JP4038764B2 - Method for gelling organic solvents or oils and fats - Google Patents

Description

【００２３】
実施例２
表２に示したゲル化対象物各１０ｇに、表１に示した重量の不均化ロジン（荒川化学工業（株）製、商品名「ロンヂスＲ」、酸価１５８）３０ｇと水酸化カルシウム７．６ｇ（０．１モル）よりなる混合物の粉末を表１に示す重量を添加し、室温で５分間攪拌した後、静置し、ゲル形成の有無を観察した。結果を表２に示す。
【００２４】
【表２】

【００２５】
実施例３
表３に示したゲル化対象物各１０ｇに、不均化ロジン部分カルシウム塩（荒川化学工業（株）製、商品名「パインクリスタルＫＲ−５０Ｍ」、酸価１０２）３０ｇと水酸化カルシウム７．６ｇ（０．１モル）よりなる混合物の粉末を表１に示した重量を添加し、室温で５分間攪拌した後、静置し、ゲル形成の有無を観察した。結果を表３に示す。
【００２６】
【表３】

【００２７】
実施例４
表４に示したゲル化対象物各１０ｇに、表１に示した重量の精製不均化ロジン（荒川化学工業（株）製、商品名「ＫＲ−６１４」、酸価１７２．５）を溶解した後、水酸化カルシウム５０ｍｇを加え、室温で５分間攪拌した後、静置し、ゲル形成の有無を観察した。結果を表４に示す。
【００２８】
【表４】

【００２９】
実施例５
表５に示したゲル化対象物各１０ｇに、表１に示した重量の精製不均化ロジン（荒川化学工業（株）製、商品名「ＫＲ−６１４」、酸価１７２．５）を溶解した後、水酸化ストロンチウム・８水和物３００ｍｇを加え、室温で５分間攪拌した後、静置し、ゲル形成の有無を観察した。結果を表５に示す。
【００３０】
【表５】

