CN110639426A - Branched alkyl sulfonate surfactant and preparation process thereof - Google Patents

Abstract

The invention discloses a branched-chain alkyl sulfonate surfactant and a preparation process thereof, comprising the following steps: (1) dimerization reaction: using a mixture of alpha-olefins and alkanes with the same carbon chain as starting materials, Under the action of the catalyst, the reaction temperature was controlled at 10~60 °C, and the reaction time was 12~30 h; vinylidene olefin compounds were obtained, and alkanes were separated at the same time; (2) Sulfonation reaction: in the presence of a catalyst, lower alcohol and Ionized water is used as a solvent, and sodium bisulfite is used as a sulfonating reagent to carry out a sulfonation reaction with the vinylidene olefin compound obtained in step (1). Sulfonate. The present invention adopts the idea of "reaction + separation" through the combined process of α-olefin dimerization reaction + sulfonation reaction, the synthesized surfactant product has clear composition and structure, high product purity, and the surfactant has excellent foaming and wetting properties. and emulsifying properties.

Description

A kind of branched chain alkyl sulfonate surfactant and preparation process thereof

technical field

The invention relates to a branched-chain alkyl sulfonate surfactant and a preparation process thereof, belonging to the technical field of fine chemical surfactants.

Background technique

Coal to synthetic oil is one of the important ways for clean and efficient utilization of coal. The content of α-olefin in coal-based synthetic oil is as high as 50%. α-olefin is an important raw material for the synthesis of fine chemicals. The use of α-olefin in coal-based synthetic oil to synthesize fine chemicals is an extension of the coal-to-liquids industry chain. It is of great significance to realize the high value-added deep processing and utilization of coal.

Coal-based synthetic oil has complex components, including alpha-olefins, alkanes and oxygenates. Among them, straight-chain alpha-olefins and n-alkanes with the same carbon chain have similar physical properties such as boiling point and melting point, so the separation of the two is very difficult. Separation methods such as rectification separation and freezing separation have high energy consumption and low efficiency, and it is difficult to obtain high-purity linear α-olefins. In view of this, it is necessary to find a suitable method to realize the separation and utilization of linear α-olefins and n-paraffins with the same carbon chain.

Surfactants are an important class of fine chemicals and indispensable functional materials in the national economy. Branched-chain surfactants have some excellent properties due to their branched-chain structure, such as low-foaming properties and superior wetting properties. By referring to the literature, the branched-chain alkyl sulfonic acid was prepared by the combined process of the dimerization of α-olefin and the sulfonation reaction of the dimerized product vinylidene olefin using straight-chain α-olefin and n-alkane of the same carbon chain as starting materials. The study of acid salt surfactants has not been reported in the literature.

SUMMARY OF THE INVENTION

The present invention aims to provide a branched-chain alkyl sulfonate surfactant and a preparation process thereof. Compared with straight-chain alpha-olefins, the boiling point of vinylidene olefin compounds is high, so the present invention utilizes the method of "reaction + separation", that is, straight-chain alpha-olefins and normal paraffins with the same carbon chain are used as raw materials to make straight The vinylidene olefin compound is synthesized by dimerization of the chain α-olefin, and then the alkane is separated by utilizing the difference in boiling point between the n-paraffin and the vinylidene olefin compound. Vinylidene olefin compounds contain branched structures and unsaturated double bonds, and can be used as raw materials to synthesize various fine chemicals with potential applications, such as lubricants, fuel additives, surfactants, etc. In this way, on the one hand, the separation of linear α-olefins and normal paraffins with the same carbon chain can be realized, and the utilization of linear α-olefins is also broadened.

The present invention takes the mixture of α-olefin and alkane with the same carbon chain as the starting material, adopts the idea of "reaction + separation" and utilizes the dimerization reaction of α-olefin to synthesize vinylidene olefin compound, and realizes the α-olefin and alkane of the same carbon chain. The alkanes are obtained by the separation of alkanes; meanwhile, the branched-chain alkanesulfonate surfactants with excellent performance are synthesized by sulfonation reaction of vinylidene olefin compounds, which are α-olefin dimerization products.

The present invention is achieved through the following technical solutions:

The present invention provides a branched-chain alkyl sulfonate surfactant having the general formula shown below:

In the formula, R is a C ₁ -C ₁₃ saturated hydrocarbon group.

