Preparation method of sulfurized alkylphenate

Abstract

The invention relates to a preparation method of sulfurized alkylphenate. The oxidation resistance of the obtained sulfurized alkylphenate is remarkably improved, and the content of free phenol is reduced to 2% or below.

Description

Technical Field

[0001] This invention belongs to the field of lubricating oil additives, and specifically relates to a method for preparing a sulfurized alkylphenol salt. Background Technology

[0002] Alkylphenol salts are among the most widely used lubricating oil detergents, second only to sulfonates in application scale. Compared to ordinary alkylphenol salts, sulfurized alkylphenol salts have become the mainstream detergent type due to their more comprehensive performance. Especially in turbocharged diesel engine oils, sulfurized alkylphenol salts exhibit excellent high-temperature detergency and are significantly effective in inhibiting carbon deposits in the piston crown ring groove area, thus being regarded as an indispensable key additive for this type of oil.

[0003] Sulfated alkylphenol salts are typically produced by reacting alkylphenols such as dodecylphenol with alkaline earth metal compounds after sulfidation. Because their molecular structure retains phenolic hydroxyl functional groups, they possess a certain intrinsic antioxidant capacity. This characteristic constitutes a key difference between phenolic salt detergents and sulfonates: while sulfonates have good colloidal dispersibility and alkali reserve capacity, their antioxidant properties are relatively weak. Therefore, in practical formulations, phenolic salts are often used in combination with sulfonates to synergistically improve the overall performance of oils, especially to compensate for the shortcomings of sulfonates in antioxidant properties.

[0004] It is worth noting that, according to the Globally Harmonized Classification and Labelling System (GHS), dodecylphenol has been identified as having reproductive toxicity. During the synthesis of sulfide alkylphenol salts, due to limitations in reaction equilibrium and process conditions, dodecylphenol is often difficult to completely convert, resulting in the presence of free phenol residues in the final product. Industrial practice shows that the free phenol content in sulfide alkylphenol salts obtained by conventional processes is typically higher than 4 wt%, posing potential health and environmental risks and potentially affecting the product's storage stability and performance.

[0005] Therefore, effectively reducing the free phenol residue in sulfurized alkylphenol salt products and further improving their antioxidant properties has become an important direction for technological research and development in this field. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing sulfidated alkylphenol salts, which can improve the antioxidant properties of sulfidated alkylphenol salts and reduce the free phenol content in sulfidated alkylphenol salts.

[0007] This invention provides a method for preparing sulfide alkylphenol salts, comprising the following steps: S1. Add C to the reactor 8-16 Alkylphenol, diluent, first alkaline earth metal source, accelerator, phase transfer catalyst and sulfiding agent are subjected to a first reaction to obtain a first reaction product liquid; after separation, sulfided alkylphenol salt is obtained. The phase transfer catalyst is a quaternary ammonium salt compound comprising or composed of a quaternary ammonium cation and anion of Formula I. (R1)(R2)3N + Formula I Among them, R1 or R2 may be the same or different, and each is independently selected from C. 1-18 Alkyl; the C 1-18 Alkyl groups are optionally C 6-10 Aryl substitution.

[0008] In some embodiments, R1 and R2 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl; wherein the methyl, ethyl, propyl, and butyl groups may be substituted with phenyl groups; Preferably, R1 is selected from methyl, ethyl, butyl, octyl, dodecyl, or tetradecyl; wherein methyl and ethyl can be substituted with phenyl; R2 is selected from methyl, ethyl, or butyl. More preferably, R1 is selected from methyl, ethyl, butyl, octyl, dodecyl, tetradecyl, or benzyl; and / or The anion is selected from chloride ion, bromide ion, bisulfate ion, sulfate ion, phosphate ion, dihydrogen phosphate ion, acetate ion, and formate ion; preferably selected from chloride ion, bromide ion, and bisulfate ion.

