Novel lubricating oil detergent as well as preparation method and application thereof

Abstract

The invention provides a novel lubricating oil detergent as well as a preparation method and application thereof, and the preparation method comprises the following steps: carrying out alkylation reaction on phenol, long-chain olefin and a solid acid catalyst to obtain a substituted alkylphenol system; the method comprises the following steps: adding an aldehyde compound and a condensation catalyst into a substituted alkylphenol system for condensation reaction to obtain an alkylphenol intermediate; a calcium source, base oil and a solvent are added into the alkylphenol intermediate for a neutralization reaction, an alcohol compound is added after the reaction is finished, then carbonation is performed, a product is subjected to aftertreatment, and the novel lubricating oil detergent is obtained. The novel lubricating oil detergent is free of sulfur and free phenol residues, and has excellent detergency, oxidation resistance and corrosion resistance.

Description

Technical Field

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

[0002] Lubricating oil detergents mainly include three categories: salicylates, sulfonates, and sulfidated alkylphenol salts. Among them, salicylates have strong neutralizing ability and good detergency, and are often used in gasoline engine oils, diesel engine oils, and marine oils. Sulfonates have good detergency, dispersibility, and rust prevention properties, and are often used to formulate various internal combustion engine oils or marine cylinder oils and engine oils. Alkylphenol salts have excellent high-temperature detergent properties, water separation properties, and antioxidant properties, and are one of the main additives in mid-to-high-end internal combustion engine oils, marine oils, and other oil products.

[0003] Alkylphenol salts are produced by neutralizing, sulfiding, carbonating, and refining alkylphenols with raw materials such as sulfur and calcium oxide. Due to their unique performance advantages, they are often used in combination with sulfonates or salicylates to complement their disadvantages. Currently, commercially available alkylphenol salt products generally contain a certain amount of residual alkylphenol (3%~10%), which can cause endocrine toxicity, reproductive toxicity, and immunotoxicity, thus limiting the application range of sulfide alkylphenol calcium products.

[0004] To reduce the free phenol content, US8198225B2 describes a process involving the phenol-aldehyde condensation reaction of dodecylphenol followed by a sulfidation reaction to produce a calcium sulfide alkylphenol product with low free phenol content. Although this reduces the free phenol content from 6.5-8.1% to 1.7-4.4%, the process is cumbersome and the free phenol content remains relatively high. CN106147937A describes a process involving the reaction of sulfide alkylphenol salts with aldehydes and amines under alkaline conditions to produce a sulfide alkylphenol salt detergent with low alkylphenol content, which can reduce free phenol to 1.3%. However, this method is still complex and leaves some free phenol residue. CN105037226A describes a process involving the mixing of sulfide alkylphenol metal salts with intermediates (obtained by reacting acid anhydrides and / or carboxylic acids with amine compounds) followed by a condensation reaction with aldehydes to obtain a sulfide alkylphenol metal salt product with low free phenol content, which can reduce free phenol to 0.26%. However, this process is complex and leaves some free phenol residue. In response, energy saving, low emissions, and long service life have become the main directions for the development of lubricating oils.

[0005] Therefore, it is of great significance to provide a novel lubricating oil detergent that is low in sulfur, phosphorus, and ash, and free of free phenol residue, while also possessing excellent performance. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide a novel lubricating oil detergent, its preparation method, and its application. This novel lubricating oil detergent is free of sulfur and free of free phenol residues, and possesses excellent detergency, antioxidant properties, and corrosion resistance.

[0007] 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:

[0008] Step 1: Alkylation reaction of phenol, long-chain olefin, and solid acid catalyst to obtain a system of substituted alkylphenols;

[0009] Step 2: Add an aldehyde compound and a condensation catalyst to the substituted alkylphenol system to carry out a condensation reaction to obtain the alkylphenol intermediate;

[0010] Step 3: Add calcium source, base oil and solvent to the alkylphenol intermediate for neutralization reaction. After the reaction is completed, add alcohol compound and then carbonate. Perform post-treatment on the product to obtain a new type of lubricating oil detergent.

[0011] The long-chain olefin is selected from C 12 -C 20 One of the olefins;

[0012] The molar ratio of phenol to long-chain olefin is 1:(2.1-4).

[0013] According to a specific embodiment of the present invention, preferably, in step one, the amount of phenol added is 1 part by weight, and the amount of solid acid catalyst added is 0.1-0.6 parts.

[0014] In step two, the amount of substituted alkylphenol added is 1 part by weight, the amount of aldehyde compound added is 0.02-0.2 parts, and the amount of condensation catalyst added is 0.002-0.02 parts.

[0015] In step three, the amount of alkylphenol intermediate added is 1 part by weight, the amount of calcium source added is 0.1-0.5 parts, and the amount of alcohol compound added is 0.05-0.3 parts.

[0016] According to a specific embodiment of the present invention, preferably, in step one, the amount of phenol added is 1 part by weight, and the amount of solid acid catalyst added is 0.3-0.6 parts.

[0017] In step two, the amount of substituted alkylphenol added is 1 part by weight, the amount of aldehyde compound added is 0.02-0.1 parts, and the amount of condensation catalyst added is 0.002-0.01 parts.

[0018] In step three, the amount of alkylphenol intermediate added is 1 part by weight, the amount of calcium source added is 0.2-0.4 parts, and the amount of alcohol compound added is 0.05-0.2 parts.

[0019] According to a specific embodiment of the present invention, preferably, the long-chain olefin is selected from C 12 -C 20 One of the olefins used is a long-chain olefin. The longer the alkyl chain of an alkylphenol, the better the oil solubility of the sample.

[0020] According to a specific embodiment of the present invention, preferably, the solid acid catalyst is selected from modified molecular sieves and / or sulfonic acid resins. More preferably, the modified molecular sieve is a crystalline aluminosilicate with a regular pore structure and acidic surface, in which acidic groups are adsorbed within the pores, enabling it to act as a catalyst for catalytic reactions. Its framework is a molecular sieve with a silica-alumina ratio of 10-60, a pore size > 0.7 nm, and an acid content > 0.4 mmol / g. The sulfonic acid resin has a polystyrene-divinylbenzene framework, functional groups of sulfonic acid groups, a particle size range of 0.2-1.5 mm (≥95%), and a total exchange capacity ≥ 4.5 mmol / g.

[0021] According to a specific embodiment of the present invention, preferably, the aldehyde compound is selected from one or more combinations of formaldehyde, propionaldehyde, and butyraldehyde.

[0022] According to a specific embodiment of the present invention, preferably, the condensation catalyst is selected from acidic catalysts or basic catalysts.

[0023] According to a specific embodiment of the present invention, preferably, the calcium source is selected from inorganic calcium.

[0024] According to a specific embodiment of the present invention, preferably, in step three, the amount of alkylphenol intermediate added is 1 part by weight, and the amount of base oil added is 0.3-5 parts.

[0025] According to a specific embodiment of the present invention, preferably, the base oil is selected from one or more combinations of 100N, 150SN, 150N, 500N, and 500SN.

[0026] According to a specific embodiment of the present invention, preferably, the alcohol compound is selected from ethylene glycol.

[0027] According to a specific embodiment of the present invention, preferably, the condensation catalyst is selected from one or more of calcium oxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, acetic acid, formic acid, methanesulfonic acid, and p-toluenesulfonic acid.

[0028] According to a specific embodiment of the present invention, preferably, the calcium source is selected from calcium oxide and / or calcium hydroxide.

[0029] According to a specific embodiment of the present invention, preferably, the solvent is selected from one or a combination of two or more of D30 solvent oil, D40 solvent oil, and xylene.

[0030] According to a specific embodiment of the present invention, preferably, the amount of solvent added is 0.3-5 parts.

[0031] According to a specific embodiment of the present invention, preferably, in step one, the substituted alkylphenol system includes disubstituted dodecylphenol (content ≥ 95%) and monosubstituted alkylphenol (content ≤ 5%).

[0032] According to a specific embodiment of the present invention, preferably, in step one, the alkylation reaction temperature is 90-120 °C and the time is 2-10 h. If the alkylation reaction temperature is below 90 °C, mainly monosubstituted alkylphenols are generated or no reaction occurs, and the reaction rate is slow; if the alkylation reaction temperature is above 120 °C, it leads to defects such as catalyst deactivation, more side reactions, and darker sample color. If the alkylation reaction time is less than 2 h, it leads to an increase in the content of monosubstituted alkylphenols; if the alkylation reaction time is more than 10 h, it leads to a decrease in sample purity, darkening of color, catalyst deactivation, and blockage.

[0033] According to a specific embodiment of the present invention, preferably, in step two, the substituted alkylphenol system is cooled to 30-80 °C and then an aldehyde compound and a condensation catalyst are added.

[0034] According to a specific embodiment of the present invention, preferably, in step two, the temperature of the condensation reaction is 60-150 °C, and the time is 1-5 h. If the temperature of the condensation reaction is below 60 °C, the reaction rate will be slow or no reaction will occur; if the temperature of the condensation reaction is above 150 °C, the sample color will darken or side reactions will occur. More preferably, the condensation reaction specifically includes: first heating to 60-100 °C and reacting for 1-3 h, then heating to 110-150 °C and reacting for 1-3 h.

[0035] According to a specific embodiment of the present invention, preferably, in step three, the temperature of the neutralization reaction is 30-180 °C and the time is 1-5 h. More preferably, the temperature of the neutralization reaction is 140-160 °C.

[0036] According to a specific embodiment of the present invention, preferably, in step three, an alcohol compound is added after the reaction is completed, and carbon dioxide is introduced for carbonation; more preferably, in step three, the amount of alkylphenol intermediate added is 1 part by weight, and the amount of carbon dioxide introduced is 0.1-0.5 parts; even more preferably, the time for introducing carbon dioxide is 1-5 h.

[0037] According to a specific embodiment of the present invention, preferably, the post-processing step includes: heating to 180-220 °C to remove the solvent and then filtering.

[0038] According to a specific embodiment of the present invention, preferably, the preparation method of the novel lubricating oil detergent includes the following steps:

[0039] Step 1: Phenol, dodecene, and a solid acid catalyst are subjected to an alkylation reaction to obtain a system of substituted alkylphenols;

[0040] Step 2: Formaldehyde and a condensation catalyst are added to the substituted alkylphenol system to carry out a condensation reaction to obtain the alkylphenol intermediate;

[0041] Step 3: Add calcium oxide, base oil and solvent to the alkylphenol intermediate for neutralization reaction. After the reaction is completed, add alcohol compound, then introduce carbon dioxide for carbonation, and perform post-treatment on the product to obtain a new type of lubricating oil detergent.

[0042] In step one above, phenol and dodecene undergo alkylation under the action of a solid acid catalyst to obtain a system of substituted alkylphenols (including disubstituted dodecylphenols (content ≥95%) and monosubstituted alkylphenols (content ≤5%)). The reaction formulas for the main reactions in step one are shown below:

[0043]

[0044] In step two above, formaldehyde and a condensation catalyst are added to the substituted alkylphenol system from step one to carry out a condensation reaction, yielding an alkylphenol intermediate. The condensation mainly occurs between disubstituted alkylphenols, and the product consists of two alkylphenols condensed together via a -CH2- linkage, without generating multi-molecular cross-linked products. The main reaction equations for step two are shown below:

[0045]

[0046] In step three above, calcium oxide, base oil, and solvent are added to the alkylphenol intermediate from step two for a neutralization reaction. After the reaction is complete, an alcohol compound is added, followed by carbon dioxide carbonated treatment. The product is then post-treated to obtain the alkylphenol calcium product (i.e., a novel lubricating oil detergent). The reaction formula for step three is shown below:

[0047] .

[0048] Secondly, the present invention also provides a novel lubricating oil detergent prepared according to the above-described preparation method.

[0049] 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.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] This invention uses long-chain olefins as starting materials, and carries out alkylation reaction with phenol and solid acid catalyst; then adds aldehyde compounds and condensation catalyst to carry out condensation reaction; then adds calcium source, base oil and solvent to carry out neutralization reaction and carbonation, and finally processes to obtain a novel lubricating oil detergent.

[0052] The novel lubricating oil detergent of this invention is sulfur-free and free of free phenols, and has excellent cleaning, antioxidant, and anti-corrosion properties. Detailed Implementation

[0053] 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.

[0054] Example 1

[0055] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0056] Step 1: Add 47 g of phenol, 185 g of dodecene, and 25 g of sulfonic acid resin catalyst (polystyrene-divinylbenzene, functional group is sulfonic acid group, particle size range is 0.2-1.5 mm (≥95%), total exchange capacity ≥4.5 mmol / g, the same below) to a four-necked flask, start stirring, heat to 105 ℃ for alkylation reaction for 5 h, then filter to remove catalyst, distill to obtain disubstituted dodecylphenol (content 96.6%) and monosubstituted alkylphenol (content 3.4%).

[0057] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 8 g of formaldehyde and 0.5 g of calcium oxide catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate.

[0058] Step 3: Add 150 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 52 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and introduce 40 g of carbon dioxide for carbonation reaction for 3 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0059] Example 2

[0060] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0061] Step 1: Add 47 g of phenol, 201.6 g of dodecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C for alkylation reaction for 8 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 98.2%) and monosubstituted alkylphenol (content 1.8%).

[0062] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 20 g of butyraldehyde and 2.1 g of acetic acid catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate;

[0063] Step 3: Add 155 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 52 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and purge with 40 g of carbon dioxide for carbonation reaction for 3 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0064] Example 3

[0065] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0066] Step 1: Add 47 g of phenol, 247 g of hexadecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C for alkylation reaction for 5 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 96.1%) and monosubstituted alkylphenol (content 3.9%).

[0067] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 7 g of formaldehyde and 1 g of acetic acid catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate.

[0068] Step 3: Add 188 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 52 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and introduce 40 g of carbon dioxide for carbonation reaction for 3 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0069] Example 4

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

[0071] Step 1: Add 47 g of phenol, 252 g of dodecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C for alkylation reaction for 5 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 99.8%) and monosubstituted alkylphenol (content 0.2%).

[0072] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 8 g of formaldehyde and 0.5 g of calcium oxide catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate.

[0073] Step 3: Add 150 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 52 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and introduce 40 g of carbon dioxide for carbonation reaction for 3 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0074] Example 5

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

[0076] Step 1: Add 47 g of phenol, 201.6 g of dodecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C for alkylation reaction for 8 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 98.0%) and monosubstituted alkylphenol (content 2.0%).

[0077] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 20 g of butyraldehyde and 2.1 g of acetic acid catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate;

[0078] Step 3: Add 155 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 53 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and introduce 42 g of carbon dioxide for carbonation reaction for 3 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0079] Example 6

[0080] This embodiment provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0081] Step 1: Add 47 g of phenol, 247 g of hexadecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C for alkylation reaction for 5 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 96.5%) and monosubstituted alkylphenol (content 3.5%).

[0082] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 7 g of formaldehyde and 1 g of acetic acid catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate.

[0083] Step 3: Add 188 g of the condensed alkylphenol intermediate, 188 g of 150N base oil, 65 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and purge with 50 g of carbon dioxide for carbonation reaction for 4 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0084] Comparative Examples 1-3

[0085] Use commercially available calcium sulfonate cleaner, commercially available alkylphenol sulfide cleaner, and commercially available calcium salicylate cleaner respectively.

[0086] Comparative Example 4

[0087] This comparative example provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0088] Step 1: Add 47 g of phenol, 168 g of dodecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C for alkylation reaction for 5 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 90.1%) and monosubstituted alkylphenol (content 9.9%).

[0089] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 8 g of formaldehyde and 0.5 g of calcium oxide catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate.

[0090] Step 3: Add 150 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 52 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and introduce 40 g of carbon dioxide for carbonation reaction for 3 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0091] Comparative Example 5

[0092] This comparative example provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0093] Step 1: Add 47 g of phenol, 201.6 g of dodecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C and carry out alkylation reaction for 1.5 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 78.5%) and monosubstituted alkylphenol (content 21.5%).

[0094] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 20 g of butyraldehyde and 2.1 g of acetic acid catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate;

[0095] Step 3: Add 155 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 52 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h to neutralize. After the temperature is maintained, add 25 g of ethylene glycol dropwise and purge with 40 g of carbon dioxide for carbonation reaction for 3 h. After the reaction is complete, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0096] Comparative Example 6

[0097] This comparative example provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0098] Step 1: Add 47 g of phenol, 201.6 g of dodecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 80 °C and carry out alkylation reaction for 8 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 3.6%) and monosubstituted alkylphenol (content 96.4%).

[0099] The reaction was poor, and the last two steps were not carried out.

[0100] Comparative Example 7

[0101] This comparative example provides a method for preparing a novel lubricating oil detergent, specifically including the following steps:

[0102] Step 1: Add 47 g of phenol, 247 g of hexadecene, and 25 g of sulfonic acid resin catalyst to a four-necked flask, start stirring, heat to 105 °C for alkylation reaction for 5 h, then filter to remove the catalyst, and distill to obtain disubstituted dodecylphenol (content 96.0%) and monosubstituted alkylphenol (content 4.0%).

[0103] Step 2: Take 200 g of the above-mentioned substituted alkylphenol, add 3 g of formaldehyde and 1 g of acetic acid catalyst at 60 ℃, start stirring, heat to 80 ℃ for condensation reaction for 1 h, then heat to 120 ℃ for condensation for 1 h, and distill to remove water to obtain alkylphenol intermediate.

[0104] Step 3: Add 188 g of the condensed alkylphenol intermediate, 150 g of 150N base oil, 52 g of calcium oxide, and 150 g of diluted D40 solvent to a four-necked flask. Start stirring and heat to 160 ℃ for 2 h for neutralization. After neutralization, add 25 g of ethylene glycol dropwise and introduce 40 g of carbon dioxide for carbonation reaction for 3 h. After the reaction, heat to 210 ℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium product (i.e., a new type of lubricating oil detergent).

[0105] Experimental Example

[0106] The novel lubricating oil detergents of the above embodiments and comparative examples were tested as follows:

[0107] (1) Alkali number: Tested according to SH / T 0251 standard;

[0108] (2) Sulfur content: Tested according to GB / T 17476 standard;

[0109] (3) Free phenol: Tested according to GB / T 16631 standard; for details, please refer to "Determination of free alkylphenol content in calcium sulfide by high performance liquid chromatography" (Wan Xinshui et al.), Vol. 48, No. 8, Petroleum Refining and Chemical Industry.

[0110] (4) Antioxidant time: Tested according to ASTM D6186;

[0111] (5) Cleanliness test: Tested according to SH / T 0300 standard;

[0112] (6) Copper strip corrosion test: The test shall be conducted in accordance with the SH / T0232 standard;

[0113] The test results are shown in Table 1.

[0114] Table 1

[0115]

[0116] Note: Comparative sample 6 had a poor response and was not evaluated.

[0117] As can be seen from the data results of the embodiments in Table 1, the novel lubricating oil detergent prepared by the present invention did not contain any free phenols or sulfur, and compared with other detergents on the market, it has excellent antioxidant, detergency and corrosion resistance.

[0118] The amount of dodecene added in Comparative Example 4 was relatively small, resulting in a lower content of disubstituted dodecylphenol, with a free phenol content of 0.5%. Furthermore, its antioxidant properties, anti-corrosion properties, and detergency were worse than those in Example 1.

[0119] In Comparative Example 5, the alkylation time was shorter, the content of disubstituted alkylphenols was reduced, the free phenol content was detected to be 0.3%, and its antioxidant properties, corrosion resistance and detergency were worse than those of Example 1.

[0120] In Comparative Example 6, the alkylation temperature was lower, the content of disubstituted alkylphenols was lower, and no further synthesis was carried out.

[0121] Comparative Example 7 reduced the amount of formaldehyde added during the condensation process, resulting in an insufficient condensation and a free phenol content of 1.5%.

Claims

1. A method for preparing a novel lubricating oil detergent, wherein, Includes the following steps: Step 1: Alkylation reaction of phenol, long-chain olefin, and solid acid catalyst to obtain a system of substituted alkylphenols; Step 2: Add an aldehyde compound and a condensation catalyst to the substituted alkylphenol system to carry out a condensation reaction to obtain the alkylphenol intermediate; Step 3: Add calcium source, base oil and solvent to the alkylphenol intermediate for neutralization reaction. After the reaction is completed, add alcohol compound and then carbonate. Perform post-treatment on the product to obtain a new type of lubricating oil detergent. The long-chain olefin is selected from C 12 -C 20 One of the olefins; The molar ratio of phenol to long-chain olefin is 1:(2.1-4).

2. The preparation method according to claim 1, wherein, In step one, the amount of phenol added is 1 part by weight, and the amount of solid acid catalyst added is 0.1-0.6 parts. In step two, the amount of substituted alkylphenol added is 1 part by weight, the amount of aldehyde compound added is 0.02-0.2 parts, and the amount of condensation catalyst added is 0.002-0.02 parts. In step three, the amount of alkylphenol intermediate added is 1 part by weight, the amount of calcium source added is 0.1-0.5 parts, and the amount of alcohol compound added is 0.05-0.3 parts.

3. The preparation method according to claim 1, wherein, The aldehyde compounds are selected from one or more of formaldehyde, propionaldehyde, and butyraldehyde; And / or, the solid acid catalyst is selected from modified molecular sieves and / or sulfonic acid resins; And / or, the condensation catalyst is selected from acidic catalysts or basic catalysts; And / or, the calcium source is selected from inorganic calcium; And / or, the base oil is selected from one or more of 100N, 150SN, 150N, 500N, and 500SN; And / or, the alcohol compound is selected from ethylene glycol.

4. The preparation method according to claim 1, wherein, The condensation catalyst is selected from one or more of calcium oxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, acetic acid, formic acid, methanesulfonic acid, and p-toluenesulfonic acid. And / or, the calcium source is selected from calcium oxide and / or calcium hydroxide; And / or, the solvent is selected from one or more of D30 solvent oil, D40 solvent oil, and xylene.

5. The preparation method according to claim 1, wherein, In step one, the alkylation reaction is carried out at a temperature of 90-120°C for 2-10 hours.

6. The preparation method according to claim 1, wherein, In step two, the substituted alkylphenol system is cooled to 30-80 °C and then an aldehyde compound and a condensation catalyst are added. And / or, in step two, the condensation reaction is carried out at a temperature of 60-150 °C for a time of 1-5 h.

7. The preparation method according to claim 1, wherein, In step three, the neutralization reaction is carried out at a temperature of 30-180 °C for 1-5 h.

8. The preparation method according to claim 1, wherein, In step three, after the reaction is complete, an alcohol compound is added, and carbon dioxide is introduced to carry out carbonation; Preferably, in step three, the amount of alkylphenol intermediate added is 1 part by weight, and the amount of carbon dioxide introduced is 0.1-0.5 parts. Preferably, the carbon dioxide is introduced for 1-5 hours.

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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