Borated glycerol ester extreme pressure anti-wear additive, preparation method and application thereof

Abstract

The application discloses a composite boronated glyceric acid ester extreme pressure anti-wear additive, which comprises a borate, compound (I), compound (II) and compound (III), and the mass ratio of the compound (I), the compound (II) and the compound (III) is 9-11:47-53:36-46. The application further discloses a preparation method of the composite boronated glyceric acid ester extreme pressure anti-wear additive, specifically comprising the following steps: mixing glycerol, a borate and a solid acid catalyst, adding C4-C 24 fatty acids to perform esterification reaction to obtain a boronated fatty acid glyceride mixture; mixing a boronating agent and a solvent, and adding the boronated fatty acid glyceride mixture to perform reaction. The application further discloses application of the composite boronated glyceric acid ester extreme pressure anti-wear additive in lubricating oil. The anti-wear additive has good oil solubility, excellent extreme pressure anti-wear performance, good thermal stability, and does not have adverse effects on corrosion performance of the lubricating oil.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of extreme pressure anti-wear additive preparation, and particularly relates to a composite boronated glycerol acid ester extreme pressure anti-wear additive, and also relates to a preparation method and application of the extreme pressure anti-wear additive. BACKGROUND

[0002] As a new type of environmentally friendly lubricating oil additive, boron-based additives are paid more and more attention due to their unique chemical properties. From the chemical structure, boron-based additives can be divided into inorganic borate and organic borate. The oil film formed by inorganic borate has good strength. It is found that inorganic borate additives have good extreme pressure effect under the conditions of low speed and high torque, and high speed and low torque. In addition, inorganic borate additives have high thermal stability, and can be used stably for a long time even at high temperature of 150 DEG C. On the other hand, the extreme pressure performance of inorganic borate additives is low in dependence on the thickness of the oil film. The extreme pressure performance of inorganic borate additives in lubricating oil will not decrease with the decrease of the viscosity of the oil, and can well cope with the challenge of low viscosity of oil caused by the requirement of fuel economy. Although inorganic borate has excellent thermal stability and good anti-wear, friction-reducing and extreme pressure properties, the low solubility of inorganic borate in lubricating oil becomes the main problem limiting its development. By reducing the particle size of inorganic borate and surface modification of inorganic borate, the dispersion stability of inorganic borate in base oil is tried to be improved, but the results are not ideal.

[0003] Borate ester additives not only have excellent thermal oxidative stability and sealing adaptability, no corrosion to copper at high temperature, good rust resistance to steel, but also improve the operating environment, have excellent load capacity and friction reducing and anti-wear performance, and have been widely used in engine oil and industrial gear oil. In recent years, in order to improve the performance of borate ester lubricating oil additives, active elements such as N, S and P are introduced into the borate ester molecule, which has become a research hotspot. Introducing nitrogen atoms into the molecular structure of borate ester and forming B-N coordination bond is an effective method to improve the hydrolysis stability of borate ester. The borate ester is generally esterified by reacting long-chain amine containing hydroxyl group with boric acid. These amine group containing borate esters have good friction reducing performance and high thermal oxidative stability. Sulfur-containing borate esters are generally esterified by reacting S-containing monohydroxy compounds or polyhydroxy compounds with boric acid. The above research work improves the performance of borate ester additives in different aspects, but the introduction of some active elements limits the application of the additives to some extent. The development of oil technology puts forward new requirements for additives, and engine oil makes more stringent restrictions on S and P elements of additives. GF-6 engine oil requires that the content of S element is not more than 0.5%, and the content of P element is not more than 0.08%; high-end industrial gear oil pays more and more attention to the odor, biodegradability and whether it meets the requirements of food grade certification of additives, and the development of biodegradable borate ester additives with low sulfur and low phosphorus will be a way to meet the demand of new oil.

