CN113444562B

CN113444562B - Functional lubricating oil and preparation method thereof

Info

Publication number: CN113444562B
Application number: CN202110693504.6A
Authority: CN
Inventors: 王硕; 王卫攀; 王学宇; 李曼曼; 梁晓凯
Original assignee: Daoqi Technology Co ltd
Current assignee: Daoqi Technology Co ltd
Priority date: 2021-06-22
Filing date: 2021-06-22
Publication date: 2022-03-11
Anticipated expiration: 2041-06-22
Also published as: CN113444562A

Abstract

The invention belongs to the technical field of lubricating oil, and particularly relates to functional lubricating oil and a preparation method thereof. The feed comprises the following raw materials in parts by weight: 100 parts of base oil; 10-25 parts of detergent; 15-25 parts of a dispersing agent; 0.5-2.5 parts of demulsifier; 0.05-0.5 part of an antifoaming agent; the base oil of the present invention has the general formula:

in the formula, R is H or alkoxy, the functional lubricating oil effectively improves the viscosity of a target product to meet the requirements of outdoor operation in cold regions and severe cold regions, and has good wear resistance and corrosion resistance.

Description

Functional lubricating oil and preparation method thereof

Technical Field

The invention relates to functional lubricating oil and a preparation method thereof, belonging to the technical field of lubricating oil.

Background

The existing biodegradable hydraulic oil base oil mainly comprises plant base oil and synthetic ester, and the synthetic ester has natural biodegradability, excellent lubricating property and viscosity-temperature performance and abundant resources, so that the biodegradable hydraulic oil base oil is the main development direction of environment-friendly lubricating oil. The synthetic ester is developed in the middle of 30's in the 20 th century, is prepared by organic synthesis method, and has certain chemical structure and special performance. The synthetic ester has the advantages of high flash point and ignition point, small evaporation loss, high viscosity index, strong corrosion resistance, good lubricating property, excellent adaptability to non-metallic materials, 80-100% of organic biodegradation rate and extremely low toxicity, does not need to replace the material of a system when replacing the traditional mineral oil type lubricating oil, is harmless to human bodies, does not pollute the environment and is green lubricating oil meeting the requirement of environmental protection. Compared with mineral lubricating oil, the lubricating oil has wide application range, can meet increasingly strict requirements of modern various mechanical equipment on good lubricity, long oil change period, low energy consumption and the like, has higher price than the mineral lubricating oil, but has excellent performance, long service life and small mechanical wear. Synthetic esters are therefore most advantageous as base oils for mineral lubricating oils.

The 201580046447.5 patent provides a lubricating oil composition containing a lubricating oil base oil, a cyclic sulfide ester or other specific sulfur compound, which exerts its effect when used at low temperatures, and is therefore suitable for use at low temperatures but not suitable for lubricating the mechanical lubricating oil in the combustion chamber.

The patent with the application number of 201810913019.3 provides a turbine lubricating oil composition, and the oxidation stability, high-temperature stability, extreme pressure performance, demulsification performance and liquid-phase rust resistance of the lubricating oil are improved by optimizing the lubricating oil formula, but the wear resistance of the product needs to be further improved.

Disclosure of Invention

The invention provides a functional lubricating oil and a preparation method thereof, aiming at solving the problems of low wear resistance and poor corrosion resistance of the existing lubricating oil.

The technical scheme for solving the problems is as follows:

a functional lubricating oil comprises the following raw materials in parts by weight:

100 parts of base oil;

10-25 parts of detergent;

15-25 parts of a dispersing agent;

0.5-2.5 parts of demulsifier;

0.05-0.5 part of an antifoaming agent;

the base oil has the general formula:

in the formula, R is H or methoxy.

The detergent is calcium dodecyl benzene sulfonate, the dispersant is stearic acid, the demulsifier comprises polyoxyethylene polyoxypropylene octadecanol ether and polyglycerol fatty acid ester, and the antifoaming agent is polydimethylsiloxane.

