KR101533580B1

KR101533580B1 - Water-soluble cutting lubricant additive useful in Ricinolic Acid

Info

Publication number: KR101533580B1
Application number: KR1020150034481A
Authority: KR
Inventors: 강희성; 이현식
Original assignee: 그린루브 주식회사
Priority date: 2015-03-12
Filing date: 2015-03-12
Publication date: 2015-07-03

Abstract

The present invention relates to a highly lubricating additive from ricinoleic acid for water-soluble cutting oil, and a preparing method thereof. More particularly, the highly lubricating additive is prepared as a highly lubricating improver by performing a condensation reaction on ricinoleic acid which is a main component of castor oil. The method according to the present invention comprises the steps of: (C1) feeding ricinoleic acid and a platinum catalyst into a container; (C2) supplying nitrogen gas (N2) to the container and sealing the container; (C3) increasing the temperature of the container by 2°C per minute until the temperature reaches 220°C; (C4) increasing the temperature of the container to 250°C, and performing a condensation reaction therein for 4 to 5 hours; (C5) cooling the container until its temperature reaches 90°C, and collecting a sample for an intermediate inspection; and (C6) performing, if the intermediate inspection indicates that the target performance is achieved, a final inspection, and preparing a final product through a filtering process, wherein if the intermediate inspection indicates that the target performance is not achieved, the steps (C2) through (C5) are repeatedly performed except that the condensation reaction is performed for 2 hours. According to the present invention, a polymer lubricating additive can be prepared by performing a condensation reaction on ricinoleic acid, with abrasion resistance increased by 17% or more in comparison with that of boric amide.

Description

[0001] The present invention relates to a water-soluble cutting lubricant additive useful in Ricinolic Acid,

The present invention relates to a water-soluble cutting-use ricinoleic acid high-lubricity additive and a process for producing the same. More particularly, the present invention relates to a water-soluble cutting aid Ricinoleic acid High lubricity additive.

The water-soluble cutting oil used in mixing with water when cutting metal is basically diluted about 10 times with water. Therefore, firstly, the oil should not be separated when water is mixed and the cream layer is not generated even when left for a long time It should be good in mixing with water.

The most important function of water-soluble cutting oil is that it is very important to ensure that the lubricating property is reduced due to water.

Domestic and overseas conventional technologies are concentrating on starting water-soluble cutting oil that is harmless to the human body. As a representative example, the known technology of KR 10-0665790 is: It is not limited to petroleum, mineral oils and amines which are harmful to humans, but may be derived from plant oils based on saturated or unsaturated fatty acids, dibasic fatty acids, benzoic and thallium lubricity improvers, amide based rust inhibitors, alcoholic solvents, It is characterized in that the additive such as surfactant, corrosion inhibitor, antioxidant and microbial inhibitor is diluted in distilled water. The emulsion type water-soluble coolant oil for environmentally friendly, rustproofing, lubricating, cooling, storage stability, . In addition, the prior art of KR 10-0611735 is known. Discloses water-soluble cutting oil compositions that are prepared without the use of amines.

The main purpose of the water-soluble cutting oil is to improve the cooling effect during cutting. However, the function of the lubricating oil is an important factor and it is necessary to improve the lubrication performance because the water is diluted 10 to 30 times.

1. KR 10-0665790 B1, 'Water soluble cutting oil composition', registered on October 10, 2006. 2. KR 10-0611735 B1, 'Water-soluble cutting oil composition using vegetable oils, synthetic esters, vegetable oil methyl esters and amines', date of registration: 2006.08.04. 3. KR 10-2012-0056196 A1, 'Environmentally friendly water-soluble cutting oil for wafer cutting and water-soluble wafer cutting fluid composition containing the same', published on Jun.

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a water-soluble cutting oil having high lubricity and abrasion resistance as a main ingredient of castor oil, and to provide a water-soluble cutting lubricant additive using Ricinolic Acid. And it is an object of the present invention.

In order to achieve the above object, the present invention discloses a process for producing a high lubricity additive by subjecting ricinoleic acid to condensation reaction using platinum or concentrated sulfuric acid as a catalyst.

Further, the present invention, as a result of a preliminary test, discloses a method in which a condensation reaction time of 4 to 5 hours, including an optimal reaction time, can be produced with a high lubricity additive.