The invention provides a preparation process of branched-chain alkyl sulfonate surfactant, comprising the following steps:

(1) Dimerization reaction:

The mixture of α-olefin and alkane with the same carbon chain was used as the starting material, zirconocene dichloride was used as the main catalyst, and methylaluminoxane was used as the cocatalyst. The reaction temperature was controlled at 10 ~ 60 ℃, and the reaction time was 12 ~ 30 h. After the reaction, adding water to quench the reaction, washing with water, extracting, drying over anhydrous sodium sulfate, and distillation under reduced pressure to obtain vinylidene olefin compounds, and simultaneously separate and obtain alkanes;

The dimerization equation:

In the formula, R is a C ₁ -C ₁₃ saturated hydrocarbon group.

(2) Sulfonation reaction:

In the presence of a catalyst, using low-carbon alcohol and deionized water (mass ratio of 1:1) as a solvent, using sodium bisulfite as a sulfonating reagent, with the α-olefin dimerization product vinylidene obtained in step (1) The sulfonated alkene compound was subjected to sulfonation reaction, the reaction temperature was controlled at 30-60 °C, and the reaction time was 12-96 h. After the reaction, water and low-carbon alcohol were distilled off under reduced pressure, and the unreacted vinylidene was removed by extraction with petroleum ether. The olefin compound is dissolved in excess absolute ethanol, heated to boiling, filtered to remove insoluble inorganic salt, and distilled under reduced pressure to remove ethanol to obtain the product branched chain alkyl sulfonate;

Sulfonation reaction equation:

In the formula, R is a C ₁ -C ₁₃ saturated hydrocarbon group.

In the above-mentioned process, the starting material used in the dimerization reaction of the step (1) is a mixture of α-olefins and alkanes with the same carbon chain, the molar ratio of α-olefins and alkanes is 2:1, and the α-olefins are C ₄ ~ Any of the C ₁₆ olefins.

In the above process, the mol ratio of α-olefin to catalyst (including zirconocene dichloride and methylaluminoxane) in the dimerization reaction of the step (1) is 1:0.015 to 0.060, wherein the cocatalyst methylaluminoxane The molar ratio of the alkane to the main catalyst dichlorozirconocene is 0.5 to 20:1.

In the above-mentioned technique, the catalysts used in the sulfonation reaction of the step (2) are tert-butyl peroxybenzoate and ferric chloride, wherein the quality of tert-butyl peroxybenzoate is α-olefin dimerization product vinylidene. The mass of the base olefin compound is 5-10%, and the mass of ferric chloride is 5-10% of the mass of tert-butyl peroxybenzoate.

In the above process, the low-carbon alcohol used in the step (2) sulfonation reaction is any one of ethanol, isopropanol, n-butanol, and tert-butanol.

In the above process, the mass ratio of the vinylidene olefin compound to the lower alcohol in the step (2) sulfonation reaction is 1:2～4.

In the above process, the molar ratio of the vinylidene olefin compound to the sulfonating reagent sodium bisulfite in the sulfonation reaction in the step (2) is 1:1 to 4.

In the above process, after the sulfonation reaction in the step (2) is completed, water and low-carbon alcohol are removed by distillation under reduced pressure, the unreacted vinylidene olefin compound is removed by extraction with petroleum ether, dissolved in excess absolute ethanol, and the ethanol is heated. To boiling, filter to remove insoluble inorganic salts, distillation under reduced pressure to remove ethanol to obtain the product branched chain alkyl sulfonate.

Beneficial effects of the present invention:

1) The method of the present invention takes the mixture of α-olefin and alkane with the same carbon chain as the starting material, and adopts the idea of "reaction + separation" through the combination process of α-olefin dimerization reaction + sulfonation reaction, which not only realizes the same carbon chain. Separation of α-olefins and alkanes to obtain alkanes, at the same time realizing the utilization of α-olefins as a resource to synthesize branched-chain alkyl sulfonate surfactants;

2) The surfactant product synthesized by the present invention has clear composition and structure, high product purity, excellent surfactant performance, and excellent foaming, wetting and emulsifying properties;

3) The process of the present invention is easy to operate and easy to implement industrially.

Description of drawings

Fig. 1 is the infrared spectrogram of the branched-chain alkyl sulfonate surfactant in Example 1 of the present invention;

FIG. 2 is a surface tension diagram of branched-chain alkyl sulfonate surfactants with different concentrations in Example 1 of the present invention.

