CN104560281B - Sulfonate, preparation method thereof, lubricating grease containing sulfonate and preparation method of lubricating grease - Google Patents

Abstract

The invention provides a sulfonate, a preparation method thereof, a lubricating grease containing the sulfonate and a preparation method thereof. The structure of sulfonate of the present invention is: Among them, M ₁ , M ₂ , and M ₃ are single metals or mixed metals in alkali metals and alkaline earth metals, n ₁ , n ₂ , and n ₃ are the valences of M ₁ , M ₂ , and M ₃ respectively, and x, y, and z are integers between 1 and 4, R ₁ , R ₂ , and R ₃ are each an alkyl group, and the sum of the carbon number in the R ₁ alkyl group and x is 8 to 28, and the carbon number in the R ₂ alkyl group is equal to The sum of y is 7~27, the sum of the carbon number in R ₃ alkyl and z is 9~29, R ₄ and R ₅ are respectively C ₅ ~C ₃₀ alkyl, e, q, r, u are respectively An integer between 1 and 10000, and t is an integer between 0 and 10000. The obtained sulfonate has a high alkali value and is especially suitable for preparing lubricating grease. When preparing grease, the amorphous carbonate is completely converted into crystalline carbonate, and the conversion time is short. The converted sulfonate grease has excellent high temperature, water resistance, colloidal stability, and anti-wear properties.

Description

Sulfonate, method for its preparation, grease containing the same and method for its preparation

technical field

The invention relates to a sulfonate, in particular to a high alkalinity sulfonate suitable for lubricating grease.

Background technique

Composite calcium sulfonate-based grease is a new type of grease, which has excellent extreme pressure performance, anti-wear performance, water resistance, salt spray resistance and corrosion resistance, and has a high dropping point and good thermal stability. It is widely used Used in automobile, steel, mining, paper making and other industries.

Composite calcium sulfonate-based lubricating grease uses Newtonian calcium sulfonate as raw material, which is transformed into non-Newtonian calcium sulfonate in the presence of active hydrogen. Among them, the calcium carbonate in the Newtonian calcium sulfonate is amorphous, and the calcium carbonate in the composite calcium sulfonate-based grease is calcite type, so the process of preparing the grease is actually to make the amorphous calcium sulfonate in the Newtonian calcium sulfonate The process of converting calcium carbonate into calcite-type calcium carbonate and finally forming non-Newtonian calcium sulfonate, therefore, it is very important to choose a suitable Newtonian calcium sulfonate.

There are many patents on the preparation of high-basic calcium sulfonate and ultra-high-basic calcium sulfonate for Newtonian body, such as US4,427,559, US4,604,219, US4,879,053, US4,929,373, US4,810,396, EP0,515,062, EP0 , 949,322, US6,015,778, US4,560,489, etc., the preparation method is generally: using alkylbenzenesulfonic acid or calcium alkylbenzenesulfonate as raw material, using various low-molecular alcohols as accelerators, passing carbon dioxide into carbonic acid After the reaction is completed, the temperature is raised to dehydrate, and after the post-treatment, the calcium sulfonate with high alkali value is obtained. The high base value calcium sulfonate (base value greater than 300mgKOH/g) and super high base value calcium sulfonate (base value greater than 395mgKOH/g) in the above patents are mainly used in internal combustion engine oil and industrial oil for solubilization , Dispersion, neutralization, anti-rust and other functions.

Calcium sulfonate in lubricating grease requires the calcium carbonate in calcium sulfonate to be amorphous and easy to transform under certain conditions. The resulting lubricating grease has good high and low temperature performance, extreme pressure and anti-wear properties, colloidal stability and water resistance. The calcium sulfonate used in lubricating oil requires excellent detergency, dispersibility and acid neutralization performance. The two products have different requirements for calcium sulfonate. Therefore, there will be some problems in the preparation of lubricating grease with the existing Newtonian calcium sulfonate used in lubricating oil, such as: slow conversion rate of calcium sulfonate or conversion effect Not good, the high temperature performance and other properties of the converted grease cannot meet the requirements, which limits the further application of calcium sulfonate in grease.

Contents of the invention

The invention provides a sulfonate, a preparation method thereof, a lubricating grease containing the sulfonate and a preparation method thereof.

The structure of sulfonate of the present invention is:

Among them, M ₁ , M ₂ , and M ₃ are single metals or mixed metals in alkali metals and alkaline earth metals, n ₁ , n ₂ , and n ₃ are the valences of M ₁ , M ₂ , and M ₃ respectively, and x, y, and z are integers between 1 and 4, R ₁ , R ₂ , and R ₃ are each an alkyl group, and the sum of the carbon number in the R ₁ alkyl group and x is 8 to 28, and the carbon number in the R ₂ alkyl group is equal to The sum of y is 7~27, the sum of the carbon number in R ₃ alkyl and z is 9~29, R ₄ and R ₅ are respectively C ₅ ~C ₃₀ alkyl, e, q, r, u are respectively An integer between 1 and 10000, and t is an integer between 0 and 10000.

The M ₁ , M ₂ , and M ₃ can be the same or different, preferably alkaline earth metals, most preferably one or more of magnesium, calcium, and barium; n ₁ , n ₂ , and n ₃ are respectively M ₁ , The valence of M ₂ and M ₃ is 1 to 2, preferably 2;

x, y, and z are integers between 1 and 4, preferably 2 or 3;

R ₁ , R ₂ , and R ₃ are alkyl groups, and the sum of the carbon number in the alkyl group of R ₁ and x is 8-28, the sum of the carbon number in the alkyl group of R ₂ and y is 7-27, and R ₃ The sum of the carbon number and z in the alkyl group is 9-29, preferably the sum of the carbon number and _x in the R1 alkyl group is 10-18, the sum of the carbon number and y in the R2 alkyl group is _9-17 , The sum of the carbon number and z in the _R3 alkyl group is 11-19;

R ₄ and R ₅ are respectively C ₅ -C ₃₀ alkyl groups, preferably C ₁₀ -C ₃₀ alkyl groups;

e, q, r, u are respectively an integer between 1-10000, preferably an integer between 1-1000; t is an integer between 0-10000, preferably an integer between 1-1000.

