JPH0384099A - Production of modified hydrogenated castor oil - Google Patents

Abstract

PURPOSE:To efficiently separate a modified oil X having high content of glycerol-tri-12-hydroxystearate (T) from a modified oil Y having low content of T by taking advantage of the solubility difference of the triglyceride component in solvents. CONSTITUTION:For example, a hydrogenated castor oil is dissolved in a solvent solution under heating and the obtained solution is cooled to obtain a precipitate and a non precipitate. The product is separated into a modified oil X having a glyceroltri-12-hydroxystearate (T) content of >=(t0+5)wt.% (t0 is wt.% of the component T in the hydrogenated castor oil) and a modified oil Y having a glycerol-di-12-hydroxystearatemonostearate (D) content of >= (d0+5)wt.% (d0 is wt.% of the component D in the hydrogenated castor oil).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing hydrogenated castor oil modified products having various properties improved over hydrogenated castor oil, in particular glycerin-tri-12- The present invention relates to a method for producing a hydrogenated castor oil modified product in which the concentrations of hydroxystearate (T) and glycerin-di-12-hydroxystearate-monostearate (D) are changed.

Conventional technology Hydrogenated castor oil is a waxy triglyceride with a melting point of around 85°C, and can be used as it is or in the form of various derivatives in greases (lubricating oils), electrical insulation materials, paint and ink additives, cosmetics and pharmaceuticals. It is widely used as a surfactant in various fields.

Since hydrogenated castor oil is a hydrogenated product of castor oil, it contains hydroxyl groups derived from ricinoleic acid units in castor oil. The main reason hydrogenated castor oil is used for the above applications is that its hydroxyl groups perform various functions.

The composition of fatty acid units in castor oil is about 90% by weight of ricinoleic acid units and about 10% by weight of other fatty acid units that do not have hydroxyl groups. In addition, free ricinoleic acid is represented by the following formula.

H CH3(CHz)rcHcH1CH=CH(()Iz)
When 7GOOR castor oil is hydrogenated, if the reaction theoretically occurs, ricinoleic acid units become 12-hydroxystearic acid units, and other fatty acid units without hydroxyl groups become mainly stearic acid units. In industry, the content of 12-hydroxystearic acid units in hydrogenated castor oil generally supplied to the market is limited because hydrogenation of double bonds is not completed completely and side reactions such as reduction of hydroxyl groups occur. is about 85 to 90% by weight, and the content of stearic acid units is about 15 to 10% by weight.

In other words, hydrogenated castor oil generally supplied on the market has a composition of glycerin tri-12-hydroxystearate (T
) Approximately 60 to 70% by weight glycerin-di-12-hydroxystearate-monostearate (
D) It is about 40 to 30% by weight, and the hydroxyl value is about 156 to 162. Note that the content of glycerin-mono-12-hydroxystearate-distearate is negligible.

Problems to be Solved by the Invention Commercially available hydrogenated castor oil is used for various purposes as mentioned above. Hydrogenated castor oil is also decomposed into its constituent fatty acids, or after being made into constituent fatty acids, it is further made into fatty acid salts and amides such as metal soaps, and these are used for similar purposes. -For example,
Lithium salts of hydrogenated castor oil fatty acids are commonly used as additives for greases based on mineral oils and the like.

However, when hydrogenated castor oil and the fatty acids (or its salts and amides) obtained by decomposing it are used as thicuntropic agents, gelling agents for organic fluids, grease thickeners, etc. Performance may be insufficient or the types of substances to be modified may be limited. When using polymers as processing aids or release agents during molding, there is a restriction that there are few polymers that can produce the desired effects.

These problems or limitations are due to the 12
This is thought to be due to the fact that the content of -hydroxystearic acid units (units having a hydroxyl group) is fixed within a certain narrow range of values as described above. The same applies to hydrogenated castor oil fatty acids obtained by decomposing hydrogenated castor oil, their salts, and amides. (Commercially available hydrogenated castor oil fatty acids are simply 1
Although it is also called 2-hydroxystearic acid, the actual content of 12-hydroxystearic acid is about 85 to 90% by weight. ) The uninventors believe that the hydrogenated castor oil currently on the market is produced by inheriting the triglyceride composition of the castor oil that is its raw material, and that similarly hydrogenated castor oil fatty acids or their salts and amides are I had doubts about the fact that Uke inherited the triglyceride composition of castor oil. And if the content of 12-hydroxystearic acid units in hydrogenated castor oil or the 12-hydroxystearic acid units in hydrogenated castor oil fatty acids (or salts or amides thereof) derived therefrom,
If the content of hydroxystearic acid (or its salt or amide) can be freely changed, it is possible to select hydrogenated castor oil or its derivatives that have the optimum proportion of hydroxyl group-containing components depending on the substance to be modified. The idea was that it would be possible to maximize the reforming effect and further expand the range of applications. It is believed that such an idea itself did not exist before.

