阅读说明：本技术 一种防锈剂及其制备方法 (Antirust agent and preparation method thereof ) 是由 程亮 程丽华 王慧 于 2020-11-27 设计创作，主要内容包括：本发明公开了一种防锈剂,为以下结构的化合物:式中,m＝0～50,n＝0～50,且m、n不同时为零,R-1为C-1～C-(30)的烷烃,R-2为氢或甲基,R-3为C-2～C-(30)的烷烃,r为1～5,R为中的一种；m、n、r为整数,且满足电荷平衡。该防锈剂具有良好的防锈性可溶解于润滑油的基础油中。与传统防锈剂相比,本发明防锈剂的防锈性能更优。(The invention discloses an antirust agent which is a compound with the following structure: wherein m is 0 to 50, n is 0 to 50, and m and n are not zero at the same time, R is 1 Is C 1 ～C 30 Of alkane, R 2 Is hydrogen or methyl, R 3 Is C 2 ～C 30 R is 1 to 5, R is)

1. An antirust agent, characterized by being a compound of the following structure:

wherein m is 0 to 50, n is 0 to 50, and m and n are not zero at the same time, R is₁Is C₁～C₃₀Of alkane, R₂Is hydrogen or methyl, R₃Is C₂～C₃₀R is 1-5; m, n and r are integers and satisfy charge balance; r isOne kind of (1).

2. The rust inhibitor according to claim 1, wherein R is₁Is C₁～C₅Of (a) an alkane.

3. The rust inhibitor according to claim 1, wherein R is₃Is C₂～C₅Of (a) an alkane.

4. The rust inhibitor as claimed in claim 1, wherein R isOne of (1) and (b).

5. The preparation method of the antirust agent is characterized by comprising the following steps:

A. weighing the following raw materials: 40-70 parts of polyether, 40-70 parts of aryl compound containing isocyanate and 0.5-3 parts of diluent, wherein the diluent is prepared from a solvent A: the solvent B is formed by mixing (10-20) and (1-5) by mass, wherein the solvent A is any one of dichloromethane, trichloromethane and tetrachloromethane, and the solvent B is any one of tetrahydrofuran, furan, pyridine, pyrazine and pyrrole;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 50-60 ℃ at the rate of 0.1-2 mL/min, and continuously stirring for 20-40min after dropwise adding;

C. and (3) heating the temperature of the reaction container to 60-90 ℃, and aging for 1-2 hours to obtain the antirust agent.

6. The method for preparing the antirust agent according to claim 5, wherein the polyether is selected from one of a mono-terminated polyethylene glycol, a mono-terminated ethylene oxide homopolymer, a mono-terminated propylene oxide homopolymer, a mono-terminated tetrahydrofuran homopolymer, a mono-terminated long-chain alkane homopolymer or a copolymer of any combination of the mono-terminated polyethylene glycol, the mono-terminated ethylene oxide homopolymer, the mono-terminated propylene oxide homopolymer, the mono-terminated tetrahydrofuran homopolymer and the mono-terminated long-chain alkane homopolymer.

7. The method for producing a rust inhibitor according to claim 5, wherein the aryl group in the isocyanate-containing aryl compound is selected from the group consisting ofAny one of them.

Technical Field

The invention belongs to the technical field of lubrication, relates to an antirust agent for lubricating oil and a preparation method thereof, and particularly relates to an antirust agent and a preparation method thereof.

Background

The lubricating oil is a liquid or semisolid lubricating medium used on various types of automobiles and mechanical equipment to reduce friction and protect machines and workpieces, and mainly plays roles in lubrication, cooling, rust prevention, cleaning, sealing, buffering and the like. The lubricating oil is generally composed 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, and the additives can make up and improve the deficiencies in the performance aspect of the base oil, endow certain new performances and also are important components of the lubricating oil. In general terms, it is difficult for the base oil component in the lubricating oil to have the function of an additive, and it is generally necessary to add a rust inhibitor to improve the rust inhibitive performance of the product, mainly because it does not have the functional requirements, such as rust inhibitive performance, etc., required by the product.

