A high performance high temperature chain oil composition and a method of making the same

Abstract

The present application relates to the technical field of lubricating oil, in particular to a high-performance high-temperature chain oil composition and a preparation method thereof.The high-temperature chain oil composition prepared by the present application overcomes the problems of poor extreme pressure wear resistance, poor stability in high-temperature and low-temperature environments, poor oxidation resistance, high evaporation loss and easy coking of chain oil in the use process.The high-temperature chain oil composition is prepared by using the prepared base oil, antioxidant and anti-wear agent in combination with other additives.The prepared anti-wear agent has good extreme pressure wear resistance.The prepared alkyl naphthalene base oil by using a supported catalyst has good high-temperature resistance and low-temperature resistance in combination with the prepared double pentaerythritol triphenyl sulfide ester base oil and low-viscosity poly-alpha-olefin as base oils.The prepared antioxidant has good oxidation resistance, small evaporation loss and is not easy to produce precipitation when the component dosage of the chain oil composition is changed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lubricating oil, in particular to a high-performance high-temperature chain oil composition and a preparation method thereof. BACKGROUND

[0002] With the rapid development of petrochemical, textile, printing and dyeing, building materials and transportation industries, the power and running rate of processing and running equipment are continuously improved, and the working temperature of the transmission system is getting higher and higher. The requirements for chain oil are also becoming more and more demanding. High-temperature chain transmission is working in an environment exposed to high and low temperatures. The temperature of high-temperature chain oil is generally 220-260℃. The lubricating oil is very easy to oxidize. Therefore, it is very important for chain lubricating oil to have high high-temperature oxidation stability and good lubricity at high temperature. High-temperature chain oil with excellent oxidation stability can prevent lubricating oil from high-temperature decomposition, polymerization coking and evaporation in high-temperature running state, has good lubricating performance, and can prolong the service life of the chain, reduce the maintenance cycle, and thus improve the production efficiency.

[0003] In order to improve the oxidation resistance and wear resistance of the lubricating oil, and reduce the coking and carbon deposition of the lubricating oil in the application to the high-temperature chain. Patent CN107304378B discloses a high-temperature chain oil composition and a preparation method thereof. The intermediate is generated by reacting aniline, sulfur chloride and 4-chloroaniline, and then the intermediate is subjected to a nucleophilic substitution reaction to synthesize an anti-oxidation and wear-resistant multi-effect additive, as shown in formula I. The anti-oxidation and wear-resistant multi-effect additive and the thio-phenolic ester type antioxidant are used in cooperation, which improves the oxidation resistance and wear resistance of the high-temperature chain oil composition.

[0004]

[0005] Patent CN107304377B discloses a high-temperature chain oil composition and a preparation method thereof. The composition is prepared from lubricating oil base oil, anti-oxidation multi-effect additive, 2,2'-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionic acid ethyl ester, zinc oxide nanoparticles and demulsifier. The structure of the anti-oxidation multi-effect additive is shown in formula II. The high-temperature chain oil composition has good wear resistance and oxidation resistance.

[0006]

[0007] Patent CN106590847B discloses a high-temperature chain oil composition and a manufacturing method thereof. The application creatively adds a shielding phenolic compound, the structure of which includes but is not limited to the following formula, and also adds an extreme pressure anti-wear agent, a rust inhibitor and a base oil. The obtained high-temperature chain oil composition has good oxidation resistance, low deposit amount in coking plate test, and good wear resistance and rust resistance.

[0008]

[0009] The above patents all synthesize compounds containing benzene ring, phenolic hydroxyl, imino, sulfur and other elements or functional groups, so as to improve the antioxidant performance, anti-wear performance and anti-coking performance of the chain oil composition. However, the phenolic antioxidant has good antioxidant effect, but the use temperature is low, while the use temperature of the amine antioxidant is high, and the durability is also good, but it is easy to discolor and precipitate, thereby increasing the coking amount. In addition, the low temperature resistance of the composition is poor; the prepared antioxidant has poor compatibility with the base oil, and long-term use can easily cause the stability of the high-temperature chain oil composition to decrease, thereby affecting the comprehensive performance of the high-temperature chain oil composition.

[0010] Patent CN105838484B discloses a high-temperature chain oil composition and a preparation method thereof. A high-temperature chain oil composition is prepared by using double pentaerythritol ester and aromatic ester as base oil, and adding alkyl phosphate extreme pressure anti-wear agent, oiliness agent, viscosity index improver, antioxidant and corrosion inhibitor. The obtained chain oil composition has excellent high-temperature performance, and has good anti-wear and anti-friction performance without coking.

[0011] At present, high-performance high-temperature chain oil still faces the following problems in actual use: low flash point, which reduces the safety factor and easily causes safety accidents; serious coking and carbon deposition; poor lubrication effect, poor extreme pressure wear resistance, which leads to short service life of the chain; in a high-temperature use environment, the evaporation loss is fast and the evaporation loss amount is large, and the antioxidant performance seriously decreases.

[0012] Therefore, a high-performance high-temperature chain oil composition and a preparation method thereof are provided. SUMMARY

[0013] The purpose of the present application is to provide a high-performance high-temperature chain oil composition and a preparation method thereof. The base oil, antioxidant and anti-wear agent are prepared, and the high-temperature chain oil composition is obtained by using other additives. The anti-wear agent 1 is prepared by using modified nano black phosphorus, which improves the extreme pressure wear resistance of the composition. The alkyl naphthalene base oil is prepared by using a supported catalyst, and the double pentaerythritol triphenyl sulfide ester base oil and the low viscosity poly-alpha olefin are used as base oils. The conversion rate of naphthalene in the alkyl naphthalene base oil is high, and the chain oil composition has high kinematic viscosity index, good high-temperature resistance and low-temperature resistance. The modified N-phenyl-alpha-naphthylamine is prepared, and the hindered phenolic antioxidant is used together. At the same time, the component dosage of the chain oil composition is changed, and the composition has good antioxidant effect, small evaporation loss and is not easy to precipitate.

