Temperature rise inhibiting additive composition as well as preparation method and application thereof

Abstract

The preparation method comprises the following steps: S1, uniformly stirring a molybdenum source, a solvent and organic amine, dropwise adding carbon disulfide, raising the temperature for reaction, raising the temperature to 40-150 DEG C again, and keeping the temperature for reflux reaction to obtain a mixed solution; and S2, cooling the mixed solution, adding a solvent, carbon disulfide and an antimony source, heating to 40-150 DEG C, and keeping the temperature for reflux reaction to obtain the temperature rise inhibition additive composition. Compared with an additive composition prepared by separately preparing and then mixing, the composition prepared by the invention has the advantages that two reactions can be combined into one, the reaction time is effectively shortened, and the loss of reaction raw materials, reaction solvents and reaction temperature is reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of lubricating oil additives, and in particular relates to a temperature rise suppression additive composition, a preparation method and an application thereof. Background Art

[0002] In the field of lubricant additives, especially in applications under high-temperature conditions, traditional additives (such as ZDDP, sulfonates, etc.) are prone to thermal decomposition or oxidation failure at extreme temperatures, resulting in reduced lubrication performance, increased carbon deposits, and increased component wear. In the prior art, although composite antioxidants or viscosity index improvers are used to improve high-temperature stability, there are still problems such as limited temperature rise suppression effect and poor compatibility with base oil. In addition, metal-containing additives may cause catalyst poisoning, while ashless additives are expensive and lack long-term effectiveness. Therefore, there is an urgent need to develop a new temperature rise suppression additive composition that effectively reduces the friction interface temperature through synergistic effects, while also having antioxidant, anti-wear and environmental protection properties to meet the long-term lubrication needs of high-power density mechanical systems. Summary of the Invention

[0003] In view of this, the present invention aims to provide a temperature rise suppression additive composition and a preparation method and application thereof, so as to solve at least one technical problem in the background technology.

[0004] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0005] A method for preparing a temperature rise suppression additive composition comprises the following steps:

[0006] S1: The molybdenum source, solvent and organic amine are stirred evenly, carbon disulfide is added dropwise, the temperature is raised to react, the temperature is raised again to 40-150°C, and the temperature is maintained for reflux reaction to obtain a mixed solution;

[0007] S2: After the mixed solution is cooled, a solvent, carbon disulfide and an antimony source are added, and the temperature is raised to 40-150° C., and the temperature is maintained under reflux reaction to obtain a temperature rise suppression additive composition.

[0008] Furthermore, the molybdenum source in step S1 is ammonium heptamolybdate tetrahydrate, and the solvent is water.

[0009] Furthermore, the molar ratio of the organic amine to carbon disulfide in step S1 is 1:1.1;

[0010] And / or, the molar ratio of the molybdenum source to the organic amine in step S1 is 0.1 to 1:1.

[0011] Furthermore, the general formula of the organic amine is R1NHR2, wherein R1 and R2 are C 10 -C 16 Straight-chain and branched alkyl groups, R1 and R2 are the same or different;

[0012] Preferably, R1 and R2 are both straight-chain tridecyl groups.

[0013] Furthermore, the antimony source in step S2 is antimony oxide or antimony chloride, and the solvent is anhydrous ethanol.

[0014] Furthermore, the molar ratio of carbon disulfide in step S2 to carbon disulfide in step S1 is 0.1-1:1, and the molar ratio of the antimony source to the molybdenum source is 0.01-100:1, preferably 0.5-2:1.

[0015] Furthermore, in step S1, the molybdenum source, solvent and organic amine are stirred uniformly in a three-necked flask equipped with a thermometer and a reflux condenser;

[0016] and / or, the temperature during the dropwise addition of carbon disulfide in step S1 is lower than 20° C.;

[0017] and / or, after adding carbon disulfide dropwise, heating and reacting for 1 to 20 hours;

[0018] And / or, in step S1, the temperature for the reflux reaction is maintained at 30-50° C. for 1-20 h.

[0019] Furthermore, the temperature at which the mixed solution is cooled in step S2 is 25-35°C;

[0020] And / or, the temperature is maintained under reflux for a reaction time of 1 to 20 hours.

[0021] A temperature-rise suppression additive composition is prepared by the method for preparing the temperature-rise suppression additive composition.

