A polyether base oil, a method for preparing the same, and an application thereof

Abstract

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

Description

Technical Field

[0001] This invention belongs to the field of lubricating oil technology, and particularly relates to a polyether base oil, its preparation method, and its application. Background Technology

[0002] Lubricating oil is an essential component of mechanical operation, playing a crucial role in reducing frictional energy loss, improving momentum transfer efficiency, and extending the service life of machinery. Lubricating oil generally consists of two parts: base oil and additives. Base oil is the main component, determining the basic properties of the lubricating oil. Polyether base oil is a linear polymer obtained by ring-opening homopolymerization and copolymerization of raw materials such as ethylene oxide, propylene oxide, and butane oxide under the action of a catalyst. It is widely used in the lubricating oil field due to its advantages such as viscosity-temperature properties, low-temperature fluidity, lubricity, non-corrosiveness, non-toxicity, and structural designability.

[0003] However, polyether base oils exhibit poor stability at high temperatures. In practical applications, functional additives such as extreme pressure anti-wear agents, rust inhibitors, antioxidants, and metal deactivators are typically added to enhance performance. However, the strong polarity of the polyether structure leads to competitive adsorption between the polyether and additives on metal surfaces, making it difficult for the additives to form an adsorption film. This results in poor rust prevention and extreme pressure anti-wear performance of the oil. Furthermore, functional additives in lubricating oils are generally oil-soluble and do not dissolve well in water-soluble polyethers, easily precipitating and affecting product performance, thus limiting their application. To address these issues, a common strategy is to blend polyether base oils with other base oils, such as polyalphaolefins or synthetic esters, to improve the oil's compatibility and sensitivity to additives. However, while this method improves oil performance to some extent, it also introduces other disadvantages, such as increased costs and increased process complexity.

[0004] Therefore, modifying the structure of polyethers is an important way to improve the performance of polyether base oils. For example, block polymerization and post-treatment end-capping can improve the oxidation resistance, anti-wear and friction reduction properties of polyether base oils. However, existing technologies can only improve one aspect of performance and cannot achieve a balance between various properties, which to some extent limits the improvement of the overall performance of polyether base oils.

[0005] Therefore, the invention of a polyether base oil that simultaneously possesses high viscosity index, low pour point, strong rust prevention, strong oxidation resistance, and excellent anti-wear and friction-reducing properties overcomes the shortcomings of existing technologies and has significant application value. Summary of the Invention

[0006] This invention provides a polyether base oil with an amine-based double-terminated polyether ester structure, which has excellent viscosity-temperature properties, antioxidant properties, rust prevention properties, and anti-wear and friction-reducing properties.

[0007] This invention provides a method for preparing polyether base oil, which has excellent viscosity-temperature properties, antioxidant properties, rust prevention properties, and anti-wear and friction-reducing properties.

[0008] The present invention provides a functional agent comprising the above-mentioned polyether base oil. Therefore, the functional agent has excellent viscosity-temperature properties, antioxidant properties, rust prevention properties, and anti-wear and friction-reducing properties.

[0009] This invention provides a polyether base oil with the structural formula shown in Formula 1.

[0010] 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;

[0011] 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;

[0012]

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

[0014]

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

[0016] The polyether base oil described above 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.

[0017] The polyether base oils described above, wherein 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-dihydroisoindol-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-di-tert-butylaniline, 4-amino-N,N-dimethylaniline, 4-aminodiphenylamine, 4,4'- At least one of 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.

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

[0019] (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.

[0020] (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.

[0021] The preparation method described above, wherein the dicarboxylic acid compound includes at least one selected from malonic acid, succinic acid, glutaric acid, and maleic acid; and / or,

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

[0023] 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.

[0024] In the preparation method described above, the molar ratio of the A-containing compound to the dicarboxylic acid compound is 1:1 to 2.5.

[0025] In the preparation method described above, the Lewis acid catalyst has a mass percentage content of 0.1% to 1% in the raw material mixture system.

