Non-phosphorus oil-soluble organic antimony additive as well as preparation method and application thereof

Abstract

The invention discloses a non-phosphorus oil-soluble organic antimony additive and a preparation method and application thereof. The preparation method comprises the following steps: mixing an antimony source, a solvent and organic amine, uniformly stirring, dropwise adding carbon disulfide for reaction, heating to 40-150 DEG C, keeping the temperature for reflux reaction, and after the reaction is finished, performing post-treatment to obtain non-phosphorus oil-soluble organic antimony. The synergistic effect of the organic antimony and the sulfur element endows the additive with excellent extreme pressure anti-wear performance, abrasion of a metal friction pair can be effectively reduced, the service life of equipment is prolonged, and meanwhile friction energy consumption is reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field, and in particular relates to a non-phosphorus oil-soluble organic antimony additive and a preparation method and application thereof. Background Art

[0002] In the field of lubricant additives, non-phosphorus, oil-soluble organoantimony compounds have attracted widespread attention due to their environmental friendliness and excellent extreme pressure and anti-wear properties. Short-chain alkyl or aryl-substituted antimony dithiocarbamates (such as dibutyl, diethyl, dioctyl, and dibenzyl derivatives) are typical examples, achieving excellent oil solubility and thermal stability through molecular structural engineering. These additives effectively reduce metal-to-metal contact by decomposing and forming an antimony sulfide tribofilm. However, their short carbon chain structure limits film durability and oxidation resistance under high-temperature and high-load conditions. Furthermore, research on long-chain alkyl derivatives is relatively scarce, restricting their application in more demanding environments.

[0003] Therefore, it is necessary to prepare a long-chain non-phosphorus oil-soluble organic antimony. Summary of the Invention

[0004] In view of this, the present invention aims to provide a non-phosphorus oil-soluble organic antimony additive and a preparation method and application thereof, so as to solve at least one technical problem in the background technology.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows: A non-phosphorus oil-soluble organic antimony additive having a structure shown in general formula (I): (I) Wherein, R1, R2, R3, R4, R5, R6 are selected from C 10 -C 16 Straight-chain and branched alkyl groups; R1, R2, R3, R4, R5, and R6 are the same or different.

[0006] A method for preparing a non-phosphorus oil-soluble organic antimony additive comprises the following steps: The antimony source, solvent and organic amine are mixed and stirred uniformly, carbon disulfide is added dropwise for reaction, and then the temperature is raised to 40-150° C. and the temperature is maintained under reflux for reaction. After the reaction is completed, non-phosphorus oil-soluble organic antimony is obtained through post-treatment.

[0007] Furthermore, the antimony source is antimony oxide or antimony chloride, and the solvent is C1-C4 monoalcohol or polyol.

[0008] Furthermore, the temperature for dropwise addition of carbon disulfide is lower than 20°C.

[0009] Furthermore, the molar ratio of the organic amine to carbon disulfide is 1:1.1, and the molar ratio of the organic amine to the antimony source is 2-6:1.

[0010] Furthermore, the general formula of the organic amine is R7NHR8, wherein R7 and R8 are C 10 -C 16 The straight chain and branched alkyl groups, R7 and R8 are the same or different.

[0011] Further, carbon disulfide is added dropwise, and the reaction time is 1 to 20 hours; And / or, the temperature is maintained at reflux for a reaction time of 1 to 20 hours.

[0012] Furthermore, the post-treatment includes centrifuging and taking the upper liquid, and rotary evaporating to obtain non-phosphorus oil-soluble organic antimony.

[0013] The non-phosphorus oil-soluble organic antimony additive prepared by the above-mentioned preparation method of the non-phosphorus oil-soluble organic antimony additive is used in lubricating oil and grease.

[0014] Furthermore, the addition amount in lubricating oil is 0.1 wt.%~1 wt.%, and the addition amount in grease is 0.4 wt.%~4 wt.%.

[0015] Compared with the prior art, the non-phosphorus oil-soluble organic antimony additive and its preparation method and application described in the present invention have the following advantages: 1. By adopting a phosphorus-free formula, this application avoids the environmental pollution issues that traditional phosphorus-based additives may cause. This conforms to the development trend of green chemistry and is particularly suitable for the lubricant field, which has strict environmental requirements. The introduction of organic amines and carbon disulfide in this application significantly improves the oil solubility of the product, enabling it to be evenly dispersed in the base oil. At the same time, the high-temperature reflux reaction ensures the chemical stability of the product, making it difficult to decompose or precipitate under high temperature or shear conditions.

[0016] 2. The synergistic effect of the organic antimony and sulfur element in the present application gives the additive excellent extreme pressure and anti-wear properties, which can effectively reduce the wear of metal friction pairs, extend the service life of equipment, and reduce friction energy consumption.

