High base number sulfurized ester type alkyl phenate detergent and method of making

Abstract

The present invention discloses a high-basicity sulfurized ester alkylphenol detergent and a preparation method. First, an ester alkylphenol is prepared by an esterification reaction. Then, the ester alkylphenol, a metal compound, a base oil, sulfur, a vulcanization accelerator, and ethylene glycol are mixed and stirred, nitrogen is introduced for purging, and the mixture is heated for neutralization and vulcanization to obtain a vulcanized mixture. Then, a cosurfactant, calcium hydroxide, and ethylene glycol are added, mixed and stirred, and carbon dioxide is introduced for high basicity reaction. After the reaction is completed, the solvent and water are removed, and the mixture is centrifuged to obtain a high-basicity sulfurized ester alkylphenol detergent. The detergent is non-biotoxic and has significant safety advantages. Furthermore, the ester alkylphenol structure has superior antioxidant and corrosion resistance compared to sulfurized phenate detergents with an alkylphenol structure.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of lubricating oil additive preparation, and particularly relates to a high-alkaline sulfidized ester type alkyl phenate detergent, and also relates to a preparation method of the detergent. BACKGROUND

[0002] In the field of lubricating oil additives, metal detergents mainly include alkyl sulfonate, alkyl salicylate and alkyl phenate. Compared with other metal detergents, sulfidized alkyl phenate detergent has excellent high-temperature cleaning performance, and also has good antioxidant and anticorrosive performance, and is widely used in high-grade internal combustion engine oil.

[0003] Dodecyl phenol is an important raw material for producing sulfidized calcium alkyl phenate, but it is an endocrine disruptor and has biological toxicity. According to GHS classification, its biological toxicity is upgraded to class 1B, and many countries have made clear restrictions on the content of alkyl phenol, so it is particularly important to develop sulfidized alkyl phenate without dodecyl phenol.

[0004] To reduce the content of alkyl phenol in phenate product, one solution is to replace dodecyl phenol with long-chain linear alkyl phenol, double-chain alkyl phenol and the like with lower toxicity, such as the methods disclosed in Chinese patents CN104529844A and CN105037226A; another solution is to reduce the content of free alkyl phenol by means of solvent extraction reduction and conversion of residual alkyl phenol into Mannich alkyl phenol, such as the methods disclosed in Chinese patents CN105462652A and CN106147937A. The alkyl phenol structures of the above solutions all have biological toxicity, in which the alkyl group is a C9-C21 straight-chain or branched-chain saturated hydrocarbon structure. Although the above solutions can reduce the content of free alkyl phenol with biological toxicity to different degrees, they cannot completely eliminate the free alkyl phenol. SUMMARY

[0005] The purpose of the present application is to provide a high-alkaline sulfidized ester type alkyl phenate detergent without biological toxicity, and with more excellent antioxidant and anticorrosive performance.

[0006] Another purpose of the present application is to provide a preparation method of high-alkaline sulfidized ester type alkyl phenate detergent.

[0007] The technical solution adopted by the present application is that the high-alkaline sulfidized ester type alkyl phenate detergent has the following structure:

[0008]

[0009] In the formula, R1 is a C10-30 ester type alkyl chain; and x is the number of sulfur, ranging from 1 to 5.

[0010] Another technical solution adopted by the present application is a preparation method of high-alkalinity sulfidized ester alkyl phenate detergent, which is implemented according to the following steps:

[0011] Step 1, ester alkyl phenol is prepared by esterification reaction;

[0012] Step 2, the ester alkyl phenol, a metal compound, base oil, sulfur, a vulcanization accelerator, and ethylene glycol are mixed and stirred, nitrogen is introduced for purging, and the temperature is raised to 125-200 DEG C for neutralization and vulcanization reaction for 1-10 hours. The generated hydrogen sulfide and water are absorbed by lye to obtain a vulcanization mixture. Then, a co-surfactant, calcium hydroxide, and ethylene glycol are mixed and stirred, the temperature is raised to 100-180 DEG 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 the high-alkalinity sulfidized ester alkyl phenate detergent.

