Polyether base oil as well as preparation method and application thereof

Abstract

The invention provides polyether base oil and a preparation method and application thereof.According to the polyether base oil, a melt polycondensation method is adopted, a diester group-COO-R-COO-is introduced into a molecular structure through hydroxyl groups at the two ends of polyalkylene oxide, a polyether ester molecular chain with ether bonds and diester bonds distributed alternately is formed, and the polyether base oil is prepared. Then, carboxyl at the end group of a molecular chain is further subjected to an end-capping reaction with an amine compound, a unique amine double-end-capped polyether ester structure is obtained, and the polyether base oil has excellent viscosity-temperature performance, oxidation resistance, anti-rust performance and anti-wear and anti-friction performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lubricating oil, and particularly relates to a polyether base oil and a preparation method and application thereof. BACKGROUND

[0002] Lubricating oil is an essential component for mechanical operation, which plays a key role in reducing mechanical friction energy loss, improving momentum transmission efficiency and increasing mechanical operation life. Lubricating oil is generally composed of two parts of base oil and additives, the base oil is the main component of lubricating oil, and determines the basic properties of lubricating oil, wherein the polyether base oil is a linear polymer prepared by ring-opening homopolymerization and copolymerization of raw materials such as ethylene oxide, propylene oxide and butylene oxide under the action of a catalyst, and is widely used in the field of lubricating oil due to its advantages of viscosity-temperature performance, low-temperature flowability, lubricity, non-corrosion, non-toxicity and structural designability.

[0003] However, the stability of the polyether base oil at high temperature is poor, and functional additives such as extreme pressure anti-wear agents, rust inhibitors, antioxidants and metal deactivators are usually added for performance reinforcement in actual application. However, the strong polarity of the polyether itself leads to competitive adsorption of the additives on the metal surface, and it is difficult for the additives to form an adsorption film on the metal surface, resulting in poor rust resistance and extreme pressure anti-wear performance of the oil product. On the other hand, the functional additives in the lubricating oil are generally oil-soluble and cannot be well dissolved in the water-soluble polyether, which is easy to precipitate and affect the performance of the product, thereby limiting its application. In order to improve the above problems, the general strategy is to use polyether base oil in combination with other base oils such as poly-alpha-olefins or synthetic esters to improve the compatibility and sensibility of the oil product to the additives. However, this method can improve the performance of the oil product to some extent, but also introduces other adverse factors, such as increased cost and improved process complexity.

[0004] Therefore, modifying the structure of the polyether itself is an important way to improve the performance of the polyether base oil. For example, through block polymerization, post-treatment capping and other methods, the antioxidant property, anti-wear and friction-reducing property of the polyether base oil can be improved. However, the existing technical means can only improve the performance of one aspect, and it is difficult to balance the performance of each aspect, which limits the improvement of the comprehensive performance of the polyether base oil to some extent.

[0005] Therefore, it is necessary to invent a polyether base oil with high viscosity index, low pour point, strong rust resistance, strong antioxidant property and excellent anti-wear and friction-reducing property, to solve the problems of the prior art and have important application value. SUMMARY

[0006] The application provides a polyether base oil, which is an amine double-capped polyether ester structure and has excellent viscosity-temperature performance, antioxidant property, rust resistance and anti-wear and friction-reducing property.

[0007] The present application provides a method for preparing a polyether base oil, and the polyether base oil obtained by the method has excellent viscosity-temperature properties, oxidation resistance, rust prevention, and anti-wear and friction-reducing properties.

[0008] The present application provides a functional agent including the above-described polyether base oil, and thus the functional agent has excellent viscosity-temperature properties, oxidation resistance, rust prevention, and anti-wear and friction-reducing properties.

[0009] The present application provides a polyether base oil having a structural formula as shown in Formula 1,

[0010] In Formula 1, x is 1 to 10; A is an epoxy copolymer having up to 5 carbon atoms; and R is selected from C1 to C5 alkylene or alkenylene.

[0011] R1 and R2 are each independently selected from a linear terminal amino compound or a substituted or unsubstituted cyclic group having 5 or more ring-forming atoms.

[0012]

[0013] The polyether base oil as described above, wherein the structural formula of A is shown in Formula 2, m is 1 to 12, and n is 1 to 10,

[0014]

[0015] The polyether base oil as described above, wherein R is selected from at least one of -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, and -CH=CH-.

[0016] The polyether base oil as described above, wherein the polyether base oil is prepared by a method including the steps of: reacting a raw material mixture system including an A-containing compound, a diacid compound, and a Lewis acid catalyst for a certain period of time, followed by vacuum distillation; and reacting an intermediate terminal carboxylated polyether ester obtained by the vacuum distillation with an amine compound to obtain the polyether base oil.