[0009] In some implementations, the C 8-16 The alkylphenol is selected from one or more of octylphenol, nonylphenol, decylphenol, dodecylphenol, tetradecylphenol, and hexadecylphenol; preferably, the C 8-16 Alkylphenol is one or more of para-octylphenol, para-nonylphenol, para-decylphenol, para-dodecylphenol, para-tetradecylphenol, or para-hexadecylphenol; and / or The diluting solvent is selected from one or more of mineral base oils, aliphatic hydrocarbon solvents, cycloalkane solvents, and aromatic solvents, preferably one or more of 150N base oil, 6# base oil, 150SN base oil, n-hexane, n-heptane, cyclohexane, methylcyclohexane, Isopar E, Isopar G, toluene, or xylene; more preferably 150N base oil, 6# base oil, or 150SN base oil; and / or The first alkaline earth metal source is selected from one or more of calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide; and / or The accelerator is water, C 1-6 fatty alcohols, C 2-6One or more of the following fatty carboxylic acids, preferably one or more of water, methanol, ethanol, isopropanol, n-butanol, propylene glycol, glycerol, ethylene glycol, 1,4-butanediol, acetic acid, propionic acid, or 2-ethylhexanoic acid, more preferably propylene glycol, glycerol, ethylene glycol, or 1,4-butanediol; and / or The vulcanizing agent is a compound that provides active sulfur, preferably sulfur; and / or The phase transfer catalyst is selected from one or more of tetrabutylammonium bisulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.

[0010] In some embodiments, 200 parts by weight of C 8-16 Alkylphenols The mass fraction of the diluent is 150-250 parts, preferably 200 parts; The mass fraction of the first alkaline earth metal source is 40 to 60 parts, preferably 45 to 52 parts; The accelerator is 6 to 18 parts by weight, preferably 8 to 15 parts by weight; The mass fraction of the phase transfer catalyst is 3 to 18 parts, preferably 5 to 10 parts; The mass fraction of the vulcanizing agent is 20 to 60 parts, preferably 30 to 40 parts.

[0011] In some embodiments, in step S1, C is added to the reactor. 8-16 The first reaction is carried out by heating alkylphenol, diluent, first alkaline earth metal source, accelerator, phase transfer catalyst and sulfiding agent; Preferably, in step S1, the temperature is raised to 130~170°C, more preferably to 140~160°C, and even more preferably to 140~150°C; and / or In step S1, the reaction temperature is 130~170℃, preferably 140~160℃, more preferably 140~150℃; the reaction time is 1~4h, preferably 1~3h, more preferably 2h.

[0012] In some embodiments, the preparation method further includes: S2. Add a second alkaline earth metal source, a carbonation reagent, and optional C to the first reaction product solution. 8-10 The fatty alcohol undergoes a second reaction to give a second reaction product liquid; after separation, a sulfurized alkylphenol salt is obtained. Preferably, the base value of the sulfide alkylphenol salt in step S2 is 50~350 mgKOH / g, more preferably 100~300 mgKOH / g, and even more preferably 200~280 mgKOH / g.

[0013] In some embodiments, the second alkaline earth metal source is selected from one or more of calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide; and / or The first alkaline earth metal source and the second alkaline earth metal source may be the same or different; and / or C 8-10 Fatty alcohols are selected from n-octanol, isooctanol, n-nonanol, or n-decanol, preferably isooctanol; and / or The carbonation reagent is carbon dioxide.

[0014] In some embodiments, 200 parts by weight of C 8-16 Alkylphenols C 8-10 The fatty alcohol is 8 to 40 parts by mass, preferably 10 to 20 parts by mass; The mass fraction of the second alkaline earth metal source is 40 to 80 parts, preferably 50 to 70 parts, and more preferably 56 to 64 parts. The carbonation reagent is present in parts by weight of 10 to 40, preferably 15 to 25.

