KR101904851B1 - Manufacturing for method water-soluble metal processing aid active surfactant - Google Patents

Abstract

The present invention relates to a method for preparing a surfactant additive agent for water-soluble metal processing oil. More specifically, the method for preparing a surfactant additive agent for water-soluble metal processing oil is used to input a stearic acid and an oleic acid to triethanolamine to stir the mixture while raising the temperature to a suitable reaction temperature, cools the mixture when a suitable target value is reached, adjusts the surface tension needed for the water-soluble metal processing oil while enhancing the lubricity, and prepare highly durable metal processing oil by preparing the surfactant additive agent not harmful to the human body. According to the present invention, the method for preparing a surfactant additive agent for water-soluble metal processing oil includes the steps of: (a) inputting and stirring the triethanolamine to a reactor and while heating the triethanolamine at 80°C; (b) inputting the stearic acid to the product of step (a) and stirring the mixture to dissolve the stearic acid therein; (c) inputting the oleic acid after dissolving the stearic acid in step (b) and stirring the mixture to remove the moisture in the reactor while raising the temperature to 120°C; (d) stirring the product in step (c) while raising the temperature; (e) extracting the reaction product after the reaction in step (d) is completed to execute an intermediate test; (f) completing the reaction when the free acid, color, pH, and surface tension values reach target values in the intermediate test and cooling the product by using an air cooling or water cooling method; and (g) executing a final test.

Description

Technical Field [0001] The present invention relates to a water-soluble metal processing aid active surfactant,

The present invention relates to a process for preparing a water soluble metalworking surfactant additive. More specifically, it is possible to control the surface tension required for the water-soluble metal to be shared and to improve the lubricity by cooling the water when the stearic acid and oleic acid are added to the triethanolamine, The present invention relates to a method for producing a water-soluble metalworking useful surfactant, which enables a high-durability metal to produce a cure.

The metal sharer is used during the process of cutting and cutting a metal material. It reduces the friction and heat between the cutting tool and the metal material, prevents the material from being deformed by heat to cool the material, The lubricant acts as a lubricant to extend the life of the cutting tool.

In general, the metal-sharing agent is classified into a water-soluble metal-sharing agent whose primary purpose is lubrication-free water-insoluble metals and whose main purpose is to cool and cool.

In the case of a water-soluble metal-sharing agent, it is classified into emulsion type, soluble type and solution type depending on the emulsion particle shape when mixed with water.

Emulsion-type water-soluble metal salt-sharing agent refers to an oil that becomes opaque when diluted with water and becomes an emulsion. It is usually diluted 10 to 30 times and contains preservatives since the oil breaks down due to cutting heat and is liable to decay.

The Soluble type is mainly composed of a surfactant additive. When the content of mineral oil is low and it is diluted with water, it becomes a translucent or transparent liquid. This type is excellent in permeability and oiliness due to its low surface tension. It is usually diluted 50 to 100 times.

Solution-type metal-scaffolding agent is an aqueous solution containing an inorganic salt such as sodium chromate, a water-soluble rust inhibitor additive to an organic alkali, and has no oil. In addition, the cooling property is extremely excellent, about twice as much as water, and is used for grinding processing. It is usually used by diluting 50 to 100 times.

At this time, in the emulsion type and the soluble type, a surfactant additive is added to emulsify the oil contained in the emulsion.

The surfactant additive is composed of various forms depending on the purpose and use. In the present invention, an additive that is harmless to human body and capable of improving lubrication performance and capable of producing high durable metal share is developed.

Prior Art Document: KR Patent Registration No. 0714084 (published on Feb. 2, 2007)

DISCLOSURE Technical Problem The present invention has been conceived to solve the problems as described above. It is an object of the present invention to provide a surface-active additive capable of controlling the surface tension necessary for sharing a water-soluble metal and improving lubricity, have.

In order to accomplish the above object, the present invention provides a method for preparing a water-soluble metalworking useful surfactant, comprising: (a) charging triethanolamine into a reactor and heating the mixture at 80 ° C with stirring; (b) adding stearic acid to the result of step (a) and stirring to dissolve the stearic acid; (c) after the stearic acid is dissolved in step (b), adding oleic acid and raising the temperature to 120 ° C with stirring to remove moisture inside the reactor; (d) heating and stirring the resultant product of step (c); (e) extracting the reaction product after the reaction of step (d) is completed, and performing an intermediate test; (f) terminating and cooling the reaction when the free acid, color, pH, and surface tension in the intermediate test reaches the target value; And (g) performing a final test.