[0014] To achieve the above purpose, the present application provides the following technical scheme:

[0015] In one aspect, the present application provides a preparation method of a high-performance high-temperature chain oil composition, comprising the following steps:

[0016] 70-92 parts of base oil, 0-4.5 parts of antioxidant (modified N-phenyl-alpha-naphthylamine and hindered phenol mixed in a ratio of 3:1), 0-2.5 parts of anti-wear agent, 1 part of anticorrosive agent, 0.5 parts of dispersant are mixed, the temperature is adjusted to 60℃, and the mixture is stirred uniformly to obtain the high-performance high-temperature chain oil composition;

[0017] The anti-wear agent is mixed by anti-wear agent one and modified nano black phosphorus in a mass ratio of 1-17:1; the temperature rising temperature of the sulfur phosphoric acid precursor in the anti-wear agent one is 60-95℃; the molar ratio of isooctanol and phosphorus pentasulfide is 1.1-1.3:1; the pH of the phosphate buffer solution in the maleimide-PEG6 solution is 6.5-7.2; the molar ratio of sulfur phosphoric acid to bismaleimide-PEG6 is 1:1.1-1.2;

[0018] The base oil is mixed by alkyl naphthalene base oil, dipentaerythritol triphenyl sulfide ester base oil and low viscosity poly-alpha olefin in a ratio of 1-4:1-6:5-13, and then vacuum dried to obtain;

[0019] The low viscosity poly-alpha olefin has a kinematic viscosity of 1.7mm 2 / s at 100℃ and a kinematic viscosity of 5.1mm 2 / s at 40℃.

[0020] The alkyl naphthalene base oil is obtained by dispersing Y-type molecular sieve in anhydrous ethanol, adding 0.1-0.4 parts of sulfated zirconium oxide to the dispersion, and ultrasonically obtaining a supported Y-type molecular sieve dispersion; naphthalene and tetradecane are added to 5.5-8.7 parts of the supported Y-type molecular sieve dispersion, and after reaction, the mixture is separated and distilled under reduced pressure to obtain;

[0021] The dipentaerythritol triphenyl sulfide ester base oil is obtained by reacting dipentaerythritol, 0-250 parts of triphenyl sulfide acid, concentrated sulfuric acid and 150-750 parts of lithium water glass solution;

[0022] The alkyl naphthalene base oil has the characteristics of alkyl and naphthalene, and has high high-temperature resistance. By reacting triphenyl sulfide acid and lithium water glass with dipentaerythritol respectively, the triphenyl sulfide acid introduced by chemical bond contains not only multiple benzene rings, but also sulfide structure, so that the chain oil composition has high high-temperature resistance. In addition, the added lithium water glass is dissolved in sodium hydroxide solution to form sodium silicate and lithium hydroxide, under heating conditions, sodium silicate hydrolyzes and crosslinks with dipentaerythritol to form a three-dimensional gel structure, and lithium elements are uniformly arranged in the gel structure. The introduced silicon and lithium elements improve the high-temperature resistance and low-temperature resistance of the chain oil composition.

[0023] The modified N-phenyl-alpha-naphthylamine is obtained by reacting 98.6-102.4 parts of benzothiazylsulfenyl hydroxybenzene bromide, copper chromite catalyst, 44 parts of N-phenyl-alpha-naphthylamine, 16.8-17.5 parts of butenoic acid.

[0024] The corrosion inhibitor includes but is not limited to benzotriazole octadecylamine salt, 2-methyl-isothiazole-3(2H)-ketone and 2-chloro-1,3-dimethyl imidazoline, zinc molybdate, methyl benzotriazole, N-di-n-butyl amino methylene benzotriazole, methylene benzotriazole.

[0025] The dispersant includes but is not limited to high-alkali-value sulfuration alkyl phenate (400 mg KOH / g), ethylene oxide-propylene oxide copolymer, sulfuration olefin cottonseed oil, sulfuration cyclohexanol cottonseed oil, triphenyl phosphite, sulfuration sperm oil, sulfuration cotton, dimer acid.

[0026] Preferably, the preparation method of the anti-wear agent comprises the following steps: reacting the isooctanol with 1 / 3 of the phosphorus pentasulfide to obtain a phosphorothioic acid precursor; heating the phosphorothioic acid precursor and adding 2 / 3 of the phosphorus pentasulfide thereto to obtain the phosphorothioic acid; adding the phosphorothioic acid and a tris(2-carboxyethyl) phosphine catalyst to the bismaleimide-PEG6 solution, increasing the temperature of the system to 50°C, and stirring under nitrogen protection for 2h to obtain an anti-wear agent precursor; adding XC-DAPOL-CPBA to the anti-wear agent precursor, adding a catalyst, adjusting the pH, and then heating to reflux for 10h to obtain the anti-wear agent one; mixing the anti-wear agent one and the modified nano black phosphorus, and grinding to an average particle size of 170nm to obtain the anti-wear agent.

[0027] wherein, the structure of XC-DAPOL-CPBA is as shown in the following formula:

[0028]

[0029] Preferably, the preparation method of the modified nano black phosphorus is as follows: dispersing nano black phosphorus in a 70°C potassium permanganate solution, stirring for 2h, filtering, and washing with deionized water to obtain pretreated nano black phosphorus; adding phenylboronic acid to the pretreated nano black phosphorus, grinding for 5h, and drying to obtain the modified nano black phosphorus.

[0030] The two-dimensional structure of nano black phosphorus and graphene is similar, and the layers are connected by van der Waals force and are easy to slide between layers, and the wear resistance is good, but as an inorganic substance, the compatibility between the nano black phosphorus and the chain oil composition is poor, and the nano black phosphorus is easy to be oxidized. After the surface of the nano black phosphorus is oxidized and treated, the surface of the nano black phosphorus is modified by using phenylboric acid, the compatibility of the nano black phosphorus with the components is improved, and in the subsequent heating and stirring process, the phenylboric acid can react with the unreacted maleimide in the bismaleimide-PEG6 to introduce the modified nano black phosphorus into the anti-wear agent through a chemical bond.