[0004] The molecule of ester fatty acid glyceride is strong in adjustability, the thermal stability of triglyceride is good, and the molecule of monoglyceride and diglyceride contains adsorption groups such as ester bond and hydroxyl group, and has good lubricating performance. A kind of complex borated glyceride extreme pressure anti-wear additive is synthesized by properly compounding borate, glycerol, fatty acid and boronizing reagent, and by reaction. The borate is reasonably introduced to improve the oil solubility of the additive, and to improve the thermal stability and extreme pressure performance of the additive. SUMMARY

[0005] The purpose of the present application is to provide a complex borated glyceride extreme pressure anti-wear additive, which has good oil solubility, excellent extreme pressure and anti-wear properties and thermal stability.

[0006] Another purpose of the present application is to provide a preparation method of the complex borated glyceride extreme pressure anti-wear additive.

[0007] The technical scheme adopted by the present application is that the complex borated glyceride extreme pressure anti-wear additive comprises: borate, compound (one), compound (two) and compound (three); the mass ratio of the compound (one), the compound (two) and the compound (three) is 9-11:47-53:36-46.

[0008] The structure of the compound (one) is shown in formula I:

[0009]

[0010] In formula I, R1, R2 and R3 are C3-C 23 hydrocarbon groups.

[0011] The structure of compound (two) is shown in formula II:

[0012]

[0013] In formula II, R is selected from C3-C 23 hydrocarbon groups, and R5 is selected from C4-C 24 alkyl groups or C6-C 18 aryl groups.

[0014] The structure of compound (three) is shown in formula III:

[0015]

[0016] In formula III, R5 is selected from C4-C 24 alkyl groups or C6-C 18 aryl groups; R4 and R6 are or R4 and R6 are the same or different;

[0017] wherein R7 and R8 are the same or different, and R7 and R8 are C3-C 23 hydrocarbon groups.

[0018] The borate salt is any one of sodium borate, potassium borate, calcium borate and magnesium borate.

[0019] Another technical solution adopted by the present application is a preparation method of the complex boronated glyceride extreme pressure anti-wear additive, which is implemented according to the following steps:

[0020] Step 1, glycerol, a borate salt and a solid acid catalyst are mixed, and the temperature is raised to dissolve the borate salt; a C4-C 24 fatty acid is added dropwise to perform esterification reaction, inert gas is introduced to remove water, and when no water is generated in the reaction system, the reaction is stopped and filtered to obtain a boronated fatty acid glyceride mixture;

[0021] Step 2, a boronating agent and a solvent are mixed, the boronated fatty acid glyceride mixture obtained in step 1 is added, inert gas is introduced to remove water, and reaction is performed; the solvent is removed by distillation under reduced pressure to obtain the complex boronated glyceride extreme pressure anti-wear additive.

[0022] The present application is also characterized in that,

[0023] In step 1, the borate salt is any one of sodium borate, potassium borate, calcium borate and magnesium borate; the borate salt is added in an amount of 0.1-10 times of the mass of the C4-C24 2wt%-26wt% of the total mass of the fatty acid and glycerol.

[0024] C4-C 24 1.1-1.8:3; the solid acid catalyst is added in an amount of 0.05wt%-1.2wt% of the total mass of the fatty acid and glycerol; the solid acid catalyst comprises one or a combination of two or more of Al2O3-SiO2, molecular sieve ZSM-5, MCM-41; the esterification reaction temperature is 90-180℃, and the esterification reaction time is 2-12h. 24 2wt%-26wt% of the total mass of the fatty acid and glycerol.

[0025] In step 2, the boronizing reagent is any one or two of an alkyl boronic acid or an aryl boronic acid; the boronizing reagent has a structure shown in formula IV:

[0026]

[0027] In formula IV, R5 is selected from C4-C 24 alkyl or C6-C 18 aryl;

[0028] The boronizing reagent is added in a molar amount of [(3a-b) / 2] to (3a-b), wherein a is the molar amount of glycerol added, and b is the total molar amount of the fatty acid added. 24 C4-C

[0029] 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, and the solvent is added in an amount of 50wt%-150wt% of the total mass of the fatty acid glyceride mixture; the reaction temperature is 80-170℃, and the reaction time is 3-12h.