[0013] In Step 1, specifically:

[0014] The alkyl alcohol with a chain length of C10-30 and the hydroxybenzoic acid are uniformly mixed and stirred, a catalyst is added, the temperature is raised to 70-200 DEG C, and the reaction is maintained for 1-24 hours. After the reaction is completed, the mixture is allowed to stand and precipitate, and impurities are removed to obtain the ester alkyl phenol.

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

[0016] The hydroxybenzoic acid is ortho-hydroxybenzoic acid, meta-hydroxybenzoic acid, or para-hydroxybenzoic acid.

[0017] In Step 2, the base oil is any one or several of a first-class base oil, a second-class base oil, a third-class base oil, and synthetic oil. The vulcanization accelerator is an acidic accelerator, an alkaline accelerator, or a neutral accelerator.

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

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

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

[0021] The product prepared by the application is an ester alkyl phenol structure, the detergent has no biological toxicity, and has obvious advantages in safety, and the ester alkyl phenol structure has more excellent oxidation resistance and corrosion resistance compared with the sulfidized phenate detergent with an alkyl phenol structure. DETAILED DESCRIPTION

[0022] The application will be described in detail below in combination with specific embodiments.

[0023] The high-alkali sulfidized ester alkyl phenol detergent of the application has the following structure:

[0024]

[0025] R1 is a C10-30 ester alkyl chain,

[0026] x is the number of sulfur, and ranges from 1 to 5;

[0027] The preparation method of the high-alkali sulfidized ester alkyl phenol detergent of the application is implemented according to the following steps:

[0028] Step 1, ester alkyl phenol is prepared by esterification reaction;

[0029] The alkyl alcohol with a chain length of C10-30 and hydroxybenzoic acid are mixed and stirred, a catalyst is added after uniform stirring, the temperature is raised to 70-200 DEG C, and the reaction is kept for 1-24 h, after the reaction is completed, the product is precipitated and impurities are removed, and the red-brown oil ester alkyl phenol product is obtained; the reaction equation is as follows:

[0030]

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

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

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

[0034] The hydroxybenzoic acid is ortho-hydroxybenzoic acid, meta-hydroxybenzoic acid, or para-hydroxybenzoic acid;

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

[0036] Step 2, the ester type alkyl phenol, metal compound, base oil, sulfur, vulcanization accelerator, ethylene glycol are mixed and stirred, nitrogen is introduced to perform purging and is heated to 125-200 DEG C to perform neutralization and vulcanization reaction for 1-10 hours, the generated hydrogen sulfide, water and the like are absorbed by lye to obtain a vulcanized mixture; then, a co-surfactant, calcium hydroxide and ethylene glycol are mixed and stirred, heated to 100-180 DEG C, and carbon dioxide is introduced at a rate of 50-200 mL / min to perform high alkalinity reaction, after the reaction is completed, the temperature is increased to above 200 DEG C to remove the solvent and water, and centrifugation is performed to obtain a high alkaline vulcanized ester type alkyl phenate detergent;

[0037] The base oil is any one or several of a first group base oil, a second group base oil, a third group base oil and synthetic oil;

[0038] The vulcanization accelerator is an acidic accelerator (2-mercaptobenzothiazole, thiuram, etc.), an alkaline accelerator (guanidine, aldehyde amine, amine, etc.) or a neutral accelerator (sulfenamide, thiourea, etc.);

[0039] The metal compound is an alkali metal hydroxide or an alkali metal oxide; the alkali metal is one or several 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 alkyl benzene sulfonic acid, stearic acid, alkyl salicylic acid and polyisobutylene succinic anhydride;

[0041] The mass ratio of the ester type alkyl phenol, 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;

[0042] The product prepared by the application does not contain dodecyl phenol which is a limited substance with biological toxicity, and has obvious advantages in safety, and the product has more excellent oxidation resistance and corrosion resistance compared with other vulcanized alkyl phenate detergents.