[0031] Preferably, the preparation method of the dipentaerythritol triphenyl sulfide ester base oil is as follows: the dipentaerythritol is added to a three-necked flask, then the triphenyl sulfide acid is added, the temperature is raised to 100℃, the vacuum degree is adjusted to 98.8KPa, then the concentrated sulfuric acid and activated carbon powder are added, and the base oil precursor is obtained after 8h of reaction; the water glass lithium is dissolved in a sodium hydroxide solution to obtain the water glass lithium solution; the water glass lithium solution is added to the base oil precursor for continuous reaction for 6h, then cooled to room temperature, and the dipentaerythritol triphenyl sulfide ester base oil is obtained by suction filtration.

[0032] Preferably, the modulus of the water glass lithium is 3.5.

[0033] Preferably, the preparation method of the modified N-phenyl-α-naphthylamine is as follows: the benzothiazole sulfenyl hydroxybenzene bromide is dissolved in an acetone solution to obtain a benzothiazole sulfenyl hydroxybenzene bromide solution; the benzothiazole sulfenyl hydroxybenzene bromide solution is heated to 140℃, and the sodium hydroxide and the copper chromite catalyst are added to obtain a reaction liquid; the reaction liquid is stirred for 12h, and after being cooled to room temperature, the benzothiazole sulfenyl hydroxybenzene phenol is obtained by suction filtration, then washed and dried; the N-phenyl-α-naphthylamine is added to a sealed reactor, then the butenoic acid and the zero-valent ruthenium catalyst are added, and the modified N-phenyl-α-naphthylamine intermediate is obtained after 7h of reaction at 130℃; the benzothiazole sulfenyl hydroxybenzene phenol and the concentrated sulfuric acid are added to the modified N-phenyl-α-naphthylamine intermediate, and the reaction is continued for 4h, then deionized water is added, and the modified N-phenyl-α-naphthylamine is obtained after multiple washing and drying.

[0034] The structure of the benzothiazole sulfenyl hydroxybenzene bromide is as follows:

[0035]

[0036] Preferably, the amount of the antioxidant is 3.8-4.5 parts.

[0037] Preferably, the amount of the anti-wear agent is 1.5-2.5 parts.

[0038] Preferably, the hindered phenol is any one of 1,1'-thiobis(2-naphthol), 2,2',4,4'-tetrahydroxydiphenyl sulfide and 2,2-dihydroxydiphenyl sulfide.

[0039]

[0040] In another aspect, the present application provides a high-performance high-temperature chain oil composition, which comprises a base oil, an antioxidant, an anti-wear agent, an anti-corrosion agent and a dispersant; the high-performance high-temperature chain oil composition is prepared by the preparation method according to any one of the above; the high-performance high-temperature chain oil composition P B has a value of 392-1236 N, an abrasion track diameter of 0.28-0.51 mm, a conversion rate of naphthalene in the alkyl naphthalene base oil of 90.1%-95.6%, a kinematic viscosity at 40°C of 232.4-375.2 mm 2 / s, a kinematic viscosity at 100°C of 24.4-34.8 mm 2 / s; the high-performance high-temperature chain oil composition has a VI value of 89-123, a flash point of 249-279°C, a pour point of -20 to -31°C; the high-performance high-temperature chain oil composition has an initial oxidation temperature of 237.9-260.5°C, an oxidation induction time at 210°C of 13.6-82.9 min, and a coking amount of 12-40 mg; the high-performance high-temperature chain oil composition has an evaporation loss of 1.98%-2.86%, an initial oxidation temperature of 235.0-265.4°C, an oxidation induction time of 21.5-98.9 min, and a coking amount of 6-38 mg.

[0041] Compared with the prior art, the present application has the following beneficial effects:

[0042] 1. The anti-wear agent I is obtained by reacting isooctanol and phosphorus pentasulfide, adding phosphorus pentasulfide into the reaction system in batches, controlling the temperature of the reaction, obtaining phosphosulfuric acid, then adding bismaleimide-PEG6 under neutral conditions, and allowing the unsaturated double bond of the maleimide in the bismaleimide-PEG6 to react with the mercapto group of the phosphosulfuric acid, and allowing the unreacted maleimide group to react with the boronic acid connected to the benzene ring in XC-DAPOL-CPBA, thereby obtaining the anti-wear agent I. The modified nano black scale is obtained by surface modification treatment of nano black scale. The anti-wear agent I is used in cooperation with the nano black scale, and the high-performance high-temperature chain oil composition obtained has excellent extreme pressure performance and wear resistance.

[0043] 2、By preparation obtained supported Y type molecular sieve, used for catalytic synthesis of alkyl naphthalene base oil, improve the conversion rate of raw material naphthalene. By with double pentaerythritol as raw material, the carboxyl of triphenyl sulfide acid esterification reaction with the hydroxyl of double pentaeryrythritol at high temperature, thereby through chemical bond connection, again with lithium water glass solution and double pentaeryrythritol reaction, preparation obtained double pentaeryrythritol triphenyl sulfide ester base oil, alkyl naphthalene base oil, double pentaeryrythritol triphenyl sulfide ester base oil and poly alpha olefin cooperate with, further get high performance high temperature chain oil composition kinematic viscosity is high.

[0044] 3、By synthesis alkyl naphthalene base oil, with the preparation of double pentaeryrythritol triphenyl sulfide ester base oil cooperate with, the naphthalene, benzene ring structure and the existence of silicon, lithium element in base oil makes high performance chain oil composition have good high temperature resistance and low temperature resistance, composition is little by temperature influence change.

[0045] 4、The bromine in benzothiazole sulfide hydroxyl phenyl bromide is replaced by hydroxyl, and then the benzothiazole sulfide hydroxyl phenol is used to modify N-phenyl-alpha-naphthylamine, the double bond of butyric acid reacts with the double bond of naphthalene ring in N-phenyl-alpha-naphthylamine after hydrogenation, and then the hydroxyl of benzothiazole sulfide hydroxyl phenol reacts with the unreacted carboxyl of butyric acid to generate modified N-phenyl-alpha-naphthylamine. The modified N-phenyl-alpha-naphthylamine has good antioxidant capacity, and the coking amount is reduced.

