JPH11180927A - Production of hydroxyfatty acid and water soluble lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially obtain the subject compound useful as an essential component for water-soluble lubricants excellent in balance of water dispersibility and lubricity by reacting a vinylfatty acid ester with a fatty acid and then saponifying the reaction product. SOLUTION: A vinylfatty acid ester (e.g. vinyl acetate or vinyl propionate) is reacted with a fatty acid (preferably ricinolic acid or lesquerolic acid) and then, the resultant vinyl fatty acid grafted fatty acid is saponified. The reaction of the vinylfatty acid ester with the fatty acid is preferably carried out in the presence of a radical initiator such as dicumyl peroxide under pressure or ordinary pressure at 50-220 deg.C for 1-20 hr. the saponification is preferably carried out by boiling the vinylfatty acid graft fatty acid with a sufficient amount of water, normally in the presence of 0.01-2 equivalent base catalyst for 1-10 hr to hydrolyze the fatty acid. The objective compound has preferably 50-300 hydroxyl value and 50-200 neutralization value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydroxy fatty acid useful as a lubricant and a wetting agent, and a water-soluble lubricant composition.

[0002]

2. Description of the Related Art According to Japanese Patent Laid-Open Publication No. 3-80200, a water-soluble cutting agent comprising a salt of a polyhydroxy fatty acid obtained by binding oxirane oxygen to an unsaturated fatty acid and hydrating it. Oil compositions are known. However, in order to bind oxirane oxygen, it is necessary to use a lower carboxylic acid solvent such as acetic acid or formic acid having high corrosiveness, and there has been a problem in industrialization. According to Japanese Patent Publication No. 2-5799, there is a demand for a water-soluble cutting and grinding oil containing an alkali metal salt or an amine salt of ricinoleic acid polycondensate (acid value 40-145). However, the balance between water dispersion stability and lubricity was not sufficient.

[0003]

The problem to be solved by the present invention is to provide an industrial method for producing hydroxy fatty acids and to provide a water-soluble lubricant having an excellent balance between water dispersibility and lubricity. .

[0004]

Means for Solving the Problems The present inventor has extensively studied a structure having both excellent dispersibility and lubricity, and reached the present invention. That is, the present invention provides: 1. A method for producing a hydroxy fatty acid, which comprises reacting a vinyl fatty acid ester with a fatty acid, followed by saponification; The present invention relates to a water-soluble lubricant composition comprising a hydroxy fatty acid and a base obtained by reacting a vinyl fatty acid ester with a fatty acid or / and its ester and then saponifying the same.

As the vinyl fatty acid ester, vinyl acetate, pinyl propionate, vinyl butanoate, vinyl pentanoate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl formate, and the like can be used. .

As the fatty acid, a saturated or unsaturated, linear or branched, hydroxy-containing or non-hydroxy-containing fatty acid having 10 to 22 carbon atoms can be used. Specifically, neutralized fatty acids such as capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachinic acid, and behenic acid, undecylenic acid, oleic acid, eicosenoic acid, erucic acid, linoleic acid, and linolenic acid , Unsaturated fatty acids such as arachidonic acid, ricinoleic acid, lescleric acid, 1
Hydroxy fatty acids such as 2-hydrostearic acid can be used. The hydroxy fatty acids may be used alone, or two or more kinds may be used as a mixture, or a dehydrated condensate thereof may be used. Further, esters of these fatty acids with various alcohols can also be used. Among these, ricinoleic acid, resquellic acid, castor oil and resquella oil containing these glycerides as main components are industrially preferable raw materials.

The reaction between a vinyl fatty acid and a fatty acid in a method for producing a hydroxy fatty acid, which comprises reacting a vinyl fatty acid ester with a fatty acid and then saponifying the fatty acid, will be described. Vinyl fatty acids and fatty acids are reacted in the presence of a radical initiator. In this case, they may be charged and reacted at the same time, or a radical initiator and / or a vinyl fatty acid may be added under radical generating conditions. The use ratio of the vinyl fatty acid ester varies depending on the quality of the intended hydroxy fatty acid, but is about 5 to 100 parts by weight based on 100 parts by weight of the fatty acid. Further, as the radical initiator, tert. Butylperoside, dicumyl peroxide, benzoyl peroxide, cumene hydroperoxide, peracetic acid, perbenzoic acid, bis (4-t-butylcyclohexyl) peroxydicarbonate, hydrogen peroxide,
Usual radical initiators such as peroxides such as potassium persulfate and azo compounds such as azobisisobutyronitrile can be used. Promoters and inhibitors of the generation of radicals can also be used. The reaction is carried out under an atmosphere of an inert gas or air under pressure or atmospheric pressure, at a temperature of 50 to 220 ° C. for about 1 to 2 times.
Conduct for about 0 hours. After the reaction, the unreacted fatty acid vinyl ester is removed by heating under reduced pressure or the like to obtain a fatty acid vinyl ester grafted fatty acid. If a fatty acid ester is used instead of a fatty acid, a fatty acid vinyl ester grafted fatty acid ester can be obtained.