Currently, the types of rust inhibitors commonly used in lubricating oils include: petroleum sulfonates, carboxylic acids, esters, and the like. These rust inhibitors still have the defects of complex process, serious pollution, low yield, limited performance, single function and the like. Aiming at the defects, the active development of a compound antirust agent which is environment-friendly, low in pollution and excellent in performance is the trend and direction of the development of future antirust agents.

Polyethers (also called polyether polyols) belong to group V base oils according to the API rule, and have the advantages of high viscosity index, low pour point, good detergency and the like, and are attracting much attention. When polyether is used as base oil, the polyether is easily oxidized due to an ether chain structure, so that metal corrosion is easily caused, and a special antirust agent is usually added to make up for the deficiency of the antirust function of the base oil.

Disclosure of Invention

The invention aims to solve the technical problem of providing a rust inhibitor with good rust-proof performance aiming at the defects of the prior art.

The invention further aims to solve the technical problem of providing a preparation method of the antirust agent, which has the advantages of simple preparation method, high generation efficiency and environment-friendly process.

The technical scheme adopted by the invention for solving the technical problems is as follows: an antirust agent is a compound with the following structure:

wherein m is 0 to 50, n is 0 to 50, and m and n are not zero at the same time, R is₁Is C₁～C₃₀Of alkane, R₂Is hydrogen or methyl, R₃Is C₂～C₃₀R is 1-5; m, n and r areInteger, and satisfy charge balance; r isOne kind of (1).

In the rust inhibitor, R₁Preferably C₁～C₅Of (a) an alkane. R₁More preferably one of methyl, ethyl, propyl and butyl.

In the rust inhibitor, R₃Preferably C₂～C₅Of (a) an alkane. R₃More preferably one of ethyl, propyl, isopropyl and butyl.

In the rust inhibitor, R is preferablyOne of (1) and (b).

A preparation method of the antirust agent comprises the following steps:

A. weighing the following raw materials: 40-70 parts of polyether, 40-70 parts of aryl compound containing isocyanate and 0.5-3 parts of diluent, wherein the diluent is prepared from a solvent A: the solvent B is formed by mixing (10-20) and (1-5) by mass, wherein the solvent A is any one of dichloromethane, trichloromethane and tetrachloromethane, and the solvent B is any one of tetrahydrofuran, furan, pyridine, pyrazine and pyrrole;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 50-60 ℃ at the rate of 0.1-2 mL/min, and continuously stirring for 20-40min after dropwise adding;

C. and (3) heating the temperature of the reaction container to 60-90 ℃, and aging for 1-2 hours to obtain the antirust agent.

In the preparation method of the rust inhibitor, the polyether is preferably selected from one of mono-terminated polyethylene glycol, mono-terminated ethylene oxide homopolymer, mono-terminated propylene oxide homopolymer, mono-terminated tetrahydrofuran homopolymer and mono-terminated long-chain alkane homopolymer or a copolymer of any combination of the mono-terminated polyethylene glycol, the mono-terminated ethylene oxide homopolymer, the mono-terminated propylene oxide homopolymer, the mono-terminated tetrahydrofuran homopolymer and the mono-terminated long-chain alkane homopolymer.

Further, the rust inhibitorIn the process for preparing (1), it is preferable that in the isocyanate-containing aryl compound, the aryl group is selected fromAny one of them.

The antirust agent of the invention is obtained by modifying polyether to have ether bond, ester group, amino group, heteroatom and other groups, so that the antirust performance of the antirust agent is superior to that of the existing antirust additive. The antirust oil can better solve the antirust property of the lubricating oil by adding the antirust oil into the lubricating oil base oil. The antirust agent can be dissolved in the base oil of the lubricating oil, has better performance compared with the traditional antirust agent, and can be used as the antirust agent of the lubricating oil.

In addition, the antirust agent has good functions of abrasion resistance, abrasion reduction and cleaning, and improves the integral abrasion resistance, abrasion reduction and cleaning performance of the lubricating oil.

Detailed Description

In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described in detail.

An antirust agent is a compound with the following structure:

wherein m is 0 to 50, n is 0 to 50, and m and n are not zero at the same time, R is₁Is C₁～C₃₀Of alkane, R₁Preferably C₁～C₅Of alkane, R₁More preferably one of methyl, ethyl, propyl and butyl. R₂Is hydrogen or methyl, R₃Is C₂～C₃₀Of alkane, R₃Preferably C₂～C₅Of (a) an alkane. R₃More preferably one of ethyl, propyl, isopropyl and butyl. r is 1-5; m, n and r are integers and satisfy charge balance; r isOne kind of (1). R is preferablyOne of (1) and (b).

