A 2,6-di-tert-butylphenol compound and its preparation method and application

Abstract

The invention discloses a 2,6-di-tert-butylphenol compound and its preparation method and application. The compound has excellent anti-wear performance and antioxidant performance at the same time, can be added to lubricating oil, grease, fuel oil, engine oil or plastic rubber as an additive, can reduce the type and dosage of additives, reduce the probability of mutual confrontation between different types of additives, prevent the product anti-oxidation, anti-wear and other performance degradation caused by the mutual confrontation of catalysts, improve product performance and stability, and have good application prospects. At the same time, its preparation process is simple, easy to operate, and the preparation raw materials are easy to obtain, with strong reproducibility and good economic benefits.

Description

Technical Field

[0001] The invention relates to a phosphonate compound and a preparation method and application thereof, and in particular to a 2,6-di-tert-butylphenol compound and a preparation method and application thereof, belonging to the field of chemical industry. Background Art

[0002] In the existing production process, the lubrication state of the mechanical sliding surface not only forms an oil film on a single plane, but also becomes an ideal fluid lubrication state. Sometimes a tiny oil film can be seen. In addition, considering the machining accuracy of the mechanical surface, there is a phenomenon of uneven surface. Some mechanical surfaces are still in a state of direct contact, and the contact parts have extremely high pressure. At this time, the lubricating oil is sandwiched between the two mechanical surfaces, the oil film of the lubricating oil becomes thinner, and the oil film ruptures at extremely high pressures. As a result, the fluid lubrication state changes to an elastic fluid lubrication state or a mixed lubrication state, and further turns to boundary lubrication.

[0003] Boundary lubrication is the critical state before the transition from liquid friction to dry friction (direct contact between friction pair surfaces). It is a lubrication condition between non-smooth surfaces with partial surface contact. At this time, the overall viscosity characteristics of the lubricant do not play a role. At this time, the tribological properties between the friction surfaces are determined by the interaction between the lubricant and the surface and the properties of the generated boundary film. Therefore, extreme pressure anti-wear agents are essential in lubricating oils under boundary lubrication conditions.

[0004] In boundary lubrication, extreme pressure anti-wear agents can react chemically with metal surfaces to form reaction films to prevent scratches, bites and fusion welding on the metal surfaces, and are used to improve the lubricity and anti-wear properties of lubricants. Extreme pressure anti-wear agents mainly include sulfur-containing extreme pressure anti-wear agents, chlorine-containing extreme pressure anti-wear agents, phosphorus-containing extreme pressure anti-wear agents, nitrogen-containing extreme pressure anti-wear agents, metal salt extreme pressure anti-wear agents, boron-containing extreme pressure anti-wear agents, etc. Among them, sulfur-phosphorus extreme pressure anti-wear agents containing both sulfur and phosphorus are widely used because of their high load-bearing capacity, good compatibility and good multi-effect properties.

[0005] At present, the extreme pressure anti-wear agents widely used in the field of lubricating oils include tricresol phosphate (T306), ammonium thiophosphate (T307), thiophosphate (IRGALUBE 353), ammonium phosphate (IRGALUBE 349), etc., but their anti-wear and friction reduction performances need to be further improved. CN 102260572B discloses a phosphorus-nitrogen type extreme pressure anti-wear agent, which has excellent antioxidant, rust-proof and corrosion-resistant properties, and has good extreme pressure anti-wear properties, but it is only used as an extreme pressure anti-wear agent and does not show antioxidant properties. CN 101724492B discloses a sulfur-zinc phosphate type extreme pressure anti-wear agent, which has good load-bearing capacity, antioxidant stability and anti-wear properties, but this invention is an organic metal salt, which is inconsistent with the development trend of lubricating oil additives without ash. At present, the anti-wear and friction reduction properties of ash-free phosphorus-containing additives are good, but the prior art does not have good antioxidant properties. Adding multiple types of additives poses a risk of antagonism between different additives, further leading to problems such as product performance degradation and failure. However, a single additive is difficult to cope with the complex situations faced in real-world applications.

[0006] Now, the development trend of additive technology is to develop multifunctional additives, avoid additive confrontation, reduce the variety and amount of additives in the formulation system, improve the applicability of the formulation, and help meet the requirements of energy conservation and environmental protection. Summary of the invention

[0007] Aiming at the problem that the additives in the prior art have a single function and there are hidden dangers of mutual confrontation between multiple additives, which easily lead to the performance degradation or even failure of the product. The present invention develops a 2,6-di-tert-butylphenol compound. The compound is easy to prepare and has excellent anti-wear, friction-reducing and antioxidant properties, and can reduce the types and addition amounts of extreme pressure anti-wear agents in lubricating oils. There are no literature or patent reports on 2,6-di-tert-butylphenol compounds and their preparation and application at home and abroad.

[0008] According to a first embodiment of the present invention, a 2,6-di-tert-butylphenol compound is provided.

[0009] A 2,6-di-tert-butylphenol compound having a general structural formula (I):

[0010]

[0011] In formula (I), R1 is a C2-C 30 Straight or branched chain alkyl:

[0012]

[0013] Preferably, in formula (I), R1 is a C2-C 30 Straight chain or branched chain alkyl.

[0014] Preferably, the 2,6-di-tert-butylphenol compound is selected from one or more of the following compounds:

[0015] 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol

[0016]

[0017] 2,6-di-tert-butyl-3-(8,9,11,12-tetrakis(diphenylphosphonate))pentadecylphenol

[0018]

[0019] 2,6-di-tert-butyl-3-(8,9,11,12,14,15-hexa(diphenylphosphonate))pentadecylphenol

[0020]

[0021] According to a second embodiment provided by the present invention, a method for preparing 2,6-di-tert-butylphenol compounds is provided.

