Organic molybdenum ionic liquid grease extreme pressure and wear-resistant additive, preparation method and application

Abstract

The application discloses an organic molybdenum ionic liquid grease extreme pressure and wear-resistant additive, a preparation method and application. The method comprises the following steps: mixing 4-methyl-5-vinylthiazole and n-bromobutane, and stirring at room temperature; increasing the temperature to 50-60 DEG C, and stirring for 6-8 hours; after stopping the reaction, removing the residue by vacuum distillation to obtain transparent liquid product A; dissolving sodium molybdate dihydrate in deionized water, and stirring at room temperature; adding hydrochloric acid into the system, continuing to stir, adding the prepared transparent liquid product A into the system, stirring at room temperature for 3-5 hours, filtering, and vacuum drying to obtain the ionic liquid additive. The additive prepared by the application has a novel molecular structure, and 3-butyl-4-methyl-5-vinylthiazole ammonium molybdate salt is synthesized for the first time; as a lithium-based lubricating grease extreme pressure and wear-resistant additive, the additive can effectively improve the extreme pressure and wear-resistant performance of the lubricating grease. Meanwhile, the application also has the advantages of simple synthesis preparation method, high product yield and the like.

Description

Technical Field

[0001] This invention relates to an organic molybdenum ionic liquid extreme pressure anti-wear additive for greases, its preparation method, and its application. The additive prepared by the method is an organic molybdenum ionic liquid extreme pressure anti-wear additive for lithium-based greases, belonging to the field of grease additive technology. Background Technology

[0002] Friction and wear are common phenomena during the operation of mechanical equipment and are also important causes of energy consumption and equipment failure. Lubricating grease is an important lubricating material for maintaining the normal operation of mechanical equipment, and friction modifiers are a key component of high-performance lubricating greases. Organic molybdenum friction modifiers have become indispensable lubricating materials due to their excellent friction-reducing, anti-wear, and anti-oxidation properties. Because organic molybdenum friction modifiers can improve engine mechanical efficiency and fuel economy, they are widely used in the automotive industry, heavy industrial machinery, and aerospace fields. Currently, molybdenum dialkyldithiocarbamate (MoDTC) additives are the most commonly used friction modifiers and possess excellent friction-reducing properties.

[0003] A search revealed no reports in existing literature on the synthesis and application of ammonium 3-butyl-4-methyl-5-vinylthiazolylmolybdate.

[0004] With the implementation of the national sustainable development strategy and the increasing awareness of environmental protection, the lubricating grease market is paying more and more attention to energy conservation, emission reduction, and environmental protection. For example, long-term use of phosphorus- and sulfur-containing lubricating greases can cause corrosion to the metal of mechanical equipment and lead to environmental pollution. Therefore, internal combustion engines with built-in exhaust gas treatment devices have an urgent need for phosphorus-free friction modifiers. This invention synthesizes and prepares an organic molybdenum ionic liquid extreme pressure anti-wear additive that does not contain phosphorus in its molecule. It can be directly applied to lithium-based lubricating greases and provides excellent extreme pressure anti-wear effects. Summary of the Invention

[0005] This invention provides an organic molybdenum ion liquid grease extreme pressure anti-wear additive, its preparation method, and its application; it also provides the first synthesis of a 3-butyl-4-methyl-5-vinylthiazolyl molybdate ammonium salt, which is added as a lubricating additive to lithium-based grease to improve the extreme pressure anti-wear performance of lithium-based grease.

[0006] The present invention adopts the following technical solution:

[0007] An organic molybdenum ion liquid grease extreme pressure anti-wear additive, wherein the organic molybdenum ion liquid grease extreme pressure anti-wear additive is 3-butyl-4-methyl-5-vinylthiazolylmolybdate ammonium salt.

[0008] The method for preparing the organic molybdenum ionic liquid grease extreme pressure anti-wear additive as described above includes the following steps:

[0009] (1) Mix 4-methyl-5-vinylthiazole and bromobutane, stir; heat up and stir to react; remove residue by vacuum distillation to obtain transparent liquid product A; preferably, the stirring reaction temperature is 45-60℃ (e.g., the reaction temperature is 45℃, 50℃, 55℃ or 60℃), and the stirring reaction time is 5-8 hours (e.g., the reaction time is 5 hours, 6 hours, 7 hours or 8 hours);

[0010] (2) Dissolve molybdate in deionized water and stir; add hydrochloric acid to the system and continue stirring; add the above-prepared transparent liquid product A to the system, stir at room temperature, filter, and vacuum dry to obtain ionic liquid additive; preferably, the stirring time at room temperature is 2 to 5 hours (e.g., stirring at room temperature for 2 hours, 3 hours, 4 hours or 5 hours).