[0015] In some embodiments, in step S2, the reaction time is 1 to 4 hours, preferably 1 to 3 hours, more preferably 2 hours; the reaction temperature is 130 to 170°C, preferably 140 to 160°C, more preferably 140 to 150°C.

[0016] In some embodiments, the reaction temperature of step S2 is the same as the reaction temperature of step S1; and / or In step S2, after the reaction is complete, the solvent is removed, and the residue is filtered out to obtain sulfide alkylphenol salt.

[0017] Compared with existing sulfide alkylphenol salts, the sulfide alkylphenol salts prepared in this application have significantly improved antioxidant properties and reduced the free phenol content to below 2%. Detailed Implementation

[0018] The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the operations involved in the embodiments are conventional techniques in the art.

[0019] This invention provides a method for preparing sulfide alkylphenol salts, comprising the following steps: S1. Add C to the reactor 8-16 Alkylphenol, diluent, first alkaline earth metal source, accelerator, phase transfer catalyst and sulfiding agent are subjected to a first reaction to obtain a first reaction product liquid; after separation, sulfided alkylphenol salt is obtained. The phase transfer catalyst is a quaternary ammonium salt compound comprising or composed of a quaternary ammonium cation and anion of Formula I. (R1)(R2)3N + Formula I Among them, R1 or R2 may be the same or different, and each is independently selected from C. 1-18 Alkyl; the C 1-18 Alkyl groups are optionally C 6-10 Aryl substitution. The sulfide alkylphenol salt can be used as a detergent for lubricating oils. In some embodiments, R1 and R2 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl; wherein the methyl, ethyl, propyl, and butyl groups can be substituted with phenyl groups. Preferably, R1 is selected from methyl, ethyl, butyl, octyl, dodecyl, or tetradecyl; wherein the methyl and ethyl groups can be substituted with phenyl groups; and R2 is selected from methyl, ethyl, and butyl. More preferably, R1 is selected from methyl, ethyl, butyl, octyl, dodecyl, tetradecyl, or benzyl.

[0020] In some embodiments, the anion is selected from chloride ions, bromide ions, bisulfate ions, sulfate ions, phosphate ions, dihydrogen phosphate ions, acetate ions, and formate ions; preferably selected from chloride ions, bromide ions, and bisulfate ions.

[0021] In some embodiments, the phase transfer catalyst is selected from one or more of tetrabutylammonium bisulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride. The addition of the phase transfer catalyst in this application can increase the proportion of disulfide bridges between sulfide alkylphenols; effectively reduce the reaction temperature; reduce the content of free phenols in the final product; and improve the antioxidant properties of sulfide alkylphenol salts. Notably, tetrabutylammonium bisulfate does not contain chlorine, making it environmentally friendly.

[0022] In some embodiments, the preparation method further includes: S2. Add a second alkaline earth metal source, a carbonation reagent, and optional C to the first reaction product solution. 8-10 The fatty alcohol undergoes a second reaction to give a second reaction product liquid; after separation, a sulfurized alkylphenol salt is obtained.

[0023] The alkylphenol salt obtained only through step S1 has a low base value (typically in the range of 0-100 mg KOH / g); the alkylphenol salt obtained through step S2 has a higher base value due to the carbonation reaction. In some embodiments, the alkylphenol salt in step S2 has a base value of 50-350 mg KOH / g, preferably 100-300 mg KOH / g, more preferably 200-280 mg KOH / g, for example, 80 mg KOH / g, 150 mg KOH / g, 180 mg KOH / g, 200 mg KOH / g, 230 mg KOH / g, 250 mg KOH / g, or 300 mg KOH / g.

[0024] In some embodiments, the free phenol content of the sulfide alkylphenol salt in step S1 or S2 is less than 2%, preferably less than 1.6%, more preferably less than 1%, for example, 0.1%, 0.5%, 0.8%, 1%, 1.2%, or 1.4%.