The preparation method of sulfonate of the present invention is:

(1) C ₁₀ ~ C ₃₀ α olefin undergoes sulfonation reaction with sulfonating agent to generate C ₁₀ ~ C ₃₀ sulfonic acid and sultone, and then undergoes neutralization reaction with alkali metal and/or alkaline earth metal hydroxide , collecting the resulting mixture of alkali metal and/or alkaline earth metal salts of C ₁₀ to C ₃₀ sulfonic acids and sultones;

(2) neutral oil, hydrocarbon solvent, C ₁ -C ₄ alcohol, calcium oxide, water, alkali metal and/or alkaline earth metal salt of C ₁₀ -C ₃₀ sulfonic acid in step (1) and sultone The mixture and optional alkali metal and/or alkaline earth metal salts of C ₅ ~C ₃₀ alkylbenzene sulfonic acid are mixed, carbon dioxide is introduced, carbonation reaction is carried out under the pressure of 0.4MPa ~ 2.0MPa, and alcohol, water and hydrocarbon are removed Solvent-like and solid residues to obtain sulfonate products.

In step (1), the C ₁₀ -C ₃₀ alpha olefin is preferably a C ₁₀ -C ₃₀ straight chain alpha olefin, most preferably a C ₁₂ -C ₂₀ straight chain alpha olefin;

The sulfonating agent is one or more of sulfur trioxide, concentrated sulfuric acid and oleum, preferably sulfur trioxide;

The molar ratio of the sulfonating agent to the C ₁₀ -C ₃₀ α-olefin is: 1.0-1.5:1, preferably 1.05-1.1:1;

The temperature of the sulfonation reaction is 0-60°C, preferably 20-40°C; the reaction time is 1-10 hours, preferably 1-4 hours;

A solvent may be added to the sulfonation reaction, such as petroleum ether, benzene, toluene, preferably a solvent.

The C ₁₀ -C ₃₀ α-olefin undergoes a sulfonation reaction with a sulfonating agent to generate a mixture of C ₁₀ -C ₃₀ sulfonic acid and sultone, and the C ₁₀ -C ₃₀ sulfonic acid includes alkenyl monosulfonic acid , alkenyl disulfonic acid, the C ₁₀ -C ₃₀ sultones include monosultone and disultone.

Take the sulfonation reaction of sulfur trioxide and C ₁₈ α-olefin as an example, the two react to form a mixture of alkenyl monosulfonic acid, monosulfonic acid and a small amount of alkenyl disulfonic acid, disulfonic acid.

An exemplary equation for the sulfonation reaction is:

CH ₃ (CH ₂ ) ₁₅ CH=CH ₂ +SO ₃ →CH ₃ (CH ₂ ) ₁₃ CH ₂ CH=CHCH ₂ SO ₃ H

(Formation of alkenyl-sulfonic acid)

In the sulfonation reaction and/or neutralization reaction described in step (1), neutral oil may or may not be added, and neutral oil is preferably added. The neutral oil is preferably lubricating base oil with kinematic viscosity at 100°C of 2-6 mm ² /s, most preferably one or more of 100SN, 150SN, 100N and 150N.

The neutralization reaction in step (1) is to neutralize C ₁₀ -C ₃₀ sulfonic acid and sultone with alkali metal and/or alkaline earth metal hydroxide, and collect the generated C ₁₀ -C ₃₀ sulfonic acid Mixtures of alkali metal and/or alkaline earth metal salts of acids and sultones and preferably added neutral oils. The number of moles of the alkali metal and/or alkaline earth metal hydroxide is 1.2 to 2 times the number of moles of the C ₁₀ to C ₃₀ α-olefin, the reaction temperature is 50°C to 70°C, and the reaction time is 10 to 40 minutes . The hydroxide of described alkali metal and/or alkaline earth metal can be single hydroxide, also can be mixed hydroxide, the hydroxide of preferred alkaline earth metal, most preferably in magnesium hydroxide, calcium hydroxide and barium hydroxide one or more of.

The neutralization reaction described in step (1) may also first neutralize the C ₁₀ -C ₃₀ sulfonic acid and sultone with the hydroxide of the alkali metal to generate the alkali metal salt of the C ₁₀ -C ₃₀ sulfonic acid and The sultone undergoes metathesis reaction with the soluble alkaline earth metal salt, and the resulting mixture of alkali metal and/or alkaline earth metal salt of C ₁₀ -C ₃₀ sulfonic acid and sultone and preferably added neutral oil is collected. The condition for the neutralization reaction between the C ₁₀ -C ₃₀ sulfonic acid and sultone and the alkali metal hydroxide is: the molar number of the alkali metal hydroxide is equal to that of the C ₁₀ -C ₃₀ α-olefin 1.2 to 2 times the number of moles, the reaction temperature is 50°C to 70°C, and the reaction time is 10 to 40 minutes. The conditions of the metathesis reaction are: the number of moles of the soluble alkaline earth metal salt is 0.3-2.0 times the number of moles of the C ₁₀ -C ₃₀ α-olefin, the reaction temperature is 60-90°C, and the reaction time is 1-4 hours . The soluble alkaline earth metal salt is preferably one or more of calcium chloride, magnesium chloride, barium chloride, calcium nitrate, magnesium nitrate and barium nitrate.

