KR101101926B1 - Composition for water soluble oil based metal working fluids - Google Patents

Abstract

 The present invention relates to a water-soluble metalworking emulsion composition, and more particularly, by combining diene-dimethyl amino propyl fatty acid amide triethylene glycol, vegetable fatty acid ester amide, and a lubricating additive in a proportion, very excellent wear resistance The present invention relates to a water-soluble metalworking emulsion composition having extreme pressure, lubricity, emulsion stability, and dispersibility.

Water-soluble metal processing emulsion, environmental friendliness, polar group, extreme pressure, wear resistance, lubrication characteristics

Description

Water-soluble metal processing emulsion composition {COMPOSITION FOR WATER SOLUBLE OIL BASED METAL WORKING FLUIDS}

The present invention relates to an environmentally friendly water-soluble metalworking emulsion composition composed of saturated / unsaturated fatty acid derivatives and lubricant additives which do not mix mineral oils, which constitute a water-soluble metalworking oil of cutting oil, rolled oil or fresh oil.

Generally, water-soluble metal processing emulsions are composed of mineral oil, surfactants, and lubricant additives. Their functions are to reduce friction and wear when processing metal products, to improve the surface characteristics, to reduce surface adhesion and fusion, to prevent thermal deformation, Serves as residue cleaning. In addition, its mechanism forms a protective film by physicochemical adsorption with a metal surface, thereby improving performances such as lubricity, abrasion resistance, and extreme pressure resistance, and depend heavily on the polarity of the compound.

However, the metal surface is destroyed by accelerating desorption and attenuation of the protective film formed by adsorption reactions under unstable or harsh conditions such as lack of emulsion stability, lack of lubricity, lack of oxidation stability, lack of wear resistance and extreme pressure. The failure rate of the product may increase due to the phenomenon of failure.

Conventional water-soluble metalworking emulsions are 50 to 80 wt% mineral oil, 0 to 50 wt% fat or fatty acid, 0 to 40 wt% lubricating additive (extreme pressure additive), 20 to 40 wt% surfactant, 3 to 10 wt% alkanolamine (pH enhancer), Anti-corrosive additive 1 ~ 5wt%, antifoam 0 ~ 2wt%, etc., low biodegradability, use of a large amount of emulsifiers, increased treatment costs in wastewater treatment, use of a large amount of lubricant additives, harmful to humans have. In order to solve these problems, the development of environmentally friendly metal processing oils to replace mineral oils has been actively conducted worldwide.

Republic of Korea Patent No. 10-0486626 is a metal covalent composition containing a methyl ester of vegetable oil, a surfactant and a lubricant additive, etc. Republic of Korea Patent No. 10-0486624 is composed of a vegetable oil, a synthetic ester, a surfactant and a lubricant additive It is a water-soluble cutting oil composition, Republic of Korea Patent No. 10-0665790 is a water-soluble cutting oil composition, such as vegetable oil, surfactant and lubricant additive, Republic of Korea Patent No. 10-0750394 is a biodiesel distillation residue, surfactant, ion exchange water and lubricant additive The metal-covalent composition composed of the like, and the Republic of Korea Patent No. 10-0761557 is a water-soluble metal covalent composition composed of soybean oil ester base oil, a surfactant and a lubricant additive, these water-soluble metal covalent agents are composed of vegetable oil and vegetable oil derivatives As the molecular weight is limited by the short chain, Hydrophilic and hydrophobic or hydrophilicity and low hydrophobicity, low solubility in water due to low double-sided hydrophobicity and low adsorption characteristics due to the limitation of polar groups, etc. There was a problem that a lubricant additive was added.

Therefore, the present inventors have problems of the conventional metal working emulsions, that is, lubrication performance and emulsification performance, such as increase in solubility in water due to the increase of both hydrophilicity and hydrophobicity, high adsorption characteristics due to the increase of the polar group, and molecular weight increase due to the long chain group. As a result of intensive studies to add a small amount of lubricating additive with improvement, the present invention has been completed.