[0046] 5、The present application adjusts the amount of base oil, antioxidant, anti-wear agent and the type of hindered phenol in the antioxidant, and the prepared high performance high temperature chain oil composition has good antioxidant performance, low coking amount and low volatility. By adjusting the amount of the base oil synthesized by the present application, the high performance high temperature chain oil composition has low volatility and stable performance. In addition, the modified N-phenyl-alpha-naphthylamine and the hindered phenol, and the synergistic effect of the sulfur phosphate ester in the anti-wear agent, have good antioxidant effect. In addition, the high performance high temperature chain oil composition is not easy to produce precipitation during use. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 It is the conversion rate result graph of naphthalene in alkyl naphthalene base oil of the embodiment 34 of the present application.

[0048] Figure 2 It is the evaporation loss result graph of high performance high temperature chain oil composition of the embodiment 56 of the present application.

[0049] Figure 3 It is the coking amount result graph of high performance high temperature chain oil composition of the embodiment 56 of the present application. DETAILED DESCRIPTION

[0050] With reference to the drawings of the embodiments of the present application, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the scope of the present application.

[0051] Referring to Figures 1 to 3 The present application provides a high-performance high-temperature chain oil composition and a preparation method thereof, and the technical scheme is as follows:

[0052] The substances involved in the present application are as follows:

[0053] XC-DAPOL-CPBA, CAS: 191231-97-7; Bismaleimide-PEG6, CAS: 2752168-26-4; Triphenyl sulfide acid, CAS: 124243-00-1; Benzothiazole sulfide hydroxyl phenyl bromide, CAS: 441292-31-5; Tris (2-carboxyethyl) phosphine, CAS: 51805-45-9; Rhodium carbon catalyst, CAS: 7440-16-6; Phenylboronic acid, CAS: 98-80-6; Dipentaerythritol, CAS: 126-58-9; 1,1'-thiobis (2-naphthol), CAS: 17096-15-0; 2,2',4,4'-tetrahydroxy diphenyl sulfide, CAS: 97-29-0; 2,2-dihydroxy diphenyl sulfide, CAS: 13693-59-9; Naphthalene, CAS: 91-20-3; Tetradecane, CAS: 1120-36-1. Nano black phosphorus is purchased from Xi'an Qiyueyang Biotechnology Co., Ltd.; Low viscosity polyalphaolefin is purchased from Shanghai Doup Chemical Co., Ltd.; Y-type molecular sieve is purchased from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd.

[0054] Other unexplained reagents, substances, instruments are products that can be purchased in the market in the field of conventional chemical experiments.

[0055] Examples 1-12

[0056] In a reaction vessel equipped with stirring, reflux condenser and thermometer, under nitrogen protection, iso-octanol was added into the reaction vessel, the temperature was raised to 60℃, then 1 / 3 mole amount of phosphorus pentasulfide was added, and the reaction was carried out for 3h to obtain a phosphorothioic acid precursor; the phosphorothioic acid precursor was heated, and the remaining 2 / 3 mole amount of phosphorus pentasulfide was added, and the reaction was carried out for 15h under reflux, then the product was filtered and refined after cooling to obtain phosphorothioic acid; the mole ratio of iso-octanol to phosphorus pentasulfide was 1.1-1.3:1; the bismaleimide-PEG6 was dissolved in a phosphate buffer solution to obtain a bismaleimide-PEG6 solution; the pH of the phosphate buffer solution was 6.5-7.2; 1 mole of phosphorothioic acid and 0.01 mole of tris(2-carboxyethyl)phosphine catalyst were added into the bismaleimide-PEG6 solution, the temperature of the system was raised to 50℃, and the system was stirred for 2h under nitrogen protection to obtain an anti-wear agent I precursor; the mole ratio of phosphorothioic acid to bismaleimide-PEG6 was 1:1.1-1.2; 0.55 mole of XC-DAPOL-CPBA and 0.01 mole of rhodium carbon catalyst were added into the anti-wear agent I precursor, potassium hydroxide solution was used to adjust the pH of the system to 8.0, the temperature was raised to 60℃, the reaction was carried out for 10h under reflux, then the system was cooled to room temperature, and the anti-wear agent I was obtained after washing with deionized water and drying.

[0057] 5 parts of nano black phosphorus were dispersed in a 70℃ 5% potassium permanganate solution, stirred for 2h, filtered, and washed with deionized water to obtain pretreated nano black phosphorus; 2 parts of phenylboronic acid were added into the pretreated nano black phosphorus, ground for 5h, and dried to obtain modified nano black phosphorus.

[0058] The anti-wear agent I and the modified nano black phosphorus were mixed in a mass ratio of 1-17:1, and ground to an average particle size of 170nm to obtain an anti-wear agent.

[0059] Zirconium oxide was dispersed in a 30% sulfuric acid solution, then filtered and dried to obtain sulfated zirconium oxide; 10 parts of Y-type molecular sieve were dispersed in 200 parts of anhydrous ethanol, then 0.2 parts of sulfated zirconium oxide were added, and ultrasonic treatment was carried out for 3h under a power of 300W to obtain a supported Y-type molecular sieve dispersion; 13 parts of naphthalene were added into 6.9 parts of the supported Y-type molecular sieve dispersion, the temperature was raised to 100℃, and 20 parts of tetradecane were added into the system within 30min, the reaction was carried out for 1h, then the system was separated, washed with deionized water after decantation, separated again, and distilled under reduced pressure to obtain an alkyl naphthalene base oil.

[0060] Put 25.4 parts of dipentaerythritol into a three-necked flask, then add 150 parts of triphenylsulfonium acid, raise the temperature to 100℃, adjust the vacuum degree to 98.8KPa, then add 1 part of concentrated sulfuric acid and 0.5 part of activated carbon powder, and react for 8h to obtain a base oil precursor; dissolve 60 parts of lithium water glass with a modulus of 3.5 in 940 parts of a 30% mass fraction sodium hydroxide solution to obtain a lithium water glass solution; add 150 parts of the lithium water glass solution to the base oil precursor and continue to react for 6h, then cool to room temperature, and filter to obtain a dipentaerythritol triphenylsulfonium ester base oil.