[0017] The polyether base oil as described above, the amine compound includes at least one of polyethylene polyamine, m-phenylenediamine, o-phenylenediamine, 2,6-diaminotoluene, aniline, 2-(4-aminophenyl)-5-aminobenzimidazole, p-toluidine, aminoquinoline, diaminquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2,3-dihydroisoindol-1-ketone, benzylamine, triphenylamine, 3-tert-butyl aniline, 4-tert-butyl aniline, 4-octyl aniline, 2,4-dimethylaniline, 4,4'-diaminodiphenylamine, 3-benzyloxy aniline, 3,3'-diaminobenzidine, 3,5-di-tert-butyl aniline, 4-amino-N,N-dimethylaniline, 4-aminoaniline, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-diphenylethylamine, 4-aminodiphenylamine, aminoimidazole, 1,2-diaminoimidazole, imidazolidine amide, 5-amino benzimidazole, 5-methyl-6-amino benzimidazolone, 1-(2-aminoethyl)imidazoline-2-ketone, aminothiadiazole, 2-aminothiadiazole, 2-amino-1,3,4-thiadiazole, 5-aminothiadiazole, 1,3,4-thiadiazol-2-ylmethylamine, 5-chloro-1,2,4-thiadiazol-3-amine, 1,2,5-thiadiazol-3-amine, and the polyethylene polyamine includes at least one of diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and heavy polyamine.

[0018] The present application also provides a method for preparing the polyether base oil as described above, comprising the following steps:

[0019] (1) mixing a raw material mixture system including an A-containing compound, a dibasic acid compound, and a Lewis acid catalyst, and reacting at 180-240°C for 8-12 hours, followed by performing vacuum distillation at 100-240°C to obtain an intermediate carboxyl-terminated polyether ester;

[0020] (2) mixing the intermediate carboxyl-terminated polyether ester with an amine compound at 100-130°C, gradually increasing the temperature to 140-180°C, followed by passing nitrogen for 3-6 hours to obtain the polyether base oil.

[0021] The method for preparing as described above, the dibasic acid compound includes at least one of malonic acid, succinic acid, glutaric acid, and maleic acid; and / or,

[0022] The Lewis acid catalyst includes at least one of stannous chloride, tetrabutyl titanate, and antimony trioxide; and / or,

[0023] The amine compound includes at least one of polyethylene polyamine, m-phenylenediamine, o-phenylenediamine, 2,6-diaminotoluene, aniline, 2-(4-aminophenyl)-5-aminobenzimidazole, p-toluidine, aminoquinoline, diaminquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2,3-dihydroisoindol-1-one, benzyl aniline, triphenylamine, 3-tert-butyl aniline, 4-tert-butyl aniline, 4-octyl aniline, 2,4-dimethylaniline, 4,4'-diaminodiphenylamine, 3-benzyloxy aniline, 3,3'-diaminobenzidine, 3,5-di-tert-butyl aniline, 4-amino-N,N-dimethylaniline, 4-aminoaniline, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-diphenylethylamine, 4-aminodiphenylamine, aminoimidazole, 1,2-diaminoimidazole, imidazolinamide, 5-amino benzimidazole, 5-methyl-6-amino benzimidazolone, 1-(2-aminoethyl)imidazoline-2-one, aminothiadiazole, 2-aminothiadiazole, 2-amino-1,3,4-thiadiazole, 5-aminothiadiazole, 1,3,4-thiadiazol-2-ylmethylamine, 5-chloro-1,2,4-thiadiazol-3-amine, at least one of polyethylene polyamine including diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and heavy polyamine.

[0024] The preparation method as described above, the substance of the compound containing A and the binary acid compound has a substance amount ratio of 1:1-2.5.

[0025] The preparation method as described above, the mass percentage content of the Lewis acid catalyst in the raw material mixed system is 0.1-1%.

[0026] The preparation method as described above, the substance amount ratio of the intermediate terminal carboxylated polyether ester and the amine compound is 1:2-2.3.

[0027] The application further provides a functional agent, which comprises the polyether base oil as described above or the polyether base oil prepared by the preparation method as described above.

[0028] The application provides a polyether base oil, which is prepared by a melt polycondensation method. The hydroxyl groups at both ends of polyalkylene oxide are used to introduce a double ester group -COO-R-COO- into a molecular structure, to form a polyether ester molecular chain with alternating distribution of ether bonds and double ester bonds, and then the carboxyl groups at the end of the molecular chain are used to further perform end-capping reaction with an amine compound, to obtain a unique amine double-end-capped polyether ester structure. The method is simple to operate, easy to control the reaction conditions more accurately, reduces the use of solvents, and has less by-products, so that a high-purity polyether base oil is obtained, waste emission in the production process is reduced, and the principle of green chemistry is met.

