Lubricating oil base oils, methods for their production and use

Abstract

The present application relates to the field of lubricating oil, discloses a kind of lubricating oil base oil and its preparation method and application, the lubricating oil base oil contains polymer including structural unit A and structural unit B, the lubricating oil base oil has excellent antioxidant property.The base oil prepared by the method of the present application has good antioxidant stability without increasing hydrogenation process, and the overall reaction condition temperature is simple and controllable.The raw material of the present application has wide sources and huge reserves, thereby further reducing the preparation cost, meeting the definition of green chemistry and the requirements of sustainable development.

Description

Technical Field

[0001] This invention relates to the field of lubricating oils, and more specifically, to a lubricating oil base oil, its preparation method, and its application. Background Technology

[0002] With the rapid development of modern industry and increasingly stringent requirements for high-quality lubricants, the global demand for and technical requirements of high-quality, low-viscosity base oils are also rising. Traditional mineral base oils are increasingly unable to meet the demanding needs of high-end lubrication applications, making fully synthetic base oils a more ideal choice. Among them, polyalphaolefin (PAO) synthetic base oils are the most widely used type of fully synthetic base oil. PAO is typically produced by oligomerizing one or more linear alpha-olefins under a catalyst to obtain olefin oligomers, followed by hydrogenation saturation of the double bonds to improve their molecular oxidation stability. However, the hydrogenation reaction requires high temperature and high pressure conditions, posing inherent fire and explosion hazards, and also consuming a large amount of energy.

[0003] US3742082A discloses a method for preparing low-viscosity PAO using a boron trifluoride catalyst. In this method, boron trifluoride / water is used as a catalyst to polymerize decene at 100°C. After the reaction is completed, the product is distilled at a pressure of 500 mmHg. The remaining product is hydrogenated using a nickel / diatomaceous earth catalyst at 177°C and 500 psig to obtain the PAO product.

[0004] US5171908A discloses a method for synthesizing polyolefin lubricating oil base oil, which uses boron trifluoride / alcohol as a catalytic system to oligomerize decene, and the hydrogenation catalyst is a nickel / diatomaceous earth catalyst. The process conditions are: 150-300℃, 300-600psig.

[0005] WO2020068527A1 discloses a method for preparing synthetic lubricating oil base oil, in which C14 and C16 olefins are fed alone or in mixture, and the olefin monomers are contacted with a catalyst system containing Lewis acids such as boron trifluoride / alcohol / ester under oligomerization conditions, and hydrogenation is carried out using a nickel catalyst. The process conditions are 232°C and 350 psi.

[0006] US5420373A discloses a method for preparing olefin oligomers, using boron trifluoride as a catalyst and hydroxycarbonyl as a co-catalyst to oligomerize C6-C20 olefin monomers (such as 1-octene and 1-decene). The catalyst can be a supported nickel catalyst, such as nickel on a diatomaceous earth support, and the method can be batch or continuous. For example, the catalyst can be added to a liquid and stirred under hydrogen pressure, or the liquid can be dripped through a fixed bed of supported catalyst under hydrogen pressure. The hydrogenation conditions are 150-300°C and a hydrogen pressure of approximately 100-1000 psig.

[0007] US4910355A discloses a method for preparing olefin oligomers, which uses boron trifluoride / alcohol catalysis to copolymerize 1-decene and intradecene, followed by hydrogenation using a nickel catalyst at 250°C and 800-900 psig.

[0008] As mentioned above, in the traditional preparation process of polyalphaolefin (PAO) base oils, hydrogenation saturation of the olefin double bonds is required under high temperature and high pressure conditions to improve the antioxidant stability of the oligomers. This invention improves the antioxidant stability of PAO base oils by starting with the raw materials, while avoiding the use of hydrogenation processes. The overall reaction conditions are mild and the operation is simple. Summary of the Invention

[0009] The purpose of this invention is to overcome the above-mentioned problems existing in the prior art and to provide a lubricating oil base oil, its preparation method and application.