Further, the present invention discloses a process for producing a high lubricity additive characterized in that the catalytic ratio of platinum or concentrated sulfuric acid of the catalyst to the weight ratio of ricinoleic acid is 5%.

The present invention has the following effects due to the above-mentioned solution.

First, ricinoleic acid can be prepared as a polymer lubrication additive by condensation reaction and exhibits abrasion resistance improved by 17% compared to boric amide.

Second, ricinoleic acid is a main component of castor, which can lower the cost of producing additives, has an advantage of shortening the reaction time under the optimum condition, and reducing the manufacturing cost as a whole.

Third, RA is an additive which is relatively simple to control HLB rather than other kinds of additives, and those skilled in the art of preparing water-soluble cutting oil can easily utilize it as an additive sufficient to expect improvement of lubricity of water-soluble cutting oil.

Fourth, it can be used as a water-soluble cutting additive package additive.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of a preferred method of manufacturing the present invention.
Fig. 2 shows the result of the test according to the condensation reaction time.
Fig. 3 is a result of the evaluation test of the abrasion resistance of the present invention. Fig.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of a preferred method of manufacturing the present invention.

The present invention discloses a method for producing ricinoleic acid, which is a main ingredient of pajama oil, as a high lubricity improving agent through a condensation reaction.

The present invention relates to a water-soluble cutting oil comprising the steps of: (C1) introducing ricinoleic acid and a platinum catalyst into a vessel to produce ricinoleic acid as a high lubricating additive; After the step C1, a step (C2) of supplying nitrogen gas (N2) to the container and sealing the container; After step C2, the step (C3) is performed to raise the temperature to 220 deg. C at about 2 deg. C per minute. After the step C3, a step (C4) in which the condensation reaction is carried out for 4 to 5 hours by raising the temperature of the vessel to 250 DEG C; (C5) after the step C4, after cooling the temperature to 90 DEG C, collecting a sample and performing an intermediate inspection; (C6) after the C5 step, if the target performance is satisfied in the intermediate inspection, final inspection is performed and then the final product is filtered through the filtration process. In the case where the intermediate inspection is not satisfied after the intermediate inspection step (C5) (C2) to the intermediate inspection step (C5) are performed repeatedly while the reaction time in the condensation reaction step (C4) is set to 2 hours.

Further, in step C1, the catalyst is replaced with concentrated sulfuric acid instead of the platinum catalyst.

In the step C1, the mixing ratio of ricinoleic acid and platinum or sulfuric acid is 0.5% based on 1 kg of ricinoleic acid by weight.

When the mixing ratio of ricinoleic acid and platinum or sulfuric acid is higher than 0.5% by weight, the condensation reaction is promoted, but the pH value is increased and the computational cost is adversely affected. When the ratio is lower than the above-mentioned ratio, the condensation reaction is not promoted, and the C5 step is repeated several times in the step C2, which leads to an increase in the total production cost.

The Ricinolic Acid of the present invention is 12-hydroxy-cis-9-octadecenoic acid, an unsaturated hydroxy acid derived from oleic acid in which one 12-carbon atom is substituted with a hydroxyl group, and the main component of castor oil , The molecular formula is C18H3403 and the molecular weight is 298.1.

The condensation reaction of the present invention refers to a reaction in which a water molecule is separated from the reaction of a carbon compound and the two are bonded together. For example, when concentrated sulfuric acid is added to ethanol and heated to 130 ° C, the -OH group in one ethanol molecule binds to the other ethanol molecule in which the -OH group is dropped to form water, and the two ethanol molecules are bonded to form an ether.

Ex.) C₂H OH + C₂H OH → C₂H O C₂H + H₂O

The basic reaction scheme for producing RA (ricinolic acid) of the present invention is as follows.

C H 3 (C H 2) C H (O H) C H 2 C H + C H 3 (C H 2) C H (O H) C H 2 C H →

C H 3 (CH 2) CHC H 2 C HOC H 3 (CH 2) CHC H 2 C HO + H 2 O

In the raw material charging step (C1), 1 kg of ricinoleic acid and a platinum catalyst (or 0.5 wt% of concentrated sulfuric acid) are put into a vessel.

