CN112521594A - Polyether derivative and process for producing the same - Google Patents

Polyether derivative and process for producing the same Download PDF

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CN112521594A
CN112521594A CN202011360672.5A CN202011360672A CN112521594A CN 112521594 A CN112521594 A CN 112521594A CN 202011360672 A CN202011360672 A CN 202011360672A CN 112521594 A CN112521594 A CN 112521594A
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polyether
compound
polyether derivative
diluent
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CN112521594B (en
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程亮
张�杰
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Guangdong University of Petrochemical Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3348—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing nitrogen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
    • C08G65/33362—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/38—Polyoxyalkylenes esterified
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
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    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/041—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

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Abstract

The invention discloses a polyether derivative and a preparation method thereof, wherein the polyether derivative is as follows:

Description

Polyether derivative and process for producing the same
Technical Field
The invention relates to a lubricant and a preparation method thereof, in particular to a polyether derivative and a preparation method thereof.
Background
The lubricating oil is a liquid or semisolid lubricating agent 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 of a lubricating oil to have the function of an additive, mainly because the functional requirements of the product, such as rust prevention, oxidation resistance, anti-wear property, etc., are not met, and the corresponding additive is usually required to be added to improve certain performance.
Polyether (also called polyether polyol) belongs to V-type base liquid, and has the advantages of high viscosity index, low pour point, good detergency and the like, so that the polyether is attracted attention. When polyether is used as base oil, functional additives such as a high-temperature antioxidant, an antiwear agent, an antirust agent and the like are required to be added to make up for the functional deficiency of the base oil.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a polyether derivative having good oxygen resistance, good abrasion resistance and rust resistance, in view of the defects of the prior art.
The invention further aims to solve the technical problem of providing a preparation method of the polyether derivative, 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:
a polyether derivative which is a compound of the following structure:
Figure BDA0002803895910000021
wherein m is 0-100, n is 0-100, and m and n are not zero at the same time, r is 0-5; m, n and r are integers and satisfy charge balance; r1Is C1～C30Of alkane, R2Is hydrogen, methyl or
Figure BDA0002803895910000022
R3Is composed of
Figure BDA0002803895910000023
Or C2～C30Of alkane, R4Is hydrogen or C1～C4Of an alkane, r4Is an integer of 1 to 20;
r is
Figure BDA0002803895910000024
Figure BDA0002803895910000025
Figure BDA0002803895910000031
Wherein R is5Is hydrogen or C1～C20An alkane of (a); x1Is S or O; r6、R7、R8Is hydrogen or C1～C5An alkane of (a); x2Is one of F, Cl and Br, and X2Any position of 1, 2 and 3 positions connected on a benzene ring; r is1Is an arbitrary integer of 1 to 3, r2Is an arbitrary integer of 0 to 2, r3Is an arbitrary integer of 1 to 3.
The above polyether derivatives can be classified into the following three types:
a first polyether derivative which is a compound of the following structure:
Figure BDA0002803895910000032
in the formula, R1Is C1-C10 alkane;
R2is composed of
Figure BDA0002803895910000033
Wherein R is4Is selected from C1～C2An alkane of (a);
R3is composed of
Figure BDA0002803895910000034
Wherein R is4Is selected from C1～C2Of an alkane, r4Is any integer of 1-10;
r is
Figure BDA0002803895910000035
Figure BDA0002803895910000036
Figure BDA0002803895910000041
Wherein R is5Selected from hydrogen or C1～C5Of (a) an alkane.
A second polyether derivative which is a compound of the following structure:
Figure BDA0002803895910000042
wherein m is 0-50, n is 0-50, and m and n are not zero at the same time;
R1is C1～C5Of alkane, R2Is hydrogen or methyl, R3Is C2～C5R is
Figure BDA0002803895910000043
Wherein X is2Is one of F, Cl and Br, and in the benzene ring, X2R in any of 1, 2, and 3 positions on the benzene ring1Is an arbitrary integer of 1 to 3, r2Is an arbitrary integer of 0 to 2, r3Is an arbitrary integer of 1 to 3.
A third polyether derivative which is a compound of the following structure:
Figure BDA0002803895910000044
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～C5Of alkane, R2Is hydrogen or methyl, R3Is C2～C5The alkane of (a) is,r is 1-5; r is
Figure BDA0002803895910000045
One kind of (1).