[0061] Mix the alkyl naphthalene base oil, the dipentaerythritol triphenylsulfonium ester base oil and the low viscosity polyalphaolefin according to a parts ratio of 1:4:5, and vacuum dry to obtain a base oil.

[0062] Dissolve 98.6 parts of benzothiazole sulfenyl hydroxybenzene bromide in an acetone solution to obtain a benzothiazole sulfenyl hydroxybenzene bromide solution; the parts ratio of benzothiazole sulfenyl hydroxybenzene bromide to acetone is 1:80; warm the benzothiazole sulfenyl hydroxybenzene bromide solution to 140℃, and add a total mass fraction of 2% sodium hydroxide and 1.5% copper chromite catalyst to obtain a reaction solution; stir the reaction solution for 12h, then filter after cooling to room temperature, and then wash and dry to obtain benzothiazole sulfenyl hydroxyphenol; add 44 parts of N-phenyl-α-naphthylamine to a sealed reactor, then add 17.2 parts of butenoic acid and 7 parts of zero-valent ruthenium catalyst, and react at 130℃ for 7h to obtain a modified N-phenyl-α-naphthylamine intermediate; add benzothiazole sulfenyl hydroxyphenol and 2.5 parts of concentrated sulfuric acid to the modified N-phenyl-α-naphthylamine intermediate, continue to react for 4h, add an equal volume of deionized water, wash multiple times, and then dry to obtain modified N-phenyl-α-naphthylamine.

[0063] Mix 90 parts of base oil (three base oils prepared in Example 29), 4.5 parts of antioxidant (modified N-phenyl-α-naphthylamine and hindered phenol 1,1'-thiobis(2-naphthol) prepared in Example 42 at a parts ratio of 3:1), 1.5 parts of anti-wear agent (anti-wear agent prepared in Example 10), 1 part of corrosion inhibitor (benzotriazole octadecylamine salt, 2-methyl-isothiazol-3(2H)-one and 2-chloro-1,3-dimethyl imidazolinium chloride at a parts ratio of 3:3:2), and 0.5 parts of dispersant (high base number sulfated alkyl phenate and ethylene oxide-propylene oxide copolymer at a parts ratio of 1:1), adjust the temperature to 60℃, and stir uniformly to obtain a high-performance high-temperature chain oil composition. The high base number sulfated alkyl phenate has a base number of 400mgKOH / g.

[0064] The detailed information of the preparation process of the examples is shown in Table 1.

[0065] Table 1 Detailed information of the preparation process of the anti-wear agent

[0066]

[0067]

[0068] Comparative Example 1

[0069] Different from Example 1, no modified nano black phosphorus was added, and only the grinding agent 1 was added as an anti-wear agent.

[0070] Comparative Example 2

[0071] Different from Example 1, the anti-wear agent of Example 1 was replaced by an alkoxy phosphate extreme pressure anti-wear agent, such as P120 phosphorus star extreme pressure anti-wear agent manufactured by Shenyang Hualun Oil Product Chemical Co., Ltd.

[0072] Example 13

[0073] The high-performance high-temperature chain oil compositions prepared in Examples 1-12 and Comparative Examples 1 and 2 were tested for extreme pressure properties and wear scar diameters. The extreme pressure properties were tested using an MRS-10G lever four-ball friction and wear tester according to GB / T 3142-2019 “Determination of Load-Carrying Capacity of Lubricating Oils-Four-Ball Method”. The wear scar diameters of the high-performance high-temperature chain oil compositions were tested according to SH / T 0204-92 “Test Method for Antiwear Performance of Lubricating Greases (Four-Ball Machine Method”). The final test results are shown in Table 2.

[0074] Table 2. Extreme pressure and wear resistance test results

[0075]

[0076] The extreme pressure properties P of the high-performance high-temperature chain oil compositions prepared in the examples and comparative examples of the present application BThe value is 392-1236N, and the wear scar diameter is 0.28-0.51mm. The results of Examples 1-4 show that as the temperature of the phosphorus sulfide precursor increases, the extreme pressure performance gradually increases and then tends to be balanced, the wear scar diameter first decreases and then increases, and the friction performance increases and then decreases. When the temperature is 85℃, as shown in Example 2, the reaction of iso-octanol and phosphorus pentasulfide is complete, which is beneficial to the subsequent reaction. The results of Examples 2, 5 and 6 show that as the molar amount of iso-octanol increases, the extreme pressure performance increases and then tends to be stable, and the wear scar diameter decreases. When the molar ratio of iso-octanol to phosphorus pentasulfide is 1.3:1, the iso-octanol not only acts as a reactant, but also acts as a diluent to reduce the viscosity and promote the reaction, so the extreme pressure and wear resistance are improved. The results of Examples 6-9 show that the pH of the buffer solution in Example 8 is 6.8, which is most beneficial to the synthesis of the anti-wear agent I, thereby improving the extreme pressure and wear resistance of the system. The results of Examples 9 and 10 show that as the molar amount of bismaleimide-PEG6 increases, the extreme pressure and wear resistance are improved. The boron element and nitrogen element introduced form a friction protection surface during friction, achieving good wear resistance. The results of Examples 10-12 show that when the molar ratio of the anti-wear agent I to the modified nano black phosphorus is 9:1, the extreme pressure and wear resistance of the anti-wear agent I in combination with the modified nano black phosphorus are the best. In Comparative Example 1, no modified nano black phosphorus is added, and the extreme pressure and wear resistance of the anti-wear agent I are reduced. B In Comparative Example 2, the commercially available alkoxy phosphate extreme pressure anti-wear agent is replaced, and the extreme pressure and wear resistance are both reduced.

[0077] Examples 14-33

[0078] The specific information of the preparation process of the base oil is shown in Table 3. The types of the three base oils in Table 3 are alkyl naphthalene base oil, dipentaerythritol triphenyl sulfide ester base oil and low viscosity poly-alpha olefin, respectively.

[0079] Table 3 Preparation of alkyl naphthalene base oil, dipentaerythritol triphenyl sulfide ester base oil and base oil

[0080]

[0081]

[0082] Comparative Example 3

[0083] Unlike Example 19, the high-performance high-temperature chain oil composition is replaced by a foreign brand oil product.