[0011] Further, in step (1), the molar ratio of 4-methyl-5-vinylthiazole to bromobutane is 1:1.05 to 1.2 (for example, the molar ratio of 4-methyl-5-vinylthiazole to bromobutane is 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09, 1:1.1, 1:1.11, 1:1.12, 1:1.13, 1:1.14, 1:1.15, 1:1.16, 1:1.17, 1:1.18, 1:1.19 or 1:1.2); preferably, the n-bromobutane is bromobutane.

[0012] Furthermore, in step (1), the stirring is carried out at room temperature for 0.5-1.0 hours.

[0013] Further, in step (2), the molar ratio of molybdate to 4-methyl-5-vinylthiazole is 1.0 to 1.1:1 (for example, the molar ratio of molybdate to 4-methyl-5-vinylthiazole is 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1 or 1.1:1); preferably, the molybdate is sodium molybdate dihydrate or sodium molybdate.

[0014] Further, in step (2), the amount of hydrochloric acid added is 0.5 mL to 6 mL, and the concentration of hydrochloric acid is 6 mol / L to 36 wt% hydrochloric acid.

[0015] Specifically, this invention utilizes 4-methyl-5-vinylthiazole, n-butane bromide, sodium molybdate dihydrate, and hydrochloric acid as raw materials to obtain the additive product through a two-step reaction. The synthetic route is as follows: Figure 1 As shown.

[0016] The specific synthesis method is as follows: 4-methyl-5-vinylthiazole and n-bromobutane are added to a three-necked flask and stirred at room temperature for 0.5-1.0 hours; the temperature is raised to 50-60℃ and the reaction is maintained while stirring for 6-8 hours; after the reaction is stopped, the residue is removed by vacuum distillation to obtain a reddish-brown transparent liquid product.

[0017] Dissolve sodium molybdate dihydrate in deionized water and stir at room temperature for 0.5-1.0 hours; add hydrochloric acid to the system and continue stirring for 0.5 hours; add the prepared reddish-brown transparent liquid product to the system and stir at room temperature for 3-5 hours; filter and vacuum dry to obtain a brown solid, which is the ionic liquid additive.

[0018] The application of the additives described above or the additives prepared by the method described in any of the preceding claims involves adding the extreme pressure anti-wear additive to the grease, wherein the mass percentage of the extreme pressure anti-wear additive is 0.5 to 3 wt% based on the total mass of the extreme pressure anti-wear additive and the grease (for example, the mass percentage of the extreme pressure anti-wear additive is 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.4 wt%, 2.6 wt%, 2.8 wt%, or 3 wt% based on the total mass of the extreme pressure anti-wear additive and the grease).

[0019] Furthermore, the grease is a lithium-based grease.

[0020] The present invention has the following beneficial effects:

[0021] This invention features an innovative molecular structure, achieving the first synthesis of ammonium 3-butyl-4-methyl-5-vinylthiazolyl molybdate, which can be used as an extreme pressure anti-wear additive in lithium-based lubricating greases to effectively improve their extreme pressure anti-wear properties. Furthermore, this invention offers advantages such as a simple synthesis method and high product yield. Attached Figure Description

[0022] Figure 1 Synthetic route diagram for ammonium 3-butyl-4-methyl-5-vinylthiazolylmolybdate;

[0023] Figure 2 The 1H NMR spectrum of ammonium 3-butyl-4-methyl-5-vinylthiazolylmolybdate is shown. Detailed Implementation

[0024] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. However, the following embodiments are only for explaining the present invention, and the scope of protection of the present invention should include all the contents of the claims. Moreover, through the description of the following embodiments, those skilled in the art can fully implement all the contents of the claims of the present invention.

[0025] The lithium-based grease used in the following embodiments of the present invention is prepared as follows: 100 parts by weight of mineral oil (Fushun Petrochemical Company, 150SN) and 30 parts by weight of hard fatty acid (Shanghai Maclean Biochemical Technology Co., Ltd., 12-hydroxystearic acid) are mixed and added to a reaction vessel. After heating and melting, 22.5 parts by weight of a 20wt% lithium hydroxide aqueous solution are added. After the temperature rises to 135°C, a saponification reaction is carried out for 2 hours. The temperature is then raised to 210°C to completely melt the grease. Then, 5 parts by weight of mineral oil are added, mixed evenly, and cooled to obtain the lithium-based grease.

[0026] Example 1:

[0027] Add 0.313 g of 4-methyl-5-vinylthiazole and 0.344 g of n-bromobutane to a three-necked flask and stir at room temperature for 0.5 hours; raise the temperature to 50°C and maintain the temperature while stirring for 6 hours; after stopping the reaction, remove the residue by vacuum distillation to obtain a reddish-brown transparent liquid product.