[0029] The amine group capped by the polyether base oil can react with free radicals, reduce the generation of free radicals, thereby inhibiting the oxidation process of the oil product; in addition, the amine group capped by the polyether base oil has excellent base retention, can neutralize acidic substances generated during the use of the oil product and adsorb the deposits in the oil product; the nitrogen, sulfur and other atoms on the cyclic amine compounds such as thiazole and imidazole can form coordination bonds with the metal surface, thereby enhancing the binding force, stability and compactness between the protective film and the metal surface, thereby forming excellent anti-wear and anti-corrosion properties. Furthermore, the ester bond in the molecular structure has good thermal stability, and the synergistic effect of the alternating distribution of the ether bond and the ester bond enables it to maintain the stability of the structure and the performance at a higher temperature. In summary, the polyether base oil described in the application has high viscosity index, low pour point, oxidation resistance, rust prevention and anti-wear and friction reduction performance. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 The specific synthesis reaction schematic diagram of the preparation method of the application is shown. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical scheme and advantages of the application more clear, the technical scheme in the embodiments of the application will be described clearly and completely below in combination with the embodiments of the application. Obviously, the described embodiments are part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0032] The first aspect of the application provides a polyether base oil, the structural formula of which is shown as formula 1, wherein x is 1-10; A is a C5 or less epoxy copolymer; R is selected from C1-C5 alkylene or alkenylene; R1 and R2 are each independently selected from a linear terminal amino compound, or a substituted or unsubstituted cyclic group with a ring atom number of not less than 5;

[0033]

[0034] The polyether base oil of the application is used to make lubricating oil. Specifically, the lubricating oil is generally composed of two parts of base oil and additives, and the base oil is the main component of the lubricating oil, which determines the basic properties of the lubricating oil.

[0035] The polyether base oil of the present application has high viscosity index, low pour point, strong rust resistance, strong oxidation resistance, excellent anti-wear and friction-reducing performance, and can improve the comprehensive performance of the oil product. It is speculated that the amine group capped at the end of the polyether base oil has excellent base retention, can neutralize acidic substances generated during the use of the oil product and adsorb the deposits in the oil product; in addition, the amine group capped at the end of the polyether base oil can react with free radicals to reduce the generation of free radicals, thereby inhibiting the oxidation process of the oil product; the nitrogen and sulfur atoms on the cyclic amine compounds such as thiazole and imidazole can form coordination bonds with the metal surface, thereby enhancing the bonding force, stability and compactness between the protective film and the metal surface, and thus having excellent anti-wear and corrosion resistance. Furthermore, the ester bond in the molecular structure has good thermal stability, and the synergistic effect of the alternating distribution of ether bonds and ester bonds enables it to maintain the stability of its structure and performance at a higher temperature.

[0036] Therefore, due to the unique amine double-capped polyether ester structure of the polyether base oil of the present application, it has high viscosity index, low pour point, strong rust resistance, strong oxidation resistance, and excellent anti-wear and friction-reducing performance.

[0037] In one embodiment, the structural formula of A is shown in Formula 2, m is 1-12, n is 1-10,

[0038]

[0039] As a preferred solution, the viscosity-temperature performance, oxidation resistance, rust resistance and anti-wear and friction-reducing performance of the polyether base oil can be further improved.

[0040] Further, R in the structure of the above polyether base oil is selected from at least one of -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, and -CH=CH-.

[0041] In one embodiment, the above polyether base oil is prepared by a method comprising the following process: reacting a raw material mixture system comprising an A-containing compound, a dibasic acid compound and a Lewis acid catalyst for a certain period of time, then performing vacuum distillation, and reacting the obtained intermediate carboxyl-terminated polyether ester with an amine compound to obtain the polyether base oil.

[0042] Further, the amine compound includes at least one of polyethylene polyamine, m-phenylenediamine, o-phenylenediamine, 2,6-diaminotoluene, aniline, 2-(4-aminophenyl)-5-aminobenzimidazole, p-toluidine, aminoquinoline, diaminquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2,3-dihydroisoindol-1-one, benzyl aniline, triphenylamine, 3-tert-butyl aniline, 4-tert-butyl aniline, 4-octyl aniline, 2,4-dimethylaniline, 4,4'-diaminodiphenylamine, 3-benzyloxy aniline, 3,3'-diaminobenzidine, 3,5-di-tert-butyl aniline, 4-amino-N,N-dimethylaniline, 4-aminoaniline, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-diphenylethylamine, 4-aminodiphenylamine, aminoimidazole, 1,2-diaminoimidazole, imidazolidine amide, 5-amino benzimidazole, 5-methyl-6-amino benzimidazolone, 1-(2-aminoethyl)imidazoline-2-one, aminothiadiazole, 2-aminothiadiazole, 2-amino-1,3,4-thiadiazole, 5-aminothiadiazole, 1,3,4-thiadiazol-2-ylmethylamine, 5-chloro-1,2,4-thiadiazol-3-amine, 1,2,5-thiadiazol-3-amine, and the polyethylene polyamine includes at least one of diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and heavy polyamine.