[0022] The temperature rise suppression additive composition is applied to lubricating oil, and the addition amount thereof in the lubricating oil is 0.1 wt.% to 1 wt.%.

[0023] Compared with the prior art, the temperature rise suppression additive composition, preparation method and application thereof of the present invention have the following advantages:

[0024] 1. This application selects organic amine (diisotridecylamine) as the long-chain amine, which can effectively improve the adsorption of additives on the friction pair surface.

[0025] 2. Those skilled in the art are aware that as metal content increases, the viscosity of additives increases. Lubricant additives are primarily in powder or oil form, and high-viscosity pastes are detrimental to oil formulation and production. The viscosity of molybdenum dialkyldithiocarbamate additives increases dramatically with increasing molybdenum content, so the molybdenum content of commercially available liquid additives is generally controlled at around 10%. Another approach is to dilute with base oil, but this also reduces the effective content. Adding base oil during the reaction slows the reaction rate, and adding it after the reaction still struggles to avoid the associated problems of high-viscosity additives during production. Antimony dialkyldithiocarbamate, however, has a lower viscosity and can replace base oil for dilution. Furthermore, it acts as an antioxidant and friction reducer, synergizing with molybdenum dialkyldithiocarbamate.

[0026] 3. The essence of the present invention is to prepare a mixture of molybdenum dialkyldithiocarbamate and antimony dialkyldithiocarbamate. Compared to additive compositions prepared separately and then mixed, the composition prepared by the present invention combines two reactions into one, effectively shortening the reaction time and reducing the loss of reaction raw materials, reaction solvent, and reaction temperature. Furthermore, synthetic reactions require controlling the conversion and yield of reactants and products. While the preparation of molybdenum dialkyldithiocarbamate can achieve essentially 100% conversion of the molybdenum source, it is difficult to simultaneously achieve high conversions of both the molybdenum source and carbamic acid, the preparation of antimony dialkyldithiocarbamate can ensure high conversion of carbamic acid, and excess antimony oxide can be removed by centrifugation, resulting in a high yield and high purity product. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0028] Figure 1 This is the infrared spectrum of the additive composition of Example 1 of the present invention. DETAILED DESCRIPTION

[0029] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features therein may be combined with each other.

[0030] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0031] Sulfurized isobutylene was purchased from Shenyang Guangda Chemical Co., Ltd., code T321.

[0032] Anti-micropitting extreme pressure and anti-wear agent (self-made), code name QT301;

[0033] Acidic phosphate amine salt was purchased from Shenyang Hualun Lubricant Additive Co., Ltd., code T308;

[0034] Triphenyl thiophosphate was purchased from Jinzhou Shengda Chemical Co., Ltd., code T309;

[0035] Phosphorus Star extreme pressure anti-wear agent was purchased from Shenyang Hualun Lubricant Additive Co., Ltd., code name P120;

[0036] Heterocyclic derivatives were purchased from Nanjing Milan Chemical Co., Ltd., code T553;

[0037] Benzotriazole acid adduct was purchased from Shenyang Hualun Lubricant Additive Co., Ltd., code T406E;

[0038] Ashless dispersant was purchased from Xinxiang Ruifeng New Materials Co., Ltd., code RF1161H;

[0039] Overbased calcium sulfonate was purchased from Xinxiang Ruifeng New Materials Co., Ltd., code number RF1106D;

[0040] Antifoaming agent was purchased from Shanghai Kaiyin Chemical Co., Ltd., code 155;

[0041] Polymethacrylate viscosity index improver was purchased from Dalian Xinyi Industry New Materials Development Co., Ltd., code V6520;

[0042] Pentaerythritol fatty acid esters were purchased from Croda Company, code 3970;

[0043] A type of deeply refined mineral oil was purchased from Suzhou Zhuxin Industrial Lubricant Co., Ltd., code name HVIS150BS;

[0044] PAO40 and PAO6 base oils were purchased from Mobil.

[0045] Antimony dialkyldithiocarbamate was purchased from Kelong Chemical Glass Instrument Supply Station in Weibin District, Baoji City, code HL622;

[0046] The process for synthesizing the product QT301 from the self-made dispersant and acidic phosphate amine salt is as follows:

[0047] 1) In a 500ml three-necked flask, add a certain amount of phosphorus pentoxide to 100ml of petroleum ether (boiling range 90-120°C) and stir until evenly dispersed (approximately 3 minutes).