In order to solve the above problems, the present invention is composed of saturated / unsaturated fatty acid derivatives and lubricating additives, so that the water-soluble metal processing having excellent lubricating performance characteristics such as lubricity, abrasion resistance, extreme pressure and emulsion stability caused during processing of metal products It is an object of the invention to provide an emulsion composition.

In order to achieve the above object,

The present invention is composed of a mixture of diene- dimethyl amino propyl octadecanoic amide triethylene glycol 20 ~ 80wt%, 20 ~ 80wt% oilseed oil fatty acid ester amide,

Composed by adding a lubricant,

Dien-dimethylaminopropyl octadecanamide amide triethylene glycol 10-80 wt%, oil-based fatty acid ester amide 10-80 wt%, lubricating additive 1.5-15 wt% of water-soluble metalworking emulsion composition composed of the main technical composition It is done.

The water-soluble metalworking emulsion composition of the present invention is composed of a mixture of diene-dimethyl amino propyl octadecanoic amide triethylene glycol and rapeseed fatty acid ester amide as a basic composition, and to improve the lubricating performance and physical properties in the basic composition. Lubricating additives are added. In the following, it will be described in detail the technical configuration on the basis of the addition of the lubricant additive.

The diene-dimethyl amino propyl octadecanamide amide triethylene glycol is synthesized through a three step reaction.

In a one-step reaction, en-dimethyl amino propyl octadecanamide is synthesized by an amide reaction of 1 mole of oleic acid and 1 mole of dimethylamino propyl amine.

Then, in a two-step reaction, N-dimethyl ammonium acetate propyl octadecanic amide is synthesized by neutralization of 1 mole of the synthesized en-dimethyl amino propyl octadecanamide amide and 1 mole of acetic acid.

And, in a three-step reaction, diene-dimethyl aminopropyl octadecanoic amide triethylene glycol is reacted by reacting 2 moles of the synthesized en-dimethyl ammonium acetate propyl octadecanoic amide with 1 mole of ethylene glycol diglycidyl ether. Is synthesized.

The amount of the diene-dimethyl amino propyl octadecanamide amide triethylene glycol is 10 to 80wt% with respect to the total composition, when the amount is less than 10wt%, problems occur in lubricating performance such as extreme pressure and wear resistance, 80wt In case of using more than%, the viscosity may increase, so the diene-dimethyl amino propyl octadecanoic amide triethylene glycol is preferably used in an amount of 10 to 80 wt% based on the total composition, More preferably, it is used within the range of 30 to 60wt%.

The rapeseed oil fatty acid ester amide is synthesized through a two-step reaction.

In a one-step reaction, a rapeseed fatty acid diester is synthesized by an ester reaction of 70 wt% of rapeseed oil, 29.5 wt% of propylene glycol, and 0.5 wt% of sodium hydroxide under a nitrogen atmosphere.

And, in a two-step reaction, the rapeseed oil fatty acid ester amide is synthesized by the amide reaction of the synthesized rapeseed oil fatty acid ester 85wt% and diethanolamine 15wt%.

The amount of the rapeseed oil fatty acid ester amide is 10 to 80wt% with respect to the total amount of the water-soluble metal working emulsion composition, and when the amount is less than 10wt%, there is a problem in physical properties such as dispersibility and emulsion stability, and it exceeds 80wt%. In this case, there is a problem in lubricating performance such as a decrease in molecular weight and extreme pressure, so that the rapeseed oil fatty acid ester amide is preferably used at 10 to 80wt% of the total amount of the water-soluble metalworking emulsion composition, more preferably 30 to 60wt%. Formulate with

The lubricating additive is composed of a mixture of any two or more selected from extreme pressure additives, antirust additives, antifoaming agents, and oxidative stabilizers. The amount of the lubricant additive is 1.5 to 15wt% based on the total amount of the water-soluble metalworking emulsion composition, and when the amount is less than 1.5wt%, there is a problem in lubricating performance such as extreme pressure and oxidation stability, and when the amount exceeds 15wt%. Since there is a problem that can lower the lubricating performance in addition to economics, the lubricating additive is preferably used at 1.5 to 15wt% of the total amount of the water-soluble metalworking emulsion composition.

