Boronated fatty acid glyceride anti-wear additive and method for producing same

Abstract

The present invention provides a boronated fatty acid glyceride anti-wear additive and a method for producing the same, the composition of the anti-wear additive comprising a compound represented by formula (I), a compound represented by formula (II), and a compound represented by formula (III), [Formula 1] TIFF2025536108000013.tif41170 In formula (I), R1, R2 and R3 are the same or different and each independently represent a C3-C 24 and In formula (II), R is C3-C 24 R5 is selected from the hydrocarbon groups of C4-C 24 Alkyl groups, C6-C 18 and selected from the aryl groups In formula (III), R5 is C4-C 24 Alkyl groups, C6-C 18 R4 and R6 are the same or different and each independently represent an aryl group represented by the formula: [chemical 2] TIFF2025536108000014.tif33114 wherein R7 and R8 are the same or different and each independently represent a C3-C 24 The antiwear additive has excellent antiwear performance and good thermal stability, and does not adversely affect the corrosion performance of the lubricating oil.

Description

[Technical Field]

[0001] The present invention is in the field of lubricating oil additives and relates to boronated fatty acid glyceride anti-wear additives and methods for making the same. [Background technology]

[0002] As a new type of environmentally friendly lubricating oil additive, boron-based additives have attracted attention due to their unique chemical properties. Based on their chemical structure, boron-based additives can be divided into inorganic borates and organic borate esters. Borate ester additives not only have excellent thermo-oxidation stability and seal compatibility, but also no corrosion effect on copper at high temperatures, good rust prevention performance for steel, and are beneficial for improving the working environment. They also have excellent load-carrying capacity and friction reduction / anti-wear performance, making them widely used in engine oils and industrial gear oils.

[0003] In recent years, the introduction of active elements such as N, S, and P into borate ester molecules has become a hot topic of research in order to improve the performance of borate ester lubricating oil additives. Currently, introducing a nitrogen atom into the molecular structure of a borate ester, so that the nitrogen atom and the boron atom form a BN coordinate bond, is an effective method for improving the hydrolysis stability of borate esters. Patents US4204972, US5084194, CN114605460, and CN100350025 all introduce amino-containing borate esters, which generally involve the direct reaction of a hydroxyl-containing long-chain amine with a boron acid to form an ester. These amino-containing borate esters often have excellent friction-reducing properties and high thermal oxidation stability. Sulfur-containing boric acid esters are reported in US Patents 4,394,277, 4,465,605, and 4,486,323, and are generally prepared by reacting an S-containing monohydroxy compound or polyhydroxy compound with boric acid to form an ester. US Patents 4,555,353, 4,536,306, 4,557,844, and 0,622,8818 each disclose boric acid ester compounds containing a phosphate ester structure. Although the above studies have improved the performance of borate ester additives in different ways, the introduction of some active elements has limited the use of additives to some extent. Developments in oil technology have put new requirements on additives. Engine oils have placed stricter restrictions on the S and P elements in additives. GF-6 engine oil requires that the S element be less than 0.5% and the P element be less than 0.08%. High-grade industrial gear oils are also concerned with additive odor, biodegradability, and whether they meet food-grade certification requirements. Developing low-sulfur, low-phosphorus, biodegradable borate ester additives is one idea to meet the needs of new oils.

[0004] Fatty acid glycerides have strong molecular control, good thermal stability of triglycerides, and contain ester bonds and adsorbing groups such as hydroxyl groups in the molecules of monoglycerides and diglycerides, resulting in good lubrication performance. Patents US4734211, US4764296, and CN105658779 disclose the use of borated oleic acid glycerides in engine oils. Patents US004507216 and US005006276 disclose the further reaction of hindered phenols and hydroxyl-containing esters with boron acid to produce mixed borate esters. Patent US5759965 discloses a method for producing boronated fatty acid glycerides using boron acid and fatty acid glycerides. The above patents primarily focus on the production of boronated fatty acid glycerides using boron acid as a boronating agent. Summary of the Invention [Problem to be solved by the invention]

[0005] In order to solve the above problems, the object of the present invention is to provide a boronated fatty acid glyceride anti-wear additive, a method for producing the same, and a lubricating oil, which has excellent anti-wear performance and good thermal stability, and does not adversely affect the corrosion performance of the lubricating oil. [Means for solving the problem]

[0006] To achieve the above object, the present invention provides a boronated fatty acid glyceride anti-wear additive, the composition comprising a compound represented by formula I, a compound represented by formula II, and a compound represented by formula III.

