CN110776976A - Preparation method of lubricating oil extreme pressure antiwear agent - Google Patents

Abstract

The invention belongs to the technical field of lubricating compositions characterized by reaction product additives with unknown or incompletely determined structures, and particularly relates to a preparation method of a lubricating oil extreme pressure antiwear agent. The preparation method of the lubricating oil extreme pressure antiwear agent comprises the following steps: A. dissolving molybdenum trioxide in a sodium hydroxide solution, reacting with triethanolamine monooleate under the protection of inert gas, and adding anhydrous sodium thiosulfate to continue reacting; B. adding dimethyl sulfoxide into the mixture obtained by the reaction in the step A, extracting and separating an upper organic phase and a lower aqueous phase, and washing the upper organic phase with water; C. adding trimethylolpropane pelargonate into the washed upper organic phase, distilling under reduced pressure, and filtering. The extreme pressure antiwear agent prepared by the method has good stability and good oil solubility.

Description

Preparation method of lubricating oil extreme pressure antiwear agent

Technical Field

The invention belongs to the technical field of lubricating compositions characterized by reaction product additives with unknown or incompletely determined structures, and particularly relates to a preparation method of a lubricating oil extreme pressure antiwear agent.

Background

The lubricating oil is a liquid or semisolid lubricating agent used on various automobiles and mechanical equipment, and mainly plays roles of lubricating, cooling, rust prevention, cleaning, sealing and buffering so as to reduce mechanical friction and protect equipment and workpieces (the application of the lubricating oil in equipment maintenance, thank you, China and foreign wine industry, 6 th in 2017, 1-2 lines in abstract on page 40, and 26 th in 2017).

The lubricating oil consists of base oil and additive. 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 deficiencies of certain properties of the oil product, endows the oil product with certain new properties, and is an important component of the lubricating oil (the biodegradation test and evaluation research progress of green lubricating oil, Zhangyi and the like, lubricating oil, No. 26, No. 3 of 2011, No. 1, No. 4 of the left column of page 62, No. 06, 30 of published 2011).

The extreme pressure antiwear agent is an additive used for preventing scratching, seizure, abrasion and sintering fusion welding, and is suitable for being used in a lubricating environment under severe working conditions such as high speed, high temperature and high load (the current development situation and action mechanism research of the extreme pressure antiwear agent, Yang hong Wei and the like, the contemporary chemical industry, vol.41, No. 9, page 961, left column, No. 1, lines 1 to 3, and published Japanese 09/30). It is known that lubricating oil with excellent performance can fully lubricate machines, reduce friction and abrasion, thereby improving energy consumption and prolonging the service life of the machines. Therefore, the development and development of the extreme pressure antiwear agent can be used for blending lubricating oil products, reducing friction, reducing wear and preventing sintering (the current situation and development trend of lubricating oil additives, voyage and the like, the 11 th annual meeting discourse corpus of fuel and lubricating oil of China society of automotive engineering, page 69, lines 2, 7-9, published 2011, 10 and 31 days), so that the extreme pressure antiwear agent has important significance in reducing energy consumption, improving mechanical efficiency and prolonging service life.

Among them, organic molybdenum is a subject of much research in recent years at home and abroad as an extreme pressure antiwear agent in lubricating oil. The organic molybdenum not only has better friction reducing performance than molybdenum disulfide, graphite and other solid particle suspensions, but also has the advantages of extreme pressure wear resistance, fatigue resistance, oxidation resistance and the like. Organic molybdenum is generally classified into three groups: containing type S, P organomolybdenum, namely molybdenum dialkyldithiophosphates; organic molybdenum without P (containing S) type, namely molybdenum dialkyl dithiocarbamate; s, P-free non-reactive organomolybdenum ("tribology of organomolybdenum as a grease extreme pressure antiwear agent", ledebye, oil merchandize, vol 28, No. 5, p 2010, left column, line 1, paragraph 1, to middle column, line 2, publication date, 12, month 31, 2010). However, the sulfur-containing and phosphorus-containing organic molybdenum extreme pressure antiwear agent can generate a large amount of harmful substances in the production and use processes, and the environment is polluted.