The molar ratio of triethanolamine, stearic acid and oleic acid introduced in steps (a) to (c) is 2: 0.1: 1, the reaction temperature in step (d) is 160 ° C or higher, Or more.

In addition, in step (e), when the measured color (ATSM), free acid content, surface tension, and pH of the resultant reaction product are not satisfied, it may further include re-reacting for 2 hours or more.

According to the present invention, triethanolamine and stearic acid and oleic acid are added to raise the temperature to an appropriate reaction temperature, and the mixture is stirred. When the temperature reaches a predetermined target value, the mixture is cooled to adjust the surface tension required for water- It is effective to make high durable metals to produce covalently.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow diagram of a method for preparing a water soluble metalworkable surfactant additive according to a preferred embodiment of the present invention. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to designate the same or similar components throughout the drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, the preferred embodiments of the present invention will be described below, but it is needless to say that the technical idea of the present invention is not limited thereto and can be variously modified by those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow diagram of a method for preparing a water soluble metalworkable surfactant additive according to a preferred embodiment of the present invention. FIG.

Referring to FIG. 1, a method for preparing a water soluble metalworkable surfactant according to a preferred embodiment of the present invention is performed according to the following process.

The first step (S110) is a step of adding triethanolamine to the reactor and heating at 80 DEG C with stirring.

The second step (S120) is a step of adding stearic acid to the result of the first step (S110) and stirring to dissolve the stearic acid.

In the third step S130, if the stearic acid is dissolved in the second step S120, oleic acid is added and the temperature is raised to 120 ° C with stirring to remove water inside the reactor.

Particularly, monoethanolamine which is conventionally used in the production process of a surfactant additive is a viscous colorless liquid which has an odor of ammonia and is corrosive and is not good for the skin. If it gets into eyes, it causes damage. Or difficulty in breathing, damage to the liver and kidney, and toxicity to the nervous system.

In addition, diethanolamine, like monoethanolamine, has harmful effects on the human body. Skin contact can cause blisters and burns and can cause abdominal pain, diarrhea, vomiting, and can act as a carcinogen There are risks.

Therefore, triethanolamine is used in the present invention in consideration of the stability of the human body due to the harmfulness of the above-mentioned diethanolamine and monoethanolamine.

Stearic acid has the function of adjusting the viscosity (hardness), emulsifying agent and conditioning agent, and oleic acid is added to produce a product with excellent absorbency.

In addition, the charging ratio of triethanolamine, stearic acid, and oleic acid added during the first step (S110) to the third step (S130) is preferably 2: 0.1: 1. This will be described in the following first embodiment.

Particularly, in the case of triethanolamine, it is added to increase PH, and the content of stearic acid is set to a minimum amount to adjust the viscosity (hardness), and also to give the function of emulsifier and conditioning agent.

The fourth step S140 is a step of heating and stirring the result of the third step S130.

In particular, oleic acid is in a liquid state at room temperature, while the melting point of stearic acid is 70 ° C, which is a solid state at room temperature. Therefore, it should be carried out at a minimum temperature necessary for dissolving stearic acid and a sufficient temperature necessary for the amide synthesis with triethanolamine, and preferably at a temperature of at least 120 ° C to a maximum of 200 ° C.

More preferably at a reaction temperature of 160 ° C. In particular, the higher the temperature, the darker the color of the mixture, and since the stability of the oleic acid against heat is weak, a temperature of 160 ° C is the most desirable so that the color of the mixture does not become too dark.

The fifth step S150 is a step of extracting reaction results and performing an intermediate test when the reaction of the fourth step S140 is completed. In the fifth step (S150), the target value of the free acid free acid test completed by chemical reaction is an intermediate test to determine whether free acid (mg / kOH) satisfies 5 mgKOH / g or less. When the free acid is less than 5 mgKOH / g It is determined that the intermediate inspection standard is satisfied, and the subsequent process is performed.

