KR100652123B1 - Vegetable modified mo-coordinative anti-wear additive with improved anti-wear property for greases and preparation method thereof - Google Patents

Abstract

A vegetable modified Mo-coordinative anti-wear additive with improved anti-wear property for greases and a preparation method thereof are provided to manufacture the anti-wear additive at a large yield rate at a low temperature by using biological enzyme reaction. The vegetable modified Mo-coordinative anti-wear additive with improved anti-wear property for greases is obtained by enzyme reaction of glycerol ester vegetable oil and diethanolamine by lipase. The vegetable oil is glycerol esters expressed by the following formula(3). In formula 3, R, R' and R'' respectively express higher fatty acid having carbon number of 10-30. The vegetable oil is selected among canola oil and castor oil. 1.0-3.0 moles of molybden compound are used based on 1 mole of a vegetable oil. The lipase enzyme is selected from candida antarctic lipase(CAL), mutated candida antarctic lipase(CALB), and pseudomonas species lipase(PSL).

Description

Vegantable Modified Mo-coordinative anti-wear additive with improved anti-wear property for greases and preparation method

The present invention relates to a vegetable oil-modified molybdenum coordination anti-wear agent for grease having excellent abrasion resistance and a method for preparing the same, and more particularly, by mixing diethanol amine with glycerol ester which is vegetable oil, and then performing an alternate amidation enzyme reaction. It is a simplified process of coordinating molybdenum compounds while removing water, which enables low temperature reaction, has excellent solubility in organic solvents, and eliminates the use of sulfur and phosphorus, which are used for volatile organic solvents and conventional wear resistance. The present invention relates to a molybdenum-coated antiwear agent for grease that is environmentally friendly and has excellent wear resistance such as friction and abrasion by carrying out the reaction.

Recently, according to the development of the industry, precision instruments and various industrial parts are required to operate under harsher environmental conditions, and to satisfy these requirements, additives having excellent wear resistance are used.

Such anti-wear additives are additives that are included in the lubricating oil to form a film on the metal surface to prevent abrasion caused by the contact between the metal and the metal to exert a load carrying capacity. It has the advantage of improving the efficiency of the machine, reducing fuel consumption and reducing energy by reducing wear caused by metal-to-metal contact.However, the disadvantage of causing soil pollution and water pollution caused by leakage during use There is a disadvantage to reduce the usage.

As the additive used to improve the wear resistance has a physical or chemical function by forming a film on the metal surface, the additive acts as an anti-wear agent according to the chemical structure and the elements contained in the additive, thereby causing friction with the metal. Significantly reduces the energy generated, showing effective wear resistance with good compatibility.

Among the well-known additives are molybdenum-containing patents related to such antiwear agents. tea. Vanderbilt's organic molybdenum compound and preparation method [US Pat. No. 4,889,647, US Pat. No. 5,137,647, US Pat. No. 5,412,130], Organic Molybdenum Complex [JP-A-5-247075], Exxon Research & Engineering's friction-reducing organic molybdenum antiwear additive [US Pat. No. 4,164,473], multifunctional additive for lubricating oil [US Pat. No. 4,474,674], lubricating oil additive manufacturing method of Mobil Oil Corporation [US Pat. No. 4,259,254], Ethyl Corporation Antioxidant System of Lubricant Base Oils [US Pat. No. 5,840,672], Lubricants coated with molybdenum compounds [US Pat. No. 6,174,842], Molybdenum compounds as multifunctional additives of oil-soluble molybdenum mixtures and lubricant compositions [European patent No. 1,136,496], oil-soluble molybdenum coating composition [European Patent No. 1,136,497], and Asahi Denka Kokyo K.K. Lubricating oil compositions [US Pat. No. 4,692,256], oil-soluble molybdenum multifunctional friction additives for lubricating compositions of Uni-Royal Chemical Company [US Pat. No. 6,103,674], lubricant additives of TEXACO Corporation [US Pat. No. 4,765,918], and the like. Known.