[0030] The borate in glycerol has good solubility, and the boronized fatty acid glyceride mixture with specific composition is prepared by the reaction of the fatty acid and glycerol, then the boronized fatty acid glyceride and the boronizing reagent are mixed in a certain proportion to synthesize a composite boronized glyceride additive by one-step esterification reaction, the production process is simple and easy to operate, safe and environmentally friendly, the post-treatment process is simple, the production cost is low, different series of extreme pressure anti-wear additive products can be prepared according to specific needs, the product has good oil solubility, excellent anti-wear performance and good thermal stability, and has no adverse effect on the corrosion performance of the lubricating oil. DETAILED DESCRIPTION

[0031] The application will be described in detail below through specific embodiments.

[0032] The compound boronated glycerol acid ester extreme pressure anti-wear additive comprises a borate, a compound (I), a compound (II) and a compound (III), and the mass ratio of the compound (I), the compound (II) and the compound (III) is 9-11:47-53:36-46.

[0033] The structure of the compound (I) is shown in formula I.

[0034]

[0035] In formula I, R1, R2 and R3 are C3-C 23 hydrocarbon groups; R1, R2 and R3 can be the same or different;

[0036] The structure of the compound (II) is shown in formula II.

[0037]

[0038] In formula II, R is selected from C3-C 23 hydrocarbon groups, and R5 is selected from C4-C 24 alkyl groups or C6-C 18 aryl groups;

[0039] The structure of the compound (III) is shown in formula III.

[0040]

[0041] In formula III, R5 is selected from C4-C 24 alkyl groups or C6-C 18 aryl groups; R4 and R6 are or R4 and R6 are the same or different;

[0042] wherein R7 and R8 are the same or different, and R7 and R8 are C3-C 23 hydrocarbon groups;

[0043] The preparation method of the compound boronated glycerol acid ester extreme pressure anti-wear additive is specifically implemented according to the following steps.

[0044] Step 1, glycerol, a borate and a solid acid catalyst are mixed, and the temperature is raised to dissolve the borate, and C4-C 24 fatty acid is added dropwise to perform esterification reaction, inert gas is introduced to remove water, when no water is generated in the reaction system, the reaction is stopped, and filtration is performed to obtain a boronated fatty acid glycerol ester mixture;

[0045] The borate is any one of sodium borate, potassium borate, calcium borate and magnesium borate.

[0046] The addition amount of the borate is C4-C 242wt%-26wt% of the total mass of the fatty acid and glycerol;

[0047] C4-C 24 The molar ratio of the fatty acid and glycerol, calculated based on carboxyl and hydroxyl, is 1.1-1.8:3.

[0048] The esterification reaction temperature is 90-180℃, and the esterification reaction time is 2-12h;

[0049] The solid acid catalyst includes one or a combination of two or more of Al2O3-SiO2, molecular sieve ZSM-5, and MCM-41.

[0050] The addition amount of the solid acid catalyst is 0.05wt%-1.2wt% of the total mass of the C4-C 24 fatty acid and glycerol;

[0051] Step 2: mixing the boronizing reagent and the solvent, adding the boronized fatty acid glycerol ester mixture obtained in step 1, introducing inert gas to remove water, heating to 80-170℃, reacting for 3-12h, removing the solvent by reduced pressure distillation, and obtaining the composite boronized glycerol acid ester extreme pressure anti-wear additive;

[0052] The boronizing reagent is any one or two of an alkyl boronic acid and an aryl boronic acid; the boronizing reagent has the structure shown in formula IV:

[0053]

[0054] In formula IV, R5 is selected from C4-C 24 alkyl or C6-C 18 aryl;

[0055] The addition amount of the boronizing reagent is [(3a-b) / 2] to (3a-b), wherein a is the addition amount of moles of glycerol, and b is the total addition amount of moles of the C4-C 24 fatty acid;

[0056] The solvent is one or a combination of two or more of petroleum ether, benzene, toluene, cyclohexane, n-heptane, n-octane, and xylene; and the addition amount of the solvent is 50wt%-150wt% of the total mass of the fatty acid glycerol ester mixture.

[0057] The inert gas is any one or two of nitrogen and helium.