【００３１】
実施例６
表６に示したゲル化対象物各１０ｇに、表１に示した重量の精製不均化ロジン（荒川化学工業（株）製、商品名「ＫＲ−６１４」、酸価１７２．５）を溶解した後、水酸化バリウム・８水和物４００ｍｇを加え、室温で５分間攪拌した後、静置し、ゲル形成の有無を観察した。結果を表６に示す。
【００３２】
【表６】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for gelling organic solvents or oils and fats. More specifically, the present invention relates to a gelation method for organic solvents, animal and vegetable oils, mineral oils and the like.
[0002]
[Prior art]
Gelling agents are widely used in various applications, such as oil recovery agents, cosmetics, quasi-drugs, viscosity regulators such as inks, sustained release agents such as agricultural chemicals and fragrances, plastics and rubber processing aids. . In recent years, low molecular weight organic gelling agents have attracted attention, and their functions have been studied in various ways. Known low-molecular organic gelling agents include sorbitol diacetal, 12-hydroxystearic acid, cholesterol-based amide compounds, sugar derivatives, and the like (for example, refer to page 312 of Gel Handbook, Inc.).
[0003]
However, such known low-molecular organic gelling agents cannot express sufficient functions. For example, generally, a desired gel strength cannot be expressed unless it is used in a high addition amount with respect to the object to be gelled. In addition, most of the gelling agent needs to be added to the gelation target, once heated and dissolved, and then cooled and gelled, so that the operation is complicated and the application is very limited. There are disadvantages such as. In addition, there is a fatal defect that once the gel is reheated, the gel strength decreases or dissolves. Therefore, development of a novel low molecular organic gelling agent and a gelation method capable of forming a gel with high gel strength with a low addition amount is strongly demanded.
[0004]
[Problems to be solved by the invention]
In light of the above problems, the present invention can form a gel with a high gel strength with a low addition amount, and can be easily gelled only by adding to a gelation object at room temperature without heating and cooling, Furthermore, it aims at providing the gelation method of the novel organic solvent or fats and oils that a gel intensity | strength falls or a gel does not melt | dissolve even if the said production | generation gel is heated.
[0005]
[Means for Solving the Problems]
In order to achieve this object, the present inventor has intensively studied and found that the object can be achieved by using resin acids and alkaline earth metal compounds.
[0006]
That is, the present invention relates to a method for gelling an organic solvent or fats and oils, characterized in that a resin acid and an alkaline earth metal compound are added to a gelation target for gelation.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the resin acids used in the present invention include abietic acid, levopimaric acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimalic acid, dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid. it can. Examples of the resin acid mixture include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, hydrogenated rosin, and dehydrogenated rosin. Furthermore, alkaline earth metals of rosins, partially neutralized metal salts of zinc and aluminum, and the like can also be suitably used. Any of these resin acids can be used alone, or two or more can be used in combination as appropriate.
[0008]
In addition, the alkaline earth metal compound used in the present invention can be used without particular limitation as long as it is an alkaline earth metal compound that forms a salt by reacting with the above resin acids. Metal oxides or alkaline earth metal hydroxides are preferred. Specific examples of the metal compound include magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium oxide, strontium hydroxide, strontium oxide, barium hydroxide, and barium oxide. Any of these alkaline earth metal compounds can be used alone, or two or more of them can be used in combination as appropriate.
[0009]
By appropriately selecting and combining these resin acids and alkaline earth metal compounds, various gelation objects can be gelled. For example, nonpolar to medium polar solvents such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene (specifically, solvents having a dielectric constant of about 3.0 or less); gasoline, kerosene, light oil, heavy oil, It can exhibit excellent gelling ability against mineral oils such as crude oil and liquid paraffin; and general animal and vegetable oils such as soybean oil, rapeseed oil and salad oil. The gelation method of the present invention will be described in detail below.
[0010]
First, there is a method of adding an alkaline earth metal compound after adding a resin acid to a gelled object and dissolving it. In this case, it is good to stir so that an alkaline-earth metal compound may disperse | distribute to the whole gelatinization target object, and desired gelatinization is realizable by leaving still after that.
[0011]
Second, there is a method in which an alkaline earth metal compound is dispersed in an object to be gelated, and then resin acids are added to the dispersion. Also in this case, the resin acid may be stirred until it is dissolved in the gelation target and then allowed to stand.
[0012]
Thirdly, there is a method in which a resin acid and an alkaline earth metal compound are simultaneously added to the object to be gelated for gelation. In this case as well, the resin acids may be stirred until dissolved in the gelation target, and then allowed to stand.
[0013]
Fourth, resin acids and alkaline earth metal compounds can be mixed in advance and added to the object to be gelled for gelation. In this case as well, the mixture is appropriately stirred and then left to stand.
[0014]
Even when any of the above methods is adopted, the amount of the resin acid added to the gelation target can be appropriately determined according to the type of the gelation target. Usually, it is about 0.05 to 30% by weight, preferably 0.1 to 10% by weight, based on the gelled object.
[0015]
In each of the above methods, the shape and size of the alkaline earth metal compound are not particularly limited, but from the viewpoint of enhancing the dispersibility in the resin acid or the gelation target, it is preferable to use a powder with a relatively uniform shape. . Further, the amount of the alkaline earth metal compound added to the gelation target may be appropriately determined according to the amount of the resin acid used, and the molar ratio of the resin acid to the alkaline earth metal compound (resin acid (number of moles)). / Alkaline earth metal compound (number of moles) is preferably 1 / 0.1-1 / 10. If the molar ratio is less than 1 / 0.1, sufficient gelation may not occur. If the molar ratio exceeds 1/10, desired gelation can be realized, but a large amount of unreacted alkaline earth metal remains or costs increase, and there is no particular advantage.
[0016]
In the present invention, the temperature for gelling the gelled object is not particularly limited, and can be appropriately set within the range from room temperature to the boiling point of the gelled object. The feature of the present invention is that it can be gelled. In addition, when making highly viscous animal and vegetable oil and mineral oil gelatinize, the time until gelatinization is completed can be shortened by heating in order to raise the melt | dissolution rate of resin acids.
[0017]
In any of the above methods, the resin acid and the alkaline earth metal compound react with each other in the presence of the object to be gelated to produce an alkaline earth metal salt of the resin acid, and the metal salt is the object to be gelled. It is presumed to act as a gelling agent.
[0018]
The gel obtained by the method of the present invention is different from the gel obtained by using the conventional low molecular organic gelling agent, and the strength does not decrease even when heated, and the gel once generated is reheated. It has the characteristic that it does not melt | dissolve in the crystallization object, and has the outstanding gelling performance which is not in the past.
[0019]
【The invention's effect】
The organic gelation method of the present invention is applicable to various gelation objects, for example, nonpolar to medium polar solvents such as hexane, heptane, cyclohexanebenzene, toluene, xylene (specifically, dielectric constant is 3.0 or less) Mineral oils such as gasoline, kerosene, light oil, heavy oil, crude oil liquid paraffin, etc .; applicable to aromatic solvents such as soybean oil, rapeseed oil, salad oil, etc. The gelling effect can be expressed. Unlike the organic gel obtained from the conventional low molecular organic gelling agent, the organic gel obtained by the organic gelation method of the present invention does not decrease in strength or dissolve even when heated. Therefore, the method of the present invention can be widely applied to oil recovery agents, cosmetics, quasi drugs, viscosity modifiers such as inks, sustained release agents such as agricultural chemicals and fragrances, plastics and rubber processing aids.
[0020]
【Example】
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
[0021]
Example 1
To each 10 g of the gelled object shown in Table 1, a weight of a mixture of 30 g (0.1 mol) of dehydroabietic acid and 3.7 g (0.05 mol) of calcium hydroxide was added as shown in Table 1. After stirring for 5 minutes at room temperature, the mixture was allowed to stand and the presence or absence of gel formation was observed. The results are shown in Table 1.
[0022]
[Table 1]