[0022] A method for preparing 2,6-di-tert-butylphenol compounds, the method comprising the following steps:

[0023] 1) A tert-butyl halide having a general structural formula (III) is reacted with a phenolic compound having a general structural formula (IV) under the action of a catalyst I, and a solvent I is optionally added or not added to obtain an intermediate compound having a general structural formula (V). The reaction formula is:

[0024]

[0025] The R2 is C2~C 30 A straight chain or branched chain olefin group.

[0026] 2) After the reaction of step 1) is completed, the intermediate compound having the general structural formula (V) is subjected to an epoxidation reaction with a peroxy acid in the presence of a catalyst II, and optionally a solvent II is added to obtain an epoxide compound having the general structural formula (VI). The reaction formula is:

[0027]

[0028] The R3 is C2~C 30 A hydrocarbon group containing an epoxy bond.

[0029] 3) After the reaction of step 2) is completed, the epoxy compound having the general structural formula (VI) is subjected to a ring-opening esterification reaction with diphenylphosphonic acid under the action of catalyst III, and solvent III is optionally added or not added to obtain a compound having the general structural formula (I) 2,6-di-tert-butylphenol compound. The reaction formula is:

[0030]

[0031] Wherein, the R1 contains C2 to C 30 Straight chain or branched chain alkyl.

[0032] Preferably, R1 is a C2-C 30 A straight chain or branched chain alkyl group. The R2 is a C2-C 30 The R3 is a C2-C 30 Straight chain or branched chain alkyl.

[0033]

[0034] Preferably, in formula (I), R1 is selected from one of the structures shown in 8,9-bis(diphenylphosphonate)pentadecyl, 8,9,11,12-tetra(diphenylphosphonate)pentadecyl, and 8,9,11,12,14,15-hexa(diphenylphosphonate)pentadecyl; R2 is one of 8-pentadecenyl, 8,11-pentadecadienyl, and 8,11,14-pentadecatrienyl; R3 is one of the formula 8,9-pentadecylindole, 8,9:11,12-diecylindole, and 8,9:11,12:14,15-tricylindole.

[0035] Preferably, in step 1), the tert-butyl halide is one of tert-butyl fluoride, tert-butyl chloride, tert-butyl bromide and tert-butyl iodide; the molar ratio of the phenolic compound having the general structural formula (IV) to the tert-butyl halide is 1:1.5-8, preferably 1:1.7-5, more preferably 1:1.8-3. The catalyst I is one or more of zinc chloride, aluminum chloride, ferric chloride, tin tetrachloride, boron trifluoride and titanium tetrachloride, preferably zinc chloride. The molar ratio of the catalyst I to the phenolic compound having the general structural formula (IV) is 1:5-30, preferably 1:7-25, more preferably 1:10-20.

[0036] Preferably, in step 2), the peracid is an acid containing a peroxy group (-OO-) in the molecule. The peracid is preferably one or more of peroxyformic acid, peracetic acid, persulfonic acid, meta-chloroperbenzoic acid, tert-butyl hydroperoxide, tert-butyl peracetate and other peracids. The peracid is more preferably hydrogen peroxide. The molar ratio of the peracid to the compound having the structure of formula (V) is 3-15:1, preferably 5-12:1, and more preferably 6-8:1. The catalyst II is one or more of sulfuric acid, hydrochloric acid, nitric acid and other inorganic acids, acetic acid, propionic acid, benzoic acid, meta-chlorobenzoic acid and other organic acids, and strongly acidic ion exchange resins, preferably sulfuric acid. The molar ratio of the catalyst II to the compound having the structure of formula (V) is 1:10-200, preferably 1:40-120, and more preferably 1:60-100.

[0037] Preferably, in step 3), the molar ratio of the amount of diphenylphosphonic acid added to the compound having the structure of formula (VI) is 1:2-10, preferably 1:2.3-8, and more preferably 1:2.5-4. The catalyst III is one or more of sulfuric acid, hydrochloric acid, nitric acid and other inorganic acids, acetic acid, propionic acid, benzoic acid, m-chlorobenzoic acid and other organic acids, preferably sulfuric acid. The molar ratio of the amount of the catalyst III to the amount of the compound having the structure of formula (VI) is 1:5-300, preferably 1:30-200, and more preferably 60-100.

[0038] Preferably, step 1) is specifically as follows: adding a compound having a structure of formula (IV) and a solvent I into a reactor, adding a catalyst I after dissolution is completed, stirring and heating to 50-70°C (preferably 55-65°C), slowly dropping a halogenated tert-butylene, and continuing to react at 50-70°C (preferably 55-65°C) for 1-8h (preferably 2-4h) after the dropping is complete. After the reaction is completed, the mixed product is cooled to room temperature, and then alkali-washed with 2-10% alkali solution (preferably 3-8% potassium hydroxide), washed with water until neutral after the alkali washing is completed, and distilled under reduced pressure at 700-1300Pa (preferably 900-1100Pa) and 100-150°C (preferably 110-130°C) for 0.5-3h (preferably 0.8-1.5h), removing the solvent, water and unreacted raw materials, and obtaining a dark brown-red viscous liquid, i.e., a compound having a structure of formula (V).

[0039] Preferably, step 2) is specifically as follows: add a compound having a structure of formula (V), solvent II and catalyst II to a reactor, stir and heat, and react at 50-90°C (preferably 60-80°C) for 1-5h (preferably 2-4h). After the reaction is completed, cool the mixed product, then wash it with 2-10% alkali solution (preferably 3-8% potassium hydroxide), wash it with water to neutrality after the alkali washing, and then distill the organic phase under reduced pressure at 70-130Pa (preferably 90-110Pa) and 100-200°C (preferably 130-170°C) for 0.5-3h (preferably 0.8-1.5h), remove water and unreacted raw materials, and obtain an orange-red transparent liquid, which is a compound having a structure of formula (VI).