[0084] Example 34

[0085] The alkyl naphthalene base oil prepared in Examples 14-20 is tested for naphthalene conversion rate, and the test results are shown in Table 4. Figure 1 Figure 1 ​The results show that the conversion rate of naphthalene in the process of preparing the alkyl naphthalene base oil in examples 14-20 is 90.1%-95.6%. By using sulfuric acid to modify zirconium oxide, and then loading the modified zirconium oxide into Y-type molecular sieve, the sulfuric acid zirconium oxide is uniformly dispersed in the Y-type molecular sieve under the action of ultrasonic waves. The molecular sieve has a large specific surface area, and contains silicon and aluminum elements, so the catalytic activity is improved, and the conversion rate of naphthalene is improved. In examples 14-17, the amount of sulfuric acid zirconium oxide loaded in the Y-type molecular sieve is changed, as shown in example 16, when the amount is 0.3 parts, the conversion rate of naphthalene is the highest. The results of examples 16, 18-20 show that when the amount of the loaded Y-type molecular sieve dispersion is 8.7 parts, the conversion rate of naphthalene is the highest, which is 95.6%.

[0086] Example 35

[0087] The high-performance high-temperature chain oil composition prepared in examples 19, 21-33 and the oil product of comparative example 3 are tested for relevant basic data, mainly the kinematic viscosity is determined, and the kinematic viscosity at 40 DEG C and 100 DEG C is tested according to GB / T265-1988 "Determination of Kinematic Viscosity of Petroleum Products and Calculation of Dynamic Viscosity", and the test results are shown in table 4.

[0088] Table 4 Kinematic viscosity test results of high-performance high-temperature chain oil composition

[0089]

[0090]

[0091] The kinematic viscosity of the high-performance high-temperature chain oil composition prepared in the examples and comparative examples of the present application is 232.4-375.2 mm 2 / s at 40 DEG C, and 24.4-34.8 mm 2 / s at 100 DEG C. The results of examples 19, 21-26 show that by changing the amount of triphenyl sulfide acid and lithium water glass solution, the kinematic viscosity of the chain oil composition changes, and when the amount of the two is 200 parts and 300 parts respectively in example 21, the kinematic viscosity is the largest. The results of example 33 show that by adjusting the amount of alkyl naphthalene base oil, dipentaerythritol triphenyl sulfide ester base oil and poly-alpha olefin, as the amount of poly-alpha olefin base oil increases, the kinematic viscosity at 40 DEG C and 100 DEG C shows a gradually decreasing trend. After introducing triphenyl sulfide acid, the relative molecular mass of the base oil increases, and the viscosity gradually increases; the introduction of lithium water glass makes the base oil form a gel product, and the viscosity of the chain oil composition gradually increases. By using low-viscosity poly-alpha olefin to dilute, the viscosity of the high-performance high-temperature chain oil composition prepared in the present application is slightly higher than that of the commercial oil of comparative example 3.

[0092] Example 36

[0093] The high-performance high-temperature chain oil compositions prepared in Examples 19, 21-33 and the oil product of Comparative Example 3 were subjected to high-temperature resistance and low-temperature resistance performance tests. The viscosity index (VI) of the high-performance high-temperature chain oil compositions was determined according to GB / T 2541-1981 "Calculation of Viscosity Index of Petroleum Products". The flash point of the high-performance high-temperature chain oil compositions of the examples and comparative examples was tested according to GB / T 3536 "Determination of Flash and Fire Points of Petroleum Products - Cleveland Open Cup Method". The pour point was determined according to GB / T 3535 "Determination of Pour Point of Petroleum Products". The final test results are shown in Table 5.

[0094] Table 5 Test results of viscosity index, flash point and pour point of high-performance high-temperature chain oil compositions

[0095]

[0096]

[0097] The high-performance high-temperature chain oil compositions prepared in the examples and comparative examples of the present application have a VI value of 89-123, a flash point of 249-279°C, and a pour point of -20 to -31°C. The results of Examples 19, 21-26 show that the VI, flash point and pour point change with the change in the amount of triphenyl sulfide acid and lithium water glass solution introduced, wherein under the conditions of Example 25, the amount of triphenyl sulfide acid is 75 parts and the amount of lithium water glass solution is 675 parts, at this time the VI value is the highest and the chain oil composition is less affected by temperature. The high-performance high-temperature chain oil composition of Example 24 has the lowest pour point of -31°C. Examples 27-33 change the amount of triphenyl sulfide acid and lithium water glass solution while also changing the mixing ratio between the three base oils, wherein as the amount of low-viscosity polyalphaolefin increases, as shown in the results of Examples 30-33, the overall pour point of the obtained high-performance high-temperature chain oil composition decreases, the low-temperature resistance performance decreases compared to other examples, but is close to the pour point of the commercial oil of the comparative example. In summary, by preparing an alkyl naphthalene base oil and introducing triphenyl sulfide acid and lithium water glass into the dipentaerythritol triphenyl sulfide ester base oil, a three-dimensional gel network structure is formed in the base oil, and the presence of naphthalene rings, benzene rings, silicon, lithium elements, etc. improves the high-temperature and low-temperature resistance performance of the high-performance high-temperature chain oil composition, and the performance of the chain oil composition is high.

[0098] Examples 37-43

[0099] The detailed information during preparation is shown in Table 6.

[0100] Comparative Example 4

[0101] Unlike Example 37, unmodified N-phenyl-alpha-naphthylamine was used as an antioxidant.

[0102] Example 44

[0103] The high performance high temperature chain oil compositions prepared in Examples 37-43 and Comparative Examples 3, 4 were tested for antioxidation performance and coking amount. Pressure Differential Scanning Calorimetry (PDSC) was used to simulate thin film oxidation of lubricating oil, and to measure oxidation induction time (230°C isothermal mode) and initial oxidation temperature (programmed temperature mode); inclined plate coking test was used to evaluate the deposit formation tendency of the oil, and the final result was expressed as the change of mass per 100 mL of oil sample. The final test results are shown in Table 6.

