阅读说明：本技术 一种高抗磨减摩润滑油添加剂芳香类含氮硼酸酯的制备 (Preparation of aromatic nitrogenous boric acid ester as high-wear-resistance antifriction lubricating oil additive ) 是由 张晨曦 张文亚 张冠军 于 2019-08-23 设计创作，主要内容包括：本发明涉及机械润滑技术领域中一种芳香类含氮硼酸酯润滑油添加剂的制备方法,该添加剂的原料包括含硫氮醇、硼酸及芳香类二乙醇酰胺；所述含硫氮醇由二胺类化合物、二硫化碳和环氧丙烷为原料制备；所述芳香类二乙醇酰胺由芳香族羧酸、二氯亚砜和二乙醇胺为原料制备；所述高抗磨减摩润滑油添加剂由含硫氮醇、硼酸及芳香类二乙醇酰胺反应得到。本发明采用的合成方法具有操作简单易行,适合大规模的产业化生产,实用性非常强。通过本方法所制备出的润滑油添加剂可有效保护易于磨损的机器零件以及发动机等设备,有效增加润滑油的抗磨擦性能并降低了能源的损耗。(The invention relates to a method for preparing an aromatic nitrogen-containing borate ester lubricating oil additive in the technical field of mechanical lubrication, wherein the raw materials of the additive comprise sulfur-containing nitrogen alcohol, boric acid and aromatic diethanolamide; the sulfur-nitrogen-containing alcohol is prepared from diamine compounds, carbon disulfide and propylene oxide serving as raw materials; the aromatic diethanolamide is prepared from aromatic carboxylic acid, thionyl chloride and diethanolamine serving as raw materials; the high wear-resistant antifriction lubricating oil additive is obtained by reacting sulfur-nitrogen-containing alcohol, boric acid and aromatic diethanolamide. The synthesis method adopted by the invention has the advantages of simple and easy operation, suitability for large-scale industrial production and very strong practicability. The lubricating oil additive prepared by the method can effectively protect easily-worn machine parts, engines and other equipment, effectively increase the anti-friction performance of the lubricating oil and reduce the energy loss.)

1. A high wear-resistant antifriction lubricating oil additive is characterized in that: the raw materials of the additive comprise aromatic diethanolamide, sulfur-nitrogen-containing alcohol and boric acid; the aromatic diethanolamide is diethanolamide containing a benzene ring; the nitrogen-containing mercaptan is a monohydric alcohol containing nitrogen and sulfur. Aromatic diethanolamide, sulfur-nitrogen-containing alcohol and boric acid are subjected to esterification reaction to prepare aromatic nitrogen-containing boric acid ester containing benzoic acid groups.

2. The additive for highly antiwear and antifriction lubricating oil according to claim 1, characterized in that: the raw materials for synthesizing the aromatic diethanolamide comprise aromatic carboxylic acid, thionyl chloride and diethanolamine, wherein the aromatic carboxylic acid comprises but is not limited to benzoic acid, phenylacetic acid, naphthoic acid and naphthylacetic acid, and also comprises derivatives of corresponding main components.

3. The additive for highly antiwear and antifriction lubricating oil according to claim 1, characterized in that: the raw materials for synthesizing the sulfur-nitrogen-containing monohydric alcohol comprise diamine and derivatives thereof, propylene oxide and carbon disulfide, wherein the diamine comprises but not limited to di-n-butylamine, propylenediamine, ethylenediamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine and the like, and also comprises derivatives of corresponding main components.

4. The additive for highly antiwear and antifriction lubricating oil according to claim 1, characterized in that: the boric acid is a white crystalline solid.