[0040] Preferably, step 3) is specifically as follows: adding a compound having a structure of formula (VI), catalyst III, water and solvent III into a reactor, stirring and heating, reflux at 60-100°C (preferably 80-90°C) for 0.5-1.5h (preferably 0.9-1.1h), then dropping diphenylphosphonic acid into the reactor at a rate of 1-5d / s (preferably 2-4d / s), and continuing the reaction reflux for 3-8h (preferably 4-6h) after the dropwise addition is completed. After the reaction is completed, the mixed product is washed with water 1-5 times (preferably 2-4 times), and then the solvent is removed by distillation to obtain a 2,6-di-tert-butylphenol compound having a structure of formula (I).

[0041] Preferably, the solvent I is C3 to C 20 Aliphatic compounds, C6~C 20 Carbocyclic compounds, C2~C 20 One or more of the heterocyclic compounds, preferably one or more of acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, ethylbenzene, chloroform and chlorobenzene.

[0042] Preferably, the solvent II is C1-C 20 Aliphatic compounds, C6~C 20 Carbocyclic compounds, C2~C 20 One or more of the heterocyclic compounds, preferably one or more of formic acid, acetic acid, benzoic acid, phenylacetic acid, and acetonitrile.

[0043] Preferably, the solvent III is C2 to C 20 Aliphatic compounds, C6~C 20 Carbocyclic compounds, C2~C 20 One or more of the heterocyclic compounds, preferably one or more of benzene, toluene, ethylbenzene, ethanol, hexane and carbon tetrachloride.

[0044] Preferably, step 1) and / or step 2) and / or step 3) are performed under the protection of an atmosphere of nitrogen or an inert gas. Preferably, the inert gas is one of helium and argon.

[0045] According to a third embodiment of the present invention, there is provided a use of a 2,6-di-tert-butylphenol compound.

[0046] A use of a 2,6-di-tert-butylphenol compound, wherein the 2,6-di-tert-butylphenol compound having a structure of formula (I) is used as an antioxidant and anti-wear dual-functional additive; preferably, the 2,6-di-tert-butylphenol compound having a structure of formula (I) is used as an antioxidant and anti-wear dual-functional additive in lubricating oil, grease, fuel oil, engine oil or plastic rubber; preferably, the addition amount of the dual-functional additive is 0.01-3wt% of the mass of the lubricating oil, grease, fuel oil, engine oil or plastic rubber, preferably 0.05-2wt%, and more preferably 0.2-1.5wt%.

[0047] In the prior art, due to the increasingly complex application scenarios, it is necessary to add extreme pressure anti-wear agents to organic oil products (lubricating oil, grease, fuel oil, engine oil or plastic rubber, etc.) to improve the performance of organic oil products in boundary lubrication. In the prior art, in order to improve the wear resistance and oxidation resistance of organic oil products, it is generally necessary to add anti-wear agents and antioxidants separately. There are many types and addition amounts of additives, and there is a hidden danger of mutual confrontation.

[0048] In the present invention, a 2,6-di-tert-butylphenol compound having a structure of formula (I) is developed. The compound has excellent anti-wear and antioxidant properties, the raw materials are easily available, the preparation process is relatively simple, and the compound can be added to a variety of organic oil products as a dual-functional additive of anti-wear agent and antioxidant, thereby reducing the types and amounts of additives and improving product performance.

[0049] In the present invention, a cardanol compound having a structure of formula (IV) is sequentially subjected to halogenated hydrocarbon substitution, epoxidation reaction, and ring-opening esterification reaction with diphenylphosphonic acid to prepare a 2,6-di-tert-butylphenol compound having a structure of formula (I). The long side chain of the cardanol compound having a structure of formula (IV) is introduced with a group represented by formula (II), so that it has excellent wear resistance and antioxidant properties. At the same time, the raw materials used in the preparation process are easily available and the method is simple.

[0050] Among the existing extreme pressure anti-wear agents, the 2,6-di-tert-butylphenol compounds having the structure of formula (I) have slightly better anti-wear performance than conventional anti-wear agents, and also have excellent antioxidant properties. Compared with conventional antioxidants, the 2,6-di-tert-butylphenol compounds having the structure of formula (I) have slightly better antioxidant performance than conventional antioxidants, and also have excellent anti-wear properties. In addition, the benzene ring structure in the 2,6-di-tert-butylphenol compounds having the structure of formula (I) can also provide better high temperature resistance, and the polar hydroxyl group can provide the lubrication system with wetting and activity on the contact surface.

[0051] In the present invention, the 2,6-di-tert-butylphenol compound having the structure of formula (I) can be applied to a variety of organic oil products and has good practicality.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] 1. The 2,6-di-tert-butylphenol compound provided by the present invention has excellent anti-wear and antioxidant properties, can reduce the types and amounts of additives, prevent the hidden danger of mutual confrontation between different types of additives, improve product performance and stability, and has good application prospects.

[0054] 2. The preparation process of a 2,6-di-tert-butylphenol compound provided by the present invention is simple, easy to operate, and the raw materials for preparation are readily available, and it has strong reproducibility and good economic benefits.

[0055] 3. The 2,6-di-tert-butylphenol compound provided by the present invention can be widely used in a variety of organic oil products and has good practicality. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 This is the infrared spectrum of the product 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphate)pentadecyl)phenol prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0057] The technical solution of the present invention is illustrated below by way of example, and the scope of protection requested by the present invention includes but is not limited to the following embodiments.

[0058] According to a first embodiment of the present invention, a 2,6-di-tert-butylphenol compound is provided.

[0059] A 2,6-di-tert-butylphenol compound having a general structural formula (I):

[0060]

[0061] In formula (I), R1 is a C2-C 30 Straight or branched chain alkyl:

[0062]

[0063] Preferably, in formula (I), R1 is a C2-C 30 Straight chain or branched chain alkyl.

[0064] Preferably, the 2,6-di-tert-butylphenol compound is selected from one or more of the following compounds:

[0065] 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol

[0066]

[0067] 2,6-di-tert-butyl-3-(8,9,11,12-tetrakis(diphenylphosphonate))pentadecylphenol

[0068]

[0069] 2,6-di-tert-butyl-3-(8,9,11,12,14,15-hexa(diphenylphosphonate))pentadecylphenol

[0070]

[0071] According to a second embodiment provided by the present invention, a method for preparing 2,6-di-tert-butylphenol compounds is provided.