The inventors of the present invention have conducted intensive research to realize this idea, and as a result, have arrived at the present invention described below.

Means for Solving the Problems The method for producing a modified hydrogenated castor oil of the present invention involves applying an operation to hydrogenated castor oil that takes advantage of the difference in solubility of triglyceride components contained in the hydrogenated castor oil in a solvent. Glycerin-tri-12-hydroxystearate (T)
and the ratio of modified product It is characterized in that it is separated into a modified product Y in which the ratio of glycerin tri-12-hydroxystearate (T) is increased and the ratio of glycerin tri-12-hydroxystearate (T) is decreased.

The invention will be explained in detail below.

Hydrogenated castor oil is obtained by hydrogenating castor oil. As mentioned earlier, the triglyceride composition of hydrogenated castor oil is glycerin-tri-12-hydroxystearate (T
) Approximately 60 to 70% by weight glycerin-di-12-hydroxystearate-monostearate (
D) It is about 40 to 30% by weight, and the hydroxyl value is about 156 to 162.

The content of glycerin-mono-12-hydroxystearate-distearate is negligible.

The hydroxyl values of component (T) and component (D) can both be derived theoretically, and are 17L8 for component (T) and 121.7 for component (D).

In the present invention, hydrogenated castor oil is subjected to an operation that utilizes the difference in solubility of triglyceride components contained in the hydrogenated castor oil in a solvent.

Specifically, this operation includes: (1) heating and dissolving hydrogenated castor oil in a solvent and cooling it to obtain a precipitate and a non-precipitate, and separating it into modified product X and modified product Y; (2) water A precipitate and a non-precipitate were obtained by contacting the solvent solution of castor oil with the poor solvent of the component of interest, and modified product X
(1) extracting hydrogenated castor oil with a solvent to obtain an extract and an extraction residue, and separating it into modified material X and modified material Y; The - operation can be repeated multiple times, or two or more operations can be performed at the same time or in succession. Among the above operations, ■ and ■ are important.

In the above, the modified substance Modified product Y is one in which the proportion of component ([l) is increased compared to the proportion of component (D) in the original hydrogenated castor oil (therefore, the proportion of component (T) is relatively low).

Solvents or poor solvents used in these operations include ketone solvents, alcohol solvents, ester solvents, ether solvents, acetal solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, nitrogen-containing solvents, and sulfur-containing solvents. Solvents include glycol-based solvents, glycol ether-based solvents, glycol ether acetate-based solvents, etc., and the optimum one or the optimum combination is selected from these.

By performing the above operation, the modified material X has a high proportion of component (T) and a low proportion of component (D), and a modified material and the modified product Y.

Now, the proportion of component (T) in hydrogenated castor oil is t.

When expressed as weight%, the proportion of component (T) in modified material X is (
to +5) weight% or more, especially < (to +lO
)% by weight or more, and it is required to set the above-mentioned operating conditions so as to achieve such a ratio.

Similarly, when the proportion of component (D) in hydrogenated castor oil is 40% by weight, the proportion of component (D) in modified product Y is (do
+5) It is desirable that the amount is at least 10% by weight, especially at least (do+10)% by weight, and it is required to set the above-mentioned operating conditions so that such a ratio is achieved.

If the ratio of component (T) in modified material X does not reach the above range, or if the ratio of component (D) in modified material X does not reach the above range, the modification effect will be insufficient, There is no significant difference compared to hydrogenated castor oil.

For the modified hydrogenated castor oil (modified product By thixotropic agents.

It can be suitably used as a gelling agent for organic fluids, a grease thickener, a toner binder, an ink ribbon binder, a magnetic tape binder, and the like. In addition, when using this as a processing aid for polymers or a mold release agent during molding, the hydroxyl groups it contains exhibit various functions, and the polarity that matches the polarity of the target polymer can be selected. It can be used not only for polymers with high polarity, but also for polymers with low polarity such as polyethylene and polypropylene.

Fatty acids obtained by decomposing hydrogenated castor oil modified products (modified product X or modified product Y), or fatty acids further converted into salts or amides, are also useful for similar purposes.

Function and Effects of the Invention According to the method of the present invention, the triglyceride composition of hydrogenated castor oil, which has conventionally been fixed within a narrow range, can be changed in various ways depending on the purpose and use. The same applies to fatty acids or their salts and amides derived from hydrogenated castor oil.

Therefore, conventional hydrogenated castor oil or its constituent fatty acids (
or its salts and amides), it can be expected to improve the performance that was limited by these conventional products, and in fact, good results can be obtained in many cases, as shown in the examples below. can. It is also intended to be used in applications where conventional products are not used.

Example Next, the present invention will be further explained with reference to Examples.

