CN102703172A - Preparation method for oil-soluble organic molybdenum-sulfur lubricating oil additive - Google Patents

Abstract

The invention provides a preparation method for an oil-soluble organic molybdenum-sulfur lubricating oil additive. The preparation method comprises the following steps: firstly, mixing and stirring a hexavalent molybdenum compound, alcohol, deionized water, alkylamine and lubricating oil basic oil to obtain a mixed solution; secondly, vacuumizing the mixed solution to remove air, dropping CS2 in the atmosphere of nitrogen gas to obtain an oily solution; thirdly, heating and reflowing the oily solution then carrying out reduced pressure distillation to obtain distillation residue; fourthly, carrying out heating treatment on the distillation residue to obtain an organic molybdenum-sulfur compound; and fifthly, uniformly mixing the organic molybdenum-sulfur compound with fatty acid ester surfactants according to the proportion to obtain the oil-soluble organic molybdenum-sulfur lubricating oil additive. The preparation process disclosed by the invention has the advantages of simple flow, strong repeatability and no complex steps such as washing and filtrating, and is suitable for large-scale industrial production. The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared by the preparation method disclosed by the invention is favorable in oil solubility and room temperature stability and is low in molybdenum content.

Description

A kind of preparation method of oil-soluble organic molybdenum sulfur lubricating oil additive

technical field

The invention relates to a preparation method of an oil additive, in particular to a preparation method of an oil-soluble organic molybdenum-sulfur lubricating oil additive. the

Background technique

The great idea of synthesizing organic molybdenum compounds and using them in the field of lubrication comes from _MoS2 , a solid lubricant with excellent friction properties. MoS ₂ is insoluble in lubricating oil and grease, which greatly limits its application field. Therefore, anti-friction and anti-wear additives with organic molybdenum compounds as the main components began to appear in the 1970s. The organic molybdenum compound in the additive is thermally decomposed to generate ultra-fine or near-nano-scale MoS ₂ , which can adhere to the surface of the friction pair, making the rough surface "fill up" and become smooth, thereby effectively reducing the friction coefficient and improving anti-wear effect. In addition, adding organic molybdenum compounds to lubricating oil or grease not only reduces the friction and wear of the lubricating surface, improves the load capacity, but also is an excellent antioxidant, and can save 3% to 4% of fuel .

The organic molybdenum market mainly includes two categories of products: molybdenum dialkyldithiophosphate (MoDDP) and molybdenum dialkyldithiocarbamate (MoDTC). MoDTC can be divided into solid MoDTC and liquid MoDTC. MoDDP and solid MoDTC appeared successively in the 1960s. They have excellent extreme pressure, anti-wear, anti-friction, and anti-oxidation properties. At the same time, they can improve the oil solubility of molybdenum disulfide, making organic molybdenum compounds a kind of lubricating oil or grease Indispensable anti-wear additives. However, with the reduction of global resources and the need for environmental protection, the requirements for lubricating oil additives are getting higher and higher. Due to the high phosphorus content of MoDDP, which affects the poisoning of exhaust gas catalysts, the current market usage is decreasing year by year; while the solid MoDTC is greatly limited in its application range due to its poor oil solubility. Liquid MoDTC is also suitable for lubricating oil. Its oil solubility, oxidation resistance, anti-friction and anti-wear properties are equivalent to those of MoDDP, and it does not contain phosphorus. It has the advantages of both MoDDP and solid MoDTC. It meets the increasingly stringent environmental protection requirements and market demand. Lubricant additives. the

Both MoDDP and MoDTC are molybdenum sulfur compounds with the structure of Mo ₂ S _x O _nx L ¹ L ² , in which Mo ₂ S _x O _nx is the core structure, and the electronic equilibrium valence is +2, and its structure is as follows:

Wherein S and O can replace each other, and n is 4. the

High sulfur can enhance the oxidation resistance of the product, but it also increases the potential corrosive hazards. Depending on the degree of vulcanization of the product, it is ideal for X to be up to 3. In the process of preparation, a highly vulcanized product can be obtained by using an excessive amount of vulcanizing agent. L is a ligand, and R in L is an alkyl group, which contains enough carbon atoms to improve the oil solubility of the product. In the MoDDP structure, L ¹ and L ² are the same, which is -S ₂ P(OR) ₂ ; in the MoDTC structure, L ₁ is -S ₂ CNR ¹ R ² , and L ₂ is -S ₂ CNR ³ R ⁴ . Depending on the selected alkylamine, R ¹ , R ² , R ³ , and R ⁴ may be the same or different. A typical MoDTC structure is shown below, where X is O or S.