[0072] A method for preparing 2,6-di-tert-butylphenol compounds, the method comprising the following steps:

[0073] 1) A tert-butyl halide having a general structural formula (III) is reacted with a phenolic compound having a general structural formula (IV) under the action of a catalyst I, and a solvent I is optionally added or not added to obtain an intermediate compound having a general structural formula (V). The reaction formula is:

[0074]

[0075] The R2 is C2~C 30 A straight chain or branched chain olefin group.

[0076] 2) After the reaction of step 1) is completed, the intermediate compound having the general structural formula (V) is subjected to an epoxidation reaction with a peroxy acid in the presence of a catalyst II, and optionally a solvent II is added to obtain an epoxide compound having the general structural formula (VI). The reaction formula is:

[0077]

[0078] The R3 is C2~C 30 A hydrocarbon group containing an epoxy bond.

[0079] 3) After the reaction of step 2) is completed, the epoxy compound having the general structural formula (VI) is subjected to a ring-opening esterification reaction with diphenylphosphonic acid under the action of catalyst III, and solvent III is optionally added or not added to obtain a compound having the general structural formula (I) 2,6-di-tert-butylphenol compound. The reaction formula is:

[0080]

[0081] Wherein, the R1 contains C2 to C 30 Straight chain or branched chain alkyl.

[0082] Preferably, R1 is a C2-C 30 A straight chain or branched chain alkyl group. The R2 is a C2-C 30 The R3 is a C2-C 30 Straight chain or branched chain alkyl.

[0083]

[0084] Preferably, in formula (I), R1 is selected from one of the structures shown in 8,9-bis(diphenylphosphonate)pentadecyl, 8,9,11,12-tetra(diphenylphosphonate)pentadecyl, and 8,9,11,12,14,15-hexa(diphenylphosphonate)pentadecyl; R2 is one of 8-pentadecenyl, 8,11-pentadecadienyl, and 8,11,14-pentadecatrienyl; R3 is one of the formula 8,9-pentadecylindole, 8,9:11,12-diecylindole, and 8,9:11,12:14,15-tricylindole.

[0085] Preferably, in step 1), the tert-butyl halide is one of tert-butyl fluoride, tert-butyl chloride, tert-butyl bromide and tert-butyl iodide; the molar ratio of the phenolic compound having the general structural formula (IV) to the tert-butyl halide is 1:1.5-8, preferably 1:1.7-5, more preferably 1:1.8-3. The catalyst I is one or more of zinc chloride, aluminum chloride, ferric chloride, tin tetrachloride, boron trifluoride and titanium tetrachloride, preferably zinc chloride. The molar ratio of the catalyst I to the phenolic compound having the general structural formula (IV) is 1:5-30, preferably 1:7-25, more preferably 1:10-20.

[0086] Preferably, in step 2), the peracid is an acid containing a peroxy group (-OO-) in the molecule. The peracid is preferably one or more of peroxyformic acid, peracetic acid, persulfonic acid, meta-chloroperbenzoic acid, tert-butyl hydroperoxide, tert-butyl peracetate and other peracids. The peracid is more preferably hydrogen peroxide. The molar ratio of the peracid to the compound having the structure of formula (V) is 3-15:1, preferably 5-12:1, and more preferably 6-8:1. The catalyst II is one or more of sulfuric acid, hydrochloric acid, nitric acid and other inorganic acids, acetic acid, propionic acid, benzoic acid, meta-chlorobenzoic acid and other organic acids, and strongly acidic ion exchange resins, preferably sulfuric acid. The molar ratio of the catalyst II to the compound having the structure of formula (V) is 1:10-200, preferably 1:40-120, and more preferably 1:60-100.

[0087] Preferably, in step 3), the molar ratio of the amount of diphenylphosphonic acid added to the compound having the structure of formula (VI) is 1:2-10, preferably 1:2.3-8, and more preferably 1:2.5-4. The catalyst III is one or more of sulfuric acid, hydrochloric acid, nitric acid and other inorganic acids, acetic acid, propionic acid, benzoic acid, m-chlorobenzoic acid and other organic acids, preferably sulfuric acid. The molar ratio of the amount of the catalyst III to the amount of the compound having the structure of formula (VI) is 1:5-300, preferably 1:30-200, and more preferably 60-100.

[0088] Preferably, step 1) is specifically as follows: adding a compound having a structure of formula (IV) and a solvent I into a reactor, adding a catalyst I after dissolution is completed, stirring and heating to 50-70°C (preferably 55-65°C), slowly dropping a halogenated tert-butylene, and continuing to react at 50-70°C (preferably 55-65°C) for 1-8h (preferably 2-4h) after the dropping is complete. After the reaction is completed, the mixed product is cooled to room temperature, and then alkali-washed with 2-10% alkali solution (preferably 3-8% potassium hydroxide), washed with water until neutral after the alkali washing is completed, and distilled under reduced pressure at 700-1300Pa (preferably 900-1100Pa) and 100-150°C (preferably 110-130°C) for 0.5-3h (preferably 0.8-1.5h), removing the solvent, water and unreacted raw materials, and obtaining a dark brown-red viscous liquid, i.e., a compound having a structure of formula (V).

[0089] Preferably, step 2) is specifically as follows: add a compound having a structure of formula (V), solvent II and catalyst II to a reactor, stir and heat, and react at 50-90°C (preferably 60-80°C) for 1-5h (preferably 2-4h). After the reaction is completed, cool the mixed product, then wash it with 2-10% alkali solution (preferably 3-8% potassium hydroxide), wash it with water to neutrality after the alkali washing, and then distill the organic phase under reduced pressure at 70-130Pa (preferably 90-110Pa) and 100-200°C (preferably 130-170°C) for 0.5-3h (preferably 0.8-1.5h), remove water and unreacted raw materials, and obtain an orange-red transparent liquid, which is a compound having a structure of formula (VI).

