Detergent for lubricating oil and preparation method thereof

Abstract

The invention relates to the field of chemical engineering, in particular to a detergent for lubricating oil and a preparation method of the detergent. The clearing agent for the lubricating oil is prepared from the following raw material components in parts by weight: 35 to 45 parts of lubricating oil base oil, 15 to 25 parts of a composite purification dispersant, 2 to 6 parts of a clearing agent, 10 to 20 parts of diluent oil, 3 to 7 parts of a copolyamide compound and 2 to 8 parts of ethylene glycol monobutyl ether, the composite purification dispersant is prepared by compounding a modified amide auxiliary agent and modified sulfamide in a mass ratio of (1-1.5): 1. The prepared copolyamide compound, the modified amide auxiliary agent and the modified sulfamide have excellent dispersing capacity on components generated in the process of oxidizing the lubricating oil into sludge, solid particles and other pollutants, and can particularly disperse the solid particles in the lubricating oil and prevent the solid particles from gathering and precipitating; meanwhile, acid-base balance of the lubricating oil can be maintained, and a good cleaning effect is achieved.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, and particularly relates to a detergent for lubricating oil and a preparation method thereof. Background Art

[0002] Oxidative degradation of lubricating oil produces organic oxygenates such as ketones and aldehydes, which are converted into harmful acids through self-oxidation, and then produce unsaturated hydrocarbons to form polymerized sludge. Detergents can chemically treat metal surfaces, neutralize acidic substances by removing deposits on the metal surface, and prohibit the deposition of solid particles in a finely dispersed state; dispersants work by suspending pollutant substances and insoluble oil segments in lubricating oil. Therefore, these two components have a great influence on the chemical properties of the entire package and the finished oil.

[0003] Therefore, there is an urgent need for a detergent with good cleaning effect for lubricating oil to improve the performance of lubricating oil. Summary of the invention

[0004] The object of the present invention is to provide a detergent for lubricating oil and a preparation method thereof, so as to solve the technical problem of poor performance of lubricating oil detergent in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The technical solution provided by the present invention is as follows:

[0007] In a first aspect, the present invention provides a detergent for lubricating oil, wherein the detergent for lubricating oil comprises the following components in parts by weight:

[0008] 35-45 parts of lubricating oil base oil, 15-25 parts of composite detergent dispersant, 2-6 parts of detergent, 10-20 parts of diluent oil, 3-7 parts of copolyamide compound, and 2-8 parts of ethylene glycol monobutyl ether.

[0009] Preferably, the diluent oil is 150SN and / or 350N.

[0010] Preferably, the detergent includes at least one of magnesium naphthenate and cerium isooctanoate.

[0011] Preferably, the composite detergent dispersant is prepared by compounding a modified amide auxiliary agent and a modified sulphamide in a mass ratio of 1-1.5:1.

[0012] Preferably, the preparation method of the modified amide auxiliary agent comprises the following steps:

[0013] S1: Add 79-160 g of acetyl chloride and 76-150 g of ammonium thiocyanate to 500-1000 mL of acetone, stir for 15-25 min, filter, add 121-250 g of tris(hydroxymethyl)aminomethane to the filtrate, continue stirring for 8-12 min, and obtain an intermediate product;

[0014] S2: Mix 22.2-45 g of the intermediate product, 1.7-3.4 g of p-toluenesulfonic acid and 84.1-168 g of linoleic acid, and stir the mixture at 135-145° C. for 12-18 h to obtain a modified amide auxiliary agent.

[0015] The structural formula of the modified amide additive is as follows:

[0016]

[0017] Among them, the modified amide additive was subjected to mass spectrometry analysis, HRMS (ESI) m / z: 93.73 (100.0%), 994.74 (66.3%), 995.74 (23.6%), 996.74 (5.7%), 995.73 (5.0%), 996.73 (3.0%), 994.73 (1.5%), 997.74 (1.4%).

[0018] Preferably, the linoleic acid is linoleic acid containing ≥50% acid.

[0019] Preferably, the preparation method of the modified thioamide comprises the following steps:

[0020] Add 30-60 g of oleoyl chloride and 15-30 g of ammonium thiocyanate to 300-600 mL of acetone, stir for 25-35 min, filter, add 16-32 g of N,N'-di(2-aminoethyl)-1,3-propylenediamine to the filtrate, continue stirring for 55-65 min, evaporate the acetone, wash with petroleum ether 4-6 times to obtain modified sulfamide.

