JP4038763B2 - Gelling agent for organic solvents or oils and fats - Google Patents

Description

Ｇ：ゲル化 Ｐ：一部ゲル化 Ｎ：ゲル化せず
【００３０】
実施例２
実施例１のデヒドロアビエチン酸３．００ｇ（１０ｍモル）に代えて１３ベータ−デルタ８−ジヒドロアビエチン酸３．０４ｇ（１０ｍモル）を用いたほかは同様な操作を行い１３ベータ−デルタ８−ジヒドロアビエチン酸カルシウム塩の溶液を得た。
固形分：１７．４重量％
ＩＲ：１５２３ｃｍ^−１、１４１６ｃｍ^−１
得られた溶液は固形分より計算しテトラヒドロフランを加え１５重量％とした。
ゲル化対象物１０ｇを試験管に取り、室温で攪拌しながら、表１に示した重量のテトラヒドロフランの１５重量％溶液を加えゲル形成の有無を観察した。結果を表２に示す。
【００３１】
【表２】

Ｇ：ゲル化 Ｐ：一部ゲル化 Ｎ：ゲル化せず
【００３２】
実施例３
実施例１のデヒドロアビエチン酸３．００ｇ（１０ｍモル）に代えて不均化ロジン（商品名：ロンヂスＲ、荒川化学工業(株)製、酸価１５８）３．５４ｇを用いたほかは同様な操作を行い不均化ロジンカルシウム塩の溶液を得た。
固形分：１９．３重量％
ＩＲ：１５２５ｃｍ^−１、１４１８ｃｍ^−１
得られた溶液は固形分より計算しテトラヒドロフランを加え１５重量％とした。
ゲル化対象物１０ｇを試験管に取り、室温で攪拌しながら、表１に示した重量のテトラヒドロフランの１５重量％溶液を加えゲル形成の有無を観察した。結果を表３に示す。
【００３３】
【表３】

Ｇ：ゲル化 Ｐ：一部ゲル化 Ｎ：ゲル化せず
【００３４】
実施例４
実施例１のデヒドロアビエチン酸３．００ｇ（１０ｍモル）に代えてトール油ロジン（商品名：ＴＯＲ３５−２４０、アリゾナケミカル社製、酸価１７１）３．２７ｇを用いたほかは同様な操作を行いトール油ロジンカルシウム塩の溶液を得た。
固形分：１８．６重量％
ＩＲ：１５２４ｃｍ^−１、１４１７ｃｍ^−１
得られた溶液は固形分より計算しテトラヒドロフラン溶液を加え１５重量％とした。
ゲル化対象物１０ｇを試験管に取り、室温で攪拌しながら、表１に示した重量のテトラヒドロフランの１５重量％溶液を加えゲル形成の有無を観察した。結果を表４に示す。
【００３５】
【表４】

Ｇ：ゲル化 Ｐ：一部ゲル化 Ｎ：ゲル化せず
【００３６】
実施例５
実施例１の水酸化カルシウム０．３７ｇ（５ｍモル）に代えて水酸化ストロンチウム・８水和物１．３３ｇ（５ｍモル）用いたほかは同様な操作を行いデヒドロアビエチン酸ストロンチウム塩の溶液を得た。
固形分：１７．６重量％
ＩＲ：１５２５ｃｍ^−１、１４０５ｃｍ^−１
得られた溶液は固形分より計算しテトラヒドロフラン溶液を加え１５重量％とした。
ゲル化対象物１０ｇを試験管に取り、室温で攪拌しながら、表１に示した重量のテトラヒドロフランの１５重量％溶液を加えゲル形成の有無を観察した。結果を表５に示す。
【００３７】
【表５】