[0090] Preferably, step 3) is specifically as follows: adding a compound having a structure of formula (VI), catalyst III, water and solvent III into a reactor, stirring and heating, reflux at 60-100°C (preferably 80-90°C) for 0.5-1.5h (preferably 0.9-1.1h), then dropping diphenylphosphonic acid into the reactor at a rate of 1-5d / s (preferably 2-4d / s), and continuing the reaction reflux for 3-8h (preferably 4-6h) after the dropwise addition is completed. After the reaction is completed, the mixed product is washed with water 1-5 times (preferably 2-4 times), and then the solvent is removed by distillation to obtain a 2,6-di-tert-butylphenol compound having a structure of formula (I).

[0091] Preferably, the solvent I is C3 to C 20 Aliphatic compounds, C6~C 20 Carbocyclic compounds, C2~C 20 One or more of the heterocyclic compounds, preferably one or more of acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, ethylbenzene, chloroform and chlorobenzene.

[0092] Preferably, the solvent II is C1-C 20 Aliphatic compounds, C6~C 20 Carbocyclic compounds, C2~C 20 One or more of the heterocyclic compounds, preferably one or more of formic acid, acetic acid, benzoic acid, phenylacetic acid, and acetonitrile.

[0093] Preferably, the solvent III is C2 to C 20 Aliphatic compounds, C6~C 20 Carbocyclic compounds, C2~C 20 One or more of the heterocyclic compounds, preferably one or more of benzene, toluene, ethylbenzene, ethanol, hexane and carbon tetrachloride.

[0094] Preferably, step 1) and / or step 2) and / or step 3) are performed under the protection of an atmosphere of nitrogen or an inert gas. Preferably, the inert gas is one of helium and argon.

[0095] According to a third embodiment of the present invention, there is provided a use of a 2,6-di-tert-butylphenol compound.

[0096] A use of a 2,6-di-tert-butylphenol compound, wherein the 2,6-di-tert-butylphenol compound having a structure of formula (I) is used as an antioxidant and anti-wear dual-functional additive; preferably, the 2,6-di-tert-butylphenol compound having a structure of formula (I) is used as an antioxidant and anti-wear dual-functional additive in lubricating oil, grease, fuel oil, engine oil or plastic rubber; preferably, the addition amount of the dual-functional additive is 0.01-3wt% of the mass of the lubricating oil, grease, fuel oil, engine oil or plastic rubber, preferably 0.05-2wt%, and more preferably 0.2-1.5wt%.

[0097] Preparation Example 1

[0098] Preparation of 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol:

[0099]

[0100] 1) Add 0.2 mol of 3-(8-pentadecenyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of zinc chloride catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the addition is complete. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1h to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, with a product conversion rate of 91.6%.

[0101] 2) 0.24 mol 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, 0.17 mol formic acid, 0.003 mol sulfuric acid and 1.68 mol hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9-epoxypentadecanyl)phenol, and the product conversion rate was 96.8%.

[0102] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9-epoxypentadecane)phenol, 0.002 mol of sulfuric acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then dropwise add 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate)pentadecane)phenol, with a P content of 9.8% and a product conversion rate of 93.2%.

[0103] Preparation Example 2

[0104] Preparation of 2,6-di-tert-butyl-3-(8,9,11,12-tetrakis(diphenylphosphonate))pentadecylphenol:

[0105]

[0106] 1) Add 0.2 mol of 3-(8,11-pentadecadienyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of zinc chloride catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the addition is complete. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1 hour to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8,11-pentadecadienyl)phenol, and the product conversion rate is 89.3%.

[0107] 2) 0.24 mol 2,6-di-tert-butyl-3-(8,11-pentadecadienyl)phenol, 0.17 mol formic acid, 0.003 mol sulfuric acid and 1.68 mol hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9:11,12-diepoxypentadecane)phenol, and the product conversion rate was 95.2%.

[0108] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9:11,12-diepoxypentadecane)phenol, 0.002 mol of sulfuric acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then dropwise add 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9,11,12-tetrakis(diphenylphosphonate))pentadecanol, with a P content of 12.2% and a product conversion rate of 92.7%.

[0109] Preparation Example 3

[0110] Preparation of 2,6-di-tert-butyl-3-(8,9,11,12,14,15-hexa(diphenylphosphonate))pentadecylphenol

[0111]

[0112] 1) Add 0.2 mol of 3-(8,11,14-pentadecatrienyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of zinc chloride catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the addition is complete. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1 hour to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8,11,14-pentadecatrienyl)phenol, and the product conversion rate is 90.3%.

[0113] 2) 0.24 mol 2,6-di-tert-butyl-3-(8,11,14-pentadecatrienyl)phenol, 0.17 mol formic acid, 0.003 mol sulfuric acid and 1.68 mol hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9:11,12:14,15-triepoxypentadecyl)phenol, and the product conversion rate was 95.9%.

[0114] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9:11,12:14,15-triepoxypentadecyl)phenol, 0.002 mol of sulfuric acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then drop 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9,11,12,14,15-hexa(diphenylphosphonate))pentadecylphenol, with a P content of 15.6% and a product conversion rate of 92.4%.

[0115] Preparation Example 4

[0116] Preparation of 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol:

[0117]

[0118] 1) Add 0.2 mol of 3-(8-pentadecenyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of aluminum oxide catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the dropwise addition. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1h to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, and the product conversion rate is 90.9%.

[0119] 2) 0.24 mol 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, 0.17 mol formic acid, 0.003 mol sulfuric acid and 1.68 mol hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9-epoxypentadecanyl)phenol, and the product conversion rate was 95.1%.

[0120] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9-epoxypentadecane)phenol, 0.002 mol of sulfuric acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then dropwise add 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate)pentadecane)phenol, with a P content of 9.8% and a product conversion rate of 93.0%.