Nitrogen gas (N 2) is supplied to the container into which the raw material is charged, and nitrogen gas is sealed until the nitrogen gas is purely present (C 2).

The primary heating step (C3) is a step (C3) of gradually raising the temperature to about 2 deg. C per minute and bringing the temperature up to 220 deg. C, and continuously reacting so that the -OH group and the -H group are sufficiently separated.

In the condensation reaction step (C4), the temperature in the vessel is further raised to 250 DEG C, and a sufficient reaction time of about 4 to 5 hours is allowed so that two molecules separated from the -OH group and the -H group can be bonded to each other well To give a complete condensation reaction.

In the intermediate inspection step (C5), when the condensation reaction is judged to be sufficiently performed, the nitrogen gas is stopped to be filled, the temperature is cooled to 80 to 90 DEG C, and a sample is taken for an intermediate inspection.

In the intermediate inspection step (C5), it means that the reaction is not sufficiently performed if it is out of the management standard (C2). Then, the temperature is raised to about 250 DEG C and the reaction is continued for about 2 hours ). After cooling, the temperature is cooled to 80 to 90 ° C, and a sample is again sampled to conduct an interim test. In this way, the reaction is repeated until the intermediate test criteria are met.

The filtration and product processing step (C6), when the intermediate inspection is satisfied, is subjected to a final inspection and, if the final inspection procedure is satisfied, the product is filtered through a filtration process.

In the intermediate test, the computation cost and the kinematic viscosity should be satisfied. In one embodiment, the computational weight is 60 mgKOH / g or less and the kinematic viscosity (40 ° CSt) is 600 cSt or less.

In one embodiment, the total solids is less than 60 mgKOH / g, the kinematic viscosity (40 ° C. cSt) is less than 600 cSt and the color (ASTM) is from 2 to 3.5 , And specific gravity (15/4 ℃) should satisfy 0.94 ± 0.2.

Fig. 2 shows test results according to the condensation reaction time.

It is preferable to have a condensation reaction time of 5 hours as a result of comparing the optimum lubrication performance by changing the condensation reaction time and the like in the course of the synthesis of ricinoleic acid.

Experimental Results According to RA Condensation Reaction Time When the reaction time was short before and after 5 hours, the reaction was not completely completed yet, and the kinetic viscosity, computation cost and lubricity were greatly changed. However, when the reaction time was more than 5 hours Although the reaction time was increased, there was almost no difference in the physical properties. The RA condensation reaction time was found to be most suitable for 5 hours.

In the present invention, the performance conditions of the high lubricity additive were determined by evaluating compatibility with water (emulsion state), lubricity, and the like. The following is a summary of the detailed analysis results.

a) Kinematic viscosity

The kinematic viscosity increased with the increase of the condensation reaction time and the kinematic viscosity increased with the increase of the condensation reaction time.

It is considered that the main reason is that the viscosity increases largely by the condensation polymerization at the initial stage of the reaction, while the condensation polymerization is almost complete after 5 hours,

Therefore, it is understood that 95% or more of the condensation reaction is completed after 5 hours in the condensation polymerization reaction time.

b) Lubrication

The lubrication was carried out with a Timken load tester, which was a liver transplantation agate test.

The lubricity increased rapidly in proportion to the reaction time, but did not show any significant change after 3 hours.

From the viewpoint of lubricity, it is judged that the reaction time is sufficient to ensure lubricity over 3 hours.

c) Computers

The acid value of the crude solution is very high but decreases with the lapse of the condensation reaction time, but it is constant after 5 hours.

After the condensation reaction, the bond between the molecules is converted to the ether state, and the acid value is greatly reduced. The reaction time of 5 hours is most suitable because the acid value is not changed even though the reaction time is increased in the condition of 5 hours or more appear.

3 shows the evaluation test results of the abrasion resistance of the present invention.

The abrasion resistance tester was a 4-ball abrasion tester and a Timken Load tester.

(KS M 2173 W1), the most commonly used emulsion type water-soluble cutting oil (KS M 2173 W1), the water-soluble cutting oil, boric amide + water soluble cutting oil (KS M 2173 W1) RA condensation products + water soluble cutting oil (KS M 2173 W1 species).