[0026] In the preparation method described above, the molar ratio of the intermediate terminal carboxylated polyether ester to the amine compound is 1:2 to 2.3.

[0027] The present invention also provides a functional agent, comprising the polyether base oil as described above or the polyether base oil prepared by the preparation method described above.

[0028] This invention provides a polyether base oil produced via melt polycondensation. The polyether base oil is introduced into the molecular structure by incorporating diester groups (-COO-R-COO-) from the hydroxyl groups at both ends of a polyepoxide alkane, forming a polyether ester molecular chain with alternating ether and diester bonds. Then, the carboxyl groups at the molecular chain ends undergo a capping reaction with amine compounds, yielding a unique amine-terminated polyether ester structure. This method is simple to operate, allows for precise control of reaction conditions, reduces solvent usage, and produces fewer byproducts, thereby obtaining a high-purity polyether base oil and reducing waste emissions during production, in line with the principles of green chemistry.

[0029] The amine groups at the end of the polyether base oil can react with free radicals, reducing their generation and thus inhibiting oil oxidation. Furthermore, these amine groups exhibit excellent alkali retention, neutralizing acidic substances generated during oil use and adsorbing deposits. Nitrogen and sulfur atoms on cyclic amine compounds such as thiadiazole and imidazole can form coordination bonds with metal surfaces, enhancing the adhesion, stability, and density of the protective film, resulting in excellent anti-wear and anti-corrosion properties. Moreover, the ester bonds in the molecular structure possess good thermal stability, and the synergistic effect of alternating ether and ester bonds allows it to maintain structural and performance stability at higher temperatures. In summary, the polyether base oil of this invention possesses high viscosity index, low pour point, antioxidant properties, rust prevention properties, and anti-wear and friction-reducing properties. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the specific synthesis reaction of the preparation method of the present invention. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0032] The first aspect of the present invention provides a polyether base oil with the structural formula of Formula 1, wherein 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; and R1 and R2 are each independently selected from linear terminal amino compounds, or cyclic groups with a number of cyclic atoms of not less than 5, whether substituted or unsubstituted.

[0033]

[0034] The polyether base oil of this invention is used to manufacture lubricating oil. Specifically, lubricating oil generally consists of two parts: base oil and additives. The base oil is the main component of the lubricating oil and determines its basic properties.

[0035] The polyether base oil of this invention exhibits high viscosity index, low pour point, strong rust prevention, strong oxidation resistance, and excellent anti-wear and friction-reducing properties, thereby improving the overall performance of the oil. This is presumably because the amine groups at the end of the polyether base oil possess excellent alkali retention properties, neutralizing acidic substances generated during oil use and adsorbing deposits in the oil. Furthermore, the amine groups at the end of the polyether base oil can react with free radicals, reducing free radical generation and thus inhibiting the oil oxidation process. The nitrogen and sulfur atoms on cyclic amine compounds such as thiadiazole and imidazole can form coordination bonds with the metal surface, enhancing the adhesion, stability, and density between the protective film and the metal surface, resulting in excellent anti-wear and anti-corrosion properties. Moreover, the ester bonds in the molecular structure have good thermal stability, and the synergistic effect of the alternating distribution of ether and ester bonds allows it to maintain structural and performance stability at higher temperatures.

[0036] Therefore, because the polyether base oil of the present invention has a unique amine-based double-terminated polyether ester structure, it has high viscosity index, low pour point, strong rust prevention, strong oxidation resistance, and anti-wear and friction-reducing properties.

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

[0038]

[0039] As a preferred option, it can further improve the viscosity-temperature properties, antioxidant properties, rust prevention properties, and anti-wear and friction-reducing properties of polyether base oils.

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

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

[0042] Further, 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-dihydroisoindol-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'-diamino At least one of diphenylmethane, 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.

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

[0044] (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.

[0045] (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.