However, known additives have limited solubility in oils, are expensive in terms of cost, and sulfur or phosphorus-containing compositions can cause corrosion of metals, In this case, curing may occur. In addition, since most of them use fatty acids that are pretreated rather than vegetable oils, various processes need to be added, and there is a problem in that a considerable amount is added. In particular, when used in addition to grease, extreme pressure prevents wear due to extreme pressure loads. Few examples show performance.

Accordingly, the present inventors have tried to solve the problems such as the solubility of the oil-containing anti-wear agent containing the molybdenum, corrosiveness due to the inclusion of phosphorus and sulfur, curability, process complexity and economical efficiency due to the multi-step process. As a result, the molybdenum coordination abrasion resistance obtained by the simplified process of coordinating the molybdenum compound while removing the water generated after performing alternating amidation enzyme reaction between glycerol ester and diethanol amine, which are vegetable oils, is capable of low temperature reaction. It is found that it is excellent in solubility in organic solvents, and it is environmentally friendly at the same time by eliminating the use of sulfur and phosphorus used for volatile organic solvents and abrasion resistance. The present invention has been completed.

Accordingly, an object of the present invention is to provide a molybdenum coordination antiwear agent which is environmentally friendly by a simplified process and at the same time has excellent wear resistance which is used as an additive of grease, and a method of manufacturing the same.

The present invention is characterized by a grease antiwear agent obtained by enzymatic reaction of glycerol ester vegetable oil and diethanol amine by lipase.

In addition, the present invention mixes 1 to 10% by weight of lipase enzyme with 1 mole of glycerol ester vegetable oil and 1.0 to 3.0 mole of diethanol amine based on the total amount of the reactants, and performs alternating amidation enzyme reaction in the temperature range of 40 to 170 ° C. After performing

Another characteristic of the method for producing an antiwear agent for preparing a molybdenum coordination compound by coordinating 1.5 mol to 2.5 mol of the molybdenum compound in a condensation reaction in the range of 110 to 150 ° C. while removing water generated with respect to 1 mol of the product obtained by the enzymatic reaction. There is this.

The present invention will be described in more detail as follows.

The present invention is a solubility, abrasion resistance and biodegradability prepared by alternately amidating the vegetable oil having a glycerol ester structure and diethanol amine using an enzyme, and then coordinating the molybdenum compound while removing the water produced It relates to an excellent molybdenum coordination antiwear agent.

Molybdenum-containing compounds conventionally used as anti-wear agents have been prepared by complex organic reaction processes such as dehydration of esters and alcohols of vegetable oils at high temperatures, and additional components such as phosphorus and sulfur to exhibit wear resistance. Together, high reaction temperatures in the range of 130 to 160 ° C. were required. However, when the organic solvent, phosphorus, sulfur, and the like, the composition containing the anti-wear agent is leaked, there is a problem of environmental pollution, there is a problem that the solubility in the oil that is used in a large amount of the anti-wear agent is oxidized in a high temperature reaction is significantly reduced there was.

However, the present invention eliminates the use of organic solvents by alternating amidation reactions by biological methods using vegetable oils and lipase enzymes, and is more easily manufactured by a simple process of coordinating an enzyme alternating amidation reaction with molybdenum. The present invention relates to a molybdenum coordinating antiwear agent having wear resistance such as friction and abrasion or higher than that of the antiwear agent.

Referring to the method of manufacturing the molybdenum coordination wear-resistant agent of the present invention in more detail as follows.

To 1 mole of glycerol ester vegetable oil, 1.0 to 3.0 moles of diethanol amine, and 1 to 10% by weight of lipase enzyme are mixed with respect to the total amount of the reactants, and alternating amidation enzyme reaction is performed at a temperature range of 40 to 170 ° C.

In one example, a glycerol ester, a diethanol amine, and an enzyme represented by the following Formula 3 are mixed to perform an altered amidation enzyme reaction to prepare a fatty acid ester of Formula 4, a fatty acid amide of Formula 5, or a mixture thereof.

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3, 4, and 5, R, R ', and R "each represent a higher fatty acid group having 10 to 30 carbon atoms, and preferably 12 to 20 carbon atoms. Specifically, the higher fatty acid group may be stearic acid, oleic acid, Fatty acid group of vegetable oil which is a mixture of linolenic acid and ricinoleic acid is shown.