[0021] The structural formula of modified sulfamide is as follows:

[0022]

[0023] Among them, the modified sulfamide was subjected to mass spectrometry analysis, HRMS (ESI) m / z: 469.38 (100.0%), 470.38 (29.7%), 471.38 (5.3%), 471.39 (3.9%), 472.38 (1.3%).

[0024] The preparation method of the copolyamide compound comprises the following steps:

[0025] P1: Add 10-20 g of acrylic acid and 37-74 g of stearyl alcohol to 40-80 mL of toluene, then add 0.042-0.084 g of p-toluenesulfonic acid and 0.028-0.056 g of hydroquinone, heat at 75-85 ° C for 10-14 h, remove toluene by rotary evaporation, and vacuum dry at 45-55 ° C for 3-4 h to obtain stearyl acrylate;

[0026] P2: In a nitrogen atmosphere, 12-24 g of maleic anhydride and 41.7-82 g of stearyl acrylate are added to 40-50 mL of toluene, stirred for 25-35 min, and then 0.24-0.48 g of benzoyl peroxide is added. The mixture is refluxed at 105-115° C. for 6-7 h, and the mixture is poured into methanol for precipitation and filtered. The filter residue is washed with methanol solvent for 3-5 times and vacuum dried at 75-85° C. for 5-6 h to obtain a polymer compound;

[0027] P3: Add 15-30 g of p-aminodiphenylamine and 40-82 g of the polymer compound into 50-100 mL of xylene, reflux at 141-146° C. for 10-14 h, remove xylene by rotary evaporation, and dry at 85-95° C. for 7-8 h to obtain a copolyamide compound.

[0028] The structural formula of the copolyamide compound is as follows:

[0029]

[0030] In a second aspect, the present invention provides a method for preparing a detergent for lubricating oil, comprising the following steps:

[0031] 15-25 parts of composite detergent dispersant, 2-6 parts of detergent, 3-7 parts of copolyamide compound and 2-8 parts of ethylene glycol monobutyl ether are added to 35-45 parts of lubricating oil base oil, stirred at 200-300 rpm for 12-18 minutes at 45-55°C, then 10-20 parts of diluent oil are added, stirred at 200-300 rpm for 20-30 minutes at 45-55°C, and cooled to room temperature to obtain the detergent for lubricating oil.

[0032] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0033] 1. The copolyamide compound, modified amide auxiliary agent and modified thioamide prepared by the present invention have excellent dispersibility for components generated during the oxidation of lubricating oil into sludge, solid particles and other pollutants, and can particularly disperse solid particles in lubricating oil to prevent them from aggregating and precipitating. At the same time, they can help maintain the acid-base balance of lubricating oil and cooperate with detergents, and have good cleaning effects.

[0034] 2. The oleophobic groups of the modified amide additive prepared by the present invention enhance the solubility in lubricating oil, and the non-polar hydrophobic tail prevents polar smoke particles from adhering to the metal surface and also prevents them from aggregating into larger clusters; the hydrophilic polar head segment is attracted to the lubricating oil pollutants and surrounds the solid pollutants; the modified amide additive and the modified thioamide contain more NH groups, and the increase of NH groups increases the neutralization force and improves the dispersing force by forming hydrogen bonds with oxidizing components such as alcohols, aldehydes, ketones, and acids, and cooperates to improve the effect as a lubricating oil dispersant; the polar secondary aniline molecules in the structure of the copolyamide compound have cleanliness, hinder sludge deposition, and have acid neutralization efficiency; the imino groups in the copolyamide compound, the modified amide additive and the modified thioamide can help maintain the acid-base balance of the lubricating oil, prevent acidic substances from corrosively affecting the metal surface under high temperature or high pressure conditions, extend the service life of the lubricating oil and machine parts, and cooperate with the detergent to maintain the performance stability and cleanliness of the lubricating oil.

