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

Abstract

The application discloses a preparation method of phosphazene modified silicone oil extreme pressure anti-wear agent. The method is characterized in that a polyfluorinated cyclotriphosphazene compound is reacted with hydroxyl groups at the ends of hydroxyl silicone oil molecules, and through vacuum distillation and cooling, a polyfluorinated cyclotriphosphazene compound modified methyl silicone oil extreme pressure anti-wear agent is obtained. The extreme pressure anti-wear agent has excellent extreme pressure and anti-wear performance, the chemical reaction process is simple, the post-treatment operation is convenient, and the industrialized mass production is facilitated.

Description

Technical Field

[0001] This invention relates to the field of synthetic lubricating materials technology, specifically to a method for preparing a phosphazene-modified silicone oil-based extreme pressure anti-wear agent. Background Technology

[0002] Compared to conventional hydrocarbon lubricants, silicone oils possess superior thermal stability, low-temperature fluidity, flame retardancy, and extremely low volatility. Therefore, they have broad application prospects as lubricants in electronics, medical devices, aerospace, and other fields. However, the poor boundary lubrication properties of ordinary silicone oil lubricants significantly limit their application range as a lubricating material.

[0003] Modifying the molecular structure of silicone oil by introducing active groups with lubricating properties is an effective way to improve its lubrication and anti-wear performance. Polyfluorocyclic triphosphazene compounds possess superior lubrication, anti-wear properties, and flame retardancy. Their nitrogen-phosphorus skeleton is highly stable, and the extremely high fluorine atom content within the molecule is a key factor in their excellent lubrication performance. This invention uses chemical modification technology to graft the polyfluorocyclic triphosphazene compound skeleton to the end of the hydroxyl silicone oil molecule, thereby preparing methyl silicone oil modified with polyfluorocyclic triphosphazene compounds. Using this as an extrusion anti-wear additive can effectively improve the extreme pressure anti-wear performance of lubricating oils. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a phosphazene-modified silicone oil-based extreme pressure anti-wear agent, so as to make up for the poor lubrication performance of silicone oil lubricants and improve their extreme pressure anti-wear performance.

[0005] The technical solution adopted in this invention includes the following steps: adding a certain proportion of hydroxyl silicone oil, polyfluorinated triphosphazene, and an alkaline compound to a three-necked flask, connecting a condenser, purging with nitrogen for protection, reacting at 20-80℃ for 12-24 hours, performing vacuum distillation, and obtaining the product of the invention after cooling. The synthetic route for preparing the triphosphazene-modified silicone oil-based extreme pressure anti-wear agent is shown in formula (I):

[0006]

[0007] In formula (I): R 1 It is a fluorine atom, an ethoxy group, or a phenoxy group; R 2 It is a fluorine atom, an ethoxy group, or a phenoxy group; n is an integer selected from 5 to 10, preferably 5, 6, 7, 8, 9, or 10.

[0008] The preparation method of the above-mentioned phosphazene-modified silicone oil extreme pressure anti-wear agent is characterized in that the molar ratio of hydroxyl silicone oil, polyfluorinated cyclic triphosphazene and alkaline compound is 1:1.0~2.0:0.6~1.2.

[0009] 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.

[0010] The preparation method of the above-mentioned phosphazene-modified silicone oil extreme pressure anti-wear agent is characterized in that: the solvent is at least one selected from hexane, diethyl ether, tetrahydrofuran, acetonitrile, and toluene.

[0011] The preparation method of the above-mentioned phosphazene-modified silicone oil extreme pressure anti-wear agent is characterized in that: the reaction temperature is 20-80℃ and the reaction time is 12-24 hours.

[0012] The phosphazene-modified silicone oil extreme pressure anti-wear agent of the present invention has the following advantages compared with existing silicone oil lubricants: 1) The product of the present invention exhibits excellent lubrication performance when used as an extreme pressure anti-wear agent; 2) The chemical reaction process involved in the present invention is simple, and the post-processing operation is convenient, which is conducive to large-scale industrial production. Attached Figure Description

[0013] Figure 1 The molecular structure of the product obtained in Example 1 of this invention is shown below.

[0014] Figure 2 The infrared spectrum of the product obtained in Example 1 of this invention; Detailed Implementation

[0015] The technical solution of the present invention will be further described in detail below through examples. In the following examples of the present invention, the hydroxyl silicone oil OF0025 is a low molecular weight, high hydroxyl value silicone oil produced by Sisbo Organosilicon Co., Ltd., with a molecular weight of approximately 450. Hexafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, and diphenoxytetrafluorocyclotriphosphazene were all prepared in the laboratory.

[0016] Example 1: The preparation method of this example includes the following steps:

[0017] 45.0 g of hydroxyl silicone oil OF0025, 49.8 g of hexafluorocyclotriphosphazene, 4.0 g of sodium hydroxide, and 100 mL of n-hexane were sequentially added to a 500 mL three-necked flask. A condenser was connected, nitrogen gas was purged, and the mixture was magnetically stirred. After reacting at 80 °C for 12 hours, vacuum distillation was performed, and the product was obtained after cooling. The reaction equation is shown in equation (II):

[0018]

[0019] Example 2: The preparation method of this example includes the following steps:

[0020] 45.0 g of hydroxyl silicone oil OF0025, 55.0 g of ethoxypentafluorocyclotriphosphazene, 4.0 g of sodium hydroxide, and 100 mL of n-hexane were sequentially added to a 500 mL three-necked flask. A condenser was connected, nitrogen was purged, and the mixture was magnetically stirred. After reacting at 80 °C for 20 hours, the mixture was distilled under reduced pressure, and the product was obtained after cooling. The reaction equation is shown in equation (III):