[0010] To achieve the above objectives, the present invention provides a lubricating oil base oil containing a polymer comprising structural unit A and structural unit B;

[0011] The structural formula of structural unit A is:

[0012] The structural formula of structural unit B is:

[0013] Wherein, R1 is selected from H or C1-C14 alkyl groups;

[0014] R2 is selected from C1-C14 alkyl groups;

[0015] R3 is selected from H, C1-C10 alkyl groups or groups represented by Formula I;

[0016] R4 is selected from C1-C10 alkylene groups or groups represented by Formula II;

[0017] R5, R6, R7, R8 and R9 are each independently selected from H, OH, C1-C20 straight-chain or branched alkyl groups;

[0018]

[0019] In formula I, R 10 Selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R in m repeating units 11 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in m repeating units 12 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in m repeating units 13They may be identical or different from each other, each independently selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R 14 Selected from hydrogen, C1-C20 straight-chain or branched alkyl groups; m is a positive integer;

[0020] In formula II, R 15 Selected from single-chain, C1-C20 straight-chain or branched alkylene groups; R in n repeating units 16 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in n repeating units 17 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in n repeating units 18 They may be the same or different from each other, and each is independently selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R 19 Selected from C1-C20 straight-chain or branched alkylene groups; n is a positive integer.

[0021] A second aspect of the present invention provides a method for preparing a lubricating oil base oil, the method comprising: polymerizing a monomer and an α-olefin in the presence of a catalyst, wherein the monomer has the structure shown in Formula III and the α-olefin has the structure shown in Formula IV.

[0022]

[0023] Among them, R3 to R9 are defined as described above, R 20 Selected from H or C1-C14 alkyl groups, R 21 Alkyl groups selected from C1-C14.

[0024] A third aspect of the present invention provides a lubricating oil base oil prepared by the method described above.

[0025] The fourth aspect of the present invention provides the use of the lubricating oil base oil as described above in improving the antioxidant stability of lubricating oils.

[0026] Through the above technical solution, this invention provides a lubricating oil base oil with good antioxidant stability. This lubricating oil base oil can be used as a fully synthetic base oil with excellent antioxidant properties, and it still maintains excellent antioxidant properties even after arbitrary blending based on kinematic viscosity. The base oil prepared by the preferred method of this invention does not require an additional hydrogenation process to achieve good antioxidant stability, and the overall reaction conditions and temperature are simple and controllable. Furthermore, the raw materials used in this invention are widely available and have huge reserves, thereby further reducing the preparation cost and meeting the definition of green chemistry and the requirements of sustainable development. Detailed Implementation

[0027] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0028] In one aspect, the present invention provides a lubricating oil base oil, wherein the lubricating oil base oil contains a polymer comprising structural unit A and structural unit B;

[0029] The structural formula of structural unit A is:

[0030] The structural formula of structural unit B is:

[0031] Wherein, R1 is selected from H or C1-C14 alkyl groups;

[0032] R2 is selected from C1-C14 alkyl groups;

[0033] R3 is selected from H, C1-C10 alkyl groups or groups represented by Formula I;

[0034] R4 is selected from C1-C10 alkylene groups or groups represented by Formula II;

[0035] R5, R6, R7, R8 and R9 are each independently selected from H, OH, C1-C20 straight-chain or branched alkyl groups;

[0036]

[0037] In formula I, R 10 Selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R in m repeating units 11 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in m repeating units 12 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in m repeating units 13 They may be identical or different from each other, each independently selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R 14 Selected from hydrogen, C1-C20 straight-chain or branched alkyl groups; m is a positive integer;

[0038] In formula II, R 15 Selected from single-chain, C1-C20 straight-chain or branched alkylene groups; R in n repeating units 16 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in n repeating units 17They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in n repeating units 18 They may be the same or different from each other, and each is independently selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R 19 Selected from C1-C20 straight-chain or branched alkylene groups; n is a positive integer.

[0039] In this invention, the lubricating oil base oil contains a polymer including structural unit A and structural unit B. The presence of structural unit B in the lubricating oil base oil gives it excellent antioxidant stability, which can further improve the performance of the lubricating oil.

[0040] In this invention, the excellent antioxidant stability of the lubricating oil base oil refers to its ability to resist permanent changes in its properties caused by the action of air (or oxygen). This is judged by the oxidation induction period. The longer the oxidation induction period, the better the antioxidant stability of the lubricating oil base oil. The shorter the oxidation induction period, the worse the antioxidant stability of the lubricating oil base oil. In this invention, an oxidation induction period of less than 5 minutes indicates that the polymer has very poor antioxidant stability, while an oxidation induction period of more than 60 minutes indicates that the polymer has very good antioxidant stability.

[0041] Any structural unit that meets the foregoing requirements can achieve the purpose of this invention. There are no special requirements for the specific selection of each group. The following is an illustrative description, but it does not limit the scope of this invention.