[0007] [ka]

[0008] In Formula I, R1, R2 and R3 are the same or different and each independently represent a C3-C 24 and

[0009] [ka]

[0010] In Formula II, R is C3-C 24 R5 is selected from the hydrocarbon groups of C4-C 24 Alkyl groups, C6-C 18 and selected from the aryl groups

[0011] [ka]

[0012] In Formula III, R5 is C4-C 24 Alkyl groups, C6-C 18 R4 and R6 are the same or different and each independently represent an aryl group represented by the formula:

[0013] [ka]

[0014] wherein R7 and R8 are the same or different and each independently represent a C3-C 24 The hydrocarbon group is selected from the group consisting of:

[0015] According to a specific embodiment of the present invention, preferably, the mass ratio of the compound represented by formula I, the compound represented by formula II, and the compound represented by formula III is (8-12):(46-52):(36-46).

[0016] The present invention further provides a method for producing the above boronated fatty acid glyceride anti-wear additive, comprising the steps of:

[0017] (1) Mix glycerin with a solid acid catalyst to obtain C4-C 25 the fatty acid is added dropwise to carry out an esterification reaction, and water is removed by introducing an inert gas to obtain a fatty acid glyceride mixture. (2) A boronating reagent and a solvent are mixed, the fatty acid glyceride mixture obtained in step (1) is added, water is removed using an inert gas, the mixture is heated to 60 to 150°C, and reacted for 3 to 8 hours to obtain the boronated fatty acid glyceride anti-wear additive, and the boronating reagent is an alkylboronic acid and / or an arylboronic acid.

[0018] According to a specific embodiment of the present invention, preferably, in step (1), glycerin and a solid acid catalyst are mixed to produce a C4-C 24 The fatty acid is added dropwise to carry out an esterification reaction, and water is removed by introducing an inert gas to obtain a fatty acid glyceride mixture.

[0019] According to a specific embodiment of the present invention, preferably, in step (1), the C4-C calculated from the carboxyl group and the hydroxyl group 25 The molar ratio of the fatty acid to glycerin is 1:3 to 2.5:3.

[0020] According to a specific embodiment of the present invention, preferably, in step (1), the C4-C calculated from the carboxyl group and the hydroxyl group 24 The molar ratio of the fatty acid to glycerin is 1:3 to 2.5:3.

[0021] According to a specific embodiment of the present invention, preferably, in step (1), the C4-C calculated from the carboxyl group and the hydroxyl group 25 The molar ratio of the fatty acid to glycerin is 1.1:3 to 1.8:3.

[0022] According to a specific embodiment of the present invention, preferably, in step (1), the C4-C calculated from the carboxyl group and the hydroxyl group 24 The molar ratio of the fatty acid to glycerin is 1.1:3 to 1.8:3.

[0023] According to a specific embodiment of the present invention, in step (1), the reaction temperature is preferably 80 to 160° C. and the reaction time is preferably 3 to 10 hours.

[0024] According to a specific embodiment of the present invention, in step (1), the solid acid catalyst preferably comprises one or a combination of two or more of Al2O3, Al2O3-SiO2, metal salts (e.g., sulfates, phosphates), molecular sieves ZSM-5, and MCM-41.

[0025] According to a specific embodiment of the present invention, preferably, in step (1), the amount of the solid acid catalyst added is 25 The amount is 0.05 wt% to 1.2 wt% of the total mass of the fatty acid and glycerin.