Ｇ：ゲル化 Ｐ：一部ゲル化 Ｎ：ゲル化せず
【００３８】
実施例６
イソプロパノール（８８重量％）、水(１２重量％)からなる混合物（以下、８８％ＩＰＡと略す）２００ｇに水酸化カルシウム３．７ｇ（０．０５モル）を加え攪拌し分散させた後、精製不均化ロジン（商品名：ＫＲ−６１４、荒川化学工業(株)製、酸価１７３）３３ｇを８８％ＩＰＡ ２００ｇに溶解した溶液を還流下で３０分かけて滴下した。さらに還流下で４時間攪拌し冷却後、ろ過し、８８％ＩＰＡ１００ｇにて洗浄した。得られたろ過物を取り出し、８０℃で４時間減圧乾燥し、２８．８ｇの白色粉末を得た。
融点：３００℃まで溶融せず
ＩＲ：１５２１ｃｍ^−１、１４１４ｃｍ^−１
このものをテトラヒドロフランに溶解し１５重量％溶液を調製した。
ゲル化対象物１０ｇを試験管に取り、室温で攪拌しながら、表１に示した重量のテトラヒドロフラン溶液の１５重量％溶液を加えゲル形成の有無を観察した。結果を表６に示す。
【００３９】
【表６】

Ｇ：ゲル化 Ｐ：一部ゲル化 Ｎ：ゲル化せず
【００４０】
実施例７
実施例６の水酸化カルシウムに代えて水酸化バリウム・８水和物を１３．３ｇ（０．０５モル）に変えた以外は同様の操作を行い２５．１ｇの白色粉末を得た。
融点：３００℃まで溶融せず
ＩＲ：１５３６ｃｍ^−１、１３９６ｃｍ^−１
このものにテトラヒドロフランを加え１５重量％分散液を調製した。
ゲル化対象物１０ｇを試験管に取り、室温で攪拌しながら、表１に示した重量のテトラヒドロフラン溶液の１５重量％分散液を加えゲル形成の有無を観察した。
結果を表７に示す。
【００４１】
【表７】