[0058] The present application also provides a lubricating oil comprising the composite boronized glycerol acid ester extreme pressure anti-wear additive. The composite boronized glycerol acid ester extreme pressure anti-wear additive can be used alone as a lubricating oil additive, or can be used in combination with other lubricating oil additives.

[0059] Preferably, the borated fatty acid glyceride anti-wear additive is added to the lubricating oil in an amount of 0.1wt%-11wt%.

[0060] In the method, first, the borate is used for its good solubility in glycerol to prepare a borated fatty acid glyceride mixture with a specific composition by reacting fatty acid with glycerol, and then the borated fatty acid glyceride and a borating agent are mixed in a certain proportion to synthesize a composite borated glycerol acid ester additive by one-step esterification. The production process is simple and easy to operate, safe and environmentally friendly, the post-treatment process is simple, the production cost is low, and different series of extreme pressure anti-wear additive products can be prepared according to specific needs. The product has good oil solubility, excellent anti-wear performance and good thermal stability, and has no adverse effect on the corrosion performance of the lubricating oil.

[0061] Example 1

[0062] The composite borated glycerol acid ester extreme pressure anti-wear additive of the present embodiment is prepared by the following method:

[0063] (1) 8.6g of potassium borate, 92.1g of glycerol (1 mole) and 2.16g of Al2O3-SiO2 catalyst were added to the reactor, stirred and mixed uniformly, 339g of oleic acid (1.2 mole) was added dropwise, the temperature was raised to 180℃, and water was carried by nitrogen. The reaction was continued for 5 hours, and when no water was generated in the system, the reaction was stopped and filtered to obtain borated oleic acid glyceride;

[0064] (2) 121.9g of phenylboronic acid (1 mole) and 400g of petroleum ether were added to the reaction container, stirred and mixed uniformly, and the borated oleic acid glyceride of step (1) was added. Water was carried by nitrogen, the temperature was raised to 95℃, and the reaction was continued for 4 hours. After that, the solvent was removed by distillation under reduced pressure to obtain the composite borated oleic acid glyceride extreme pressure anti-wear additive A.

[0065] Example 2

[0066] The composite borated glycerol acid ester extreme pressure anti-wear additive of the present embodiment is prepared by the following method:

[0067] (1) 72.7g of sodium borate, 92.1g of glycerol (1 mole) and 0.22g of ZSM-5 catalyst were added to the reactor, stirred and mixed uniformly, 187.5g of isooctanoic acid (1.3 mole) was added dropwise, the temperature was raised to 170℃, and water was carried by nitrogen. The reaction was continued for 4.5 hours, and when no water was generated in the system, the reaction was stopped and filtered to obtain borated isooctanoic acid glyceride;

[0068] (2) 136 g of p-methylphenylboronic acid (1 mole) and 300 g of dimethylbenzene were added into a reaction vessel, stirred and mixed uniformly, the borated glyceryl hexadecenoate in step (1) was added, water was carried by nitrogen, 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 a composite borated glyceryl hexadecenoate extreme pressure anti-wear additive C.

[0069] Example 3

[0070] A composite borated glycerol acid ester extreme pressure anti-wear additive was prepared according to the following method:

[0071] (1) 11.2 g of calcium borate, 92.1 g of glycerol (1 mole) and 3.6 g of MCM-41 catalyst were added into a reactor, stirred and mixed uniformly, 356.2 g of hexadecenoic acid (1.4 moles) was added dropwise, the temperature was raised to 160°C, water was carried by nitrogen, and the reaction was continued for 4 hours. When no water was generated in the system, the reaction was stopped and filtered to obtain borated glyceryl hexadecenoate;

[0072] (2) 136 g of p-methylphenylboronic acid (1 mole) and 300 g of dimethylbenzene were added into a reaction vessel, stirred and mixed uniformly, the borated glyceryl hexadecenoate in step (1) was added, water was carried by nitrogen, 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 a composite borated glyceryl hexadecenoate extreme pressure anti-wear additive C.

