Non-phosphorus oil-soluble organic molybdenum additive as well as preparation method and application thereof

Abstract

The preparation method comprises the following steps that carbon disulfide is dropwise added into organic amine for a reaction, a molybdenum source is added for continuous stirring, the temperature is increased to 60-150 DEG C, the temperature is kept for a first reflux reaction, cooling is carried out, carbon disulfide is dropwise added, the temperature is increased to 60-150 DEG C, stirring is carried out, and a second reflux reaction is carried out; and keeping the temperature, carrying out secondary reflux reaction, and carrying out post-treatment to obtain a mixture of the compound A and the compound B. According to the preparation method provided by the invention, raw materials and process conditions are optimized, high-temperature and high-pressure or vacuum conditions are not needed, toxic and harmful reagents are prevented from being used, and good stability, oil solubility, corrosion resistance and oxidation resistance are achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of lubricating oil additive preparation, and in particular relates to a non-phosphorus oil-soluble organic molybdenum additive, a preparation method and application thereof. Background Art

[0002] Currently, RT Vanderbilt's Molyvan 3000 (10 wt.% molybdenum content) and Pacific Union Petrochemical's Poupc 1002 (10 wt.% molybdenum content) represent the cutting-edge of non-phosphorus organic molybdenum additives. Chinese patent CN111875639A reports a method for preparing dialkyl dithioorganomolybdenum. This involves dispersing dithiophosphoric acid or dithiocarbamic acid in anhydrous ethanol, then using organic molybdenum as a molybdenum precursor. The overall reaction is a homogeneous oil-phase reaction to produce mononuclear MoDTC. This is reported in Chinese patent CN102311841A. French scholars M. Al Kharboutly et al. explored the differences between mononuclear and binuclear MoDTC and found distinct tribological behaviors under high load conditions. Italian scholar Maria Clelia Righi and others explored that single-core MoDTC can achieve friction reduction from the early stage of friction, but the friction reduction effect is worse than that of dual-core MoDTC. Dual-core MoDTC has a better friction reduction effect, but requires a certain running-in period.

[0003] Therefore, it is necessary to prepare a single-core / dual-core controllable MoDTC. Summary of the Invention

[0004] In view of this, the present invention aims to provide a non-phosphorus oil-soluble organic molybdenum additive and its preparation method and application, so as to solve at least one technical problem in the background technology.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows: A non-phosphorus oil-soluble organic molybdenum additive comprising compound A and compound B; The structural formula of compound A is:

[0006] The structural formula of compound B is:

[0007] wherein R1, R2, R3, R4, R5, R6, R7, and R8 are selected from C7-C 13 The straight chain and branched alkyl groups, R1, R2, R3, R4, R5, R6, R7, R8 are the same or different.

[0008] The preparation method of the above-mentioned non-phosphorus oil-soluble organic molybdenum additive comprises the following steps: Carbon disulfide is added dropwise to the organic amine for reaction, a molybdenum source is added and stirring is continued, the temperature is raised to 60-150°C, the temperature is maintained for a first reflux reaction, the temperature is lowered, carbon disulfide is added dropwise, the temperature is raised to 60-150°C, the temperature is maintained for a second reflux reaction, and a mixture of compound A and compound B is obtained after post-treatment.

[0009] Furthermore, an organic amine is added to a three-necked flask equipped with a thermometer and a reflux condenser, and carbon disulfide is then added dropwise; and / or, adding carbon disulfide dropwise at a temperature below 20°C; and / or, the reaction time of adding carbon disulfide dropwise to the organic amine is 1 to 20 hours; And / or, the temperature of adding the molybdenum source and continuing stirring is 25° C. and the stirring time is 1 to 20 hours.

[0010] Furthermore, the temperature is maintained for the first reflux reaction for a reaction time of 1 to 20 hours; and / or, maintaining the temperature for the first reflux reaction, and cooling to 40° C.; And / or, the temperature is maintained for a second reflux reaction for a reaction time of 1 to 20 hours.

[0011] Furthermore, the molybdenum source includes a mixed aqueous solution containing a +6 valent molybdenum source and a +5 valent molybdenum source.

