Phosphazene modified silicone oil extreme pressure anti-wear agent and preparation method thereof

Abstract

The invention discloses a preparation method of a phosphazene modified silicone oil extreme pressure anti-wear agent. According to the method, a polyfluorocyclotriphosphazene compound reacts with hydroxyl at the tail end of a hydroxyl silicone oil molecule, and the polyfluorocyclotriphosphazene compound modified methyl silicone oil extreme pressure anti-wear agent is obtained through reduced pressure distillation and cooling. The extreme pressure anti-wear agent has excellent extreme pressure anti-wear performance, the related chemical reaction process is simple in technology, post-treatment operation is convenient and fast, and industrial mass production is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of synthetic lubricating materials, and in particular to a method for preparing a phosphazene-modified silicone oil extreme pressure anti-wear agent. Background Art

[0002] Compared with conventional hydrocarbon lubricants, silicone oil has better thermal stability, low-temperature fluidity, flame retardancy and extremely low volatility. Therefore, it has broad application prospects as a lubricant in the fields of electronic appliances, medical equipment, aerospace, etc. However, the boundary lubrication performance of ordinary silicone oil lubricants is poor, which greatly limits the application scope of silicone oil as a lubricating material.

[0003] Modifying the molecular structure of silicone oil and introducing active groups with lubricating effects into its structure is an effective means to improve the lubricating and anti-wear properties of silicone oil. Polyfluorinated cyclotriphosphazene compounds have excellent lubrication, anti-wear and flame retardancy. Their nitrogen-phosphorus skeleton is very stable, and the extremely high fluorine atom content in the molecule is the key factor for their excellent lubrication properties. The present invention adopts chemical modification technology to graft the polyfluorinated cyclotriphosphazene compound skeleton to the end of the hydroxy silicone oil molecular structure, thereby preparing methyl silicone oil modified with polyfluorinated cyclotriphosphazene compounds. Using it as an extrusion anti-wear additive can effectively improve the extreme pressure and anti-wear properties of lubricating oil. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing a phosphazene-modified silicone oil extreme pressure anti-wear agent, so as to make up for the defect of poor lubrication performance of silicone oil lubricant and improve its extreme pressure anti-wear performance.

[0005] The technical solution adopted by the present invention comprises the following steps: adding a certain proportion of hydroxy silicone oil, polyfluorocyclotriphosphazene and alkaline compound into a three-necked flask, connecting a condenser, passing nitrogen protection, reacting at 20-80°C for 12-24 hours, performing reduced pressure distillation, and cooling to obtain the invented product. The synthetic route for preparing the cyclotriphosphazene-modified silicone oil extreme pressure anti-wear agent is shown in formula (I):

[0006] In formula (I): R 1 is a fluorine atom, an ethoxy group, or a phenoxy group; R 2 is a fluorine atom, an ethoxy group, or a phenoxy group; n is an integer selected from 5-10, preferably 5, 6, 7, 8, 9 or 10.

[0007] The method for preparing the phosphazene-modified silicone oil extreme pressure anti-wear agent is characterized in that the molar ratio of hydroxy silicone oil, polyfluorocyclotriphosphazene and basic compound is 1:1.0-2.0:0.6-1.2.

[0008] The preparation method of the above-mentioned phosphazene-modified silicone oil extreme pressure anti-wear agent is characterized in that the alkaline compound includes but is not limited to at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, calcium hydride, triethylamine, pyridine, etc.

[0009] The method for preparing the phosphazene-modified silicone oil extreme pressure anti-wear agent is characterized in that the solvent is at least one of n-hexane, ether, tetrahydrofuran, acetonitrile and toluene.

[0010] The method for preparing the phosphazene-modified silicone oil extreme pressure anti-wear agent is characterized in that the reaction temperature is 20-80° C. and the reaction time is 12-24 hours.