[0035] 3. The copolyamide compound prepared by the present invention has a diphenylamine group, and the long alkyl chain polymer reduces the absorbance of 2,2-diphenyl-pyridinylhydrazide (DPPH) to a greater extent, thereby having a greater free radical scavenging ability and having a good antioxidant; due to the availability of protons, this proton is easily transferred from diphenylamine to hydrocarbon groups, and hydrocarbon groups are further converted into hydrocarbons to prevent degradation, thereby improving the oxidation stability of the lubricating oil, and at the same time contains nitrogen-based phenylenediamine, so it also has a good anti-corrosion effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0037] Figure 1 The present invention is a flow chart of the preparation process of the detergent for lubricating oil. DETAILED DESCRIPTION

[0038] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] Example 1

[0040] This embodiment discloses a method for preparing a modified amide auxiliary agent, comprising the following steps:

[0041] S1: 120 g of acetyl chloride and 114 g of ammonium thiocyanate were added to 750 mL of acetone, stirred for 20 min, filtered, 181.5 g of tris(hydroxymethyl)aminomethane was added to the filtrate, and the stirring was continued for 10 min to obtain an intermediate product;

[0042] S2: 33.3 g of the intermediate product, 2.6 g of p-toluenesulfonic acid and 126.2 g of linoleic acid were mixed, and stirred at 140° C. for 15 h to obtain a modified amide auxiliary agent.

[0043] Example 2

[0044] This embodiment discloses a method for preparing a modified thioamide, comprising the following steps:

[0045] 45 g of oleoyl chloride and 22.5 g of ammonium thiocyanate were added to 450 mL of acetone, stirred for 30 min, filtered, 24 g of N, N'-di(2-aminoethyl)-1,3-propylenediamine was added to the filtrate, and the stirring was continued for 60 min. The acetone was evaporated and washed with petroleum ether 5 times to obtain modified sulfamide.

[0046] Example 3

[0047] This embodiment discloses a method for preparing a copolyamide compound, comprising the following steps:

[0048] P1: 15 g of acrylic acid and 55.5 g of stearyl alcohol were added to 60 mL of toluene, and then 0.063 g of p-toluenesulfonic acid and 0.042 g of hydroquinone were added, and the mixture was heated at 80° C. for 12 h, and the toluene was removed by rotary evaporation, and then vacuum dried at 50° C. for 3.5 h to obtain stearyl acrylate;

[0049] P2: In a nitrogen atmosphere, 18 g of maleic anhydride and 62.6 g of stearyl acrylate were added to 45 mL of toluene, stirred for 30 min, and then 0.36 g of benzoyl peroxide was added. The mixture was refluxed at 110° C. for 6.5 h, and the mixture was poured into methanol for precipitation and filtered. The filter residue was washed with methanol solvent for 4 times and vacuum dried at 80° C. for 5.5 h to obtain a polymer compound;

[0050] P3: 22.5 g of p-aminodiphenylamine and 61 g of the polymer compound were added to 75 mL of xylene, and the mixture was refluxed at 143° C. for 12 h. The xylene was removed by rotary evaporation, and the mixture was dried at 90° C. for 7.5 h to obtain a copolyamide compound.

[0051] Example 4

[0052] See also Figure 1As shown, this embodiment discloses a method for preparing a detergent for lubricating oil, comprising the following steps:

[0053] 22.5 g of the composite detergent dispersant, 4 g of the detergent, 5 g of the copolyamide compound prepared in Example 3, and 5 g of ethylene glycol monobutyl ether were added to 40 g of the lubricating oil base oil, stirred at 250 rpm for 16 min at 50°C, then 15 g of the diluent oil was added, stirred at 250 rpm for 25 min at 50°C, and cooled to room temperature to obtain the detergent for lubricating oil.

[0054] The diluent oil is 150SN.

[0055] The detergent is magnesium naphthenate.

[0056] The composite detergent dispersant is prepared by compounding the modified amide auxiliary agent prepared in Example 1 and the modified thioamide prepared in Example 2 at a mass ratio of 1.3:1.

[0057] Example 5

[0058] See also Figure 1 As shown, this embodiment discloses a method for preparing a detergent for lubricating oil, comprising the following steps:

[0059] 15 g of the composite detergent dispersant, 6 g of the detergent, 3 g of the copolyamide compound prepared in Example 3, and 8 g of ethylene glycol monobutyl ether were added to 35 g of the lubricating oil base oil, stirred at 200 rpm at 55°C for 18 min, then 10 g of the diluent oil was added, stirred at 200 rpm at 55°C for 30 min, and cooled to room temperature to obtain the detergent for lubricating oil.

[0060] The diluent oil is 350N.

[0061] The detergent includes at least one of cerium isooctanoate.

[0062] The composite detergent dispersant is prepared by compounding the modified amide auxiliary agent prepared in Example 1 and the modified thioamide prepared in Example 2 in a mass ratio of 1:1.