After the neutralization reaction described in step (1) is completed, the reaction product is preferably washed with water and filtered to obtain more pure alkali metal and/or alkaline earth metal salts and sultones of C ₁₀ to C ₃₀ sulfonic acids and preferably added mixture of neutral oils.

An example equation for the neutralization reaction is:

CH ₃ (CH2) ₁₃ CH ₂ CH=CHCH ₂ SO ₃ H+NaOH→CH ₃ (CH ₂ ) ₁₃ CH ₂ CH=CHCH ₂ SO ₃ Na+H ₂ O

(Sodium salt of alkenyl monosulfonic acid to monosulfonic acid)

An exemplary equation for the metathesis reaction is:

2CH ₃ (CH ₂ ) ₁₃ CH ₂ CH=CHCH ₂ SO ₃ Na+CaCl ₂ →(CH ₃ (CH ₂ ) ₁₃ CH ₂ CH=CHCH ₂ SO ₃ ) ₂ Ca+2NaCl

(sodium salt of monosulfonic acid generates calcium salt of monosulfonic acid)

In step (2), the neutral oil preferably added in step (1) is a lubricating base oil with a kinematic viscosity of 2-6mm ² /s at 100°C, most preferably 100SN, 150SN, 100N and One or more of 150N;

The hydrocarbon solvent can be alkanes or aromatic hydrocarbons, preferably alkanes and/or aromatic hydrocarbons with a distillation range of 60°C to 180°C, most preferably n-octane, benzene, toluene, xylene and a distillation range of 60°C to 180°C. One or more of 180°C straight-run gasoline;

The C ₁ -C ₄ alcohol can be selected from one or more of methanol, ethanol, propanol, butanol and ethylene glycol, preferably a mixture of methanol and C ₃ -C ₄ alcohol, and the methanol and C ₃ -C The mass ratio of ₄ alcohols is 2:1-10:1, preferably 2:1-4:1. In the method of the present invention, the C ₁ -C ₄ alcohol can make the mass transfer rate between the gas, liquid and solid phases in the reaction mixture faster, and the oil phase and the water phase are mixed uniformly, so that the reaction is easy to carry out;

In step (2), the alkali metal and/or alkaline earth metal salt of C ₅ ~C ₃₀ alkylbenzene sulfonic acid may be added, or the alkali metal and/or alkaline earth metal salt of C ₅ ~C ₃₀ alkylbenzene sulfonic acid may not be added Salts, preferably alkali metal and/or alkaline earth metal salts of C ₅ -C ₃₀ alkylbenzenesulfonic acids.

The structure of the alkali metal and/or alkaline earth metal salt of C ₅ -C ₃₀ alkylbenzene sulfonic acid is:

Wherein M3 is alkali metal and/or alkaline earth metal, n3 is the valence _of alkali metal and/or alkaline earth metal, one _{of R4} and R5 is _C5 ～ _{C30 alkyl} , the other is H or both Both are C ₅ -C ₃₀ alkyl groups, R ₄ , R ₅ preferably one of them is a C ₁₀ -C ₃₀ alkyl group, the other is H, or both are C ₁₀ -C ₃₀ alkyl groups.

The alkali metal and/or alkaline earth metal salt of C ₅ -C ₃₀ alkylbenzene sulfonic acid is obtained by neutralizing the hydroxide of C ₅ -C ₃₀ alkylbenzene sulfonic acid and alkali metal and/or alkaline earth metal The preparation method is to neutralize the two at 70°C to 100°C, react for 1 to 3 hours, then raise the temperature to remove the water generated by the reaction, and filter to obtain C ₅ to C ₃₀ alkylbenzene sulfonic acid Alkali metal and/or alkaline earth metal salts, neutral oil is preferably added to the reaction to prepare a mixture of alkali metal and/or alkaline earth metal salts of C ₅ -C ₃₀ alkylbenzenesulfonic acid and neutral oil.

The C ₅ -C ₃₀ alkylbenzene sulfonic acid can be selected from C ₂₀ -C ₂₈ alkylbenzene sulfonic acid and/or high boiler sulfonic acid with C ₅ -C ₂₄ carbon number, and the C ₂₀ -C ₂₈ sulfonic acid _The acid can be alkylbenzene sulfonic acid obtained by benzene alkylation reaction of C ₂₀ ~C _{28 α} olefins, and then sulfonation reaction with sulfonating agent. Acid is a by-product high boiler sulfonic acid obtained during the production of dodecylbenzene. The carbon number of this high boiler sulfonic acid is C ₅ ~ C ₂₄ , mainly containing dialkylbenzenesulfonic sulfonic acid.

When the alkali metal and/or alkaline earth metal salt of C ₅ ~C ₃₀ alkylbenzene sulfonic acid is added in step (2), the alkali metal and/or alkaline earth metal salt of C ₁₀ ~C ₃₀ sulfonic acid in the step (1) The ratio of the mixture of metal salt and sultone to the alkali metal and/or alkaline earth metal salt of C ₅ -C ₃₀ alkylbenzene sulfonic acid is 0.3-3:1-3, preferably 0.3-1:1- 2.

In step (2), the mixture of alkali metal and/or alkaline earth metal salt of C ₁₀ ~C ₃₀ sulfonic acid and sultone and optional C ₅ ~C ₃₀ alkylbenzenesulfonate in step (1) The amount of acid alkali metal and/or alkaline earth metal salt is calculated as 100 parts, and the total amount of neutral oil is 50 to 400 parts, preferably 100 to 200 parts, including the preparation of C ₁₀ to C ₃₀ sulfur in step (1). The neutral oil preferably added when alkali metal and/or alkaline earth metal salts of acids and sultones and the neutral oil preferably added when preparing alkali metal and/or alkaline earth metal salts of C ₅ -C ₃₀ alkylbenzene sulfonic acids ; The consumption of C ₁ -C ₄ alcohol is 20-200 parts, preferably 30-100 parts; the consumption of hydrocarbon solvent is 50-1000 parts, preferably 100-500 parts; the consumption of the calcium oxide is 50-400 parts parts, preferably 50 to 100 parts; the amount of water used is 10 to 150 parts, preferably 10 to 50 parts.