[0042] According to the present invention, preferably, the weight ratio of the structural unit A and the structural unit B is 100:0.3-30, which can be any two values ​​from 100:0.3, 100:0.5, 100:0.7, 100:0.9, 100:1, 100:5, 100:8, 100:10, 100:15, 100:20, 100:25, 100:30, or any value within that range, and more preferably 100:0.5-10.

[0043] According to the present invention, preferably, the total number of carbons in R1 and R2 is 4-14, and can be 4, 5, 6, 8, 9, 10, 12, 13, or 14.

[0044] According to the present invention, preferably, each of the R3 in the structural unit B is independently selected from H or C1-C8 alkyl groups, and more preferably C6 alkyl groups.

[0045] According to the present invention, preferably, R4 in the structural unit B is selected from C1-C8 alkylene groups, and more preferably C7 alkylene groups.

[0046] According to the present invention, preferably, R5, R6, R7, R8 and R9 in the structural unit B are each independently selected from H, OH, and C1-C10 straight-chain or branched alkyl groups.

[0047] According to the present invention, preferably, at least one OH group is present among R5, R6, R7, R8 and R9.

[0048] According to the present invention, preferably, R in formula I 10 Selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R in m repeating units 11 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in m repeating units 12 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in m repeating units 13 They may be identical or different from each other, each independently selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R 14 Selected from hydrogen, C1-C4 straight-chain or branched alkyl groups; m is a positive integer from 1 to 10, which can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and more preferably a positive integer from 1 to 3.

[0049] According to the present invention, preferably, R in formula II 15 Selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R in n repeating units 16 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in n repeating units 17 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in n repeating units 18 They may be the same or different from each other, and each is independently selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R 19 Selected from C1-C4 straight-chain or branched alkylene groups; n is a positive integer from 1 to 10, which can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and is more preferably a positive integer from 1 to 3.

[0050] According to the present invention, preferably, R5, R7 and R9 in the structural unit B are each independently selected from H, C1-C4 straight-chain or branched alkyl groups.

[0051] According to the present invention, preferably, R6 and R8 in the structural unit B are each independently selected from H, OH, C1-C10 straight-chain or branched alkyl groups, and more preferably, at least one of R6 and R8 in the structural unit B is OH.

[0052] According to the present invention, preferably, in the structural unit B, R5 and R9 are each independently selected from H, C1-C4 straight-chain or branched alkyl, R7 is tert-butyl, one of R6 and R8 is OH and the other is H. It can be understood that the symmetrical positions of R6 and R8 on the benzene ring are such that when R6 is OH, R8 is H, and when R6 is H, R8 is OH.

[0053] According to the present invention, preferably, based on the weight of the polymer, the content of structural unit A is 77-99.7 wt%, and the content of structural unit B is 0.3-23 wt%. When the content of structural unit A and structural unit B in the polymer is within the above range, the overall performance of the lubricating oil base oil can be further improved.

[0054] According to a preferred embodiment of the present invention, the content of structural unit A is 90-99.5 wt% and the content of structural unit B is 0.5-10 wt% based on the weight of the polymer.

[0055] In this invention, the kinematic viscosity at 100°C is determined using the method in GB / T 265-1988.

[0056] A second aspect of the present invention provides a method for preparing a lubricating oil base oil, the method comprising: polymerizing a monomer and an α-olefin in the presence of a catalyst, wherein the monomer has the structure shown in Formula III and the α-olefin has the structure shown in Formula IV.

[0057]

[0058] Among them, R3 to R9 are defined as described above, R 20 Selected from H or C1-C14 (straight-chain or branched) alkyl groups, R 21 Alkyl groups selected from C1-C14 (straight-chain or branched-chain).

[0059] According to the present invention, preferably, the weight ratio of the α-olefin to the monomer is 100:0.3-30, more preferably 100:0.5-10.

[0060] According to the present invention, preferably, the amount of the monomer is 0.3-23 wt%, and the amount of the α-olefin is 77-99.7 wt%. In the present invention, the amounts of the monomer and α-olefin are within the above ranges, which can further improve the overall performance of the lubricating oil base oil.

[0061] According to a preferred embodiment of the present invention, the amount of the monomer is 0.5-10 wt%, and the amount of the α-olefin is 90-99.5 wt%.