The following patent documents relate to research on organic molybdenum sulfur additives. the

U.S. Patent US5631213 dissolves molybdenum trioxide with 40wt% NaHS deionized aqueous solution, then reduces hexavalent molybdenum to a lower valence state with 85wt% sodium dithionite, then catalyzes it with 35wt% sulfuric acid, and then in methanol, diiso Octylamine and carbon disulfide were reacted at 72°C for 5h. The deionized water-methanol layer was removed, washed and dried under reduced pressure to obtain MoDTC as a yellow solid. the

U.S. Patent No. 5,494,608 dissolves molybdenum trioxide in NaHS deionized aqueous solution, then adds toluene, acidifies with HCl, reacts with dibutylamine and carbon disulfide at 95-102°C for 4 hours, washes with toluene and deionized water, and dries to obtain solid MoDTC. the

U.S. Patent US20080220999 reacts coconut oil with diethanolamine, deionized water, and molybdenum trioxide to prepare a precursor, and then reacts with bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidine) Decanediamine was reacted at 80°C for 3 hours, cooled and filtered with diatomaceous earth to obtain a light red oily substance containing 5.8% molybdenum. the

U.S. Patent US2006007175 mixes Ergon Hygold oil, deionized water, 2-ethylhexyltridecylamine and molybdenum trioxide at 20°C, adds carbon disulfide in a cold deionized water bath, reacts at 60°C for 0.5h, and then heats to reflux Temperature reaction for 4.5h, distill deionized water, add another part of Ergon Hygold oil to obtain a dark brown liquid. the

The above methods use different reagents to transfer molybdenum atoms into the solution, catalyze with different acids at different temperatures, react with different amines, and finally wash and filter to generate solid MoDTC or liquid MoDTC. These methods also have problems such as low molybdenum recovery rate, cumbersome washing steps, and difficult filtration of oily matter to varying degrees. the

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive in view of the above-mentioned deficiencies in the prior art. The preparation process of the present invention is simple, repeatable, and does not require complicated procedures such as washing and filtering, and is suitable for large-scale industrial production; the organic molybdenum-sulfur lubricating oil additive prepared by the present invention has good oil solubility, low molybdenum content, and good room temperature stability. the

In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is: a kind of preparation method of oil-soluble organic molybdenum sulfur lubricating oil additive, it is characterized in that, this method comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:5~20:1.0~2.2 at a temperature of 60~90°C to form the hexavalent molybdenum compound Completely dissolve, then add lubricating oil base oil, add lubricating oil base oil 200g~500g per mole of hexavalent molybdenum compound, stir for 1min~60min to get a mixed solution; or mix hexavalent molybdenum compound, alcohol, deionized water and trioxane The base amine is mixed at a molar ratio of 1:3:5 to 20:2 at a temperature of 60 to 90°C until the hexavalent molybdenum compound is completely dissolved, and then lubricating oil base oil and dialkylamine are added. Add 200g to 500g of lubricating base oil and 1.0mol to 2.2mol of dialkylamine to the molybdenum compound, and stir for 1min to 60min to obtain a mixed solution; the lubricating base oil is vegetable oil or mineral oil;

Step 2, vacuumize the mixed solution described in step 1 to remove the air, then feed nitrogen, under the protection of a nitrogen atmosphere, add CS ₂ dropwise to the mixed solution, the added CS ₂ and step 1 The molar ratio of the hexavalent molybdenum compound is 2.0 to 4.0:1, and after the dropwise addition, the mixture is stirred for 5h to 24h at a temperature of 20°C to 30°C to obtain an oily solution;

Step 3: Heat the oily solution described in step 2 to a temperature of 60°C-75°C and keep it for 1h-2h, then raise the temperature to 90°C-105°C and reflux for 2-6h, then carry out vacuum distillation to obtain a distillation residue ;

Step 4, heating the distillation residue described in step 3 at a temperature of 110°C to 150°C for 1h to 6h, and cooling naturally to obtain an organic molybdenum sulfur compound;

Step 5. Mix the organic molybdenum-sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:0.5-50 to obtain an oil-soluble organic molybdenum-sulfur lubricating oil additive. the

The above method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the hexavalent molybdenum compound in step 1 is molybdenum trioxide, sodium molybdate or ammonium molybdate. the

The above-mentioned method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the dialkylamine in step 1 is an aliphatic diamine of C ₁₆ to C ₂₆ or an alicyclic diamine of C ₁₄ to C ₂₄ diamine.