[0025] In some embodiments, the sulfide alkylphenol salt in step S1 or S2 has an antioxidant time of more than 28 min at 210°C, preferably more than 30 min. For example, the antioxidant time can be 31 min, 32 min, 33 min, 34 min, 35 min, 36 min, 37 min, 38 min, 39 min, 40 min, 41 min, 42 min, 43 min, 44 min, or 45 min.

[0026] In some implementations, the C 8-16 Alkylphenols are C 8-16 Alkyl-substituted para-alkylphenols, wherein the alkyl group is a straight-chain or branched structure, preferably C16. 10-14 Alkylphenol, more preferably para-dodecylphenol. In some embodiments, the C 8-16 The alkylphenol is one or more selected from octylphenol, nonylphenol, decylphenol, dodecylphenol, tetradecylphenol, or hexadecylphenol; preferably, the C 8-16 The alkylphenol is one or more of para-octylphenol, para-nonylphenol, para-decylphenol, para-dodecylphenol, para-tetradecylphenol, or para-hexadecylphenol. It is well known in the art that the para-isomers of alkylphenols are conventional raw materials for preparing sulfurized alkylphenol salt detergents due to their excellent reactivity and thermal stability.

[0027] The term "first alkaline earth metal source" as used herein refers to a compound capable of providing alkaline earth metal ions, preferably a calcium or magnesium source, such as one or more of calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide. In some embodiments, the first alkaline earth metal source and the second alkaline earth metal source may be the same or different, and each may be independently selected from one or more of calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide.

[0028] In some embodiments, the diluent is selected from one or more of mineral base oils, aliphatic hydrocarbon solvents, cycloalkane solvents, and aromatic solvents, preferably one or more of 150N base oil, 6# base oil, 150SN base oil, n-hexane, n-heptane, cyclohexane, methylcyclohexane, Isopar E, Isopar G, toluene, or xylene; more preferably 150N base oil, 6# base oil, or 150SN base oil; and even more preferably 150N base oil. In some embodiments, the accelerator is water, C 1-6 fatty alcohols, C 2-6 One or more of the following fatty carboxylic acids, preferably one or more of water, methanol, ethanol, isopropanol, n-butanol, propylene glycol, glycerol, ethylene glycol, 1,4-butanediol, acetic acid, propionic acid or 2-ethylhexanoic acid, more preferably propylene glycol, glycerol, ethylene glycol or 1,4-butanediol.

[0029] In some embodiments, the vulcanizing agent is a compound that provides active sulfur, preferably sulfur.

[0030] 200 parts by weight of C 8-16 Based on alkylphenols, the mass fraction of the diluent is 150-250 parts, preferably 200 parts. In some embodiments, 200 parts by mass of C... 8-16 Based on alkylphenols, the mass fractions of the diluent are 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 205, 210, 215, 220, 225, 230, 235, 240, 245, or 250 parts.

[0031] 200 parts by weight of C 8-16 Based on alkylphenols, the mass fraction of the first alkaline earth metal source is 40-60 parts, preferably 45-52 parts. In some embodiments, 200 parts by mass of C 8-16 Based on alkylphenols, the mass fraction of the first alkaline earth metal source is 42, 44, 46, 48, 50, 52, 54, 56, 58, or 60 parts.

[0032] 200 parts by weight of C 8-16Based on alkylphenols, the accelerator comprises 6 to 18 parts by mass, preferably 8 to 15 parts. In some embodiments, 200 parts by mass of C 8-16 Based on alkylphenols, the mass fraction of the accelerator is 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 parts.

[0033] 200 parts by weight of C 8-16 Based on alkylphenols, the phase transfer catalyst comprises 3 to 18 parts by mass, preferably 5 to 10 parts. In some embodiments, 200 parts by mass of C 8-16 Based on alkylphenols, the mass fractions of the phase transfer catalyst are 3, 5, 7, 9, 11, 13, 15, or 17 parts.