The extreme pressure additive is used to improve the lubricating performance of the water-soluble metalworking emulsion composition, specific examples are any one selected from zinc dialkyl dithio phosphate (ZDDP), paraffin chloride, tricrezyl phosphate, dialkyl phenol sulfide Use more than one species.

The rust preventive additive is used for the purpose of increasing the rust preventive effect, and specific examples thereof include any one or more selected from fatty acid amine salts, barium sulfonate, calcium selphonate, and benzotriazole.

The antifoaming agent uses a silicone compound.

In addition, the oxidative stabilizer is used for the purpose of enhancing the oxidative stability, and specific examples thereof include an effect alkylamine or an alkyl phenol.

In particular, the rust preventive additives and the antifoaming agent is added to the lubricating additive as needed.

Hereinafter, the manufacturing process of the water-soluble metal processing emulsion composition will be described in detail.

Diene-dimethyl aminopropyl octadecanamide amide triethylene glycol synthesis step

Diene-dimethylamino propyl octadecanamide amide triethylene glycol is synthesized by a three-step reaction. In a one-step reaction, 1 mole of oleic acid and 1 mole of dimethylamino propylamine are placed in a reactor and the reaction temperature is 140 in a nitrogen atmosphere. En-dimethyl amino propyl octadecanic amide is synthesized by an amide reaction with a reaction time of 1 to 3 hours at ˜200 ° C.

In a two-step reaction, 1 mole of en-dimethyl amino propyl octadecanamide amide synthesized in step 1 and 1 mole of acetic acid are added to a reactor and reacted at a reaction temperature of 40 to 90 ° C. for 1 to 3 hours to produce en-dimethyl ammonia. Um acetate propyl octadecanic amide is synthesized.

Then, in a three-step reaction, 2 moles of en-dimethyl ammonium acetate propyl octadecane amide synthesized in step 2 and 1 mole of ethylene glycol diglycidyl ether were added to a reactor, and a reaction time was performed at a reaction temperature of 60 to 120 ° C. 10. Reaction for ˜ 20 hours to synthesize diene-dimethyl amino propyl octadecanamide amide triethylene glycol.

Rapeseed Oil Fatty Acid Ester Amide Synthesis

Rapeseed fatty acid ester amides are synthesized by a two-step reaction.

In a one-step reaction, 70 wt% of rapeseed oil, 29.5 wt% of propylene glycol, and 0.5 wt% of sodium hydroxide were added to a reactor under a nitrogen atmosphere, and the rapeseed oil fatty acid ester was synthesized by reaction at 180 ° C. for 3 hours.

In a two-step reaction, 85 wt% of the rapeseed oil fatty acid ester synthesized in the first step and 15 wt% of diethanolamine were added to the reactor, and the rapeseed oil fatty acid ester amide was synthesized by reacting the reaction temperature at 90 ° C. for 3 hours.

As described above, the water-soluble metalworking emulsion composition according to the present invention has increased solubility in water due to the increase in hydrophilicity and hydrophobicity of both sides than conventional water-soluble metalworking emulsions, and has high adsorption characteristics and long chains due to an increase in polar groups. As it has the characteristic of increasing the molecular weight according to the group, the lubricating performance of emulsion stability, abrasion resistance and extreme pressure is excellent.

In particular, the lubricating performance is very excellent due to the long-chain hydrophobic group of 30 or more carbon atoms and composed of three hydrophobic groups and three hydrophilic groups to increase the emulsification performance and dispersibility.