[0073] Example 4

[0074] A composite borated glycerol acid ester extreme pressure anti-wear additive was prepared according to the following method:

[0075] (1) 40.8 g of magnesium borate, 46.1 g of glycerol (0.5 mole) and 2.16 g of Al2O3-SiO2 catalyst were added into a reactor, stirred and mixed uniformly, 226 g of oleic acid (0.8 mole) was added dropwise, the temperature was raised to 155°C, water was carried by industrial helium, and the reaction was continued for 8 hours. When no water was generated in the system, the reaction was stopped and filtered to obtain borated glyceryl oleate;

[0076] (2) 54.4 g of p-methylphenylboronic acid (0.4 mole) and 200 g of toluene were added into a reaction vessel, stirred and mixed uniformly, the borated glyceryl oleate in step (1) was added, water was carried by helium, 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 a composite borated glyceryl oleate extreme pressure anti-wear additive D.

[0077] Comparative Example 1

[0078] A borated fatty acid glycerol ester anti-wear additive was prepared according to the following method:

[0079] (1) 92.1 g of glycerol (1 mole) and 2.16 g of Al2O3-SiO2 catalyst were added into a reactor, stirred and mixed uniformly, 339 g of oleic acid (1.2 mole) was added dropwise, heated to 150°C, water was carried by nitrogen, and the reaction was continued for 5 hours. When no water was generated in the system, the reaction was stopped, filtered, and glycerol oleate was obtained;

[0080] (2) 121.9 g of phenylboronic acid (1 mole) and 400 g of petroleum ether were added into a reaction container, stirred and mixed uniformly, and the glycerol oleate in step (1) was added. Water was carried by nitrogen, heated to 95°C, and the reaction was continued for 4 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronized glycerol oleate anti-wear additive E.

[0081] Comparative Example 2

[0082] A boronized fatty acid glycerol ester anti-wear additive was prepared as follows:

[0083] (1) 92.1 g of glycerol (1 mole) and 2.16 g of Al2O3-SiO2 catalyst were added into a reactor, stirred and mixed uniformly, 339 g of oleic acid (1.2 mole) was added dropwise, heated to 150°C, water was carried by nitrogen, and the reaction was continued for 5 hours. When no water was generated in the system, the reaction was stopped, filtered, and glycerol oleate was obtained;

[0084] (2) 61.83 g of boric acid (1 mole) and 400 g of petroleum ether were added into a reaction container, stirred and mixed uniformly, and the glycerol oleate in step (1) was added. Water was carried by nitrogen, heated to 95°C, and the reaction was continued for 4 hours. After that, the solvent was removed by distillation under reduced pressure to obtain boronized glycerol oleate anti-wear additive F.

[0085] Comparative Example 3

[0086] A boronized fatty acid glycerol ester anti-wear additive was prepared as follows:

[0087] (1) 8.6 g of potassium borate, 92.1 g of glycerol (1 mole) and 2.16 g of Al2O3-SiO2 catalyst were added into a reactor, stirred and mixed uniformly, 339 g of oleic acid (1.2 mole) was added dropwise, heated to 180°C, water was carried by nitrogen, and the reaction was continued for 5 hours. When no water was generated in the system, the reaction was stopped, filtered, and boronized glycerol oleate G was obtained.

[0088] Comparative Example 4

[0089] A boronized fatty acid monoglyceride anti-wear additive was prepared as follows:

[0090] Into a reaction vessel were added 136 g of p-tolylboronic acid (1 mole) and 400 g of petroleum ether, the mixture was stirred and mixed uniformly, 164.3 g of glycerol monohexadecenoate (0.5 moles) was added, water was carried by nitrogen, the temperature was raised to 105°C, and the reaction was continued for 6 hours, then the solvent was removed by distillation under reduced pressure to obtain boronized hexadecenoic acid monoglyceride anti-wear additive G.

[0091] The boronized fatty acid glyceride anti-wear additives obtained in the examples and comparative examples were adjusted into GL-5 gear oil at an addition amount of 1.0 wt%, and then the wear scar diameter under a load of 392 N, the sintering load (P D value) under a load of 392 N, the friction coefficient and the copper strip corrosion performance of the lubricating oil were determined, and the results are shown in Table 1; at the same time, the adjusted oil was stored at 0°C for 90 days to investigate the storage stability of the oil.