[0121] Preparation Example 5

[0122] Preparation of 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol:

[0123]

[0124] 1) Add 0.2 mol of 3-(8-pentadecenyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of iron oxide catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the dropwise addition. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1h to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, with a product conversion rate of 91.2%.

[0125] 2) 0.24 mol 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, 0.17 mol formic acid, 0.003 mol sulfuric acid and 1.68 mol hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9-epoxypentadecanyl)phenol, and the product conversion rate was 96.7%.

[0126] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9-epoxypentadecane)phenol, 0.002 mol of sulfuric acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then dropwise add 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate)pentadecane)phenol, with a P content of 9.8% and a product conversion rate of 93.4%.

[0127] Preparation Example 6

[0128] Preparation of 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol:

[0129]

[0130] 1) Add 0.2 mol of 3-(8-pentadecenyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of aluminum oxide catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the dropwise addition. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1h to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, with a product conversion rate of 91.8%.

[0131] 2) 0.24 mol of 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, 0.17 mol of formic acid, 0.003 mol of hydrochloric acid and 1.68 mol of hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9-epoxypentadecanyl)phenol, and the product conversion rate was 94.9%.

[0132] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9-epoxypentadecane)phenol, 0.002 mol of sulfuric acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then dropwise add 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate)pentadecane)phenol, with a P content of 9.8% and a product conversion rate of 93.7%.

[0133] Preparation Example 7

[0134] Preparation of 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol:

[0135]

[0136] 1) Add 0.2 mol of 3-(8-pentadecenyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of aluminum oxide catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the dropwise addition. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1h to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, and the product conversion rate is 92.0%.

[0137] 2) 0.24 mol 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, 0.17 mol formic acid, 0.003 mol sulfuric acid and 1.68 mol hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9-epoxypentadecanyl)phenol, and the product conversion rate was 95.5%.

[0138] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9-epoxypentadecane)phenol, 0.002 mol of acetic acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then dropwise add 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate)pentadecane)phenol, with a P content of 9.8% and a product conversion rate of 91.3%.

[0139] Preparation Example 8

[0140] Preparation of 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol:

[0141]

[0142] 1) Add 0.2 mol of 3-(8-pentadecenyl)phenol and 150 ml of acetone to a three-necked flask, stir and dissolve, then add 0.01 mol of aluminum oxide catalyst, heat to 60°C, then slowly drop 0.4 mol of tert-butyl chloride into the reaction flask, and continue to react for 3 hours after the dropwise addition. After the reaction is completed, cool down to obtain a brownish red transparent liquid. The brownish red transparent liquid is alkaline washed with 5% KOH solution, then washed with distilled water until neutral, and distilled under reduced pressure at 1000 Pa and 120°C for 1h to remove the solvent acetone, water and unreacted raw materials to obtain a dark brownish red viscous liquid, i.e. 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, with a product conversion rate of 91.4%.

[0143] 2) 0.24 mol 2,6-di-tert-butyl-3-(8-pentadecenyl)phenol, 0.17 mol formic acid, 0.003 mol sulfuric acid and 1.68 mol hydrogen peroxide were added to a three-necked flask, stirred and heated to 70°C, and reacted for 3 hours. After the reaction was completed, the temperature was lowered to obtain a brown-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution and washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove water and unreacted raw materials to obtain an orange-red transparent liquid, namely 2,6-di-tert-butyl-3-(8,9-epoxypentadecanyl)phenol, and the product conversion rate was 96.6%.

[0144] 3) Add 0.18 mol of 2,6-di-tert-butyl-3-(8,9-epoxypentadecane)phenol, 0.002 mol of nitric acid, 10 ml of water, and 120 ml of toluene into a three-necked flask, stir and heat to 85°C, reflux for 1 hour, then dropwise add 0.48 mol of diphenylphosphonic acid, continue reflux for 5 hours after the dropwise addition, and stop the reaction. Wash the product with water 3 times and evaporate the solvent to obtain 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate)pentadecane)phenol, with a P content of 9.8% and a product conversion rate of 90.9%.

[0145] The product of Preparation Example 1, 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphate)pentadecyl)phenol, was subjected to infrared spectroscopy analysis. The infrared spectrum is shown in FIG. Figure 1 , the analysis results are shown in Table 1.

[0146] Table 1 Infrared analysis results of products

[0147]

[0148]

[0149] Table 1 shows that the product has characteristic peaks such as C-OH stretching vibration peak, P=O stretching vibration peak, benzene ring skeleton stretching vibration peak, POC stretching vibration peak and PO stretching vibration peak, which can indicate that the synthesized product is the target compound.

[0150] The products of the above-mentioned preparation examples 1-8, as well as commercially available extreme pressure anti-wear agent TCP, hindered phenol antioxidant T501 (2,6-di-tert-butyl-p-cresol), and T512 (3,5-di-tert-butyl-4-hydroxyphenyl propionate) were dissolved in 150SN base oil, and 150SN base oil without anti-wear agent was set separately to measure its anti-wear and friction reduction performance. The measurement conditions of the SRV anti-wear and friction reduction evaluation experiment are: temperature 30°C, load 200N, stroke 1mm, test time 1h, frequency 50Hz. The SRV method is shown in the National Energy Administration standard NB / SH / T0847-2010. The test results are shown in Table 2.

[0151] Table 2 SRV test results

[0152]

[0153]

[0154] The products of the above-mentioned preparation examples 1-8, as well as commercially available extreme pressure anti-wear agent TCP, hindered phenol antioxidant T501 (2,6-di-tert-butyl-p-cresol), and T512 (3,5-di-tert-butyl-4-hydroxyphenyl propionate) were dissolved in 150SN base oil, and 150SN base oil without adding antioxidant was set up separately to measure its antioxidant performance. The test instrument is a TA5000 model DSC instrument of TA Company of the United States, and the test conditions are 190°C, oxygen pressure 0.5MPa, and heating rate 10°C / min. The test results are shown in Table 3.