In step (2), the number of moles of carbon dioxide introduced is 50% to 120% of the number of moles of calcium oxide, preferably 80% to 100%; the temperature of the carbonation reaction is 50°C to 200°C, preferably 80 ℃～180℃; the reaction pressure is 0.4MPa～2.0MPa, preferably 0.5MPa～1.5MPa.

In step (2), the sultone will be hydrolyzed into alkenyl sulfonic acid and hydroxy sulfonic acid, and react with calcium oxide and water to generate alkenyl sulfonate and hydroxy sulfonate, and these sulfonates will be combined with step (1) Alkali metal and/or alkaline earth metal salts of C ₁₀ to C ₃₀ sulfonic acids and optional alkali metal and/or alkaline earth metal salts of C ₅ to C ₃₀ alkylbenzene sulfonic acids are coated around calcium carbonate . After the carbonation reaction is completed, the temperature is raised to remove the solvent, and the solid slag is separated to obtain the sulfonate of the present invention.

An exemplary equation for the hydrolysis reaction of the sultones to form alkenyl sulfonates and hydroxy sulfonates is:

An exemplary equation for preparing the sulfonate of the present invention in step (2) is:

Ca(OH) ₂ +CO ₂ →CaCO ₃ +H ₂ O

The lubricating grease of the present invention comprises the above-mentioned sulfonate and lubricating base oil, the mass ratio of the sulfonate and lubricating base oil is 30-70:70-30, preferably 40-60:60-40. Other additives such as antioxidants, thickeners, and anti-wear agents can also be added to the grease. The lubricating base oil can be selected from one or more of API I, II, III, IV, V class lubricating base oils, preferably one or more of API I, II, III class lubricating base oils, most preferably 90BS, 120BS, 150BS.

The preparation method of described lubricating grease is:

Mix the lubricating base oil and the sulfonate of the present invention at 100-150°C, and at the same time carry out infrared detection on the calcium carbonate in the sulfonate, when its infrared absorption peak gradually shifts from 863.1cm ^-1 to 881.5cm ^-1 At this time, it can be considered that the calcium carbonate coated in the sulfonate is gradually transformed from amorphous to calcite crystal, and the grease product is collected after the transformation is complete.

The prepared grease product is non-Newtonian.

The high alkalinity sulfonate in the prior art is mainly used in internal combustion engine oil and industrial oil, and plays effects such as solubilizing, dispersing, neutralizing, antirust, and there will be some problems when using it to synthesize lubricating grease, as The conversion speed of Newtonian sulfonate is slow or the conversion effect is not good, and the performance of the converted lubricating grease is not good.

The obtained sulfonate has a high alkali value and is especially suitable for preparing lubricating grease. When preparing grease, the amorphous carbonate is completely converted into crystalline carbonate, and the conversion time is short. The converted sulfonate grease has excellent high temperature, water resistance, colloidal stability, and anti-wear properties.

detailed description

The present invention is further illustrated by examples below, but the present invention is not limited.

Unless otherwise specified, the percentages mentioned below are all percentages by mass.

Analytical method used:

Analysis of sulfonic acid composition: 1) HP6890 gas chromatography (Agilent), HP-5 column, FID detector, injection temperature: 300°C, split ratio 10:1; 2) Waters liquid chromatography, C8 silica gel column, The mobile phase is n-octane, and the detector is an ultraviolet detector and a parallax refraction detector 2414.

Olefin content analysis: NMR spectrometer, model: INOVA500, Varian Corporation, USA.

Sulfonic acid content analysis: Determination of sulfonic acid content in alkylbenzene sulfonic acid (RIPP48-90).

Product base value analysis: SH/T0251 Determination of base value of petroleum products (perchloric acid potentiometric titration method).

Product Viscosity Analysis: GB/T265 Petroleum Products Kinematic Viscosity Measurement Method and Dynamic Viscosity Calculation Method.

Raw materials used: 60～90℃ petroleum ether, sulfur trioxide, sodium hydroxide, No. 120 solvent gasoline, xylene, methanol, isopropanol, n-butanol, isobutanol, distilled water, calcium oxide, carbon dioxide, C ₁₈ α Olefins, C ₁₂ ～C ₁₈ α olefins, high boiler calcium sulfonate, C ₂₀ ～C ₂₈ calcium alkylbenzene sulfonate, 150SN, 150N, 150BS neutral oil.

The preparation of embodiment 1C ₁₈ alpha olefin sulfonate calcium

Add 101 grams of C ₁₈ α-olefin (molecular weight 252, 0.397 mol, purchased from Chevron, purity 99%) and 100 grams of petroleum ether (60-90°C) into a 1000-mL three-necked flask equipped with stirring and cooling and heating devices. A solution is formed, and then 34.94 grams of sulfur trioxide gas sulfonating agent (0.437 mol) is introduced. At this time, a sulfonation reaction occurs and the exotherm is violent. The reaction temperature is controlled at 30°C to 35°C. React for 2 hours to generate mixtures of alkenyl monosulfonic acid, monosulfonic acid, alkenyl disulfonic acid and disulfonic acid.