[0012] Furthermore, the preparation method of the molybdenum source is as follows: add water and ammonium heptamolybdate tetrahydrate into an open beaker, stir until dissolved, add carbon disulfide and react for 1 to 20 hours, at which time the solution is a light blue + 5-valent molybdenum source solution, continue to add ammonium heptamolybdate tetrahydrate and stir until dissolved.

[0013] And / or, the molar ratio of the +5-valent molybdenum source to the +6-valent molybdenum source is 0.1-10:1, and the amount of water added is sufficient to ensure that the solution system is clear and transparent.

[0014] Furthermore, the molar ratio of the organic amine to carbon disulfide is 1:1.1; and / or, the molar ratio of the organic amine to the molybdenum source is 1 to 2:1; And / or, the molar ratio of the organic amine to the second carbon disulfide is 1:0-0.5.

[0015] Furthermore, the general formula of the organic amine is R9NHR 10 , where R9, R 10 C7-C 13 Straight and branched alkyl groups, R9, R 10 Same or different.

[0016] Furthermore, after the reaction is completed, the upper organic phase is separated and distilled under reduced pressure to obtain a brown oily product (a mixture of compound A and compound B).

[0017] The non-phosphorus, oil-soluble organic molybdenum additive prepared by the above-mentioned preparation method can be used in lubricating oils or greases. When used as engine oil, the additive can effectively reduce fuel consumption. When used as high-speed rail gear oil or wind turbine gear oil, the additive can effectively reduce friction and suppress temperature rise.

[0018] Furthermore, the addition amount in lubricating oil is 0.1 wt.%~1 wt.%, and the addition amount in grease is 0.4 wt.%~4 wt.%.

[0019] Compared with the prior art, the non-phosphorus oil-soluble organic molybdenum additive and its preparation method and application described in the present invention have the following advantages: 1. Currently, existing non-phosphorus organic molybdenum products mostly use small amines for the reaction, resulting in solid reaction products. Simple solid-liquid separation and cleaning can achieve high conversion rates and yields. However, large amines, as raw materials, cannot be purified by conventional solid-liquid separation methods due to their liquid products, and often require complex post-processing steps. This application uses larger molecular chain organic amines for the reaction, achieving a molybdenum atom conversion rate exceeding 99% through optimized reaction processes, with extremely high atom economy. This eliminates a large number of post-processing steps, simplifies the reaction process, and reduces production costs.

[0020] 2. This application uses ammonium heptamolybdate as the molybdenum source instead of molybdenum trioxide. Ammonium heptamolybdate has high molecular activity. After mixing with carbon disulfide, it can form a +5-valent molybdenum precursor, thereby undergoing further reaction. However, molybdenum trioxide and ammonium tetramolybdate cannot react with carbon disulfide, thereby failing to achieve valence state conversion and failing to implement this method.

[0021] 3. This application uses carbon disulfide as both a reducing agent and a sulfurizing agent. The entire reaction process eliminates the need for highly toxic and hazardous reagents such as hydrogen sulfide, sulfide salts, inorganic bases, inorganic acids, and organic solvents, making the reaction raw materials and process green and simplified. By optimizing reaction conditions, the controlled synthesis of binuclear and mononuclear organomolybdenum compounds is achieved, reducing the number of reaction steps, simplifying post-processing steps, and shortening reaction time. This allows for targeted synthesis in different application environments and precise control of the additive molybdenum / sulfur content. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is the infrared spectrum of Example 1-4; Figure 2 It is the infrared spectrum of comparative example 1-2. DETAILED DESCRIPTION

[0022] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0023] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0024] The specific implementation method is to first prepare a molybdenum source solution, add 0.02 mol of ammonium tetramolybdate heptahydrate to 94 g of water, then dropwise add 0.28 mol of carbon disulfide, react for 2 hours after the dropwise addition, and then add 0.01 mol of ammonium tetramolybdate heptahydrate and retain it for later use.

