A boronated fatty acid glyceride anti-wear additive and preparation method thereof

Abstract

The present invention provides a boronated fatty acid glyceride anti-wear additive and a preparation method thereof. The anti-wear additive comprises: a compound represented by formula I, a compound represented by formula II, and a compound represented by formula III: wherein R1, R2, and R3 are the same or different and are independently selected from C3-C 24 In formula II, R is selected from C3-C 24 The hydrocarbon group, R5 is selected from C4-C 24 Alkyl, C6-C 18 In formula III, R5 is selected from C4-C 24 Alkyl, C6-C 18 R4 and R6 are the same or different, each independently selected from wherein, R7 and R8 are the same or different, each independently selected from C3-C 24 The anti-wear additive has excellent anti-wear performance and good thermal stability, and has no adverse effect on the corrosion performance of the lubricating oil.

Description

Technical Field

[0001] The invention belongs to the field of lubricating oil additives and relates to a boronated fatty acid glyceride anti-wear additive and a preparation method thereof. Background Art

[0002] As a new class of environmentally friendly lubricant additives, boron additives are gaining increasing attention for their unique chemical properties. Based on their chemical structure, boron additives can be divided into inorganic borates and organic borate esters. Borate ester additives not only exhibit excellent thermal and oxidative stability and sealing compatibility, are non-corrosive to copper at high temperatures, and provide excellent rust prevention for steel, but also improve the operating environment, possess excellent load-bearing capacity, and reduce friction and anti-wear properties. They are widely used in engine oils and industrial gear oils.

[0003] In recent years, the introduction of active elements such as nitrogen, sulfur, and phosphorus into borate molecules has become a hot topic of research to enhance the performance of borate lubricant additives. Introducing nitrogen atoms into the molecular structure, forming BN coordination bonds with boron atoms, is an effective method for improving the hydrolytic stability of borate esters. Patents US4204972, US5084194, CN114605460, and CN100350025 all describe amine-containing borate esters. These esters are typically formed by the direct reaction of long-chain amines containing hydroxyl groups with boric acid. These amine-containing borate esters often exhibit excellent friction-reducing properties and high thermo-oxidative stability. Patents US4394277, US4465605, and US4486323 report on sulfur-containing borate esters. These esters are typically formed by the reaction of sulfur-containing monohydroxy or polyhydroxy compounds with boric acid. Patents US4555353, US4536306, US4557844, and US006228818 respectively disclose borate compounds containing a phosphoric acid ester structure. These studies have improved the performance of borate additives in various aspects, but the introduction of some active elements has limited their application to a certain extent. Oil product technology developments have placed new demands on additives. Engine oils have stricter limits on the sulfur and phosphorus content of additives, with GF-6 engine oil requiring no more than 0.5% sulfur and no more than 0.08% phosphorus. High-end industrial gear oils are increasingly concerned with additives' odor, biodegradability, and compliance with food-grade certification requirements. Developing low-sulfur, low-phosphorus, biodegradable borate additives is one approach to meeting these demands.

[0004] Fatty acid glycerides have strong molecular adjustability, triglycerides have good thermal stability, and the molecules of monoglycerides and diesters contain adsorption groups such as ester bonds and hydroxyl groups, which have good lubrication properties. Patents US4734211, US4764296 and CN105658779 disclose the use of borated oleic acid glycerides in engine oils. Patents US004507216 and US005006276 disclose the use of hindered phenols and hydroxyl-containing esters reacted with boric acid to produce a mixed borate ester. Patent US5759965 discloses a method for preparing borated fatty acid glycerides using boric acid and fatty acid glycerides. The above patents mainly use boric acid as a boronating agent to prepare borated fatty acid glycerides. Summary of the Invention

[0005] In order to solve the above problems, the purpose of the present invention is to provide a boronated fatty acid glyceride anti-wear additive and a preparation method thereof and a lubricating oil, wherein the anti-wear additive has excellent anti-wear performance and good thermal stability, and does not adversely affect the corrosion performance of the lubricating oil.

[0006] In order to achieve the above object, the present invention provides a boronated fatty acid glyceride anti-wear additive, which comprises: a compound represented by formula I, a compound represented by formula II, and a compound represented by formula III;

[0007]

[0008] In Formula I, R1, R2 and R3 are the same or different and are independently selected from C3-C 24 of hydrocarbon groups;

[0009]

[0010] In formula II, R is selected from C3-C 24 The hydrocarbon group, R5 is selected from C4-C 24 Alkyl, C6-C 18 aromatic groups;

[0011]

[0012] In formula III, R5 is selected from C4-C 24 Alkyl, C6-C 18 R4 and R6 are the same or different and are independently selected from Wherein, R7 and R8 are the same or different and are independently selected from C3-C 24 of hydrocarbon groups.

[0013] 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).