Ｇ：ゲル化 Ｐ：一部ゲル化 Ｎ：ゲル化せず[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic solvent or an oil or fat gelling agent. More specifically, the present invention relates to a gelling agent for adding an organic solvent, animal or vegetable oil, mineral oil or the like to gel the organic solvent or oil.
[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, since the number of low-molecular organic gelling agents is still small and their functions are limited, low-molecular gelling agents having a novel function are required. In addition, since the known low molecular organic gelling agents as described above generally cannot exhibit a desired gel strength unless used in a high addition amount, a gel having a high gel strength can be formed with a low addition amount. There is a need for low molecular weight organic gelling agents that can be produced.
[0004]
In addition, most of these organic gelling agents need to be added to the object to be gelled, once heated and dissolved, and then cooled to be gelled. Has been. Furthermore, when the gel gelled with the gelling agent is heated again, there are fatal drawbacks that the gel strength is reduced and the gel is dissolved.
[0005]
[Problems to be solved by the invention]
The present invention can form a gel with high gel strength with a low addition amount, and can be easily gelled by adding to a gelation object at room temperature without heating and cooling, and further gelation. It is an object of the present invention to provide a novel organic solvent or oil and fat gelling agent in which gel strength does not decrease even when a gel gelled with an agent is heated or the gel does not dissolve.
[0006]
[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 an alkaline earth metal salt of a resin acid.
[0007]
That is, the present invention relates to a gelling agent for organic solvents or oils and fats, characterized by comprising an alkaline earth metal salt of a resin acid as an active ingredient.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The alkaline earth metal salt of a resin acid, which is an active ingredient in the gelling agent of the present invention, is usually a compound composed of two resin acid residues and an alkaline earth metal.
[0009]
Alkaline earth metal salts of resin acids can be obtained by reacting resin acids with alkaline earth metal compounds.
[0010]
Examples of the resin acids include abietic acid, levopimaric acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimalic acid, dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid. Also included are gum rosin, wood rosin, tall oil rosin, disproportionated rosin, hydrogenated rosin, dehydrogenated rosin and the like, which are a mixture of the resin acids.
[0011]
The alkaline earth metal compound is not particularly limited as long as it is an alkaline earth metal compound that reacts with resin acids to form a salt, and can be used. Specific examples include calcium compounds, strontium compounds, barium compounds, magnesium compounds, and the like. Among these, those using a calcium compound are preferable from the viewpoint of cost and the like. Among these, from the viewpoint of reactivity with resin acids, alkaline earth metal oxides or alkaline earth metal hydroxides, specifically magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium oxide, It is preferable to use strontium hydroxide, strontium oxide, barium hydroxide, barium oxide, or the like.
[0012]
Examples of the method for synthesizing the alkaline earth metal salt of the resin acid used in the present invention include a method of reacting the resin acid in an appropriate solvent. The solvent is not particularly limited as long as it does not react with the resin acid and the alkaline earth metal compound and dissolves the resin acid, and a known solvent can be used. Specifically, for example, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2-methoxyethanol, acetone, 2-butanone, etc. Ketones, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfur-containing solvents such as dimethyl sulfoxide and sulfolane, nitrogen-containing solvents such as nitromethane and nitropropane, diethyl ether, methyl t-butyl ether, di-t- Examples thereof include ether solvents having at least one ether bond such as butyl ether, dimethoxyethanol, dimethoxyethylene glycol, tetrahydrofuran, and dioxane. Among these, when an ether solvent is used as the reaction solvent, the alkaline earth metal salt of the resin acid after the reaction is obtained in a state dissolved in these solvents, and this can be used as a gelling agent as it is. Therefore, it is preferable to use these ether solvents. The presence of a small amount of water in the solvent is particularly preferable because the reaction rate between the resin acid and the alkaline earth metal compound can be increased.
[0013]
The molar ratio of the resin acid to the alkaline earth metal compound when the resin acid and the alkaline earth metal compound are reacted is not particularly limited. Generally, when an ether solvent is used, 1 mole of the resin acid is used. On the other hand, it is preferable to use 0.2 mol or more of alkaline earth metal compound. When the amount of the alkaline earth metal compound is less than 0.2 mol with respect to 1 mol of the resin acids, a large amount of unreacted resin acids may remain and the gelling performance may not be sufficiently exhibited. In addition, when the alkaline earth metal compound is used in an amount exceeding 0.5 mol with respect to 1 mol of the resin acid, unreacted alkaline earth metal compound remains, but there is no problem in gelling performance. If necessary, unreacted alkaline earth metal compound can be removed by filtration or centrifugation. In addition, when a solvent other than the ether solvent is used, it is usually preferable to use 0.2 mol or more of the alkaline earth metal compound with respect to 1 mol of the resin acid. In addition, when the alkaline earth metal compound is used in an amount exceeding 0.5 mol with respect to 1 mol of the resin acid, an unreacted alkaline earth metal compound remains, but there is no problem in gelling performance.