[0155] Table 3 Antioxidant test results

[0156] Oxidation induction period / min Preparation Example 1 Product 7.03 Preparation Example 2 Product 6.84 Preparation Example 3 Product 6.79 Preparation Example 4 Product 6.91 Preparation Example 5 Product 6.93 Preparation Example 6 Product 6.90 Preparation Example 7 Product 6.95 Preparation Example 8 Product 6.88 TCP ＜1 T501 6.21 T512 6.08 none ＜1

[0157] According to the test results of Table 2 and Table 3, the anti-wear and anti-oxidation properties of a 2,6-di-tert-butylphenol compound provided by the present invention can be improved by applying it to the base oil. Compared with existing additives, a 2,6-di-tert-butylphenol compound provided by the present invention has two properties at the same time. Compared with existing anti-wear agents, the friction coefficient and wear spot diameter of the base oil containing 2,6-di-tert-butylphenol compounds are smaller, and it also has good anti-oxidation properties. Compared with existing antioxidants, the oxidation induction period of the base oil containing 2,6-di-tert-butylphenol compounds is longer, and it also has good anti-wear properties. The 2,6-di-tert-butylphenol compound provided by the present invention can reduce the types and amounts of additives and improve product performance and stability.

[0158] The sources and requirements of the reagents used in the embodiments of the present invention are as follows:

[0159] 3-(8-pentadecenyl)phenol, Shanghai Wujing Chemical Technology Co., Ltd., industrial products.

[0160] 3-(8,11-pentadecadienyl)phenol, Shanghai Wujing Chemical Technology Co., Ltd., industrial products.

[0161] 3-(8,11,14-pentadecatrienyl)phenol, Shanghai Wujing Chemical Technology Co., Ltd., industrial product. Zinc chloride, Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0162] Concentrated sulfuric acid was from Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0163] Potassium hydroxide was from Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0164] Hydrogen peroxide (30%), Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0165] Formic acid was from Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0166] Diphenoxyphosphoric acid was purchased from Sinopharm Chemical Reagent Co., Ltd., chemically pure.

[0167] Tert-butyl chloride was from Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0168] Antioxidant T501, Xingpu Company, Institute of Petrochemical Science, industrial product.

[0169] Antioxidant T512, Xingpu Company, Institute of Petrochemical Science and Technology, industrial product.

[0170] Toluene was from Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0171] Acetone was from Sinopharm Chemical Reagent Co., Ltd., analytical grade.

[0172] Tricresyl phosphate (TCP) was purchased from Sinopharm Chemical Reagent Co., Ltd., chemically pure.

[0173] 150SN base oil, Sinopec Yanshan Petrochemical Branch, industrial product.

Claims

1. A 2,6-di-tert-butylphenol compound, characterized in that: The compound is a compound having the general structural formula (I): In formula (I), R1 is a C2-C 30 Straight or branched chain alkyl:

2. The compound according to claim 1, characterized in that: In formula (I), R1 is a C2-C3-C6-substituted group containing 2 to 6 substituents represented by formula (II). 30 Straight chain or branched chain alkyl.

3. The compound according to claim 1, characterized in that: The 2,6-di-tert-butylphenol compound is selected from one of the following compounds: 2,6-di-tert-butyl-3-(8,9-bis(diphenylphosphonate))pentadecylphenol 2,6-di-tert-butyl-3-(8,9,11,12-tetrakis(diphenylphosphonate))pentadecylphenol 4. The method for preparing 2,6-di-tert-butylphenol compounds as claimed in claim 1, characterized in that: The method comprises the following steps: 1) reacting a tert-butyl halide having a general structural formula (III) with a phenolic compound having a general structural formula (IV) under the action of a catalyst I, and optionally adding or not adding a solvent I, to obtain an intermediate compound having a general structural formula (V); the reaction formula is: R2 is C2~C 30 Straight or branched olefin groups; 2) After the reaction of step 1) is completed, the intermediate compound having the general structural formula (V) is subjected to an epoxidation reaction with a peroxy acid in the presence of a catalyst II, and a solvent II is optionally added or not added to obtain an epoxide compound having the general structural formula (VI); the reaction formula is: R3 is C2~C 30 Hydrocarbon groups containing epoxy bonds; 3) After the reaction of step 2) is completed, the epoxy compound having the general structural formula (VI) is subjected to a ring-opening esterification reaction with diphenylphosphonic acid in the presence of a catalyst III, and a solvent III is optionally added or not added to obtain a compound having the general structural formula (I) 2,6-di-tert-butylphenol compound; the reaction formula thereof is: Wherein, R1 contains a C2-C 30 Straight chain or branched chain alkyl.

5. The method according to claim 4, characterized in that: The R2 is a C2-C 30 Straight or branched olefin group; R3 is C2-C 30 Straight or branched chain alkyl; 6. The method according to claim 5, characterized in that: In formula (I), R1 is selected from one of 8,9-bis(diphenylphosphonate)pentadecyl, 8,9,11,12-tetra(diphenylphosphonate)pentadecyl, and 8,9,11,12,14,15-hexa(diphenylphosphonate)pentadecyl; R2 is one of 8-pentadecenyl, 8,11-pentadecadienyl, and 8,11,14-pentadecatrienyl; R3 is one of 8,9-pentadecylidene, 8,9:11,12-diecylidene, and 8,9:11,12:14,15-tricylidene.

7. The method according to claim 4, characterized in that: In step 1), the tert-butyl halide is one of tert-butyl fluoride, tert-butyl chloride, tert-butyl bromide and tert-butyl iodide; the molar ratio of the phenolic compound having the general structural formula (IV) to the tert-butyl halide is 1:1.5-8; the catalyst I is one or more of zinc chloride, aluminum chloride, ferric chloride, tin tetrachloride, boron trifluoride and titanium tetrachloride; the molar ratio of the catalyst I to the phenolic compound having the general structural formula (IV) is 1:5-30; and / or In step 2), the peroxy acid is an acid containing a peroxy group (-OO-) in the molecule; the molar ratio of the peroxy acid to the compound having the structure of formula (V) is 3-15:1; the catalyst II is one or more of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, propionic acid, benzoic acid, m-chlorobenzoic acid, and a strongly acidic ion exchange resin; the molar ratio of the catalyst II to the compound having the structure of formula (V) is 1:10-200; and / or In step 3), the molar ratio of the added amount of diphenylphosphonic acid to the compound having the structure of formula (VI) is 1:2-10; the catalyst III is one or more of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, propionic acid, benzoic acid, and m-chlorobenzoic acid; the molar ratio of the added amount of the catalyst III to the compound having the structure of formula (VI) is 1:5-300.