As a preferred technical scheme of the invention, the preparation method of the base oil comprises the following steps:

s1: introducing halogen gas into allyl alcohol, and generating an intermediate I under the action of a catalyst Pt, wherein the structural formula of the intermediate I is as follows:

s2: taking oleic acid and an intermediate I as raw materials, taking tributyl phosphate as a solvent and cerium sulfate tetrahydrate as a catalyst in an inert atmosphere to obtain an intermediate II, wherein the structural formula of the intermediate II is as follows:

s3: taking the intermediate II and substituted aniline as raw materials, and synthesizing an intermediate III in the presence of catalyst copper powder, wherein the structural formula is as follows:

s4: the intermediate III reacts with elemental sulfur in an inert atmosphere to obtain a target product, and the structural formula of the target product is as follows:

as a preferred technical scheme of the invention, the general formula of the substituted aniline is as follows:

wherein R is H or methoxyl.

In a preferred embodiment of the present invention, the inert gas used in the inert atmosphere is argon or nitrogen.

As a preferred embodiment of the present invention, the halogen gas is chlorine gas or bromine gas.

As a preferred technical scheme of the invention, the reaction temperature in the step S2 is 120 ℃, and the reaction time is 6 h.

As a preferred embodiment of the present invention, the sulfur is added in 3 portions in step S4.

As a preferred technical scheme of the invention, the detergent is calcium dodecyl benzene sulfonate, the dispersant is stearic acid, the demulsifier comprises polyoxyethylene polyoxypropylene octadecanol ether and polyglycerol fatty acid ester, and the antifoaming agent is polydimethylsiloxane.

And on the other hand, the preparation method of the functional lubricating oil is provided, the detergent and the dispersant are added into the base oil according to the selected mass ratio, the mixture is stirred for 10min at the temperature of 50 ℃, the temperature is raised to 70 ℃, the demulsifier and the antifoaming agent are added, and the mixture is stirred for 20min to obtain the functional lubricating oil.

The invention has the following beneficial effects: the invention introduces an anti-wear substance and an anti-oxidation substance into oleic acid to form base oil with anti-wear property and anti-oxidation property, and adds corresponding additives into the base oil to prepare the functional lubricating oil, thereby effectively improving the viscosity of the lubricating oil to ensure that the lubricating oil meets the requirements of outdoor operation in cold regions and severe cold regions.

Drawings

FIG. 1 is an IR spectrum of an intermediate I of the present invention;

FIG. 2 is an IR spectrum of an intermediate II of the present invention;

FIG. 3 is an IR spectrum of an intermediate III of the present invention;

FIG. 4 is an IR spectrum of a target product of a base oil synthesized according to the present invention.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Propenol CAS number 107-18-6; pt catalyst CAS number 7440-06-4; cerium sulfate tetrahydrate CAS number 10294-42-5; oleic acid CAS number 112-80-1; tributyl phosphate CAS number 123-73-8; 3, 4-dimethoxyaniline 6315-89-5; copper powder CAS number 744-50-8; dimethylformamide CAS number 68-12-8; ethylenediamine CAS number 38734-69-9; sulfur CAS number 1239262-36-2; aniline CAS number 62-53-3; polyoxyethylene polyoxypropylene stearyl ether CAS number 9082-00-2; calcium dodecylbenzene sulfonate CAS number 26264-06-2; stearic acid CAS number 57-11-4; the CAS number of the polyoxyethylene polyoxypropylene octadecanol ether is 9005-00-9; polyglycerin fatty acid ester CAS No. 67784-82-1; polydimethylsiloxane CAS number 107-46-0. All chemicals were commercially available and chlorine was prepared using a chlorine generator with a nitrogen purity of 99%.

Example 1

This example provides a method of making a base oil:

the method comprises the following specific steps:

s1: adding 6.4ml of allyl alcohol and 0.04g of catalyst Pt into a reaction bottle, introducing chlorine under the normal pressure into the liquid level of the uniform mixture of the allyl alcohol and the catalyst Pt for carrying out bubbling reaction, wherein the introduction time of the chlorine is 20min, sealing and reacting for 2h after the introduction of the chlorine is finished, and carrying out reduced pressure distillation after the reaction is finished to obtain an intermediate I (8.2 ml).