[0046] Specifically, in step (1), a raw material mixture including compound A, dicarboxylic acid compound and Lewis acid catalyst is added to a reactor equipped with a stirring and temperature control device, stirring is started, the temperature is raised to 180-240℃ and reacted for 8-12 hours, and then vacuum distillation is carried out at 100-240℃ to obtain intermediate carboxylated 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] A third aspect of the present invention provides a functional agent, including but not limited to internal combustion engine oil, gear oil, metalworking fluid, compressor oil, and refrigeration oil. The functional agent comprises a polyether base oil prepared by the above-mentioned polyether base oil or the polyether base oil prepared by the above-mentioned preparation method as the base oil. Therefore, the functional agent has excellent viscosity-temperature properties, antioxidant properties, rust prevention properties, and anti-wear and friction-reducing properties, thereby effectively reducing mechanical wear, mitigating mechanical friction energy loss, and increasing mechanical service life.

[0055] The polyether base oil of the present invention will be described in detail below through specific embodiments.

[0056] Example 1

[0057] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0058] (1) Under stirring conditions, a raw material mixture including 200g of compound A (ethylene oxide EO: propylene oxide PO = 4:5, Mn = 546), 60.8g of succinic acid (the molar ratio of compound A and dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE1 (Mn = 3672).

[0059] (2) 200g of intermediate carboxylated polyether ester PEE1, 7.2g of 5-aminobenzimidazole and 5.6g of 2-amino-1,3,4-thiadiazole were added to a 500mL reactor equipped with a stirring and temperature control device. The stirring was started and the temperature was raised to 113℃. After stirring for one hour, the temperature was gradually raised to 150℃ at a rate of 10℃ / h. Nitrogen gas was introduced for stripping for 6 hours to obtain polyether ester PEEA1.

[0060] Example 2

[0061] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0062] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 4:5, Mn = 546), 60.8g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE1 (Mn = 3672).

[0063] (2) Add 200g of intermediate carboxylated polyether ester PEE1, 7.2g of 5-aminobenzimidazole and 10g of 4-aminodiphenylamine to a 500mL reactor equipped with a stirring and temperature control device, start stirring, raise the temperature to 113℃, stir for one hour, gradually raise the temperature to 150℃ at a rate of 10℃ / h, and purge with nitrogen gas for 6 hours to obtain polyether ester PEEA2.

[0064] Example 3

[0065] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0066] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 4:5, Mn = 546), 60.8g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE1 (Mn = 3672).

[0067] (2) 200g of intermediate carboxylated polyether ester PEE1, 7.2g of 5-aminobenzimidazole and 10.8g of 4,4'-diaminodiphenylmethane were added to a 500mL reactor equipped with a stirring and temperature control device. The stirring was started and the temperature was raised to 113℃. After stirring for one hour, the temperature was gradually raised to 150℃ at a rate of 10℃ / h. Nitrogen gas was introduced for stripping for 6 hours to obtain polyether ester PEEA3.

[0068] Example 4

[0069] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0070] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 4:4, Mn = 498), 67.4g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE2 (Mn = 3656).

[0071] (2) 200g of intermediate carboxylated polyether ester PEE2, 5.4g of 2-amino-1,3,4-thiadiazole and 9.8g of 4-aminodiphenylamine were added to a 500mL reactor equipped with a stirring and temperature control device. The stirring was started and the temperature was raised to 115℃. After stirring for one hour, the temperature was gradually raised to 155℃ at a rate of 10℃ / h. Nitrogen gas was introduced for stripping for 6 hours to obtain polyether ester PEEA4.

[0072] Example 5

[0073] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0074] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 4:4, Mn = 498), 67.4g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE2 (Mn = 3656).

[0075] (2) 200g of intermediate carboxylated polyether ester PEE2, 5.4g of 2-amino-1,3,4-thiadiazole and 10.5g of 4,4'-diaminodiphenylmethane were added to a 500mL reactor equipped with a stirring and temperature control device. The stirring was started and the temperature was raised to 115℃. After stirring for one hour, the temperature was gradually raised to 155℃ at a rate of 10℃ / h. Nitrogen gas was introduced for stripping for 6 hours to obtain polyether ester PEEA5.