[0034] 200 parts by weight of C 8-16 Based on alkylphenols, the vulcanizing agent comprises 20-60 parts by mass, preferably 30-40 parts. In some embodiments, 200 parts by mass of C... 8-16 Based on alkylphenols, the mass fraction of the vulcanizing agent is 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts.

[0035] In step S1, C is added to the reactor. 8-16 Alkylphenol, diluent, first alkaline earth metal source, accelerator, phase transfer catalyst, and sulfiding agent are added, followed by heating to carry out the first reaction. In some embodiments, the temperature is raised to 130-170°C, preferably to 140-160°C, and more preferably to 140-150°C. In some embodiments, the reaction time is 1-4 hours, preferably 1-3 hours, and more preferably 2 hours. In some embodiments, the reaction temperature is 130-170°C, preferably 140-160°C, and more preferably 140-150°C. In some embodiments, the first reaction is a sulfidation reaction.

[0036] In some embodiments, the second alkaline earth metal source is selected from those providing Ca 2+ or Mg 2+ The alkaline metal compound is preferably one or more of calcium hydroxide, calcium oxide, magnesium hydroxide, or magnesium oxide. In some embodiments, the carbonating agent is carbon dioxide. In some embodiments, C 8-10 The fatty alcohol is a saturated monohydric alcohol with a branched or straight-chain structure, preferably one or more of n-octanol, isooctanol, n-nonanol or n-decanol, with isooctanol being the most preferred.

[0037] 200 parts by weight of C 8-16 Based on alkylphenols, the second alkaline earth metal source comprises 40-80 parts by mass, preferably 50-70 parts, and more preferably 56-64 parts by mass. In some embodiments, 200 parts by mass of C... 8-16Based on alkylphenols, the mass fraction of the second alkaline earth metal source is 45, 50, 55, 60, 62, 65, 70, 75, or 80 parts.

[0038] 200 parts by weight of C 8-16 alkylphenols, C 8-10 The fatty alcohol is present in a mass fraction of 8 to 40 parts, preferably 10 to 20 parts. In some embodiments, 200 parts by mass of C... 8-16 alkylphenols, C 8-10 The fatty alcohols are available in parts by weight of 13, 15, 17, 21, 25, 30, or 35.

[0039] 200 parts by weight of C 8-16 Based on alkylphenols, the carbonating agent comprises 10 to 40 parts by mass, preferably 15 to 25 parts. In some embodiments, 200 parts by mass of C 8-16 Based on alkylphenols, the mass fractions of the carbonation reagent are 15, 20, 25, 30, or 35 parts.

[0040] In step S2, a second alkaline earth metal source, a carbonation reagent, and optional C are added to the first reaction product solution. 8-10 The fatty alcohol undergoes a second reaction to obtain a second reaction product liquid. In some embodiments, the reaction time is 1-4 hours, preferably 1-3 hours, and more preferably 2 hours. In some embodiments, the reaction temperature is 130-170°C, preferably 140-160°C, and more preferably 140-150°C.

[0041] In some embodiments, the reaction temperature of step S2 is the same as that of step S1. The reaction temperature is lower than that of a conventional reaction. In some embodiments, the reaction in step S2 is a carbonation reaction.

[0042] In step S1 or S2, after the reaction is complete, the solvent is removed, and the residue is filtered to obtain the sulfide alkylphenol salt. In some embodiments, the solvent is removed by distillation, preferably at a distillation temperature of 190°C.

[0043] The reactor is equipped with a stirrer, thermometer, condenser, heating device, and gas absorption device; preferably, it also includes a water separator. In some embodiments, the gas absorption device is an acidic gas absorption device; preferably, the gas absorption device is connected to an aqueous NaOH solution.