8. The method according to claim 7, characterized in that: In step 1), the molar ratio of the amount of the phenolic compound having the general structural formula (IV) to the amount of the halogenated tert-butylene is 1:1.7-5; the catalyst I is zinc chloride; the molar ratio of the amount of the catalyst I to the amount of the phenolic compound having the general structural formula (IV) is 1:7-25; and / or In step 2), the peracid is one or more of hydrogen peroxide, performic acid, peracetic acid, persulfonic acid, m-chloroperbenzoic acid, and tert-butyl hydroperoxide; the molar ratio of the peracid to the compound having the structure of formula (V) is 5-12:1; the catalyst II is sulfuric acid; the molar ratio of the catalyst II to the compound having the structure of formula (V) is 1:40-120; and / or In step 3), the molar ratio of the diphenylphosphonic acid to the compound having the structure of formula (VI) is 1:2.3-8; the catalyst III is sulfuric acid; the molar ratio of the catalyst III to the compound having the structure of formula (VI) is 1:30-200.

9. The method according to claim 8, characterized in that: In step 1), the molar ratio of the amount of the phenolic compound having the general structural formula (IV) to the amount of the halogenated tert-butylene is 1:1.8-3; the molar ratio of the amount of the catalyst I to the amount of the phenolic compound having the general structural formula (IV) is 1:10-20; and / or In step 2), the peroxy acid is hydrogen peroxide; the molar ratio of the peroxy acid to the compound having the structure of formula (V) is 6-8:1; the molar ratio of the catalyst II to the compound having the structure of formula (V) is 1:60-100; and / or In step 3), the molar ratio of the diphenylphosphonic acid to the compound having the structure of formula (VI) is 1:2.5-4; the molar ratio of the catalyst III to the compound having the structure of formula (VI) is 60-100.

10. The method according to claim 4, characterized in that: Step 1) is specifically as follows: adding a compound having a structure of formula (IV) and a solvent I into a reactor, adding a catalyst I after dissolution is completed, stirring and heating to 50-70° C., slowly dropping a halogenated tert-butane, and continuing to react at 50-70° C. for 1-8 hours after the dropwise addition is completed; after the reaction is completed, cooling the mixed product to room temperature, then washing it with 2-10% alkali solution, washing it with water until it is neutral after the alkali washing is completed, and distilling it under reduced pressure at 700-1300 Pa and 100-150° C. for 0.5-3 hours to remove the solvent, water and unreacted raw materials to obtain a compound having a structure of formula (V); and / or Step 2) is specifically: adding a compound having a structure of formula (V), solvent II and catalyst II to a reactor, stirring and heating, and reacting at 50-90° C. for 1-5 hours; after the reaction is completed, cooling the mixed product, and then washing it with 2-10% alkali solution, washing it with water until it is neutral, and then distilling the organic phase under reduced pressure at 70-130 Pa and 100-200° C. for 0.5-3 hours to remove water and unreacted raw materials to obtain a compound having a structure of formula (VI); and / or Step 3) is specifically as follows: adding a compound having a structure of formula (VI), catalyst III, water and solvent III into a reactor, stirring and heating, and refluxing at 60 to 100° C. for 0.5 to 1.5 hours, then dropping diphenylphosphonic acid into the reactor at a rate of 1 to 5 d / s, and continuing the reaction and reflux for 3 to 8 hours after the dropwise addition is completed; after the reaction is completed, washing the mixed product with water for 1 to 5 times, and then distilling to remove the solvent, thereby obtaining a 2,6-di-tert-butylphenol compound having a structure of formula (I).

11. The method according to claim 10, characterized in that: The solvent I is one or more of acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, ethylbenzene, chloroform and chlorobenzene; and / or The solvent II is one or more of formic acid, acetic acid, benzoic acid, phenylacetic acid, and acetonitrile; and / or The solvent III is one or more of benzene, toluene, ethylbenzene, ethanol, hexane and carbon tetrachloride.

12. The method according to any one of claims 4 to 11, characterized in that: The step 1) and / or step 2) and / or step 3) are performed under the protection of an atmosphere of nitrogen or an inert gas.

13. The method according to claim 12, characterized in that: The inert gas is one of helium and argon.

14. A use of 2,6-di-tert-butylphenol compounds, characterized in that: The 2,6-di-tert-butylphenol compound having the structure of formula (I) according to any one of claims 1 to 3 or the 2,6-di-tert-butylphenol compound having the structure of formula (I) prepared by the method according to any one of claims 4 to 13 is used as an antioxidant and anti-wear dual-functional additive.

15. The use according to claim 14, characterized in that: The 2,6-di-tert-butylphenol compound having the structure of formula (I) is used as an antioxidant and anti-wear dual-function additive in lubricating oil, grease, fuel oil, engine oil or plastic rubber.

16. The use according to claim 15, characterized in that: The addition amount of the dual-function additive is 0.01-3wt% of the mass of lubricating oil, grease, fuel oil, engine oil or plastic rubber.

17. The use according to claim 16, characterized in that: The addition amount of the dual-function additive is 0.05-2wt% of the mass of lubricating oil, grease, fuel oil, engine oil or plastic rubber.

18. The use according to claim 17, characterized in that: The addition amount of the dual-function additive is 0.2-1.5wt% of the mass of lubricating oil, grease, fuel oil, engine oil or plastic rubber.

Images