CN112680261B - Polyether type multifunctional antioxidant and preparation method thereof - Google Patents

Abstract

The invention discloses a polyether type multifunctional antioxidant and a preparation method thereof, wherein the polyether type multifunctional antioxidant is a compound with the following structure:

Description

Polyether type multifunctional antioxidant and preparation method thereof

Technical Field

The invention belongs to the field of lubricating oil additives, relates to an antioxidant for lubricating oil, and particularly relates to a polyether type multifunctional antioxidant and a preparation method thereof.

Background

The lubricating oil is a liquid or semisolid lubricating medium used for reducing friction and protecting machinery and workpieces on various types of automobiles and mechanical equipment, and mainly plays roles of lubrication, cooling, rust prevention, cleaning, sealing, buffering and the like. Lubricating oil additives can impart new properties to lubricating oils and are an important component of lubricating oils. The antioxidant is an important additive in the lubricating oil additive, and is required to be added in almost all oil products such as engine oil, gear oil, turbine oil, compressor oil and the like, and the addition amount is different from 0.1-5%.

Currently, the types of antioxidants commonly used in lubricating oils include: phenols, amines and ashless carbamates. The antioxidant has the function of preventing oil from oxidative deterioration or preventing metal from corrosion. The mechanism is generally to prevent or scavenge the formation of free radicals and hydroperoxides in the oil. In addition, a mechanism of the antioxidant is to prevent oxidation corrosion of the metal by adsorbing on the surface of the metal to form a protective film on the metal.

Polyethers (also called polyether polyols) belong to group V base oils according to the API rules, and have the advantages of high viscosity index, low pour point, good detergency and the like, thus being of great interest. When the polyether is used as the base oil, a large number of ether bonds exist in a molecular chain, so that the polyether has a certain antifriction effect, but the antioxidant performance of the polyether is poor, and an antioxidant is often required to be added for use.

Disclosure of Invention

The invention aims to provide a polyether type multifunctional antioxidant with good oxygen resistance.

The technical scheme adopted by the invention for solving the technical problems is as follows: a polyether type multifunctional antioxidant is a compound with the following structure:

wherein m is 0 to 50, n is 0 to 50, m and n are not zero at the same time, and R is₁Is C₁～C₁₅Alkyl groups of (a);

R₂is composed of

Wherein R is₄Is hydrogen or C₁～C₄Alkyl radical, R₃Is composed of

Wherein R is₄Is hydrogen or C₁～C₄And r is any integer of 1-20.

Further, the polyether type multifunctional antioxidant is preferably R₁Is C₁～C₁₀The alkyl group of (1).

Further, the polyether type multifunctional antioxidant is preferably R₂Is benzotriazole and derivatives thereof, wherein R4 is hydrogen or C₁～C₂The alkyl group of (1).

Further, the preferable R3 of the polyether type multifunctional antioxidant is benzotriazole and derivatives thereof, wherein R is₄Is hydrogen or C₁～C₂R is any integer of 1 to 10.

A preparation method of polyether type multifunctional antioxidant comprises the following steps:

A. weighing the following raw materials: 40-50 parts of chlorinated alkylene oxide, a proper amount of catalyst and C₁～C₁₅Alkyl alcohol compounds, benzotriazole or benzotriazole derivatives;

B. adding a catalyst into a dry reaction kettle protected by inert gas, wherein the adding amount of the catalyst is 20-100 ppm of the prepared product according to the weight, and then adding C₁～C₁₅Alkyl alcohol chemical combinationAnd chlorinated alkylene oxides, C₁～C₁₅The molar ratio of the alkyl alcohol compound to the chlorinated alkylene oxide is 0.1: 1-1: heating the reaction kettle to 30-100 ℃, keeping the pressure less than 1.5MPa, when the temperature begins to rise and the pressure begins to fall, indicating that the reaction begins, continuously adding another chlorinated alkylene oxide into the reaction kettle at the speed of 0.5-3 mL/min, continuing aging for 1-3 hours, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;

C. and (3) placing the reaction bottle with the polyether into a reaction container at 50-80 ℃, slowly adding benzotriazole or benzotriazole derivatives, heating, keeping the reaction temperature at 100-120 ℃, reacting for 1-12 hours, and obtaining the polyether multifunctional antioxidant.

Further, in the preparation method of the polyether type multifunctional antioxidant, the catalyst is a bimetallic catalyst or an alkaline catalyst.