In addition, by the secondary function of improving the anti-foaming, antiseptic and anti-rusting, such as a small amount of lubricating additive is added compared to the conventional product has many advantages in terms of functionality and economics.

Let us look at the specific content of the above technical configuration through the embodiment.

Example 1: Synthesis of diene-dimethyl aminopropyl octadecanoic amide triethylene glycol

1 mole of oleic acid and 1 mole of dimethyl amino propyl amine were added to the reactor and reacted under a nitrogen atmosphere for 2 hours at 160 ° C., to give N- (dimethyl amino propyl octadecanoic amide, hereinafter DAPOA Is synthesized).

In addition, 1 mole of the synthesized en-dimethyl amino propyl octadecanic amide and 1 mole of acetic acid are reacted at a reaction temperature of 70 ° C. for 2 hours to form en-dimethyl ammonium acetate propyl octadecanic amide (N- (dimethyl ammonium acetate propyl). ) octadecanoic amide, hereinafter referred to as DAAPOA).

Next, 2 moles of the synthesized N-dimethyl ammonium acetate propyl octadecanic amide and 1 mole of ethylene glycol diglycidyl ether were reacted at a reaction temperature of 100 ° C. for 16 hours to determine diene-dimethyl amino propyl octadecanic amide. Triethylene glycol (1,6-Di [N- (dimethyl amino propyl) octadecanoic amide] triethylene glycol, hereinafter referred to as DDAPOATG) is synthesized.

Example 2 Rapeseed Oil Fatty Acid Ester Amide Synthesis

Into the reactor, 70 wt% of vegetable oil, 29.5 wt% of propylene glycol (molecular weight 400), and 0.5 wt% of sodium hydroxide were reacted for 3 hours at a reaction temperature of 180 ° C. in a nitrogen atmosphere, followed by rapeseed fatty acid ester (RFE). Is synthesized.

Next, 85% by weight of the synthesized rapeseed oil fatty acid ester and 15 wt% diethanolamine were added to a reactor and reacted at 90 ° C. for 3 hours to synthesize rapeseed fatty acid ester amide (hereinafter referred to as RFAEA). .

Example 3 Preparation of Water-Soluble Metal Processing Emulsion

DDAPOATG and RFAEA synthesized in Examples 1 and 2 were added to the reactor according to the composition ratios shown in Tables 1 and 2 below, and kneaded at a temperature of 80 ° C. for 30 minutes to prepare a water-soluble metalworking emulsion.

In addition, according to the composition ratios shown in Table 3, a lubricating additive is added and kneaded to DDAPOATG and RFAEA to prepare a water-soluble metalworking emulsion.

Test Example 1

The abrasion resistance test of the water-soluble metalworking emulsion composition prepared in Example 3 was conducted according to ASTM D2255 standard using Four Ball Wear Tester and is represented by a wear scar diameter (mm) and a coefficient of friction.

In the extreme pressure test, torque was measured according to ASTM D 3233 standard using a Falex tester, and it was expressed as a load at failure (lb _f ).

pH and emulsification stability were carried out in accordance with KS M 2525 standard, and the rust prevention test was evaluated for the presence of rust generated in cast iron chip specimens in accordance with ASTM D 4627-92, the test method for cast iron chip corrosion.

In addition, it compared the performance with the existing commercially available water-soluble metal co-coating agent (Castrol, product name-Hysol R-VW; mineral oil content 40%, pH 9.4; German product). In addition, it was analyzed using the FT-IR analyzer to identify the synthesized reaction compound.

In addition, the reactants DDAPOATG and RFAEA obtained in Examples 1 and 2 confirmed the reaction through an FT-IR apparatus, and the results are shown in FIGS. 1 and 2.

In FIG. 1, (a) shows DAPOA, (b) shows DAAPOA, and (c) shows DDAPOATG.