[0043] The second aspect of the present application provides a method for preparing the above-mentioned polyether base oil, comprising the following steps:

[0044] (1) mixing a raw material mixture including an A-containing compound, a dibasic acid compound, and a Lewis acid catalyst, and reacting at 180-240°C for 8-12 hours, and then performing vacuum distillation at 100-240°C to obtain an intermediate carboxyl-terminated polyether ester;

[0045] (2) mixing the intermediate carboxyl-terminated polyether ester with an amine compound at 100-130°C, gradually increasing the temperature to 140-180°C, and then introducing nitrogen for 3-6 hours to obtain the polyether base oil.

[0046] Specifically, in step (1), the raw material mixture including the A-containing compound, the dibasic acid compound, and the Lewis acid catalyst is added to a reactor equipped with a stirring device and a temperature control device, the stirring is started, the temperature is increased to 180-240°C, and the reaction is performed for 8-12 hours, and then vacuum distillation is performed at 100-240°C to obtain the intermediate carboxyl-terminated polyether ester.

[0047] This invention does not specifically limit the A-containing compounds, dicarboxylic acid compounds, and Lewis acid catalysts. For example, dicarboxylic acid compounds include at least one of malonic acid, succinic acid, glutaric acid, and maleic acid, and Lewis acid catalysts include at least one of stannous chloride, tetrabutyl titanate, and antimony trioxide.

[0048] In step (2), the intermediate carboxylated polyether ester and amine compound obtained in step (1) are added to a reactor equipped with a stirring and temperature control device. The stirring is started, the temperature is raised to 100-130°C, and after stirring for one hour, the temperature is gradually raised to 140-180°C at a rate of 5-12°C / h. Nitrogen gas is introduced for stripping for 3-6 hours to obtain the polyether ester.

[0049] This invention does not specifically limit the amine compounds, and for example, can be polyethylenepolyamine, m-phenylenediamine, o-phenylenediamine, 2,6-diaminotoluene, aniline, 2-(4-aminophenyl)-5-aminobenzimidazole, p-toluidine, aminoquinoline, diaminoquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2,3-dihydroisoindole-1-one, diphenylmethylamine, triphenylmethylamine, 3-tert-butylaniline, 4-tert-butylaniline, 4-octylaniline, 2,4-dimethylaniline, 4,4'-diaminodiphenylamine, 3-benzyloxyaniline, 3,3'-diaminobenzidine, 3,5-ditert-butylaniline, 4-amino-N,N-dimethylaniline, 4-aminodiphenylamine, 4,4'-diphenylamine, etc. At least one of the following: diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-diphenylethylamine, 4-aminodiphenylamine, aminoimidazole, 1,2-diaminoimidazole, imidazolinamide, 5-aminobenzimidazole, 5-methyl-6-aminobenzimidazole one, 1-(2-aminoethyl)imidazolin-2-one, aminothiadiazole, 2-aminothiadiazole, 2-amino-1,3,4-thiadiazole, 5-aminothiadiazole, 1,3,4-thiadiazole-2-ylmethylamine, 5-chloro-1,2,4-thiadiazole-3-amine, and 1,2,5-thiadiazole-3-amine, wherein the polyethylenepolyamine includes at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heavy polyamines.

[0050] In one embodiment, the molar ratio of compound A to dicarboxylic acid compound is 1:1 to 2.5.

[0051] The Lewis acid catalyst content of the present invention is preferably 0.1% to 1% by mass in the raw material mixing system.

[0052] In one embodiment, the molar ratio of the intermediate terminal carboxylated polyether ester to the amine compound is 1:2 to 2.3.

[0053] The preparation method of this invention is environmentally friendly and produces pure products.

[0054] The third aspect of the present application provides a functional agent, including but not limited to internal combustion engine oil, gear oil, metalworking fluid, compressor oil and refrigerator oil, which comprises the polyether base oil prepared by the above method or the polyether base oil prepared by the above method as base oil, so that the functional agent has excellent viscosity-temperature performance, oxidation resistance, anti-rust performance and anti-wear and friction reduction performance, thereby effectively reducing the wear and tear of the machine, reducing the mechanical friction energy loss and increasing the service life of the machine.

[0055] Hereinafter, the polyether base oil of the present application will be described in detail through specific examples.

[0056] Example 1

[0057] The preparation method of the polyether base oil of the present embodiment comprises the following steps:

[0058] (1) Under the condition of stirring, a raw material mixed system comprising 200 g of A-containing compound (ethylene oxide EO: propylene oxide PO = 4:5, Mn = 546), 60.8 g of succinic acid (the mass ratio of A-containing compound and dibasic acid compound is 1:1.4) and 0.8 g of Lewis acid catalyst stannous chloride is added into a 500 mL four-necked flask, and then the temperature is raised to 185 °C for 9 hours, followed by vacuum distillation at 195 °C, and finally the catalyst is removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE1 (Mn = 3672).