5. A method for preparing a highly antiwear and antifriction lubricating oil additive according to any of claims 1-5, comprising the steps of:

preparation of a sulfur-nitrogen containing monohydric alcohol: adding diamine compounds into a reaction vessel, sequentially adding equimolar amounts of carbon disulfide and propylene oxide, and reacting for 1.5 hours to obtain target compounds;

preparation of aromatic diethanolamide: sequentially adding aromatic carboxylic acid and thionyl chloride with equal molar weight into a reaction vessel, reacting for 4 hours, distilling under reduced pressure to remove excessive raw materials to obtain an aromatic acyl chloride intermediate product, sequentially adding diethanolamine and dichloromethane with equal molar weight, and reacting for 6 hours to obtain a target product;

preparation of aromatic nitrogen-containing boric acid ester: adding equimolar amounts of sulfur-nitrogen-containing alcohol, boric acid and aromatic diethanolamide into a reaction vessel, heating and reacting for 2 hours under the protection of nitrogen, and evaporating to remove the solvent to obtain yellow oily liquid, namely the aromatic nitrogen-containing boric acid ester.

6. The method of claim 5, wherein the aromatic diethanolamide and the sulfur-nitrogen containing alcohol are reacted with boric acid to produce the antiwear lubricant additive, wherein the boron content of the antiwear lubricant additive is about 1-3%.

7. The lubricating oil additive according to any one of claims 1 to 6, which is added to a lubricating oil in an amount of 0.5 to 10% by mass, preferably 0.5 to 3% by mass, based on the lubricating oil.

Technical Field

The invention relates to the technical field of mechanical friction lubrication, in particular to a high-abrasion-resistance lubricating oil additive.

Background

The lubricating oil generally consists of base oil and additives, wherein the base oil is the main component of the lubricating oil and determines the basic properties of the lubricating oil; the additive can make up and improve the deficiency of the base oil performance and endow new performance, the organic borate is a multifunctional lubricating oil additive, has excellent wear resistance and antifriction performance, excellent oil film strength, long service life, no phosphorus, no toxicity, no pollution, wide antirust application range and the like. The introduction of aromatic groups into borate additives can make borate have better oil solubility. The introduction of elements such as sulfur, nitrogen and the like into the boric acid ester can lead the lubricating oil to have better antiwear performance. The boric acid lubricating oil used at present is added with two types of borate and boric acid ester, and the borate has the defects of being slightly soluble in water and unstable in the presence of water, so that the boric acid lubricating oil is not suitable for equipment which is contacted with a large amount of water and regularly drains water. Therefore, borate-based lubricant additives are widely used.

The application principle of the borate ester lubricating oil additive is as follows: the boron additive has boronizing effect on the boron atom and the metal surface in the contact friction with metal to produce extreme pressure metal boride film, and the surface film has high hardness, high wear resistance, high oxidation resistance, high corrosion resistance, capacity of bearing the contact between metal and especially the impact load. In order to improve the wear resistance of the borate ester lubricating oil additive, elements of nitrogen and sulfur with wear resistance are introduced into borate ester, and the elements and boron in molecules form a high wear resistance and friction reduction effect.

Although the organoborates have the characteristics of environmental friendliness, multifunction, low addition amount, high thermal stability and the like when used as lubricating oil additives, the organoborates have the disadvantage of poor hydrolytic stability as all ester compounds. When organic boric acid ester is hydrolyzed, the loss of boron active ingredients in the additive can be caused, so that the friction reduction and wear resistance of the lubricating oil are reduced. It is urgent to develop a method for preparing organoborate ester lubricating oil additives with high hydrolytic stability to overcome the above-mentioned disadvantages. From the aspect of space factors, along with the increase of a carbon chain in a borate molecule, groups such as a benzene ring and the like are introduced, so that the steric hindrance is increased, and the hydrolysis stability is correspondingly improved. The hydrolysis stability of the borate ester can also be improved by introducing an atom having an unshared electron pair such as a nitrogen atom into the molecular internal structure of the borate ester to form an intramolecular coordinate bond between the nitrogen atom and the boron atom. Therefore, the method effectively improves the hydrolytic stability of the borate ester.

Disclosure of Invention

Aiming at the research background, the invention aims to provide a preparation method of the aromatic nitrogen-containing borate ester high-wear-resistance antifriction lubricating oil additive, which can improve the friction resistance and lubricity of lubricating oil.

As one aspect of the invention, the invention provides preparation of an aromatic nitrogen-containing borate lubricating oil additive.