The reaction formula is as follows:

the resulting intermediate I was analyzed:

FIG. 1 is the IR spectrum of intermediate I.

S2: adding 6.2ml of the intermediate I, 2.14g of catalyst cerium sulfate tetrahydrate and 20.8ml of oleic acid into a reaction bottle, adding 50ml of tributyl phosphate as a solvent, introducing nitrogen, stirring, heating to 100 ℃, slowly heating to 120 ℃ after water is discharged, reacting for 6 hours, reducing the temperature to room temperature, separating generated water by using a moisture separator, and distilling to obtain an oily substance, namely an intermediate II (25.98 g).

The reaction formula is as follows:

analysis of the resulting intermediate II:

FIG. 2 is the IR spectrum of intermediate II. IR (KBr, vmax): at 1740cm^-1Has a C ═ O stretching vibration absorption peak of 1245cm^-1And 1167cm^-1Two points are C-O stretching vibration absorption peaks, which indicates that the intermediate II contains ester groups.

S3: 17.32g of intermediate II was weighed into a reaction flask, 13.47g of 3, 4-dimethoxyaniline was added, 0.14g of copper powder was added as a catalyst, nitrogen was introduced, stirring was carried out at room temperature for 45min, 50ml of dimethylformamide was added as a solvent, reaction was carried out at 100 ℃ for 2.5h, natural cooling was carried out to room temperature, and distillation was carried out to obtain intermediate III (27.58 g).

The reaction formula is as follows:

analysis of the resulting intermediate III:

FIG. 3 is the IR spectrum of intermediate III. IR (KBr, vmax): compared with the IR spectrum of the intermediate II in FIG. 2, the IR spectrum is 3360cm^-1、3389cm^-1Has an N-H absorption peak at 2978cm^-1A methoxy C-H absorption peak appears.

S4: measuring 12.54g of the intermediate III, putting the intermediate III into a reaction bottle, adding 100ml of ethylenediamine, introducing nitrogen, stirring and heating to 105 ℃ under the nitrogen atmosphere, adding 0.71g of elemental sulfur into the reaction bottle for 3 times, heating to 120 ℃ for reaction for 6 hours, naturally cooling to room temperature, and filtering to obtain a target product (14.56 g).

The reaction formula is as follows:

analyzing the obtained target product:

FIG. 4 shows the IR spectrum of the target product, compared with the IR spectrum of intermediate III in FIG. 3, the ester group is 1740cm^-1C ═ O stretching vibration absorption peak and 1245cm^-1And 1167cm^-1The C-O stretching vibration absorption peaks at the two positions are not changed, which indicates that the ester group does not participate in the vulcanization reaction, and the length of the reaction zone is 797cm after the reaction^-1A new absorption peak is generated, namely C-S-C characteristic stretching vibration of the cyclic thioether, namely sulfur and C ═ C double bond are subjected to addition reaction to generate the cyclic sulfide.

Example 2

This example provides a method of making a base oil:

the method comprises the following specific steps:

s1: adding 6.4ml of allyl alcohol and 0.04g of catalyst Pt into a reaction bottle, introducing chlorine under normal pressure into the liquid level of a uniform mixture of the allyl alcohol and the catalyst Pt for carrying out bubbling reaction, wherein the introduction time of the chlorine is 20min, after the introduction of the chlorine is finished, carrying out sealed reaction for 2h, and after the reaction is finished, carrying out reduced pressure distillation to obtain an intermediate I (8.2 ml);

s2: adding 6.2ml of the intermediate I, 2.14g of catalyst cerium sulfate tetrahydrate and 20.8ml of oleic acid into a reaction bottle, adding 50ml of tributyl phosphate as a solvent, introducing nitrogen, stirring, heating to 100 ℃, slowly heating to 120 ℃ after yielding water, reacting for 6 hours, reducing the temperature to room temperature, separating generated water by using a moisture separator, and distilling to obtain an oily substance, namely an intermediate II (25.98 g);