A process for preparing a first polyether derivative comprising the steps of:
A. selecting raw materials: 40-50 parts of chlorinated alkylene oxide, catalyst and C1～C1540-50 parts of alkyl alcohol compound, benzotriazole or derivative thereof and 40-50 parts of isocyanate compound; 0.5-3 parts of a diluent; the catalyst is a Zn-Co bimetallic catalyst or an alkaline catalyst; the diluent consists of a solvent A: the solvent B is used in a mass ratio of (10-20) to (1-5); solvent A is selected from dichloromethane, trichloromethane and tetrachloromethane, and solvent B is selected from tetrahydrofuran, furan, pyridine, pyrazine and pyrrole;
B. adding a catalyst into a dry reaction kettle protected by inert gas, wherein the adding amount of the catalyst is 20-100 ppm (mass ratio) of the prepared product, and adding an initiator C1～C15Heating a 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, continuously aging for 1-3 hours, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;
C. heating a reaction container with polyether to 50-80 ℃, slowly adding benzotriazole or a derivative thereof into the container, heating and keeping the reaction temperature at 100-120 ℃, reacting for 1-12 hours, and obtaining a compound 1 with one end being hydroxyl and the main chain containing benzotriazole after the reaction is finished.
D. Dissolving 40-50 parts of isocyanate compound in 0.5-3 parts of diluent, keeping the temperature at 40-50 ℃, and stirring for 20-40 minutes to prepare a solution 1;
E. and dropwise adding the solution 1 into 40-50 parts of the compound 1, heating to 50-90 ℃ after dropwise adding, and aging for 1.5-2 hours to obtain the polyether derivative.
A second process for preparing a polyether derivative, comprising the steps of:
A. weighing the following raw materials: 40-50 parts of polyether, 40-70 parts of carbonyl compound containing isocyanate and 1-3 parts of diluent; 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 and mono-terminated long-chain alkylene oxide homopolymer or a copolymer of any combination of the mono-terminated polyethylene glycol, the mono-terminated ethylene oxide homopolymer and the mono-terminated propylene oxide homopolymer; the carbonyl compounds containing isocyanate being selected from the group consisting of
Figure BDA0002803895910000061
Figure BDA0002803895910000062
Any one of the groups, wherein X2Is one of F, Cl and Br, and X2Any position of 1, 2 and 3 positions connected on the benzene ring, r is any integer of 1-3, r1Is an arbitrary integer of 1 to 3, r2Is an arbitrary integer of 0 to 2;
B. dissolving 40-70 parts of carbonyl compound containing isocyanate in 1-3 parts of diluent, keeping the temperature at 40-50 ℃, and stirring for 20-40 minutes to prepare solution 1;
C. dripping the solution 1 into 40-50 parts of polyether at the speed of 0.1-1 mL/min, heating to 50-90 ℃, and aging for 1.5-2 hours to obtain the polyether derivative.
A third process for preparing a polyether derivative, comprising the steps of:
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 polyether derivative.
Further, in the preparation method of the polyether derivative, the polyether is preferably 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.
Further, in the method for producing the polyether derivative, it is preferable that in the isocyanate-containing aryl compound, the aryl group is selected from the group consisting of
Figure BDA0002803895910000071
Any one of them.
The polyether derivative is obtained by modifying polyether, and functional groups are introduced into a polyether chain to enable the polyether chain to have groups such as ether bonds, ester groups, amino groups, heteroatoms and the like, so that the polyether derivative does not have terminal hydroxyl groups, the problems of poor high-temperature stability, poor oxygen resistance and the like are solved, the polyether derivative has multiple functions such as oxygen resistance, wear resistance, antirust performance and the like, and no or few additional additives are needed to make up for the functional deficiency of the base oil. And because the modification groups are different, the polyether derivative has relatively more outstanding functions on the basis of simultaneously having multiple functions.
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.
Examples 1-12, which are a first type of polyether derivative, have more outstanding rust inhibitive performance.