[0028] Dissolve 0.121 g of sodium molybdate dihydrate in 2 g of deionized water and stir at room temperature for 0.5 hours. Add 0.5 mL of 6 mol / L hydrochloric acid to the system and continue stirring for 0.5 hours. Add 0.132 g of the prepared reddish-brown transparent liquid product to the system and stir at room temperature for 3 hours. Filter and vacuum dry to obtain a gray solid, which is the ionic liquid additive.

[0029] Figure 2 The 1H NMR spectrum of the ammonium 3-butyl-4-methyl-5-vinylthiazolylmolybdate salt prepared in this invention.

[0030] 3-Butyl-4-methyl-5-vinylthiazolylmolybdate ammonium salt was added to lithium-based grease at a mass fraction of 1.0% (based on the total mass of 3-butyl-4-methyl-5-vinylthiazolylmolybdate ammonium salt and lithium-based grease). Tribological performance tests using a four-ball testing machine showed that, after adding the ionic liquid additive of this invention, the maximum non-seize load (P0.05) of the lithium-based grease sample was... B The weight of the lithium-based grease was increased from 23 kg to 48 kg, the coefficient of friction decreased from 0.090 to 0.081, and the wear scar diameter decreased from 0.659 mm to 0.581 mm. However, with the addition of the same mass fraction of the traditional commercial additive molybdenum dialkyldithiocarbamate (MoDTC), the maximum non-seize load (P) of the lithium-based grease sample was significantly reduced. B The weight was increased from 23kg to 44kg, the coefficient of friction decreased from 0.090 to 0.078, and the wear scar diameter decreased from 0.659mm to 0.518mm.

[0031] Example 2:

[0032] Add 3.13 g of 4-methyl-5-vinylthiazole and 3.44 g of n-bromobutane to a three-necked flask and stir at room temperature for 0.5 hours; raise the temperature to 60°C and maintain the temperature while stirring for 7 hours; after stopping the reaction, remove the residue by vacuum distillation to obtain a reddish-brown transparent liquid product.

[0033] Dissolve 1.21 g of sodium molybdate dihydrate in 15 g of deionized water and stir at room temperature for 0.5 hours. Add 5 mL of 6 mol / L hydrochloric acid to the system and continue stirring for 0.5 hours. Add 1.321 g of the prepared reddish-brown transparent liquid product to the system and stir at room temperature for 4 hours. Filter and vacuum dry to obtain a gray solid, which is the ionic liquid additive.

[0034] 3-Butyl-4-methyl-5-vinylthiazolylmolybdate ammonium salt was added to lithium-based grease at a mass fraction of 1.0% (based on the total mass of 3-butyl-4-methyl-5-vinylthiazolylmolybdate ammonium salt and lithium-based grease). Tribological performance tests using a four-ball testing machine showed that, after adding the ionic liquid additive of this invention, the maximum non-seize load (P0.05) of the lithium-based grease sample was... B The load capacity of the lithium-based grease increased from 23 kg to 48 kg, the coefficient of friction decreased from 0.089 to 0.080, and the wear scar diameter decreased from 0.663 mm to 0.592 mm. However, with the addition of the same mass fraction of the traditional commercial additive MoDTC, the maximum non-seize load (P0.05) of the lithium-based grease sample increased. B The weight was increased from 23kg to 44kg, the coefficient of friction decreased from 0.089 to 0.077, and the wear scar diameter decreased from 0.663mm to 0.526mm.

[0035] Example 3:

[0036] Add 6.26 g of 4-methyl-5-vinylthiazole and 7.20 g of n-bromobutane to a three-necked flask and stir at room temperature for 0.5 hours; raise the temperature to 60°C and maintain the temperature while stirring for 8 hours; after stopping the reaction, remove the residue by vacuum distillation to obtain a reddish-brown transparent liquid product.

[0037] Dissolve 2.42 g of sodium molybdate dihydrate in 30 g of deionized water and stir at room temperature for 0.5 hours. Add 1 mL of 36 wt% hydrochloric acid to the system and continue stirring for 0.5 hours. Add 2.642 g of the prepared reddish-brown transparent liquid product to the system and stir at room temperature for 5 hours. Filter and vacuum dry to obtain a gray solid, which is the ionic liquid additive.

[0038] 3-Butyl-4-methyl-5-vinylthiazolylmolybdate ammonium salt was added to lithium-based grease at a mass fraction of 1.0% (based on the total mass of 3-butyl-4-methyl-5-vinylthiazolylmolybdate ammonium salt and lithium-based grease). Tribological performance tests using a four-ball testing machine showed that, after adding the ionic liquid additive of this invention, the maximum non-seize load (P0.05) of the lithium-based grease sample was... B The load capacity of the lithium-based grease increased from 23 kg to 48 kg, the coefficient of friction decreased from 0.089 to 0.080, and the wear scar diameter decreased from 0.668 mm to 0.588 mm. However, with the addition of the same mass fraction of the traditional commercial additive MoDTC, the maximum non-seize load (P0.05) of the lithium-based grease sample increased. B The weight was increased from 23kg to 44kg, the coefficient of friction decreased from 0.089 to 0.078, and the wear scar diameter decreased from 0.668mm to 0.511mm.