After the sulfonation reaction is completed, add 64 grams of 30% sodium hydroxide solution to the sulfonic acid-petroleum ether solution for neutralization reaction, which contains 0.48 mol of sodium hydroxide, and the reaction temperature is 60 ° C, and the reaction is carried out for 20 minutes. Alkenyl sulfonic acid generates sodium alkenyl sulfonate. After the reaction, the temperature is lowered to 40°C, and the material is discharged. Put it into a separatory funnel to separate the water layer, and obtain about 229 grams of a light yellow oil layer, which is transferred to a 1000mL tank with stirring and temperature control. In the three-necked flask, add 40 grams of 150SN neutral oil, stir evenly, add 200 grams of 20% calcium chloride solution, which contains 0.36 mol of calcium chloride, control the reaction temperature at 70 ° C, react for 2 hours, and wash with distilled water for two Second, the solution is layered and left to stand, the water layer is separated, the oil layer is retained, and then the oil layer is distilled out of sherwood oil to obtain a total of 174.5 grams of the mixture of C ₁₈ alpha olefin sulfonate calcium and sultone and neutral oil, wherein the active substance The content is 77.1%, and the active substance contains 48% calcium salt of alkenyl monosulfonic acid, 49% monosultone, 2% calcium salt of alkenyl disulfonic acid and 1% disulfone.

Example 2 Preparation of C ₁₂ -C ₁₈ α-olefin sulfonate calcium

Add 100 grams of C ₁₂ ~ C ₁₈ α-olefins (average molecular weight 224, 0.393 mol, purchased from Lanzhou Lubrizol Additive Company, purity 88%) into a 1000 mL three-neck flask with a stirring and cooling device, first add 90 grams of petroleum Ether (90-120°C), stirred to form a solution, and then passed 34.58 grams of sulfur trioxide gas sulfonating agent (0.432mol), at this time the sulfonation reaction occurred, exothermic violent, control the reaction temperature at 30-35°C, At this time, the sulfonation reaction between sulfur trioxide and α-olefins generates alkenyl monosulfonic acid, monosulfonic acid, alkenyl disulfonic acid, disulfonic acid and other mixtures.

After the sulfonation reaction is over, add 75 grams of 25% sodium hydroxide solution to the sulfonic acid-petroleum ether solution to carry out neutralization reaction, which contains 0.47mol of sodium hydroxide, and the reaction temperature is controlled at 60°C for 10 minutes. Alkenyl sulfonic acid generates sodium alkenyl sulfonate. After the reaction finishes, put it into a separatory funnel and separate the water layer to obtain about 213 grams of the light yellow oil layer, which is transferred to a 1000 mL three-necked flask with stirring and temperature control. Add 39 grams of 150N neutral oil, stir evenly, add 267 grams of 15% calcium chloride solution, which contains 0.36 moles of calcium chloride, control the reaction temperature at 70 ° C, react for 2 hours, wash with distilled water twice after reaction Finally, separate the water layer, retain the oil layer, and then distill the oil layer to remove petroleum ether to obtain a total of 174.1 grams of a mixture of C ₁₂ ~ C ₁₈ α olefin sulfonate calcium and sultone and neutral oil, in which the active substance content is 77.6 %, the active substance contains 49% calcium salt of alkenyl monosulfonic acid, 47% monosultone, 2.6% calcium salt of alkenyl disulfonic acid and 1.4% disulfone.

Example 3

Preparation of overbasic value calcium sulfonate from high boiler calcium sulfonate, C ₁₈ α olefinic calcium sulfonate and sultone

Add 34 grams of 150SN neutral oil (produced by Sinopec Yanshan Petrochemical Company), 100 grams of No. 120 solvent gasoline (industrial product), and 20 grams of methanol into a 500-ml autoclave equipped with a motor stirrer and temperature control facilities. 5 grams of n-propanol, 10 grams of distilled water, 37 grams of calcium oxide, 50 grams of a mixture of high-boiler calcium sulfonate and neutral oil (prepared from high-boiler sulfonic acid, calcium hydroxide and 150SN neutral oil, wherein The content of calcium sulfonate is 61.6%), the product that embodiment 1 obtains (contains the mixture of C ₁₈ alpha olefin sulfonate calcium and sultone and neutral oil, active matter content 77.1%) 16 grams, be warming up to 145 ℃ , feed carbon dioxide, and control the reaction pressure at 0.9-1.2MPa. When the carbon dioxide absorption reaches 92% of the molar number of calcium oxide, stop the ventilation, lower the pressure, and then raise the temperature to 120°C for dealcoholization and water. Add 100 milliliters of gasoline to the material obtained, then put it into a medical centrifuge, and centrifuge at a speed of 4000rpm, put the centrifuged flash product into a distillation bottle with a decompression facility, first heat up to 120°C for atmospheric distillation, and then Distilled under reduced pressure to finally obtain 149 g of brown viscous calcium sulfonate product, the product has a base number of 398 mgKOH/g and a kinematic viscosity of 100°C of 167 mm ² /s.

Example 4

Preparation of calcium sulfonate with high base value from C ₂₀ ～C ₂₈ calcium alkylbenzene sulfonate, C ₁₂ ～C ₁₈ calcium α-olefin sulfonate and sultone

