Boronized fatty glyceride anti-wear additive and preparation method thereof

Abstract

The invention provides a boronized fatty glyceride anti-wear additive and a preparation method thereof, the anti-wear additive comprises a compound shown as a formula I, a compound shown as a formula II and a compound shown as a formula III: # imgabs0 #, in the formula I, R1, R2 and R3 are the same or different and are respectively and independently selected from C3-C24 alkyl; in the formula II, R is selected from C3-C24 alkyl groups, and R5 is selected from C4-C24 alkyl groups and C6-C18 aryl groups; in the formula III, R5 is selected from alkyl groups of C4-C24 and aryl groups of C6-C18; r4 and R6 are the same or different and are independently selected from # imgabs 1 #, and R7 and R8 are the same or different and are independently selected from C3-C24 alkyl groups. The anti-wear additive has excellent anti-wear performance and good thermal stability, and does not generate adverse effects on the corrosion performance of 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 type of environmentally friendly lubricant additive, boron additives are gaining more and more attention due to their unique chemical properties. Boron additives can be divided into inorganic borates and organic borates from the perspective of chemical structure. Borate additives not only have excellent thermal oxidation stability and sealing adaptability, no corrosion to copper at high temperatures, and good anti-rust properties for steel, but also help improve the operating environment, have excellent load-bearing capacity and anti-friction and anti-wear properties, and have been widely used in engine oils and industrial gear oils.

[0003] In recent years, in order to improve the performance of borate lubricant additives, the introduction of active elements such as N, S, and P into borate molecules has become a hot topic of research. Introducing nitrogen atoms into the molecular structure of borate to form BN coordination bonds between nitrogen atoms and boron atoms is an effective method for improving the hydrolysis stability of borate. Patents US4204972, US5084194, CN114605460, and CN100350025 all introduce amine-containing borate. These borate esters are generally formed by the direct reaction of hydroxyl-containing long-chain amines with boric acid to form esters. Most of these amine-containing borate esters have good friction reduction properties and high thermal oxidation stability. Patents US4394277, US4465605, and US4486323 report sulfur-containing borate esters. These borate esters are generally formed by the reaction of S-containing monohydroxy compounds or polyhydroxy compounds with boric acid to form esters. Patents US4555353, US4536306, US4557844, and US006228818 respectively disclose borate compounds containing phosphoric acid ester structures. The above research work has improved the performance of borate additives in different aspects, but the introduction of some active elements has limited the application of additives to a certain extent. The development of oil technology has put forward new requirements for additives. Engine oil has made stricter restrictions on the S and P elements of additives. GF-6 engine oil requires that the S element is not more than 0.5% and the P element is not more than 0.08%. High-end industrial gear oils are increasingly concerned about the odor, biodegradability, and whether they meet food grade certification requirements of additives. The development of low-sulfur, low-phosphorus biodegradable borate additives will be a way to meet the needs of new oil products.

[0004] The molecular adjustability of fatty acid glycerides is strong, triglycerides have good thermal stability, and the molecules of monoglycerides and diesters contain adsorption groups such as ester bonds and hydroxyls, which have good lubrication properties. Patents US4734211, US4764296 and CN105658779 disclose the use of boronized 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 generate a mixed borate ester. Patent US5759965 discloses a method for preparing boronized fatty acid glycerides using boric acid and fatty acid glycerides. The above patents mainly use boric acid as a boronating agent to prepare boronized 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 has no adverse effect on 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 shown in formula I, a compound shown in formula II, and a compound shown in formula III;

[0007]

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

[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 The aromatic group;

[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 a 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 boronized reagent and a solvent, adding the fatty acid glyceride mixture obtained in step (1), an inert gas with water, heating to 60-150° C., 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 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 boronating agent has a structure shown in Formula IV:

[0024]

[0025] In Formula IV, R5 is selected from C4-C 24 Alkyl, C6-C 18 The aromatic group.

[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, and 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, which includes 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 Straight-chain or branched monobasic fatty acid and glycerol are used as raw materials, and a certain amount of solid acid catalyst is used; the glycerol and the solid acid catalyst are put into a reactor at one time, fatty acid is added dropwise, the temperature is increased to react, 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) adding a certain amount of one or more boronating agents of alkyl boronic acid or aryl boronic acid with a specific structure and a solvent into a reactor, stirring and mixing evenly, adding the fatty acid glyceride mixture obtained in step (1), inert gas with water, heating to 60-150° C., continuing the reaction for 3-8 hours, and removing the solvent by reduced pressure distillation to obtain a boronated fatty acid glyceride anti-wear additive.