(A) of Fig. 1, the C = O peak at 1,680cm ^-1, 1,555cm ^-1 in the NH peak appears and, in Fig. (B) 1 OH seen that the peaks are increased from 3,000 ~ 3,500cm ^-1 It can be seen that the ammonium ion peak appears at 1,950 cm ^-1 . And Fig. 1 (c) and the OH peak and a more significant increase in 3,000 ~ 3,500cm ^-1 at 1,125 cm ^-1 The ether (-COC-) peak was confirmed, indicating that the synthesis was well done.

In FIG. 2, (a) shows rapeseed oil, (b) shows RFAE, and (c) shows RFAEA.

In Figure 2 (a) it can be seen the carboxyl group of the C = O peak disappeared at 1,705cm ^-1 found in canola oil, coupling site, carboxylic ester groups are shown in the saturated ester found in 1,745cm ^-1 It was masked by the peak of the cyclic group, and an ether (-COC-) peak appeared at 1,128 cm ^-1 after the reaction.

In Figure 2 (b) at 1635 cm ^-1 The C = O peak is appearing and the OH peak is confirmed to increase more at 3,000 to 3500cm ^-1 , indicating that the synthesis was well performed.

Therefore, in Example 3, the reactants and lubricating additives of DAPAEGDO and RFAEA were kneaded according to the composition ratio, diluted to a certain amount in water to prepare an emulsion solution, and their lubricating properties such as lubricity, abrasion resistance, extreme pressure, pH, emulsion stability and The physical properties such as rust resistance were investigated, and the results are shown in Table 1, and in Comparative Example 7 of Table 3, conventional commercially available water-soluble metal processing oils (Castrol, product name-Hysol R-VW; mineral oil content 40% , pH 9.4; made in Germany).

Lubrication Performance According to Composition Ratio of DDAPOATG and RFAEA One 2 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 ingredient Composition ratio (wt%) DDAPOATG
RFAEA
Mineral oil 80
20
0 50
50
0 20
80
0 100
0
0 0
100
0 0
0
100 Item Lubrication Performance Abrasion Resistance (mm)
Coefficient of friction 0.58
0.062 0.61
0.063 0.62
0.065 0.47
0.055 0.64
0.068 0.85
0.129

As shown in Table 1, it can be seen that DDAPOATG has better abrasion resistance and friction characteristics than RFAEA. Compared to mineral oil, DDAPOATG and RFAEA show very good lubrication performance. This is due to the strong physicochemical adsorption because the reactants of the present invention have high polarity.

Lubrication Performance of Aqueous Solution of DDAPOATG and RFAEA Composition Mixtures 4 5 6 Comparative Example 4 Comparative Example 5 Comparative Example 6 ingredient Composition ratio (wt%) DDAPOATG
Mineral oil
RFAEA
water 8
0
2
90 2
0
8
90 5
0
5
90 10
0
0
90 0
0
10
90 3
2
5
90 Item Lubrication Performance Abrasion Resistance (mm)
Coefficient of friction
Extreme Pressure (lb _f ) 0.65
0.095
2000 0.64
0.093
2000 0.62
0.090
2250 0.67
0.097
2250 0.60
0.085
2000 0.72
0.108
1500

Table 2 shows the lubricating performance after kneading the composition of DDAPOATG and RFAEA in a 10% aqueous solution phase, the aqueous solution kneaded with DDAPOATG is excellent in extreme pressure, and the aqueous solution kneaded with RFAEA is excellent in wear resistance. This is because, in the case of DDAPOATG, the dissolution solubility in water is lower than that of RFAEA, but it has strong adsorption due to high polarity. In Comparative Example 6 in which mineral oil was kneaded, the lubricating performance was very low.