[0026] According to a specific embodiment of the present invention, preferably, in step (1), the amount of the solid acid catalyst added is 24 The amount is 0.05 wt% to 1.2 wt% of the total mass of the fatty acid and glycerin.

[0027] According to a specific embodiment of the present invention, in step (2), the boronating reagent preferably has a structure represented by formula IV:

[0028] [ka]

[0029] In Formula IV, R5 is C4-C 24 Alkyl groups, C6-C 18 The aryl group is selected from the group consisting of: According to a specific embodiment of the present invention, in step (2), the molar amount of the boronating reagent added is preferably [(3a-b) / 2] to (3a-b), where a is the molar amount of glycerin added, and b is the molar amount of C4-C 25 The molar amount of fatty acid added.

[0030] According to a specific embodiment of the present invention, in step (2), the molar amount of the boronating reagent added is preferably [(3a-b) / 2] to (3a-b), where a is the molar amount of glycerin added, and b is the molar amount of C4-C 24 The molar amount of fatty acid added.

[0031] According to a specific embodiment of the present invention, in step (2), the solvent is preferably one or a combination of two or more of petroleum ether, benzene, toluene, cyclohexane, n-heptane, n-octane, and xylene.

[0032] According to a specific embodiment of the present invention, in step (2), the amount of the solvent added is preferably 50 wt % to 150 wt % of the total mass of the fatty acid glyceride mixture.

[0033] According to a specific embodiment of the present invention, the inert gas is preferably nitrogen gas and / or helium gas.

[0034] The present invention provides a lubricating oil containing the boronated fatty acid glyceride antiwear additive, which may be used alone as a lubricating oil antiwear / wear-reducing additive or in combination with other lubricating oil additives.

[0035] According to a specific embodiment of the present invention, the amount of the boronated fatty acid glyceride anti-wear additive added to the base oil is preferably 0.2 wt% to 10 wt%.

[0036] According to a specific embodiment of the present invention, the above manufacturing method includes the following specific steps: (1) C4-C 25 Using linear or branched monovalent fatty acid and glycerin as raw materials, prepare a certain amount of solid acid catalyst, charge the glycerin and the solid acid catalyst into a reactor all at once, add fatty acid dropwise, raise the temperature to react, remove water by introducing inert gas, and when no water is generated in the reaction system, stop the reaction and filter to obtain a fatty acid glyceride mixture. (2) A certain amount of one or more boronating reagents, such as alkylboronic acids or arylboronic acids having a specific structure, and a solvent are placed in a reactor, and the mixture is stirred to homogeneity. The fatty acid glyceride mixture obtained in step (1) is then added, and water is removed using an inert gas. The mixture is then heated to a temperature of 60 to 150°C. oC, and the reaction is continued for 3 to 8 hours, after which the solvent is removed by distillation under reduced pressure to obtain the boronated fatty acid glyceride anti-wear additive.

[0037] The present invention first reacts fatty acids with glycerin to prepare a fatty acid glyceride mixture with a specific composition, and then a certain proportion of fatty acid glyceride is esterified with a boronating reagent in one step to synthesize a boronated fatty acid glyceride additive. The production process is simple, easy to handle, safe, and clean, with a simple post-treatment process and low production costs. Different series of anti-wear additive products can be produced according to specific needs, and these products have excellent anti-wear performance and good thermal stability without adversely affecting the corrosion performance of lubricating oils. [Brief explanation of the drawings]

[0038] [Figure 1] FIG. 1 is a gel chromatography diagram of boronated oleic acid glyceride. DETAILED DESCRIPTION OF THE INVENTION

[0039] In order to make the technical features, objectives and beneficial effects of the present invention more clearly understood, the technical solutions of the present invention are described in detail below, but should not be understood to limit the scope of the present invention.

[0040] Example 1 This example provides a boronated fatty acid glyceride anti-wear additive, the method of preparation of which was as follows.