[0011] The phosphazene-modified silicone oil extreme pressure anti-wear agent described in the present invention has the following advantages compared with existing silicone oil lubricants: 1) the product of the present invention exhibits excellent lubricating properties when used as an extreme pressure anti-wear agent; 2) the chemical reaction process involved in the present invention is simple in technology, and the post-processing operation is convenient, which is conducive to large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 The molecular structure formula of the product obtained in Example 1 of the present invention;

[0013] Figure 2 This is the infrared spectrum of the product obtained in Example 1 of the present invention; DETAILED DESCRIPTION

[0014] The technical scheme of the present invention is further described in detail below through examples. In the following examples of the present invention, hydroxy silicone oil OF0025 is a low molecular weight, high hydroxyl value silicone oil produced by Sysbo Organic Silicone Co., Ltd., with a molecular weight of about 450. Hexafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, and diphenoxytetrafluorocyclotriphosphazene are all homemade in the laboratory.

[0015] Embodiment 1: The preparation method of this embodiment comprises the following steps:

[0016] 45.0 g of hydroxy silicone oil OF0025, 49.8 g of hexafluorocyclotriphosphazene, 4.0 g of sodium hydroxide and 100 mL of n-hexane were added to a 500 mL three-necked flask in sequence, connected to a condenser, nitrogen protection, magnetic stirring, reacted at 80° C. for 12 hours, and then distilled under reduced pressure. After cooling, the product of the invention was obtained. The reaction equation is as follows:

[0017] Embodiment 2: The preparation method of this embodiment comprises the following steps:

[0018] 45.0 g of hydroxy silicone oil OF0025, 55.0 g of ethoxy pentafluorocyclotriphosphazene, 4.0 g of sodium hydroxide and 100 mL of n-hexane were added to a 500 mL three-necked flask in sequence, connected to a condenser, nitrogen protection, magnetic stirring, reacted at 80° C. for 20 hours, and then distilled under reduced pressure. After cooling, the product of the invention was obtained. The reaction equation is as follows:

[0019] Embodiment 3: The preparation method of this embodiment comprises the following steps:

[0020] 45.0 g of hydroxy silicone oil OF0025, 60.0 g of diethoxytetrafluorocyclotriphosphazene, 4.0 g of sodium hydroxide and 100 mL of n-hexane were added to a 500 mL three-necked flask in sequence, connected to a condenser, nitrogen protection, magnetic stirring, reacted at 80° C. for 20 hours, and then distilled under reduced pressure. After cooling, the product of the invention was obtained. The reaction equation is as follows (IV):

[0021] Embodiment 4: The preparation method of this embodiment comprises the following steps:

[0022] 45.0 g of hydroxy silicone oil OF0025, 64.6 g of phenoxy pentafluorocyclotriphosphazene, 4.0 g of sodium hydroxide and 100 mL of n-hexane were added to a 500 mL three-necked flask in sequence, connected to a condenser, nitrogen protection, magnetic stirring, reacted at 80° C. for 24 hours, and then distilled under reduced pressure. After cooling, the product of the invention was obtained. The reaction equation is as follows (V):

[0023] Embodiment 5: The preparation method of this embodiment comprises the following steps:

[0024] 45.0 g of hydroxy silicone oil OF0025, 79.4 g of diphenoxytetrafluorocyclotriphosphazene, 4.0 g of sodium hydroxide and 100 mL of n-hexane were added to a 500 mL three-necked flask in sequence, connected to a condenser, nitrogen protection, magnetic stirring, reacted at 80° C. for 24 hours, and then distilled under reduced pressure. After cooling, the product of the invention was obtained. The reaction equation is as follows (VI):

[0025] Using MVI500 base oil, the extreme pressure anti-wear additive prepared in the above examples 1-5 was added to the base oil, stirred and dispersed evenly to obtain an extreme pressure anti-wear lubricating oil, and the weight ratio of the extreme pressure anti-wear additive to the base oil was 1:99.