s3: weighing 17.32g of the intermediate II in a reaction bottle, adding 8.2ml of aniline, adding 0.14g of copper powder as a catalyst, introducing nitrogen, stirring at room temperature for 45min, adding 50ml of dimethylformamide as a solvent, reacting at 100 ℃ for 2.5h, naturally cooling to room temperature, and distilling to obtain an intermediate III (22.30 g);

s4: weighing 11.15g of the intermediate III, putting the intermediate III into a reaction bottle, adding 100ml of ethylenediamine, introducing nitrogen, stirring and heating to 105 ℃ under the nitrogen atmosphere, adding 0.71g of elemental sulfur into the reaction bottle for 3 times, heating to 120 ℃ for reaction for 6 hours, naturally cooling to room temperature, and filtering to obtain a target product (11.85 g).

Example 3

The embodiment provides a functional lubricating oil and a preparation method thereof:

the functional lubricating oil is prepared from the following components in parts by weight:

100 parts of base oil, 10 parts of detergent, 15 parts of dispersant, 0.5 part of demulsifier and 0.05 part of anti-foaming agent, wherein the detergent is calcium dodecyl benzene sulfonate, the dispersant is stearic acid, the demulsifier comprises polyoxyethylene polyoxypropylene octadecanol ether and polyglycerol fatty acid ester, and the anti-foaming agent is polydimethylsiloxane.

The preparation method of the functional lubricating oil comprises the following steps: adding 10 parts of detergent and 15 parts of dispersant into 100 parts of base oil, raising the temperature to 50 ℃, stirring for 10min at the temperature of 50 ℃ to completely dissolve the raw materials, raising the temperature to 70 ℃, adding 0.5 part of demulsifier and 0.05 part of antifoaming agent, and stirring for 20min to obtain the required functional lubricating oil.

Example 4

100 parts of base oil, 25 parts of detergent, 25 parts of dispersant, 2.5 parts of demulsifier and 0.5 part of anti-foaming agent, wherein the detergent is calcium dodecyl benzene sulfonate, the dispersant is stearic acid, the demulsifier comprises polyoxyethylene polyoxypropylene octadecanol ether and polyglycerol fatty acid ester, and the anti-foaming agent is polydimethylsiloxane.

The preparation method of the functional lubricating oil comprises the following steps: adding 25 parts of detergent and 25 parts of dispersant into 100 parts of base oil, raising the temperature to 50 ℃, stirring for 10min at the temperature of 50 ℃ to completely dissolve the raw materials, raising the temperature to 70 ℃, adding 2.5 parts of demulsifier and 0.5 part of antifoaming agent, and stirring for 20min to obtain the required functional lubricating oil.

Examples of the experiments

Using the base oils prepared in example 1, performance measurements were made on the functional lubricating oils prepared in examples 3 and 4.

The resulting data are shown in table 1:

TABLE 1

Item	Quality index	Example 3	Example 4	Comparative sample	Test method
						Appearance of the product	Is transparent	Is transparent	Is transparent	Is transparent	Visual inspection of
Chroma/number	Report on	—	—	<0.5	GB/T6540
						Kinematic viscosity (40 ℃ C.)/mm²/s	41.4～＜50.6	46.69	46.56	46.19	GB/T265
Viscosity index	Not less than 95	135	128	118	GB/T1995
						Pour point/. degree.C	Not higher than-15	-43	-38	-31	GB/T3535
Mechanical impurities (mass fraction)/%)	Is free of	Is free of	Is free of	Is free of	GB/T511
						Abrasive grain diameter/mm	Report on	0.35	0.39	0.45	SH/T0189

Wherein, the comparison sample is a certain domestic product.

