Novel lubricating oil detergent, preparation method thereof and lubricating oil composition

Abstract

The invention provides a novel lubricating oil detergent, a preparation method thereof and a lubricating oil composition. The preparation method comprises the following steps: mixing alkylphenol, base oil, a vulcanizing agent and a first part of calcium source, adding a first part of accelerant, and carrying out vulcanization reaction; then adding cyclic anhydride to carry out esterification reaction; and adding a second part of accelerant and a second part of calcium source, then carrying out carbonation reaction, and purifying the product after the reaction is finished to obtain the novel lubricating oil detergent. Wherein the cyclic anhydride is selected from one or a combination of more than two of maleic anhydride, succinic anhydride, adipic anhydride and phthalic anhydride; the addition amount of the cyclic anhydride is 0.01-0.25 part by weight based on 1 part by weight of alkylphenol. The cyclic anhydride participates in the reaction, so that the content of free phenol in the product can be reduced, and the wear resistance of the product can be improved. The novel lubricating oil detergent provided by the invention has no free phenol residue, and has more excellent detergency, oxidation resistance, wear resistance and the like.

Description

Technical Field

[0001] This invention relates to a novel lubricating oil detergent, its preparation method, and a lubricating oil composition, belonging to the field of detergent technology. Background Technology

[0002] Traditional lubricating oil detergents mainly include sulfidated alkylphenol salts, sulfonates, and salicylates. Among them, sulfidated alkylphenol salts possess unique high-temperature detergency and are highly effective in reducing carbon deposits in piston ring grooves, making them an indispensable key component in lubricating oil detergents. However, due to limitations in processing technology, a certain degree of alkylphenol residue is unavoidable in current sulfidated alkylphenol salt products. This residual alkylphenol has various effects, including reproductive toxicity and harm to aquatic organisms. The presence of residual free alkylphenol in these products limits their application in the lubricating oil field.

[0003] Existing technologies employ different processes to reduce free alkylphenols in lubricating oil detergents. CN113677780B uses organic solvent distillation to remove free phenols, which involves adding organic solvents to calcium alkylphenol sulfide and then distilling. While this method can reduce the free phenol content to some extent, it fails to effectively address issues such as high energy consumption during distillation and the potential for residual organic solvents. CN105037226A uses carboxylic acids and amines to synthesize an intermediate containing activated hydrogen, which is then reacted with formaldehyde to reduce free phenols. However, this preparation method is extremely cumbersome and introduces nitrogen heteroatoms, which may adversely affect the performance of alkylphenol sulfide salts.

[0004] Therefore, it is of great significance to develop a new type of lubricating oil detergent that does not contain free phenol and has excellent anti-wear and anti-oxidation properties. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide a novel lubricating oil detergent, its preparation method, and a lubricating oil composition thereof.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing a novel lubricating oil detergent, comprising the following steps:

[0007] Alkylphenol, base oil, vulcanizing agent, and first calcium source are mixed, and first accelerator is added to carry out the vulcanization reaction;

[0008] Then, cyclic anhydrides are added to carry out the esterification reaction;

[0009] Add a second part of accelerator and a second part of calcium source, and then carry out a carbonation reaction. After the reaction is completed, purify the product to obtain a new type of lubricating oil detergent.

[0010] The cyclic anhydride is selected from one or more of maleic anhydride, succinic anhydride, adipic anhydride, and phthalic anhydride.

[0011] The amount of cyclic anhydride added is 0.01-0.25 parts per part by weight of the alkylphenol.

[0012] According to a specific embodiment of the present invention, preferably, the amount of cyclic anhydride added is 0.05-0.15 parts based on 1 part by weight of the alkylphenol.

[0013] According to a specific embodiment of the present invention, preferably, the amount of base oil added is 0.8-1.2 parts, the amount of vulcanizing agent added is 0.1-0.2 parts, the amount of the first calcium source added is 0.05-0.25 parts, the amount of the first accelerator added is 0.05-0.1 parts, the amount of the second calcium source added is 0.05-0.3 parts, and the amount of the second accelerator added is 0.04-0.1 parts.

[0014] According to a specific embodiment of the present invention, preferably, the alkylphenol is selected from one or more combinations of dodecylphenol, tetradecylphenol, hexadecylphenol, and octadecylphenol. More preferably, the alkylphenol is dodecylphenol.