However, the sulfur-and phosphorus-free inactive organomolybdenum is insufficient in extreme pressure anti-wear performance ("tribology of organomolybdenum as a grease extreme pressure anti-wear agent", ledebye, oil mercantile, vol 28, No. 5, p 48 middle column, No. 3, lines 1-2, publication date 2010, 12, month 31).

In order to solve the problems, the novel non-sulfur-phosphorus organic molybdenum additive N-octadecylimine diethanolylmethyl molybdic acid diester is synthesized by taking diethoxyethyl octadecylamine and ammonium molybdate as raw materials by Gong Min and the like of Shanghai university of transportation, and experiments prove that the novel non-sulfur-phosphorus organic molybdenum additive N-octadecylimine diethanolmethyl molybdic acid diester has better wear resistance (the preparation of the non-sulfur-phosphorus organic molybdenum additive and the tribological performance research thereof, Gong Min and the like, at the No. 4 of volume 42 in 2017, lines 1 to 6 of abstract on page 29, and the published day 2017, month 06. The Zhangjian et al of air force service institute synthesizes sulfur-phosphorus-free organic molybdenum oil-soluble antiwear additive by using soybean oil, triethanolamine and molybdenum trioxide as raw materials, and has good antiwear and antioxidant effects when used in cooperation with amine antioxidant (the synergistic performance of sulfur-phosphorus-free molybdate as antioxidant additive and amine antioxidant, Zhangjian et al, Petroleum institute (petroleum processing), Vol.35, 2, pp.261, abstract, lines 1-4, published 2019, 06, 10).

However, the above non-sulfur and phosphorus synthetic organic molybdenum additive has problems of poor stability and poor oil solubility.

Disclosure of Invention

In view of the above, an object of the present invention is to provide an extreme pressure antiwear agent for lubricating oil, which has good stability and excellent oil solubility.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the preparation method of the lubricating oil extreme pressure antiwear agent comprises the following steps:

A. dissolving molybdenum trioxide in a sodium hydroxide solution, reacting with triethanolamine monooleate under the protection of inert gas, and adding anhydrous sodium thiosulfate to continue reacting;

B. adding dimethyl sulfoxide into the mixture obtained by the reaction in the step A, extracting and separating an upper organic phase and a lower aqueous phase, and washing the upper organic phase with water;

C. adding trimethylolpropane pelargonate into the washed upper organic phase, distilling under reduced pressure, and filtering.

The inventor unexpectedly finds that the method comprises the following steps:

A. dissolving molybdenum trioxide in a sodium hydroxide solution, reacting with triethanolamine monooleate under the protection of inert gas, and adding anhydrous sodium thiosulfate to continue reacting;

B. adding dimethyl sulfoxide into the mixture obtained by the reaction in the step A, extracting and separating an upper organic phase and a lower aqueous phase, and washing the upper organic phase with water;

C. adding trimethylolpropane pelargonate into the washed upper organic phase, carrying out reduced pressure distillation, and filtering;

the lubricating oil extreme pressure antiwear agent prepared by the method has good stability and excellent oil solubility.

Further, in the step A, the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 19.0-20.0%.

Further, in the step A, the mass ratio of the molybdenum trioxide to the sodium hydroxide solution is 1:3.

Further, in the step A, the dissolving temperature is 50-60 ℃.

Further, in step a, the inert gas includes nitrogen, helium, neon, argon, krypton, xenon, and radon.

Further, in the step A, the mass ratio of the molybdenum trioxide to the triethanolamine monooleate is 1:3-1: 3.5.

Further, in the step A, the reaction temperature is 80-90 ℃, and the reaction time is 6-10 h.

Further, in the step A, the temperature of the continuous reaction is 80-90 ℃, and the reaction time is 4-6 h.

Further, in the step A, the mass ratio of the anhydrous sodium thiosulfate to the molybdenum trioxide is 1:0.5-1: 0.75.

Further, in the step B, the ratio of the dosage of the dimethyl sulfoxide to the total mass of the sodium hydroxide solution, the molybdenum trioxide and the triethanolamine monooleate in the step A is 0.5:1-1: 1.