[0059] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE1, 7.2 g of 5-amino benzimidazole and 5.6 g of 2-amino-1,3,4-thiadiazole are added into a 500 mL reactor with stirring and temperature control device, and then the stirring is started, the temperature is raised to 113 °C, and after one hour of stirring, the temperature is gradually raised to 150 °C at a speed of 10 °C / h, and nitrogen gas stripping is carried out for 6 hours to obtain a polyether ester PEEA1.

[0060] Example 2

[0061] The preparation method of the polyether base oil of the present embodiment comprises the following steps:

[0062] (1) Under the condition of stirring, a raw material mixed system comprising 200 g of A-containing compound (ethylene oxide EO: propylene oxide PO = 4:5, Mn = 546), 60.8 g of succinic acid (the mass ratio of A-containing compound and dibasic acid compound is 1:1.4) and 0.8 g of Lewis acid catalyst stannous chloride is added into a 500 mL four-necked flask, and then the temperature is raised to 185 °C for 9 hours, followed by vacuum distillation at 195 °C, and finally the catalyst is removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE1 (Mn = 3672).

[0063] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE1, 7.2 g of 5- aminobenzimidazole, and 10 g of 4,4'-diaminodiphenylmethane were added to a 500 mL reactor equipped with a stirrer and a temperature controller, and stirring was started. The temperature was raised to 113°C, and after one hour of stirring, the temperature was gradually raised to 150°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 6 hours to obtain a polyether ester PEEA3.

[0064] Example 3

[0065] The method for preparing the polyether base oil of this example includes the following steps:

[0066] (1) A raw material mixture system including 200 g of an A-containing compound (EO:PO = 4:5, Mn = 546), 60.8 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound was 1:1.4), and 0.8 g of a Lewis acid catalyst, stannous chloride, was added to a 500 mL four-necked flask under stirring, and the temperature was raised to 185°C for 9 hours of reaction, followed by distillation under reduced pressure at 195°C, and finally, the catalyst was removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE1 (Mn = 3672).

[0067] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE1, 7.2 g of 5- aminobenzimidazole, and 10.8 g of 4,4'-diaminodiphenylmethane were added to a 500 mL reactor equipped with a stirrer and a temperature controller, and stirring was started. The temperature was raised to 113°C, and after one hour of stirring, the temperature was gradually raised to 150°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 6 hours to obtain a polyether ester PEEA3.

[0068] Example 4

[0069] The method for preparing the polyether base oil of this example includes the following steps:

[0070] (1) A raw material mixture system including 200 g of an A-containing compound (EO:PO = 4:4, Mn = 498), 67.4 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound was 1:1.4), and 0.8 g of a Lewis acid catalyst, stannous chloride, was added to a 500 mL four-necked flask under stirring, and the temperature was raised to 185°C for 9 hours of reaction, followed by distillation under reduced pressure at 195°C, and finally, the catalyst was removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE2 (Mn = 3656).

[0071] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE2, 5.4 g of 2-amino-1,3,4-thiadiazole, and 9.8 g of 4-aminodiphenylamine were added to a 500 mL reactor equipped with a stirrer and a temperature controller, and stirring was started. The temperature was raised to 115°C, and after one hour of stirring, the temperature was gradually raised to 155°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 6 hours to obtain the polyether ester PEEA4.

[0072] Example 5

[0073] The preparation method of the polyether base oil of the present example includes the following steps:

[0074] (1) A raw material mixture system including 200 g of an A-containing compound (EO:PO = 4:4, Mn = 498), 67.4 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound was 1:1.4), and 0.8 g of a Lewis acid catalyst, stannous chloride, was added to a 500 mL four-necked flask under stirring, and the temperature was raised to 185°C for 9 hours of reaction, followed by distillation under reduced pressure at 195°C, and finally, the catalyst was removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE2 (Mn = 3656).

[0075] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE2, 5.4 g of 2-amino-1,3,4-thiadiazole, and 9.8 g of 4-aminodiphenylamine were added to a 500 mL reactor equipped with a stirrer and a temperature controller, and stirring was started. The temperature was raised to 115°C, and after one hour of stirring, the temperature was gradually raised to 155°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 6 hours to obtain the polyether ester PEEA4.

[0076] Example 6

[0077] The preparation method of the polyether base oil of the present example includes the following steps:

[0078] (1) A raw material mixture system including 200 g of an A-containing compound (EO:PO = 4:4, Mn = 498), 67.4 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound was 1:1.4), and 0.8 g of a Lewis acid catalyst, stannous chloride, was added to a 500 mL four-necked flask under stirring, and the temperature was raised to 185°C for 9 hours of reaction, followed by distillation under reduced pressure at 195°C, and finally, the catalyst was removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE2 (Mn = 3656).