[0062] According to the present invention, preferably, the amount of catalyst used is 1-200g relative to the total weight of 1kg of monomer and α-olefin, and can be any two values ​​formed by 1, 3, 5, 8, 10, 20, 30, 40, 50, 80, 100, 120, 150, 180 and 200, or values ​​within the range. More preferably, the amount of catalyst used is 5-15g relative to the total weight of 1kg of monomer and α-olefin.

[0063] According to the present invention, preferably, R 20 For H, R 21 It is a C4-C14 (straight-chain or branched) alkyl group.

[0064] According to the present invention, preferably, the α-olefin is a single olefin or a mixed olefin of C6-C18. It is understood that the single olefin refers to containing only one type of olefin, which can be a straight-chain α-olefin or a branched α-olefin. The mixed olefin contains two or more α-olefins. More preferably, the α-olefin is a single olefin or a mixed olefin of C8-C12. There are no particular requirements on the proportions of the various olefins in the mixed olefin. For example, the weight ratio of C8, C10, and C12 in the mixed olefin can be 1:0.5-1.5:1-3, preferably 1:1:2.

[0065] In this invention, structural unit B or the monomer is provided by cashew phenol and / or alkylated cashew phenol. Cashew phenol is a natural phenolic compound and a major component of cashew nut shell oil, with abundant and plentiful sources. Therefore, using this type of abundant and low-cost natural compound as a raw material to modify polyalphaolefin synthetic base oil, and preparing a fully synthetic base oil with excellent antioxidant stability without hydrogenation saturation, conforms to the definition of green chemistry.

[0066] According to a preferred embodiment of the present invention, the monomer is selected from at least one of cashew phenol, o-methyl cashew phenol and tert-butyl cashew phenol, more preferably tert-butyl cashew phenol; the inventors of the present invention have found that using tert-butyl cashew phenol as a monomer can produce lubricating oil base oil with better antioxidant stability.

[0067] In this invention, the tert-butyl cashew phenol is prepared by cashew phenol and an alkylating agent under the action of an alkylation catalyst, wherein the alkylating agent is at least one selected from tert-butyl chloride, tert-butyl bromide, tert-butyl iodine, and isobutylene; the o-methyl cashew phenol is prepared by cashew phenol and an alkylating agent under the action of an alkylation catalyst, wherein the alkylating agent is at least one selected from iodomethane, dimethyl sulfate, dimethyl carbonate, methanol, methyl chloride, and diazomethane; the alkylation catalyst is at least one selected from metal chloride, inorganic acid, organic acid, and Lewis acid, and more preferably, the alkylation catalyst is at least one selected from zinc chloride, aluminum chloride, and boron trifluoride diethyl ether. The alkylation reaction conditions include a temperature of 20-100℃ and a time of 3-8 hours.

[0068] According to the present invention, preferably, the catalyst is at least one of a cationic catalyst and a free radical initiator.

[0069] According to the present invention, preferably, the cationic catalyst is a Lewis acid, more preferably at least one selected from aluminum halide, alkyl aluminum halide, alkyl aluminum, boron halide, boron halide complexes, tin halide, iron halide, copper halide, titanium halide, antimony halide, zinc halide, and gallium halide. It is understood that the halide refers to at least one selected from fluorides, chlorides, bromides, and iodides, preferably fluorides. More preferably, the cationic catalyst is at least one selected from aluminum trichloride, boron trifluoride, and boron trifluoride complexes.

[0070] According to the present invention, preferably, the free radical initiator is an organic peroxide initiator and / or an azo initiator, more preferably at least one of cumene hydroperoxide, 2,2'-azobis(2,4-dimethylbutyronitrile) and 2,2'-azobis(2,4-dimethylpentanonitrile).

[0071] According to the present invention, preferably, the catalyst is at least one of BF3 catalyst and a complex formed by BF3 and a catalyst promoter; more preferably, the catalyst is a complex formed by BF3 and a catalyst promoter and BF3, wherein the catalyst promoter is at least one of C1-C10 alcohol, C1-C10 acid, C1-C10 acetate and C1-C10 propionate, preferably at least one of n-propanol, n-butanol, ethyl acetate and butyl acetate.

[0072] In this invention, the complex formed by BF3 and the catalyst promoter can be commercially available or prepared in-house. Preferably, the complex is obtained by directly mixing BF3 and the catalyst promoter. In this invention, the molar ratio of BF3 to the catalyst promoter is 1:0.5-5.