[0041] (1) 92.1 g of glycerin (1 mol) and 2.16 g of Al2O3-SiO2 catalyst were placed in a reactor and stirred to mix uniformly. 339 g of oleic acid (1.2 mol) was added dropwise, the temperature was raised to 150°C, water was removed using nitrogen gas, and the reaction was continued for 5 hours. When no water was produced in the system, the reaction was stopped and the mixture was filtered to obtain oleic acid glyceride. (2) 121.9 g of benzeneboronic acid (1 mole) and 400 g of petroleum ether were placed in a reaction vessel and stirred to mix uniformly. The oleic acid glyceride from step (1) was then added, water was removed using nitrogen gas, the temperature was raised to 95°C, and the reaction was continued for 4 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronated oleic acid glyceride anti-wear additive A.

[0042] Example 2 This example provides a boronated fatty acid glyceride anti-wear additive, the method of preparation of which was as follows.

[0043] (1) 92.1 g of glycerin (1 mole) and 0.22 g of ZSM-5 catalyst were placed in a reactor and stirred to mix uniformly. 187.5 g of isooctanoic acid (1.3 moles) was added dropwise, the temperature was raised to 130°C, water was removed with nitrogen gas, and the reaction was continued for 4.5 hours. When no water was produced in the system, the reaction was stopped and the mixture was filtered to obtain isooctanoic acid glyceride. (2) 142.2 g of octylboronic acid (0.9 mol) and 300 g of toluene were placed in a reaction vessel and stirred to mix uniformly. The isooctanoic acid glyceride from step (1) was then added, water was removed using nitrogen gas, the temperature was raised to 90°C, and the reaction was continued for 5 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronated isooctanoic acid glyceride anti-wear additive B.

[0044] Example 3 This example provides a boronated fatty acid glyceride anti-wear additive, the method of preparation of which was as follows.

[0045] (1) 92.1 g of glycerin (1 mole) and 3.6 g of MCM-41 catalyst were placed in a reactor and stirred to mix uniformly. 356.2 g of palmitoleic acid (1.4 moles) was added dropwise, the temperature was raised to 160°C, water was removed using nitrogen gas, and the reaction was continued for 4 hours. When no water was produced in the system, the reaction was stopped and the mixture was filtered to obtain palmitoleic acid glyceride. (2) 136 g of p-methylbenzeneboronic acid (1 mole) and 300 g of xylene were placed in a reaction vessel and stirred to mix uniformly. The palmitoleic acid glyceride from step (1) was then added, water was removed using nitrogen gas, the temperature was raised to 105°C, and the reaction was continued for 6 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronated palmitoleic acid glyceride anti-wear additive C.

[0046] Example 4 This example provides a boronated fatty acid glyceride anti-wear additive, the method of preparation of which was as follows.

[0047] (1) 46.1 g of glycerin (0.5 mol) and 2.16 g of K2SO4 catalyst were placed in a reactor and stirred to mix uniformly. 226 g of oleic acid (0.8 mol) was added dropwise, the temperature was raised to 155°C, and water was removed using industrial helium gas. The reaction was continued for 8 hours. When no water was produced in the system, the reaction was stopped and the mixture was filtered to obtain oleic acid glyceride. (2) 54.4 g of p-methylbenzeneboronic acid (0.4 mol) and 200 g of toluene were placed in a reaction vessel and stirred to mix uniformly. The oleic acid glyceride from step (1) was then added, water was removed using helium gas, the temperature was raised to 110°C, and the reaction was continued for 8 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronated oleic acid glyceride anti-wear additive D.

[0048] Comparative Example 1 This comparative example provides a boronated fatty acid glyceride anti-wear additive, the method of preparation of which is as follows.

[0049] (1) 92.1 g of glycerin (1 mol) and 2.16 g of Al2O3-SiO2 catalyst were placed in a reactor and stirred to mix uniformly. 339 g of oleic acid (1.2 mol) was added dropwise, the temperature was raised to 150°C, water was removed using nitrogen gas, and the reaction was continued for 5 hours. When no water was produced in the system, the reaction was stopped and the mixture was filtered to obtain oleic acid glyceride. (2) 61.83 g of boric acid (1 mole) and 400 g of petroleum ether were placed in a reaction vessel and stirred to mix uniformly. The oleic acid glyceride from step (1) was then added, water was removed using nitrogen gas, the temperature was raised to 95°C, and the reaction was continued for 4 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronated oleic acid glyceride anti-wear additive E.