Detailed ways

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

Example 1:

1) Dimerization reaction: 22.442 g (0.2 mol) of n-octene was added to a three-necked flask equipped with a magnetic stirrer, and the molar ratio of olefin:alkane:catalyst was 2:1:0.03, wherein methylaluminoxane:di The molar ratio of zirconocene chloride was 0.5:1. In the glove box, 11.423 g (0.1 mol) of n-octane, 0.058 g (1.0 mmol) of methylaluminoxane, and 0.585 g (2.0 mmol) of zirconocene dichloride were successively added. ). The reaction was stirred at 25 °C for 12 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 20.512 g of the dimerized vinylidene olefin compound was obtained. The product purity was 95.26%.

2) Sulfonation reaction: 17.958 g (0.08 mol) of the dimerization product vinylidene olefin compound obtained in the above 1) reaction was added to a 100 mL beaker, and then the mass ratio of vinylidene olefin compound to alcohol was 1:2 To this, 35.916 g of isopropanol was added, and the mixture was thoroughly stirred to mix uniformly. Take another three-necked flask, add 16.650 g (0.16 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:2, according to the mass ratio of deionized water and isopropanol Add 35.916 g of deionized water in a ratio of 1:1 to fully dissolve sodium bisulfite, then add 0.898 g of tert-butyl peroxybenzoate (5 % mass fraction in vinylidene olefin compound), 0.054 g of ferric chloride (6% mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 40 °C for 24 h. After the reaction is completed, water and isopropanol are distilled off under reduced pressure, the unreacted vinylidene olefin compound is removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and decompressed. Ethanol is distilled off to obtain the product branched chain alkyl sulfonate.

Fig. 1 shows the infrared spectrogram of the branched chain alkyl sulfonate obtained by the present invention, and it can be seen from the figure that the stretch vibration peaks of -CH ₃ and -CH ₂ - are at the wavenumbers 2925 and 2856 cm ^-1 , and the wavenumbers are 1462 cm ^-1 is the stretching vibration peak of -CH, and the characteristic peaks corresponding to wavenumbers 3075 cm ^-1 (CH stretching vibration peak of olefin) and 886 cm ^-1 (=CH out-of-plane bending vibration peak) do not appear in Fig. 1. The characteristic stretching vibration peaks of sulfonates appear at wavenumbers 625, 1184 and 1050 cm ^-1 . It can be seen that the synthesized product is the target product branched chain alkyl sulfonate.

FIG. 2 shows the surface tension graph of the branched chain alkyl sulfonates obtained in the present invention at different concentrations. Weigh 1.0 g of the surfactant sample synthesized in Example 1 to prepare an aqueous surfactant solution with a concentration of 1 g/L. The instrument used in the test is the German KRUSS K100C surface tension tester, which is based on the platinum plate method (Wilhelmy Plate method) technology by using a platinum plate to contact the surface of an aqueous solution containing a certain concentration of surfactant to test the surface tension. The company's circulating water bath controls the test temperature at 25 ºC ± 0.5 ºC. When the instrument starts to test, first measure the surface tension of pure water, and keep injecting an equal volume of surfactant solution into the test container while keeping the volume of the measured solution constant, and accurately extract the corresponding volume of solution, so that the surface active The concentration of the agent solution changes continuously from dilute to concentrated, corresponding to the surface tension of the solution at different concentrations, and the relationship between surface tension and concentration can be obtained after the test (as shown in Figure 2). From Fig. 2, it can be determined that the critical micelle concentration (CMC) of the surfactant is 2.629 mmol/L and the corresponding surface tension (γ@CMC) at this concentration is 26.50 mN/m, which shows that the branch synthesized in Example 1 is obtained. Alkyl sulfonate surfactants have typical surfactant properties and can effectively reduce the surface tension of water.

Weigh 1.0 g of the surfactant sample synthesized in Example 1 to prepare an aqueous surfactant solution with a concentration of 1 g/L. According to the testing principle of the Ross-Miles method, the prepared aqueous surfactant solution is subjected to a foaming test, and a stopwatch is used to record the test. The foam volume after 30 s and after 5 min is calculated according to foam stability=(foam volume measured after 5 minutes/foam volume measured after 30 s)×100%. It can be seen from Table 1 that the branched-chain alkyl sulfonate surfactant synthesized in Example 1 has excellent foaming performance, produces many foams, and has good foam stability.