The above-mentioned method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the trialkylamine in step 1 is a C ₆ -C ₉ trialkylamine.

The above-mentioned preparation method of an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the alcohol in step 1 is n-butanol or n-pentanol. the

The above method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the vegetable oil in step 1 is one or more of corn oil, cottonseed oil, peanut oil and soybean oil. the

The above-mentioned preparation method of an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the mineral oil in step 1 is naphthenic oil. the

The above-mentioned method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the rate of adding CS ₂ in step 2 is 0.1 g/min-3.0 g/min.

The above-mentioned preparation method of an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the specific process of vacuum distillation described in step 3 is: the oily solution after reflux is vacuum-0.060MPa～-0.099MPa Distilled under certain conditions for 10min to 100min to obtain a distillation residue. the

The above-mentioned preparation method of an oil-soluble organic molybdenum-sulfur lubricating oil additive is characterized in that the fatty acid ester surfactant described in step 5 is fatty acid methyl ester, fatty acid ethylene glycol ester, fatty acid glyceride and fatty acid sucrose ester. one or more of. the

Compared with the prior art, the present invention has the following advantages:

(1) The present invention effectively solves the common problems of poor oil solubility and low molybdenum content in current organic molybdenum-sulfur lubricating oil additives. Since the active ingredient in the organic molybdenum-sulfur lubricating oil additive is the organic molybdenum-sulfur compound, the oil solubility of the organic molybdenum-sulfur lubricating oil additive mainly depends on the hydrocarbon group carried by the organic molybdenum-sulfur compound itself, which has a long-chain structure and a high degree of branching The oil solubility of the hydrocarbyl group is better, but the synthesis difficulty is high; the short-chain hydrocarbyl group is easier to synthesize, but it is poor in stability at room temperature after it is mixed with an oily solvent, and it is easy to produce delamination and precipitation; the present invention is precisely based on this According to the screening of raw materials and process optimization, the finally obtained organic molybdenum-sulfur lubricating oil additive has good room temperature stability, and no precipitation or stratification occurs when placed at room temperature of 25°C for 72 hours. the

(2) The present invention makes organic molybdenum-sulfur compounds with weak polarity more easily dispersed in oily solvents by adding a certain amount of fatty acid ester surfactants in organic molybdenum-sulfur compounds, further improving the performance of organic molybdenum-sulfur lubricating oil additives. oil soluble. the

(3) the present invention is by vacuumizing the reaction system and charging nitrogen before adding CS ₂ , the reducing atmosphere of the reaction system is maintained before the reaction, and the low-valence state can be stably maintained after the reduction reaction of the molybdenum element occurs, It is not easy to be oxidized by air to a high valence state, so it is easier to link with the carbamic acid characteristic group. Therefore, there is basically no solid precipitate in the organic molybdenum-sulfur compound prepared by the method, most of the molybdenum element exists in the form of molybdenum carbamate, and the prepared organic molybdenum-sulfur lubricating oil additive has a relatively high molybdenum content.

(4) The preparation process of the present invention is simple, repeatable, and is suitable for large-scale industrial production; the by-product distilled out in the vacuum distillation process of the present invention can be recycled, and the distillation process has no harmful gas discharge; no filtration is required in the preparation process , washing and other cumbersome processes, no waste liquid is generated. the

The present invention is described in further detail below in conjunction with embodiment. the