In a 500 ml autoclave equipped with a motor stirrer and temperature control facilities, add 28 grams of 150N neutral oil (produced by Sinopec Shanghai Gaoqiao Petrochemical Company), add 150 ml of xylene (chemically pure), 16 grams of methanol, and 8 grams of butanol, 38 grams of calcium oxide, 12 grams of distilled water, 51 grams of a mixture of _C20 - _C28 alkylbenzene sulfonate calcium and neutral oil (prepared from alkylbenzene sulfonic acid, calcium hydroxide and neutral oil) obtained, wherein the content of calcium sulfonate is 61.8%), the product obtained in Example 2 (C ₁₂ ~ C ₁₈ α olefin sulfonate calcium and sultone and neutral oil mixture, active matter content 77.6%) 21 grams , raise the temperature to 146°C, feed carbon dioxide, and control the reaction pressure at 0.9-1.1MPa. When the carbon dioxide absorption reaches 91% of the molar number of calcium oxide, stop the aeration, lower the pressure, and then raise the temperature to 120°C for dealcoholization and water. Add 100 milliliters of gasoline to the material obtained, then put it into a medical centrifuge, and centrifuge at a speed of 4000rpm, put the centrifuged flash product into a distillation bottle with a decompression facility, first heat up to 120°C for atmospheric distillation, and then The system was distilled under reduced pressure to finally obtain 147 grams of tan viscous calcium sulfonate, the alkali value of the product was 396 mgKOH/g, and the kinematic viscosity of the product at 100°C was 171 mm ² /s.

Example 5

Preparation of high-basic calcium sulfonate from high-boiler calcium sulfonate, C ₁₂ ～C ₁₈ α-olefin sulfonate calcium and sultone

Add 33 grams of 150SN neutral oil (produced by Sinopec Yanshan Petrochemical Company), 100 grams of No. 120 solvent gasoline (industrial product), and 24 grams of methanol into a 500-milliliter autoclave equipped with a motor stirrer and temperature control facilities. 6 grams of isobutanol, 12 grams of distilled water, 39 grams of calcium oxide, 44 grams of a mixture of high boiling calcium sulfonate and neutral oil (prepared from alkylbenzene sulfonic acid, calcium hydroxide and neutral oil, wherein sulfonate Calcium acid calcium content is 61.6%), the product that embodiment 2 obtains (C ₁₂ ～C ₁₈ α olefin sulfonate calcium and sultone and the mixture of neutral oil, active substance content 77.6%) 21 grams, heat up after adding To 138°C, feed carbon dioxide, and control the pressure of the reactor at 0.9-1.2MPa. When the carbon dioxide absorption reaches 93% of the molar number of calcium oxide, stop the ventilation, and then raise the temperature to 120°C to deal with alcohol and water. Add 100 milliliters of gasoline to the material obtained, then put it into a medical centrifuge, and centrifuge at a speed of 4000rpm, put the centrifuged flash product into a distillation bottle with a decompression facility, first heat up to 120°C for atmospheric distillation, and then Distilled under reduced pressure to finally obtain 151 g of brown viscous calcium sulfonate product, the product has a base value of 392 mgKOH/g and a kinematic viscosity at 100°C of 158 mm ² /s.

Example 6 Preparation of calcium sulfonate with high basic value by using C ₁₈ calcium α-olefin sulfonate and sultone as raw materials

Add 44 grams of 150SN neutral oil (manufactured by Sinopec Yanshan Petrochemical Company), 100 grams of No. 120 solvent gasoline (industrial product), and 20 grams of methanol into a 500 ml autoclave equipped with a motor stirrer and temperature control facilities. 5 grams of n-propanol, 10 grams of distilled water, 37 grams of calcium oxide, 56 grams of the product obtained in Example 1 (C ₁₈ alpha olefin sulfonate calcium and sultone and neutral oil mixture, active matter content 77.1%), Raise the temperature to 145°C, feed carbon dioxide, and control the reaction pressure at 0.9-1.2MPa. When the carbon dioxide absorption is 92% of the molar number of calcium oxide, stop the ventilation, lower the pressure, and then raise the temperature to 120°C for dealcoholization and water. Add 100 milliliters of gasoline to the material obtained, then put it into a medical centrifuge, and centrifuge at a speed of 4000rpm, put the centrifuged flash product into a distillation bottle with a decompression facility, first heat up to 120°C for atmospheric distillation, and then Distill under reduced pressure to finally obtain 139 grams of tan viscous calcium sulfonate, the alkali value of the product = 337 mgKOH/g, and the kinematic viscosity of the product at 100°C = 159 mm ² /s.

Comparative example 1,2 repeat the operation of embodiment 3 respectively, just do not add the product that embodiment 1 obtains in the comparative example 1, comparative example 2 is that the carbonation reaction takes place under normal pressure and prepares calcium sulfonate with high alkalinity.

Comparative example 1 prepares high alkali value calcium sulfonate with high boiler calcium sulfonate as raw material

Add 34 grams of 150SN neutral oil (produced by Sinopec Yanshan Petrochemical Company), 100 grams of No. 120 solvent gasoline (industrial product), and 20 grams of methanol into a 500-ml autoclave equipped with a motor stirrer and temperature control facilities. 5 grams of n-propanol, 10 grams of distilled water, 37 grams of calcium oxide, 66 grams of a mixture of high-boiler calcium sulfonate and neutral oil (prepared from high-boiler sulfonic acid, calcium hydroxide and neutral oil, wherein sulfonate The content of calcium oxide is 65.8%), the temperature is raised to 145 ° C, carbon dioxide is introduced, and the reaction pressure is controlled at 0.9-1.2 MPa. When the carbon dioxide absorption is 92% of the molar number of calcium oxide, the ventilation is stopped, the pressure is reduced, and then Heat up to 120°C to dealcoholize and water. Add 100 milliliters of gasoline to the material obtained, then put it into a medical centrifuge, and centrifuge at a speed of 4000rpm, put the centrifuged flash product into a distillation bottle with a decompression facility, first heat up to 120°C for atmospheric distillation, and then Distilled under reduced pressure to finally obtain 150 g of tan viscous calcium sulfonate, the product's base value = 403 mgKOH/g, product 100 ° C kinematic viscosity = 175 mm ² /s.