Example 1, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000072
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000073
40 parts of aryl compound containing isocyanate
Figure BDA0002803895910000081
40 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 polyether derivative, a compound of the following structure:
Figure BDA0002803895910000082
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000083
40 parts of aryl compound containing isocyanate
Figure BDA0002803895910000084
50 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 polyether derivative, a compound of the following structure:
Figure BDA0002803895910000085
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000091
60 parts of aryl compound containing isocyanate
Figure BDA0002803895910000092
60 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 polyether derivative, a compound of the following structure:
Figure BDA0002803895910000095
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000093
70 parts of aryl compound containing isocyanate
Figure BDA0002803895910000094
70 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 polyether derivative, a compound of the following structure:
Figure BDA0002803895910000106
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000101
55 parts of aryl compound containing isocyanate
Figure BDA0002803895910000102
60 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 polyether derivative, a compound of the following structure:
Figure BDA0002803895910000103
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000104
55 parts of aryl compound containing isocyanate
Figure BDA0002803895910000105
70 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 polyether derivative, a compound of the following structure:
Figure BDA0002803895910000111
the polyether derivative of this example was prepared in the same manner as in any of examples 1 to 6, using the following starting materials: polyether
Figure BDA0002803895910000112
45 parts of aryl compound containing isocyanate
Figure BDA0002803895910000113
50 parts of diluent (dichloromethane: pyrrole in a mass ratio of 20: 2)2 parts;
example 8, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000114
the procedure for preparing the polyether derivative of this example was the same as in examples 1 to 6Selecting any one of the following raw materials: polyether
Figure BDA0002803895910000115
55 parts of aryl compound containing isocyanate
Figure BDA0002803895910000116
60 parts of diluent (trichloromethane: furan in a mass ratio of 20: 6)3 parts;
example 9, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000117
the preparation procedure of the polyether derivative of the above example is the same as that of any one of examples 1 to 6, and the raw materials are selected as follows: polyether
Figure BDA0002803895910000121
65 parts of aryl compound containing isocyanate
Figure BDA0002803895910000122
70 parts of diluent (tetrachloromethane: furan in a mass ratio of 15: 6)0.5 part;
example 10, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000123
the polyether derivative of this example was prepared in the same manner as in any of examples 1 to 6, using the following starting materials: polyether
Figure BDA0002803895910000124
65 parts of aryl compound containing isocyanate
Figure BDA0002803895910000125
70 parts of diluent (dichloromethane: furan in a mass ratio of 15: 7)1.5 parts;
example 11, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000126
the polyether derivative of this example was prepared in the same manner as in any of examples 1 to 6, using the following starting materials: polyether
Figure BDA0002803895910000127
70 parts of aryl compound containing isocyanate
Figure BDA0002803895910000128
70 parts of diluent (dichloromethane: pyrrole in a mass ratio of 15: 9)2.5 parts;
example 12, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000129
the polyether derivative of this example was prepared in the same manner as in any of examples 1 to 6, using the following starting materials: polyether
Figure BDA0002803895910000131
40 parts of aryl compound containing isocyanate
Figure BDA0002803895910000132
40 parts of diluent (trichloromethane: tetrahydrofuran in a mass ratio of 15: 9)2 parts;
in examples 1 to 12, the above examples have more outstanding anticorrosive ability in addition to the anti-wear property, anticorrosive property and oxygen resistance due to the modifying group, and the anticorrosive ability of the above examples will be described by comparative experiments.
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
Figure BDA0002803895910000133
Figure BDA0002803895910000141
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.
Examples 13-22, which are the second type of polyether derivatives, are more distinguished by oxygen resistance.
Example 13, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000142
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: 40 parts of chlorocyclohexane and chlorocyclopropane (the mol ratio of the chlorocyclohexane to the chlorocyclopropane is 1:6), 20ppm of bimetallic catalyst (Zn-Co bimetallic catalyst), 0.1 part of methanol and benzotriazole
Figure BDA0002803895910000143
40 parts and 0.5 part of diluent consisting of dichloromethane: tetrahydrofuran in a mass ratio of 10: 1, preparing a composition; isocyanate compound
Figure BDA0002803895910000151
40 parts of a mixture;
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. heating a reaction container with polyether to 50 ℃, slowly adding benzotriazole into the container, heating and keeping the reaction temperature at 100 ℃, reacting for 1 hour, and obtaining a compound 1 with a hydroxyl at one end and a benzotriazole-containing main chain.
D. Dissolving an isocyanate compound in a diluent to form a solution 1, dropwise adding the solution 1 into a container containing the compound 1 at the temperature of 50 ℃ at the rate of 0.1 mL/min, and continuously stirring for 20 minutes after dropwise adding is finished;
E. the reaction vessel was warmed to 60 ℃ and aged for 1 hour to give the product of example 13.
Example 14, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000152
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: 50 parts of chlorocyclohexane and chlorocyclopropane (the molar ratio of the chlorocyclohexane to the chlorocyclopropane is 1:2), 100ppm of bimetallic catalyst, 10 parts of n-hexanol and 50 parts of methylbenzotriazole; 1 part of a diluent consisting of dichloromethane: furan in a mass ratio of 10: 3, preparing a composition; isocyanate compound
Figure BDA0002803895910000161
40 parts of a mixture;
B. adding a catalyst into a dry reaction kettle protected by inert gas, and then adding initiators of n-hexanol and chlorocyclohexane, wherein the molar ratio of the initiators to the chlorocyclohexane is 0.1: 1-1: heating the reaction kettle to 30-100 ℃, keeping the pressure less than 1.5MPa, continuously adding chlorocyclopropane 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, continuously aging for 3 hours, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;
C. heating a reaction container with polyether to 80 ℃, slowly adding methylbenzotriazole into the container, heating and keeping the reaction temperature at 120 ℃, reacting for 12 hours, and obtaining a compound 1 with one end being hydroxyl and the main chain containing the benzotriazol.