At this time, the enzyme reaction conditions are carried out for 1 to 12 hours, preferably for 3 to 6 hours at 40 to 170 ℃, preferably 60 to 100 ℃, amide carbonyl in the FT-IR spectrum as the reaction proceeds Reaction until the peak of 1620 cm ^-1 due to the size of 1740 cm ^-1 due to the ester carbonyl group contained in the vegetable oil is at least 1.0 to obtain a dark red oil.

If the reaction temperature is less than 40 ℃ because of the lack of enzyme activity and the reaction does not occur very well and the reaction time must be very long, it is not economical, if it exceeds 170 ℃ oxidation reaction by double bonds contained in vegetable oil Actively progressed, it is difficult to expect abrasion resistance. In addition, when the reaction time is less than 1 hour, the production of the desired product of amide is significantly less than that of the ester of vegetable oil and is not economical when it exceeds 12 hours.

The vegetable oil may be a fatty acid group of vegetable oil which is a mixture of stearic acid, oleic acid, linolenic acid, and ricinoleic acid with at least 12 carbon atoms having at least 12 carbon atoms. Specifically, castor oil and rapeseed oil may be used.

The diethanol amine is preferably used in 1.0 to 3.0 molar ratio, preferably 1.5 to 2.5 molar ratio with respect to 1 mole of vegetable oil. When the amount is less than 1.0 molar ratio, the amount of amide produced is significantly lower than that of ester, so molybdenum It is difficult to cope with and harden to be added to grease, and when it exceeds 3.0 molar ratio, the amount of amide produced is significantly higher than that of ester, and the amount of glycerol is produced, so that molybdenum is dissolved in oil. It is not easy to be difficult to add to the grease and anticipate wear resistance.

Enzymes used in the enzymatic reactions are easy to ester and amidation reaction, specifically Candida Antarctic Lipase (CAL), Candida Antarctic Lipase (CALB), Pseudomonas spysis Derived lipase (Pseudomonas Species Lipase, PSL) and the like can be used. These enzymes are used in an amount of 1 to 10% by weight, preferably 5 to 8% by weight, based on a mixture of vegetable oil and diethanol amine. When the amount is less than 1% by weight, the product is hardly produced and exceeds 10% by weight. It is not economical and cannot exclude the possibility of side reactions.

Next, the molybdenum coordination compound is prepared by coordinating 1.5 mol to 2.5 mol of the molybdenum compound in a condensation reaction in the range of 110 to 150 ° C with respect to 1 mol of the product obtained by the enzymatic reaction.

Specifically, in the fatty acid ester of the formula (4), the fatty acid amide of the formula (5) obtained in the above example, or a mixture thereof, the molybdenum compound is coordinated by condensation reaction while removing the generated water so that the mole of the formula Prepare the ribidenium coordination compound.

[Formula 1]

[Formula 2]

In Formulas 3, 4, and 5, R, R ', and R "each represent a higher fatty acid group having 10 to 30 carbon atoms, and preferably 12 to 20 carbon atoms. Specifically, the higher fatty acid group may be stearic acid, oleic acid, Fatty acid group of vegetable oil which is a mixture of linolenic acid and ricinoleic acid is shown.

The molybdenum coordinating antiwear agent is prepared according to the condensation reaction and is carried out at high temperature in order to accelerate the reaction and to remove water generated in the reaction. At this time, the reaction temperature is in the range of 100 to 150 ℃, preferably 110 to 130 ℃, the reaction time is preferably performed for 2 to 8 hours, preferably for 3 to 5 hours.

When the reaction temperature is less than 100 ℃, the formation of coordination compound is not easy, so the content of molybdenum contained in the anti-wear agent is very low, it is difficult to expect the wear resistance by adding to the grease, the reaction temperature exceeds 150 ℃ The reaction proceeds quickly, but the oxidation reaction proceeds, making it difficult to expect the properties of the antiwear agent and economical. If the reaction time is less than 2 hours, the molybdenum coordination reaction is not sufficiently progressed, it is difficult to expect the physical properties of the wear-resistant agent, when the reaction time is more than 8 hours, it is not economical because there is a lot of energy loss.