Wherein, the raw materials in the synthesis of the aromatic diethanolamide comprise benzoic acid, phenylacetic acid, naphthoic acid and naphthylacetic acid, and also comprise derivatives of corresponding main components.

Wherein, the content of boron element in the borate additive is about 1 to 3 percent.

As another aspect of the invention, the invention provides a preparation method for preparing a high anti-wear lubricating oil additive by using aromatic nitrogen-containing boric acid ester, which comprises the following steps:

preparation of a sulfur-nitrogen containing monohydric alcohol: adding di-n-butylamine or propylenediamine, ethylenediamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine and the like into a reaction vessel, sequentially adding carbon disulfide and propylene oxide with equimolar amount, and reacting for 1.5 hours to obtain a target compound;

preparation of aromatic diethanolamide: adding equimolar amount of benzoic acid or phenylacetic acid, naphthoic acid, naphthylacetic acid and thionyl chloride into a reaction vessel, reacting for 4 hours, and removing excessive raw materials by reduced pressure distillation to obtain an aromatic acyl chloride intermediate product. Then, sequentially adding diethanolamine and dichloromethane with equal molar amount, and reacting for 6 hours to obtain a target product;

preparation of aromatic nitrogen-containing boric acid ester: adding equimolar amounts of sulfur-nitrogen-containing monohydric alcohol, boric acid and aromatic diethanolamide into a reaction vessel, heating and reacting for 2 hours under the protection of nitrogen, and evaporating to remove the solvent to obtain yellow oily liquid, namely the aromatic nitrogen-containing boric acid ester.

The mass percentage of the lubricating oil additive prepared by the esterification reaction of the prepared nitrogen-containing aromatic compound and boric acid in the lubricating oil is 0.5-10%, and preferably 0.5-3%.

The method is simple and easy to operate, does not cause a great deal of damage to operators, has relatively high atom utilization rate, and reduces the pollution of the prior additive to the environment. The additive has low economic cost and high production safety, so that the additive can be put into production in large quantity. The lubricating oil additive prepared by the method can effectively protect easily-worn machine parts, engines and other equipment, effectively increase the anti-friction performance of the lubricating oil and reduce the energy loss.

Drawings

Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:

FIG. 1 is a flow chart of a method for preparing a lubricating oil according to the present invention

FIG. 2 is P in base oil for different amounts of additives_BValue of

FIG. 3 shows the coefficient of friction of different amounts of additives in base oils

Detailed Description

Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.

The raw materials of the additive comprise aromatic diethanolamide, sulfur-nitrogen-containing alcohol and boric acid; the aromatic diethanolamide is diethanolamide containing a benzene ring; the nitrogen-containing sulfur alcohol is a nitrogen-containing monohydric alcohol. The two are subjected to esterification reaction with boric acid to prepare a final product.

The raw materials for synthesizing the aromatic diethanolamide comprise aromatic carboxylic acid, thionyl chloride and diethanolamine, wherein the aromatic carboxylic acid comprises but is not limited to benzoic acid, phenylacetic acid, naphthoic acid and naphthylacetic acid, and also comprises derivatives of corresponding main components.

The high wear-resistant antifriction lubricating oil additive is characterized in that: the raw materials for synthesizing the nitrogen-containing mercaptan comprise diamine and derivatives thereof, propylene oxide and carbon disulfide, wherein the diamine comprises but is not limited to di-n-butylamine, propylenediamine, ethylenediamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine and the like, and also comprises derivatives of corresponding main components.

The invention discloses a preparation method of a borate additive containing unsaturated benzene fatty acid, which comprises the steps of adding additives with different contents into base oil after the synthesis of a lubricating oil additive is finished, and then carrying out corresponding performance tests. The addition content of the lubricating oil additive is 0.5-10%, preferably 0.5-3%.

As shown in figure 1, the invention discloses a preparation method for preparing a high anti-wear lubricating oil additive by introducing aromatic diethanolamide and sulfur-nitrogen-containing monohydric alcohol.