As can be seen from the comparison of Table 1, the viscosities of the functional lubricating oils prepared in example 3 and example 4 are all improved as compared with the viscosities of the comparative samples, wherein the performance measured in example 3 is superior to the performance measured in example 4, and if the viscosity is too low in oil fluidity determination, the lubricating surface is easily worn, the internal leakage and the external leakage of the system are increased, the volumetric efficiency of the pump is reduced, the oil temperature is increased, and a higher viscosity index is required because the viscosity of the hydraulic oil has a large influence on the operation of the hydraulic system. The viscosity index of hydraulic oil of indoor fixed hydraulic systems is usually more than 90, and the viscosity index is required to be more than 130 for outdoor operation in cold regions and severe cold regions. The higher the viscosity index is, the higher the viscosity index can be used in a wider temperature range, the viscosity index of the embodiment 3 in the invention reaches 135, while the viscosity index of the domestic current like products is 118, and the target product in the invention meets the requirements of open-air operation in cold regions and severe cold regions.

The pour point refers to the lowest temperature at which the oil product is cooled to continue flowing under specified conditions, the pour point of the example 3 is-43 ℃ in the invention, the pour point of the comparative sample is-31 ℃, the pour point of the example 1 is 12 ℃ lower than that of the comparative sample, the lower the pour point, the better the low-temperature flowing property of the oil product is, the pour point plus 10 ℃ can be used as the lowest service temperature of the hydraulic oil, namely the lowest service temperature of the example 1 in the invention is-33 ℃, and the operation requirements of the target product in a cold region and a severe cold region are further verified.

Comparing the wear scar diameter of example 3 with that of the comparative sample, the wear scar diameter of the invention is 0.35mm, the wear scar diameter of the comparative sample is 0.45mm, which is reduced by 22.22% compared with the comparative sample, which shows that the wear resistance of example 3 is improved compared with the comparative sample, and the improvement of the wear resistance of example 3 may come from the fact that the target product has a longer molecular chain, and the longer molecular chain can cause the two friction surfaces to be far away from each other, thereby improving the lubrication efficiency.

In order to compare the corrosion performance of the example 3 and the comparative sample of the invention, the polished copper sheets are respectively immersed in the example 3 and the comparative sample, the measurement is carried out after 3h at the temperature of 100 ℃, the grading is carried out according to the color of the copper sheets, the result of the measured copper corrosion grade of the example 3 reaches 1a, and the copper corrosion grade of the comparative sample is 1b, which shows that the invention has good corrosion resistance.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.

Claims

1. The functional lubricating oil is characterized by comprising the following raw materials in parts by weight:

100 parts of base oil;

10-25 parts of detergent;

15-25 parts of a dispersing agent;

0.5-2.5 parts of demulsifier;

0.05-0.5 part of an antifoaming agent;

the dispersant is stearic acid;

the base oil has the general formula:

in the formula, R is H or methoxy.

2. The functional lubricating oil of claim 1, wherein:

the preparation method of the base oil comprises the following steps:

s1: introducing halogen gas into allyl alcohol to generate an intermediate I under the action of a catalyst Pt, wherein the structural formula of the intermediate I is shown in the specification

S2: taking oleic acid and an intermediate I as raw materials, taking tributyl phosphate as a solvent and cerium sulfate tetrahydrate as a catalyst in an inert atmosphere to obtain an intermediate II, wherein the structural formula is shown in the specification

3. the functional lubricating oil of claim 2, wherein the substituted aniline has the formula:

wherein R is H or methoxyl.

4. The functional lubricating oil according to claim 2, characterized in that: the inert gas used in the inert atmosphere is argon or nitrogen.

5. The functional lubricating oil according to claim 2, characterized in that: in step S2, the reaction temperature is 120 ℃ and the reaction time is 6 h.

6. The functional lubricating oil according to claim 2, characterized in that: in step S4, sulfur was added in 3 portions.

7. The functional lubricating oil of claim 1, wherein: the detergent is calcium dodecyl benzene sulfonate, the demulsifier comprises polyoxyethylene polyoxypropylene octadecanol ether and polyglycerol fatty acid ester, and the antifoaming agent is polydimethylsiloxane.

8. The method for producing a functional lubricating oil according to any one of claims 1 to 7, characterized in that: adding a detergent and a dispersant into base oil according to a selected mass ratio, stirring for 10min at the temperature of 50 ℃, heating to 70 ℃, adding a demulsifier and an antifoaming agent, and stirring for 20min to obtain the functional lubricating oil.