[0048] 2) Add a certain amount of isooctyl alcohol dropwise using a dropping funnel while stirring. Keep the reaction liquid temperature below 40°C during the addition. After the addition is complete, raise the temperature to 72-75°C and react for 4 hours to obtain the intermediate product (acidic phosphate ester).

[0049] 3) After cooling the intermediate product, a certain amount of T152 (polyisobutylene bissuccinimide) and dodecylamine were added, and then the temperature was raised to 90-94°C and reacted for 3 hours;

[0050] 4) After distilling off the petroleum ether solvent, QT301 is obtained.

[0051] The process of making the self-made non-sulfur-phosphorus organic molybdenum friction reducing additive QT403 is as follows:

[0052] 1) In a three-necked flask, a long-chain unsaturated acid chloride and pyridine were dissolved in petroleum ether (boiling range 90-120°C). Diethanolamine was added dropwise to the reaction system at 20-30°C while stirring. After the addition was complete, the temperature was maintained at 20-30°C and the reaction was continued for 4-5 hours until the raw materials were completely reacted. The reaction solution was filtered, and the organic phase was washed with a buffer solution (15% sodium bicarbonate), stripped with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain a long-chain unsaturated amide.

[0053] 2) A long-chain unsaturated amide is dissolved in an organic solvent (N,N-dimethylformamide), a certain amount of catalyst (triethylamine) is added, and the temperature is controlled at 90-120°C. An aqueous ammonium molybdate solution is added dropwise to the reaction system while stirring. The reaction is then refluxed at 60-120°C for 7-8 hours. The solvent is removed by filtration and reduced pressure distillation to obtain QT403.

[0054] Example

[0055] In a three-necked flask equipped with a thermometer and a reflux condenser, add a molybdenum source, a solvent, and an organic amine and stir evenly. Then, add carbon disulfide dropwise at a temperature below 20°C and heat to T. 1反应温度 , reaction S1,

[0056] Then heat up to T 2反应温度 , keep the temperature reflux reaction S2, cool to 25 ℃, add solvent, carbon disulfide and antimony source, and heat to T 3反应温度 After the reaction is completed, the upper liquid is collected by centrifugation, separated, and rotary evaporated to obtain the additive composition.

[0057] Table 1 Implementation parameters of Examples 1 to 6

[0058]

[0059] Comparative Example 1

[0060] In a three-necked flask equipped with a thermometer and a reflux condenser, 0.2 mol of ammonium heptamolybdate tetrahydrate, 300 g of water and 0.26 mol of ditridecylamine were added, and then 0.4 mol of carbon disulfide was added dropwise below 20°C. The mixture was reacted at 30°C for 4 h, heated to 80°C, maintained at reflux for 8 h, cooled, and rotary evaporated to obtain molybdenum dialkyldithiocarbamate.

[0061] To a three-necked flask equipped with a thermometer and a reflux condenser, add 0.05 mol of antimony trioxide, 120 g of ethanol, and 0.3 mol of isomeric ditridecylamine and stir thoroughly. Then, add carbon disulfide dropwise below 20°C. Allow to react for 1 hour. Then, raise the temperature to 80°C and maintain reflux for 2 hours. After the reaction is complete, centrifuge the supernatant and rotary evaporate to obtain antimony dialkyldithiocarbamate.

[0062] Comparative Example 1 was prepared by mixing molybdenum dialkyldithiocarbamate and antimony dialkyldithiocarbamate in a mass ratio of 8:5.

[0063] Comparative Example 2

[0064] Comparative Example 2 was prepared by mixing QT403 and HL622 in a mass ratio of 8:5.

[0065] Application Example 1

[0066] The molybdenum content, antimony content, sulfur content and oil solubility of the additive were tested. The molybdenum content and sulfur content were tested using the ASTM D5185-12 method, and the antimony content was tested using the ICP-OES method. The oil solubility was tested by dissolving the additive at 1% in 120# solvent oil and stirring at 65°C for 1 hour. The results are shown in Table 2.