[0014] The present invention also provides a method for preparing the boronated fatty acid glyceride anti-wear additive, which comprises the following steps:

[0015] (1) Mix glycerol with solid acid catalyst and add C4-C 24 The fatty acids are subjected to esterification reaction, and an inert gas with water is introduced to obtain a fatty acid glyceride mixture;

[0016] (2) mixing a boronization reagent and a solvent, adding the fatty acid glyceride mixture obtained in step (1), an inert gas with water, heating to 60-150° C., and reacting for 3-8 hours to obtain the boronized fatty acid glyceride anti-wear additive;

[0017] The boronating agent is an alkyl boronic acid and / or an aryl boronic acid.

[0018] According to a specific embodiment of the present invention, preferably, in step (1), the C4-C 24 The molar ratio of fatty acids and glycerol calculated based on carboxyl groups and hydroxyl groups is 1:3-2.5:3.

[0019] According to a specific embodiment of the present invention, preferably, in step (1), the C4-C 24 The molar ratio of fatty acids and glycerol calculated based on carboxyl groups and hydroxyl groups is 1.1:3-1.8:3.

[0020] According to a specific embodiment of the present invention, preferably, in step (1), the reaction temperature is 80-160° C., and the reaction time is 3-10 h.

[0021] According to a specific embodiment of the present invention, preferably, in step (1), the solid acid catalyst includes one or a combination of two or more of Al2O3, Al2O3-SiO2, metal salts (such as sulfates, phosphates), molecular sieve ZSM-5, and MCM-41.

[0022] According to a specific embodiment of the present invention, preferably, in step (1), the amount of the solid acid catalyst added is the C4-C 24 0.05wt%-1.2wt% of the total mass of fatty acids and glycerol.

[0023] According to a specific embodiment of the present invention, preferably, in step (2), the boronation reagent has a structure shown in Formula IV:

[0024]

[0025] In formula IV, R5 is selected from C4-C 24 Alkyl, C6-C 18 of aromatic groups.

[0026] According to a specific embodiment of the present invention, preferably, in step (2), the molar amount of the boronating agent added is [(3a-b) / 2] to (3a-b), wherein a is the molar amount of glycerol added, b is the molar amount of C4-C 24 The molar amount of fatty acid added.

[0027] According to a specific embodiment of the present invention, preferably, 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.

[0028] According to a specific embodiment of the present invention, preferably, in step (2), the amount of solvent added is 50 wt%-150 wt% of the total mass of the fatty acid glyceride mixture.

[0029] According to a specific embodiment of the present invention, preferably, the inert gas is nitrogen and / or helium.

[0030] The present invention also provides a lubricating oil comprising the boronized fatty acid glyceride anti-wear additive. The boronized fatty acid glyceride anti-wear additive can be used alone as a lubricating oil anti-wear and friction-reducing additive, or can be used in combination with other lubricating oil additives.

[0031] According to a specific embodiment of the present invention, preferably, the boronated fatty acid glyceride anti-wear additive is added to the base oil in an amount of 0.2 wt% to 10 wt%.

[0032] According to a specific embodiment of the present invention, the above preparation method comprises the following specific steps:

[0033] (1) C4-C 24 A linear or branched monobasic fatty acid and glycerol are used as raw materials, and a certain amount of solid acid catalyst is added; the glycerol and the solid acid catalyst are put into a reactor at one time, the fatty acid is added dropwise, the temperature is increased to react, an inert gas is introduced to carry out water, and when no water is produced in the reaction system, the reaction is stopped and filtered to obtain a fatty acid glyceride mixture;

[0034] (2) A certain amount of one or more boronating reagents of a specific structure of alkyl boronic acid or aryl boronic acid and a solvent are added to a reactor, stirred and mixed evenly, and the fatty acid glyceride mixture obtained in step (1) is added, and inert gas is carried out with water. The temperature is raised to 60-150° C., and the reaction is continued for 3-8 hours. The solvent is removed by distillation under reduced pressure to obtain a boronated fatty acid glyceride anti-wear additive.

[0035] The present invention first utilizes the reaction of fatty acids and glycerol to prepare a fatty acid glyceride mixture of a specific composition, and then synthesizes a boronized fatty acid glyceride additive by a one-step esterification reaction of the fatty acid glyceride and a boronating agent in a certain proportion. The production process is simple and easy to operate, safe and environmentally friendly, and has a simple post-processing process and low production cost. Different series of anti-wear additive products can be prepared according to specific needs. The product has excellent anti-wear performance and good thermal stability, and will not have a negative impact on the corrosion performance of lubricating oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a gel chromatogram of boronated olein. DETAILED DESCRIPTION

[0037] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0038] Example 1

[0039] This embodiment provides a boronated fatty acid glyceride anti-wear additive, and its preparation method is as follows:

[0040] (1) 92.1 g of glycerol (1 mol) and 2.16 g of Al2O3-SiO2 catalyst were added to a reactor, stirred and mixed uniformly, and 339 g of oleic acid (1.2 mol) was added dropwise. The temperature was raised to 150°C, and nitrogen was used to carry out the reaction for 5 hours. When no water was produced in the system, the reaction was stopped and filtered to obtain oleic acid glyceride;

[0041] (2) 121.9 g of phenylboric acid (1 mol) and 400 g of petroleum ether were added to a reaction vessel, stirred and mixed evenly, and olein from step (1) was added, nitrogen was passed through with water, and the temperature was raised to 95° C. After continuing the reaction for 4 hours, the solvent was removed by distillation under reduced pressure to obtain boronized olein anti-wear additive A.

[0042] Example 2

[0043] This embodiment provides a boronated fatty acid glyceride anti-wear additive, and its preparation method is as follows:

[0044] (1) 92.1 g of glycerol (1 mol) and 0.22 g of ZSM-5 catalyst were added to a reactor, stirred and mixed uniformly, and 187.5 g of isooctanoic acid (1.3 mol) was added dropwise. The temperature was raised to 130° C., and nitrogen was used to carry out the reaction for 4.5 hours. When no water was produced in the system, the reaction was stopped and filtered to obtain isooctanoic acid glyceride;

[0045] (2) 142.2 g of octylboric acid (0.9 mol) and 300 g of toluene were added to a reaction vessel, stirred and mixed uniformly, and glyceryl isooctanoate in step (1) was added, nitrogen was passed through with water, and the temperature was raised to 90° C. After continuing the reaction for 5 hours, the solvent was removed by distillation under reduced pressure to obtain boronized glyceryl isooctanoate anti-wear additive B.

[0046] Example 3

[0047] This embodiment provides a boronated fatty acid glyceride anti-wear additive, and its preparation method is as follows:

[0048] (1) 92.1 g of glycerol (1 mol) and 3.6 g of MCM-41 catalyst were added to a reactor, stirred and mixed uniformly, and 356.2 g of hexadecenoic acid (1.4 mol) was added dropwise. The temperature was raised to 160° C., and nitrogen was used to carry out the reaction for 4 hours. When no water was produced in the system, the reaction was stopped and filtered to obtain hexadecenoic acid glyceride;

[0049] (2) 136 g of p-methylphenylboronic acid (1 mol) and 300 g of xylene were added to a reaction vessel, stirred and mixed evenly, and the hexadecenoic acid glyceride in step (1) was added, nitrogen was passed through with water, and the temperature was raised to 105° C. After continuing the reaction for 6 hours, the solvent was removed by distillation under reduced pressure to obtain the boronated hexadecenoic acid glyceride anti-wear additive C.

[0050] Example 4

[0051] This embodiment provides a boronated fatty acid glyceride anti-wear additive, and its preparation method is as follows:

[0052] (1) 46.1 g of glycerol (0.5 mol) and 2.16 g of K2SO4 catalyst were added to a reactor, stirred and mixed uniformly, and 226 g of oleic acid (0.8 mol) was added dropwise. The temperature was raised to 155°C, and industrial helium was used to carry water. The reaction was continued for 8 hours. When no water was produced in the system, the reaction was stopped and filtered to obtain oleic acid glyceride;

[0053] (2) 54.4 g of p-methylphenylboronic acid (0.4 mol) and 200 g of toluene were added to a reaction vessel, stirred and mixed evenly, and olein from step (1) was added, helium was passed through with water, and the temperature was raised to 110° C. After continuing the reaction for 8 hours, the solvent was removed by distillation under reduced pressure to obtain boronized olein anti-wear additive D.

[0054] Comparative Example 1

[0055] This comparative example provides a boronated fatty acid glyceride anti-wear additive, and its preparation method is as follows:

[0056] (1) 92.1 g of glycerol (1 mol) and 2.16 g of Al2O3-SiO2 catalyst were added to a reactor, stirred and mixed uniformly, and 339 g of oleic acid (1.2 mol) was added dropwise. The temperature was raised to 150°C, and nitrogen was used to carry out the reaction for 5 hours. When no water was produced in the system, the reaction was stopped and filtered to obtain oleic acid glyceride;

[0057] (2) 61.83 g of boric acid (1 mol) and 400 g of petroleum ether were added to a reaction vessel, stirred and mixed evenly, and olein from step (1) was added, nitrogen was used to carry water, and the temperature was raised to 95° C. After continuing the reaction for 4 hours, the solvent was removed by distillation under reduced pressure to obtain boronized olein anti-wear additive E.