[0050] Comparative Example 2 This comparative example provides a boronated fatty acid glyceride anti-wear additive, the method of preparation of which is as follows.

[0051] 61.83 g of boric acid (1 mole) and 400 g of petroleum ether were placed in a reaction vessel and stirred to mix uniformly. 213.9 g of glycerin monooleate (0.6 mole) was then added, water was removed using nitrogen gas, the temperature was raised to 95°C, and the reaction was continued for 4 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronated glycerin monooleate anti-wear additive F.

[0052] Comparative Example 3 This comparative example provides a boronated fatty acid monoglyceride anti-wear additive, the preparation method of which was as follows.

[0053] 136 g of p-methylbenzeneboronic acid (1 mol) and 400 g of petroleum ether were placed in a reaction vessel and stirred to mix uniformly. 164.3 g of glycerin monopalmitoleate (0.5 mol) was then added, water was removed using nitrogen gas, the temperature was raised to 105°C, and the reaction was continued for 6 hours. After that, the solvent was removed by distillation under reduced pressure, and boronated palmitoleic acid monoglyceride anti-wear additive G was obtained.

[0054] The boronated oleic acid glycerides produced in the examples and comparative examples were characterized by gel chromatography. The gel chromatography of Example 1 is shown in FIG. 1, and the component contents of each example and comparative example are shown in Table 1.

[0055] The boronated fatty acid glyceride anti-wear additives obtained in the examples and comparative examples were blended into GL-5 gear oil at an addition amount of 1.0 wt %, and then the wear scar diameter and seizure load (P D The friction coefficient at a load of 392 N and corrosion performance against copper sheets were measured, and the results are shown in Table 1.

[0056] According to the method of GB / T 3142-1982, the maximum non-seizure load (P D The wear scar diameter of the steel ball was measured in accordance with the method of NB / SH / T 0189-2017, the coefficient of friction was measured in accordance with the method of SH / T 0762-2005, and the corrosion of the copper sheet was measured in accordance with the method of GB / T 5096-2017.

[0057] [Table 1]

[0058] The results show that the antiwear additive of the present invention has excellent antiwear / friction reducing performance while not adversely affecting the corrosion performance of the lubricating oil.

Claims

1. The composition is a boronated fatty acid glyceride anti-wear additive comprising a compound of formula I, a compound of formula II, and a compound of formula III. 【Chemistry 1】 In Formula I, R 1 , R 2 and R 3 are the same or different and each independently, C 3 -C 24 and 【Chemistry 2】 In Formula II, R is C 3 -C 24 R 5 is C 4 -C 24 Alkyl groups of C 6 -C 18 and selected from the aryl groups 【Transformation 3】 In Formula III, R 5 is C 4 -C 24 Alkyl groups of C 6 -C 18 and R 4 and R 6 are the same or different and each independently: 【Chemistry 4】 where R 7 and R 8 are the same or different and each independently, C 3 -C 24 The hydrocarbon group is selected from the group consisting of:

2. 2. The boronated fatty acid glyceride antiwear additive of claim 1, wherein the mass ratio of the compound of formula I to the compound of formula II to the compound of formula III is (8-12):(46-52):(36-46).

3. 3. A method for producing the boronated fatty acid glyceride antiwear additive of claim 1 or 2, comprising the steps of: (1) Glycerin and a solid acid catalyst are mixed, and C 4 -C 25 the fatty acid is added dropwise to carry out an esterification reaction, and water is removed by introducing an inert gas to obtain a fatty acid glyceride mixture. (2) Mixing a boronating reagent with a solvent, adding the fatty acid glyceride mixture obtained in step (1), removing water with an inert gas, heating to 60 to 150°C, and reacting for 3 to 8 hours to obtain the boronated fatty acid glyceride anti-wear additive; The boronating reagent is an alkylboronic acid and / or an arylboronic acid.