Comparative example 2

Preparation of Calcium Sulfonate Using High Boiler Calcium Sulfonate, Calcium C ₁₈ α-Alkenyl Sulfonate and Sultone as Raw Materials at Normal Pressure

Add 34 grams of 150SN neutral oil (produced by Sinopec Yanshan Petrochemical Company), 100 grams of No. 120 solvent gasoline (industrial product), and 20 grams of methanol to a 500 ml three-neck flask equipped with a motor stirrer and a condenser tube, 5 grams of propanol, 2 grams of distilled water, 13 grams of calcium oxide, 50 grams of a mixture of high-boiler calcium sulfonate and neutral oil (prepared from high-boiler sulfonic acid, calcium hydroxide and neutral oil, wherein the sulfonic acid The content of calcium is 61.6%), the product that embodiment 1 obtains (the mixture of C ₁₈ α olefin sulfonate calcium and sultone and neutral oil, active matter content 77.1%) 16 grams, after adding, control reaction temperature at 45 ℃～50℃, pass in carbon dioxide, when the absorption rate of carbon dioxide is 92% of the moles of calcium oxide, add 25 grams of calcium oxide and 8 grams of distilled water, continue to introduce carbon dioxide, when the absorption of carbon dioxide is 92% of the moles of calcium oxide , stop the ventilation, lower the pressure, and then raise the temperature to 120°C to deal with alcohol and water. Add 100 milliliters of gasoline to the material obtained, then put it into a medical centrifuge, and centrifuge at a speed of 4000rpm, put the centrifuged flash product into a distillation bottle with a decompression facility, first heat up to 120°C for atmospheric distillation, and then Distilled under reduced pressure to finally obtain 145 grams of tan viscous calcium sulfonate, the alkali value of the product = 361 mgKOH/g, and the viscosity of the product at 100°C = 166 mm ² /s.

Commercially available calcium sulfonate T107 (400TBN calcium sulfonate with high base value) was used as the sulfonate in Comparative Example 3.

Grease Examples 7-11 and Comparative Examples 4-6

Examples 7-11 and comparative examples 4-6 of grease were prepared by mixing the sulfonate salt of examples 3-6 and comparative examples 1-3 with lubricating base oil respectively. The lubricating base oil used is 150BS.

The calcium sulfonate synthesized in Examples 3-6 and Comparative Examples 1 and 2, the commercially available calcium sulfonate used in Comparative Example 3, and lubricating base oil are mixed at 100-150° C., and the calcium carbonate in the sulfonate is simultaneously Carry out infrared detection, when its infrared absorption peak gradually shifts from 863.1cm- ¹ to 881.5cm ^-1 , it can be considered that the calcium carbonate coated in the sulfonate is gradually transformed from amorphous to calcite crystal, and the grease is collected after the transformation is complete Product, obtain the embodiment 7～11 of lubricating grease product and comparative example 4～6. Wherein the lubricating grease of embodiment 7～10 and comparative example 4～6 is obtained by converting the calcium sulfonate prepared in embodiment 3～6 and comparative example 1～3 respectively, wherein the mass ratio of calcium sulfonate and lubricating base oil is 42:58 ; The grease of Example 11 is converted from the calcium sulfonate prepared in Example 3, wherein the mass ratio of calcium sulfonate to lubricating base oil is 51:49.

Various performance tests were carried out on Examples 7-11 and Comparative Examples 4-6 of the grease products, and the test results are shown in Table 1.

Table 1 Performance evaluation of grease products

As can be seen from Table 1, the calcium sulfonate of the present invention has a short conversion time when preparing grease, and the prepared grease has excellent high-temperature performance, colloidal stability, water resistance and anti-wear performance.

Claims (17)

