阅读说明：本技术 一种润滑油金属减活剂混合物及其制备方法 (Lubricating oil metal deactivator mixture and preparation method thereof ) 是由 张程 蔺国兴 于 2020-12-14 设计创作，主要内容包括：本发明提供了一种润滑油金属减活剂混合物及其制备方法,包括：在水溶性溶剂中加入二巯基噻二唑、硫醇和双氧水,反应生成一种噻二唑衍生物及其它二硫化物,经清洗后可获得透明纯净的金属减活剂混合物。本发明的金属减活剂产物硫含量高,添加到润滑油中具有优良的金属减活效果及抗氧化效果。(The invention provides a lubricating oil metal deactivator mixture and a preparation method thereof, wherein the lubricating oil metal deactivator mixture comprises the following steps: adding dimercaptothiadiazole, mercaptan and hydrogen peroxide into a water-soluble solvent, reacting to generate a thiadiazole derivative and other disulfides, and cleaning to obtain a transparent and pure metal deactivator mixture. The metal deactivator product of the invention has high sulfur content, and has excellent metal deactivation effect and oxidation resistance when being added into lubricating oil.)

1. A lubricating oil metal deactivator mixture, characterized in that the raw material mass ratio is: thiadiazole: n-mercaptan: n-hydrogen peroxide is 0.5-1.0: 2.0-2.2: 2.4-2.7.

2. The lubricating oil metal deactivator mixture according to claim 1, characterised in that,

the thiadiazole is 2, 5-dimercapto-1, 3, 4-thiadiazole, is white or light yellow crystalline powder in appearance, and has effective content of more than or equal to 98 wt%.

3. The lubricating oil metal deactivator mixture according to claim 1, characterised in that,

the mercaptan is any one of n-octyl mercaptan or tert-nonyl mercaptan, and the content is more than or equal to 98 percent.

4. The lubricating oil metal deactivator mixture according to claim 1, characterised in that,

the hydrogen peroxide is industrial grade hydrogen peroxide, and the concentration is more than or equal to 27.5 percent.

5. The lubricating oil metal deactivator mixture according to claim 1, characterised in that,

the metal deactivator is synthesized by using a mixed solution of alcohol and water, wherein the volume fraction of the alcohol is not less than 50%; the mass of the mixed solution of the alcohol and the water is 4-6 times of that of the thiadiazole.

6. The lubricating oil metal deactivator mixture according to claim 1, characterised in that,

the hydrogen peroxide feeding form adopts a dropping form or a small quantity multiple adding form.

7. A preparation method of a lubricating oil metal deactivator mixture is characterized by comprising the following steps:

adding mercaptan, alcohol and thiadiazole into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant-pressure dropping funnel according to the mass ratio, and adding hydrogen peroxide into the constant-pressure dropping funnel; starting stirring and starting heating, stopping heating when reflux occurs and starting dropping hydrogen peroxide, keeping the system always having reflux in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped;

and cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

Technical Field

The invention relates to the technical field of lubricating oil additives, in particular to a lubricating oil metal deactivator mixture and a preparation method thereof.

Background

With the development of equipment manufacturing and automobile industry, the types of lubricating oil additives for vehicles and industry are more and more abundant, but the types of commonly used metal deactivators are mainly benzotriazole derivatives and thiadiazole derivatives. Among them, thiadiazole derivatives can form stable complexes with metals, and have more excellent metal deactivation than benzotriazole derivatives at the same dosage. In recent years, thiadiazole derivative metal deactivators have become the popular development direction of various large additive companies.

In the field of existing lubricating oil additives, metal deactivators mainly serve to protect metals from corrosion. The thiadiazole derivative can efficiently capture active sulfur in lubricating oil products, and the thiadiazole derivative with unit mass can capture a huge amount of active sulfur, thereby effectively reducing the corrosion of the active sulfur to mechanical equipment and greatly prolonging the service life of the equipment.

In addition, some thiadiazole derivatives can be matched with phenol or amine antioxidants, so that the oxidation resistance of the oil product can be greatly improved, and the service life of the lubricating oil product can be prolonged.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art or the related art.

At present, the existing metal deactivator in the field of lubricating oil additives is few in variety, and the purpose of metal deactivation can be achieved by adding a small amount of metal deactivator during the blending of lubricating oil. The traditional T551 can reach the level of copper corrosion 2c by blending 0.25% of T551+ 4.75% of T321+150N, the traditional T561 can reach the level of copper corrosion 1b by blending 0.15% + 4.85% of T321+150N, and the metal deactivator mixture provided by the invention can reach the level of copper corrosion 1a by blending 0.05% + 4.95% of T321+ 150N. The addition amount is greatly reduced. The sulfur content of T561 is 26% -27%, while the sulfur content of the metal deactivator mentioned in the invention can reach 28% -34%, and the sulfur content is greatly increased. The invention provides a metal deactivator mixture and a preparation method thereof.