[0058] Comparative Example 2

[0059] This comparative example provides a boronated fatty acid glyceride anti-wear additive, and its preparation method is as follows:

[0060] 61.83 g of boric acid (1 mol) and 400 g of petroleum ether were added to a reaction vessel, stirred and mixed evenly, 213.9 g of glycerol monooleate (0.6 mol) was added, nitrogen was passed through with water, the temperature was raised to 95° C., the reaction was continued for 4 hours, and the solvent was removed by distillation under reduced pressure to obtain boronated glycerol monooleate anti-wear additive F.

[0061] Comparative Example 3

[0062] This comparative example provides a boronated fatty acid monoglyceride anti-wear additive, and its preparation method is as follows:

[0063] 136 g of p-methylphenylboric acid (1 mol) and 400 g of petroleum ether were added to a reaction vessel, stirred and mixed evenly, 164.3 g of glycerol monohexadecenoate (0.5 mol) was added, nitrogen was passed through with water, the temperature was raised to 105° C., the reaction was continued for 6 hours, and the solvent was removed by distillation under reduced pressure to obtain boronated hexadecenoic acid monoglyceride anti-wear additive G.

[0064] The boronized olein prepared in the examples and comparative examples was characterized by gel chromatography, wherein the gel chromatography of Example 1 showed Figure 1 The component content ratios of the embodiments and comparative examples are shown in Table 1.

[0065] The boronized fatty acid glyceride anti-wear additive obtained in the examples and comparative examples was added to GL-5 gear oil at an addition amount of 1.0 wt %. The wear spot diameter, sintering load (P D The friction coefficient under the load of 392N was measured, and the results are shown in Table 1.

[0066] The maximum no-seizure load (P DThe wear spot diameter of the steel ball was measured according to the method of NB / SH / T0189-2017, and the friction coefficient was measured according to the method of SH / T 0762-2005.

[0067] Table 1 Performance evaluation of boronated fatty acid glyceride anti-wear additives

[0068]

[0069] The results show that the anti-wear additive of the present invention has excellent anti-wear and friction reducing properties.

Claims

1. A boronated fatty acid glyceride anti-wear additive, comprising: The compound represented by formula I, the compound represented by formula II, and the compound represented by formula III; In Formula I, R1, R2 and R3 are the same or different and are independently selected from C3-C 24 of hydrocarbon groups; In formula II, R is selected from C3-C 24 The hydrocarbon group, R5 is selected from C4-C 24 Alkyl, C6-C 18 aromatic groups; In formula III, R5 is selected from C4-C 24 Alkyl, C6-C 18 R4 and R6 are the same or different and are independently selected from Wherein, R7 and R8 are the same or different and are independently selected from C3-C 24 of hydrocarbon groups.

2. The boronated fatty acid glyceride anti-wear additive according to claim 1, wherein 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).

3. The method for preparing the boronated fatty acid glyceride anti-wear additive according to claim 1 or 2, comprising the steps of: (1) Mix glycerol with solid acid catalyst and add C4-C 24 The fatty acids are subjected to esterification reaction, and an inert gas with water is introduced to obtain a fatty acid glyceride mixture; (2) mixing a boronization reagent and a solvent, adding the fatty acid glyceride mixture obtained in step (1), an inert gas with water, heating to 60-150° C., and reacting for 3-8 hours to obtain the boronized fatty acid glyceride anti-wear additive; The boronating agent is an alkyl boronic acid and / or an aryl boronic acid.

4. The preparation method according to claim 3, wherein In step (1), the C4-C 24 The molar ratio of fatty acids and glycerol calculated based on carboxyl groups and hydroxyl groups is 1:3-2.5:

3.

5. The preparation method according to claim 4, wherein In step (1), the C4-C 24 The molar ratio of fatty acids and glycerol calculated based on carboxyl groups and hydroxyl groups is 1.1:3-1.8:

3.

6. The preparation method according to claim 3, wherein In step (1), the reaction temperature is 80-160° C., and the reaction time is 3-10 h.

7. The preparation method according to claim 3, wherein In step (1), the solid acid catalyst includes one or a combination of two or more of Al2O3, Al2O3-SiO2, metal salts, molecular sieve ZSM-5, and MCM-41.

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

9. The preparation method according to claim 3, wherein In step (2), the boronation reagent has a structure shown in Formula IV: In formula IV, R5 is selected from C4-C 24 Alkyl, C6-C 18 of aromatic groups.

10. The preparation method according to claim 3, wherein In step (2), the molar amount of the boronating agent added is [(3a-b) / 2] to (3a-b), wherein a is the molar amount of glycerol added, b is the molar amount of C4-C 24 The molar amount of fatty acid added.

11. The preparation 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.

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

13. The preparation method according to claim 3, wherein The inert gas is nitrogen and / or helium.

14. A lubricating oil comprising the boronated fatty acid glyceride anti-wear additive according to claim 1 or 2.

15. The lubricating oil according to claim 14, 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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