[0063] Example 6

[0064] See also Figure 1 As shown, this embodiment discloses a method for preparing a detergent for lubricating oil, comprising the following steps:

[0065] 25 g of the composite detergent dispersant, 2 g of the detergent, 7 g of the copolyamide compound prepared in Example 3, and 2 g of ethylene glycol monobutyl ether were added to 45 g of the lubricating oil base oil, stirred at 300 rpm for 12 min at 45°C, then 20 g of the diluent oil was added, stirred at 300 rpm for 20 min at 45°C, and cooled to room temperature to obtain the detergent for lubricating oil.

[0066] The diluent oil is 350N.

[0067] The detergent is magnesium naphthenate.

[0068] The composite detergent dispersant is prepared by compounding the modified amide auxiliary agent prepared in Example 1 and the modified thioamide prepared in Example 2 at a mass ratio of 1.5:1.

[0069] Example 7

[0070] See also Figure 1 As shown, this embodiment discloses a method for preparing a detergent for lubricating oil, comprising the following steps:

[0071] 17 g of the composite detergent dispersant, 5 g of the detergent, 4 g of the copolyamide compound prepared in Example 3, and 7 g of ethylene glycol monobutyl ether were added to 38 g of the lubricating oil base oil, stirred at 220 rpm at 52°C for 16 min, then 18 g of the diluent oil was added, stirred at 280 rpm at 48°C for 24 min, and cooled to room temperature to obtain the detergent for lubricating oil.

[0072] The diluent oil is 150SN.

[0073] The detergent is cerium isooctanoate.

[0074] The composite detergent dispersant is prepared by compounding the modified amide auxiliary agent prepared in Example 1 and the modified thioamide prepared in Example 2 at a mass ratio of 1.1:1.

[0075] Example 8

[0076] See also Figure 1 As shown, this embodiment discloses a method for preparing a detergent for lubricating oil, comprising the following steps:

[0077] 23 g of the composite detergent dispersant, 3 g of the detergent, 6 g of the copolyamide compound prepared in Example 3, and 4 g of ethylene glycol monobutyl ether were added to 42 g of the lubricating oil base oil, stirred at 280 rpm at 48°C for 14 min, then 12 g of the diluent oil was added, stirred at 220 rpm at 52°C for 28 min, and cooled to room temperature to obtain the detergent for lubricating oil.

[0078] The diluent oil is 350N.

[0079] The detergent is cerium isooctanoate.

[0080] The composite detergent dispersant is prepared by compounding the modified amide auxiliary agent prepared in Example 1 and the modified thioamide prepared in Example 2 in a mass ratio of 1-1.5:1.

[0081] Comparative Example 1

[0082] Comparative Example 1 Compared with Example 4, in the process of preparing the detergent for lubricating oil in Comparative Example 1, no copolyamide compound was added, and other conditions remained unchanged.

[0083] Comparative Example 2

[0084] Comparative Example 2 Compared with Example 4, in the process of preparing the detergent for lubricating oil in Comparative Example 2, no modified thioamide was added, that is, the composite detergent dispersant was a modified amide additive, and other conditions remained unchanged.

[0085] Comparative Example 3

[0086] Comparative Example 3 Compared with Example 4, in the process of preparing the detergent for lubricating oil in Comparative Example 3, no modified amide auxiliary agent is added, that is, the composite detergent dispersant is modified thioamide, and other conditions remain unchanged.

[0087] Experimental example

[0088] The performance of the detergents for lubricating oil prepared in Examples 4-8 and Comparative Examples 1-3 was tested. 1.5 parts of the detergents for lubricating oil were added to 100 parts of the lubricating base oil without additives. The efficiency of sediment particles (engine sludge) suspended in the lubricating oil and coke deposition (mg) were determined by the standard federal test method. After oxidation for 72 hours, the dispersibility was tested. The precipitation of colloids was based on the crankcase simulation test method (QZX method) of SH / T0300-92. The effect test results are shown in Table 1:

[0089] Table 1

[0090]

[0091]

[0092] It can be seen from Table 1 that the detergents for lubricating oil prepared in Examples 4-8 can significantly improve the cleaning and dispersing effect of lubricating oil; from the comparison between Comparative Example 1 and Example 4, it can be seen that in the process of preparing the detergent for lubricating oil, the present invention adds a copolyamide compound, which can significantly improve the cleaning effect of lubricating oil; from the comparison between Comparative Example 2 and Example 4, it can be seen that in the process of preparing the detergent for lubricating oil, the present invention adds a modified thioamide, which can significantly improve the cleaning effect of lubricating oil; from the comparison between Comparative Example 3 and Example 4, it can be seen that in the process of preparing the detergent for lubricating oil, the present invention adds a modified amide auxiliary agent, which can significantly improve the cleaning effect of lubricating oil.