Detailed ways

Example 1

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and trialkylamine in a molar ratio of 1:3:7:2 at a temperature of 60°C until the hexavalent molybdenum compound is completely dissolved, and then add the mineral oil and dialkylamine, add 250g of mineral oil and 1.0mol of dialkylamine per mole of hexavalent molybdenum compound, and stir to obtain a mixed solution after 30min; the hexavalent molybdenum compound is preferably molybdenum trioxide; the dioxane The base amine is an aliphatic diamine of C ₁₆ -C ₂₆ , preferably diisotridecylamine; the alcohol is preferably n-butanol; the trialkylamine is a trialkylamine of C ₆ -C ₉ , preferably Be triethylamine; Described mineral oil is preferably naphthenic oil;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 1.0 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 4:1, and after the dropwise addition is completed, stir for 18 hours at a temperature of 25° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 65°C and keep it for 1h, then raise the temperature to 100°C and reflux for 4h, and then distill for 60min under a vacuum of -0.08MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 120° C. for 3 hours, and cooling naturally to obtain an organic molybdenum-sulfur compound;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:20 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid ethylene glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably fatty acid sucrose esters. the

The mass percentage of molybdenum element in the organomolybdenum-sulfur compound prepared in this embodiment is 8.5%, and the mass percentage of sulfur element is 8.4%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 2

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and trialkylamine in a molar ratio of 1:3:5:2 at a temperature of 70°C until the hexavalent molybdenum compound is completely dissolved, and then add the mineral oil and dialkylamine, add 500g of mineral oil and 2.0mol of dialkylamine per mole of hexavalent molybdenum compound, and stir for 1min to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the trioxane The base amine is trialkylamine of _C6 ～ _C9 , preferably tripropylamine; the dialkylamine is aliphatic diamine of _C16 ～ _C26 , preferably diisodecylamine; the mineral oil is preferably naphthenic oil; the alcohol is preferably n-pentanol;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 3.0 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 3:1, and after the dropwise addition is completed, stir for 5 hours at a temperature of 30° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 75° C. for 1 h, then raise the temperature to 105° C. and reflux for 2 h, and then distill for 10 min under a vacuum of -0.099 MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 150° C. for 1 hour, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:50 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of fatty acid esters, fatty acid ethylene glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably fatty acid methyl esters. the

The mass percentage of molybdenum element in the organic molybdenum sulfur compound prepared in this embodiment is 7.1%, and the mass percentage of sulfur element is 6.8%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 3

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and trialkylamine in a molar ratio of 1:3:20:2 at a temperature of 60-90°C until the hexavalent molybdenum compound is completely dissolved, and then Add vegetable oil and dialkylamine, add 500g of vegetable oil and 2.2mol of dialkylamine per mole of hexavalent molybdenum compound, and stir for 1min to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the trioxane The base amine is a C6 _{- C9} trialkylamine, preferably tripropylamine; the dialkylamine is a _C16 - _C26 aliphatic diamine, preferably diisooctylamine; the vegetable oil is preferably corn oil; the alcohol is preferably n-butanol;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 0.1 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 24 hours at a temperature of 20° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 60°C for 2h, then raise the temperature to 105°C and reflux for 2h, then distill for 100min under a vacuum of -0.060MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. for 6 hours, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:0.5 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably a mixture of fatty acid glycerides and fatty acid sucrose esters. the

The mass percentage of molybdenum element in the organomolybdenum-sulfur compound prepared in this embodiment is 7.3%, and the mass percentage of sulfur element is 7.8%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 4

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and trialkylamine in a molar ratio of 1:3:5:2 at a temperature of 80°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil and dialkylamine, adding 300g of vegetable oil and 1.5mol of dialkylamine into every mole of hexavalent molybdenum compound, and stirring for 30min to obtain a mixed solution; the hexavalent molybdenum compound is preferably ammonium molybdate; the dialkylamine C ₁₄ -C ₂₄ alicyclic diamine, preferably N,N-isooctylcyclohexylamine; the alcohol is preferably n-pentanol; the trialkylamine is C ₆ -C ₉ trioxane Base amine, preferably tripropylamine; Described vegetable oil is preferably cottonseed oil;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 0.1 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 3:1, and after the dropwise addition is completed, stir for 5 hours at a temperature of 30° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 75° C. for 1 h, then raise the temperature to 90° C. and reflux for 6 h, and then distill for 100 min under a vacuum of -0.060 MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. for 6 hours, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:50 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably a mixture of fatty acid methyl esters, fatty acid glycol esters and fatty acid glycerides. the

The mass percentage of molybdenum element in the organic molybdenum sulfur compound prepared in this embodiment is 7.8%, and the mass percentage of sulfur element is 7.5%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 5