D. Dissolving an isocyanate compound in a diluent to form a solution 1, dropwise adding the solution 1 into a container containing the compound 1 at the temperature of 60 ℃ at the rate of 2 mL/min, and continuously stirring for 20 min after dropwise adding;
E. the reaction vessel was warmed to 90 ℃ and aged for 2 hours to give the product of example 14.
Example 15, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000162
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: 50 parts of chlorocyclohexane and chlorocyclopropane (the molar ratio of the chlorocyclohexane to the chlorocyclopropane is 100:71), 30ppm of potassium hydroxide catalyst, 1 part of n-hexanol and 50 parts of benzotriazole; 10 parts of isopropanol and 2 parts of a diluent, wherein the diluent is prepared from trichloromethane: and (2) furan in a mass ratio of 15: 5 component (b) an isocyanate compound
Figure BDA0002803895910000171
40 parts of a mixture;
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 chlorocyclopropane into the reaction kettle at the speed of 2.5 mL/min, continuously aging for 3 hours, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;
C. heating a reaction container with polyether to 70 ℃, slowly adding benzotriazole into the container, heating and keeping the reaction temperature at 110 ℃, reacting for 10 hours, and obtaining a compound 1 with a hydroxyl at one end and a benzotriazole-containing main chain.
D. Dissolving an isocyanate compound in a diluent to form a solution 1, dropwise adding the solution 1 into a container containing the compound 1 at the temperature of 55 ℃ at the rate of 1.5 mL/min, and continuously stirring for 30 minutes after dropwise adding is finished;
E. the reaction vessel was warmed to 70 ℃ and aged for 1.5 hours to give the product of example 15.
Example 16, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000181
A. weighing the following raw materials: 50 parts of chlorocyclohexane and chlorocyclooctane (the molar ratio of the chlorocyclohexane to the chlorocyclopropane is 20:48), 50ppm of sodium hydroxide catalyst, 7 parts of nonyl-3-ol and 50 parts of benzotriazole; 3 parts of a diluent, wherein the diluent is prepared from tetrachloromethane: pyridine is mixed according to a mass ratio of 20: 5 component (b) an isocyanate compound
Figure BDA0002803895910000182
40 parts of a mixture;
B. adding a sodium hydroxide catalyst into a dry reaction kettle protected by inert gas, adding nonyl-3-alcohol and chlorocyclooctane, heating the reaction kettle to 60 ℃, 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 chlorocyclooctane into the reaction kettle at the speed of 1 mL/min, continuously aging for 1.5 hours, stopping heating, reducing the temperature of the reaction kettle to room temperature, and filtering to obtain polyether;
C. heating a reaction container with polyether to 60 ℃, slowly adding benzotriazole into the container, heating and keeping the reaction temperature at 110 ℃, reacting for 6 hours, and obtaining a compound 1 with a hydroxyl at one end and a benzotriazole-containing main chain.
D. Dissolving an isocyanate compound in a diluent to form a solution 1, dropwise adding the solution 1 into a container containing the compound 1 at the temperature of 60 ℃ at the rate of 2 mL/min, and continuously stirring for 20 min after dropwise adding;
E. the reaction vessel was warmed to 80 ℃ and aged for 1 hour to give the product of example 16.
Example 17, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000191
the procedure for the preparation of the polyether derivative of this example was the same as in example 13, except that the following raw materials were selected: 45 parts of chlorocyclohexane and chlorocyclopropane (the molar ratio of the chlorocyclohexane to the chlorocyclopropane is 30:71), 60ppm of sodium hydroxide catalyst, 7 parts of decyl-4-alcohol, 45 parts of benzotriazole and 2 parts of diluent, wherein the diluent is prepared from tetrachloromethane: pyrazine is prepared from 20: 3, preparing a composition; isocyanate compound
Figure BDA0002803895910000192
45 parts of the raw materials.
Example 18, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000193
the procedure for the preparation of the polyether derivative of this example was the same as in example 13, except that the following raw materials were selected: 50 parts of chlorocyclododecane, 70ppm of bimetallic catalyst, 8 parts of n-hexadecanol and 50 parts of methylbenzotriazole; 1 part of a diluent consisting of dichloromethane: pyrrole is mixed according to a mass ratio of 20: 1 composition of an isocyanate compound
Figure BDA0002803895910000194
50 parts of the raw materials.