In order to achieve the above object, a first aspect of the present invention provides a metal deactivator mixture, wherein the ratio of the amounts of the raw material substances is: n (thiadiazole): n (thiol): n (hydrogen peroxide) is 0.3-1.0: 1.8-2.5: 2.2-2.8;

preferably, the metal deactivator mixture is synthesized by the following reactant materials in the ratio of: n (thiadiazole): n (thiol): n (hydrogen peroxide) is 0.5-1.0: 1.8-2.3: 2.3-2.8;

still more preferred is n (thiadiazole): n (thiol): n (hydrogen peroxide) is 0.5-1.0: 2.0-2.2: 2.4-2.7.

In the technical scheme, the component ratio of the thiadiazole derivative synthesis reactant is further optimized, and the stability of the metal deactivator mixture is further improved.

Preferably, the thiadiazole is 2, 5-dimercapto-1, 3, 4-thiadiazole, is white or light yellow crystalline powder in appearance, and has the effective content of more than or equal to 98%.

Preferably, the mercaptan is any one of n-octyl mercaptan and tert-nonyl mercaptan, and the content of the mercaptan is more than or equal to 98 percent.

Preferably, the hydrogen peroxide is industrial grade hydrogen peroxide, and the concentration is more than or equal to 27.5%.

Preferably, the metal deactivator is synthesized by using a mixed solution of alcohol and water, wherein the volume fraction of the alcohol is not less than 50%; the mass of the mixed solution of the alcohol and the water is 4-6 times of that of the thiadiazole.

Preferably, the hydrogen peroxide feeding form can adopt a dropping form or a small quantity multiple adding form.

In the technical scheme, the raw materials for producing the metal deactivator mixture are common, the synthesis process is simple, the metal deactivator mixture provided by the invention can be dissolved in various mineral oils, the sensitivity to various mineral oils is good, meanwhile, the metal deactivator performance is greatly improved in various mineral oils compared with the traditional T561 metal deactivator, and the copper sheet corrosion resistance is stronger. The metal deactivator mixture provided by the invention is compounded with other antioxidants, so that a better antioxidant effect can be obtained.

The invention also provides a preparation method of the corresponding lubricating oil metal deactivator mixture, which comprises the following steps: mercaptan, alcohol and thiadiazole are added into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant pressure dropping funnel according to the mass ratio, and hydrogen peroxide is added into the constant pressure dropping funnel. Starting stirring and starting heating, stopping heating when reflux occurs, starting dropping hydrogen peroxide, keeping the system always refluxing in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped.

And cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

In the technical scheme, the preparation method of the metal deactivator mixture is simple, the process is simple, the operability is strong, the preparation cost is low, and the wide-range popularization and use are facilitated.

The rotating speed of stirring can be 80 r/min; the alcohol used in the reaction can be recycled after rectification, so that the cost is reduced. The product is light yellow, if 1.5 percent of the additive amount is uniformly stirred with 500N base oil at normal temperature, the mixture is transparent, no turbidity exists, and the moisture content does not exceed the trace amount, the inspection is qualified.

Through the technical scheme, (1) the raw materials for preparing the metal deactivator mixture are easy to obtain and low in price. (2) The metal deactivator mixture provided by the invention can be dissolved in various mineral oils, and has good sensitivity to various mineral oils. (3) The sulfur content of the metal deactivator mixture provided by the invention can reach 28% -32%, and the sulfur content exceeds that of the traditional T561 metal deactivator. (4) Compared with the traditional T561 metal deactivator, the metal deactivator mixture provided by the invention has better copper sheet corrosion prevention performance. The antioxidant is compounded with the antioxidant, and also has excellent synergistic antioxidation. (5) The thiadiazole derivative provided by the invention is light in color, free of pungent smell, less in influence on the appearance and smell of blended oil products, and wide in variety of the oil products which can be blended.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Detailed Description

The invention discloses a lubricating oil metal deactivator and a preparation method thereof, and the technical personnel can use the contents to reference the contents and properly improve the process parameters to realize the purpose. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

Wherein the thiadiazole is 2, 5-dimercapto-1, 3, 4-thiadiazole, is white or light yellow crystalline powder in appearance, and has effective content of more than or equal to 98%;

the mercaptan is any one of n-octyl mercaptan or tert-nonyl mercaptan, and the content is more than or equal to 98 percent;

the hydrogen peroxide is industrial grade hydrogen peroxide, and the concentration is more than or equal to 27.5 percent;

the metal deactivator is synthesized by using a mixed solution of alcohol and water, wherein the volume fraction of the alcohol is not less than 50%; the mass of the mixed solution of the alcohol and the water is 4-6 times of that of the thiadiazole;

the raw materials are all available in the market, are common and have low price.