A preparation method of the antirust agent comprises the following steps:

A. weighing the following raw materials: 40-70 parts of polyether, 40-70 parts of aryl compound containing isocyanate and 0.5-3 parts of diluent, wherein the diluent is prepared from a solvent A: the solvent B is formed by mixing (10-20) and (1-5) by mass, wherein the solvent A is any one of dichloromethane, trichloromethane and tetrachloromethane, and the solvent B is any one of tetrahydrofuran, furan, pyridine, pyrazine and pyrrole; preferably, the polyether is selected from one of mono-terminated polyethylene glycol, mono-terminated ethylene oxide homopolymer, mono-terminated propylene oxide homopolymer, mono-terminated tetrahydrofuran homopolymer, mono-terminated long-chain alkane homopolymer or copolymer of any combination of the above. Preferably, in the isocyanate-containing aryl compound, the aryl group is selected fromAny one of them.

B. Dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 50-60 ℃ at the rate of 0.1-2 mL/min, and continuously stirring for 20-40min after dropwise adding;

C. and (3) heating the temperature of the reaction container to 60-90 ℃, and aging for 1-2 hours to obtain the antirust agent.

The following is a detailed description of specific examples.

Example 1, a rust inhibitor, is a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether40 parts of aryl compound containing isocyanate40 parts of diluent, 0.5 part of diluent, wherein the diluent is prepared from dichloromethane: tetrahydrofuran in a mass ratio of 10: 1, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 50 ℃ at the rate of 0.1 mL/min, and continuously stirring for 20 min after the dropwise addition is finished;

C. the reaction vessel was warmed to 60 ℃ and aged for 1 hour to give the product of example 1.

Example 2, a rust inhibitor, a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether40 parts of aryl compound containing isocyanate50 parts of diluent, 1 part of dichloromethane: furan in a mass ratio of 10: 3, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 60 ℃ at the speed of 2 mL/min, and continuously stirring for 40min after dropwise adding;

C. the reaction vessel was warmed to 90 ℃ and aged for 2 hours to give the product of example 2.

Example 3, a rust inhibitor, a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether60 parts of aryl compound containing isocyanate60 parts of diluent, 2 parts of trichloromethane: and (2) furan in a mass ratio of 15: 5, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 55 ℃ at the rate of 1.5 mL/min, and continuously stirring for 30 minutes after the dropwise addition is finished;

C. the reaction vessel was warmed to 70 ℃ and aged for 1.5 hours to give the product of example 3.

Example 4, a rust inhibitor, is a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether70 parts of aryl compound containing isocyanate70 parts of diluent, and 3 parts of diluent, wherein the diluent is prepared from tetrachloromethane: pyridine is mixed according to a mass ratio of 20: 5, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 60 ℃ at the speed of 2 mL/min, and continuously stirring for 20 min after dropwise adding;

C. the reaction vessel was warmed to 80 ℃ and aged for 1 hour to give the product of example 4.

Example 5, a rust inhibitor, is a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether55 parts of aryl compound containing isocyanate60 parts of diluent, 2 parts of tetrachloromethane: pyrazine is prepared from 20: 3, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 50 ℃ at the rate of 1.5 mL/min, and continuously stirring for 30 minutes after dropwise adding;

C. the reaction vessel was warmed to 86 ℃ and aged for 1.5 hours to give the product of example 5.

Example 6, a rust inhibitor, is a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether55 parts of aryl compound containing isocyanate70 parts of diluent, 1 part of which is prepared from dichloromethane: pyrrole is mixed according to a mass ratio of 20: 1, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 55 ℃ at the speed of 2 mL/min, and continuously stirring for 40min after dropwise adding;

C. the reaction vessel was warmed to 75 ℃ and aged for 2 hours to give the product of example 6.

Example 7, a rust inhibitor, is a compound of the following structure:

the preparation steps of the antirust agent in the embodiment are the same as those in any one of embodiments 1 to 6, and the raw materials are selected as follows: polyether45 parts of aryl compound containing isocyanate50 parts of diluent (dichloromethane: pyrrole in a mass ratio of 20: 2)2 parts.