Table 1 Example 1 Foaming situation of branched alkyl sulfonate surfactant (25°C)

Take a certain amount of the synthetic surfactant sample of Example 1 to prepare the aqueous surfactant solution of a certain concentration, measure 40 mL aqueous surfactant solution and 40 mL liquid paraffin liquid respectively and join in the measuring cylinder with stopper, at 25 ± 1 ° Under the condition of constant temperature, shake the stoppered measuring cylinder vigorously up and down 5 times, let it stand for 1 minute, and repeat the operation 5 times. Record the time required to separate out 10 mL of the aqueous phase in the graduated cylinder. This time is used to describe the emulsifying ability of different concentrations of aqueous surfactant solutions. The longer the time required to separate out 10 mL of the aqueous phase, the better the emulsifying ability of the surfactant. It can be seen from Table 2 that the branched-chain alkyl sulfonate obtained in the present invention has good emulsifying ability (the corresponding emulsifying time is 215s when the surfactant concentration is 1 g/L).

Table 2 Example 1 Emulsifying ability of branched-chain alkyl sulfonate surfactant at different concentrations (25°C)

Wetting properties of surfactants were measured using standard canvas sheets. Weigh a certain amount of synthetic surfactant samples of Example 1 to prepare a certain concentration of surfactant aqueous solution, under 25 ± 1 °C constant temperature, use immersion clips to fix standard canvas sheets, and canvas sheets are placed in surfactant In the solution, the time from immersion to sinking (wetting time) was recorded to evaluate the wetting performance of surfactants. The shorter the wetting time, the better the wetting performance of the surfactant. It can be seen from Table 3 that the branched-chain alkyl sulfonate obtained in the present invention has good wetting performance (the corresponding wetting time is 17 s when the surfactant concentration is 1 g/L).

Table 3 Wetting properties (25°C) of branched-chain alkyl sulfonate surfactants in Example 1 at different concentrations

Example 2:

1) Dimerization reaction: 21.040 g (0.25 mol) of n-hexene was added to a three-necked flask equipped with a magnetic stirrer, and the molar ratio of olefin:alkane:catalyst was 2:1:0.05, wherein methylaluminoxane:dichloromethane The molar ratio of zirconocene was 1:1, and 10.773 g (0.125 mol) of n-hexane, 0.181 g (3.125 mmol) of methylaluminoxane, and 0.914 g (3.125 mmol) of zirconocene dichloro were successively added to the glove box. The reaction was stirred at 15 °C for 18 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 19.567 g of the dimerized vinylidene olefin compound was obtained. The product purity was 96.73%.

2) Sulfonation reaction: 16.832 g (0.1 mol) of the dimerized product vinylidene olefin compound obtained in the above 1) reaction was added to a 100 mL beaker, and then the mass ratio of vinylidene olefin compound to alcohol was 1:3 To this, 50.496 g of n-butanol was added, and the mixture was stirred well and mixed uniformly. Take another three-necked flask, add 31.218 g (0.3 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:3, and according to the mass ratio of deionized water and n-butanol Add 50.496 g of deionized water to it in a ratio of 1:1 to fully dissolve sodium bisulfite, then add 1.178 g of tert-butyl peroxybenzoate (7% mass fraction in vinylidene olefin compound), 0.071 g of ferric chloride (6% mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 30 °C for 30 h. After the reaction, water and n-butanol were removed by distillation under reduced pressure, the unreacted vinylidene olefin compound was removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and distilled under reduced pressure. Removal of ethanol yields the product branched chain alkyl sulfonate.

Example 3:

1) Dimerization reaction: 21.041 g (0.15 mol) of n-decene was added to a three-necked flask equipped with a magnetic stirrer, and the molar ratio of olefin:alkane:catalyst was 2:1:0.06, wherein methylaluminoxane:di The molar ratio of zirconocene chloride was 5:1. In the glove box, 10.672 g (0.075 mol) of n-decane, 0.218 g (3.75 mmol) of methylaluminoxane, 0.219 g (0.75 mmol) of zirconocene dichloride were successively added. ). The reaction was stirred at 20 °C for 20 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 19.955 g of the dimerized vinylidene olefin compound was obtained. The product purity was 95.57%.