The invention is further illustrated by the following examples:

example 1

A metal deactivator mixture having the ratio of the amounts of the reactant materials: n (dimercaptothiadiazole): n (n-octyl mercaptan): n (hydrogen peroxide) ═ 0.3:1.8: 2.2.

The preparation method of the metal deactivator mixture comprises the following steps:

weighing the reactants with corresponding mass according to the amount ratio of the reactant substances and the effective content of the used reactants.

Mercaptan, alcohol and thiadiazole are added into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant pressure dropping funnel according to the mass ratio, and hydrogen peroxide is added into the constant pressure dropping funnel. Starting stirring and starting heating, stopping heating when reflux occurs, starting dropping hydrogen peroxide, keeping the system always refluxing in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped.

And cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

And (4) after the metal deactivator mixture is qualified, preparing the metal deactivator mixture provided by the invention.

The metal deactivator mixture prepared above was mixed well with 0.05% of the inventive product + 4.95% of T321+150N and tested, the test results are shown in Table 1.

Example 2

A metal deactivator mixture having the ratio of the amounts of the reactant materials: n (dimercaptothiadiazole): n (tert-nonyl mercaptan): n (hydrogen peroxide) ═ 1.0:1.8: 2.2.

The preparation method of the metal deactivator mixture comprises the following steps:

weighing the reactants with corresponding mass according to the amount ratio of the reactant substances and the effective content of the used reactants.

Mercaptan, alcohol and thiadiazole are added into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant pressure dropping funnel according to the mass ratio, and hydrogen peroxide is added into the constant pressure dropping funnel. Starting stirring and starting heating, stopping heating when reflux occurs, starting dropping hydrogen peroxide, keeping the system always refluxing in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped.

And cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

And (4) after the metal deactivator mixture is qualified, preparing the metal deactivator mixture provided by the invention.

The metal deactivator mixture prepared above was mixed well with 0.05% of the inventive product + 4.95% of T321+150N and tested, the test results are shown in Table 1.

Example 3

A metal deactivator mixture having the ratio of the amounts of the reactant materials: n (dimercaptothiadiazole): n (tert-nonyl mercaptan): n (hydrogen peroxide) ═ 1.0:2.2: 2.8.

The preparation method of the metal deactivator mixture comprises the following steps:

weighing the reactants with corresponding mass according to the amount ratio of the reactant substances and the effective content of the used reactants.

Mercaptan, alcohol and thiadiazole are added into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant pressure dropping funnel according to the mass ratio, and hydrogen peroxide is added into the constant pressure dropping funnel. Starting stirring and starting heating, stopping heating when reflux occurs, starting dropping hydrogen peroxide, keeping the system always refluxing in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped.

And cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

And (4) after the metal deactivator mixture is qualified, preparing the metal deactivator mixture provided by the invention.

The metal deactivator mixture prepared above was mixed uniformly at 0.05% of the inventive product + 4.95% of T321+150N and tested, and the test results are shown in Table 1

Example 4

A metal deactivator mixture having the ratio of the amounts of the reactant materials: n (dimercaptothiadiazole): n (n-octyl mercaptan): n (hydrogen peroxide) ═ 0.3:2.5: 2.2.

The preparation method of the metal deactivator mixture comprises the following steps:

weighing the reactants with corresponding mass according to the amount ratio of the reactant substances and the effective content of the used reactants.

Mercaptan, alcohol and thiadiazole are added into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant pressure dropping funnel according to the mass ratio, and hydrogen peroxide is added into the constant pressure dropping funnel. Starting stirring and starting heating, stopping heating when reflux occurs, starting dropping hydrogen peroxide, keeping the system always refluxing in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped.

And cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

And (4) after the metal deactivator mixture is qualified, preparing the metal deactivator mixture provided by the invention.