[0015] According to a specific embodiment of the present invention, preferably, the base oil is selected from one or more combinations of 100N, 150SN, 150N, 150BS, 500N, and 500SN.

[0016] According to a specific embodiment of the present invention, preferably, the vulcanizing agent is sulfur.

[0017] According to a specific embodiment of the present invention, preferably, the first part of the accelerator and the second part of the accelerator are ethylene glycol.

[0018] According to a specific embodiment of the present invention, preferably, the first calcium source and the second calcium source are selected from calcium oxide and / or calcium hydroxide.

[0019] According to a specific embodiment of the present invention, preferably, alkylphenol, base oil, vulcanizing agent, and first calcium source are mixed, and the first accelerator is added after heating to 140-170 °C.

[0020] According to a specific embodiment of the present invention, preferably, the temperature of the vulcanization reaction is 155-180 °C; more preferably, the time of the vulcanization reaction is 3-8 h.

[0021] According to a specific embodiment of the present invention, preferably, in the preparation method, the cyclic anhydride is heated to 160-200 °C to remove the solvent before undergoing the esterification reaction, and then cooled to 50-80 °C before being added.

[0022] According to a specific embodiment of the present invention, preferably, the temperature of the esterification reaction is 80-150 °C; more preferably, the time of the esterification reaction is 1-5 h.

[0023] According to a specific embodiment of the present invention, preferably, in the preparation method, a second part of accelerator and a second part of calcium source are added, and then carbon dioxide is introduced to carry out a carbonation reaction; more preferably, the amount of carbon dioxide introduced is 0.1-0.3 parts based on 1 part by weight of the alkylphenol; the carbon dioxide introduction rate is 50-200 mL / min, and more preferably, the carbon dioxide introduction rate is 50-110 mL / min.

[0024] According to a specific embodiment of the present invention, preferably, the temperature for carrying out the carbonation reaction is 140-180 °C.

[0025] According to a specific embodiment of the present invention, preferably, the purification step includes: heating to 180-220 °C to remove the solvent and then filtering.

[0026] According to a specific embodiment of the present invention, preferably, the preparation method of the novel lubricating oil detergent includes the following steps:

[0027] Step 1: Mix alkylphenol, base oil, sulfur, and the first portion of calcium oxide, add the first portion of accelerator, and carry out the vulcanization reaction;

[0028] Step 2: Then add cyclic anhydrides to carry out the esterification reaction;

[0029] Step 3: Add the second part of accelerator and the second part of calcium oxide, and pass carbon dioxide into the mixture to carry out a carbonation reaction. After the reaction is completed, purify the product to obtain a new type of lubricating oil detergent.

[0030] In step one above, alkylphenol, sulfur, and the first portion of calcium oxide undergo a neutralization and sulfidation reaction under the action of the first accelerator (i.e., alkylphenol neutralizes with calcium oxide to form a salt, and simultaneously undergoes a sulfidation reaction with sulfur). This reaction generates a calcium sulfide intermediate (i.e., forms a calcium sulfide skeleton). The reaction formula for step one is shown below:

[0031]

[0032] Wherein, R is dodecyl, tetradecyl, hexadecyl or octadecyl, more preferably dodecyl.

[0033] In step two above, taking maleic anhydride as an example, the unreacted alkylphenol from step one and maleic anhydride undergo an esterification reaction to generate alkylphenol ester. The alkylphenol ester then reacts with the unreacted calcium oxide from step one to generate calcium alkylphenol ester. The reaction formula for step two is shown below:

[0034] ;

[0035] ;

[0036] Anhydrides undergo esterification with unreacted alkylphenols, and the reaction products remain in the system. This not only reduces the free phenol content in the product but also improves its abrasion resistance.

[0037] In step three above, the sulfide alkylphenol calcium intermediate, alkylphenol ester calcium, the second part of calcium oxide, the second part of accelerator, and carbon dioxide undergo a carbonation reaction. The reaction formula for step three is shown below:

[0038] .

[0039] Secondly, the present invention also provides a novel lubricating oil detergent prepared according to the above-described preparation method.

[0040] Thirdly, the present invention also provides a lubricating oil composition, which is prepared by the above-described preparation method using a novel lubricating oil detergent or by the above-described novel lubricating oil detergent.

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

[0042] This invention involves mixing alkylphenols, base oil, a vulcanizing agent, and a first calcium source, adding a first accelerator, and performing a vulcanization reaction. Then, a cyclic anhydride is added for esterification; followed by a carbonation reaction, and purification yields a novel lubricating oil detergent. The cyclic anhydride in this invention not only reduces the free phenol content in the product but also improves its anti-wear properties.

[0043] The novel lubricating oil detergent of this invention has no free phenol residue and has superior cleaning, anti-oxidation, and anti-wear properties. Detailed Implementation

[0044] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0045] Example 1

[0046] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0047] Add 100 g of dodecylphenol, 100 g of 150N base oil, 18 g of sulfur, and 21 g of the first part of calcium oxide to a four-necked flask. Start stirring, heat to 155 °C, add 5 g of accelerator ethylene glycol, and maintain the system temperature at 165 °C for 4 hours to carry out the sulfidation reaction.

[0048] The system temperature was raised to 200 °C, ethylene glycol and water were removed by distillation, the temperature was lowered to 60 °C, 8 g of maleic anhydride was added, and the reaction was carried out at 90 °C for 3 hours to carry out the esterification reaction.

[0049] Add 6 g of accelerator ethylene glycol, add 17 g of the second part of calcium oxide, and pass 20 g of carbon dioxide to carry out the carbonation reaction at a rate of 80 mL / min. Carry out the carbonation reaction at 160 °C. After the reaction is completed, remove the solvent by distillation at 200 °C, filter to remove residue, and obtain a new type of lubricating oil detergent.

[0050] Example 2

[0051] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0052] Add 100 g of dodecylphenol, 100 g of 150N base oil, 18 g of sulfur, and 21 g of the first part of calcium oxide to a four-necked flask. Start stirring, heat to 155 °C, add 5 g of accelerator ethylene glycol, and maintain the system temperature at 165 °C for 4 hours to carry out the sulfidation reaction.

[0053] The system temperature was raised to 200 °C, ethylene glycol and water were removed by distillation, the temperature was lowered to 60 °C, 9 g of succinic anhydride was added, and the reaction was carried out at 100 °C for 4 hours to carry out the esterification reaction.

[0054] Add 5 g of accelerator ethylene glycol, add 17 g of the second part of calcium oxide, and pass 20 g of carbon dioxide to carry out the carbonation reaction at a rate of 80 mL / min. Carry out the carbonation reaction at 160 °C. After the reaction is completed, remove the solvent by distillation at 200 °C, filter to remove residue, and obtain a new type of lubricating oil detergent.

[0055] Example 3

[0056] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0057] Add 100 g of dodecylphenol, 100 g of 150N base oil, 18 g of sulfur, and 21 g of the first part of calcium oxide to a four-necked flask. Start stirring, heat to 155 °C, add 5 g of accelerator ethylene glycol, and maintain the system temperature at 165 °C for 4 hours to carry out the sulfidation reaction.

[0058] The system temperature was raised to 200 °C, ethylene glycol and water were removed by distillation, the temperature was lowered to 60 °C, 11 g of adipic anhydride was added, and the reaction was carried out at 110 °C for 4 hours to carry out the esterification reaction.

[0059] Add 4 g of accelerator ethylene glycol, add 17 g of the second part of calcium oxide, and pass 20 g of carbon dioxide to carry out the carbonation reaction at a rate of 80 mL / min. Carry out the carbonation reaction at 160 °C. After the reaction is completed, remove the solvent by distillation at 200 °C, filter to remove residue, and obtain a new type of lubricating oil detergent.

[0060] Example 4

[0061] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0062] Add 100 g of dodecylphenol, 100 g of 150N base oil, 18 g of sulfur, and 21 g of the first part of calcium oxide to a four-necked flask. Start stirring, heat to 155 °C, add 5 g of accelerator ethylene glycol, and maintain the system temperature at 165 °C for 4 hours to carry out the sulfidation reaction.

[0063] The system temperature was raised to 200 °C, ethylene glycol and water were removed by distillation, the temperature was lowered to 60 °C, 12 g of maleic anhydride was added, and the reaction was carried out at 110 °C for 4 hours to carry out the esterification reaction.

[0064] Add 6 g of accelerator ethylene glycol, add 17 g of the second part of calcium oxide, and pass 20 g of carbon dioxide to carry out the carbonation reaction at a rate of 80 mL / min. Carry out the carbonation reaction at 160 °C. After the reaction is completed, remove the solvent by distillation at 200 °C, filter to remove residue, and obtain a new type of lubricating oil detergent.

[0065] Comparative Example 1

[0066] This comparative example provides a method for preparing a lubricating oil detergent, specifically including the following steps:

[0067] Add 100 g of dodecylphenol, 100 g of 150N base oil, 18 g of sulfur, and 21 g of the first part of calcium oxide to a four-necked flask. Start stirring, heat to 155 °C, add 5 g of accelerator ethylene glycol, and maintain the system temperature at 165 °C for 4 hours to carry out the sulfidation reaction.

[0068] After the constant temperature is reached, 6 g of accelerator ethylene glycol is added, along with 17 g of the second calcium oxide. 20 g of carbon dioxide is then introduced to carry out the carbonation reaction at a rate of 80 mL / min. The carbonation reaction is carried out at 160 °C. After the reaction is completed, the solvent is removed by distillation at 200 °C, and the residue is removed by filtration to obtain the lubricating oil detergent.

[0069] Comparative Example 2

[0070] This comparative example provides a method for preparing a lubricating oil detergent, specifically including the following steps:

[0071] Add 100 g of dodecylphenol, 100 g of 150N base oil, 18 g of sulfur, and 21 g of the first part of calcium oxide to a four-necked flask. Start stirring, heat to 155 °C, add 5 g of accelerator ethylene glycol, and maintain the system temperature at 165 °C for 4 hours to carry out the sulfidation reaction.

[0072] The system temperature was raised to 200 °C, ethylene glycol and water were removed by distillation, the temperature was lowered to 60 °C, 8 g of acetic anhydride was added, and the reaction was carried out at 90 °C for 3 hours to carry out the esterification reaction.

[0073] Add 6 g of accelerator ethylene glycol, add 17 g of the second part of calcium oxide, and pass 20 g of carbon dioxide to carry out the carbonation reaction at a rate of 80 mL / min. Carry out the carbonation reaction at 160 °C. After the reaction is completed, distill at 200 °C to remove the solvent, filter to remove the residue, and obtain the lubricating oil detergent.

[0074] Comparative Example 3

[0075] This comparative example provides a method for preparing a lubricating oil detergent, specifically including the following steps:

[0076] Add 100 g of dodecylphenol, 100 g of 150N base oil, 18 g of sulfur, and 21 g of the first part of calcium oxide to a four-necked flask. Start stirring, heat to 155 °C, add 5 g of accelerator ethylene glycol, and maintain the system temperature at 165 °C for 4 hours to carry out the sulfidation reaction.

[0077] The system temperature was raised to 200 °C, ethylene glycol and water were removed by distillation, the temperature was lowered to 60 °C, 30 g of maleic anhydride was added, and the reaction was carried out at 90 °C for 3 hours to carry out the esterification reaction.

[0078] Add 6 g of accelerator ethylene glycol, add 17 g of the second part of calcium oxide, and pass 20 g of carbon dioxide to carry out the carbonation reaction at a rate of 80 mL / min. Carry out the carbonation reaction at 160 °C. After the reaction is completed, distill at 200 °C to remove the solvent, filter to remove the residue, and obtain the lubricating oil detergent.

[0079] Experimental Example

[0080] The lubricating oil detergents of the above embodiments and comparative examples were tested as follows:

[0081] 1. Alkali number: Tested according to ASTM D2896 standard;

[0082] 2. Viscosity: Tested according to ASTM D445 standard;

[0083] 3. Sulfur content: Tested according to ASTM D1552 standard;

[0084] 4. Free phenols: determined by HPLC.

[0085] 5. Oxidation induction period: The oxygen antioxidant properties of the samples were tested using the high differential scanning calorimetry (PDSC) method according to the ASTM D6186 standard. Under the same test conditions, the longer the oxidation induction period, the better the antioxidant properties of the sample.

[0086] 6. High-temperature cleaning performance: It is evaluated according to the SH / T 0645 standard through heat pipe oxidation test and scoring criteria; among which, the cleaning performance is expressed by a rating, the lower the rating, the better the cleaning performance of the sample;

[0087] 7. Four-ball anti-wear WSD wear scar diameter: The samples were evaluated according to SH / T 0189 - Test method for anti-wear performance of lubricating oil (four-ball test method), and the test results were expressed as wear scar diameter (WSD). The smaller the WSD wear scar diameter, the better the anti-wear performance of the sample.

[0088] 8. Sintering load pd value of four balls: The load-bearing capacity was tested according to GB / T 3142 standard, and the test results are expressed as sintering load pd value. Among them, the higher the sintering load pd value, the better the extreme pressure performance of the sample.

[0089] The test results are shown in Table 1.

[0090] Table 1

[0091]

[0092] As can be seen from the data results of the embodiments in Table 1, the alkalinity of the novel lubricating oil detergent of the present invention is not less than 250 mgKOH / g, and no free phenols were detected; the oxidation induction period tested by PDSC is more than 35 min, indicating good antioxidant performance; its high-temperature detergency rating is 1-2, indicating good detergency performance; the diameter of the four-ball anti-wear WSD wear scar is less than 0.5 mm, indicating better anti-wear performance; the four-ball sintering load pd value is more than 1700 N, indicating good extreme pressure performance.

[0093] In Comparative Example 1, no cyclic anhydride was added for esterification during the preparation of the lubricating oil detergent. Instead, a carbonation reaction was carried out directly. The free phenol content of the lubricating oil detergent was relatively high at 5.12%, and the anti-wear properties, high-temperature detergency, and antioxidant properties were all worse.

[0094] In Comparative Example 2, acetic anhydride was added during the preparation of the lubricating oil detergent to carry out the esterification reaction. Its base value was low, and its anti-wear, high-temperature detergent and antioxidant properties were also poor.

[0095] In Comparative Example 3, an excessive amount of cyclic anhydride was added during the preparation of the lubricating oil detergent. This anhydride had a low base value and poor anti-wear properties, high-temperature detergency, and antioxidant performance.

[0096] In summary, the novel lubricating oil detergent of the present invention has no free phenol residue and has superior cleaning, antioxidant, and anti-wear properties.

Claims

1. A method for preparing a novel lubricating oil detergent, wherein, Includes the following steps: Alkylphenol, base oil, vulcanizing agent, and first calcium source are mixed, and first accelerator is added to carry out the vulcanization reaction; Then, cyclic anhydrides are added to carry out the esterification reaction; Add a second part of accelerator and a second part of calcium source, and then carry out a carbonation reaction. After the reaction is completed, purify the product to obtain a new type of lubricating oil detergent. The cyclic anhydride is selected from one or more of maleic anhydride, succinic anhydride, adipic anhydride, and phthalic anhydride. The amount of cyclic anhydride added is 0.01-0.25 parts per part by weight of the alkylphenol.

2. The preparation method according to claim 1, wherein, The amount of base oil added is 0.8-1.2 parts, the amount of vulcanizing agent added is 0.1-0.2 parts, the amount of the first calcium source added is 0.05-0.25 parts, the amount of the first accelerator added is 0.05-0.1 parts, the amount of the second calcium source added is 0.05-0.3 parts, and the amount of the second accelerator added is 0.03-0.1 parts. And / or, the alkylphenol is selected from one or more combinations of dodecylphenol, tetradecylphenol, hexadecylphenol, and octadecylphenol; And / or, the base oil is selected from one or more of 100N, 150SN, 150N, 150BS, 500N, and 500SN.

3. The preparation method according to claim 1, wherein, The vulcanizing agent is sulfur; And / or, the first and second accelerators are ethylene glycol; And / or, the first calcium source and the second calcium source are selected from calcium oxide and / or calcium hydroxide.

4. The preparation method according to claim 1, wherein, In the preparation method, alkylphenol, base oil, vulcanizing agent, and first calcium source are mixed, and the first accelerator is added when the temperature is raised to 140-170 °C.

5. The preparation method according to claim 1, wherein, The temperature of the sulfidation reaction is 155-180 ℃; And / or, the vulcanization reaction takes 3-8 hours.

6. The preparation method according to claim 1, wherein, In the preparation method, the cyclic anhydride is heated to 160-200 °C to remove the solvent before undergoing the esterification reaction, and then cooled to 50-80 °C before being added.

7. The preparation method according to claim 1, wherein, The esterification reaction is carried out at a temperature of 80-150 ℃; And / or, the esterification reaction takes 1-5 h.

8. The preparation method according to claim 1, wherein, In the preparation method, the carbonation reaction is carried out at a temperature of 140-180 °C.

9. A novel lubricating oil detergent prepared by any one of claims 1-8.

10. A lubricating oil composition, which is prepared by the preparation method of any one of claims 1-8 or the novel lubricating oil detergent of claim 9.

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