[0079] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE2, 10.5 g of 4,4'-diaminodiphenyl methane, and 9.8 g of 4-aminodiphenylamine were added to a 500 mL reactor equipped with a stirrer and a temperature control device, and stirring was started. The temperature was raised to 115°C, and after one hour of stirring, the temperature was gradually raised to 155°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 6 hours to obtain the polyether ester PEEA6.

[0080] Example 7

[0081] The method for preparing the polyether base oil of this example includes the following steps:

[0082] (1) A raw material mixture system including 200 g of an A-containing compound (EO:PO = 3:5, Mn = 512), 67.2 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound was 1:1.5), and 0.8 g of a Lewis acid catalyst, stannous chloride, was added to a 500 mL four-necked flask under stirring, and the temperature was raised to 185°C for 9 hours of reaction, followed by distillation under reduced pressure at 195°C, and finally, the catalyst was removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0083] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE3, 15.5 g of 5-amino benzimidazole was added to a 500 mL reactor equipped with a stirrer and a temperature control device, and stirring was started. The temperature was raised to 120°C, and after one hour of stirring, the temperature was gradually raised to 160°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 5 hours to obtain the polyether ester PEEA7.

[0084] Example 8

[0085] The method for preparing the polyether base oil of this example includes the following steps:

[0086] (1) A raw material mixture system including 200 g of an A-containing compound (EO:PO = 3:5, Mn = 512), 67.2 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound was 1:1.5), and 0.8 g of a Lewis acid catalyst, stannous chloride, was added to a 500 mL four-necked flask under stirring, and the temperature was raised to 185°C for 9 hours of reaction, followed by distillation under reduced pressure at 195°C, and finally, the catalyst was removed by filtration to obtain an intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0087] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE3, 11.8 g of 2-amino-1,3,4-thiadiazole was added to a 500 mL reactor equipped with a stirrer and a temperature control device, and stirring was started. The temperature was raised to 120°C, and after one hour of stirring, the temperature was gradually raised to 160°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 5 hours to obtain the polyether ester PEEA8.

[0088] Example 9

[0089] The method for preparing the polyether base oil of this example includes the following steps:

[0090] (1) A raw material mixture system including 200 g of the A-containing compound (EO:PO = 3:5, Mn = 512), 67.2 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound is 1:1.5), and 0.8 g of the Lewis acid catalyst stannous chloride was added to a 500 mL four-necked flask under stirring, warmed to 185°C for 9 hours, then subjected to reduced-pressure distillation at 195°C, and finally filtered to remove the catalyst, thereby obtaining an intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0091] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE3 and 23.1 g of 4,4'-diaminodiphenylmethane were added to a 500 mL reactor equipped with a stirrer and a temperature controller, the stirring was started, and the temperature was raised to 120°C. After one hour of stirring, the temperature was gradually raised to 160°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 5 hours, thereby obtaining a polyether ester PEEA9.

[0092] Example 10

[0093] The method for preparing the polyether base oil of this example includes the following steps:

[0094] (1) A raw material mixture system including 200 g of the A-containing compound (EO:PO = 3:5, Mn = 512), 67.2 g of succinic acid (the amount-of-substance ratio of the A-containing compound and the dibasic acid compound is 1:1.5), and 0.8 g of the Lewis acid catalyst stannous chloride was added to a 500 mL four-necked flask under stirring, warmed to 185°C for 9 hours, then subjected to reduced-pressure distillation at 195°C, and finally filtered to remove the catalyst, thereby obtaining an intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0095] (2) 200 g of the intermediate carboxyl-terminated polyether ester PEE3 and 21.4 g of 4-aminodiphenylamine were added to a 500 mL reactor equipped with a stirrer and a temperature controller, the stirring was started, and the temperature was raised to 120°C. After one hour of stirring, the temperature was gradually raised to 160°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 5 hours, thereby obtaining a polyether ester PEEA10.

[0096] Comparative Example 1

[0097] A commercially available product PAG460 (wherein m = 31, n = 38, Mn = 3554), the structural formula of which is as follows:

[0098]

[0099] Comparative Example 2

[0100] The preparation method of the polyether base oil of the present embodiment includes the following steps:

[0101] (1) A raw material mixture system including 200 g of A-containing compound (EO:PO = 4:4, Mn = 498), 85.5 g of adipic acid (the amount-of-substance ratio of A-containing compound and dibasic acid compound is 1:1.4), and 0.8 g of Lewis acid catalyst stannous chloride was added to a 500 mL four-necked flask under stirring, warmed to 185°C for 9 hours, then subjected to reduced-pressure distillation at 195°C, and finally filtered to remove the catalyst to obtain intermediate carboxyl-terminated polyether ester PEE5 (Mn = 3662).