The metal deactivator mixture prepared above was mixed uniformly at 0.05% of the inventive product + 4.95% of T321+150N and tested, and the test results are shown in Table 1

Example 5

A metal deactivator mixture having the ratio of the amounts of the reactant materials: n (dimercaptothiadiazole): n (n-octyl mercaptan): n (hydrogen peroxide) ═ 1.0:2.5: 2.8.

The preparation method of the metal deactivator mixture comprises the following steps:

weighing the reactants with corresponding mass according to the amount ratio of the reactant substances and the effective content of the used reactants.

Mercaptan, alcohol and thiadiazole are added into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant pressure dropping funnel according to the mass ratio, and hydrogen peroxide is added into the constant pressure dropping funnel. Starting stirring and starting heating, stopping heating when reflux occurs, starting dropping hydrogen peroxide, keeping the system always refluxing in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped.

And cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

And (4) after the metal deactivator mixture is qualified, preparing the metal deactivator mixture provided by the invention.

The metal deactivator mixture prepared above was mixed uniformly at 0.05% of the inventive product + 4.95% of T321+150N and tested, and the test results are shown in Table 1

Example 6

A metal deactivator mixture having the ratio of the amounts of the reactant materials: n (dimercaptothiadiazole): n (tert-nonyl mercaptan): n (hydrogen peroxide) ═ 1.0:2.5: 2.8.

The preparation method of the metal deactivator mixture comprises the following steps:

weighing the reactants with corresponding mass according to the amount ratio of the reactant substances and the effective content of the used reactants.

Mercaptan, alcohol and thiadiazole are added into a three-neck flask provided with a stirring and refluxing condenser pipe and a constant pressure dropping funnel according to the mass ratio, and hydrogen peroxide is added into the constant pressure dropping funnel. Starting stirring and starting heating, stopping heating when reflux occurs, starting dropping hydrogen peroxide, keeping the system always refluxing in the dropping process, and keeping the reflux temperature to continue stirring and reacting for 3 hours after all hydrogen peroxide is dropped.

And cooling to room temperature after the reaction is finished, standing and separating the reaction product, washing the lower organic layer for three times by using alcohol and water, distilling under reduced pressure to remove the alcohol and the water after the washing is finished, cooling to room temperature, and filtering to obtain the product.

And (4) after the metal deactivator mixture is qualified, preparing the metal deactivator mixture provided by the invention.

The metal deactivator mixture prepared above was mixed uniformly at 0.05% of the present product + 4.95% of T321+150N and tested, and the test results are shown in Table 1

After the oil products prepared by the thiadiazole derivatives provided in the embodiments 1 to 6 of the present invention are tested, the test results are shown in the following table 1,

t561 metal deactivator sold by a certain additive company in China is added into 150N base oil at different adding amounts for testing as comparison. The test results are shown in Table 2.

Test method GB/T5096 is characterized in that a polished copper sheet is immersed in a sample with a certain volume, heated to a specified temperature according to the product type of the sample, and kept for a certain time. And (4) when the heating period is finished, taking out the copper sheet, washing the copper sheet, comparing the copper sheet with the copper sheet corrosion standard color plate, evaluating the color change condition of the copper sheet, and determining the corrosion grade.

Test method SH/T0303 specifically involves the combustion decomposition of a sample at a high temperature of 1000 ℃ in an oxygen stream, in which sulfur is combusted to form SO₂And SO₃And titrating the total sulfur content in the additive by adopting a coulometry method after absorption.

Application example 1

The metal deactivator mixture provided by the invention is added into the gear oil for the automobile GL-585W-90 in a proportion of 0.05%, and the mixture is uniformly mixed.

Application example 2

The metal deactivator mixture provided by the invention is added into the gear oil for GL-585W-110 vehicle according to the proportion of 0.05%, and the mixture is uniformly mixed.

Application example 3

The metal deactivator mixture provided by the invention is added into HM 68# antiwear hydraulic oil in a proportion of 0.01% and is uniformly mixed.

Application example 4

The metal deactivator mixture provided by the invention is added into L-QC320 heat conduction oil according to the proportion of 0.01% and is uniformly mixed.

The samples obtained in application examples 1 to 4 were subjected to the test, and the test results are shown in table 2 below:

item	Test method	Application example 1	Application example 2	Application example 3	Application example 4
						Corrosion of copper sheet, grade	GB/T 5096	1a	1a	1a	1a

From the test results obtained in application examples 1, 2, 3 and 4, the metal deactivator mixture provided by the invention is suitable for blending various oil products, can greatly reduce the corrosion of active sulfur to lubricated parts, and is very small in dosage.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.