[0092] The maximum non-seizure load (P D value) was determined according to the method of GB / T 3142-1982, the wear scar diameter of the steel ball was determined according to the method of NB / SH / T 0189-2017, the friction coefficient was determined according to the method of SH / T0762-2005, and the copper strip corrosion was determined according to the method of GB / T 5096-2017.

[0093] Table 1 Performance evaluation of the composite boronized glyceride acid ester extreme pressure anti-wear additive

[0094]

[0095] The results show that the composite boronized glyceride acid ester extreme pressure anti-wear additive has good oil solubility, excellent extreme pressure anti-wear and friction reduction performance, and no adverse effect on the corrosion performance of the lubricating oil.

Claims

1. Composite boronated glycerate extreme pressure and anti-wear additive, characterized in that: include: borate, compound (1), compound (2), compound (3); the mass ratio of compound (1), compound (2), compound (3) is 9-11:47-53:36-46; The structure of the compound (I) is shown in Formula I: Formula I In Formula I, R1, R2 and R3 are C3-C 23 of hydrocarbon groups; The structure of the compound (II) is shown in Formula II: Formula II In formula II, R is selected from C3-C 23 The hydrocarbon group, R5 is selected from C4-C 24 Alkyl or C6-C 18 aryl groups; The structure of the compound (III) is shown in Formula III: Formula III In formula III, R5 is selected from C4-C 24 Alkyl or C6-C 18 R4 and R6 are or ; R4 and R6 are the same or different; Wherein, R7 and R8 are the same or different, and R7 and R8 are C3-C 23 of hydrocarbon groups.

2. The composite boronated glycerate extreme pressure and anti-wear additive according to claim 1, characterized in that: The borate is any one of sodium borate, potassium borate, calcium borate and magnesium borate.

3. The method for preparing the composite boronated glycerate extreme pressure and anti-wear additive according to any one of claims 1 to 2, characterized in that: Please follow the steps below to implement it: Step 1: Mix glycerol, borate and solid acid catalyst, heat until the borate is dissolved, and add C4-C 24 The fatty acid is subjected to esterification reaction, and an inert gas with water is introduced. When no water is produced in the reaction system, the reaction is stopped and filtered to obtain a boronated fatty acid glyceride mixture; Step 2: mixing the boronation reagent and the solvent, adding the boronated fatty acid glyceride mixture obtained in step 1, introducing inert gas with water to react, and removing the solvent by vacuum distillation to obtain a composite boronated glyceride extreme pressure and anti-wear additive.

4. The method for preparing the composite boronated glycerate extreme pressure and anti-wear additive according to claim 3, wherein: In step 1, the borate is any one of sodium borate, potassium borate, calcium borate, and magnesium borate; the amount of borate added is C4-C 24 2wt%-26wt% of the total mass of fatty acids and glycerol.

5. The method for preparing the composite boronated glycerate extreme pressure and anti-wear additive according to claim 3, wherein: The C4-C 24 The molar ratio of fatty acid and glycerol calculated by carboxyl group and hydroxyl group is 1.1-1.8:3; the amount of solid acid catalyst added is C4-C 24 The esterification reaction temperature is 90-180°C, and the esterification reaction time is 2-12h.

6. The method for preparing the composite boronated glycerate extreme pressure and anti-wear additive according to claim 3, wherein: In step 2, the boronating agent is any one or both of an alkyl boronic acid and an aryl boronic acid; the boronating agent has a structure shown in Formula IV: Formula IV In formula IV, R5 is selected from C4-C 24 Alkyl or C6-C 18 aryl groups; 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 total molar amount of fatty acids added.

7. The method for preparing the composite boronated glycerate extreme pressure and anti-wear additive 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, and the amount of solvent added is 50wt%-150wt% of the total mass of the fatty acid glyceride mixture; the reaction temperature is 80-170°C, and the reaction time is 3-12h.

8. Use of the composite boronated glycerate extreme pressure and anti-wear additive according to claim 1 in lubricating oil.

9. The use according to claim 8, characterized in that The addition amount of the composite boronated glycerate extreme pressure and anti-wear additive in the lubricating oil is 0.1 wt %-11 wt %.

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