[0076] Example 6

[0077] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0078] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 4:4, Mn = 498), 67.4g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE2 (Mn = 3656).

[0079] (2) 200g of intermediate carboxylated polyether ester PEE2, 10.5g of 4,4'-diaminodiphenylmethane and 9.8g of 4-aminodiphenylamine were added to a 500mL reactor equipped with a stirring and temperature control device. The stirring was started and the temperature was raised to 115℃. After stirring for one hour, the temperature was gradually raised to 155℃ at a rate of 10℃ / h. Nitrogen gas was introduced for stripping for 6 hours to obtain polyether ester PEEA6.

[0080] Example 7

[0081] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0082] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 3:5, Mn = 512), 67.2g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.5) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain the intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0083] (2) Add 200g of intermediate carboxylated polyether ester PEE3 and 15.5g of 5-aminobenzimidazole to a 500mL reactor equipped with a stirring and temperature control device, start stirring, raise the temperature to 120℃, stir for one hour, gradually raise the temperature to 160℃ at a rate of 10℃ / h, and purge with nitrogen gas for 5 hours to obtain polyether ester PEEA7.

[0084] Example 8

[0085] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0086] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 3:5, Mn = 512), 67.2g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.5) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain the intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0087] (2) Add 200g of intermediate carboxylated polyether ester PEE3 and 11.8g of 2-amino-1,3,4-thiadiazole to a 500mL reactor equipped with a stirring and temperature control device. Start stirring and heat to 120℃. After stirring for one hour, gradually increase the temperature to 160℃ at a rate of 10℃ / h. Purge with nitrogen gas for 5 hours to obtain polyether ester PEEA8.

[0088] Example 9

[0089] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0090] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 3:5, Mn = 512), 67.2g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.5) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain the intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0091] (2) Add 200g of intermediate carboxylated polyether ester PEE3 and 23.1g of 4,4'-diaminodiphenylmethane to a 500mL reactor equipped with a stirring and temperature control device. Start stirring and heat to 120℃. After stirring for one hour, gradually increase the temperature to 160℃ at a rate of 10℃ / h. Purge with nitrogen gas for 5 hours to obtain polyether ester PEEA9.

[0092] Example 10

[0093] The preparation method of the polyether base oil in this embodiment includes the following steps:

[0094] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 3:5, Mn = 512), 67.2g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.5) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain the intermediate carboxyl-terminated polyether ester PEE3 (Mn = 3436).

[0095] (2) Add 200g of intermediate carboxylated polyether ester PEE3 and 21.4g of 4-aminodiphenylamine to a 500mL reactor equipped with a stirring and temperature control device, start stirring, raise the temperature to 120℃, stir for one hour, gradually raise the temperature to 160℃ at a rate of 10℃ / h, and purge with nitrogen gas for 5 hours to obtain polyether ester PEEA10.

[0096] Comparative Example 1

[0097] The commercially available product PAG460 (where m = 31, n = 38, Mn = 3554) has the following structural formula:

[0098]

[0099] Comparative Example 2

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

[0101] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 4:4, Mn = 498), 85.5g of adipic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE5 (Mn = 3662).

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

[0103] Comparative Example 3

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

[0105] (1) Under stirring conditions, a raw material mixture including 200g of compound A (EO:PO = 4:4, Mn = 498), 67.4g of succinic acid (the molar ratio of compound A to dicarboxylic acid compound is 1:1.4) and 0.8g of Lewis acid catalyst stannous chloride was added to a 500mL four-necked flask, heated to 185℃ and reacted for 9 hours, then distilled under reduced pressure at 195℃, and finally filtered to remove the catalyst to obtain intermediate carboxylated polyether ester PEE2 (Mn = 3656).