As another aspect of the invention, the invention provides a preparation method for preparing a high-antiwear antifriction lubricating oil additive, which comprises the following steps:

preparation of a sulfur-nitrogen containing monohydric alcohol: adding di-n-butylamine into a reaction vessel, sequentially adding equimolar amounts of carbon disulfide and propylene oxide, and reacting for 1.5 hours to obtain a target compound;

preparation of aromatic diethanolamide: sequentially adding aromatic carboxylic acid and thionyl chloride with equal molar weight into a reaction vessel, reacting for 4 hours, distilling under reduced pressure to remove excessive raw materials to obtain an aromatic acyl chloride intermediate product, sequentially adding diethanolamine and dichloromethane with equal molar weight, and reacting for 6 hours to obtain a target product;

preparation of aromatic nitrogen-containing boric acid ester: adding equimolar amounts of sulfur-nitrogen-containing monohydric alcohol, boric acid and aromatic diethanolamide into a reaction vessel, heating and reacting for 2 hours under the protection of nitrogen, and evaporating to remove the solvent to obtain yellow oily liquid, namely the aromatic nitrogen-containing boric acid ester.

Lubricating oil is a liquid or semisolid lubricant used on various types of automobiles and mechanical equipment to reduce friction between mechanical parts and protect machinery and machined parts, mainly plays roles of lubrication, cooling, rust prevention, cleaning, sealing, buffering and the like, and is classified into four categories of animal oil, vegetable oil, petroleum lubricating oil and synthetic lubricating oil according to the source of the lubricating oil. The lubricating oil used in the present invention is all types of commercial lubricating oils for vehicles.

The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

The present invention is described in more detail below with reference to specific examples.

Example 1

Preparing a high-wear-resistance antifriction lubricating oil additive:

sequentially adding equimolar amounts of benzoic acid and thionyl chloride into a reaction vessel, reacting for 4 hours, distilling under reduced pressure to remove excessive raw materials to obtain benzoyl chloride, sequentially adding equimolar amounts of diethanolamine and dichloromethane, and reacting for 6 hours to obtain benzoic acid diethanolamide;

adding di-n-butylamine into a reaction vessel, sequentially adding equimolar amounts of carbon disulfide and propylene oxide, and reacting for 1.5 hours to obtain monohydric alcohol containing sulfur and nitrogen;

adding equimolar amounts of sulfur-nitrogen-containing monohydric alcohol, boric acid and benzoic acid diethanolamide into a reaction vessel, heating and reacting for 2 hours under the protection of nitrogen, and evaporating to remove the solvent to obtain yellow oily liquid, namely the aromatic nitrogen-containing boric acid ester.

Example 2

The preparation method is the same as 1, and is different from the method in that the benzoic acid is replaced by the phenylacetic acid.

Example 3

The preparation method is the same as 1, and is different from the method in that benzoic acid is replaced by naphthoic acid.

Example 4

The preparation method is the same as 1, and is different from the method in that the benzoic acid is replaced by the naphthylacetic acid.

Example 5

The preparation method is the same as 1, and is different from the method in that di-n-butylamine is replaced by ethylenediamine.

Example 6

The preparation method is the same as 1, and is different from the method in that di-n-butylamine is replaced by propane diamine.

Example 7

The preparation method is the same as 1, and is different from the method in that di-n-butylamine is replaced by di-n-pentylamine.

Example 8

The preparation method is the same as 1, except that di-n-butylamine is replaced by di-n-hexylamine.

Example 9

The preparation method is the same as 1, and is different from the method in that di-n-butylamine is replaced by di-n-heptylamine.

Testing of hydrolytic stability

And (3) standing the prepared target product for 5 days, 10 days, 15 days, 20 days, 25 days and 30 days in an open manner, and observing the condition of the target product. Through experiments, the high anti-wear lubricating oil additive has no turbidity after 10 days, and even after 30 days, the high anti-wear lubricating oil additive also has no turbidity, which indicates that the lubricating oil additive has high hydrolysis stability.

Table 1 shows the results of the hydrolytic stability tests for examples 1-9, as follows:

the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.