[0044] This invention provides a method for preparing sulfide alkylphenol salts, comprising the following steps: S1. Add C to the reactor 8-16Alkylphenol, diluent, first alkaline earth metal source, accelerator, phase transfer catalyst and sulfiding agent are subjected to a first reaction to obtain the first reaction product liquid; S2. Add a second alkaline earth metal source, a carbonation reagent, and optional C to the first reaction product solution. 8-10 The fatty alcohol undergoes a second reaction to give a second reaction product liquid; after separation, a sulfurized alkylphenol salt is obtained. The phase transfer catalyst is a quaternary ammonium salt compound comprising or composed of a quaternary ammonium cation and anion of Formula I. (R1)(R2)3N + Formula I Among them, R1 or R2 may be the same or different, and each is independently selected from C. 1-18 Alkyl; the C 1-18 Alkyl groups are optionally C 6-10 Aryl substitution. This invention utilizes a one-pot process, where sulfidation and carbonation reactions are carried out sequentially in the same reactor. Intermediates do not require separation and purification before proceeding to subsequent reactions, simplifying the operation process and reducing losses and contamination risks during material transfer.

[0045] The following embodiments are examples to illustrate the technical solution of the present invention: Example 1 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0046] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of tetrabutylammonium hydrogen sulfate, and 36 g of sulfur to a flask. Start stirring, heat to 160°C, maintain the temperature at 150-160°C, and react for 2 hours.

[0047] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and purge with 20 g of carbon dioxide. Maintain the reaction temperature at 150-160℃ and react for 2 h. After the reaction is complete, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0048] Example 2 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0049] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of tetrabutylammonium hydrogen sulfate, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 hours.

[0050] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0051] Example 3 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0052] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 10 g of tetrabutylammonium hydrogen sulfate, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 hours.

[0053] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0054] Example 4 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0055] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 12 g of tetrabutylammonium hydrogen sulfate, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 hours.

[0056] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0057] Example 5 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0058] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of dodecyltrimethylammonium chloride, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 h.

[0059] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0060] Example 6 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0061] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of tetradecyltrimethylammonium chloride, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 h.

[0062] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0063] Example 7 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0064] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of benzyltriethylammonium chloride, and 36 g of sulfur to a flask. Start stirring, heat to 140°C, maintain the temperature at 140-150°C, and react for 2 hours.

[0065] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0066] Example 8 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0067] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of tetrabutylammonium bromide, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 h.

[0068] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0069] Example 9 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0070] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of tetrabutylammonium chloride, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 h.

[0071] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0072] Example 10 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0073] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of trioctylmethylammonium chloride, and 36 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 hours.

[0074] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0075] Comparative Example 1 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0076] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 20 g of ethylene glycol, and 36 g of sulfur to a flask. Start stirring, heat to 160°C, maintain the temperature at 150-160°C, and react for 2 h.

[0077] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and purge with 20 g of carbon dioxide. Maintain the reaction temperature at 150-160℃ and react for 2 h. After the reaction is complete, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0078] Comparative Example 2 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0079] Add 220 g of p-dodecylphenol, 200 g of 150N base oil, 52 g of calcium hydroxide, 20 g of ethylene glycol, 8 g of tetrabutylammonium hydrogen sulfate, and 46 g of sulfur to a flask. Start stirring, heat to 140℃, maintain the temperature at 140-150℃, and react for 2 hours.

[0080] Add 82 g of calcium hydroxide (calcium hydroxide was added in three equal portions, one hour apart), 20 g of isooctanol, and 42 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 hours. After the reaction is complete, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the alkylphenol calcium sulfide product.

[0081] Comparative Example 3 A stirrer, thermometer, water separator, condenser, heating mantle, and gas absorption device connected to a 20 wt% NaOH aqueous solution are respectively mounted on a 1000 mL four-necked round-bottom flask.

[0082] Add 200 g of p-dodecylphenol, 200 g of 150N base oil, 48 g of calcium hydroxide, 12 g of ethylene glycol, 8 g of 18-crown ether-6, and 36 g of sulfur to a flask. Start stirring, heat to 140°C, maintain the temperature at 140-150°C, and react for 2 h.