[0073] According to a preferred embodiment of the present invention, the catalyst is BF3 and a complex formed by BF3 and n-propanol, wherein the molar ratio of BF3 to n-propanol is 1:0.8-2. The inventors of the present invention have found that the combined action of BF3 and the complex formed by BF3 and n-propanol has better catalytic performance.

[0074] According to the present invention, preferably, the conditions for the polymerization reaction include: a temperature of 10-50°C, a pressure of 0.08-0.5 MPa, and a time of 0.1-6 h; more preferably, the conditions for the polymerization reaction include: a temperature of 15-35°C, a pressure of 0.1-0.3 MPa, and a time of 0.5-3 h.

[0075] According to the present invention, the polymerization product can be used directly as a base oil for lubricating oil. However, in order to obtain base oils with different kinematic viscosities to meet different needs, the method may further include: sequentially distilling the polymerization product (to remove light components with boiling points below 280°C) and vacuum distilling to obtain components with different kinematic viscosities, and blending the components with different kinematic viscosities to obtain a base oil with the desired kinematic viscosity. In the present invention, the distillation and vacuum distillation conditions are conventional choices in the art, and those skilled in the art can adjust them according to actual needs. The blending principle in the present invention is: the polymerization product is cut into three or more components with different kinematic viscosities by vacuum distillation, and the components with different kinematic viscosities are mixed by conventional methods in the art to obtain a base oil product with the desired kinematic viscosity. The inventors of the present invention have found that the higher the viscosity of the blended base oil product, the greater its oxidation induction period. Therefore, the method of the present invention is more suitable for obtaining a kinematic viscosity greater than 3 mm at 100°C. 2 / s (e.g., 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5mm) 2 Lubricating oil base oil (the range formed by any two values ​​of / s and the values ​​within the range).

[0076] According to a preferred embodiment of the present invention, the method for preparing the lubricating oil base oil includes the following steps:

[0077] (1) Preparation of 2-tert-butyl cashew phenol: Dissolve cashew phenol in cyclohexane (the amount of cyclohexane should be such that the cashew phenol is completely dissolved in cyclohexane), and after dissolution, put it into a three-necked reaction flask, add zinc chloride catalyst, and start stirring and heating. Maintain the reaction temperature at 40-55℃, and slowly add tert-butyl chloride dropwise to the reaction flask. After the addition is complete, continue the reaction for 4-6 hours. The molar ratio of cashew phenol to tert-butyl chloride is 1:0.93-1.1. The amount of zinc chloride catalyst used is 1.8-2.1g relative to 50g cashew phenol and tert-butyl chloride. After the reaction is completed, cool down to obtain a brownish-red transparent liquid. Filter the reaction product and wash it with 4-6wt% KOH solution, then wash it with distilled water until neutral. Distill under reduced pressure at 0.8-1.5kPa and 110-130℃ for 0.5-1.5h to remove solvent, water and unreacted raw materials. After cooling, a brownish-yellow liquid (2-tert-butylcainol) is obtained.

[0078] (2) Add 2-tert-butylcainol and 1-decene to the polymerization reactor, start stirring, and introduce boron trifluoride gas into the reactor to control the reaction pressure at 0.1-0.3 MPa. Add boron trifluoride complex catalyst (the boron trifluoride complex is a complex formed by boron trifluoride and n-propanol, with a molar ratio of boron trifluoride to n-propanol of 1:0.8-1.5). The weight ratio of 1-decene to 2-tert-butylcainol is 100:0.5-5. The amount of boron trifluoride complex catalyst used is 7-12 g relative to 1 kg of 2-tert-butylcainol and 1-decene. Use a cooling circulation system to adjust and control the reaction temperature at 20-40℃ and the reaction time at 0.5-1.5 h. After the reaction is completed, remove the catalyst from the product by alkali washing and water washing.

[0079] In this invention, conventional methods in the prior art can be used to test the content of each structural unit in the polymer, such as infrared spectroscopy, nuclear magnetic resonance, and the amount of monomers fed during polymerization. Preferably, the content of each structural unit in the polymer is determined by the amount of monomers fed. Specifically, the actual feeding ratio of each monomer participating in polymerization is determined by testing the content of unreacted monomers, thereby determining the content of each structural unit in the polymer. Specifically, the content of residual monomers is determined by liquid chromatography.

[0080] A third aspect of the present invention provides a lubricating oil base oil prepared by the method described above.