[0014]
The reaction temperature is not particularly limited, but usually the range of room temperature without requiring a special apparatus to the boiling point of the solvent used for the reaction is suitable.
[0015]
The reaction time varies depending on the reaction temperature, but is usually about 5 minutes to 24 hours. If it is less than 5 minutes, the reaction may not proceed sufficiently, and there is no particular advantage even if the reaction is carried out for 24 hours or longer.
[0016]
When a solvent other than an ether solvent is used, the alkaline earth metal salt of the resin acid is usually dispersed as a powder in the reaction solvent after completion of the reaction, and separated from the reaction solvent by filtration or centrifugation. If necessary, it can be washed with a solvent that does not dissolve the alkaline earth metal salt of the resin acid. The alkaline earth metal salt of the obtained resin acid is, for example, a solvent containing an ether bond such as diethyl ether, methyl t-butyl ether, di-t-butyl ether, dimethoxyethanol, dimethoxyethylene glycol, tetrahydrofuran, dioxane, or an alkali of a resin acid. It can be used in the present invention after being dissolved in a solvent that dissolves the earth metal salt.
[0017]
If it is difficult to synthesize an alkaline earth metal salt of a resin acid by the above method, a method generally called a metathesis method can also be adopted. The metathesis method is a method in which a resin acid is once reacted with an alkali metal hydroxide to obtain an alkali metal salt of the resin acid and then reacted with an alkaline earth metal compound.
[0018]
In the metathesis method, water-soluble organic alkaline earth metal salts and inorganic alkaline earth metal salts are usually used as the alkaline earth metal compound with which the alkali metal salt of the resin acid is reacted. Specific examples include alkaline earth metal acetates, sulfates, nitrates, chlorides and hydrates thereof.
[0019]
In the case of the metathesis method, after completion of the reaction, the product exists in a dispersed state in water as a reaction solvent, and therefore can be easily separated from water by filtration or centrifugation. It is also possible to wash the product with water.
[0020]
The alkaline earth metal salt of a resin acid obtained by the metathesis method can be used in the present invention after being dissolved in the ether solvent or a solvent capable of dissolving the alkaline earth metal salt of a resin acid.
[0021]
The alkaline earth metal salt of the resin acid thus obtained can be applied to various gelation objects. For example, nonpolar to medium polar solvents such as hexane, heptane, cyclohexane, benzene, toluene, xylene (specifically, solvents having a dielectric constant of about 3.0 or less), gasoline, kerosene, light oil, heavy oil, crude oil, Excellent gelling ability can be expressed against mineral oils such as liquid paraffin, and general animal and vegetable oils such as soybean oil, rapeseed oil and salad oil.
[0022]
The gelling agent of the present invention is usually used after being dissolved in a solvent capable of dissolving the gelling agent. Examples of the solvent that dissolves the gelling agent include the ether solvents, but are not limited thereto.
[0023]
In general, the concentration of the alkaline earth metal salt solution is preferably 2% by weight or more with respect to the solvent, and is preferably as high as possible. If it is less than 2% by weight, the gelation ability may not be fully exhibited. Usually, 10% by weight or more is particularly preferable.
[0024]
By adding the obtained alkaline earth metal salt solution to gelled objects such as various solvents, mineral oil, animal and vegetable oils, the gelled object can be rapidly gelled.
[0025]
The amount of the alkaline earth metal salt solution used is appropriately determined according to the type of the gelation target and the type of the active ingredient in the organic gelling agent. Usually, the content of the alkaline earth metal salt is about 0.05 to 30% by weight, preferably 0.1 to 10% by weight with respect to the object to be gelled.
[0026]
【The invention's effect】
The gelling agent of the present invention includes various gelling objects, for example, nonpolar to medium polar solvents such as hexane, heptane, cyclohexane, benzene, toluene, xylene, gasoline, kerosene, light oil, heavy oil, crude oil, liquid paraffin. It exhibits an excellent gelling effect at a low addition rate with respect to aromatic solvents such as mineral oils such as soybean oil, rapeseed oil, and general animal and vegetable oils such as salad oil. Unlike the conventional low molecular weight organic gelling agent, the obtained gel does not decrease in strength or dissolve even when heated. Therefore, taking advantage of the effects of the organic gelling agent of the present invention, oil recovery agents, cosmetics, quasi drugs, viscosity regulators such as inks, sustained release agents such as agricultural chemicals and fragrances, plastics, rubber processing aids It can be applied widely.
[0027]
【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.
[0028]
Example 1
3.00 g (10 mmol) of dehydroabietic acid was dissolved in a mixed solvent consisting of 14.5 g of tetrahydrofuran and 0.5 g of water, 0.37 g (5 mmol) of calcium hydroxide was added thereto, and the mixture was stirred and reacted at room temperature. After the reaction, insolubles were filtered to obtain a solution of calcium dehydroabietic acid. A portion of this was taken and dried at 105 ° C. for 2 hours, the solid content was determined from the loss on drying, and the IR spectrum of the dried solid was measured.
Solid content: 17.2% by weight
IR: 1521 cm ⁻¹ , 1415 cm ⁻¹
Calculated from the solid content, tetrahydrofuran was added to make a 15 wt% solution.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 1.
[0029]
[Table 1]