Example 19, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000201
the procedure for the preparation of the polyether derivative of this example was the same as in example 14, except that the following raw materials were selected: 50 parts of chlorocyclohexane and chlorocyclododecane (the molar ratio of the chlorocyclohexane to the chlorocyclododecane is 10:51), 100ppm of bimetallic catalyst, 8 parts of n-heptanol and 50 parts of butyl benzotriazole; 1 part of a diluent consisting of dichloromethane: pyrrole is mixed according to a mass ratio of 20: 1 composition of an isocyanate compound
Figure BDA0002803895910000202
50 parts of the raw materials.
Example 20, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000203
the procedure for preparing the polyether derivative of this example was the same as in example 15, except that the following raw materials were selected: 60 parts of chlorocyclohexane and chlorocycloheptane (the molar ratio of the chlorocyclohexane to the chlorocycloheptane is 50:21), 60ppm of bimetallic catalyst, 7 parts of isopropanol and 60 parts of ethyl benzotriazole; 2 parts of diluent (dichloromethane: pyrrole in a mass ratio of 20: 2) and isocyanate compound
Figure BDA0002803895910000204
50 parts of the raw materials.
Example 21, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000211
the procedure for preparing the polyether derivative of this example was the same as in example 15, except that the following raw materials were selected: 60 parts of chlorocyclohexane and chlorocycloundecane (the molar ratio of the chlorocyclohexane to the chlorocycloundecane is 15:81), 60ppm of a sodium hydroxide catalyst, 8 parts of heptyl-2-alcohol and 50 parts of methylbenzotriazole; diluent (chloroform:
and furan in a mass ratio of 20: 6)3 parts of an isocyanate compound
Figure BDA0002803895910000212
60 parts;
example 22, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000213
the procedure for preparing the polyether derivative of this example was the same as in example 15, except that the following raw materials were selected: 60 parts of chlorocyclohexane and chlorocyclobutane (the molar ratio of the chlorocyclohexane to the chlorocyclobutane is 5:26), 50ppm of sodium hydroxide catalyst, 1 part of decyl-3-alcohol and 60 parts of methylbenzotriazole; 0.5 part of diluent (tetrachloromethane: furan in a mass ratio of 15: 6), and an isocyanate compound
Figure BDA0002803895910000221
60 parts.
In examples 13 to 22, the above examples have more outstanding antioxidant properties in addition to abrasion resistance, rust resistance and oxygen resistance due to the modifying group, and the antioxidant properties of the above examples are described below by comparative experiments.
Comparative experiment:
selecting the prior common antioxidant: zinc dialkyldithiophosphate (ZDDP), dialkyldithiocarbamate (ADTC), dialkyldithiophosphate (ADDP) were used as comparative antioxidants.
1. Pressurized differential calorimetry (PDSC) experiments; the determination was carried out according to ASTM D6186-1998 using the standard test method for testing the oxidation induction time of lubricating oils using Pressure Differential Scanning Calorimetry (PDSC). A3.0 mg sample was taken at a pressure of 3.5MPa, 210 ℃.
2. Oxidation experiment in a rotary pressurized container: according to the national standard ASTM D2272-2009 "method for measuring oxidation stability of lubricating oil", the antioxidant characteristics of the compound and the existing antioxidant are examined, and the longer the time is, the better the antioxidant effect is.
3. Copper corrosion test: according to the determination of GB 5096-2017 & lt & ltliquefied petroleum gas copper sheet corrosion test method & gt, the corrosion resistance of the compound and the existing antioxidant is examined. Wherein, the lower the number of the copper corrosion test result is, the better the corrosion prevention effect is represented.
4. The detergency test: the results were classified into seven grades, No. 0-6, according to SH/T0269-1992, determination of detergency of lubricating oil for internal combustion engines. 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
Figure BDA0002803895910000231
As can be seen from the tables, the antioxidant properties of the compounds of the present invention are superior to those of conventional antioxidants, demonstrating that the polyether derivatives of the present invention have excellent antioxidant effects. Meanwhile, the coating has better corrosion resistance and cleaning performance.
Examples 23-37, a third type of polyether derivative, have more outstanding abrasion resistance properties.