In the fifth step (S150), the intermediate target value is set so that the reaction state of the reactant after the first agitation is firstly checked to increase the physical properties of the final product.

Here, the free acid is an acid which does not form a salt and does not bind to a substance existing in the form of an acid or another chemical substance. In the present invention, the free acid means an acid which does not react in the reaction of the reaction product.

The phenomenon that free acid remains in the reactant is when the content of acid is higher than that of the salt (when the molar ratio is not matched) or when the reaction is not sufficiently performed. When the content of free acid is high, If the content of the free acid is high, the oxidation process proceeds rapidly during the use of the product, thereby affecting the quality of the water-soluble metalworking oil or the product of the cutting oil, resulting in shortening the service life. It is necessary to confirm whether free acid is detected below a predetermined value.

If the result of the reaction extracted in the intermediate test does not satisfy the appropriate target value in the fifth step S150, the reaction is performed for about 2 hours so that a product that can satisfy the standard target value can be derived.

In the sixth step (S160), when the free acid, color, and pH values in the intermediate test reach the target value, the reaction is terminated and cooled.

More specifically, in the sixth step (S160), when the target value is met in the intermediate test, the reaction is terminated and gradually cooled in the atmosphere, or cooling water is allowed to flow outside the reactor, followed by cooling with water until the temperature is normal Can be used.

The seventh step S170 is a step of performing a final inspection. More specifically, in the seventh step (S170), the final target content of the free acid is preferably 3 mgKOH / g or less.

In the seventh step S170, the final inspection is performed after the sixth step S160, and when the final target value is satisfied, it is filled with the product.

[Example 1]

Triethanolamine was added to the reactor and heated at 80 占 폚 with stirring. Stearic acid was then added and stirred to dissolve the stearic acid. After the stearic acid was dissolved, oleic acid was added and the temperature was elevated to 120 占 폚 while stirring. The mixture was heated to 160 DEG C and stirred. When the reaction was completed, the reaction was terminated and cooled. Then, the color, free acid content, emulsion stability, and surface property were checked. Table 1 below shows the results of verifying the optimum quality of the water-soluble cutting-use surfactant as a final product produced by applying different molar ratios of triethanolamine, stearic acid and oleic acid.

Table 1 below shows the results of basic physical properties test for color (ASTM), free acid (mgKOH / g), emulsion stability to oil, and surface tension.

Mole ratio Test Items Stea
Rick Eshid Oleic acid Triethanolamine color
(ASTM) Free acid
(mgKOH / g) Emulsion stability
(General tap water) Surface tension
(dyne / cm) 0.1 One One L1.5 2.8 Good 33 0.1 2 One L2.5 3.7 Bad 38 0.2 One One L1.5 3.2 Good 30 0.1 One 2 L1.5 1.8 Good 22 0.1 2 2 L2.0 2.4 Good 25

1. Color

Stearic acid and triethanolamine are colorless or white and do not significantly affect the color of the reactants, but oleic acid is light yellow and red. The color changes with increasing water content.

2. Free acid (mg KOH / g)

It was confirmed that the content of free acid after the reaction was increased with an increase in the molar ratio of stearic acid and oleic acid. This is because stearic acid and oleic acid still remain unreacted as the total amount increases after reaction with triethanolamine, which is a base.

Particularly, it can be seen that the higher the molar ratio of triethanolamine, the lower the content of the free acid. The higher the content of amine in the reaction of the acid, stearic acid, oleic acid and triethanolamine, the higher the ratio of stearic acid to oleic acid I could confirm.

3. Emulsion stability

Here, the emulsion stability was evaluated by diluting 3.5 g of the reactant sample in 100 ml of the oil (P-8, base oil), dropping it in water and loosening it to water.

The emulsion stability, that is, the releasability to water, was not good when the molar ratio of stearic acid to oleic acid was higher than the molar ratio of triethanolamine.

4. Surface tension (dyne / cm)

Among the properties of the water-soluble metal-sharing, permeability, density, and adsorption are the most important requirements.

Particularly, the surfactant additive adsorbs at each interface of the solute in the solution to change the characteristics of the interface, and has the property of reducing the surface tension. Therefore, the smaller the value of the surface tension, the better the surfactant performance.