[0039] The performance parameter testing method is as follows: Organic molybdenum ionic liquid additive products are added to lithium-based grease, and the P of the lithium-based grease samples is evaluated using a four-ball machine according to GB3142-82. B (Maximum non-seizure load), P D (Sintering load) Test conditions: room temperature, rotation speed 1770 rpm, time 10 s. Long-term grinding evaluation test conditions: 75℃, rotation speed 1200 rpm, load 40 kg, time 60 min. After the long-term grinding test, the friction coefficient was recorded to evaluate the friction reduction performance of the additive; the wear scar diameter (WSD) of three lower balls was measured using an optical microscope, and the average diameter was used to evaluate the anti-wear performance of the additive.

[0040] Table 1 Maximum non-seize load (P) of lubricant samples in the examples B )

[0041] sample Lithium-based grease The additive of this invention (1%) MoDTC (1%) Example 1 23kg 48kg 44kg Example 2 23kg 48kg 44kg Example 3 23kg 48kg 44kg

[0042] Table 2. Average friction coefficient of lubricant samples in long-term wear examples.

[0043]

[0044] Table 3. Wear scar diameters of lubricant samples from the examples.

[0045]

[0046] Ammonium 3-butyl-4-methyl-5-vinylthiazolylmolybdate was added to the lithium-based grease at a mass fraction of 1.0% (based on the total mass of the ammonium 3-butyl-4-methyl-5-vinylthiazolylmolybdate and the lithium-based grease); the conventional commercial anti-wear additive MoDTC (Ruifeng New Materials) was also added to the lithium-based grease at a mass fraction of 1.0% (based on the total mass of MoDTC and the lithium-based grease). Tribological performance tests using a four-ball testing machine showed that, after adding the ionic liquid additive of this invention, the maximum non-seize load (P) of the lithium-based grease sample was significantly reduced. B The load capacity increased from 23 kg to 48 kg, the coefficient of friction decreased from 0.090 to 0.081, and the wear scar diameter decreased from 0.659 mm to 0.581 mm; while the maximum non-seize load (P) of the lithium-based grease sample increased after adding the traditional commercial additive MoDTC. B The pressure was increased from 23 kg to 44 kg, the coefficient of friction decreased from 0.090 to 0.078, and the wear scar diameter decreased from 0.659 mm to 0.518 mm. The test results demonstrate that the ionic liquid additive prepared in this invention possesses excellent extreme pressure anti-wear properties.

[0047] The parts of this invention not described in detail are well-known to those skilled in the art. The embodiments described above are merely preferred embodiments of the invention, and do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Various modifications and improvements to the technical solutions of this invention made by those skilled in the art without departing from the spirit of the invention should fall within the protection scope defined by the claims of this invention.

Claims

1. An organomolybdenum ionic liquid grease extreme pressure antiwear additive characterized in that, The organic molybdenum ionic liquid grease extreme pressure anti-wear additive is .

2. A process for the preparation of the organo-molybdenum ionic liquid grease extreme pressure anti-wear additive as claimed in claim 1, characterized in that, The method comprises the following steps: (1) mixing 4-methyl-5-vinylthiazole and bromobutane and stirring; Warming, stirring reaction; remove the residue under reduced pressure by distillation to obtain transparent liquid product A, the transparent liquid product A is ; (2) dissolving a molybdate in deionized water and stirring; adding hydrochloric acid into the system and continuing to stir; adding the prepared transparent liquid product A into the system; stirring at room temperature; filtering; and vacuum drying to obtain an ionic liquid additive; wherein the molybdate is sodium molybdate dihydrate or sodium molybdate; the amount of the hydrochloric acid added is 0.5 mL to 6 mL, and the concentration of the hydrochloric acid is 6 mol / L to 36 wt%.

3. The method of claim 2, wherein, In step (1), the molar ratio of 4-methyl-5-vinylthiazole to bromobutane is 1:1.05 to 1.

2.

4. The method of claim 2, wherein, In step (1), the stirring is room temperature stirring, and the stirring time is 0.5 to 1.0 hours.

5. The method of claim 2, wherein, In step (2), the molar ratio of the molybdate to 4-methyl-5-vinylthiazole is 1.0 to 1.1:

1.

6. Use of the additive of claim 1 or the additive produced by the method of any one of claims 2-5, characterized in that, The extreme pressure anti-wear additive is added into the grease, and the mass percentage of the extreme pressure anti-wear additive in the total mass of the extreme pressure anti-wear additive and the grease is 0.5 to 3 wt%.

7. Use according to claim 6, characterized in that, The grease is a lithium-based grease.

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