Example 23, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000232
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000241
50 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000242
50 parts of diluent (a mixture of toluene and dichloromethane is selected) 3 parts, and the weight ratio of toluene: the mass ratio of the dichloromethane is 5: 1;
B. dissolving carbonyl compound containing isocyanate in a diluent, keeping the temperature at 40 ℃, and stirring for 20 minutes to prepare solution 1;
C. solution 1 was added dropwise to polyether at a rate of 0.1 mL/min, and after the addition was complete, the temperature was raised to 85 ℃ and aging was carried out for 1.5 hours to give the product of example 23.
Example 24, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000243
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000244
40 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000245
70 parts, 2 parts of diluent (a mixture of toluene and trichloromethane is selected), toluene: the mass ratio of the trichloromethane is 6: 3;
B. dissolving carbonyl compound containing isocyanate in a diluent, keeping the temperature at 45 ℃, and stirring for 30 minutes to prepare solution 1;
C. solution 1 was added dropwise to polyether at a rate of 0.5 mL/min, and after the addition was completed, the temperature was raised to 90 ℃ and aging was carried out for 1.7 hours, thereby obtaining the product of example 24.
Example 25, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000251
the polyether derivative is prepared by the following steps:
A. weighing the following raw materials: polyether
Figure BDA0002803895910000252
45 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000253
40 parts of diluent (a mixture of xylene and dichloromethane is selected) 1 part of xylene: the mass ratio of the dichloromethane is 10: 3;
B. dissolving carbonyl compound containing isocyanate in a diluent, keeping the temperature at 50 ℃, and stirring for 40 minutes to prepare solution 1;
C. solution 1 was added dropwise to polyether at a rate of 1 mL/min, and after the addition was completed, the temperature was maintained at 50 ℃ and aging was carried out for 2 hours to obtain the product of example 25.
Example 26, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000254
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000255
42 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000256
60 parts of diluent (a mixture of mesitylene and dichloromethane is selected) 2.5 parts, wherein the weight ratio of mesitylene: the mass ratio of the dichloromethane is 10: 4.
example 27, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000261
the procedure for preparing the polyether derivative of this example was the same as in example 24, except that the polyether as the starting material was selected
Figure BDA0002803895910000262
46 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000263
45 parts of diluent (a mixture of mesitylene and tetrachloromethane is selected) 1.5 parts, and the weight ratio of mesitylene: the mass ratio of tetrachloromethane is 6: 1.
example 28, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000264
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000265
49 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000266
65 parts, 1.5 parts of diluent (a mixture of xylene and dichloromethane is selected), and the weight ratio of xylene: the mass ratio of the dichloromethane is 7: 1.
example 29, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000271
the procedure for preparing the polyether derivative of this example was the same as in example 23, and the starting materials were selectedPolyether
Figure BDA0002803895910000272
43 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000273
55 parts of diluent (a mixture of mesitylene and trichloromethane is selected) 1.8 parts, and the weight ratio of mesitylene: the mass ratio of the trichloromethane is 8: 1.
example 30, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000274
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000275
44 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000276
52 parts of diluent (a mixture of toluene and trichloromethane is selected), 2.8 parts of toluene: the mass ratio of the trichloromethane is 9: 1.
example 31, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000281
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000282
47 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000283
58 portions of diluent (mixture of dimethylbenzene and dichloromethane is selected) 1.8 portions ofToluene: the mass ratio of the dichloromethane is 10: 1.
example 32, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000284
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000285
41 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000286
59 parts of diluent (a mixture of toluene and tetrachloromethane is selected) 2.8 parts, and the weight ratio of toluene: the mass ratio of tetrachloromethane is 10: 4.
example 33 a polyether derivative which is a compound of the following structure:
Figure BDA0002803895910000287
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000291
43 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000292
47 parts, 2.2 parts of diluent (a mixture of mesitylene and dichloromethane is selected), and weight parts of mesitylene: the mass ratio of the dichloromethane is 7: 3.
example 34, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000293
this exampleThe procedure of example 23 was repeated to select polyether as a raw material
Figure BDA0002803895910000294
48 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000295
51 parts, diluent (a mixture of toluene and dichloromethane is selected) 2.5 parts, toluene: the mass ratio of the dichloromethane is 5: 1.
example 35, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000296
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000297
46 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000298
62 parts of diluent (a mixture of toluene and trichloromethane is selected), 2.5 parts of toluene: the mass ratio of the trichloromethane is 7: 2.
example 36, a polyether derivative, a compound of the structure:
Figure BDA0002803895910000301
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000302
46 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000303
53 portions of diluent (selected fromWith a mixture of toluene and tetrachloromethane) 2 parts, toluene: the mass ratio of tetrachloromethane is 8: 3.
example 37, a polyether derivative, a compound of the following structure:
Figure BDA0002803895910000304
the procedure for preparing the polyether derivative of this example was the same as in example 23, except that the polyether as the starting material was selected
Figure BDA0002803895910000305
48 parts of carbonyl compound containing isocyanate
Figure BDA0002803895910000306
66 parts of diluent (a mixture of xylene and dichloromethane is selected) 3 parts of xylene: the mass ratio of the dichloromethane is 9: 5.
in examples 23 to 37, the above examples have more outstanding anti-wear properties on the basis of simultaneously having anti-wear properties, rust prevention properties and oxygen resistance due to the modifying group, and the anti-wear properties of the above examples are illustrated by comparative experiments below.