[0035] The present invention firstly utilizes the reaction of fatty acid 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, the post-treatment process is simple, and the production cost is low. 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 adverse effects 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, purposes 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 construed as limiting the applicable scope of the present invention.

[0038] Example 1

[0039] This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof 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 evenly, 339 g of oleic acid (1.2 mol) was added dropwise, the temperature was raised to 150° C., nitrogen was used to carry water, and the reaction was continued 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 the olein in step (1) 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 reduced pressure distillation to obtain the boronized olein anti-wear additive A.

[0042] Example 2

[0043] This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof 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, 187.5 g of isooctanoic acid (1.3 mol) was added dropwise, the temperature was raised to 130° C., nitrogen was used to carry water, and the reaction was continued 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 evenly, and glyceryl isooctanoate in step (1) was added, nitrogen was passed through with water, the temperature was raised to 90° C., the reaction was continued for 5 hours, and the solvent was removed by reduced pressure distillation to obtain boronized glyceryl isooctanoate anti-wear additive B.

[0046] Example 3

[0047] This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof 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 evenly, 356.2 g of hexadecenoic acid (1.4 mol) were added dropwise, the temperature was raised to 160° C., nitrogen was used to carry water, and the reaction was continued 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-methylphenylboric acid (1 mol) and 300 g of xylene are added to a reaction container, stirred and mixed evenly, and the hexadecenoic acid glyceride in step (1) is added, nitrogen is passed through with water, the temperature is raised to 105° C., the reaction is continued for 6 hours, and the solvent is removed by reduced pressure distillation to obtain the boronized hexadecenoic acid glyceride anti-wear additive C.

[0050] Example 4

[0051] This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof 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 evenly, 226 g of oleic acid (0.8 mol) was added dropwise, the temperature was raised to 155° C., industrial helium was used to carry water, and 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-methylphenylboric acid (0.4 mol) and 200 g of toluene were added to a reaction vessel, stirred and mixed evenly, and the olein in step (1) was added, helium gas was passed through with water, the temperature was raised to 110° C., the reaction was continued for 8 hours, and the solvent was removed by reduced pressure distillation to obtain the boronized olein anti-wear additive D.

[0054] Comparative Example 1

[0055] This comparative example provides a boronized 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 evenly, 339 g of oleic acid (1.2 mol) was added dropwise, the temperature was raised to 150° C., nitrogen was used to carry water, and the reaction was continued for 5 hours. When no water was produced in the system, the reaction was stopped and filtered to obtain oleic acid glyceride;

[0057] (2) Add 61.83 g of boric acid (1 mol) and 400 g of petroleum ether into a reaction container, stir and mix evenly, add olein from step (1), nitrogen with water, heat to 95° C., continue the reaction for 4 hours, and remove the solvent by vacuum distillation to obtain boronized olein anti-wear additive E.

[0058] Comparative Example 2

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

[0060] 61.83 g of boric acid (1 mole) and 400 g of petroleum ether were added into a reaction vessel, stirred and mixed evenly, 213.9 g of glycerol monooleate (0.6 mole) 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 reduced pressure distillation to obtain boronated glycerol monooleate anti-wear additive F.

[0061] Comparative Example 3

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

[0063] 136 g of p-methylphenylboric acid (1 mol) and 400 g of petroleum ether were added into 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 reduced pressure distillation to obtain the boronated hexadecenoic acid monoglyceride anti-wear additive G.

[0064] The boronated oleyl glyceride 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 in an amount of 1.0 wt %. The wear spot diameter and sintering load (P D The friction coefficient under 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 Evaluation of the performance 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 The hydrocarbon group; In Formula II, R is selected from C3-C 24 The hydrocarbon group, R5 is selected from C4-C 24 Alkyl, C6-C 18 The aromatic group; 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 boronized fatty acid glyceride anti-wear additive according to claim 1 or 2, comprising the following steps: (1) Mix glycerol with a 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 boronized reagent and a solvent, adding the fatty acid glyceride mixture obtained in step (1), an inert gas with water, heating to 60-150° C., 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 the 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 boronating agent has a structure shown in Formula IV: In Formula IV, R5 is selected from C4-C 24 Alkyl, C6-C 18 The aromatic group.

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, and b is 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 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 in an amount of 0.2 wt% to 10 wt% in the base oil.

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