[0093] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0094] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A detergent for lubricating oil, characterized in that: The raw materials of the detergent for lubricating oil are composed of the following components in parts by weight: 35-45 parts of lubricating oil base oil, 15-25 parts of composite detergent dispersant, 2-6 parts of detergent, 10-20 parts of diluent oil, 3-7 parts of copolyamide compound, and 2-8 parts of ethylene glycol monobutyl ether.

2. The detergent for lubricating oil according to claim 1, characterized in that: The diluent oil is 150SN and / or 350N.

3. The detergent for lubricating oil according to claim 1, characterized in that: The detergent includes at least one of magnesium naphthenate and cerium isooctanoate.

4. The detergent for lubricating oil according to claim 1, characterized in that: The composite detergent dispersant is prepared by compounding a modified amide auxiliary agent and a modified sulphamide in a mass ratio of 1-1.5:

1.

5. The detergent for lubricating oil according to claim 4, characterized in that: The preparation method of the modified amide auxiliary agent comprises the following steps: S1: Add 79-160 g of acetyl chloride and 76-150 g of ammonium thiocyanate to 500-1000 mL of acetone, stir for 15-25 min, filter, add 121-250 g of tris(hydroxymethyl)aminomethane to the filtrate, continue stirring for 8-12 min, and obtain an intermediate product; S2: Mix 22.2-45 g of the intermediate product, 1.7-3.4 g of p-toluenesulfonic acid and 84.1-168 g of linoleic acid, and stir the mixture at 135-145° C. for 12-18 h to obtain a modified amide auxiliary agent.

6. The detergent for lubricating oil according to claim 5, characterized in that: The linoleic acid is linoleic acid with an acid content of ≥50%.

7. The detergent for lubricating oil according to claim 4, characterized in that: The preparation method of the modified thioamide comprises the following steps: Add 30-60 g of oleoyl chloride and 15-30 g of ammonium thiocyanate to 300-600 mL of acetone, stir for 25-35 min, filter, add 16-32 g of N,N'-di(2-aminoethyl)-1,3-propylenediamine to the filtrate, continue stirring for 55-65 min, evaporate the acetone, wash with petroleum ether 4-6 times to obtain modified sulfamide.

8. The detergent for lubricating oil according to claim 1, characterized in that: The preparation method of the copolyamide compound comprises the following steps: P1: Add 10-20 g of acrylic acid and 37-74 g of stearyl alcohol to 40-80 mL of toluene, then add 0.042-0.084 g of p-toluenesulfonic acid and 0.028-0.056 g of hydroquinone, heat at 75-85 ° C for 10-14 h, remove toluene by rotary evaporation, and vacuum dry at 45-55 ° C for 3-4 h to obtain stearyl acrylate; P2: In a nitrogen atmosphere, 12-24 g of maleic anhydride and 41.7-82 g of stearyl acrylate are added to 40-50 mL of toluene, stirred for 25-35 min, and then 0.24-0.48 g of benzoyl peroxide is added. The mixture is refluxed at 105-115° C. for 6-7 h, and the mixture is poured into methanol for precipitation and filtered. The filter residue is washed with methanol solvent for 3-5 times and vacuum dried at 75-85° C. for 5-6 h to obtain a polymer compound; P3: Add 15-30 g of p-aminodiphenylamine and 40-82 g of the polymer compound into 50-100 mL of xylene, reflux at 141-146° C. for 10-14 h, remove xylene by rotary evaporation, and dry at 85-95° C. for 7-8 h to obtain a copolyamide compound.

9. A method for preparing a detergent for lubricating oil according to any one of claims 1 to 8, characterized in that: The steps include: 15-25 parts of composite detergent dispersant, 2-6 parts of detergent, 3-7 parts of copolyamide compound and 2-8 parts of ethylene glycol monobutyl ether are added to 35-45 parts of lubricating oil base oil, stirred at 200-300 rpm for 12-18 minutes at 45-55°C, then 10-20 parts of diluent oil are added, stirred at 200-300 rpm for 20-30 minutes at 45-55°C, and cooled to room temperature to obtain the detergent for lubricating oil.

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