The RA condensation product of the present invention and boric amide were subjected to abrasion resistance tester with only 5% addition.

The 4-ball tester rotates four intermeshing ball beads at a speed of 1200 rpm for one hour, and measures the extent of wear of the ball beads to visually confirm oil performance.

As a result of analysis, it was found that the water-soluble cutting oil had an average diameter of 0.54 mm and the addition of boric amide had an average diameter of 0.40 mm, while the addition of 5% of the RA additive of the present invention was the best at 0.34 mm. And 17% more abrasion resistance than amide.

In the Timken Load tester, a load-carrying tester, the water-soluble cutting oil was 1.0 kg and the addition of 5% boric amide was 2.9 kg, while the addition of 5% of the RA additive of the present invention was 3.6 kg.

Therefore, the RA additive of the present invention shows excellent performance as a high lubricity additive, and it is confirmed that the abrasion resistance is much better than that of mineral oil based water-soluble cutting oil itself or boric amide.

Comparison of physical properties after condensation with Rishinoleic acid stock solution Item Amount of money Reaction product Exterior Translucent liquid at room temperature Transparent liquid at room temperature Color (ASTM) L 2.0 L 2.5 Specific Gravity (15/4 ℃) 0.946 0.940 Kinematic viscosity (40 ° C, cSt) 133.0 565.5 (MgKOH / g) 156.4 54.2 Lubrication (kg / cm, abrasion testing machine for liver transplantation) 1.5 to 1.8 3.5 to 3.7

The etherified product obtained by the condensation reaction using the ricinolic acid of the present invention is excellent in the performance in comparison with the additive used as the lubrication improving agent of the conventional water-soluble cutting oil in the lubrication, and the lubrication (abrasion resistance) .

Package additive made of water-soluble cutting oil is a product that can be easily mixed with water-soluble cutting oil even by non-specialist by making package lubricant additive and various kinds of surfactants.

The present invention can also be utilized as a package additive of water-soluble cutting oil.

Ricinolic Acid of the present invention is not water-soluble like sebacamide or boric amide. Therefore, in order to use it as a package additive, it is necessary to control the HLB of oil added to water-soluble cutting oil and other surfactants.

However, RA is relatively easy to control HLB than other kinds of additives, so it is expected that it will be used as an additive sufficient to expect the improvement of lubricity of water-soluble cutting oil by using this water-soluble cutting oil.

The present invention was supported by national R & D projects. The details are as follows. (R & D) technology development project, project title: Renewable oil and SA & RS system synthetic additive (R & D), R & D project name: R0002994, Subdivision: Ministry of Commerce, Industry and Energy, Development of eco-friendly metal processing oil, Contribution rate: 1/1, Organizer: Greenruv Co., Research period: 2014. 07.01. It is ~ 2015. 06.30.

Claims

(C1) introducing ricinoleic acid and a platinum catalyst into the vessel;
After the step C1, a step (C2) of supplying nitrogen gas (N2) to the container and sealing the container;
After step C2, the step (C3) is performed to raise the temperature to 220 deg. C at about 2 deg. C per minute.
After the step C3, a step (C4) in which the condensation reaction is carried out for 4 to 5 hours by raising the temperature of the vessel to 250 DEG C;
(C5) after the step C4, after cooling the temperature to 90 DEG C, collecting a sample and performing an intermediate inspection;
(C6) after the step C5, if the target performance is satisfied in the intermediate inspection, final inspection is performed and then the product is filtered through a filtration process (C6)
If the intermediate inspection is not satisfied after the intermediate inspection step (C5), the nitrogen gas sealing step (C2) to the intermediate inspection step (C5) are repeatedly performed, and the reaction time in the condensation reaction step is set to 2 hours Wherein the water-soluble cutting oil is a water-soluble lubricant.

The method according to claim 1,
In the step (C1) of feeding the raw material into the vessel,
A process for preparing a water-soluble cutting useful ricinoleic acid high-lubrication additive characterized by being replaced by concentrated sulfuric acid instead of a platinum catalyst.

3. The method according to any one of claims 1 to 2,
In the step (C1) of feeding the raw material into the vessel,
Wherein the mixing ratio of ricinoleic acid and platinum or sulfuric acid is 0.5% by weight based on 1 kg of ricinoleic acid by weight.