[0083] Add 62 g of calcium hydroxide and 15 g of isooctyl alcohol, and introduce 20 g of carbon dioxide. Maintain the reaction temperature at 140-150℃ and react for 2 h. After the reaction is completed, raise the temperature to 190℃ to distill off the solvent, filter to remove residue, and obtain the sulfide alkylphenol calcium product.

[0084] Test Example 1 The performance of Examples 1-4 and Comparative Examples 1-2 was evaluated for its base number, viscosity, sulfur content, calcium content, free phenol content, and antioxidant time. Specifically, the base number was determined using GB / T4945-2002; viscosity using ASTM D2270; sulfur content using ASTM D1552; calcium content using ASTM D2894-73; free phenol content using HPLC; and antioxidant time using PDSC according to SH / T0719-2002.

[0085] The results are shown in Table 1.

[0086] Table 1

[0087] As shown in Table 1, compared with Comparative Example 1, the introduction of a quaternary ammonium salt phase transfer catalyst during the preparation of calcium alkylphenolate in this application significantly promotes the reaction, is more conducive to the formation of polymers, and the viscosity of the resulting calcium alkylphenolate is also improved. In Comparative Example 2, the high-base-value calcium alkylphenolate already has a high viscosity; adding a phase transfer catalyst would further increase the viscosity of the system, which is detrimental to process operation and product stability. In Comparative Example 3, the introduction of 18-crown ether-6 as a phase transfer catalyst during the preparation of calcium alkylphenolate resulted in a decrease in the antioxidant properties of the product. Therefore, the preparation method of this application is suitable for the preparation of medium- and low-base-value calcium alkylphenolate, but not for high-base-value calcium alkylphenolate. Using the preparation method of this application can lower the reaction temperature, resulting in lower levels of free phenol in the reaction product and a significant improvement in antioxidant properties.

[0088] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a sulfurized alkylphenol salt, characterized in that, Includes the following steps: S1. Add C to the reactor 8-16 Alkylphenol, diluent, first alkaline earth metal source, accelerator, phase transfer catalyst and sulfiding agent are subjected to a first reaction to obtain the first reaction product liquid; After separation, sulfide alkylphenol salts were obtained; The phase transfer catalyst is a quaternary ammonium salt compound comprising or composed of a quaternary ammonium cation and anion of Formula I. (R1)(R2)3N + Formula I Among them, R1 or R2 may be the same or different, and each is independently selected from C. 1-18 Alkyl; the C 1-18 Alkyl groups are optionally C 6-10 Aryl substitution.

2. The preparation method according to claim 1, characterized in that, R1 and R2 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl; wherein the methyl, ethyl, propyl, and butyl groups may be substituted with phenyl groups; Preferably, R1 is selected from methyl, ethyl, butyl, octyl, dodecyl, or tetradecyl; wherein methyl and ethyl can be substituted with phenyl; R2 is selected from methyl, ethyl, or butyl. More preferably, R1 is selected from methyl, ethyl, butyl, octyl, dodecyl, tetradecyl, or benzyl; and / or The anion is selected from chloride ion, bromide ion, bisulfate ion, sulfate ion, phosphate ion, dihydrogen phosphate ion, acetate ion, and formate ion; preferably selected from chloride ion, bromide ion, and bisulfate ion.