[0025] In a 500 mL three-necked flask equipped with a thermometer and a reflux condenser, 0.26 mol of isomeric ditridecylamine was added, and then 1反应温度 Add 0.5 mol of carbon disulfide dropwise, reaction S1, add the prepared molybdenum source solution, and 2反应温度 At the temperature, reaction S2, heating to T 3反应温度 , reflux reaction S3, cool to 40 ° C, add 0.1 mol carbon disulfide dropwise, and continue to heat to T 4反应温度 Reflux reaction S4; after the reaction is completed, the mixture is allowed to stand and the lower aqueous phase is separated, and then the upper oil phase is distilled under reduced pressure to obtain a brown oily product.

[0026] Table 1 Parameters of Examples 1-8 Implementation parameters

[0027] Comparative Example 1 RT Vanderbilt's MOLYVAN 3000 was used as comparative product 1.

[0028] Comparative Example 2 Poupc1002 produced by Pacific Union Petrochemicals was used as comparison product 2.

[0029] Application Example 1 The molybdenum content, sulfur content and oil solubility of the additive were tested. The molybdenum content and sulfur content were tested using ASTM D5185-12. The oil solubility was tested by dissolving the additive at 1% in 120# solvent oil and stirring at 65°C for 1 hour. The acid value was tested using GB / T 264. The results are shown in Table 2.

[0030] Table 2 Oil solubility results sample Molybdenum content, % Sulfur content, % Oil-soluble Acid value, mgKOH Example 1 12.1 14.1 Clarity and transparency 3.0 Example 2 10.8 12.2 Clarity and transparency 3.1 Example 3 11.2 12.9 Clarity and transparency 3.9 Example 4 12.1 14.1 Clarity and transparency 5.0 Example 5 6.8 7.6 Clarity and transparency 2.5 Example 6 13.1 14.3 Clarity and transparency 2.6 Example 7 15.5 18.0 Clarity and transparency / Example 8 13.8 16.1 Clarity and transparency / Comparative Example 1 10.1 11.1 Clarity and transparency 28.2 Application Example 2 The tribological properties were tested using an SRV-5 friction and wear tester. The test oil was 150N+1%T202+0.5% of the embodiment. T202 was purchased from Xinxiang Ruifeng New Materials Co., Ltd. The SRV test conditions were 120°C, 2mm, 50Hz, 2h, GCr15 steel sheet / steel ball, and the wear spots were directly observed under a microscope.

[0031] Table 3 Friction reduction and anti-wear properties sample CoF Wear scar width / μm blank 0.148 925.0 Example 1 0.098 632.6 Example 2 0.100 723.7 Example 3 0.103 699.3 Example 4 0.104 718.0 Example 5 0.108 757.0 Example 6 0.096 446.5 Example 7 0.096 667.2 Example 8 0.101 682.7 Comparative Example 1 0.105 742.0 Comparative Example 2 0.110 798.0 The aqueous phase of the liquid separation in Example 3 is light red, while the aqueous phase of the liquid separation in Example 1 is yellow, indicating that the secondary addition of carbon disulfide effectively improves the conversion rate. From the molybdenum / sulfur content, it can be seen that the theoretical molybdenum content of Example 1 is 12.2%, the actual molybdenum content is 12.1%, and the molybdenum atom utilization rate is >99.1%. Moreover, the acid value shows that the additive does not contain substantially free dialkyldithiocarbamic acid, achieving a high conversion rate, high yield, and controllable selectivity of the reaction. The higher acid value of Example 4 indicates the presence of free carbamic acid. The acid value requirement for additives in engine oil cannot be too high, otherwise it may cause corrosiveness. The higher molybdenum / sulfur content in Example 6 is due to the addition of equimolar amounts of organic amine and molybdenum atoms, resulting in a lower molybdenum atom utilization rate. The excessively high acid value in the comparative example may be due to excessive free carbamic acid to ensure the molybdenum atom conversion rate.

[0032] and through the attachment Figure 1 and 2 , 967 cm -1 The absorption peak of binuclear Mo=O is at 920 cm -1 The absorption peak of single-core Mo=O is 476 cm -1 The absorption peak of Mo-S-Mo ring is at 967 cm -1 The absorption peak at 975 cm -1 The carbon chain methyl deformation peak at 920 cm is distinguished. -1 The absorption peak of mononuclear Mo=O is at 920 cm -1 The absorption peak intensity of the mononuclear Mo=O is also inconsistent, which can be used as a basis for qualitative judgment. Referring to the acid value and reaction conditions, this rule also proves that this method can effectively control the ratio of mononuclear and binuclear in the additive.