Hereinafter, "%" means % by weight.

The triglyceride composition was determined by thin layer chromatography and gas chromatography.

Example 1 Commercially available hydrogenated castor oil (hydroxyl value 158.9) 285
g was heated and dissolved in 2500 g of methyl imbutyl ketone,
It was left standing at room temperature.

When the solution temperature dropped to 36℃, crystals started to precipitate, so we continued to stand still, and after 2 hours the solution temperature decreased to 30℃.
When the temperature decreased to , the precipitated crystals were filtered off. The filtered crystals were washed with a fresh cold solvent (methyl isobutyl ketone) and dried to obtain 149 g of first crystals.

When the mother liquor was further allowed to stand at room temperature for 12 hours, crystals were deposited again. The solution temperature was 15°C. The crystals were filtered and treated in the same manner as above to obtain 111 g of second crystals.

The solvent is distilled off from the mother liquor from which the second crystals have been filtered,
24 g of the third batch was obtained.

The hydroxyl value and triglyceride composition of the raw material hydrogenated castor oil, the first crystal, the second crystal, and the third crystal were as follows. The first crystal corresponds to the modified material X, and the second crystal corresponds to the modified material Y.

Hydrogenated castor oil C.

1st crystal 100 g of one crystal was heated and dissolved in 1000 ml of methyl imbutyl ketone, and after cooling to 40° C., 500 ml of cold n-hexane was added with stirring to precipitate crystals. The precipitate was filtered off to obtain 90 g of the first precipitate.

The solvent was distilled off from the mother liquor to obtain 10 g of the second component.

The hydroxyl value and triglyceride composition of the first precipitate and the second precipitate were as follows. The first precipitate corresponds to the modified product X, and the second component corresponds to the modified product Y.

OH value Insects ■ iHen is also the first precipitate X2 178.7 98! 2% second
Ibun Y 2 122.0 0.5$ 99.52
Example 3 Commercially available hydrogenated castor oil (hydroxyl value 158.9) 200
Dissolve g in 700 g of methyl isobutyl ketone by heating.
0~65℃), cooled to 45℃ and then heated to a temperature of 45℃
- 50 g of hexane was added, mixed, and allowed to cool.

Crystals began to precipitate as the solution temperature decreased, so when the temperature dropped to 36° C., the precipitated crystals were filtered out to obtain 133 g of first crystals.

The mother liquor was further allowed to stand at room temperature for 12 hours, and the crystals precipitated during that time were filtered off to obtain 45 g of second crystals.

The solvent is distilled off from the mother liquor after filtering off the second crystal by distillation,
20.5 g of the third batch was obtained.

The hydroxyl values and triglyceride compositions of the raw material hydrogenated castor oil, the first crystal, the second crystal, and the third component were as follows. The first crystal corresponds to the modified material X, and the second crystal corresponds to the modified material Y.

OH value Out l Shihiki hydrogenated castor oil Co 15B, 9 El(H4(H 1st crystal X3 1B8.5 812 19% 2nd crystal Y 3 140.0 31% 89% 3rd crystal
118.2 (Evaluation of gelling, thixotropic or thickening ability) Test Example 1 (thixotropic effect of varnish) Raw material hydrogenated castor oil (Co), first crystal obtained in Example 1 (
Modified product XI), second crystal (modified product Y 1), and first precipitate obtained in Example 2 (modified product X2) were used as thixotropic
The thixotropy of epoxy varnish was investigated.

Bisphenol A epoxy resin (Epicoat 11001 manufactured by Yuka Shell Epoxy Chichishiki Company) 60, xylene 2
A resin liquid consisting of 6 g of methyl isobutyl ketone and 14 g of methyl isobutyl ketone was prepared.

To this resin liquid, 1% of each of the above four types of thixotropes, which had been pulverized in advance in a mortar, was added, and the mixture was kept at 50°C.
After stirring at 0 rpm for 5 minutes, the mixture was left at 25° C. overnight, and the viscosity at 6 Orpm and 6 rpm was measured using a B-type viscometer. The results are shown below.

Co 158.9 Go/40
5900/1B70 = 3.5Y 1 14
6.0 42158 1140/ 804
= 1.9XI 173.0 8
8/12 11800/2630 =4.5X2
178.7 98/ 2 200
00/3050 = 6.6 Note: The viscosity of BO rpm in the case of no thixotropic addition is 275 cps Test Example 2 (Thixotropic effect of solvent-free resin) Raw material hydrogenated castor oil (comparative amount Co), obtained in Example 3 The first
The thixotropy of the solvent-free resin was investigated using the crystals (modified product X3) and the first precipitate obtained in Example 2 (modified product X2) as thixotropes.