Further, the washing with water means washing with distilled water.

Furthermore, in the step C, the dosage of the trimethylolpropane pelargonate is 1.0 to 1.5 times of the mass of the molybdenum trioxide in the step A.

Further, in the step C, the reduced pressure distillation refers to that the treatment is carried out for 2 to 3 hours at the temperature of 80 to 100 ℃ under the pressure of 1.01KPa to 0.70kPa, and then the treatment is carried out for 2 to 4 hours at the temperature of 150 to 170 ℃ under the pressure of 1.01KPa to 0.70 kPa.

Further, the preparation method of the lubricating oil extreme pressure antiwear agent comprises the following steps:

A. dissolving molybdenum trioxide in a sodium hydroxide solution with the mass fraction of 19.0% -20.0% at the temperature of 50-60 ℃, then reacting with triethanolamine monooleate under the protection of inert gas, and then adding anhydrous sodium thiosulfate to continue reacting;

wherein the mass ratio of the molybdenum trioxide to the sodium hydroxide solution is 1:3, and the mass ratio of the molybdenum trioxide to the triethanolamine monooleate is 1:3-1: 3.5; the mass ratio of the anhydrous sodium thiosulfate to the molybdenum trioxide is 1:0.5-1: 0.75;

B. adding dimethyl sulfoxide into the mixture obtained by the reaction in the step A, extracting and separating an upper organic phase and a lower aqueous phase, and washing the upper organic phase with water; wherein the dosage of the dimethyl sulfoxide is 0.5:1-1:1 of the mass ratio of the dimethyl sulfoxide to the total mass of the sodium hydroxide solution, the molybdenum trioxide and the triethanolamine monooleate in the step A;

C. adding trimethylolpropane pelargonate into the washed upper organic phase, treating at 80-100 deg.C under 1.01KPa-0.70kPa for 2-3h, treating at 150-170 deg.C under 1.01KPa-0.70kPa for 2-4h, and filtering;

wherein the dosage of the trimethylolpropane pelargonate is 1.0 to 1.5 times of the mass of the molybdenum trioxide in the step A.

The invention has the beneficial effects that:

the lubricating oil extreme pressure antiwear agent prepared by the method has good stability, and does not precipitate after standing for 30 days.

The lubricating oil extreme pressure antiwear agent prepared by the method has excellent oil solubility, and does not precipitate after standing for 30 days after being dissolved in mineral oil.

The lubricating oil extreme pressure antiwear agent prepared by the method has good antiwear effect, when 0.1 percent of the organic molybdenum antifriction agent prepared by the method is added into 150SN base oil, the friction coefficient is reduced from 0.116 to 0.047-0.057, and the wear-pattern diameter (392N) is reduced from 0.42mm to 0.26-0.30 mm.

The lubricating oil extreme pressure antiwear agent prepared by the method does not contain sulfur and phosphorus components, and has the environmental protection advantages of low toxicity and low corrosion.

Detailed Description

The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.

The following friction coefficients were measured according to SH/T0762-2005 lubricating oil friction coefficient measurement method (four-ball method).

The following four-ball machine test-the wear-resistance diameter (392N) is detected according to the condition B method in the four-ball method for measuring the wear resistance of NB/SH/T0189-2017 lubricating oil;

test on four ball machine-sintering load P _DThe test was carried out according to GB/T3142-1982 method for measuring the load-carrying capacity of lubricants (four-ball method);

the following stability tests were carried out by visual inspection.