[0043] Example 1

[0044] At room temperature, 100 ml of xylene, 70 g of hydroxybenzoic acid and 135 g of octadecanol are added to a 500 ml three-necked flask with a stirrer, nitrogen is introduced for protection and the temperature is increased to 140 DEG C, 5 g of a catalyst methyl sulfonic acid is added, reflux is performed and the separated water is collected, when the collected water reaches 9 g, the reaction is completed, the temperature is reduced to room temperature, the excess hydroxybenzoic acid is removed by filtration, then the solvent xylene is recovered by heating and evaporation, and the raw material ester type alkyl phenol is obtained.

[0045] Example 2

[0046] At room temperature, 100 ml of xylene, 70 g of hydroxybenzoic acid, 100 g of dodecanol, 10 g of a solid super acid catalyst (TiO2 / SO4 2- ) were added to a 500 ml three-necked flask equipped with a stirrer, and the mixture was heated to 140°C. Water separated was collected, and when 9 g of water was collected, the reaction was terminated. After cooling to room temperature, the excess hydroxybenzoic acid was removed by filtration, and then the solvent xylene was distilled off and recovered to obtain the raw material ester-type alkylphenol.

[0047] Example 3

[0048] At room temperature, 40 g of the ester-type alkylphenol, 50 g of base oil, 10 g of calcium hydroxide, 8 g of sulfur, 4 g of a vulcanization accelerator (accelerator M: 2-mercaptobenzothiazole), and 30 g of ethylene glycol were mixed in a 500 ml three-necked flask equipped with a stirrer, and the mixture was heated to 180°C while blowing off hydrogen sulfide with nitrogen and absorbing it with a caustic solution. After 2 h, a low-alkalinity vulcanized ester-type alkylphenate product was obtained.

[0049] The temperature was lowered to 160°C, and then 10 g of ethylene glycol, 10 g of alkylbenzenesulfonic acid, and 20 g of calcium hydroxide were added. Carbon dioxide was blown in at a rate of 70 ml / min for 7 L to perform a high-alkalinity reaction. After the reaction was terminated, the temperature was raised to 220°C, and water and ethylene glycol were distilled off. After cooling, gasoline was added to dilute and settle the product, and then the product was separated by centrifugation (filtration) to remove the residue. The solvent was then distilled off to obtain a high-alkalinity vulcanized ester-type alkylphenate product.

[0050] Example 4

[0051] At room temperature, 50 g of the ester-type alkylphenol, 50 g of base oil, 10 g of calcium hydroxide, 10 g of sulfur, 4 g of a vulcanization accelerator (accelerator D: diphenyl guanidine), and 30 g of ethylene glycol were mixed in a 500 ml three-necked flask equipped with a stirrer, and the mixture was heated to 180°C while blowing off hydrogen sulfide with nitrogen and absorbing it with a caustic solution. After 8 h, a low-alkalinity vulcanized ester-type alkylphenate product was obtained.

[0052] The temperature was lowered to 160°C, and then 10 g of ethylene glycol, 10 g of stearic acid, and 20 g of calcium hydroxide were added. Carbon dioxide was blown in at a rate of 70 ml / min for 7 L to perform a high-alkalinity reaction. After the reaction was terminated, the temperature was raised to 220°C, and water and ethylene glycol were distilled off. After cooling, gasoline was added to dilute and settle the product, and then the product was separated by centrifugation (filtration) to remove the residue. The solvent was then distilled off to obtain a high-alkalinity vulcanized ester-type alkylphenate product.