[0081] The fourth invention provides the application of the lubricating oil base oil as described above in improving the oxidation stability of lubricating oils.

[0082] Unless otherwise specified, all percentages mentioned in this application are percentages by mass.

[0083] In this invention, all raw materials are commercially available;

[0084] In this invention, the kinematic viscosity of the polymer at 100°C was measured according to the method provided in standard GB / T 265-1988;

[0085] In this invention, the conditions for determining the oxidation induction period of the polymer are as follows: the differential scanning calorimetry curve of the lubricating oil is measured under pure oxygen conditions at a pressure of 0.5 MPa and constant temperature conditions at 160°C, and the oxidation induction period is calculated. The oxidation induction period of ">60 min" means that the experiment only lasted for 60 min. It can be expected that the actual effect is much greater than 60 min, such as possibly greater than 70, 80, 90, or 100 min.

[0086] Product yield = m 产物实际量 / m 产物理论量 100%.

[0087] Preparation Example 1

[0088] 30g of cashew nut shell powder was dissolved in 100mL of cyclohexane. The solution was then transferred to a 250mL three-necked reaction flask, and 1.5g of zinc chloride catalyst was added. Stirring and heating were initiated. The reaction temperature was maintained at 50℃. 9.5g of tert-butyl chloride was slowly added dropwise to the reaction flask. After the addition was complete, the reaction continued for 5 hours. After the reaction was completed, the temperature was lowered to obtain a brownish-red transparent liquid. The reaction product was filtered and washed with 5wt% KOH solution, then washed with distilled water until neutral. The product was then distilled under reduced pressure at 1kPa and 120℃ for 1 hour to remove the solvent, water, and unreacted reactants. After cooling, a brownish-yellow liquid (2-tert-butylcainol) was obtained. The product recovery rate was 81.3%.

[0089] Preparation Example 2

[0090] 30g of cashew nut shell powder was dissolved in 100mL of cyclohexane. The solution was then transferred to a 250mL three-necked reaction flask, and 1.5g of zinc chloride catalyst was added. Stirring and heating were initiated. The reaction temperature was maintained at 50℃. 15g of iodomethane was slowly added dropwise to the reaction flask, and the reaction continued for 5 hours after the addition was complete. After the reaction was completed, the temperature was lowered to obtain a brownish-red transparent liquid. The reaction product was filtered and washed with 5% KOH solution, then washed with distilled water until neutral. The product was then distilled under reduced pressure at 1kPa and 120℃ for 1 hour to remove the solvent, water, and unreacted reactants. After cooling, a brownish-yellow liquid (o-methyl cashew nut shell powder) was obtained. The product yield was 85%.

[0091] Example 1

[0092] 108 g of 2-tert-butylcainol (Preparation Example 1) and 15 kg of 1-decene were added to a polymerization reactor. Stirring was started, and boron trifluoride gas was introduced into the reactor to control the reaction pressure at 0.15 MPa. 150 g of boron trifluoride complex catalyst (the boron trifluoride complex is a complex formed by boron trifluoride and n-propanol, with a molar ratio of boron trifluoride to n-propanol of 1:1) was added. A cooling circulation system was used to regulate and control the reaction temperature at 30°C and the reaction time at 1 h. After the reaction, the catalyst in the products of the examples and comparative examples was removed by alkali washing and water washing to obtain crude base oil products. Then, light components with boiling points below 280°C were removed by distillation. The obtained components were subjected to vacuum distillation and blending to obtain three fully synthetic lubricating oil base oil products, A, B, and C, with kinematic viscosities of 4, 6, and 8 mmHg at 100°C, respectively. 2 Approximately / s. The kinematic viscosity and oxidation induction period of the product at 100℃ are shown in Table 1.

[0093] Example 2

[0094] The method is described in Example 1, except that 1-decene is replaced with 1-octene.

[0095] Example 3

[0096] The method is described in Example 1, except that 1-decene is replaced with a mixed α-olefin of C8-C12 (where the weight ratio of C8:C10:C12 is 1:1:2).

[0097] Example 4

[0098] The method described in Example 1 was followed, except that 108g of 2-tert-butyl cashew phenol was replaced with 108g of o-methyl cashew phenol (obtained from Preparation Example 2).

[0099] Example 5

[0100] The method described in Example 1 is the same, except that 108g of 2-tert-butyl cashew phenol is replaced with 108g of cashew phenol.