Referring to Table 1, it was confirmed that the higher the molar ratio of stearic acid and oleic acid, the lower the surface tension. That is, the higher the molar ratio of triethanolamine, the lower the surface tension.

Thus, when the molar ratio of triethanolamine, stearic acid and oleic acid is 2: 0.1: 1, the color of the final product is low, the amount of free acid is small, the surface tension is low, and the emulsion stability is excellent .

[Example 2]

2 mol of triethanolamine was added to the reactor, and the mixture was heated at 80 DEG C while stirring. Then, 0.1 mol of stearic acid was added and stirred to dissolve the stearic acid. 1 mol of oleic acid was added and the mixture was heated to 120 DEG C , And the mixture was heated to 160 DEG C and stirred. When the reaction was completed, the reaction was terminated and cooled, and then the color, free acid content, and surface property were checked. Table 2 below shows the results of verifying the optimum quality of the water-soluble cutting-use surfactant as a final product produced by varying the reaction time at the step of heating and stirring up to 160 ° C.

  Test item / reaction time 4 hours 6 hours 8 hours Color (ASTM) L1.5 L 1.5 L 2.0 Emulsion stability (common tap water) Good Good Good Surface tension (dyne / cm) 23 22 22

1. Color (ASTM)

When the reaction temperature was high and the reaction time exceeded 6 hours, it was confirmed that the color was thickened. It was confirmed that oleic acid was due to weak heat stability and reaction time was appropriate for 4 hours and 6 hours when the color did not darken.

2. Emulsion stability

The solubility in water was good at least over 4 hours, and it was confirmed that the water - solubility was good even in the reaction time of 6 hours or more.

3. Surface tension (dyne / cm)

The surface tension was the best at reaction time 6.

Therefore, when the color, emulsion stability, and surface tension were all considered, it was confirmed that the reaction time was most preferably 6 hours.

[Example 3]

2 mol of triethanolamine was added to the reactor, and the mixture was heated at 80 DEG C while stirring. Then, 0.1 mol of stearic acid was added and stirred to dissolve the stearic acid. 1 mol of oleic acid was added and the mixture was heated to 120 DEG C , And the mixture was stirred under different temperature conditions. When the reaction was completed, the reaction was terminated and cooled, and then the color, free acid content, and surface property were checked. Table 3 below shows the results of verifying the optimized quality group as a water-soluble cutting-use surfactant that is finally produced by differently applying the reaction temperature for raising the final temperature.

  Test item / reaction temperature 120 DEG C 160 ° C 200 ℃ Color (ASTM) L1.5 L 1.5 L 2.0 Emulsion stability (common tap water) Good Good Good Surface tension (dyne / cm) 24 22 23

1. Color (ASTM)

Referring to Table 3, it can be confirmed that the color becomes thicker as the reaction temperature is higher. This seems to be due to the weak stability of oleic acid to heat. Therefore, it was confirmed that the temperature of 160 占 폚, which does not affect the quality of the product, and the color is not excessively darkened, was found to be proper.

2. Emulsion stability

The releasability to water was good when the reaction temperatures were 120 캜, 160 캜 and 200 캜.

3. Surface tension (dyne / cm)

The surface tension was good when the reaction temperature was 120 ° C, 160 ° C, and 200 ° C, similar to the emulsion stability. However, it was confirmed that the surface tension was excellent when the reaction temperature was 160 ° C.

Thus, it can be seen from Table 3 that the reaction temperature is 160 캜, which is not excessively darkened and excellent in surface tension and emulsion stability.

Based on the above-described Examples 1 to 3, the most suitable optimum reaction conditions to satisfy the basic physical properties as the surfactant closest to the HLB of the base oil used in the production of the water-soluble metal chelate are 2 mol of triethanolamine, 0.1 mol of stearic acid and 1 mol of oleic acid for 6 hours at a reaction temperature of 160 占 폚.

Table 4 below shows the basic physical properties and other test results of the final reaction products.