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and trialkylamine in a molar ratio of 1:3:5:2 at a temperature of 90°C until the hexavalent molybdenum compound is completely dissolved, and then add minerals oil and dialkylamine, add 300g of mineral oil and 1.2mol of dialkylamine per mole of hexavalent molybdenum compound, and stir for 10min to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the hexavalent molybdenum compound is preferably sodium molybdate; The molybdenum compound is preferably sodium molybdate; the dialkylamine is a C ₁₄ -C ₂₄ alicyclic diamine, preferably N,N-tetradecylcyclohexylamine; the trialkylamine is C ₆ ~C _{Trialkylamine} , preferably triethylamine; the mineral oil is preferably naphthenic oil; the alcohol is preferably n-pentanol;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 3.0 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 24 hours at a temperature of 20° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 75° C. for 1 h, then raise the temperature to 105° C. and reflux for 2 h, and then distill for 50 min under a vacuum of -0.060 MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. for 4 hours, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:20 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid ethylene glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably a mixture of fatty acid methyl esters and fatty acid sucrose esters. the

The mass percent of molybdenum element in the organic molybdenum-sulfur compound prepared in this embodiment is 9.1%, and the mass percent of sulfur element is 9.2%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 6

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and trialkylamine in a molar ratio of 1:3:9:2 at a temperature of 60°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil and dialkylamine, adding 200g of mineral oil and 1.0mol of dialkylamine into every mole of hexavalent molybdenum compound, and stirring for 15min to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the hexavalent molybdenum compound The compound is preferably molybdenum trioxide; the trialkylamine is a C ₆ -C ₉ trialkylamine, preferably tripropylamine; the dialkylamine is a C ₁₄ -C ₂₄ alicyclic diamine, preferably It is N, N-octadecylcyclohexylamine; the vegetable oil is preferably peanut oil; the alcohol is preferably n-butanol;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 3.0 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 24 hours at a temperature of 20° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 60°C for 2h, then raise the temperature to 105°C and reflux for 2h, then distill for 100min under a vacuum of -0.099MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 150° C. for 1 hour, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound and the fatty acid ester surfactant described in step 4 uniformly in a mass ratio of 100:10 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably fatty acid glycol esters. the

The mass percentage of molybdenum element in the organomolybdenum-sulfur compound prepared in this embodiment is 6.3%, and the mass percentage of sulfur element is 6.1%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 7

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:7:1.5 at a temperature of 90°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil , adding 250 g of vegetable oil per mole of hexavalent molybdenum compound, and stirring for 10 minutes to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the dialkylamine is C ₁₄ ~ C ₂₄ alicyclic diamine, It is preferably N, N-tetradecylcyclohexylamine; the vegetable oil is preferably peanut oil; the alcohol is preferably n-butanol;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 3.0 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 5 hours at a temperature of 30° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 75° C. for 1 h, then raise the temperature to 105° C. and reflux for 2 h, and then distill for 10 min under a vacuum of -0.099 MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. for 1 hour, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound and the fatty acid ester surfactant described in step 4 uniformly in a mass ratio of 100:10 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably fatty acid glycerides. the

The mass percent of molybdenum element in the organic molybdenum-sulfur compound prepared in this embodiment is 11.9%, and the mass percent of sulfur element is 11.3%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 8

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:5:2.2 at a temperature of 60°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil , adding 500 g of vegetable oil per mole of hexavalent molybdenum compound, and stirring for 1 min to obtain a mixed solution; the hexavalent molybdenum compound is preferably molybdenum trioxide; the dialkylamine is C ₁₄ ~ C ₂₄ alicyclic diamine, It is preferably N, N-octadecylcyclohexylamine; the alcohol is preferably n-butanol, and the vegetable oil is preferably soybean oil;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 0.1 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 3:1, and after the dropwise addition is completed, stir for 5 hours at a temperature of 30° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 75°C for 1 hour, raise the temperature to 105°C and reflux for 2 hours, and then distill for 100 minutes under a vacuum of -0.060 MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. for 6 hours, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:30 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably a mixture of fatty acid methyl esters and fatty acid glycol esters. the

The mass percentage of molybdenum element in the organomolybdenum-sulfur compound prepared in this embodiment is 7.2%, and the mass percentage of sulfur element is 7.3%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 9