2) Sulfonation reaction: 16.832 g (0.06 mol) of the dimerized product vinylidene olefin compound obtained in the above 1) reaction was added to a 100 mL beaker, and then the mass ratio of vinylidene olefin compound to alcohol was 1:4 To this, 67.328 g of tert-butanol was added, and the mixture was thoroughly stirred to mix uniformly. Take another three-necked flask, add 24.974 g (0.24 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:4, and add 24.974 g (0.24 mol) of sodium bisulfite to the flask. Add 67.328 g of deionized water to it in a ratio of 1:1 to fully dissolve sodium bisulfite, then add 1.515 g of tert-butyl peroxybenzoate (9 % mass fraction in vinylidene olefin compound), 0.121 g of ferric chloride (8% mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 50 °C for 48 h. After the reaction, water and tert-butanol were removed by distillation under reduced pressure, the unreacted vinylidene olefin compound was removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and then reduced under reduced pressure. Ethanol is distilled off to obtain the product branched chain alkyl sulfonate.

Example 4:

1) Dimerization reaction: add 23.564 g (0.12 mol) of n-tetradecene to a three-necked flask equipped with a magnetic stirrer, according to the olefin:alkane:catalyst molar ratio of 2:1:0.1, wherein methylaluminoxane: The molar ratio of zirconocene dichloride is 10:1. In the glove box, 11.903 g (0.06 mol) of n-tetradecane, 0.316 g (5.45 mmol) of methylaluminoxane, 0.159 g (0.159 g of zirconocene dichloride) ( 0.545 mmol). The reaction was stirred at 30 °C for 24 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 21.874 g of the dimerized vinylidene olefin compound was obtained. The product purity was 92.39%.

2) Sulfonation reaction: 19.637 g (0.05 mol) of the dimerized product vinylidene olefin compound obtained in the above 1) reaction was added to a 100 mL beaker, and then the mass ratio of vinylidene olefin compound to alcohol was 1:4 To this, 78.548 g of isopropyl alcohol was added, and the mixture was stirred well to mix it uniformly. Take another three-necked flask, add 5.203 g (0.05 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:1, and add 5.203 g (0.05 mol) of sodium bisulfite to the flask. Add 78.548 g of deionized water to it in a ratio of 1:1 to fully dissolve sodium bisulfite, then add 1.964 g of tert-butyl peroxybenzoate (10% mass fraction in vinylidene olefin compound), 0.098 g of ferric chloride (5% mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 60 °C for 24 h. After the reaction is completed, water and isopropanol are distilled off under reduced pressure, the unreacted vinylidene olefin compound is removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and decompressed. Ethanol is distilled off to obtain the product branched chain alkyl sulfonate.

Example 5:

1) Dimerization reaction: add 22.442 g (0.1 mol) of n-hexadecene to a three-necked flask equipped with a magnetic stirrer, according to the olefin:alkane:catalyst molar ratio of 2:1:0.08, wherein methylaluminoxane: The molar ratio of zirconocene dichloride was 19:1, and 11.322 g (0.05 mol) of n-hexadecane, 0.221 g (3.8 mmol) of methylaluminoxane, and 0.059 g (0.059 g of zirconocene dichloride) were successively added to the glove box. 0.2 mmol). The reaction was stirred at 50 °C for 24 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 21.091 g of the dimerized vinylidene olefin compound was obtained. The product purity was 93.21%.

2) Sulfonation reaction: take 17.954 g (0.04 mol) of the dimerization product vinylidene olefin compound obtained in the above 1) reaction into a 100 mL beaker, and then according to the mass ratio of vinylidene olefin compound to alcohol 1:3 To this, 53.862 g of n-butanol was added, and the mixture was thoroughly stirred to mix uniformly. Take another three-necked flask, add 12.487 g (0.12 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:3, and according to the mass ratio of deionized water and n-butanol Add 53.862 g of deionized water to it at a ratio of 1:1 to fully dissolve sodium bisulfite, then add 1.436 g of tert-butyl peroxybenzoate (8 % mass fraction in vinylidene olefin compound), 0.144 g of ferric chloride (10% mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 50 °C for 96 h. After the reaction, water and n-butanol were removed by distillation under reduced pressure, the unreacted vinylidene olefin compound was removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and distilled under reduced pressure. Removal of the ethanol yields the product branched chain alkyl sulfonate.

Example 6:

1) Dimerization reaction: 23.705 g (0.13 mol) of n-tridecene was added to a three-necked flask equipped with a magnetic stirrer, and the molar ratio of olefin:alkane:catalyst was 2:1:0.12, wherein methylaluminoxane: The molar ratio of zirconocene dichloride was 20:1, and 11.987 g (0.065 mol) of n-tridecane, 0.431 g (7.429 mmol) of methylaluminoxane, and 0.109 g (0.109 g of zirconocene dichloride) were successively added to the glove box. 0.371 mmol). The reaction was stirred at 60 °C for 30 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 21.897 g of the dimerized vinylidene olefin compound was obtained. The product purity was 94.82%.