In addition, since a vacuum pump of 20 to 50 mmHg is used to remove water generated during the reaction, the reaction time becomes long and is not economical unless water is removed using the vacuum pump.

The molybdenum compound may use molybdenum oxide or nitrified molybdenum capable of reacting with a hydroxyl group, but molybdenum oxide is industrially more economical than molybdenum nitrogen. Molybdenum compounds may be specifically used molybdenum trioxide, hepta- molybdate, mixtures thereof and mixtures of molybdenum trioxide and ammonia water.

The molybdenum compound is preferably used in the fatty acid ester of the formula (4), the fatty acid amide of the formula (5) or a mixture of 0.5 to 4.0 molar ratio, preferably 1.5 to 2.5 molar ratio with respect to 1 mole. If the amount is less than 0.5 molar ratio, the molybdenum content is low, it is difficult to expect the wear resistance properties, if the amount exceeds 4.0 molar ratio, the amount of unreacted molybdenum oxide is not economical.

Evaluation of abrasion resistance of the molybdenum coordination antiwear agent prepared as described above was added to 0.5 ~ 5.0% by weight in a conventional Li-grease composition according to the experimental method specified in ASTM D5706 (Schwingung Reibung Und Verschleiss, SRV) experiment Evaluation was made using the apparatus. At this time, when using the molybdenum coordination wear-resistant agent as a wear-resistant additive, it is good to use about 0.5 to 5.0% by weight relative to the grease. If the amount of use is less than 0.5% by weight, the reduction of friction is insufficient, so it is difficult to expect wear resistance as a product, and when the added amount is more than 5.0% by weight, the wear resistance does not increase significantly and it is not economical.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

Example 1

Alternating amidation enzyme reaction was carried out by heating 22.5 g (0.022 mol) of castor oil, 4.6 g (0.044 mol) of diethanol amine, and 1.4 g of CALB enzyme at a temperature of 75 ° C. in the reactor. In the FT-IR spectrum, the ratio of the size of 1620 cm ⁻¹ peak due to amide carbonyl and 1740 cm ⁻¹ due to ester carbonyl group contained in vegetable oil was 1.5 in the FT-IR spectrum.

Thereafter, 4.3 g of molybdenum trioxide was added thereto, followed by heating for 6 hours while removing water in a vacuum state at 125 ° C. to prepare a compound in which molybdenum was coordinated. Filtration of the reaction product after the reaction gave a brown product, wherein the molybdenum content of the product was 4.8%.

Example 2

In the same manner as in Example 1, a compound in which molybdenum was coordinated was prepared by carrying out the reaction using a rapeseed oil instead of castor oil.

After the reaction, the reaction product was filtered to give a brown product, wherein the molybdenum content of the product was 5.0%.

Example 3

In the same manner as in Example 1, castor oil (Castor oil) using 28.0 g (0.03 mol), diethanolamine 6.3 g (0.06 mol), CALB enzyme 1.7 g, 5.51 g of molybdenum trioxide and ammonia water 2.56 g was used to prepare compounds molybdenum coordinated.

After the reaction, the reaction product was filtered to give a brown product, wherein the molybdenum content of the product was 3.4%.

Example 4

A compound in which molybdenum was coordinated was prepared in the same manner as in Example 1, using 8.6 g of a product reacted with rapeseed oil and diethanolamine and 8.6 g of molybdenum trioxide.

Filtration of the reaction product after the reaction gave a brown product, wherein the molybdenum content of the product was 6.9%.

Example 5

In the same manner as in Example 1, 93.3 g (0.1 mol) of rapeseed oil, 21 g (0.2 mol) of diethanol amine, and 5.7 g of CALB enzyme were used, and 32.6 g of ammonium hepta-molybdate was added to molybdenum. Coordinated compounds were prepared.

Filtration of the reaction product after the reaction gave a brown product, wherein the molybdenum content of the product was 5.0%.

Comparative Example 1

Alternating amidation enzyme reaction was carried out by heating 22.5 g (0.022 mol) of castor oil and 4.6 g (0.044 mol) of diethanol amine at a temperature of 150 ° C. in the reactor. In the FT-IR spectrum, the ratio of the size of 1620 cm ⁻¹ peak due to amide carbonyl and 1740 cm ⁻¹ due to ester carbonyl group contained in vegetable oil was 1.0 in the FT-IR spectrum.