4. 4. The method of claim 3, comprising the steps of: (1) Glycerin and a solid acid catalyst are mixed, and C 4 -C 24 the fatty acid is added dropwise to carry out an esterification reaction, and water is removed by introducing an inert gas to obtain a fatty acid glyceride mixture. (2) Mixing a boronating reagent with a solvent, adding the fatty acid glyceride mixture obtained in step (1), removing water with an inert gas, heating to 60 to 150°C, and reacting for 3 to 8 hours to obtain the boronated fatty acid glyceride anti-wear additive; The boronating reagent is an alkylboronic acid and / or an arylboronic acid.

5. In step (1), the C calculated for the carboxyl group and the hydroxyl group 4 -C 25 4. The method according to claim 3, wherein the molar ratio of the fatty acid to glycerin is 1:3 to 2.5:

3.

6. In step (1), the C calculated for the carboxyl group and the hydroxyl group 4 -C 24 4. The method according to claim 3, wherein the molar ratio of the fatty acid to glycerin is 1:3 to 2.5:

3.

7. In step (1), the C calculated for the carboxyl group and the hydroxyl group 4 -C 25 6. The method according to claim 5, wherein the molar ratio of the fatty acid to glycerin is 1.1:3 to 1.8:

3.

8. In step (1), the C calculated for the carboxyl group and the hydroxyl group 4 -C 24 7. The method according to claim 6, wherein the molar ratio of the fatty acid to glycerin is 1.1:3 to 1.8:

3.

9. 4. The method according to claim 3, wherein in step (1), the reaction temperature is 80 to 160°C and the reaction time is 3 to 10 hours.

10. In step (1), the solid acid catalyst is Al 2 O 3 , Al 2 O 3 -SiO 2 4. The method according to claim 3, wherein the catalyst comprises one or a combination of two or more of: a metal salt, a molecular sieve ZSM-5, and a molecular sieve MCM-41.

11. In step (1), the amount of the solid acid catalyst added is 4 -C 25 4. The method according to claim 3, wherein the amount of the fatty acid is 0.05 wt % to 1.2 wt % of the total mass of the fatty acid and glycerin.

12. In step (1), the amount of the solid acid catalyst added is 4 -C 24 4. The method according to claim 3, wherein the amount of the fatty acid is 0.05 wt % to 1.2 wt % of the total mass of the fatty acid and glycerin.

13. 4. The method of claim 3, wherein in step (2), the boronating reagent has a structure represented by formula IV: 【Transformation 5】 In Formula IV, R 5 is C 4 -C 24 Alkyl groups of C 6 -C 18 The aryl group is selected from the group consisting of:

14. In step (2), the molar amount of the boronating reagent added is [(3a-b) / 2] to (3a-b), where a is the molar amount of glycerin added, and b is C 4 -C 25 The method according to claim 3, wherein the molar amount of fatty acid added is 100%.

15. In step (2), the molar amount of the boronating reagent added is [(3a-b) / 2] to (3a-b), where a is the molar amount of glycerin added, and b is C 4 -C 24 The method according to claim 3, wherein the molar amount of fatty acid added is 100%.

16. 4. The method according to claim 3, wherein in step (2), the solvent is one or a combination of two or more of petroleum ether, benzene, toluene, cyclohexane, n-heptane, n-octane, and xylene.

17. 4. The method according to claim 3, wherein in step (2), the amount of the solvent added is 50 wt % to 150 wt % of the total mass of the fatty acid glyceride mixture.

18. 4. The manufacturing method according to claim 3, wherein the inert gas is nitrogen gas and / or helium gas.

19. 3. A lubricating oil comprising the boronated fatty acid glyceride anti-wear additive of claim 1 or 2.

20. 20. The lubricating oil of claim 19, wherein the boronated fatty acid glyceride anti-wear additive is added to the base oil in an amount of 0.2 wt% to 10 wt%.

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