2) Sulfonation reaction: take 18.235 g (0.05 mol) of the dimerization product vinylidene olefin compound obtained in the above 1) reaction into a 100 mL beaker, and then according to the mass ratio of vinylidene olefin compound to alcohol 1:4 To this, 72.940 g of isopropyl alcohol was added, and the mixture was thoroughly stirred to mix uniformly. Take another three-necked flask, add 5.203 g (0.05 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:1, and add 5.203 g (0.05 mol) of sodium bisulfite to the flask. Add 72.940 g of deionized water to it at 1:1 to fully dissolve sodium bisulfite, then add 1.094 g of tert-butyl peroxybenzoate (6 % mass fraction in vinylidene olefin compound), 0.077 g of ferric chloride (7% mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 60 °C for 80 h. After the reaction is completed, water and isopropanol are distilled off under reduced pressure, the unreacted vinylidene olefin compound is removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and decompressed. Ethanol is distilled off to obtain the product branched chain alkyl sulfonate.

Example 7:

1) Dimerization reaction: add 16.832 g (0.1 mol) of n-dodecene to a three-necked flask equipped with a magnetic stirrer, according to the olefin:alkane:catalyst molar ratio of 2:1:0.1, wherein methylaluminoxane: The molar ratio of zirconocene dichloride is 7:1. In the glove box, 8.517 g (0.05 mol) of n-dodecane, 0.254 g (4.375 mmol) of methylaluminoxane, 0.183 g (0.183 g of zirconocene dichloride) ( 0.625 mmol). The reaction was stirred at 35 °C for 18 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 15.512 g of the dimerized vinylidene olefin compound was obtained. The product purity was 94.82%.

2) Sulfonation reaction: take 10.099 g (0.03 mol) of the dimerized product vinylidene olefin compound obtained in the above 1) reaction into a 100 mL beaker, and then according to the mass ratio of vinylidene olefin compound to alcohol 1:2 To this, 20.198 g of tert-butanol was added, and the mixture was stirred well and mixed uniformly. Take another three-necked flask, add 12.487 g (0.12 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:4, and according to the mass ratio of deionized water and tert-butanol Add 20.198 g of deionized water to it in a ratio of 1:1 to fully dissolve sodium bisulfite, then add 0.808 g of tert-butyl peroxybenzoate (8 % mass fraction in vinylidene olefin compound), 0.057 g of ferric chloride (7% mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 35 °C for 90 h. After the reaction, water and tert-butanol were removed by distillation under reduced pressure, the unreacted vinylidene olefin compound was removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and then reduced under reduced pressure. Ethanol is distilled off to obtain the product branched chain alkyl sulfonate.

Example 8:

1) Dimerization reaction: add 25.248 g (0.2 mol) of n-nonene to a three-necked flask equipped with a magnetic stirrer, according to the olefin:alkane:catalyst molar ratio of 2:1:0.09, wherein methylaluminoxane:di The molar ratio of zirconocene chloride was 15:1. In the glove box, 12.826 g (0.1 mol) of n-nonane, 0.490 g (8.437 mmol) of methylaluminoxane, and 0.164 g (0.563 mmol) of dichlorozirconocene were successively added. ). The reaction was stirred at 40 °C for 24 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 23.664 g of the dimerized vinylidene olefin compound was obtained. The product purity was 93.18%.

2) Sulfonation reaction: 20.198 g (0.08 mol) of the dimerized product vinylidene olefin compound obtained in the above 1) reaction was added to a 100 mL beaker, and then the mass ratio of vinylidene olefin compound to alcohol was 1:2 To this, 40.396 g of ethanol was added, and the mixture was thoroughly stirred to mix uniformly. Take another three-necked flask, add 16.650 g (0.16 mol) of sodium bisulfite to the flask according to the molar ratio of vinylidene olefin compound and sodium bisulfite as 1:2, and according to the mass ratio of deionized water and ethanol as 1 : 1 Add 40.396 g of deionized water to it to fully dissolve sodium bisulfite, then add 1.010 g of tert-butyl peroxybenzoate (5% by mass in vinylidene olefin compound), 0.051 g of ferric chloride (5 % mass fraction in tert-butyl peroxybenzoate). The mixed solution of alkene and alcohol was poured into the flask, and the reaction was stirred at 50 °C for 72 h. After the reaction is completed, water and ethanol are removed by distillation under reduced pressure, the unreacted vinylidene olefin compound is removed by extraction with petroleum ether, dissolved in excess absolute ethanol, heated to boiling with ethanol, filtered to remove insoluble inorganic salts, and removed by distillation under reduced pressure. Ethanol yields the product branched alkyl sulfonate.