[0053] Comparative Example 1

[0054] In a 500 mL four-necked flask, add dodecyl phenol 100 g, 150N base oil 100 g, sulfur 18 g, calcium oxide 15 g, heat to 155℃, drop in promoter ethylene glycol 20 g, after drop completion, keep 140-150℃ for 5 hours. Continue to add 20 g of calcium oxide, fill in carbon dioxide gas 22 g. Then cool down, add 10 g of diatomite filter aid, filter, distill the filtrate to remove solvent, to obtain sulfidized alkyl phenol calcium detergent. Then cool down, add 6 g of diatomite filter aid, filter, distill the filtrate to remove solvent, to obtain sulfidized alkyl phenol calcium detergent.

[0055] Comparative Example 2

[0056] In a 500 mL four-necked flask, add dodecyl phenol 100 g, 150N base oil 100 g, sulfur 18 g, calcium oxide 15 g, heat to 155℃, drop in promoter ethylene glycol 20 g, after drop completion, keep 140-150℃ for 5 hours. Continue to add 20 g of calcium oxide, fill in carbon dioxide gas 22 g. Then cool down, add 10 g of diatomite filter aid, filter, distill the filtrate to remove solvent, to obtain sulfidized alkyl phenol calcium detergent. Then cool down, add 6 g of diatomite filter aid, filter, distill the filtrate to remove solvent, to obtain sulfidized alkyl phenol calcium detergent.

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

[0058]

[0059] The performance detection methods are respectively calcium content determination method in additives SH / T 0297, kinematic viscosity GB / T 265, sulfur content determination method (electricity method) in additives SH / T 0303, free phenol is detected by HPLC method, and PDSC pressurized differential scanning calorimetry.

[0060] As can be seen from the table, compared with the comparative examples, the examples do not contain free phenol, and the oxidation induction period is obviously better than that of the comparative examples. It shows that the application has obvious advantages in safety, anti-oxidation and corrosion resistance.

Claims

1. A high base value sulfurized ester type alkyl phenol detergent, characterized in that: Its structure is as follows: Wherein: R1 is a C10-30 ester-type alkyl chain; x is the number of sulfur atoms, ranging from 1 to 5; The preparation method of the high base value sulfurized ester type alkyl phenol salt detergent is specifically implemented according to the following steps: Step 1, preparing ester-type alkylphenol by esterification reaction; specifically: Mix and stir an alkyl alcohol with a chain length of C10-30 and hydroxybenzoic acid, then add a catalyst, heat to 70-200°C, and keep the temperature to react for 1-24 hours. After the reaction is completed, let it settle and remove impurities to obtain an ester-type alkylphenol. Step 2: ester-type alkylphenol, metal compound, base oil, sulfur, vulcanization accelerator, and 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 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 to carry out a high alkalinity reaction. After the reaction is completed, the solvent and water are removed, and the mixture is centrifuged to obtain a high-alkalinity sulfide ester-type alkylphenol salt detergent.

2. The method for preparing the high base value sulfurized ester type alkyl phenol detergent according to claim 1, wherein: Please 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, and 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 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 to carry out a high alkalinity reaction. After the reaction is completed, the solvent and water are removed, and the mixture is centrifuged to obtain a high-alkalinity sulfide ester-type alkylphenol salt detergent.

3. The method for preparing the high base value sulfurized ester type alkyl phenol detergent according to claim 2, wherein: In the step 1, specifically: Mix and stir alkyl alcohol with a chain length of C10-30 and hydroxybenzoic acid evenly, then add a catalyst, 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 ester-type alkylphenol.

4. The method for preparing the high base value sulfurized ester type alkyl phenol detergent according to claim 3, wherein: The catalyst is any one of an inorganic acid, an organic sulfonic acid, and a solid acid; and 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 detergent according to claim 3, wherein: 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 detergent according to claim 2, wherein: 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.

7. The method for preparing the high base value sulfurized ester type alkyl phenol detergent according to claim 2, wherein: In step 2, the metal compound is an alkali metal hydroxide or an alkali metal oxide; and 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 detergent according to claim 2, wherein: In the step 2, 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.

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

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