[0021]

[0022] Example 3: The preparation method of this example includes the following steps:

[0023] 45.0 g of hydroxyl silicone oil OF0025, 60.0 g of diethoxytetrafluorocyclotriphosphazene, 4.0 g of sodium hydroxide, and 100 mL of n-hexane were sequentially added to a 500 mL three-necked flask. A condenser was connected, nitrogen gas was purged, and the mixture was magnetically stirred. After reacting at 80 °C for 20 hours, vacuum distillation was performed, and the product was obtained after cooling. The reaction equation is shown in equation (Ⅳ):

[0024]

[0025] Example 4: The preparation method of this example includes the following steps:

[0026] 45.0 g of hydroxyl silicone oil OF0025, 64.6 g of phenoxypentafluorocyclotriphosphazene, 4.0 g of sodium hydroxide, and 100 mL of n-hexane were sequentially added to a 500 mL three-necked flask. A condenser was connected, nitrogen gas was purged, and the mixture was magnetically stirred. After reacting at 80 °C for 24 hours, the mixture was distilled under reduced pressure, and the product was obtained after cooling. The reaction equation is shown in equation (V):

[0027]

[0028] Example 5: The preparation method of this example includes the following steps:

[0029] 45.0 g of hydroxyl silicone oil OF0025, 79.4 g of diphenoxytetrafluorocyclotriphosphazene, 4.0 g of sodium hydroxide, and 100 mL of n-hexane were sequentially added to a 500 mL three-necked flask. A condenser was connected, nitrogen gas was purged, and the mixture was magnetically stirred. After reacting at 80 °C for 24 hours, the mixture was distilled under reduced pressure, and the product was obtained after cooling. The reaction equation is shown in equation (VI):

[0030]

[0031] Using MVI500 base oil, the extreme pressure anti-wear additives prepared in Examples 1-5 above were added to the base oil and stirred to disperse evenly to obtain extreme pressure anti-wear lubricating oil. The weight ratio of extreme pressure anti-wear additives to base oil was 1:99.

[0032] Comparative Example 1:

[0033] Hydroxy silicone oil OF0025 was directly added to MVI500 base oil and stirred to disperse evenly to obtain extreme pressure anti-wear lubricating oil. The weight ratio of hydroxy silicone oil OF0025 to base oil was 1:99.

[0034] Comparative Example 2:

[0035] MVI500 base oil is pure and requires no addition of any extreme pressure anti-wear additives.

[0036] Extreme pressure anti-wear agent performance evaluation: The frictional performance of the extreme pressure anti-wear agent was tested according to GB / T3142 standard using an MS-10J four-ball tester and high-carbon chromium bearing steel balls conforming to GB / T 308.1-2013 standard. The maximum non-seizure load (P) was tested. B ), sintering load (P) D Extreme pressure performance was evaluated by comprehensive wear value (ZMZ); wear scar diameter (WSD) was evaluated by wear resistance. The test conditions were: load 196N, temperature 75℃, rotation speed 1200r / min, and time 60min.

[0037] The test results of Examples 1-5 and Comparative Examples 1-2 are shown in Table 1.

[0038] Table 1. Test results of wear resistance of each sample:

[0039]

[0040] The experimental results in Table 1 show that compared to MVI500 base oil without any additives, adding 1% OF0025 hydroxyl silicone oil slightly improves the extreme pressure and anti-wear properties of the lubricating oil. Adding 1% hexafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, or diethoxytetrafluorocyclotriphosphazene modified hydroxyl silicone oils significantly improves both extreme pressure and anti-wear properties, with the hexafluorocyclotriphosphazene modified hydroxyl silicone oil in Example 1 showing the best effect. In Example 4, adding 1% phenoxypentafluorocyclotriphosphazene modified hydroxyl silicone oil does not improve extreme pressure and anti-wear properties. In Example 5, the diethoxytetrafluorocyclotriphosphazene modified hydroxyl silicone oil significantly improves the extreme pressure properties of the lubricating oil, while having little impact on anti-wear properties.

[0041] The extreme pressure anti-wear performance tests of Examples 1-5 above show that the hydroxyl silicone oil modified with hexafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, and diethoxytetrafluorocyclotriphosphazene in this invention can effectively improve the extreme pressure anti-wear performance of MVI500 base oil as an additive.

[0042] Some embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. All variations, modifications, substitutions, and alterations to the above embodiments are within the scope of protection of the present invention.

Claims

1. A process for the preparation of phosphazene-modified silicone oil-based extreme pressure anti-wear agent comprising the steps of: A 250 mL three-necked flask is charged with hydroxyl silicone oil, polyfluorinated cyclotriphosphazene, a basic compound, and a solvent, a condenser is connected, and the reaction is carried out under nitrogen protection at 20-80℃ for 12-24 hours, followed by vacuum distillation, and the product is obtained after cooling. The polyfluorinated cyclotriphosphazene has the following structural formula: wherein R1 is a fluorine atom, an ethoxy group, or a phenoxy group, R2 is a fluorine atom, an ethoxy group, or a phenoxy group, and n is an integer selected from 5-10, and the molar ratio of the hydroxyl silicone oil, the polyfluorinated cyclotriphosphazene, and the basic compound is 1:1.0-2.0:0.6-1.

2.

2. The process for preparing phosphazene-modified silicone oil extreme pressure anti-wear agent according to claim 1, characterized by: The basic compound is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, calcium hydride, triethylamine, and pyridine.

3. The process for preparing phosphazene-modified silicone oil extreme pressure anti-wear agent according to claim 1, characterized by: The solvent is at least one of n-hexane, diethyl ether, tetrahydrofuran, acetonitrile, and toluene.

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