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:20:1.0 at a temperature of 90°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil , adding 200 g of vegetable oil per mole of hexavalent molybdenum compound, and stirring for 60 minutes to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the dialkylamine is C ₁₄ ~ C ₂₄ alicyclic diamine, It is preferably N, N-isooctylcyclohexylamine; the alcohol is preferably n-amyl alcohol; the vegetable oil is preferably corn oil;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass in nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 3.0 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 10 h at a temperature of 20° C. to obtain an oily solution;

Step 3: Heat the oily solution described in step 2 to a temperature of 70°C for 1 hour, raise the temperature to 100°C and reflux for 4 hours, then distill for 100 minutes under a vacuum of -0.060 MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 150° C. for 1 hour, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:0.5 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of fatty acid esters, fatty acid ethylene glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably fatty acid methyl esters. the

The mass percentage of molybdenum element in the organomolybdenum-sulfur compound prepared in this embodiment is 10.3%, and the mass percentage of sulfur element is 9.7%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 10

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:7:2 at a temperature of 90°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil , adding 400 g of vegetable oil per mole of hexavalent molybdenum compound, and stirring for 20 minutes to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the dialkylamine is C ₁₆ ~ C ₂₆ aliphatic diamine, preferably Be diisooctylamine; The vegetable oil is preferably corn oil; The alcohol is preferably n-butanol;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, then feed nitrogen, and under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 0.1 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 24 hours at a temperature of 20° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 60°C for 2h, then raise the temperature to 105°C and reflux for 2h, then distill for 100min under a vacuum of -0.060MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. for 6 hours, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:0.5 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably a mixture of fatty acid glycerides and fatty acid sucrose esters. the

The mass percentage of molybdenum element in the organic molybdenum sulfur compound prepared in this embodiment is 8.3%, and the mass percentage of sulfur element is 7.8%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 11

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:10:1.8 at a temperature of 80°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil , adding 400 g of vegetable oil per mole of hexavalent molybdenum compound, and stirring for 50 minutes to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the dialkylamine is C ₁₆ ~ C ₂₆ aliphatic diamine, preferably Be diisodecylamine; The vegetable oil is preferably soybean oil; The alcohol is preferably n-amyl alcohol;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 3.0 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 5 hours at a temperature of 30° C. to obtain an oily solution;

Step 3. Heat the oily solution described in step 2 to a temperature of 75°C and keep it for 1h, then raise the temperature to 105°C and reflux for 2h, then distill for 10min under a vacuum of -0.095MPa to obtain a distillation residue;

Step 4, heating the distillation residue described in step 3 at a temperature of 150° C. for 1 hour, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:50 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably a mixture of fatty acid methyl esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters. the

The mass percentage of molybdenum element in the organomolybdenum-sulfur compound prepared in this embodiment is 8.9%, and the mass percentage of sulfur element is 8.2%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

Example 12

The preparation method of the oil-soluble organic molybdenum sulfur lubricating oil additive of the present embodiment comprises the following steps:

Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:5:1.8 at a temperature of 80°C until the hexavalent molybdenum compound is completely dissolved, then add vegetable oil , adding 200 g of vegetable oil to each mole of hexavalent molybdenum compound, and stirring for 5 minutes to obtain a mixed solution; the hexavalent molybdenum compound is preferably sodium molybdate; the dialkylamine is C ₁₆ ~ C ₂₆ aliphatic diamine, preferably It is diisotridecylamine; the alcohol is preferably n-amyl alcohol; the vegetable oil is preferably corn oil;

Step 2. Vacuumize the mixed solution described in step 1 to remove the air, and then pass nitrogen gas. Under the protection of nitrogen atmosphere, add CS ₂ dropwise to the mixed solution at a rate of 0.5 g/min. The added CS ₂ The molar ratio to the hexavalent molybdenum compound described in step 1 is 2:1, and after the dropwise addition is completed, stir for 20 h at a temperature of 20° C. to obtain an oily solution;

Step 3: Heat the oily solution described in step 2 to a temperature of 70°C and keep it for 1.5h, then raise the temperature to 100°C and reflux for 4h, then distill for 100min under a vacuum of -0.060MPa to obtain a distillation residue ;

Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. for 6 hours, and obtaining an organic molybdenum-sulfur compound after natural cooling;

Step 5. Mix the organic molybdenum sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:50 to obtain an oil-soluble organic molybdenum sulfur lubricating oil additive; the fatty acid ester surfactant is fatty acid methyl One or more of esters, fatty acid glycol esters, fatty acid glycerides and fatty acid sucrose esters, preferably fatty acid glycol esters. the