Example 1

The lubricating oil extreme pressure antiwear agent is prepared by the following steps:

A. putting 120g of 19.0 mass percent sodium hydroxide solution and 40g of molybdenum trioxide into a 500ml reaction kettle, stirring at 50 ℃ until the molybdenum trioxide is completely dissolved, putting 120g of triethanolamine monooleate into the system, introducing nitrogen for protection, controlling the reaction temperature to be 80 ℃, stirring for reaction for 10 hours, and then adding 20g of anhydrous sodium thiosulfate to continue the reaction for 4 hours under the condition;

B. after the reaction in the step A is finished, adding 140g of dimethyl sulfoxide into the reaction system, fully stirring, transferring to a separating funnel, separating a lower aqueous phase, and washing an upper organic phase with distilled water for 3 times at normal temperature;

C. adding 40g of trimethylolpropane pelargonate into the washed organic phase, uniformly stirring, transferring into a distillation flask, controlling the vacuum pressure to be 1.01kPa and the temperature to be 80 ℃, carrying out reduced pressure distillation and dehydration for 2h, then carrying out reduced pressure distillation for 4h under the vacuum pressure of 1.01kPa and the temperature to be 150 ℃, and filtering to obtain the trimethylolpropane pelargonate.

Example 2

The lubricating oil extreme pressure antiwear agent is prepared by the following steps:

A. putting 120g of 20.0 mass percent sodium hydroxide solution and 40g of molybdenum trioxide into a 500ml reaction kettle, stirring at 50 ℃ until the molybdenum trioxide is completely dissolved, putting 140g of triethanolamine monooleate into the system, introducing nitrogen for protection, controlling the reaction temperature to be 85 ℃, stirring for reaction for 8 hours, and then adding 30g of anhydrous sodium thiosulfate to continue the reaction for 4 hours under the condition;

B. after the reaction is finished, 200g of dimethyl sulfoxide is added into the reaction system, the mixture is transferred to a separating funnel after being fully stirred, and after a lower-layer water phase is separated, an upper-layer organic phase is washed for 3 times by distilled water at normal temperature;

C. adding 50g of trimethylolpropane pelargonate into the organic phase after water washing, uniformly stirring, transferring into a distillation flask, controlling the vacuum pressure to be 0.70kPa and distilling and dehydrating for 4h at 90 ℃, then distilling for 2h at 0.70kPa and 170 ℃, and filtering.

And (5) obtaining the product.

Example 3

The lubricating oil extreme pressure antiwear agent is prepared by the following steps:

A. putting 120g of 19.5 mass percent sodium hydroxide solution and 40g of molybdenum trioxide into a 500ml reaction kettle, stirring at 50 ℃ until the molybdenum trioxide is completely dissolved, putting 130g of triethanolamine monooleate into the system, introducing nitrogen for protection, controlling the reaction temperature to be 90 ℃, stirring for reaction for 8 hours, and then adding 20g of anhydrous sodium thiosulfate to continue the reaction for 6 hours under the condition;

B. after the reaction is finished, adding 280g of dimethyl sulfoxide into the reaction system, fully stirring, transferring to a separating funnel, separating a lower aqueous phase, and washing an upper organic phase with distilled water for 3 times at normal temperature;

C. adding 60g of trimethylolpropane pelargonate into the washed organic phase, uniformly stirring, transferring into a distillation flask, controlling the vacuum pressure to be 0.90kPa and the temperature to be 90 ℃, carrying out reduced pressure distillation and dehydration for 4h, then carrying out reduced pressure distillation for 4h at the temperature of 0.90kPa and 170 ℃, and filtering to obtain the trimethylolpropane pelargonate.

Performance detection

The extreme pressure anti-wear agents prepared in examples 1 to 3 were added to 150SN base oil in a ratio of 0.1 mass%, and then the friction coefficient, the wear scar diameter, the sintering load (Pd), the stability (observed after standing for 30 days) and other indexes were measured, and at the same time, the friction coefficient, the wear scar diameter, the sintering load (Pd) and other indexes were measured for 150SN base oil to which no extreme pressure anti-wear agent was added (i.e., blank control), and the results are shown in table 1;

table 1 results of performance testing

Detecting items	Blank control group	Example 1	Example 2	Example 3
					Coefficient of friction	0.116	0.049	0.047	0.057
Abrasive grain diameter (392N)/mm	0.42	0.26	0.25	0.30
					Sintering load Pd/N	1224.5	3089	3089	2451
Standing for 30 days and observing	--	No precipitation	No precipitation	No precipitation

As can be seen from Table 1, when 0.1% of the organomolybdenum friction reducers obtained in examples 1 to 3 were added to 150SN base oil, there was no precipitation after standing for 30 days. Therefore, the extreme pressure antiwear agent prepared by the method has good stability and excellent oil solubility.