[0102] (2) 200 g of intermediate carboxyl-terminated polyether ester PEE5, 5.4 g of 2-amino-1,3,4-thiadiazole, and 10.5 g of 4,4'-diaminodiphenylmethane were added to a 500 mL reactor equipped with a stirring and temperature control device, the stirring was started, and the temperature was raised to 115°C. After stirring for one hour, the temperature was gradually raised to 155°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 6 hours to obtain polyether ester PEEA11.

[0103] Comparative Example 3

[0104] The preparation method of the polyether base oil of the present embodiment includes the following steps:

[0105] (1) A raw material mixture system including 200 g of A-containing compound (EO:PO = 4:4, Mn = 498), 85.5 g of adipic acid (the amount-of-substance ratio of A-containing compound and dibasic acid compound is 1:1.4), and 0.8 g of Lewis acid catalyst stannous chloride was added to a 500 mL four-necked flask under stirring, warmed to 185°C for 9 hours, then subjected to reduced-pressure distillation at 195°C, and finally filtered to remove the catalyst to obtain intermediate carboxyl-terminated polyether ester PEE5 (Mn = 3662).

[0106] (2) 200 g of intermediate carboxyl-terminated polyether ester PEE5, 5.4 g of 2-amino-1,3,4-thiadiazole, and 10.5 g of 4,4'-diaminodiphenylmethane were added to a 500 mL reactor equipped with a stirring and temperature control device, the stirring was started, and the temperature was raised to 115°C. After stirring for one hour, the temperature was gradually raised to 155°C at a rate of 10°C / h, and nitrogen gas stripping was performed for 6 hours to obtain polyether ester PEEA11.

[0107] Test Example

[0108] 1. The polyether base oils prepared in the above examples and comparative examples were subjected to various physical and chemical property evaluations, and the results are shown in Table 1.

[0109] Table 1. Physical and chemical property evaluations of examples and comparative examples

[0110]

[0111] From Table 1, it can be seen that:

[0112] Compared with the comparative example, the polyether base oil of the present application has higher viscosity index, lower pour point and less evaporation loss.

[0113] 2. The polyether base oils prepared in the above examples and comparative example were subjected to oxidation resistance evaluation. The oxidation resistance was evaluated according to SH / T0193-1992 rotating pressure vessel oxidation test method (RPVOT). The longer the RPVOT time, the better the oxidation resistance. The high temperature oxidation resistance was evaluated according to SH / T 0719 high pressure differential scanning calorimetry (PDSC). The higher the PDSC initial oxidation temperature, the better the high temperature oxidation resistance. The results are shown in Table 2.

[0114] 3. The polyether base oils prepared in the above examples and comparative example were subjected to rust prevention evaluation. The evaluation was carried out by standard method GB / T1114 liquid phase rusting (synthetic seawater). The rusting was mainly divided into no rust, light rust, medium rust and heavy rust. The results are shown in Table 2.

[0115] 4. The polyether base oils prepared in the above examples and comparative example were subjected to friction property evaluation.

[0116] (1) Four-ball friction machine test

[0117] The maximum non-seizure load (PB value) of the examples and comparative example was determined according to the method of GB / T 3142-1982 "Lubricant load capacity determination method (four-ball method)". The results are shown in Table 2.

[0118] (2) SRV friction and wear test

[0119] The SRV4 high frequency reciprocating linear vibration tester produced by OPTIMOL Company in Germany was used to determine the wear scar diameter of the oil test piece according to the industry standard NB / SH / T 0847 "Extreme pressure lubricating oil friction and wear determination SRV tester method". The wear scar diameter and average friction coefficient were measured under constant conditions using face-to-face contact upper and lower test piece copper discs. The test conditions were: load 250N, frequency 50Hz, time 2h, temperature 80℃, stroke 1mm. The results are shown in Table 2.

[0120] Table 2 Performance evaluation of examples and comparative example

[0121]

[0122] From Table 2, it can be seen that:

[0123] Compared with the comparative example, the polyether base oil of the present application has better oxidation resistance, rust prevention performance and anti-wear and friction reduction performance.

[0124] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions recorded in the above embodiments can be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A polyether base oil, characterized in that, Its structural formula is as shown in Formula 1. In Formula 1, x is 1 to 10; A is an epoxy copolymer of C5 or less; R is selected from C1 to C5 alkylene or alkenylene groups; R1 and R2 are each independently selected from straight-chain terminal amino compounds, or cyclic groups with substituted or unsubstituted cyclic atoms having a number of not less than 5; 2. The polyether base oil according to claim 1, characterized in that, The structural formula of A is shown in Formula 2, where m is 1 to 12 and n is 1 to 10.

3. The polyether base oil according to claim 1 or 2, characterized in that, The R is selected from at least one of -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, and -CH=CH-.