[0104] Table 6 Preparation of modified N-phenyl-α-naphthylamine and antioxidation performance and coking amount results with varying amounts of anti-wear agent

[0105] The high performance high temperature chain oil compositions prepared in the present application have an initial oxidation temperature of 237.9-260.5°C, an oxidation induction time of 13.6-82.9 min at 210°C, and a coking amount of 12-40 mg. In Examples 37-40, as the amount of butyric acid increases, the initial oxidation temperature and oxidation induction time gradually increase, and the coking amount gradually decreases. As the amount of the chemical species incorporated increases, the antioxidation performance gradually increases, and the high performance high temperature chain oil composition is less likely to precipitate out of the system during grinding. The results of Examples 40-43 show that as the amount of benzothiazole sulfide hydroxybenzyl bromide increases, the antioxidation performance further increases, and the coking amount significantly decreases. The sulfur ether, sulfur, nitrogen and other electron-accepting elements and functional groups contained in the benzothiazole sulfide hydroxybenzyl bromide have an adsorbing and capturing effect on free radicals, thereby improving the antioxidation performance of the high performance high temperature chain oil composition. Comparative Example 3 uses unmodified N-phenyl-α-naphthylamine as an antioxidant, and the antioxidation effect is significantly lower than that of the examples, and in addition, the coking amount is also increased, and precipitation is easily produced. Comparative Example 4 uses a commercial oil product, and the antioxidation performance is lower than that of the examples, and the coking amount is moderate. In summary, the high performance high temperature chain oil composition prepared in the present application has good antioxidation performance, and in addition, the coking amount is low, and does not affect the normal use of the equipment.

[0106] Examples 45-55 Comparative Examples 5-8

[0107] The detailed information of the preparation process of the examples is shown in Table 7.

[0108] Table 7 Changes in the amounts of components of the high performance high temperature chain oil composition

[0109]

[0110]

[0111] Example 56

[0112] The high performance high temperature chain oil compositions prepared in Examples 45-55 and Comparative Examples 5-8 were subjected to evaporation loss test and oxidation and coking amount test. The evaporation loss was determined according to SH / T 0059-1996 "Determination of Evaporation Loss of Lubricating Oil (Noack Method)" with slight modification, test condition: 250°C, 5h. The oxidation and coking resistance test was performed according to Example 44. The final test results are shown in Figure 2 、 Figure 3 and Table 8.

[0113]

[0114]

[0115] As shown in Table 8 and Figure 2 , the evaporation loss of the high performance high temperature chain oil compositions prepared in the present application is 1.98%-2.86%. Figure 3The results of Examples 45-48 show that the initial oxidation temperature is 235.0-265.4°C, the oxidation induction time is 21.5-98.9 min, and the coking amount is 6-38 mg. In Examples 45-48, as the amount of base oil increases, the evaporation loss gradually decreases, the increase of base oil has a protective effect on the substances in the high-performance high-temperature chain oil composition, reduces the evaporation loss, improves the antioxidant performance, and reduces the coking amount. In Comparative Example 5, the amount of base oil is reduced to 70 parts, and the comprehensive performance of the high-performance high-temperature chain oil composition decreases. The results of Examples 48-50 show that as the amount of antioxidant increases, the antioxidant performance gradually improves, and the modified N-phenyl-α-naphthylamine and the hindered phenol antioxidant have a synergistic effect, preventing the oxidation process of the high-performance high-temperature chain oil composition. As shown in Comparative Example 8, only the modified N-phenyl-α-naphthylamine is used without using a hindered phenol as an antioxidant, the initial oxidation temperature is lower than that of Example 45, the oxidation induction time is reduced, and the coking amount is increased. The results of Examples 49, 51, and 52 show that by changing the type of hindered phenol, Example 49 uses 1,1'-thiobis(2-naphthol) as a hindered phenol, which improves the overall heat resistance and antioxidant properties of the high-performance high-temperature chain oil composition due to the benzene ring, sulfur, and multiple phenolic hydroxyl structures. The results of Examples 52-55 show that as the amount of anti-wear agent increases, the antioxidant performance gradually increases; in Comparative Example 7, without adding an anti-wear agent, the antioxidant performance decreases; the modified anti-wear agent composed of the modified nano black phosphorus and the antioxidant has a good antioxidant effect. However, as shown in Example 55, when the amount of anti-wear agent continues to increase, the coking amount increases, and as the amount of anti-wear agent increases, the modified black phosphorus is precipitated during the use of the high-performance high-temperature chain oil composition, so the coking amount increases. In Comparative Example 6, without adding an antioxidant, the initial oxidation temperature decreases, the oxidation induction time decreases, and the coking amount increases. The evaporation loss of Examples 54 and 55 is lower than that of Examples 52 and 53, and as the amount of anti-wear agent increases, the benzene boronic acid in the modified nano black phosphorus reacts with the free hydroxyl groups in the base oil under high temperature conditions, which end-caps the hydroxyl groups and reduces the evaporation of the substances.

