner as in Synthesis Example 1 to obtain 116 g of the esterified product of the present invention (sample code: C). This has an acid value:
It was 0.8, the hydroxyl value was 145, and the melting point was 67 to 73 ° C.

Example 1 Esterification products obtained in Synthesis Examples 1 to 3 (Sample symbol: A to
C), 12-hydroxystearic acid and carnauba wax were tested for their ability to solidify in ethanol. The results are shown in Table 1. The test method was to take ethanol and 7% of each sample in a beaker, heat to 70 ° C. with stirring to melt, and let stand for 3 hours at room temperature to observe the state of the solid obtained. did. The evaluation was ⊚: hard, uniform and smooth gelled or solidified product, ◯: uniform and smoothed gelled or solidified product, Δ: part of solid-liquid separated, x: not solidified.

[0019]

[Table 1]

It can be seen from Table 1 that the esterification products of the present invention (sample symbols: A to C) are uniform in ethanol, though the amount thereof is smaller than that of conventional gelling agents and waxes. It was found to form a smooth, viscous gel or solid. Further, when these were stored at room temperature for one month, it was confirmed that the product to which the esterification product of the present invention was added maintained a uniform state and was stable. In addition, 12-hydroxystearic acid and carnauba wax could not solidify ethanol with the same addition amount.

Example 2 The solidification ability of the esterification product (Sample Code: B) obtained in Synthesis Example 1 with respect to various alcohols was examined in the same manner as in Example 1. The results are shown in Table 2. The reference symbols for evaluation are the same as those in the first embodiment. From Table 2, the esterification product of the present invention had a gelling or solidifying ability with respect to various alcohols in a small amount, and all the solids had a uniform and smooth viscous property.

[0022]

[Table 2]

[0023]

According to the present invention, an esterification product of glycerin or its condensate, a linear saturated fatty acid having 18 to 28 carbon atoms and an aliphatic saturated dibasic acid having 20 to 28 carbon atoms is used. Yes, one of the hydroxyl groups of the glycerin or its condensate
A partially esterified product left over / 2 is obtained, and it is a uniform and smooth viscosity by adding a small amount of it to a liquid alcohol (excluding monohydric alcohols having 4 or more carbon atoms) at room temperature. It is possible to form a stable and stable gelled or solidified product. Therefore, the esterification product of the present invention can be used as a gelling agent or a solidifying agent for the above-mentioned alcohol, which has not been possible with the conventional gelling agents or waxes. Mold agent,
It can be effectively used as an adhesive, a binder, a sealing agent, a coating agent, a coating agent, a volatile component modifier, and the like.

Claims (4)

(57) [Claims] 1. Glycerin or glycerin having an average degree of polymerization of 2 or more
An esterification product of a condensate of serine, a linear saturated fatty acid having 18 to 28 carbon atoms , and an aliphatic saturated dibasic acid having 20 to 28 carbon atoms, which is the glycerin or the average degree of polymerization.
Gelling or solidifying agent of an alcohol (excluding monohydric alcohol having 4 or more carbon atoms) which is liquid at room temperature and consists of a partial esterification product in which more than 1/2 of hydroxyl groups of a condensate of 2 or more glycerin remains . 2. A glycerin condensate having an average degree of polymerization of 2 to 1
The gelling or solidifying agent according to claim 1, which is 0. 3. The glycerin condensate has an average degree of polymerization of 5 to 1
The gelling or solidifying agent according to claim 1, which is 0. 4. An alcohol which is liquid at room temperature is a polyhydric alcohol.
, Monohydric alcohols with less than 4 carbon atoms, or nitrogen-containing alcohols
The gel according to any one of claims 1 to 3, which is rucor.
Solidifying or solidifying agent.