[0033] It should be noted that chemical reactions have conversion rates and selectivity. The ratio of molybdenum source, the ratio of molybdenum source to carbon disulfide, and the ratio of molybdenum source to organic amine controlled in the early stage are not simply corresponding to the ratio of compound A and compound B in the product. Their specific ratios are also related to the reaction conditions. This method provides a controllable ratio preparation method for a non-phosphorus organic molybdenum mixture, and its specific ratio can be calculated comprehensively through the feed amount, acid value, molybdenum content, and sulfur content.

[0034] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A non-phosphorus oil-soluble organic molybdenum additive, characterized in that: Comprising compound A and compound B; The structural formula of compound A is: The structural formula of compound B is: wherein R1, R2, R3, R4, R5, R6, R7, and R8 are selected from C7-C 13 The straight chain and branched alkyl groups, R1, R2, R3, R4, R5, R6, R7, R8 are the same or different.

2. The method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to claim 1, characterized in that: The steps include: Carbon disulfide is added dropwise to the organic amine for reaction, a molybdenum source is added and stirring is continued, the temperature is raised to 60-150°C, the temperature is maintained for a first reflux reaction, the temperature is lowered, carbon disulfide is added dropwise, the temperature is raised to 60-150°C, the temperature is maintained for a second reflux reaction, and a mixture of compound A and compound B is obtained after post-treatment.

3. The method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to claim 2, wherein: Add organic amine to a three-necked flask equipped with a thermometer and a reflux condenser, and then add carbon disulfide dropwise; and / or, adding carbon disulfide dropwise at a temperature below 20°C; and / or, the reaction time of adding carbon disulfide dropwise to the organic amine is 1 to 20 hours; And / or, the temperature of adding the molybdenum source and continuing stirring is 25° C. and the stirring time is 1 to 20 hours.

4. The method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to claim 2, wherein: The reaction time of the first reflux reaction is maintained at the temperature for 1 to 20 hours; and / or, maintaining the temperature for the first reflux reaction, and cooling to 40° C.; And / or, the temperature is maintained for a second reflux reaction for a reaction time of 1 to 20 hours.

5. The method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to claim 2, wherein: The molybdenum source includes a mixed aqueous solution containing a +6 valent molybdenum source and a +5 valent molybdenum source.

6. The method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to claim 5, wherein: The preparation method of the molybdenum source comprises the steps of: mixing water and ammonium heptamolybdate tetrahydrate, stirring until dissolved, adding carbon disulfide and reacting for 1 to 20 hours, and continuously adding ammonium heptamolybdate tetrahydrate and stirring until dissolved to obtain the molybdenum source; And / or, the molar ratio of the +5-valent molybdenum source to the +6-valent molybdenum source is 0.1-10:

1.

7. The method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to claim 2, wherein: The molar ratio of organic amine to carbon disulfide is 1:1.1; and / or, the molar ratio of the organic amine to the molybdenum source is 1 to 2:1; And / or, the molar ratio of the organic amine to the second carbon disulfide is 1:0-0.

5.

8. The method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to claim 2, wherein: The general formula of the organic amine is R9NHR 10 , where R9, R 10 C7-C 13 Straight and branched alkyl groups, R9, R 10 Same or different; And / or, the post-treatment includes separating the upper organic phase and distilling under reduced pressure to obtain a mixture of compound A and compound B.

9. A non-phosphorus oil-soluble organic molybdenum additive prepared by the method for preparing a non-phosphorus oil-soluble organic molybdenum additive according to any one of claims 2 to 8, wherein the non-phosphorus oil-soluble organic molybdenum additive is used in lubricating oil or grease.

10. The use according to claim 9, characterized in that: The addition amount in lubricating oil is 0.1 wt.%~1 wt.%, and the addition amount in grease is 0.4 wt.%~4 wt.%.

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