Lubricating oil products are widely applied to mechanical transmission and control mechanisms, some antiwear additives are often added into the lubricating oil products to reduce abrasion, and for example, a proper amount of antiwear additives are properly added into hydraulic oil for a high-pressure oil pump to prepare antiwear hydraulic oil. Both U.S. Pat. No. 5, 4537696 (1985) and PCT patent WO8404319 propose zinc dialkyldithiophosphates (ZPTP) as antiwear additives. Zinc dialkyl dithiophosphate is an organic salt of zinc metal dithiophosphate, and is a surface active compound. Is easy to hydrolyze in water, and can generate alkyl thiophosphoric acid and sulfur in the hydrolysis process. Thiophosphoric acid is an emulsifier which emulsifies lubricating oil from water and is difficult to separate, so that the lubricating oil deteriorates and fails, for example, in winter, the lubricating oil in a tank is emulsified by contacting with condensed water which may be generated, and the lubricating oil must be replaced with new lubricating oil. Sulfur is corrosive to copper and silver, mechanical parts such as bearings are made of more copper, and the service life of the mechanical parts is affected by the corrosion of sulfur generated after hydrolysis to the mechanical parts.
The invention aims to provide a phosphorus-nitrogen type ashless organic anti-wear additive which has strong anti-emulsifying property, good hydrolytic resistance and better anti-wear property and does not contain sulfur. The novel additive is not easy to hydrolyze, is not easy to emulsify oil and water, does not contain sulfur, does not corrode copper and silver parts, and is ashless and excellent in wear resistance.
The antiwear additive provided by the invention is an organic reaction mixture of aryl phosphate, long-chain organic amine, polyhydroxy alcohol fatty acid ester or polybasic acid fatty alcohol ester and phenyl-o-triazole. The weight percentage of the components is that aryl phosphate ester accounts for 40 percent to 90 percent, long-chain organic amine accounts for 2 percent to 15 percent, polyhydroxy alcohol fatty acid ester or polybasic acid fatty alcohol ester can be used together with one or both of the aryl phosphate ester and the long-chain organic amine, the total weight percentage is 10 percent to 50 percent, and phenyl-methyl triazole accounts for 0.5 percent to 5 percent. In the application, tricresyl phosphate can be used as aryl phosphate, octadecylamine can be used as long-chain organic amine, sorbitol fatty acid ester or pentaerythritol fatty acid ester can be used as polyhydroxy alcohol fatty acid ester, and dioctyl sebacate can be used as polybasic acid fatty acid ester.
The manufacturing process method comprises the following steps: firstly, adding the aryl phosphate, the long-chain organic amine and the phenyl-o-triazole into a reaction kettle according to the weight percentage, mixing, heating to 70-150 ℃, then maintaining the temperature, stirring for 6-20 hours, then adding the polybasic acid fatty alcohol ester or the polyhydroxy alcohol fatty acid ester according to the weight percentage, continuing to stir for 1-4 hours under heat preservation, cooling and discharging. The discharged mixed solution is the concentrated solution of the phosphorus-nitrogen type ashless organic anti-wear additive, the concentrated solution is a light yellow oily substance at room temperature, the freezing point is lower than 0 ℃, and the flash point is higher than 200 ℃. The concentrate can be diluted with diluent which can be high oxygen content polyhydroxy or polybasic acid esters, such as dicarboxylic acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, trimethylolpropane ester.
The novel antiwear additive can be mixed with lubricating oil products in any proportion, and the freezing point of the lubricating oil products cannot be influenced after the novel antiwear additive is mixed. The antiwear effect can be exhibited by adding 0.1-1% of this antiwear additive to a lubricating oil product, and the addition amount is generally 0.1-10% by weight. The antiwear additive may be compounded with other additives, such as antioxidant, tackifier, pour point depressant, defoaming agent, etc. and may be compounded with extreme pressure additive, such as dibenzyl disulfide, isobutylene polysulfide and zinc dialkyl dithiophosphate, to form composite antiwear extreme pressure additive for preparing extreme pressure industrial gear oil, hyperbolic gear oil, etc.
The antiwear hydraulic oil prepared from the phosphorus-nitrogen type ashless antiwear additive provided by the invention has excellent antiwear performance, the antiwear performance is higher than that of the antiwear hydraulic oil prepared from the zinc dialkyl dithiophosphate antiwear additive at the temperature of more than 90 ℃, the copper weight loss is close to trace measured by an ASTM.D-2619 hydrolysis test, the layering time at 54 ℃ is less than 30 minutes measured by an ASTM.D-1401 demulsibility test, the index is advanced, and the performance is excellent. The antiwear additive may be used in preparing various antiwear lubricating oils, such as ashless antiwear hydraulic oil, antiwear bearing oil for recorder, low torque lubricating oil for sewing machine, composite extreme pressure industrial gear oil, etc. and has obvious application benefit. For example, the ashless anti-wear hydraulic oil has no obvious wear and basically no corrosion to copper parts when being applied to a plunger pump and a high-pressure vane pump for one to two years.
The formulation and manufacturing examples of the phosphorus-nitrogen type ashless anti-wear additive are as follows:
the formula (weight percentage) is as follows:
tricresyl phosphate: 80 percent of
Octadecylamine: 10 percent of
Benzene and triazole: 0.8 percent
Sorbitol fatty acid ester: 1.4 percent
Diisooctyl sebacate: 1.8 percent
The manufacturing process comprises the following steps:
placing tricresyl phosphate, octadecylamine and phenyl-o-triazole into a reaction kettle, mixing, heating to 110 ℃, keeping the temperature, stirring for 14 hours, adding sorbitol fatty acid ester and diisooctyl sebacate, continuing to stir for 3 hours, cooling, and discharging. If necessary, adding proper amount of diluent.