[0017] 3. The mild reaction conditions (40-150°C), recyclable solvents, and simple post-processing steps make this product suitable for large-scale production, reducing overall costs. Furthermore, the readily available raw materials avoid the use of precious metals or complex ligands. The product exhibits excellent compatibility with common lubricant additives (such as detergents and dispersants) and can be widely used in industrial lubricant systems such as internal combustion engine oils and gear oils, meeting diverse needs. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] 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: Figure 1 This is the infrared spectrum of the additive composition of Example 1 of the present invention. DETAILED DESCRIPTION

[0019] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0020] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0021] The specific implementation method is to add antimony source, solvent and organic amine into a three-necked flask equipped with a thermometer and a reflux condenser and stir them evenly, then add carbon disulfide dropwise at a temperature below 20°C, react for 1 to 20 hours, and heat to T 反应温度 ℃, keep the temperature under reflux reaction 反应时间 After the reaction is completed, the upper liquid is collected by centrifugation and rotary evaporation to obtain non-phosphorus oil-soluble organic antimony.

[0022] Table 1 Implementation parameters of Examples 1-6 Application Example 1 The antimony content, sulfur content and oil solubility of the additive were tested. The sulfur content was tested using the ASTM D5185-12 method, the antimony content was tested using the ICP-OES method, and 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.

[0023] Table 2 Oil solubility results sample Antimony content, % Sulfur content, % Oil-soluble Example 1 7.4 9.1 Clarity and transparency Example 2 7.6 9.3 Clarity and transparency Example 3 7.4 9.2 Clarity and transparency Example 4 8.8 10.3 Clarity and transparency Example 5 10.9 12.8 Clarity and transparency Example 6 13.5 11.1 Clarity and transparency Application Example 2 The tribological properties were tested using a four-ball friction and wear tester. The test oil was 150N+1%T202+0.5% additive. T202 was purchased from Xinxiang Ruifeng New Materials Co., Ltd. The four-ball test conditions were 245N, 2700r / min, and free heating.

[0024] Table 3 Tribological properties sample Thermal equilibrium temperature, °C Wear spot diameter, mm CoF blank 67.3 0.56 0.101 Example 1 58.0 0.35 0.076 Example 4 61.8 0.35 0.083 Example 6 63.5 0.38 0.087 By attaching Figure 1 , 2957cm -1 、2925 cm -1 、2856 cm -1 These are all stretching vibration peaks of saturated -CH3, 1418 cm -1is the bending vibration absorption peak of saturated -CH2-, 1480 cm -1 is the stretching vibration absorption peak of CN, 1205 cm -1 , 970 cm -1 is the stretching vibration absorption peak of C=S and CS, 727 cm -1 Yes - (CH2) n - n ≥ 4 is the CH in-plane bending vibration, 605 cm -1 It is the Sb-S absorption peak.

[0025] 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 non-phosphorus oil-soluble organic antimony additive, characterized in that: It has the structure shown in general formula (I): （Ⅰ） Wherein, R1, R2, R3, R4, R5, R6 are selected from C 10 -C 16 Straight-chain and branched alkyl groups; R1, R2, R3, R4, R5, and R6 are the same or different.

2. The method for preparing a non-phosphorus oil-soluble organic antimony additive according to claim 1, characterized in that: The steps include: The antimony source, solvent and organic amine are mixed and stirred uniformly, carbon disulfide is added dropwise for reaction, and then the temperature is raised to 40-150° C. and the temperature is maintained under reflux for reaction. After the reaction is completed, non-phosphorus oil-soluble organic antimony is obtained through post-treatment.

3. The method for preparing a non-phosphorus oil-soluble organic antimony additive according to claim 2, characterized in that: The antimony source is antimony oxide or antimony chloride, and the solvent is C1-C4 monoalcohol or polyol.

4. The method for preparing a non-phosphorus oil-soluble organic antimony additive according to claim 2, wherein: The temperature for dropwise addition of carbon disulfide was lower than 20°C.

5. The method for preparing a non-phosphorus oil-soluble organic antimony additive according to claim 2, characterized in that: The molar ratio of the organic amine to carbon disulfide is 1:1.1, and the molar ratio of the organic amine to the antimony source is 2-6:

1.

6. The method for preparing a non-phosphorus oil-soluble organic antimony additive according to claim 2, characterized in that: The general formula of the organic amine is R7NHR8, wherein R7 and R8 are C 10 -C 16 The straight chain and branched alkyl groups, R7 and R8 are the same or different.

7. The method for preparing a non-phosphorus oil-soluble organic antimony additive according to claim 2, characterized in that: Add carbon disulfide dropwise, and the reaction time is 1~20h; And / or, the temperature is maintained at reflux for a reaction time of 1 to 20 hours.

8. The method for preparing a non-phosphorus oil-soluble organic antimony additive according to claim 2, characterized in that: The post-treatment includes centrifuging and taking the upper liquid, and rotary evaporating to obtain non-phosphorus oil-soluble organic antimony.

9. The non-phosphorus oil-soluble organic antimony additive prepared by the method for preparing the non-phosphorus oil-soluble organic antimony additive according to any one of claims 2 to 8 is used in lubricating oils and greases.

10. The use according to claim 9, characterized in that: The addition amount in lubricating oil is 0.1 wt.%~1wt.%, and the addition amount in grease is 0.4 wt.%~4 wt.%.

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