Comparative experiment:
selecting the existing common antiwear agent: zinc dialkyldithiophosphate (ZDDP), dialkyldithiocarbamate (ADTC), dialkyldithiophosphate (ADDP) were used as comparative antiwear agents.
1. Four-ball experiment: the anti-wear characteristics of the compound and the conventional anti-wear agent are examined according to ASTM D2783-2003(2014) Standard test method for measuring the extreme pressure Performance of lubricating fluid and ASTM D2596-1997(2002) e1 Standard test method for the extreme pressure Performance of lubricating grease, wherein the four-ball test condition is rotating speed of 1770r/min and time of 10 s; characteristic index is PBAnd PDThe smaller the value, the better the abrasion resistance.
2. Antifriction experiment: the additives were tested for anti-friction properties using MTM. The experimental conditions are as follows: the MTM tester adopts a ball-disk (52100 steel) contact mode, the load is 35N, the sliding/rolling ratio is 50%, the measurement temperature is 40 ℃, and the smaller the data is, the better the antifriction performance is represented.
3. Detergency test: the method is carried out by adopting an SH/T0269-92 method, and the result is divided into seven grades of No. 0-6. 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
Figure BDA0002803895910000311
Figure BDA0002803895910000321
As can be seen from the table, the compound of the invention has far better abrasion resistance than the traditional antiwear agent, and simultaneously has better antifriction and cleaning performances.

Claims (9)

1. A polyether derivative characterized by being a compound of the structure:
Figure FDA0002803895900000011
wherein m is 0-100, n is 0-100, and m and n are not zero at the same time, r is 0-5; m, n and r are integers and satisfy charge balance; r1Is C1～C30Of alkane, R2Is hydrogen, methyl or
Figure FDA0002803895900000012
R3Is composed of
Figure FDA0002803895900000013
Or C2～C30Of alkane, R4Is hydrogen or C1～C4R4 is any integer of 1-20;
r is
Figure FDA0002803895900000014
Figure FDA0002803895900000015
Figure FDA0002803895900000016
Wherein R is5Is hydrogen or C1～C20An alkane of (a); x1Is S or O; r6、R7、R8Is hydrogen or C1～C5An alkane of (a); x2Is one of F, Cl and Br, and X2Any position of 1, 2 and 3 positions connected on a benzene ring; r is1Is an arbitrary integer of 1 to 3, r2Is an arbitrary integer of 0 to 2, r3Is an arbitrary integer of 1 to 3.
2. The polyether derivative of claim 1, wherein the polyether derivative is a compound of the following structure:
Figure FDA0002803895900000021
in the formula, R1Is C1～C10An alkane of (a);
R2is composed of
Figure FDA0002803895900000022
Wherein R is4Is selected from C1～C2An alkane of (a);
R3is composed of
Figure FDA0002803895900000023
Wherein R is4Is selected from C1～C2R4 is any integer of 1-10;
r is
Figure FDA0002803895900000024
Figure FDA0002803895900000025
Figure FDA0002803895900000026
Wherein R is5Selected from hydrogen or C1～C5Of (a) an alkane.
3. The polyether derivative of claim 1, wherein the polyether derivative is a compound of the following structure:
Figure FDA0002803895900000027
wherein m is 0-50, n is 0-50, and m and n are not zero at the same time;
R1is C1～C5Of alkane, R2Is hydrogen or methyl, R3Is C2～C5R is
Figure FDA0002803895900000031
Wherein X is2Is one of F, Cl and Br, and in the benzene ring, X2R in any of 1, 2, and 3 positions on the benzene ring1Is an arbitrary integer of 1 to 3, r2Is an arbitrary integer of 0 to 2, r3Is an arbitrary integer of 1 to 3.
4. The polyether derivative of claim 1, wherein the polyether derivative is a compound of the following structure:
Figure FDA0002803895900000032
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～C5Of alkane, R2Is hydrogen or methyl, R3Is C2～C5R is 1-5; r is
Figure FDA0002803895900000033
One kind of (1).