1. A sulfonate, its structure is: Among them, M ₁ , M ₂ , and M ₃ are single metals or mixed metals in alkali metals and alkaline earth metals, n ₁ , n ₂ , and n ₃ are the valences of M ₁ , M ₂ , and M ₃ respectively, and x, y, and z are integers between 1 and 4, R ₁ , R ₂ , and R ₃ are each an alkyl group, and the sum of the carbon number in the R ₁ alkyl group and x is 8 to 28, and the carbon number in the R ₂ alkyl group is equal to The sum of y is 7~27, the sum of the carbon number in R ₃ alkyl and z is 9~29, R ₄ and R ₅ are respectively C ₅ ~C ₃₀ alkyl, e, q, r, u are respectively An integer between 1 and 10000, and t is an integer between 0 and 10000. 2. The sulfonate according to claim 1, characterized in that: said M ₁ , M ₂ , M ₃ are alkaline earth metals; n ₁ , n ₂ , n ₃ take a value of 2; x, y, z ₂ or 3 respectively _; the sum of the carbon number and x in the R1 alkyl group is 10-18, the sum of the carbon number and y in the R2 alkyl group is 9-17, and the carbon number and z in the _R3 alkyl group The sum is 11 to 19; R ₄ and R ₅ are respectively C ₁₀ to C ₃₀ alkyl groups; e, q, r, u and t are integers between 1 and 1000, respectively. 3. A preparation method of sulfonate, comprising: (1) C ₁₀ ~ C ₃₀ alpha olefin undergoes sulfonation reaction with sulfonating agent to generate C ₁₀ ~ C ₃₀ sulfonic acid and sultone, and then undergoes neutralization reaction with alkali metal and/or alkaline earth metal hydroxide , collecting the resulting mixture of alkali metal and/or alkaline earth metal salts of C ₁₀ -C ₃₀ sulfonic acid and sultone; the molar ratio of the sulfonating agent to the C ₁₀ -C ₃₀ α-olefin is: 1.0- 1.5:1; the number of moles of the alkali metal and/or alkaline earth metal hydroxide is 1.2 to 2 times the number of moles of the C ₁₀ -C ₃₀ α-olefin; (2) neutral oil, hydrocarbon solvent, C ₁ -C ₄ alcohol, calcium oxide, water, alkali metal and/or alkaline earth metal salt of C ₁₀ -C ₃₀ sulfonic acid in step (1) and sultone The mixture and optional alkali metal and/or alkaline earth metal salts of C ₅ ~C ₃₀ alkylbenzene sulfonic acid are mixed, carbon dioxide is introduced, carbonation reaction is carried out under the pressure of 0.4MPa ~ 2.0MPa, and alcohol, water and hydrocarbon are removed Solvent-like solvent and solid residue to obtain sulfonate product; the mixture of alkali metal and/or alkaline earth metal salt and sultone of C ₁₀ ~C ₃₀ sulfonic acid in the step (1) and non-essential C ₅ ~C ₃₀ The amount of alkali metal and/or alkaline earth metal salt of alkylbenzenesulfonic acid is calculated as 100 parts by mass, the total amount of neutral oil is 50-400 parts; the amount of C ₁ ~C ₄ alcohol is 20-200 parts; The amount of solvent-like solvent is 50-1000 parts; the amount of calcium oxide is 50-400 parts; the amount of water is 10-150 parts; the number of moles of carbon dioxide introduced is 50%-120% of the number of moles of calcium oxide ; The temperature of the carbonation reaction is 50°C-200°C; the reaction pressure is 0.4MPa-2.0MPa. 4. The method according to claim 3, characterized in that, in step (1), the C ₁₀ -C ₃₀ α-olefin is a C ₁₀ -C ₃₀ linear α-olefin. 5. The method according to claim 3, characterized in that neutral oil is added in the sulfonation reaction and/or neutralization reaction described in step (1). 6. The method according to claim 3, characterized in that, in step (1), the temperature of the sulfonation reaction is 0-60°C; the reaction time is 1-10 hours. 7. The method according to claim 3, characterized in that, in the neutralization reaction in step (1), the reaction temperature is 50°C-70°C, and the reaction time is 10-40 minutes. 8. The method according to claim 3, characterized in that, in step (1), the hydroxide of the alkali metal and/or alkaline earth metal is a single hydroxide or a mixed hydroxide. 9. The method according to claim 3, wherein the neutralization reaction in step (1) is to first neutralize the sulfonic acid and sultone of C ₁₀ to C ₃₀ and the hydroxide of alkali metal The reaction generates alkali metal salts and sultones of C ₁₀ ~ C ₃₀ sulfonic acids, and then undergoes metathesis reaction with soluble alkaline earth metal salts, and collects the generated alkali metal and/or alkaline earth metal salts and sultones of C ₁₀ ~ C ₃₀ sulfonic acids mixture of esters. 10. according to the described method of claim 9, it is characterized in that, in step (1), the condition that the sulfonic acid of described C ₁₀ ～C ₃₀ and sultone and the hydroxide generation of alkali metal neutralization reaction is : the number of moles of the alkali metal hydroxide is 1.2 to 2 times the number of moles of the C ₁₀ to C ₃₀ α-olefin, the reaction temperature is 50°C to 70°C, and the reaction time is 10 to 40 minutes; The conditions of the metathesis reaction are as follows: the mole number of the soluble alkaline earth metal salt is 0.5-2.0 times the mole number of the C ₁₀ -C ₃₀ α-olefin, the reaction temperature is 60-90° C., and the reaction time is 1-4 hours. 11. The method according to claim 9, wherein the soluble alkaline earth metal salt is selected from one or more of calcium chloride, magnesium chloride, barium chloride, calcium nitrate, magnesium nitrate and barium nitrate. 12. The method according to claim 3, characterized in that, in step (2), the neutral oil is a lubricating base oil with a kinematic viscosity of 2 to 6 mm ² /s at 100°C, and the hydrocarbon solvent is Alkanes and/or aromatics. 13. The method according to claim 3, characterized in that, in step (2), alkali metal and/or alkaline earth metal salts of C ₅ -C ₃₀ alkylbenzenesulfonic acids are added, and the C ₅ -C ₃₀ alkane The structure of the alkali metal and/or alkaline earth metal salt of phenylsulfonic acid is: Wherein M3 is alkali metal and/or alkaline earth metal, n3 is the valence _of alkali metal and/or alkaline earth metal, one _{of R4} and R5 is _C5 ～ _{C30 alkyl} , the other is H or both All are C ₅ -C ₃₀ alkyl groups. 14. The method according to claim 13, characterized in that, in step (2), the alkali metal and/or alkaline earth metal salt and sultone of C ₁₀ to C ₃₀ sulfonic acid in the step (1) The mass ratio of the mixture to the alkali metal and/or alkaline earth metal salt of C ₅ -C ₃₀ alkylbenzene sulfonic acid is 0.3-3:1-3. 15. The method according to any one of claims 3-14, characterized in that, in step (2), the C ₁ -C ₄ alcohol is a mixture of methanol and C ₃ -C ₄ alcohol, and the methanol The mass ratio to C ₃ -C ₄ alcohols is 2:1-10:1. 16. A lubricating grease, comprising the sulfonate according to claims 1 to 2 or the sulfonate and lubricating base oil prepared according to any one of claims 3 to 14, said sulfonate and lubricating base The mass ratio of oil is 30-70:70-30. 17. The preparation method of the lubricating grease according to claim 16, comprising: mixing the lubricating base oil and the sulfonate at 100-150° C., while performing infrared detection on the calcium carbonate in the sulfonate, when the infrared absorption When the peak shifted from 863.1cm ^-1 to 881.5cm ^-1 , the calcium carbonate coated in the sulfonate changed from amorphous to calcite crystal, and the grease product was collected.