Example 8, a rust inhibitor, a compound of the following structure:

the preparation steps of the antirust agent in the embodiment are the same as those in any one of embodiments 1 to 6, and the raw materials are selected as follows: polyether55 parts of aryl compound containing isocyanate60 parts of diluent (trichloromethane: furan in a mass ratio of 20: 6) and 3 parts of diluent.

Example 9, a rust inhibitor, a compound of the following structure:

the preparation steps of the antirust agent in the above embodiment are the same as those in any one of embodiments 1 to 6, and the raw materials are selected as follows: polyether65 parts of aryl compound containing isocyanate70 parts of diluent (tetrachloromethane: furan in a mass ratio of 15: 6)0.5 part of the reaction product.

Example 10, a rust inhibitor, a compound of the following structure:

the preparation steps of the antirust agent in the embodiment are the same as those in any one of embodiments 1 to 6, and the raw materials are selected as follows: polyether65 parts of aryl compound containing isocyanate70 parts of diluent (dichloromethane: furan in a mass ratio of 15: 7)1.5 parts.

Example 11, a rust inhibitor, is a compound of the following structure:

procedure for preparation of Rust preventive in this exampleAs in any of examples 1-6, the starting materials were selected: polyether70 parts of aryl compound containing isocyanate70 parts of diluent (dichloromethane: pyrrole in a mass ratio of 15: 9)2.5 parts.

Example 12, a rust inhibitor, a compound of the following structure:

the preparation steps of the antirust agent in the embodiment are the same as those in any one of embodiments 1 to 6, and the raw materials are selected as follows: polyether40 parts of aryl compound containing isocyanate40 parts of a diluent, and 2 parts of a diluent (trichloromethane: tetrahydrofuran in a mass ratio of 15: 9).

Example 13, a rust inhibitor, a compound of the following structure:

the preparation steps of the antirust agent in the embodiment are the same as those in any one of embodiments 1 to 6, and the raw materials are selected as follows: polyether70 parts of aryl compound containing isocyanate70 parts of diluent (dichloromethane: pyrrole in a mass ratio of 15: 9)2.5 parts.

Example 14, a rust inhibitor, is a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether40 parts of aryl compound containing isocyanate50 parts of diluent, 1 part of dichloromethane: pyridine is mixed according to a mass ratio of 14: 5, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 54 ℃ at the speed of 2 mL/min, and continuously stirring for 40min after dropwise adding;

C. the reaction vessel was warmed to 60 ℃ and aged for 2 hours to give the product of example.

Example 15, a rust inhibitor, a compound of the following structure:

the rust inhibitor is prepared by the following steps:

A. weighing the following raw materials: polyether70 parts of aryl compound containing isocyanate59 parts of diluent, 2.6 parts of tetrachloromethane: pyrrole is mixed according to a mass ratio of 16: 1, preparing a composition;

B. dissolving an aryl compound containing isocyanate in a diluent to obtain a solution 1, dropwise adding the solution 1 into a reaction container containing polyether at the temperature of 58 ℃ at the rate of 1.5 mL/min, and continuously stirring for 40min after the dropwise addition is finished;

C. the reaction vessel was warmed to 90 ℃ and aged for 1 hour to give the product of example.

Comparative experiment:

the corrosion resistance of the compound and the existing antirust agent is examined by selecting the existing commonly used antirust agent barium petroleum sulfonate (T701), dodecenylsuccinic acid and dodecenylsuccinic acid half ester as comparison antirust agents and carrying out copper corrosion experiments and salt spray box experiments.

1. Copper corrosion test: experiments were carried out using GB/T5096 at 100 ℃. The lower the number of results, the better the corrosion prevention effect.

2. Salt spray box experiment: the experimental conditions are that 150SN is used as base oil, the additive amount is 1 percent), and the larger the result number is, the better the anticorrosion effect is represented.

3. Antioxidant experiment: GM6137-M test K.

4. High temperature stability test: and heating to detect the decomposition temperature.

The result of the detection

As can be seen from the above table, the rust inhibitive performance of the compounds of the present invention is more excellent than that of the prior art. And the oxidation resistance and the high-temperature stability are far better than those of the existing antirust agent.