[0026] Comparative Example 1:

[0027] The hydroxy silicone oil OF0025 was directly added into the MVI500 base oil, and the mixture was stirred and dispersed evenly to obtain an extreme pressure anti-wear lubricating oil. The weight ratio of the hydroxy silicone oil OF0025 to the base oil was 1:99.

[0028] Comparative Example 2:

[0029] MVI500 base oil is pure and does not require any extreme pressure and anti-wear additives.

[0030] Performance evaluation of extreme pressure anti-wear agent: Using MS-10J four-ball machine and high carbon chromium bearing steel balls that meet GB / T 308.1-2013 standard, the friction performance of extreme pressure anti-wear agent was tested according to GB / T3142 standard. B ), sintering load (P D ), comprehensive wear value (ZMZ) was used to evaluate the extreme pressure performance; wear spot diameter (WSD) was used to evaluate the anti-wear performance. The test conditions were: measuring load 196N, temperature 75℃, speed 1200r / min, time 60min.

[0031] The test results of Examples 1-5 and Comparative Examples 1-2 are shown in Table 1.

[0032] Table 1 Anti-wear performance test results of each sample:

[0033] It can be seen from the experimental results in Table 1 that compared with the MVI500 base oil without any additives, the addition of 1% hydroxy silicone oil OF0025 can slightly improve the extreme pressure and anti-wear properties of the lubricating oil; the addition of 1% hexafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene modified hydroxy silicone oils can significantly improve the extreme pressure and anti-wear properties, among which the hexafluorocyclotriphosphazene modified hydroxy silicone oil in Example 1 has the best effect; in Example 4, the addition of 1% phenoxypentafluorocyclotriphosphazene modified hydroxy silicone oil cannot improve the extreme pressure and anti-wear properties; in Example 5, the diphenoxytetrafluorocyclotriphosphazene modified hydroxy silicone oil has a significant improvement on the extreme pressure performance of the lubricating oil, but has little effect on the anti-wear performance.

[0034] The extreme pressure and anti-wear performance tests of Examples 1-5 above show that the hydroxy silicone oil modified with hexafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, and diethoxytetrafluorocyclotriphosphazene in the present invention as an additive can effectively improve the extreme pressure and anti-wear performance of the MVI500 base oil.

[0035] Some embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Any changes, modifications, substitutions and variations of the above embodiments are within the protection scope of the present invention.

Claims

1. A method for preparing a phosphazene-modified silicone oil extreme pressure anti-wear agent, comprising the following steps: A certain proportion of hydroxy silicone oil, polyfluorocyclotriphosphazene and alkaline compound were added to a 250 mL three-necked flask, and a condenser was connected. Nitrogen was passed through for protection. After reacting at 20-80° C. for 12-24 hours, vacuum distillation was performed, and the product of the invention was obtained after cooling. The reaction equation is as follows: In the equation: R 1 is a fluorine atom, an ethoxy group, or a phenoxy group; R 2 is a fluorine atom, an ethoxy group, or a phenoxy group; n is an integer selected from 5-10, preferably 5, 6, 7, 8, 9 or 10.

2. The method for preparing a phosphazene-modified silicone oil extreme pressure anti-wear agent according to claim 1, characterized in that: The molar ratio of hydroxy silicone oil, polyfluorocyclotriphosphazene and basic compound is 1:1.0-2.0:0.6-1.

2.

3. The method for preparing a phosphazene-modified silicone oil extreme pressure anti-wear agent according to claim 1, characterized in that: The alkaline compound includes, but is not limited to, at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, calcium hydride, triethylamine, and pyridine.

4. The method for preparing a phosphazene-modified silicone oil extreme pressure anti-wear agent according to claim 1, characterized in that: The solvent is at least one of n-hexane, ether, tetrahydrofuran, acetonitrile and toluene.

5. The method for preparing a phosphazene-modified silicone oil extreme pressure anti-wear agent according to claim 1, characterized in that: The reaction temperature is 20-80° C., and the reaction time is 12-24 hours.

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