[0116] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements, and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A process for the preparation of a high performance high temperature chain oil composition characterized by: The method comprises the following steps: 70-92 parts of base oil, 3.8-4.5 parts of antioxidant, 1.5-2.5 parts of anti-wear agent, 1 part of corrosion inhibitor, 0.5 part of dispersant are mixed, the temperature is adjusted to 60 DEG C, and stirring is uniformly obtained; the antioxidant is obtained by mixing modified N-phenyl-alpha-naphthylamine and hindered phenol in a ratio of 3:1; The preparation method of the anti-wear agent comprises the following steps: in mole ratio, isooctanol is reacted with 1 / 3 of phosphorus pentasulfide to obtain a sulfur phosphoric acid precursor; the sulfur phosphoric acid precursor is heated to 60-95 DEG C, 2 / 3 of the phosphorus pentasulfide is added, and the reaction is carried out to obtain the sulfur phosphoric acid; the sulfur phosphoric acid and the tris (2-carboxyethyl) phosphine catalyst are added to the bismaleimide-PEG6 solution, the temperature of the system is increased to 50 DEG C, and stirring is carried out under nitrogen protection for 2h to obtain an anti-wear agent precursor; the XC-DAPOL-CPBA is added to the anti-wear agent precursor, the catalyst is added, the pH is adjusted, and then the temperature is increased, and reflux reaction is carried out for 10h to obtain the anti-wear agent one; the anti-wear agent one and the modified nano black phosphorus are mixed in a mass ratio of 1-17:1, and are ground to an average particle size of 170nm to obtain the anti-wear agent; The mole ratio of the isooctanol and the phosphorus pentasulfide is 1.1-1.3:1; the pH of the phosphate buffer solution in the bismaleimide-PEG6 solution is 6.5-7.2; the mole ratio of the sulfur phosphoric acid and the bismaleimide-PEG6 is 1:1.1-1.2; The base oil is obtained by mixing alkyl naphthalene base oil, dipentaerythritol triphenyl sulfide ester base oil and low viscosity poly-alpha olefin in a ratio of 1-4:1-6:5-13, and then vacuum drying; The alkyl naphthalene base oil is obtained by dispersing Y type molecular sieve in anhydrous ethanol, adding 0.1-0.4 parts of sulfated zirconium oxide to the Y type molecular sieve dispersion liquid, and ultrasonic treatment to obtain a supported Y type molecular sieve dispersion liquid; naphthalene and tetradecane are added to 5.5-8.7 parts of the supported Y type molecular sieve dispersion liquid, and after reaction, liquid separation and reduced pressure distillation are carried out to obtain the alkyl naphthalene base oil; The dipentaerythritol triphenyl sulfide ester base oil is obtained by reacting dipentaerythritol, 50-250 parts of triphenyl sulfide acid, concentrated sulfuric acid and 150-750 parts of lithium water glass solution; The modified N-phenyl-alpha-naphthylamine is obtained by reacting 98.6-102.4 parts of benzothiazole sulfide hydroxyl benzene bromide, copper chromite catalyst, 44 parts of N-phenyl-alpha-naphthylamine, and 16.8-17.5 parts of butenoic acid.

2. A process for the preparation of a high performance high temperature chain oil composition as claimed in claim 1, characterized in that: The preparation method of the modified nano black phosphorus is as follows: nano black phosphorus is dispersed in a 70 DEG C potassium permanganate solution, stirred for 2h, filtered, washed with deionized water, and then a pretreated nano black phosphorus is obtained; phenylboronic acid is added to the pretreated nano black phosphorus, ground for 5h, and then dried to obtain the modified nano black phosphorus.

3. A process for the preparation of a high performance high temperature chain oil composition as claimed in claim 1, wherein: The preparation method of the dipentaerythritol triphenyl sulfide ester base oil is as follows: the dipentaerythritol is added into a three-necked flask, then the triphenyl sulfide acid is added, the temperature is increased to 100 DEG C, the vacuum degree is adjusted to 98.8 KPa, then the concentrated sulfuric acid and activated carbon powder are added, and the base oil precursor is obtained after 8 h of reaction; the water glass lithium is dissolved in a sodium hydroxide solution to obtain the water glass lithium solution; the water glass lithium solution is added into the base oil precursor for continuous reaction for 6 h, then cooled to room temperature, and the dipentaerythritol triphenyl sulfide ester base oil is obtained after filtration.

4. A process for the preparation of a high performance high temperature chain oil composition as claimed in claim 3, wherein: The modulus of the water glass lithium is 3.

5.

5. A process for the preparation of a high performance high temperature chain oil composition as claimed in claim 1, wherein: The preparation method of the modified N-phenyl-alpha-naphthylamine is as follows: the benzothiazole sulfenyl hydroxybenzene bromide is dissolved in an acetone solution to obtain a benzothiazole sulfenyl hydroxybenzene bromide solution; the benzothiazole sulfenyl hydroxybenzene bromide solution is heated to 140 DEG C, and the sodium hydroxide and the copper chromite catalyst are added to obtain a reaction liquid; the reaction liquid is stirred for 12 h, and then filtered after being cooled to room temperature; then the benzothiazole sulfenyl hydroxybenzene phenol is obtained after washing and drying; the N-phenyl-alpha-naphthylamine is added into a sealed reactor, then the butenoic acid and the zero-valent ruthenium catalyst are added, and the modified N-phenyl-alpha-naphthylamine intermediate is obtained after 7 h of reaction at 130 DEG C; the benzothiazole sulfenyl hydroxybenzene phenol and the concentrated sulfuric acid are added into the modified N-phenyl-alpha-naphthylamine intermediate, and the reaction is continued for 4 h; then deionized water is added, and the modified N-phenyl-alpha-naphthylamine is obtained after washing and drying.

6. A process for the preparation of a high performance high temperature chain oil composition as claimed in claim 1, wherein: The hindered phenol is any one of 1,1'-thio bis(2-naphthol), 2,2',4,4'-tetrahydroxy diphenyl sulfide and 2,2-dihydroxy diphenyl sulfide.

7. A high performance high temperature chain oil composition characterized in that: The high-performance high-temperature chain oil composition comprises base oil, antioxidant, anti-wear agent, anticorrosive agent and dispersant; the high-performance high-temperature chain oil composition is prepared by the preparation method in any one of claims 1-6; the high-performance high-temperature chain oil composition P B has a value of 392-1236 N, an abrasion track diameter of 0.28-0.51 mm, a conversion rate of naphthalene in the alkyl naphthalene base oil of 90.1%-95.6%, a kinematic viscosity at 40℃ of 232.4-375.2 mm 2 / s, a kinematic viscosity at 100℃ of 24.4-34.8 mm 2 / s; the high-performance high-temperature chain oil composition has a VI value of 89-123, a flash point of 249-279℃, a pour point of -20 to -31℃; the high-performance high-temperature chain oil composition has an initial oxidation temperature of 237.9-260.5℃, an oxidation induction time at 210℃ of 13.6-82.9 min, and a coking amount of 12-40 mg; the high-performance high-temperature chain oil composition has an evaporation loss of 1.98%-2.86%, an initial oxidation temperature of 235.0-265.4℃, an oxidation induction time of 21.5-98.9 min, and a coking amount of 6-38 mg.

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