Thereafter, 4.3 g of molybdenum trioxide was added thereto and heated at 125 ° C. for 6 hours to prepare a compound in which molybdenum was coordinated. Filtration of the reaction product after the reaction gave a brown product, wherein the molybdenum content of the product was 0.8%.

Comparative Example 2

A compound in which molybdenum was coordinated was carried out in the same manner as in Comparative Example 1 except that castor oil was used instead of castor oil to carry out the reaction.

After the reaction, the reaction product was filtered to give a green product, where the molybdenum content was 0.5%.

Comparative Example 3

A compound in which molybdenum was coordinated was prepared in the same manner as in Comparative Example 1, using 8.6 g of a product reacted with rapeseed oil and diethanolamine and 8.6 g of molybdenum trioxide.

After the reaction, the reaction product was filtered to give a brown product, wherein the molybdenum content of the product was 0.9%.

Comparative Example 4

In the same manner as in Comparative Example 1, 93.3 g (0.1 mol) of rapeseed oil, 21 g (0.2 mol) of diethanol amine were used, and 32.6 g of ammonium hepta-molybdate was added to prepare a compound in which molybdenum was coordinated. It was.

After the reaction, the reaction product was filtered to give a brown product, where the molybdenum content was 1.0%.

Comparative Example 5

In Comparative Example 5, Molyvan 855 sold by R. T. Vanderbilt Company, Inc. was used as a comparative example.

Experimental Example

The molybdenum coordination antiwear agent prepared in Examples 1 to 5 and Comparative Examples 1 to 5 was added to grease (lithium-type grease) in the range of 0.5, 1, 3 and 5% by weight according to the method described in ASTM D2596. A four ball wear test was performed.

At this time, the rotation speed is 1200 ± 10 rpm, the test temperature is 75 ± 1.7 ℃, the load is 20 kg, the test time was 60 ± 1 min. Abrasion was measured as three ball trace diameters after the test was completed, and the results are shown in Table 1 below.

division Ball trace diameter ¹⁾ (mm) 0.5 wt% 1 wt% 3 wt% 5 wt% Example 1 0.46 0.43 0.43 0.42 Example 2 0.46 0.43 0.42 0.45 Example 3 0.48 0.43 0.45 0.45 Example 4 0.47 0.40 0.39 0.43 Example 5 0.47 0.44 0.42 0.46 Comparative Example 1 0.63 0.59 0.58 0.50 Comparative Example 2 0.67 0.51 0.51 0.48 Comparative Example 3 0.67 0.54 0.53 0.51 Comparative Example 4 0.71 0.68 0.59 0.58 Comparative Example 5 0.50 0.49 0.48 0.48 1): Li-base grease-0.73 mm

As shown in Table 1 above, even when Examples 1 to 5 according to the present invention were added in small amounts as compared with Comparative Examples 1 to 4, the ball trace diameter was low, and it was confirmed that the wear resistance was excellent. In addition, the wear resistance was slightly better than that of Molyvan 855 of Comparative Example 5.

In addition, the molybdenum coordination antiwear agent prepared in Examples 1 to 5 and Comparative Examples 1 to 5 was added with 1, 3% by weight of grease (lithium-type grease) and 100% by weight of the stock solution according to ASTM D5706. According to the SRV test using a standard ball of 10 mm diameter and a test disk of diameter and 24 × 7.85 mm in diameter and the results are shown in Table 2 below. At this time, the applied frequency is 50 Hz, the test temperature is 50 ° C., and the friction coefficient is an average value of the friction coefficient measured over 15 seconds at the end of the test period.

division SRV, N 100% One % 3% Temperature after 100% test (℃) Friction Coefficient (C.O.F) Example 1 > 2000 600 600 56.3 0.107 Example 2 > 2000 500 600 54.7 0.107 Example 3 1800 400 500 56.6 0.111 Example 4 > 2000 500 600 53.5 0.108 Example 5 > 2000 500 600 54.2 0.104 Comparative Example 1 1000 300 300 60.1 0.123 Comparative Example 2 1500 300 400 59.3 0.117 Comparative Example 3 1700 300 400 57.5 0.114 Comparative Example 4 1000 300 300 60.3 0.120 Comparative Example 5 > 2000 400 400 56.3 0.113

As shown in Table 2, in Examples 1 to 5 according to the present invention, the SRV result of the stock solution was 1800-> 2000N, and the comparative example was 1000-> 2000N, and it was confirmed that the wear resistance of the example was excellent. .