In a glass bottle, add 70 g of bisphenol A epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Chichishiki Company).
, 30 g of dioctyl adipate (plasticizer), and 1 g of the above-mentioned thixotropic agent, which had been previously pulverized in a mortar, were added, heated to 90° C. to dissolve, and cooled.

This resin liquid was left in a constant temperature bath at 25° C. overnight, and the viscosity at 60 rpm and 6 rpm was measured using a B-type viscometer. The results are shown below.

Co 15Ei, 9 80/40 1
840/980 = 1.9X3 113
8.5 81/19 5000/1840
=2.7X2 17E17 98/2
5700/1870 = 3.05 Note: The viscosity at 8 Orpm without thixotropic addition is 390 cps Test Example 3
(Gelification effect of mineral oil) Raw material hydrogenated castor oil (comparative amount Co), the first
The fluidity of mineral oil was investigated using the crystals (modified product X3) and the first precipitate obtained in Example 2 (modified product X2) as gelling agents.

Put 100 g of mineral oil (high-grade lubricating oil base "Cosmo Neutral 700J" manufactured by Cosmo Oil Co., Ltd.) and a predetermined amount (1.5 to 12 g) of the gelling agent of 314 above in a glass bottle,
After heating and dissolving with a heater, the mixture was naturally cooled.

The observation results of the state after night release M at room temperature (20° C.) were as follows.

08 value 15B, 9 178.7 188.5 liquidity
1.5g added 3g added 6g added to g added 12g added ○ Δ × 0 0 × OO Δ OO In the fluidity item, 0 means paste-like and no fluidity;
Δ is a state where the material is about to flow, and × is a state where there is fluidity.

- Not measured.

Among the above examples, the flow start temperature (dropping point) was measured for the mineral oil/gelling agent blending ratio of 100,710. The results were as follows.

'y' tlz 4Tc peeling
(Zan Co Fluid at 20°C x Melts from the surroundings at 286°C. Flows x Melts from the surroundings at 384°C and flows Test Example 4 (Gelification or thickening effect of organic solvent) Raw material hydrogenated castor oil ( Using a comparative amount of Co and the first crystal (modified product X3) obtained in Example 3 as a gelling agent or thickening agent, the gelling property or thickening property of an organic solvent was investigated.

Co or
3 g or 9 g was added and dissolved, and the viscosity at 25° C. was measured and the state was observed. The results were as follows.

Viscosity 152cps 1680cps > 100,000cps State Liquid Liquid Partially solid
Chart of thin layer chromatography> Raw material hydrogenated castor oil (comparative amount Co), second crystal obtained in Example 1 (modified product Yl)
), the thin layer chromatography charts of the first precipitate (modified product X2) obtained in Example 2 and the first crystal (modified product X3) obtained in Example 3 are shown in FIGS. 1 and 2, respectively. Third
It is shown in Fig. 4.

[Brief explanation of drawings]

Figures 1 to 4 show raw material hydrogenated castor oil (comparative amount Go).
), the second crystal obtained in Example 1 (i!ni material Yl), the first precipitate obtained in Example 2 (modified material X2), and the first crystal obtained in Example 3 (modified material X3). It is a chart of thin layer chromatography.

Claims (1)

[Claims] 1. Hydrogenated castor oil is subjected to an operation that takes advantage of the difference in solubility of triglyceride components contained in the hydrogenated castor oil in solvents to obtain glycerin-tri-12-hydroxystearate ( T) and glycerin di-
12-Hydroxystearate-monostearate (D
) and glycerin di-1
2-Hydroxystearate-monostearate (D)
1. A method for producing a modified hydrogenated castor oil, which comprises separating the modified product Y into a modified product Y in which the ratio of glycerin-tri-12-hydroxystearate (T) is increased and the ratio of glycerin-tri-12-hydroxystearate (T) is decreased. 2. The proportion of component (T) in hydrogenated castor oil is t_0% by weight
When the ratio of component (T) in the modified material X is (t_0
+5) The manufacturing method according to claim 1, wherein the amount is at least 5% by weight. 3. The proportion of component (D) in hydrogenated castor oil is d_0% by weight
When, the proportion of component (D) in the modified material Y is (d_0
+5) The manufacturing method according to claim 1, wherein the amount is at least 5% by weight. 4. An operation that takes advantage of the difference in solubility is as follows: [1] Hydrogenated castor oil is heated and dissolved in a solvent, then cooled to obtain a precipitate and a non-precipitate, and separated into modified product X and modified product T. Operation, [2] Operation of contacting a solvent solution of hydrogenated castor oil with a poor solvent of the component of interest to obtain a precipitate and a non-precipitate, and separating it into modified product X and modified product Y, [3] Hydrogenation Extract and extraction residue are obtained by extracting castor oil with a solvent,
2. The production method according to claim 1, wherein the step of separating into modified material X and modified material Y is at least one operation selected from the group consisting of: