High-base-number sulfurized ester type alkylphenate detergent and preparation method thereof

Abstract

The invention discloses a high-base-number sulfurized ester type alkylphenate detergent and a preparation method thereof. The preparation method comprises the following steps: firstly, preparing ester type alkylphenol by utilizing esterification reaction; mixing and stirring ester type alkylphenol, a metal compound, base oil, sulfur, a vulcanization accelerator and ethylene glycol, introducing nitrogen for purging, and heating for neutralization and vulcanization reaction to obtain a vulcanized mixture; and then adding a cosurfactant, calcium hydroxide and ethylene glycol, mixing and stirring, introducing carbon dioxide, carrying out high alkalinity reaction, and after the reaction is finished, removing the solvent and water, and centrifuging to obtain the high-base-number sulfide ester type alkylphenate detergent. The detergent does not have biotoxicity and has obvious advantages in the aspect of safety, and meanwhile, compared with a sulfurized phenate detergent with an ester type alkylphenol structure, the sulfurized phenate detergent with the ester type alkylphenol structure has more excellent oxidation and corrosion resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating oil additive preparation, and in particular relates to a high base value sulfurized ester type alkyl phenol salt detergent, and also relates to a preparation method of the detergent. Background Art

[0002] In the field of lubricant additives, metal detergents mainly include alkyl sulfonates, alkyl salicylates and alkyl phenols. Compared with other metal detergents, sulfurized alkyl phenol detergents have excellent high-temperature cleaning performance and good anti-oxidation and anti-corrosion properties, and are widely used in high-grade internal combustion engine oils.

[0003] Dodecylphenol is an important raw material for the production of calcium alkylphenol sulfide, but because it is an endocrine disruptor, it has biological toxicity. According to the GHS classification, its biological toxicity is upgraded to Class 1B. Many countries have clearly restricted the content of alkylphenol, so it is particularly important to develop alkylphenol sulfide salts that do not contain dodecylphenol.

[0004] In order to reduce the alkylphenol in the phenol salt product, one solution is to replace dodecylphenol with long-chain linear alkylphenol, dialkylphenol, etc. with lower toxicity, such as the method disclosed in Chinese patents CN104529844A and CN105037226A; another solution is to reduce the content of free alkylphenol by solvent extraction reduction, conversion of residual alkylphenol into Mannich alkylphenol and other technical means, such as the method disclosed in Chinese patents CN105462652A and CN106147937A. The alkylphenol salt structures of the above-mentioned solutions are all alkylphenols with biological toxicity, wherein the alkyl group is a straight or branched saturated hydrocarbon structure of C9-C21. Although the free alkylphenol with biological toxicity can be reduced to varying degrees, it cannot be completely eliminated. Summary of the invention

[0005] The purpose of the present invention is to provide a high base value sulfurized ester type alkylphenol salt detergent, which has no biological toxicity and has better antioxidant and anti-corrosion properties.

[0006] Another object of the present invention is to provide a method for preparing a high base value sulfurized ester type alkyl phenol salt detergent.

[0007] The technical solution adopted by the present invention is a high base value sulfurized ester type alkyl phenol salt detergent, the structure of which is as follows:

[0008]

[0009] Where: R 1 is an ester-type alkyl chain of C10-30; x is the number of sulfur atoms, ranging from 1-5.

[0010] Another technical solution adopted by the present invention is a method for preparing a high base value sulfurized ester type alkyl phenol salt detergent, which is specifically implemented according to the following steps:

[0011] Step 1, preparing ester type alkylphenol by esterification reaction;

[0012] Step 2, ester type alkylphenol, metal compound, base oil, sulfur, vulcanization accelerator, ethylene glycol are mixed and stirred, nitrogen is introduced for purging, and the temperature is raised to 125-200°C for neutralization and vulcanization reaction for 1-10 hours, and the generated hydrogen sulfide and water are absorbed by alkali solution to obtain a sulfide mixture; then, a co-surfactant, calcium hydroxide, and ethylene glycol are added and mixed and stirred, the temperature is raised to 100-180°C, and carbon dioxide is introduced for high alkalinity reaction. After the reaction is completed, the solvent and water are removed, and centrifugation is performed to obtain a high alkalinity ester type alkylphenol salt detergent.

[0013] In step 1, specifically:

[0014] Mix and stir alkyl alcohol with a chain length of C10 to 30 and hydroxybenzoic acid, add a catalyst, raise the temperature to 70-200°C, and keep the temperature to react for 1-24 hours. After the reaction is completed, let it stand and precipitate, remove impurities, and obtain ester-type alkylphenol.

[0015] The catalyst is any one of inorganic acid, organic sulfonic acid and solid acid; the added amount of the catalyst is 0.1% to 10% of the total amount of the alkyl alcohol and the hydroxybenzoic acid.

[0016] The hydroxybenzoic acid is o-hydroxybenzoic acid, m-hydroxybenzoic acid or p-hydroxybenzoic acid.

[0017] In step 2, the base oil is any one or more of Class I base oil, Class II base oil, Class III base oil, and synthetic oil; and the vulcanization accelerator is an acidic accelerator, an alkaline accelerator, or a neutral accelerator.

[0018] In step 2, the metal compound is an alkali metal hydroxide or an alkali metal oxide; the co-surfactant is any one of alkylbenzene sulfonic acid, stearic acid, alkyl salicylic acid, and polyisobutylene succinic anhydride.

[0019] In step 2, the mass ratio of ester type alkylphenol, co-surfactant, base oil, metal compound, sulfur, vulcanization accelerator and ethylene glycol is 100-200:1-20:250-50:20-150:10-40:0-10:20-100.

[0020] In step 2, the rate of introduction of carbon dioxide is 50 to 200 mL / min.

[0021] The beneficial effects of the present invention are as follows: the product prepared by the present invention is an ester-type alkylphenol structure, the detergent has no biological toxicity and has obvious advantages in safety. At the same time, the ester-type alkylphenol structure has better antioxidant and anti-corrosion properties than the sulfurized phenol salt detergent of the alkylphenol structure. DETAILED DESCRIPTION

[0022] The present invention is described in detail below in conjunction with specific implementation modes.

[0023] The high base value sulfurized ester type alkyl phenol salt detergent of the present invention has the following structure:

[0024]

[0025] Where: R 1 It is a C10-30 ester type alkyl chain,

[0026] x is the number of sulfurs, ranging from 1 to 5;

[0027] The preparation method of the high base value sulfurized ester type alkyl phenol salt detergent of the present invention is specifically implemented according to the following steps:

[0028] Step 1, preparing ester type alkylphenol by esterification reaction;

[0029] Mix and stir the alkyl alcohol with a chain length of C10 to 30 and hydroxybenzoic acid, add the catalyst after stirring evenly, raise the temperature to 70-200°C, keep the temperature to react for 1-24 hours, and after the reaction is completed, let it stand and precipitate, remove impurities, and obtain a reddish brown oily ester type alkylphenol product; the reaction equation is as follows:

[0030]

[0031] Wherein, R is a C10-30 alkyl chain;

[0032] The catalyst is any one of an inorganic acid (concentrated sulfuric acid), an organic sulfonic acid (anhydrous alkyl sulfonic acid and anhydrous aryl sulfonic acid), a solid acid, aminosulfonic acid, methanesulfonic acid, and benzenesulfonic acid;

[0033] The amount of catalyst added is 0.1% to 10% of the total amount of alkyl alcohol and hydroxybenzoic acid;

[0034] The hydroxybenzoic acid is o-hydroxybenzoic acid, m-hydroxybenzoic acid or p-hydroxybenzoic acid;

[0035] The raw material long-chain alkyl alcohol has a long chain R of C10 to 30, including straight chain and branched chain;

[0036] Step 2, ester type alkylphenol, metal compound, base oil, sulfur, vulcanization accelerator, ethylene glycol are mixed and stirred, nitrogen is introduced for purging, and the temperature is raised to 125-200°C for neutralization and vulcanization reaction for 1-10 hours, and the generated hydrogen sulfide, water, etc. are absorbed with alkali solution to obtain a vulcanized mixture; then, a co-surfactant, calcium hydroxide, and ethylene glycol are added and mixed and stirred, the temperature is raised to 100-180°C, and carbon dioxide is introduced at a rate of 50-200mL / min to perform a high alkalinity reaction, and after the reaction is completed, the temperature is raised to above 200°C to remove the solvent and water, and centrifuged to obtain a high alkalinity ester type alkylphenol salt detergent;

[0037] The base oil is any one or more of Class I base oil, Class II base oil, Class III base oil, and synthetic oil;

[0038] The vulcanization accelerator is an acidic accelerator (2-mercaptobenzothiazole, thiuram, etc.), a basic accelerator (guanidines, aldehyde amines, amines, etc.) or a neutral accelerator (sulfonamides, thioureas, etc.);

[0039] The metal compound is an alkali metal hydroxide or an alkali metal oxide; the alkali metal is one or more of lithium, sodium, potassium, calcium, magnesium and barium, such as calcium hydroxide / calcium oxide, magnesium oxide, etc.;

[0040] The co-surfactant is any one of alkylbenzene sulfonic acid, stearic acid, alkyl salicylic acid, and polyisobutylene succinic anhydride;

[0041] The mass ratio of ester type alkylphenol, cosurfactant, base oil, metal compound, sulfur, vulcanization accelerator and ethylene glycol is 100-200: 1-20: 250-50: 20-150: 10-40: 0-10: 20-100;

[0042] The product prepared by the present invention does not contain restricted substances with biological toxicity such as dodecylphenol, and has obvious advantages in terms of safety. At the same time, the product has better antioxidant and anti-corrosion properties than other sulfurized alkylphenol salt detergents.

[0043] Example 1

[0044] At room temperature, add 100 ml of xylene, 70 g of hydroxybenzoic acid, and 135 g of octadecyl alcohol to a 500 ml three-necked flask with a stirrer, and heat to 140° C. under nitrogen protection, and add 5 g of methylsulfonic acid as a catalyst. Reflux and collect the separated water. When the collected water reaches 9 g, the reaction is finished. Cool to room temperature, filter to remove excess hydroxybenzoic acid, and then heat to remove and recover the solvent xylene to obtain the raw material ester type alkylphenol.

[0045] Example 2

[0046] At room temperature, add 100 ml of xylene, 70 g of hydroxybenzoic acid, and 100 g of dodecanol to a 500 ml three-necked flask with a stirrer, raise the temperature to 140°C, and add a catalyst solid superacid (TIO 2 / SO 4 2- ) 10g. Reflux and collect the separated water. When the collected water reaches 9g, the reaction is finished. Then cool to room temperature, filter to remove excess hydroxybenzoic acid, then heat up to evaporate and recover the solvent xylene to obtain the raw material ester type alkylphenol.

[0047] Example 3

[0048] At room temperature, add 40g of ester type alkylphenol, 50g of base oil, 10g of calcium hydroxide, 8g of sulfur, 4g of vulcanization accelerator (accelerator M: 2-mercaptobenzothiazole), and 30g of ethylene glycol to a 500ml three-necked flask with a stirrer, mix, heat to 180°C, use nitrogen to purge hydrogen sulfide and absorb with alkali solution. After 2 hours, a low-base value sulfurized ester type alkylphenol salt product is obtained.

[0049] The temperature was lowered to 160°C, and then 10g of ethylene glycol, 10g of alkylbenzene sulfonic acid, and 20g of calcium hydroxide were added, and 7L of carbon dioxide was introduced at a ventilation rate of 70ml / min to carry out a high basicity reaction. After the reaction was completed, the temperature was raised to 220°C, and water, ethylene glycol, etc. were evaporated. After the temperature was lowered, gasoline was added for dilution, sedimentation, centrifugation (filtration) to remove slag, and then the solvent was distilled to obtain a high basicity sulfurized ester type alkylphenol salt product.

[0050] Example 4

[0051] At room temperature, add 50g of ester type alkylphenol, 50g of base oil, 10g of calcium hydroxide, 10g of sulfur, 4g of vulcanization accelerator (accelerator D: diphenylguanidine) and 30g of ethylene glycol to a 500ml three-necked flask with a stirrer, mix, heat to 180°C, purge hydrogen sulfide with nitrogen and absorb with alkali solution. After 8 hours, a low-base value sulfurized ester type alkylphenol salt product is obtained.

[0052] The temperature was lowered to 160°C, and then 10g of ethylene glycol, 10g of stearic acid, and 20g of calcium hydroxide were added, and 7L of carbon dioxide was introduced at a ventilation rate of 70ml / min to carry out a high alkalinity reaction. After the reaction was completed, the temperature was raised to 220°C, and water, ethylene glycol, etc. were evaporated. After the temperature was lowered, gasoline was added for dilution, sedimentation, centrifugation (filtration) to remove slag, and then the solvent was distilled to obtain a high alkalinity sulfurized ester type alkylphenol salt product.

[0053] Comparative Example 1

[0054] Add 100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur, and 15g of calcium oxide to a 500mL four-necked bottle, raise the temperature to 155°C, add 20g of ethylene glycol as a promoter, and maintain the temperature at 140-150°C for 5 hours after the addition is complete. Continue to add 20g of calcium oxide and inject 22g of carbon dioxide gas. Then cool down and add 10g of diatomaceous earth filter aid to filter, and distill the filtrate to remove the solvent to obtain sulfide alkylphenol calcium detergent. Then cool down and add 6g of diatomaceous earth filter aid to filter, and distill the filtrate to remove the solvent to obtain sulfide alkylphenol calcium detergent.

[0055] Comparative Example 2

[0056] Add 100g dodecylphenol, 100g 150N base oil, 18g sulfur, 15g calcium oxide into a 500mL four-necked bottle, heat to 160℃, add 20g ethylene glycol as promoter, and keep the temperature at 165-175℃ for 3 hours after the addition is complete. Cool the material to 40℃, add 42g formaldehyde solution (37%), 36g diethylenetriamine, 100g 200# diluent oil, and heat to 230℃ at a constant speed of about 0.5℃ / min. After cooling, centrifuge to remove slag, and distill the clear liquid to remove the solvent to obtain alkylphenol detergent.

[0057] The results of the above examples and comparative examples are shown in Table 1;

[0058]

[0059] The performance testing methods are as follows: base value SH / T 0297 "Determination of calcium content in additives", kinematic viscosity GB / T 265 "Determination of kinematic viscosity of petroleum products and calculation of dynamic viscosity", sulfur content SH / T 0303 "Determination of sulfur content in additives (coulometric method)", free phenol is tested by HPLC, and PDSC pressure differential scanning calorimetry.

[0060] It can be seen from the table that compared with the comparative example, the embodiment does not contain free phenol and the oxidation induction period is significantly better than that of the comparative example, which shows that the present invention has obvious advantages in terms of safety and anti-oxidation and anti-corrosion performance.

Claims

1. A high base value sulfurized ester type alkylphenol detergent, characterized in that: Its structure is as follows: Wherein: R1 is an ester-type alkyl chain of C10 to 30; x is the number of sulfur atoms, ranging from 1 to 5.

2. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 1, characterized in that: Follow the steps below to implement it: Step 1, preparing ester type alkylphenol by esterification reaction; Step 2, ester type alkylphenol, metal compound, base oil, sulfur, vulcanization accelerator, ethylene glycol are mixed and stirred, nitrogen is introduced for purging, and the temperature is raised to 125-200°C for neutralization and vulcanization reaction for 1-10 hours, and the generated hydrogen sulfide and water are absorbed by alkali solution to obtain a sulfide mixture; then, a co-surfactant, calcium hydroxide, and ethylene glycol are added and mixed and stirred, the temperature is raised to 100-180°C, and carbon dioxide is introduced for high alkalinity reaction. After the reaction is completed, the solvent and water are removed, and centrifugation is performed to obtain a high alkalinity ester type alkylphenol salt detergent.

3. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 2, characterized in that: In the step 1, specifically: Mix and stir alkyl alcohol with a chain length of C10 to 30 and hydroxybenzoic acid, add a catalyst, raise the temperature to 70-200°C, and keep the temperature to react for 1-24 hours. After the reaction is completed, let it stand and precipitate, remove impurities, and obtain ester-type alkylphenol.

4. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 3, characterized in that: The catalyst is any one of inorganic acid, organic sulfonic acid and solid acid; the added amount of the catalyst is 0.1% to 10% of the total amount of the alkyl alcohol and the hydroxybenzoic acid.

5. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 3, characterized in that: The hydroxybenzoic acid is o-hydroxybenzoic acid, m-hydroxybenzoic acid or p-hydroxybenzoic acid.

6. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 2, characterized in that: In the step 2, the base oil is any one or more of a Class I base oil, a Class II base oil, a Class III base oil, and a synthetic oil; and the vulcanization accelerator is an acidic accelerator, an alkaline accelerator, or a neutral accelerator.

7. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 2, characterized in that: In the step 2, the metal compound is an alkali metal hydroxide or an alkali metal oxide; the co-surfactant is any one of alkylbenzene sulfonic acid, stearic acid, alkyl salicylic acid, and polyisobutylene succinic anhydride.

8. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 2, characterized in that: In the step 2, the mass ratio of ester type alkylphenol, co-surfactant, base oil, metal compound, sulfur, vulcanization accelerator and ethylene glycol is 100-200: 1-20: 250-50: 20-150: 10-40: 0-10: 20-100.

9. The method for preparing the high base value sulfurized ester type alkyl phenol salt detergent according to claim 2, characterized in that: In the step 2, the rate of introduction of carbon dioxide is 50 to 200 mL / min.

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