[0101] Example 6

[0102] The method described in Example 1 is the same, except that the amount of 2-tert-butyl cashew phenol (obtained from Preparation Example 1) added is 1000g.

[0103] Example 7

[0104] The method described in Example 1 is the same, except that the amount of 2-tert-butyl cashew phenol (obtained from Preparation Example 1) added is 2000g.

[0105] Example 8

[0106] The method described in Example 1 was followed, except that 150g of boron trifluoride complex was replaced with 200g of cumene hydroperoxide, and the cooling circulation system was used to adjust and control the reaction temperature to 40°C and the reaction time to 3h.

[0107] Comparative Example 1

[0108] The method described in Example 1 was followed, except that 2-tert-butylcatechol was not added. A cooling circulation system was used to regulate and control the reaction temperature at 30°C, and the reaction time was 1 hour.

[0109] Comparative Example 2

[0110] The method described in Example 1 is the same, except that 2-tert-butyl cashew phenol is replaced with styrene.

[0111] Comparative Example 3

[0112] The method described in Comparative Example 1 was followed, except that different kinematic viscosity components were obtained after vacuum distillation and then subjected to hydrorefining. The hydrorefining process was controlled at a hydrogen partial pressure of 8 MPa, a temperature of 250 °C, and a volume hourly space velocity of 0.5 h / h. The hydrorefined components were then blended to obtain three fully synthetic lubricating oil base products, A, B, and C, with kinematic viscosities of 4, 6, and 8 mmHg at 100 °C, respectively. 2 Approximately / s. The kinematic viscosity and oxidation induction period of the product at 100℃ are shown in Table 1.

[0113] Table 1

[0114]

[0115]

[0116] By comparing the embodiments and comparative examples of the present invention, it can be found that the lubricating oil base oil provided by the present invention has excellent antioxidant properties. The lubricating oil base oil prepared by the preferred embodiment of the present invention has better antioxidant stability. Different kinematic viscosities and good performance can also be obtained by blending. By comparing Example 1, Comparative Example 1 and Comparative Example 2, it can be found that the lubricating oil provided by the present invention has good antioxidant stability. By comparing Example 1 and Comparative Example 3, it can be found that the base oil provided by the present invention does not need to add a hydrogenation process to have good antioxidant stability. Alkylated cashew phenol is more effective in improving the antioxidant stability of the product.

[0117] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. However, these simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A lubricating oil base oil, characterized in that, The lubricating oil base oil contains a polymer including structural unit A and structural unit B; The structural formula of structural unit A is: The structural formula of structural unit B is: Wherein, R1 is selected from H or C1-C14 alkyl groups; R2 is selected from C1-C14 alkyl groups; R3 is selected from H, C1-C10 alkyl groups or groups represented by Formula I; R4 is selected from C1-C10 alkylene groups or groups represented by Formula II; R5, R6, R7, R8 and R9 are each independently selected from H, OH, C1-C20 straight-chain or branched alkyl groups; In formula I, R 10 Selected from single-chain, C1-C20 straight-chain or branched alkylene groups; R in m repeating units 11 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in m repeating units 12 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in m repeating units 13 They may be identical or different from each other, each independently selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R 14 Selected from hydrogen, C1-C20 straight-chain or branched alkyl groups; m is a positive integer; In formula II, R 15 Selected from single-chain, C1-C20 straight-chain or branched alkylene groups; R in n repeating units 16 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in n repeating units 17 They may be identical or different from each other, each independently selected from H, C1-C20 straight-chain or branched alkyl groups; R in n repeating units 18 They may be the same or different from each other, and each is independently selected from single-bonded, C1-C20 straight-chain or branched alkylene groups; R 19 Selected from C1-C20 straight-chain or branched alkylene groups; n is a positive integer.