[0067] Table 2 Oil solubility results

[0068]

[0069] Application Example 2

[0070] The temperature rise suppression test was carried out on a four-ball testing machine produced by Xiamen Tianji Automation Co., Ltd.: the room temperature was controlled between 23.2-23.5℃, the heating of the test oil was stopped after it reached a certain temperature, and then the test was started at 784N, 2000r / min. When thermal equilibrium was reached and the temperature no longer increased (the temperature remained unchanged within 2 minutes), the test was stopped, and the time (s) was recorded at each certain temperature interval.

[0071] Test oils: anti-scuffing agent (T321) 3.35%, extreme pressure anti-wear agent (1.0% QT301, 0.3% T308, 0.36% T309, 0.8% P120) 2.46%, metal deactivator (0.05% T553, 0.05% T406E) 0.10%, ashless dispersant (RF1161H) 0.12%, rust inhibitor (RF1106D) 0.05%, anti-foaming agent (155) 0.03%, viscosity index improver (V6520) 5%, ester oil (3970) 9%, HVIS150BS 5%, PAO (61.61% PAO6 and 11.98% PAO40) 73.59%.

[0072] Table 3 Friction temperature rise test results

[0073]

[0074] It can be seen that compared with the comparative example of a mixture of two additives, the total metal content of the present invention is higher, and the kinematic viscosity is also within an acceptable range. Comparison of Example 1 and Example 5 shows that the introduction of antimony does not lead to a decrease in the original molybdenum content. Comparison of Example 2 and Comparative Examples 1 and 2 shows that the additive prepared by the present invention has higher molybdenum content, antimony content, and total metal content than the additives prepared and mixed separately, and can achieve the same metal content in the lubricating oil with a smaller addition amount.

[0075] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a temperature rise suppression additive composition, characterized in that: The steps include: S1: The molybdenum source, solvent, and organic amine are stirred evenly, carbon disulfide is added dropwise, and the temperature is raised to react, and the temperature is raised again to 40-150°C, and the temperature is maintained for reflux reaction to obtain a mixed solution; S2: After the mixed solution is cooled, a solvent, carbon disulfide and an antimony source are added, and the temperature is raised to 40-150° C., and the temperature is maintained under reflux reaction to obtain a temperature rise suppression additive composition.

2. The method for preparing a temperature rise suppression additive composition according to claim 1, characterized in that: The molybdenum source in step S1 is ammonium heptamolybdate tetrahydrate, and the solvent is water.

3. The method for preparing a temperature rise suppression additive composition according to claim 1, characterized in that: The molar ratio of the organic amine to carbon disulfide in step S1 is 1:1.1; And / or, the molar ratio of the molybdenum source to the organic amine in step S1 is 0.1-1:

1.

4. The method for preparing a temperature rise suppression additive composition according to claim 1, wherein: The general formula of the organic amine is R1NHR2, wherein R1 and R2 are C 10 -C 16 The straight chain and branched chain alkyl groups, R1 and R2 are the same or different.

5. The method for preparing a temperature rise suppression additive composition according to claim 1, characterized in that: The antimony source in step S2 is antimony oxide or antimony chloride, and the solvent is anhydrous ethanol.

6. The method for preparing a temperature rise suppression additive composition according to claim 1, wherein: The molar ratio of carbon disulfide in step S2 to carbon disulfide in step S1 is 0.1-1:1, and the molar ratio of the antimony source to the molybdenum source is 0.01-100:1, preferably 0.5-2:

1.

7. The method for preparing a temperature rise suppression additive composition according to claim 1, characterized in that: In step S1, the molybdenum source, solvent and organic amine are stirred uniformly in a three-necked flask equipped with a thermometer and a reflux condenser; and / or, the temperature during the dropwise addition of carbon disulfide in step S1 is lower than 20° C.; and / or, after adding carbon disulfide dropwise, heating and reacting for 1 to 20 hours; And / or, in step S1, the temperature for the reflux reaction is maintained at 30-50° C. for 1-20 h.

8. The method for preparing a temperature rise suppression additive composition according to claim 1, characterized in that: The temperature of the mixed solution in step S2 is cooled to 25-35°C; And / or, the temperature is maintained at reflux for a reaction time of 1 to 20 hours.

9. A temperature-rise suppression additive composition prepared by the method for preparing a temperature-rise suppression additive composition according to any one of claims 1 to 8.

10. The temperature rise suppression additive composition according to claim 9 is used in lubricating oil, characterized in that: The addition amount in lubricating oil is 0.1 wt.%~1 wt.%.

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