The mass percent of molybdenum element in the organic molybdenum-sulfur compound prepared in this embodiment is 10.5%, and the mass percent of sulfur element is 9.3%. the

The oil-soluble organic molybdenum-sulfur lubricating oil additive prepared in this example has good stability at room temperature, and there is no precipitation or layering after being placed at room temperature of 25° C. for 72 hours. the

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention. the

Claims (10)

1. a preparation method of oil-soluble organic molybdenum-sulfur lubricating oil additive, is characterized in that, the method comprises the following steps: Step 1. Mix the hexavalent molybdenum compound, alcohol, deionized water and dialkylamine in a molar ratio of 1:3:5~20:1.0~2.2 at a temperature of 60~90°C to form the hexavalent molybdenum compound Completely dissolve, then add lubricating oil base oil, add lubricating oil base oil 200g~500g per mole of hexavalent molybdenum compound, stir for 1min~60min to get a mixed solution; or mix hexavalent molybdenum compound, alcohol, deionized water and trioxane The base amine is mixed at a molar ratio of 1:3:5 to 20:2 at a temperature of 60 to 90°C until the hexavalent molybdenum compound is completely dissolved, and then lubricating oil base oil and dialkylamine are added. Add 200g-500g of lubricating oil base oil to the molybdenum compound, add 1.0mol-2.2mol of dialkylamine, and stir for 1min-60min to obtain a mixed liquid; the lubricating oil base oil is vegetable oil or mineral oil; Step 2. Vacuumize _{the mixed solution described in step 1 to remove air, and then pass nitrogen gas into it. Under the protection of nitrogen atmosphere, add CS 2 dropwise} to the mixed solution. The molar ratio of the hexavalent molybdenum compound is 2.0 to 4.0:1, and after the dropwise addition, the mixture is stirred for 5h to 24h at a temperature of 20°C to 30°C to obtain an oily solution; Step 3: Heat the oily solution described in step 2 to a temperature of 60°C-75°C and keep it for 1h-2h, then raise the temperature to 90°C-105°C and reflux for 2-6h, then carry out vacuum distillation to obtain a distillation residue ; Step 4, heating the distillation residue described in step 3 at a temperature of 110° C. to 150° C. for 1 h to 6 h, and cooling naturally to obtain an organic molybdenum sulfur compound; Step 5. Mix the organic molybdenum-sulfur compound described in step 4 with the fatty acid ester surfactant in a mass ratio of 100:0.5-50 to obtain an oil-soluble organic molybdenum-sulfur lubricating oil additive. 2. The preparation method of a kind of oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1, characterized in that, the hexavalent molybdenum compound described in step 1 is molybdenum trioxide, sodium molybdate or ammonium molybdate. 3. A method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1, wherein the dialkylamine in step 1 is an aliphatic diamine of C ₁₆ to C ₂₆ or a C ₁₄ ~ _C24 cycloaliphatic diamine. 4 . The method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1 , wherein the trialkylamine in step 1 is a C ₆ -C ₉ trialkylamine. 5. The preparation method of a kind of oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1, characterized in that, the alcohol described in step 1 is n-butanol or n-pentanol. 6. the preparation method of a kind of oil-soluble organic molybdenum sulfur lubricating oil additive according to claim 1 is characterized in that, the vegetable oil described in step 1 is one or more in corn oil, cottonseed oil, peanut oil and soybean oil kind. 7. The preparation method of a kind of oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1, characterized in that, the mineral oil described in step 1 is naphthenic oil. 8 . The method for preparing an oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1 , wherein the rate of adding CS ₂ in step 2 is 0.1 g/min to 3.0 g/min. 9. the preparation method of a kind of oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1 is characterized in that, the concrete process of underpressure distillation described in step 3 is: the oily solution after backflow is in vacuum degree of Distill under the condition of -0.060MPa～-0.099MPa for 10min～100min to obtain the distillation residue. 10. The preparation method of a kind of oil-soluble organic molybdenum-sulfur lubricating oil additive according to claim 1, it is characterized in that, the fatty acid ester surfactant described in step 5 is fatty acid methyl ester, fatty acid ethylene glycol ester, fatty acid One or more of glycerides and fatty acid sucrose esters.