G: Gelled P: Partially gelled N: Not gelled [0030]
Example 2
The same procedure was performed except that 3.04 g (10 mmol) of 13 beta-delta 8-dihydroabietic acid was used instead of 3.00 g (10 mmol) of dehydroabietic acid of Example 1, and 13 beta-delta 8-dihydro was used. A solution of calcium abietic acid salt was obtained.
Solid content: 17.4% by weight
IR: 1523 cm ⁻¹ , 1416 cm ⁻¹
The obtained solution was calculated from the solid content, and tetrahydrofuran was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 2.
[0031]
[Table 2]

G: Gelled P: Partially gelled N: Not gelled [0032]
Example 3
The same procedure except that 3.54 g of disproportionated rosin (trade name: Longis R, manufactured by Arakawa Chemical Industries, Ltd., acid value 158) was used instead of 3.00 g (10 mmol) of dehydroabietic acid of Example 1. Operation was performed to obtain a solution of disproportionated rosin calcium salt.
Solid content: 19.3% by weight
IR: 1525 cm ⁻¹ , 1418 cm ⁻¹
The obtained solution was calculated from the solid content, and tetrahydrofuran was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 3.
[0033]
[Table 3]

G: Gelled P: Partially gelled N: Not gelled [0034]
Example 4
The same operation was performed except that 3.27 g of tall oil rosin (trade name: TOR35-240, manufactured by Arizona Chemical Co., acid value 171) was used instead of 3.00 g (10 mmol) of dehydroabietic acid of Example 1. A solution of tall oil rosin calcium salt was obtained.
Solid content: 18.6% by weight
IR: 1524 cm ⁻¹ , 1417 cm ⁻¹
The obtained solution was calculated from the solid content, and the tetrahydrofuran solution was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 4.
[0035]
[Table 4]

G: Gelled P: Partially gelled N: Not gelled [0036]
Example 5
A solution of strontium dehydroabietic acid salt was obtained in the same manner as in Example 1 except that 1.33 g (5 mmol) of strontium hydroxide octahydrate was used instead of 0.37 g (5 mmol) of calcium hydroxide. It was.
Solid content: 17.6% by weight
IR: 1525 cm ⁻¹ , 1405 cm ⁻¹
The obtained solution was calculated from the solid content, and the tetrahydrofuran solution was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 5.
[0037]
[Table 5]

G: Gelled P: Partially gelled N: Not gelled [0038]
Example 6
After adding 3.7 g (0.05 mol) of calcium hydroxide to 200 g of a mixture of isopropanol (88 wt%) and water (12 wt%) (hereinafter abbreviated as 88% IPA) and stirring and dispersing, A solution prepared by dissolving 33 g of averaged rosin (trade name: KR-614, manufactured by Arakawa Chemical Industries, Ltd., acid value 173) in 200 g of 88% IPA was added dropwise over 30 minutes under reflux. The mixture was further stirred for 4 hours under reflux, cooled, filtered, and washed with 100 g of 88% IPA. The obtained filtrate was taken out and dried under reduced pressure at 80 ° C. for 4 hours to obtain 28.8 g of white powder.
Melting point: not melted to 300 ° C. IR: 1521 cm ⁻¹ , 1414 cm ⁻¹
This was dissolved in tetrahydrofuran to prepare a 15% by weight solution.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15% by weight solution of a tetrahydrofuran solution having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 6.
[0039]
[Table 6]

G: Gelled P: Partially gelled N: Not gelled [0040]
Example 7
The same operation was carried out except that barium hydroxide octahydrate was changed to 13.3 g (0.05 mol) instead of calcium hydroxide in Example 6 to obtain 25.1 g of white powder.
Melting point: not melted to 300 ° C. IR: 1536 cm ⁻¹ , 1396 cm ⁻¹
Tetrahydrofuran was added to this to prepare a 15 wt% dispersion.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% dispersion of a tetrahydrofuran solution having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed.
The results are shown in Table 7.
[0041]
[Table 7]

G: Gelled P: Partially gelled N: Not gelled

Claims (4)

An organic solvent or oil or fat gelling agent characterized by comprising an alkaline earth metal salt of a resin acid as an active ingredient. 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, sandaracopimaric acid, dehydroabietic acid, dihydroabietic acid and tetrahydroabietic acid Item 2. A gelling agent according to Item 1. The gelling agent according to claim 1 or 2, wherein the alkaline earth metal salt is at least one selected from the group consisting of calcium salt, strontium salt, barium salt and magnesium salt. The gelling agent according to claim 1 or 2, wherein the alkaline earth metal salt is a calcium salt.