[0106] (2) Add 200g of intermediate carboxylated polyether ester PEE2 and 18.5g of diphenylamine to a 500mL reactor equipped with a stirring and temperature control device, start stirring, raise the temperature to 115℃, stir for one hour, gradually raise the temperature to 155℃ at a rate of 10℃ / h, and purge with nitrogen for 6 hours to obtain polyether ester PEEA12.

[0107] Test case

[0108] 1. The physicochemical properties of the polyether base oils prepared in the above examples and comparative examples were evaluated, and the results are shown in Table 1.

[0109] Table 1. Evaluation of physicochemical properties of the examples and comparative examples.

[0110]

[0111] As shown in Table 1:

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

[0113] 2. The antioxidant properties of the polyether base oils prepared in the above examples and comparative examples were evaluated. The antioxidant performance was evaluated according to the Rotating Bomb Oxygen Test (RPVOT) method of SH / T0193-1992. The longer the RPVOT time, the better the antioxidant performance. The high-temperature antioxidant performance was evaluated according to the High Pressure Differential Scanning Calorimetry (PDSC) method of SH / T 0719. The higher the PDSC initial oxidation temperature, the better the high-temperature oxidation resistance. The results are shown in Table 2.

[0114] 3. The rust prevention properties of the polyether base oils prepared in the above examples and comparative examples were evaluated using the standard method GB / T1114 liquid phase corrosion (synthetic seawater). The evaluation was mainly divided into no rust, light rust, medium rust, and heavy rust. The results are shown in Table 2.

[0115] 4. The tribological properties of the polyether base oils prepared in the above examples and comparative examples were evaluated;

[0116] (1) Four-ball friction test

[0117] The maximum non-seize load (PB value) of the examples and comparative examples was determined according to the method of GB / T 3142-1982 "Determination of Lubricant Load Capacity (Four-Ball Method)", and the results are shown in Table 2.

[0118] (2) SRV friction and wear test

[0119] The SRV4 high-frequency reciprocating linear vibration testing machine manufactured by OPTIMOL GmbH, Germany, was used to determine the wear scar diameter of the oil test pieces according to the industry standard NB / SH / T 0847 "Extreme Pressure Lubricating Oil Friction and Wear Determination SRV Testing Machine Method". The wear scar diameter and average friction coefficient were measured under constant conditions using copper discs of upper and lower test pieces in surface-to-surface contact. The test conditions were: load 250N, frequency 50Hz, time 2h, temperature 80℃, and stroke 1mm. The results are shown in Table 2.

[0120] Table 2 Performance Evaluation of Examples and Comparative Examples

[0121]

[0122] As shown in Table 2:

[0123] Compared with the comparative example, the polyether base oil of the present invention has better antioxidant properties, rust prevention properties, and anti-wear and friction reduction properties.

[0124] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

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; Formula 1 The structural formula of A is shown in Formula 2, where m is 1~12 and n is 1~10. Equation 2.

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

3. The polyether base oil according to claim 1, 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.

4. The polyether base oil according to claim 3, 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, 4,4 The polyethylene polyamine comprises at least one of '-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-amino-1,3,4-thiadiazole, 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.

5. A method for preparing the polyether base oil according to any one of claims 1-4, 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℃ for 8~12 hours, and then subjected to vacuum distillation at 100~240℃ 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.

6. The preparation method according to claim 5, 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, 4,4 The polyethylene polyamine comprises at least one of '-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-amino-1,3,4-thiadiazole, 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.

7. The preparation method according to claim 5, characterized in that, The molar ratio of the A-containing compound to the dicarboxylic acid compound is 1:1 to 2.

5.

8. The preparation method according to claim 5, characterized in that, The Lewis acid catalyst has a mass percentage of 0.1% to 1% in the raw material mixture.

9. The preparation method according to claim 5, characterized in that, The molar ratio of the intermediate carboxylated polyether ester to the amine compound is 1:2 to 2.

3.

10. A functional agent, characterized in that, This includes the polyether base oil according to any one of claims 1-4 or the polyether base oil prepared by the preparation method according to any one of claims 5-9.

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