5. A process for producing the polyether derivative according to claim 2, comprising the steps of:
A. selecting raw materials: 40-50 parts of chlorinated alkylene oxide, catalyst and C1～C1540-50 parts of alkyl alcohol compound, benzotriazole or derivative thereof and 40-50 parts of isocyanate compound; 0.5-3 parts of a diluent; the catalyst is a Zn-Co bimetallic catalyst or an alkaline catalyst; the diluent consists of a solvent A: the solvent B is used in a mass ratio of (10-20) to (1-5); solvent A is selected from dichloromethane, trichloromethane and tetrachloromethane, and solvent B is selected from tetrahydrofuran, furan, pyridine, pyrazine and pyrrole;
B. adding a catalyst into a dry reaction kettle protected by inert gas, wherein the adding amount of the catalyst is 20-100 ppm (mass ratio) of the prepared product, and adding an initiator C1～C15Heating a 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, continuously aging for 1-3 hours, stopping heating, cooling the reaction kettle to room temperature, and filtering to obtain polyether;
C. heating a reaction container with polyether to 50-80 ℃, slowly adding benzotriazole or a derivative thereof into the container, heating and keeping the reaction temperature at 100-120 ℃, reacting for 1-12 hours, and obtaining a compound 1 with one end being hydroxyl and the main chain containing benzotriazole after the reaction is finished.
D. Dissolving 40-50 parts of isocyanate compound in 0.5-3 parts of diluent, keeping the temperature at 40-50 ℃, and stirring for 20-40 minutes to prepare a solution 1;
E. and dropwise adding the solution 1 into 40-50 parts of the compound 1, heating to 50-90 ℃ after dropwise adding, and aging for 1.5-2 hours to obtain the polyether derivative.
6. A process for producing the polyether derivative according to claim 3, comprising the steps of:
A. weighing the following raw materials: 40-50 parts of polyether, 40-70 parts of carbonyl compound containing isocyanate and 1-3 parts of diluent; 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 and mono-terminated long-chain alkylene oxide homopolymer or a copolymer of any combination of the mono-terminated polyethylene glycol, the mono-terminated ethylene oxide homopolymer and the mono-terminated propylene oxide homopolymer; the carbonyl compounds containing isocyanate being selected from the group consisting of
Figure FDA0002803895900000041
Figure FDA0002803895900000042
Any one of the groups, wherein X2 is one of F, Cl and Br, X2 is connected to any position of 1, 2 and 3 positions on a benzene ring, r is any integer of 1-3, r is1Is an arbitrary integer of 1 to 3, r2Is an arbitrary integer of 0 to 2;
B. dissolving 40-70 parts of carbonyl compound containing isocyanate in 1-3 parts of diluent, keeping the temperature at 40-50 ℃, and stirring for 20-40 minutes to prepare solution 1;
C. dripping the solution 1 into 40-50 parts of polyether at the speed of 0.1-1 mL/min, heating to 50-90 ℃, and aging for 1.5-2 hours to obtain the polyether derivative.
7. A process for preparing the polyether derivative of claim 4, comprising the steps of:
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 polyether derivative.
8. The method for preparing polyether derivative according to claim 7, wherein 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 a copolymer of any combination thereof.
9. The process for producing polyether derivative according to claim 7, wherein the aryl group in the isocyanate-containing aryl compound is selected from the group consisting of
Figure FDA0002803895900000051
Any one of them.
CN202011360672.5A 2020-11-27 2020-11-27 Polyether derivative and process for producing the same Active CN112521594B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990005172A1 (en) * 1988-11-11 1990-05-17 Asahi Glass Company Ltd. Tetrafluoroethane composition for a regrigerator
CN109679086A (en) * 2018-12-24 2019-04-26 联泓(江苏)新材料研究院有限公司 A kind of polyether macromonomer and preparation method thereof and polycarboxylate water-reducer prepared therefrom
CN111378110A (en) * 2018-12-27 2020-07-07 联泓(江苏)新材料研究院有限公司 High-ignition-point polyether and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990005172A1 (en) * 1988-11-11 1990-05-17 Asahi Glass Company Ltd. Tetrafluoroethane composition for a regrigerator
CN109679086A (en) * 2018-12-24 2019-04-26 联泓(江苏)新材料研究院有限公司 A kind of polyether macromonomer and preparation method thereof and polycarboxylate water-reducer prepared therefrom
CN111378110A (en) * 2018-12-27 2020-07-07 联泓(江苏)新材料研究院有限公司 High-ignition-point polyether and preparation method and application thereof

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