[0023]
Example 2
For each 10 g of the gelation target shown in Table 2, 30 g of disproportionated rosin (trade name “Longis R”, acid value 158, manufactured by Arakawa Chemical Industries, Ltd.) with the weight shown in Table 1 and calcium hydroxide 7 The powder shown in Table 1 was added to a powder composed of .6 g (0.1 mol), stirred for 5 minutes at room temperature, and allowed to stand, and the presence or absence of gel formation was observed. The results are shown in Table 2.
[0024]
[Table 2]

[0025]
Example 3
To each 10 g of the gelation target shown in Table 3, disproportionated rosin partial calcium salt (Arakawa Chemical Industries, trade name “Pine Crystal KR-50M”, acid value 102) 30 g and calcium hydroxide 7. The powder of the mixture consisting of 6 g (0.1 mol) was added with the weight shown in Table 1, stirred for 5 minutes at room temperature, and allowed to stand to observe the presence or absence of gel formation. The results are shown in Table 3.
[0026]
[Table 3]

[0027]
Example 4
In each 10 g of the gelation target shown in Table 4, purified disproportionated rosin (trade name “KR-614”, acid value 172.5, manufactured by Arakawa Chemical Industries, Ltd.) having the weight shown in Table 1 was dissolved. After that, 50 mg of calcium hydroxide was added, stirred at room temperature for 5 minutes, and then allowed to stand, and the presence or absence of gel formation was observed. The results are shown in Table 4.
[0028]
[Table 4]

[0029]
Example 5
In 10 g of each gelled object shown in Table 5, purified disproportionated rosin (trade name “KR-614”, acid value 172.5, manufactured by Arakawa Chemical Industries, Ltd.) having the weight shown in Table 1 was dissolved. Then, 300 mg of strontium hydroxide octahydrate was added, stirred for 5 minutes at room temperature, and allowed to stand to observe the presence or absence of gel formation. The results are shown in Table 5.
[0030]
[Table 5]

[0031]
Example 6
In each 10 g of the gelation target shown in Table 6, the purified disproportionated rosin (trade name “KR-614”, acid value 172.5, manufactured by Arakawa Chemical Industries, Ltd.) having the weight shown in Table 1 was dissolved. After that, 400 mg of barium hydroxide octahydrate was added, stirred at room temperature for 5 minutes, and then allowed to stand to observe the presence or absence of gel formation. The results are shown in Table 6.
[0032]
[Table 6]

Claims (4)

A method for gelling an organic solvent or oil or fat, comprising adding a resin acid and an alkaline earth metal compound to an object to be gelled for gelation. The resin acid is at least one selected from the group consisting of abietic acid, levopimaric acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimalic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid Item 2. The gelation method according to Item 1. The gelling method according to claim 1 or 2, wherein the alkaline earth metal compound is at least one selected from the group consisting of calcium hydroxide, strontium hydroxide, barium hydroxide, calcium oxide, strontium oxide, and barium oxide. The gelling method according to any one of claims 1 to 3, wherein the gelation target is at least one selected from the group consisting of organic solvents, animal and vegetable oils and mineral oils.