Next, a method for producing a hydroxy fatty acid by saponifying a fatty acid vinyl ester grafted fatty acid or an ester thereof will be described. Fatty acid vinyl ester grafted fatty acid or its ester is hydrolyzed under a base catalyst,
Hydroxy fatty acids. Bases include hydroxides, bicarbonates, carbonates, ammonia, and amine compounds of one or more alkali metals. For alkali metal compounds, NaOH, KOH, LiOH, NaHCO3, KH
CO3, Na2CO3 and the like are exemplified. Among amine compounds, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, cyclohexylamine, benzylamine, morpholine, pyrrole, pyrrolidine, pyridine , Ethanolamine, diethanolamine, triethanolamine,
Examples include N, N-dimethylaminoethanol, N, N-diethylaminoethanol, ethylenediamine, diethylenetriamine, triethylenetetramine, 1,2-propylenediamine, dipropylenetriamine, tripropylenetetramine, and quaternary ammonium hydroxide salts thereof. . The base is usually used in an amount of about 0.01 to 2 equivalents of the vinyl fatty acid-grafted fatty acid or an ester thereof, and is boiled with a sufficient amount of water for 1 to 10 hours. Next, by adding sulfuric acid, hydrochloric acid, or the like, the mixture is acidified, washed with water, and dehydrated under reduced pressure to obtain a hydroxy fatty acid.

The hydroxy fatty acid of the present invention undergoes condensation depending on conditions such as post-reaction treatment, and the hydroxyl value and the acid value decrease, but the hydroxyl value is 50 to 300 and the neutralization value is 50 to 200.
Is not particularly limited as long as it is within the preferable range.

The hydroxy fatty acids of the present invention are used as lubricity improvers for lubricating oils in mineral oils and synthetic oils, as wetting agents for yarns, fabrics and cosmetics, and as water-soluble lubricants together with bases and water. .

The method for producing the water-soluble lubricant composition of the present invention will be described. When a water-soluble lubricant is used, the fatty acid vinyl ester-grafted fatty acid or its ester may be used as a lubricant.
It can be used without saponification with about 1 to 2 equivalents of a base without purification. Of course, the hydroxy fatty acid may be isolated and then mixed with the aforementioned base and water. In the latter, the hydroxy fatty acid and the above base may be separately added to water, or may be added to water after forming a salt. Then, it can be dispersed in water by stirring and mixing under normal pressure or pressure, at normal temperature or under heating.

The composition of the composition of the present invention will be described.
The composition of the present composition is determined in consideration of required performance and economy. In general, a concentrated solution of the hydroxycarboxylic acid salt of the present invention during transportation and storage, 0.01 to 50% by weight of the hydroxycarboxylic acid of the present invention during use, 10 to 99% by weight of water, and a base Is adjusted to be approximately equivalent or more to the acid component. Other known water-soluble lubricants and known additives as additives for water-soluble lubricants, such as surfactants, rust inhibitors, lubricity improvers, antibacterial agents, antifungal agents, antifreeze components, etc. You may add in the range which does not impair the effect of this invention.

The use of the composition of the present invention will be described. Broadly speaking, there are two uses. One of them is a processing lubricant for various materials. Cutting of metal, concrete, asphalt, rock, glass, ceramics, plastics, etc., deep drawing of metal, plastics, etc.
In bending, drawing, and spinning, the composition of the present invention is useful for preventing troubles due to friction due to lubrication and cooling. That is, it is a processing lubricant of various materials for preventing wear of the cutting edge of the processing tool, increase of processing energy, damage of processed products, and noise.

Another application is a pressure transmitting medium.
As the pressure transmission medium, an aqueous medium which is a mixture of a non-aqueous medium of mineral oil, animal and vegetable oil, or synthetic oil and water used for hydraulic reloading, or a water-soluble oil is used. Conventionally, non-aqueous pressure media have the drawback of being flammable, and aqueous pressure media have the drawback of lack of lubricity, and a non-flammable pressure medium having excellent lubricity has been desired. The composition of the present invention provides a non-flammable pressure medium having excellent lubricity.