3. The preparation method according to claim 1, characterized in that, The C 8-16 The alkylphenol is selected from one or more of octylphenol, nonylphenol, decylphenol, dodecylphenol, tetradecylphenol, and hexadecylphenol; preferably, the C 8-16 Alkylphenol is one or more of para-octylphenol, para-nonylphenol, para-decylphenol, para-dodecylphenol, para-tetradecylphenol, or para-hexadecylphenol; and / or The diluting solvent is selected from one or more of mineral base oils, aliphatic hydrocarbon solvents, cycloalkane solvents, and aromatic solvents, preferably one or more of 150N base oil, 6# base oil, 150SN base oil, n-hexane, n-heptane, cyclohexane, methylcyclohexane, IsoparE, Isopar G, toluene, or xylene; more preferably 150N base oil, 6# base oil, or 150SN base oil; and / or The first alkaline earth metal source is selected from one or more of calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide; and / or The accelerator is water, C 1-6 fatty alcohols, C 2-6 One or more of the following fatty carboxylic acids, preferably one or more of water, methanol, ethanol, isopropanol, n-butanol, propylene glycol, glycerol, ethylene glycol, 1,4-butanediol, acetic acid, propionic acid, or 2-ethylhexanoic acid, more preferably propylene glycol, glycerol, ethylene glycol, or 1,4-butanediol; and / or The vulcanizing agent is a compound that provides active sulfur, preferably sulfur; and / or The phase transfer catalyst is selected from one or more of tetrabutylammonium bisulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.

4. The preparation method according to claim 1, characterized in that, 200 parts by weight of C 8-16 Alkylphenols The mass fraction of the diluent is 150-250 parts, preferably 200 parts; The mass fraction of the first alkaline earth metal source is 40 to 60 parts, preferably 45 to 52 parts; The accelerator is 6 to 18 parts by weight, preferably 8 to 15 parts by weight; The mass fraction of the phase transfer catalyst is 3 to 18 parts, preferably 5 to 10 parts; The mass fraction of the vulcanizing agent is 20 to 60 parts, preferably 30 to 40 parts.

5. The preparation method according to claim 1, characterized in that, In step S1, C is added to the reactor. 8-16 The first reaction is carried out by heating alkylphenol, diluent, first alkaline earth metal source, accelerator, phase transfer catalyst and sulfiding agent; Preferably, in step S1, the temperature is raised to 130~170°C, more preferably to 140~160°C, and even more preferably to 140~150°C; and / or In step S1, the reaction temperature is 130~170℃, preferably 140~160℃, more preferably 140~150℃; the reaction time is 1~4h, preferably 1~3h, more preferably 2h.

6. The preparation method according to claim 1, characterized in that, The preparation method further includes: S2. Add a second alkaline earth metal source, a carbonation reagent, and optional C to the first reaction product solution. 8-10 The fatty alcohol undergoes a second reaction to give a second reaction product liquid; after separation, a sulfurized alkylphenol salt is obtained. Preferably, the base value of the sulfide alkylphenol salt in step S2 is 50~350 mgKOH / g, more preferably 100~300 mgKOH / g, and even more preferably 200~280 mgKOH / g.

7. The preparation method according to claim 6, characterized in that, The second alkaline earth metal source is selected from one or more of calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide; and / or The first alkaline earth metal source and the second alkaline earth metal source may be the same or different; and / or C 8-10 Fatty alcohols are selected from n-octanol, isooctanol, n-nonanol, or n-decanol, preferably isooctanol; and / or The carbonation reagent is carbon dioxide.

8. The preparation method according to claim 6, characterized in that, 200 parts by weight of C 8-16 Alkylphenols C 8-10 The fatty alcohol is 8 to 40 parts by mass, preferably 10 to 20 parts by mass; The mass fraction of the second alkaline earth metal source is 40 to 80 parts, preferably 50 to 70 parts, and more preferably 56 to 64 parts. The carbonation reagent is present in parts by weight of 10 to 40, preferably 15 to 25.

9. The preparation method according to claim 6, characterized in that, In step S2, the reaction time is 1-4 hours, preferably 1-3 hours, and more preferably 2 hours; the reaction temperature is 130-170°C, preferably 140-160°C, and more preferably 140-150°C.

10. The preparation method according to claim 6, characterized in that, The reaction temperature in step S2 is the same as the reaction temperature in step S1; and / or In step S2, after the reaction is complete, the solvent is removed, and the residue is filtered out to obtain sulfide alkylphenol salt.

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