The polyether type multifunctional antioxidant has ether bond, triazole and other groups, can prevent the generation of free radicals and hydroperoxide, and can be adsorbed on the surface of metal to prevent the oxidation corrosion of the metal. The additive has good solubility in base oil, and compared with the traditional antioxidant, the antioxidant has better performance and can be used as a multifunctional antioxidant for 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.

The following is a detailed description of specific examples.

Example 1, a polyether multifunctional antioxidant, is a compound of the following structure:

the polyether type multifunctional antioxidant is prepared by the following steps:

A. weighing the following raw materials: 40 parts of chlorocyclohexane and chlorocyclopropane (the molar ratio of the chlorocyclohexane to the chlorocyclopropane is 1:5), 20ppm of bimetallic catalyst, 0.1 part of methanol and 40 parts of benzotriazole;

B. adding a catalyst into a dry reaction kettle protected by inert gas, adding initiators of methanol and chlorocyclohexane, heating the reaction kettle to 30 ℃, keeping the pressure less than 1.5MPa, when the temperature begins to rise and the pressure begins to fall, indicating that the reaction begins, continuously adding chlorocyclopropane into the reaction kettle at the speed of 0.5 mL/min, continuing aging for 1 hour, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;

C. and (3) placing the reaction bottle with the polyether into a reaction container at 50 ℃, slowly adding benzotriazole, heating, keeping the reaction temperature at 100 ℃, reacting for 1 hour, and finishing the reaction to obtain the product of the example 1.

Example 2, a polyether multifunctional antioxidant, which is a compound of the following structure:

the polyether type multifunctional antioxidant is prepared by the following steps:

A. weighing the following raw materials: 50 parts of chlorinated epoxy dodecyl alkane, 100ppm of bimetallic catalyst, 10 parts of pentadecanol and 50 parts of methylbenzotriazole;

B. adding a catalyst into a dry reaction kettle protected by inert gas, and then adding an initiator pentadecanol and chloroepoxydodecane, wherein the molar ratio of the initiator to one kind of chloroepoxyalkane is 0.1: 1-1: 5, heating the reaction kettle to 30-100 ℃, keeping the pressure less than 1.5MPa, continuing to age for 3 hours after the temperature begins to rise and the pressure begins to fall, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;

C. and (3) placing the reaction bottle with the polyether into a reaction container at 80 ℃, slowly adding the benzotriazole derivative, heating, keeping the reaction temperature at 120 ℃, reacting for 12 hours, and obtaining the product of the example 2 after the reaction is finished.

Example 3, a polyether multifunctional antioxidant, is a compound of the following structure:

the polyether type multifunctional antioxidant is prepared by the following steps:

A. weighing the following raw materials: 50 parts of chlorocyclohexane and chlorocyclododecane (the molar ratio of the chlorocyclohexane to the chlorocyclododecane is 1:5), 30ppm of a potassium hydroxide catalyst, 1 part of n-hexanol and 50 parts of butyl benzotriazole;

B. adding a potassium hydroxide catalyst into a dry reaction kettle protected by inert gas, adding n-hexanol and chlorocyclohexane, heating the reaction kettle to 50 ℃, keeping the pressure to be less than 1.5MPa, when the temperature begins to rise and the pressure begins to fall, indicating that the reaction begins, continuously adding chlorocyclododecane into the reaction kettle at the speed of 2.5 mL/min, continuing aging for 23 hours, stopping heating, reducing the temperature of the reaction kettle to room temperature, and filtering to obtain polyether;

C. and (3) placing the reaction bottle with the polyether into a reaction container at 70 ℃, slowly adding butyl benzotriazole, heating, keeping the reaction temperature at 110 ℃, and reacting for 10 hours to obtain the product of the example 3.

Example 4, a polyether multifunctional antioxidant, is a compound of the following structure:

A. weighing the following raw materials: 50 parts of chlorocyclohexane and chlorocycloheptane (the molar ratio of the chlorocyclohexane to the chlorocycloheptane is 5:2), 50ppm of sodium hydroxide catalyst, 7 parts of isopropanol and 50 parts of ethyl benzotriazole;

B. adding a sodium hydroxide catalyst into a dry reaction kettle protected by inert gas, adding isopropanol and chlorocyclohexane, heating the reaction kettle to 60 ℃, keeping the pressure to be less than 1.5MPa, continuously adding chlorocycloheptane into the reaction kettle at the speed of 1 mL/min when the temperature begins to rise and the pressure begins to fall, indicating that the reaction begins, continuing aging for 1.5 hours, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;

C. and (3) putting the reaction bottle with the polyether into a reaction container at 60 ℃, slowly adding the ethyl benzotriazole derivative, heating, keeping the reaction temperature at 110 ℃, reacting for 6 hours, and finishing the reaction to obtain the product of the example 4.