As can be seen from Table 1, when 0.1% of the organomolybdenum friction reducers obtained in examples 1-3 were added to 150SN base oil, the friction coefficient was reduced from 0.116 to 0.047-0.057, and the wear-leveling diameter (392N) was reduced from 0.42mm to 0.26-0.30 mm. Therefore, the extreme pressure antiwear agent prepared by the method has good antiwear effect.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. The preparation method of the lubricating oil extreme pressure antiwear agent is characterized by comprising the following steps:

A. dissolving molybdenum trioxide in a sodium hydroxide solution, reacting with triethanolamine monooleate under the protection of inert gas, and adding anhydrous sodium thiosulfate to continue reacting;

B. adding dimethyl sulfoxide into the mixture obtained by the reaction in the step A, extracting and separating an upper organic phase and a lower aqueous phase, and washing the upper organic phase with water;

C. adding trimethylolpropane pelargonate into the washed upper organic phase, distilling under reduced pressure, and filtering.

2. The method according to claim 1, wherein in the step A, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 19.0% to 20.0%.

3. The production method according to claim 1 or 2, wherein in step a, the mass ratio of molybdenum trioxide to sodium hydroxide solution is 1:3.

4. The production method according to any one of claims 1 to 3, wherein the temperature of the dissolution in the step A is 50 to 60 ℃.

5. The production method according to any one of claims 1 to 4, wherein in the step A, the mass ratio of molybdenum trioxide to triethanolamine monooleate is 1:3 to 1: 3.5.

6. The production method according to any one of claims 1 to 5, wherein in the step A, the anhydrous sodium thiosulfate is used in an amount of 1:0.5 to 1:0.75 in terms of a mass ratio to the molybdenum trioxide.

7. The production method according to any one of claims 1 to 6, wherein in the step B, the amount of dimethyl sulfoxide is 0.5:1 to 1:1 relative to the total mass of the sodium hydroxide solution, molybdenum trioxide and triethanolamine monooleate in the step A.

8. The production method according to any one of claims 1 to 7, wherein in step C, trimethylolpropane pelargonate is used in an amount of 1.0 to 1.5 times the mass of molybdenum trioxide in step A.

9. The method according to any one of claims 1 to 8, wherein in step C, the reduced pressure distillation is carried out at 1.01KPa to 0.70kPa at 80 to 100 ℃ for 2 to 3 hours, and then at 1.01KPa to 0.70kPa at 150 ℃ to 170 ℃ for 2 to 4 hours.

10. The method for preparing according to any one of claims 1 to 9, comprising the steps of:

A. dissolving molybdenum trioxide in a sodium hydroxide solution with the mass fraction of 19.0% -20.0% at the temperature of 50-60 ℃, then reacting with triethanolamine monooleate under the protection of inert gas, and then adding anhydrous sodium thiosulfate to continue reacting;

wherein the mass ratio of the molybdenum trioxide to the sodium hydroxide solution is 1:3, and the mass ratio of the molybdenum trioxide to the triethanolamine monooleate is 1:3-1: 3.5; the mass ratio of the anhydrous sodium thiosulfate to the molybdenum trioxide is 1:0.5-1: 0.75;

B. adding dimethyl sulfoxide into the mixture obtained by the reaction in the step A, extracting and separating an upper organic phase and a lower aqueous phase, and washing the upper organic phase with water; wherein the dosage of the dimethyl sulfoxide is 0.5:1-1:1 of the mass ratio of the dimethyl sulfoxide to the total mass of the sodium hydroxide solution, the molybdenum trioxide and the triethanolamine monooleate in the step A;

C. adding trimethylolpropane pelargonate into the washed upper organic phase, treating at 80-100 deg.C under 1.01KPa-0.70kPa for 2-3h, treating at 150-170 deg.C under 1.01KPa-0.70kPa for 2-4h, and filtering;

wherein the dosage of the trimethylolpropane pelargonate is 1.0 to 1.5 times of the mass of the molybdenum trioxide in the step A.