Test Items standard Test result Emulsion stability (common tap water) - Good Surface tension (dyne / cm) - 22 Free acid (mg KOH / g) 3 or less 1.8 Color (ASTM): 2.0 or less L 1.5 Specific Gravity (15/4 ℃) - 1.02

[Example 5]

In order to determine the functionality as a surfactant additive according to a preferred embodiment of the present invention using a substance capable of replacing triethanolamine and a substance capable of replacing oleic acid and stearic acid, a substance capable of replacing triethanolamine , The basic synthesis was carried out using palmitic acid and lauric acid as materials capable of replacing oleic acid and stearic acid by using diethanolamine and monoethanolamine and the test results of the final reactants are shown in Table 5 below Respectively.

The following Table 5 shows the results of the final reaction according to the preferred embodiment of the present invention in terms of molar ratios (0.1: 1: 2), reaction temperatures (160 ° C) and reaction times (6 hours) Of the amine and fatty acid.

Mole ratio division Palmitic acid Lauric acid Stearic acid Olein
mountain Mono
Ethanolamine D
Ethanolamine tree
Ethanolamine A - - 0.1 One - - 2 B - - 0.1 One 2 - - C - - 0.1 One - 2 - D 0.1 0.1 - - - - 2 E 0.1 0.1 - - 2 - - F 0.1 0.1 - - - 2 -

As a result of the synthesis according to the above molar ratio, the following test results were derived.

Test Items Examination division color
(ASTM) Free acid
(mgKOH / g) Emulsion stability
(General tap water) Surface tension
(dyne / cm) A L1.5 1.8 Good 25 B L1.5 1.3 Good 28 C L1.5 1.7 Good 29 D L0.5 0.7 Good 32 E L0.5 1.0 Good 30 F L0.5 0.8 Good 33

1. Color (ASTM)

When palmitic acid and lauric acid except oleic acid and stearic acid were synthesized with amine series, the color was white and the color was lighter than that of oleic acid and stearic acid.

2. Free acid (mg KOH / g)

In the case of oleic acid - containing reactants, free acid values were slightly higher than those not otherwise. This is because the acid value of oleic acid was relatively higher than that of other fatty acids, but it did not affect the overall product quality.

3. Surface tension (dyne / cm)

There was a slight change in the surface tension regardless of the type of amine, depending on the presence or absence of oleic acid. That is, when oleic acid is contained, it can be confirmed that the value of the surface tension is low. Particularly, in order to be used as a surfactant additive of a water-soluble metalworking oil or a water-soluble cutting oil, In fact, it was found that the substance added with oleic acid is a better product because it is better in quality.

It will be apparent to those skilled in the art that various modifications, substitutions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. will be. Therefore, the embodiments disclosed in the present invention and the accompanying drawings are intended to illustrate and not to limit the technical spirit of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments and the accompanying drawings . The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

S110 - adding triethanolamine to the reactor and heating at 80 캜 with stirring
Stearic acid is added to the result of S120 - S110 and stirred to dissolve the stearic acid
After the stearic acid is dissolved in S130 - S120, oleic acid is added and the temperature is raised to 120 deg. C with stirring to remove water inside the reactor
Step S140-S130 is a step of heating the resultant and stirring
When the reaction of S150 - S140 is completed, the reaction result is extracted and the intermediate test is performed
S160 - When the free acid, color, pH, and surface tension in the intermediate test reaches the target value, the reaction is terminated and the cooling step
S170 - Steps to carry out final inspection

Claims (3)

(a) adding triethanolamine to the reactor and heating at 80 DEG C with stirring;
(b) adding stearic acid to the result of step (a) and stirring to dissolve the stearic acid;
(c) after the stearic acid is dissolved in step (b), adding oleic acid and raising the temperature to 120 ° C with stirring to remove moisture inside the reactor;
(d) heating and stirring the resultant product of step (c);
(e) a fifth step of extracting reaction products after completion of the reaction of step (d) and performing an intermediate test;
(f) terminating and cooling the reaction when the free acid, color, pH, and surface tension in the intermediate test reaches the target value; And
(g) Steps to carry out final inspection
Lt; / RTI >
the molar ratio of triethanolamine, stearic acid, and oleic acid introduced in steps (a) to (c) is 2: 0.1: 1,
the reaction temperature in step (d) is at least 160 ° C., and the reaction time is at least 6 hours,
In step (e), if the color of the reaction product (ATSM), free acid content, surface tension, and pH are measured, if the target value is not satisfied, re-
By weight based on the weight of the water-soluble metal-working surfactant.



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