4. The polyether base oil according to any one of claims 1-3, characterized in that, The polyether base oil is prepared by a method comprising the following steps: reacting a raw material mixture containing compound A, a dicarboxylic acid compound and a Lewis acid catalyst for a certain period of time, followed by vacuum distillation, and reacting the resulting intermediate carboxylated polyether ester with an amine compound to obtain the polyether base oil.

5. The polyether base oil according to claim 4, characterized in that, The amine compounds include polyethylenepolyamine, m-phenylenediamine, o-phenylenediamine, 2,6-diaminotoluene, aniline, 2-(4-aminophenyl)-5-aminobenzimidazole, p-toluidine, aminoquinoline, diaminoquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2,3-dihydroisoindole-1-one, diphenylmethylamine, triphenylmethylamine, 3-tert-butylaniline, 4-tert-butylaniline, 4-octylaniline, 2,4-dimethylaniline, 4,4'-diaminodiphenylamine, 3-benzyloxyaniline, 3,3'-diaminobenzidine, 3,5-ditert-butylaniline, 4-amino-N,N-dimethylaniline, 4-aminodiphenylamine, and 4,4'-diaminodiphenylamine. The polyethylene polyamine comprises at least one of the following: alkyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-diphenylethylamine, 4-aminodiphenylamine, aminoimidazole, 1,2-diaminoimidazole, imidazolinamide, 5-aminobenzimidazole, 5-methyl-6-aminobenzimidazole one, 1-(2-aminoethyl)imidazolin-2-one, aminothiadiazole, 2-aminothiadiazole, 2-amino-1,3,4-thiadiazole, 5-aminothiadiazole, 1,3,4-thiadiazole-2-ylmethylamine, 5-chloro-1,2,4-thiadiazole-3-amine, and 1,2,5-thiadiazole-3-amine, wherein the polyethylene polyamine comprises at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heavy polyamines.

6. A method for preparing the polyether base oil according to any one of claims 1-5, characterized in that, Includes the following steps: (1) A raw material mixture including compound A, dicarboxylic acid compound and Lewis acid catalyst is reacted at 180-240°C for 8-12 hours, and then subjected to vacuum distillation at 100-240°C to obtain intermediate carboxylated polyether ester. (2) The intermediate carboxylated polyether ester is mixed with an amine compound at 100-130°C, and the temperature is gradually increased to 140-180°C. Nitrogen gas is then introduced for 3-6 hours to obtain the polyether base oil.

7. The preparation method according to claim 6, characterized in that, The dicarboxylic acid compound includes at least one selected from malonic acid, succinic acid, glutaric acid, and maleic acid; and / or, The Lewis acid catalyst comprises at least one of stannous chloride, tetrabutyl titanate, and antimony trioxide; and / or, The amine compounds include polyethylenepolyamine, m-phenylenediamine, o-phenylenediamine, 2,6-diaminotoluene, aniline, 2-(4-aminophenyl)-5-aminobenzimidazole, p-toluidine, aminoquinoline, diaminoquinoline, 2-amino-8-hydroxyquinoline, 7-amino-4-methyl-2-quinolinone, 5-amino-2,3-dihydroisoindole-1-one, diphenylmethylamine, triphenylmethylamine, 3-tert-butylaniline, 4-tert-butylaniline, 4-octylaniline, 2,4-dimethylaniline, 4,4'-diaminodiphenylamine, 3-benzyloxyaniline, 3,3'-diaminobenzidine, 3,5-ditert-butylaniline, 4-amino-N,N-dimethylaniline, 4-aminodiphenylamine, and 4,4'-diaminodiphenylamine. The polyethylene polyamine comprises at least one of the following: alkyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-diphenylethylamine, 4-aminodiphenylamine, aminoimidazole, 1,2-diaminoimidazole, imidazolinamide, 5-aminobenzimidazole, 5-methyl-6-aminobenzimidazole one, 1-(2-aminoethyl)imidazolin-2-one, aminothiadiazole, 2-aminothiadiazole, 2-amino-1,3,4-thiadiazole, 5-aminothiadiazole, 1,3,4-thiadiazole-2-ylmethylamine, 5-chloro-1,2,4-thiadiazole-3-amine, and 1,2,5-thiadiazole-3-amine, wherein the polyethylene polyamine comprises at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heavy polyamines.

8. The preparation method according to claim 6 or 7, characterized in that, The molar ratio of the A-containing compound to the dicarboxylic acid compound is 1:1 to 2.

5.

9. The preparation method according to any one of claims 6-8, characterized in that, The Lewis acid catalyst has a mass percentage of 0.1% to 1% in the raw material mixture.

10. The preparation method according to any one of claims 6-9, characterized in that, The molar ratio of the intermediate carboxylated polyether ester to the amine compound is 1:2 to 2.

3.

11. A functional agent, characterized in that, This includes the polyether base oil according to any one of claims 1-5 or the polyether base oil prepared by the preparation method according to any one of claims 6-10.

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