Lubrication Performance and Physical Properties of Water-Soluble Metal Processing Oil Composition 7 8 9 10 11 12 Comparative Example 7 ingredient Composition ratio (wt%) DDAPOATG
RFAEA
ZDDP
Paraffin chloride
Octylamine
Barium Selphate 74.8
18.7
5
0
0.5
One 70.8
17.7
5
5
0.5
One 46.75
46.75
5
0
0.5
One 44.25
44.25
5
5
0.5
One 18.7
74.8
5
0
0.5
One 17.7
70.8
5
5
0.5
One Commercially available water-soluble metal-coating agent (Castrol, Germany) Item Lubrication performance and physical properties (10wt% aqueous solution) Abrasion Resistance (mm)
Coefficient of friction
Extreme Pressure (lb _f )
pH
Emulsification stability (ml)
Antirust (3wt%) 0.70
0.093
2250
9.0
2
No rust 0.71
0.096
2250
9.0
2
No rust 0.59
0.086
2250
9.2
2
No rust 0.65
0.088
2250
9.1
2
No rust 0.63
0.090
2000
9.3
One
No rust 0.68
0.091
2000
9.3
One
No rust 0.93
0.114
2000
9.4
3
No rust

Table 3 shows the lubrication performance and physical properties according to the composition of the present invention, as shown in Table 3 DDAPOATG shows a low lubrication performance with low lubrication additives, while RFAEA has a high miscibility with lubricating additives It shows lubrication performance and physical properties.

1 is a graph showing the FT-IR spectrum results of the DDAPOATG reactant according to the present invention.

2 is a graph showing the FT-IR spectral results of the RFAEA reactants according to the present invention.

Claims (5)

A water-soluble metalworking emulsion composition comprising diene-dimethyl amino propyl octadecanamide amide triethylene glycol 20 to 80 wt%, and 20 to 80 wt% of a rapeseed oil fatty acid ester amide. Water-soluble metalworking emulsion composition, characterized in that the composition is composed of a mixture of diene-dimethyl amino propyl octadecanamide amide triethylene glycol 10 ~ 80wt%, oilseed oil fatty acid ester amide 10 ~ 80wt%, lubricating additive 1.5 ~ 15wt% . The method according to claim 1 or 2, The diene-dimethyl amino propyl octadecanamide amide triethylene glycol is synthesized through a three step reaction, In a one-step reaction, en-dimethyl amino propyl octadecanamide is synthesized by an amide reaction of 1 mole of oleic acid and 1 mole of dimethylamino propyl amine, In a two-step reaction, N-dimethyl ammonium acetate propyl octadecanamide is synthesized by neutralization of 1 mole of the synthesized en-dimethyl amino propyl octadecanamide amide and 1 mole of acetic acid, In a three-step reaction, diene-dimethyl aminopropyl octadecanoic amide triethylene glycol was synthesized by reacting 2 moles of the synthesized en-dimethyl ammonium acetate propyl octadecanic amide with 1 mole of ethylene glycol diglycidyl ether. Water-soluble metalworking emulsion composition, characterized in that. The method according to claim 1 or 2, Seed oil fatty acid ester amide is synthesized through a two-step reaction, In a one-step reaction, a rapeseed oil fatty acid ester is synthesized by esterification of 70 wt% of rapeseed oil, 29.5 wt% of propylene glycol, and 0.5 wt% of sodium hydroxide under a nitrogen atmosphere. In a two-stage reaction, the rapeseed oil fatty acid ester amide is synthesized by the amide reaction of the synthesized rapeseed oil fatty acid ester 85wt% and diethanolamine 15wt%. The method according to claim 2, Lubricating additive is composed of a mixture of any two or more selected from extreme pressure additives, antirust additives, antifoaming agents, oxidative stabilizers, The extreme pressure additive is any one or more selected from zinc dialkyl dithio phosphate (ZDDP), paraffin chloride, tricresyl phosphate, dialkyl phenol sulfide, The anti-rust additive is any one or more selected from fatty acid amine salts, barium sulfonate, calcium selphonate, benzotriazole, The antifoaming agent is a silicone compound, The oxidation stabilizer is a water-soluble metalworking emulsion composition, characterized in that the alkylamine or alkyl phenol.

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