In this case, the temperature after the 100% test indicates the temperature of the stock solution after the test of the stock solution, and the coefficient of friction (COF) indicates the average friction coefficient value during the test. In the present invention, the temperature is low and the friction coefficient value is The lower the value, the better the results. However, the temperature and the friction coefficient after the test in the Example showed lower values than those of the comparative example, and it was confirmed that the wear performance was excellent.

As described above, the present invention can be produced in high yield at low temperature by using a biological enzyme reaction instead of a chemical method, and the reaction process can be simplified as much as possible, eliminating the use of solvents of organic compounds, and using inexpensive raw materials. It is economical and does not contain the above organic solvents, sulfur and phosphorus elements, so the effect is expected from the environmentally friendly point.

Claims (13)

A glycerol ester vegetable oil and a diethanol amine obtained by an enzymatic reaction with lipases. The anti-wear agent for grease according to claim 1, wherein the vegetable oil is a vegetable oil comprising glycerol esters represented by the following general formula (3). [Formula 3]

In Formula 3, R, R 'and R "each represent a higher fatty acid group having 10 to 30 carbon atoms. The antiwear agent for grease of claim 1 or 2, wherein the vegetable oil is selected from rapeseed oil and castor oil. The anti-wear agent for grease of claim 1, wherein the molybdenum compound is molybdenum trioxide, hepta-molybdate, molybdenum trioxide / ammonia water mixture, and a mixture of one or two or more thereof. The antiwear agent for grease according to claim 1, wherein the molybdenum compound is used in a molar ratio of 1.0 to 3.0 per mole of vegetable oil. The method of claim 1, wherein the lipase enzyme is Candida Antarctic Lipase (CAL), Candida Antarctic Lipase (CALB), Pseudomonas Species Lipase (PSL) Anti-wear agent for grease, characterized in that selected from. The anti-wear agent for grease according to claim 1, wherein the lipase enzyme is used in an amount of 1 to 10% by weight based on the total amount of vegetable oil and diethanol amine. The antiwear agent for grease according to claim 1, wherein the antiwear agent is a molybdenum coordination compound containing a modified ester represented by the following Chemical Formula 1, a modified amide represented by the following Chemical Formula 2, or a mixture thereof as an active ingredient. [Formula 1]

[Formula 2]

In Formula 3, R, R 'and R "each represent a higher fatty acid group having 10 to 30 carbon atoms. 1 mole of glycerol ester vegetable oil and 1.0 to 3.0 mole of diethanol amine were mixed with 1 to 10% by weight of lipase enzyme with respect to the total amount of the reactants, followed by alternating amidation enzyme reaction in a temperature range of 40 to 170 ° C. A molybdenum anticorrosion agent for producing a molybdenum coordination compound by coordinating 1.5 mol to 2.5 mol of the molybdenum compound in a condensation reaction in the range of 110 to 150 ° C with respect to 1 mol of the product obtained by the enzymatic reaction. 10. The method of claim 9, wherein the vegetable oil is a vegetable oil comprising glycerol esters represented by the following formula (3). [Formula 3]

In Formula 3, R, R 'and R "each represent a higher fatty acid group having 10 to 30 carbon atoms. The method of claim 9 or 10, wherein the vegetable oil is selected from castor oil and rapeseed oil. 10. The method of claim 9, wherein the molybdenum compound is molybdenum trioxide, hepta-molybdate, molybdenum trioxide / ammonia water mixture, and a mixture of one or two or more selected from them. . The method of claim 9, wherein the lipase enzyme is Candida Antarctic Lipase (CAL), Candida Antarctic Lipase (CALB), Pseudomonas Species Lipase (PSL) Method for producing a grease wear-resistant agent, characterized in that selected from.