[0015]

The embodiments of the present invention will be described with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, the neutralization value and the hydroxyl value were measured by the standard oil and fat analysis test method established by the Japan Oil Chemical Association. The unit is mg-KOH / g
It is.

The method of making the hydroxy fatty acid soluble in water and the method of evaluation are as follows. <Water-solubilizing method> 1% by weight of a hydroxy fatty acid and 1% by weight of triethanolamine are added to 98 parts by weight of tap water heated to 80 ° C, and the mixture is stirred and mixed at 400 rpm for 5 minutes with a stirrer. <Performance Evaluation Method of Water-Soluble Lubricant> (a) Emulsion stability: The aqueous dispersion was allowed to stand at room temperature in a 100-ml container, and changes over time up to one week were observed. ：: dispersion state maintained, ×: separation (b) Friction coefficient and abrasion amount: Measured with a Falex type friction tester under the following conditions. Test piece: ASTM standard steel Load (kg) / time (min): 113/5 + 227 /
5 Coefficient of friction: Average coefficient of friction at a load of 227 kg Amount of wear: Total weight change of test piece before and after use (mg) (c) Drill cutting property: L-shaped iron plate of 5 mm thickness with a 3 mmφ drill for metal on pole board During the drilling operation, the sample liquid was continuously supplied to the tip of the drill at a rate of 1 drop / sec. 10 points for the best sharpness, 0 points for water alone, 3 points
Cycle repetition was shown by their average value. (D) Rust-generating property: The surface of the wire of the gem clip was sanded, cut into 1 cm lengths, placed in an aqueous dispersion, and observed for changes in the surface up to one week. ：: The surface is darkened but there is no further change. ×: Invention of corrosion progress due to red rust.

Example 1 298 g of ricinoleic acid (COFA manufactured by Toyokuni Oil Co., Ltd., neutralization value: 182, hydroxyl value: 161), 86 g of vinyl acetate and bis (4-t) were placed in a 500 ml four-necked flask equipped with a stirrer, a thermometer and a condenser. -Butylcyclohexyl) peroxy dicarbonate (10 g) and stirring
React at ~ 80 ° C for 5 hours. Then, the distilling tube was replaced and concentrated to a pot temperature of 160 ° C. to obtain 332 g of a pale yellow liquid.
Next, a 150 g aqueous solution of 10% sodium hydroxide was added thereto, and the mixture was boiled for 2 hours. After cooling, the solution was acidified with sulfuric acid and then washed with water until the solution became almost neutral. The mixture was concentrated under reduced pressure at 90 ° C. to obtain 314 g of a translucent liquid. Neutralization value 93.7, hydroxyl value 12
It was 5.

Example 2 The procedure of Example 1 was repeated except that vinyl acetate was used in an amount of 43 g and bis (4-t-butylcyclohexyl) peroxy dicarbonate in an amount of 7 g, to obtain 302 g of a hydroxylated castor oil fatty acid. The neutralization value was 95.5 and the hydroxyl value was 108.

Reference Example 1 Ricinoleic acid was heated to 200 ± 10 ° C. according to a conventional method.
Condensed ricinoleic acid was obtained (neutralization value 96.9)

Embodiments 3 and 4 Embodiments 1 and 2. A water-soluble lubricant was prepared from the reaction product of Reference Example 1, triethanolamine and tap water by the method described above, and evaluated. Table 1 shows the results.

Comparative Example 1 1 part by weight of condensed ricinoleic acid, 1 part by weight of triethanolamine and 98 parts by weight of water were mixed with a stirrer and evaluated in the same manner as in the example.

Comparative Example 2 1 part by weight of ricinoleic acid, 1 part by weight of triethanolamine and 98 parts by weight of water were mixed with a stirrer, and evaluated in the same manner as in the example.

[0023]

The composition of the present invention provides a cutting oil and a pressure medium having excellent dispersion stability and lubricity.

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Claims (2)

[Claims] 1. A method for producing hydroxy fatty acid, comprising reacting a vinyl fatty acid ester with a fatty acid and then saponifying the fatty acid. 2. A water-soluble lubricant composition comprising a hydroxy fatty acid and a base obtained by reacting a vinyl fatty acid ester with a fatty acid or / and its ester and then saponifying it.