2. The lubricating oil base oil according to claim 1, wherein, The weight ratio of structural unit A to structural unit B is 100:0.3-30, preferably 100:0.5-10; Preferably, the total number of carbons in R1 and R2 is 4-14; Preferably, R3 in structural unit B is selected from H or C1-C8 alkyl groups; Preferably, R4 in structural unit B is selected from C1-C8 alkylene groups; Preferably, in the structural unit B, R5, R6, R7, R8 and R9 are each independently selected from H, OH, and C1-C10 straight-chain or branched alkyl groups; More preferably, at least one OH group is present in R5, R6, R7, R8, and R9; Preferably, R in formula I 10 Selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R in m repeating units 11 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in m repeating units 12 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in m repeating units 13 They may be identical or different from each other, each independently selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R 14 Selected from hydrogen, C1-C4 straight-chain or branched alkyl groups; m is a positive integer from 1 to 10, more preferably a positive integer from 1 to 3; Preferably, R in formula II 15 Selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R in n repeating units 16 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in n repeating units 17 They may be identical or different from each other, each independently selected from H, C1-C4 straight-chain or branched alkyl groups; R in n repeating units 18 They may be the same or different from each other, and each is independently selected from single-bonded, C1-C4 straight-chain or branched alkylene groups; R 19 Selected from C1-C4 straight-chain or branched alkylene groups; n is a positive integer from 1 to 10, more preferably a positive integer from 1 to 3.

3. The lubricating oil base oil according to claim 1, wherein, In the structural unit B, R5, R7, and R9 are each independently selected from H, C1-C4 straight-chain or branched alkyl groups; Preferably, in the structural unit B, R6 and R8 are each independently selected from H, OH, C1-C10 straight-chain or branched alkyl groups; More preferably, in structural unit B, at least one of R6 and R8 is OH; More preferably, in the structural unit B, R5 and R9 are each independently selected from H, C1-C4 straight-chain or branched alkyl groups, R7 is tert-butyl, and one of R6 and R8 is OH and the other is H.

4. The lubricating oil base oil according to claim 1, wherein, Based on the weight of the polymer, the content of structural unit A is 77-99.7 wt%, and the content of structural unit B is 0.3-23 wt%. Preferably, based on the weight of the polymer, the content of structural unit A is 90-99.5 wt%, and the content of structural unit B is 0.5-10 wt%.

5. A method for preparing lubricating oil base oil, characterized in that, The method includes: polymerizing a monomer and an α-olefin under the action of a catalyst, wherein the structure of the monomer is shown in Formula III and the structure of the α-olefin is shown in Formula IV. Wherein, R3 to R9 are defined identically to any one of claims 1-3, R 20 Selected from H or C1-C14 alkyl groups, R 21 Alkyl groups selected from C1-C14.

6. The method according to claim 5, wherein, The weight ratio of the α-olefin to the monomer is 100:0.3-30, preferably 100:0.5-10; And / or, based on the total weight of the monomer and the α-olefin, the amount of the monomer is 0.3-23 wt%, and the amount of the α-olefin is 77-99.7 wt%. Preferably, the amount of the monomer is 0.5-10 wt%, and the amount of the α-olefin is 90-99.5 wt%. And / or, relative to a total weight of 1 kg of monomer and α-olefin, the amount of catalyst used is 1-200 g; Preferably, the amount of catalyst used is 5-15g relative to the total weight of 1kg of monomer and α-olefin.

7. The method according to claim 5, wherein, R 20 For H, R 21 It is a C4-C14 alkyl group; And / or, the α-olefin is a single olefin or a mixture of olefins of C6-C18; Preferably, the α-olefin is a single olefin or a mixture of C8-C12 olefins.

8. The method according to claim 5, wherein, The catalyst is at least one of a cationic catalyst and a free radical initiator; Preferably, the cationic catalyst is a Lewis acid, and more preferably at least one of aluminum halide, alkyl aluminum halide, alkyl aluminum, boron halide, boron halide complexes, tin halide, iron halide, copper halide, titanium halide, antimony halide, zinc halide and gallium halide; Preferably, the free radical initiator is an organic peroxide initiator and / or an azo initiator, more preferably at least one of cumene hydroperoxide, 2,2'-azobis(2,4-dimethylbutyronitrile) and 2,2'-azobis(2,4-dimethylpentanonitrile); More preferably, the catalyst is a complex formed by BF3 and a catalyst promoter, and BF3; Preferably, the catalyst is at least one selected from C1-C10 alcohol, C1-C10 acid, C1-C10 acetate and C1-C10 propionate.

9. The method according to claim 5, wherein, The conditions for the polymerization reaction include: a temperature of 10-50℃, a pressure of 0.08-0.5MPa, and a time of 0.1-6h; Preferably, the conditions for the polymerization reaction include: a temperature of 15-35°C, a pressure of 0.1-0.3 MPa, and a time of 0.5-3 h.

10. The lubricating oil base oil prepared by the method according to any one of claims 5-9.

11. The use of the lubricating oil base oil according to any one of claims 1-4 and 10 in improving the oxidation stability of lubricating oil.

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