Example 5, a polyether multifunctional antioxidant, which is a compound of the following structure:

the preparation steps of the polyether type multifunctional antioxidant are the same as those of the embodiment 1, and the raw materials are selected as follows: 45 parts of chlorocyclohexane and chloroundecane (the molar ratio of the chlorocyclohexane to the chlorocycloheptane is 3:4), 60ppm of a sodium hydroxide catalyst, 7 parts of isooctanol and 45 parts of methylbenzotriazole.

Example 6, a polyether multifunctional antioxidant, a compound of the following structure:

the preparation steps of the polyether type multifunctional antirust agent in the embodiment are the same as those of the embodiment 1, and the raw materials are selected as follows: 50 parts of chlorocyclohexane and chloron-butane (the molar ratio of the chlorocyclohexane to the chloron-butane is 1:5), 70ppm of bimetallic catalyst, 8 parts of 2-ethyl-n-octanol and 50 parts of methylbenzotriazole.

Comparative experiment:

selecting the prior common antioxidant: zinc Dialkyl Dithiophosphate (ZDDP), dialkyl dithiocarbamate (ADTC) and dialkyl dithiophosphate (ADDP) are used as comparison antioxidants, and a pressure differential calorimetry (PDSC) experiment and a rotary pressure container oxidation experiment are carried out to examine the antioxidant characteristics of the compound of the invention and the existing antioxidants, wherein the longer the time is, the better the antioxidant effect is. Copper corrosion experiments were conducted to examine the corrosion resistance of the compound of the present invention and the existing antioxidant. Wherein, the lower the number of the copper corrosion test result is, the better the corrosion prevention effect is represented. The detergency test was carried out by using SH/T0269-92 method, and the results were classified into No. 0-6 and seven grades. No. 0 is cleanest, the color is lightest, No. 6 is dirtiest, the color is darkest, and the smaller the number, the better the detergency is.

The result of the detection

As can be seen from the table, the compound of the present invention has superior antioxidant performance to the conventional antioxidant and also has good anticorrosive and detergent properties.

Claims (6)

1. A polyether type multifunctional antioxidant is characterized by being a compound with the following structure:

wherein m is 0 to 50, n is 0 to 50, m and n are not zero at the same time, and R is₁Is C₁～C₁₅Alkyl groups of (a);

R₂is composed of

Wherein R is₄Is hydrogen or C₁～C₄An alkyl group;

R₃is composed of

Wherein R is₄Is hydrogenOr C₁～C₄And r is any integer of 1-20.

2. The polyether multifunctional antioxidant as claimed in claim 1, wherein R is₁Is C₁～C₁₀The alkyl group of (1).

3. The polyether multifunctional antioxidant as claimed in claim 1, wherein R is₂Is benzotriazole and derivatives thereof, wherein R₄Is hydrogen or C₁～C₂Alkyl group of (1).

4. The polyether multifunctional antioxidant as claimed in claim 1, wherein R is₃In the structural formula (II), R₄Is hydrogen or C₁～C₂And r is any integer of 1-10.

5. A method for preparing the polyether multifunctional antioxidant of any one of claims 1 to 4, comprising the steps of:

A. weighing the following raw materials: 40-50 parts of chlorinated alkylene oxide, a proper amount of catalyst and C₁～C₁₅Alkyl alcohol compounds, benzotriazole or benzotriazole derivatives;

B. adding a catalyst into a dry reaction kettle protected by inert gas, wherein the adding amount of the catalyst is 20-100 ppm of the prepared product according to the weight, and then adding C₁～C₁₅Alkyl alcohols and chlorinated alkylene oxides, C₁～C₁₅The molar ratio of the alkyl alcohol compound to the chlorinated alkylene oxide is 0.1: 1-1: heating the reaction kettle to 30-100 ℃, keeping the pressure less than 1.5MPa, continuously adding another chlorinated alkylene oxide into the reaction kettle at the speed of 0.5-3 mL/min when the temperature begins to rise and the pressure begins to fall and selecting two chlorinated alkylene oxides, continuing aging for 1-3 hours, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;

C. and (3) placing the reaction bottle with the polyether into a reaction container at 50-80 ℃, slowly adding benzotriazole or benzotriazole derivatives, heating, keeping the reaction temperature at 100-120 ℃, reacting for 1-12 hours, and obtaining the polyether multifunctional antioxidant.

6. The method for preparing polyether-type multifunctional antioxidant as claimed in claim 5, wherein the catalyst is selected from bimetallic catalyst or alkaline catalyst.