Claims (9)

1. a branched chain alkyl sulfonate surfactant is characterized in that having the general formula shown below: In the formula, R is a C ₁ -C ₁₃ saturated hydrocarbon group. 2. a preparation technique of branched chain alkyl sulfonate surfactant according to claim 1, is characterized in that comprising the following steps: (1) Dimerization reaction: The mixture of α-olefin and alkane with the same carbon chain was used as the starting material. Under the action of a catalyst, the reaction temperature was controlled at 10-60 °C, and the reaction time was 12-30 h; after the reaction was completed, water was added to quench the reaction, and after washing, extraction, Anhydrous sodium sulfate is dried and distilled under reduced pressure to obtain vinylidene olefin compounds, and simultaneously, alkanes are obtained by separation; (2) Sulfonation reaction: In the presence of a catalyst, using low-carbon alcohol and deionized water as a solvent, and using sodium bisulfite as a sulfonating reagent, conduct a sulfonation reaction with the vinylidene olefin compound obtained in step (1), a dimerization product of α-olefin, The reaction temperature is controlled at 30 ~ 60 ℃, and the reaction time is 12 ~ 96 h. After the reaction is completed, the water and low-carbon alcohol are removed by distillation under reduced pressure, and the unreacted vinylidene olefin compound is removed by extraction with petroleum ether. Dissolve the ethanol, heat the ethanol to boiling, filter to remove the insoluble inorganic salt, and remove the ethanol by distillation under reduced pressure to obtain the product branched chain alkyl sulfonate. 3. the preparation technology of branched-chain alkyl sulfonate surfactant according to claim 2, is characterized in that: The dimerization reaction equation is:

The sulfonation reaction equation is:

In the formula, R is a C ₁ -C ₁₃ saturated hydrocarbon group. 4 . The preparation process of branched-chain alkyl sulfonate surfactant according to claim 2 , wherein the starting material used in the dimerization reaction of the step (1) is α-olefin with the same carbon chain. 5 . And the alkane mixture, the molar ratio of α-olefin and alkane is 2:1, and the α-olefin is any one of C ₄ ~ C ₁₆ olefins. 5. the preparation technology of branched chain alkyl sulfonate surfactant according to claim 2, is characterized in that: in described step (1) dimerization reaction, the mol ratio of α-olefin and catalyst is 1:0.015～ 0.060; the catalyst comprises zirconocene dichloride and methylaluminoxane, zirconocene dichloride is the main catalyst, and methylaluminoxane is the co-catalyst, wherein the co-catalyst methylaluminoxane and the main catalyst zirconocene dichloride are the co-catalysts. The molar ratio of 0.5 ~ 20:1. 6. The preparation process of branched-chain alkyl sulfonate surfactant according to claim 2, characterized in that: the mass ratio of vinylidene olefin compound and lower alcohol in the sulfonation reaction of the step (2) is: 1:2 to 4. 7. The preparation process of branched-chain alkyl sulfonate surfactant according to claim 2, characterized in that: in the step (2) sulfonation reaction, the vinylidene olefin compound and the sulfonating reagent sodium bisulfite The molar ratio is 1:1~4. 8 . The preparation process of branched-chain alkyl sulfonate surfactant according to claim 2 , wherein the catalyst used in the sulfonation reaction of the step (2) is tert-butyl peroxybenzoate and trimethyl benzoate. 9 . Ferric chloride, wherein the quality of tert-butyl peroxybenzoate is 5～10% of the quality of α-olefin dimerization product vinylidene olefin compound, and the quality of ferric chloride is the quality of tert-butyl peroxybenzoate 5 to 10%. 9. The preparation technology of branched-chain alkyl sulfonate surfactant according to claim 2, characterized in that: the low-carbon alcohol used in the sulfonation reaction of the step (2) is ethanol, isopropanol, normal Any one of butanol and tert-butanol; the mass ratio of low-carbon alcohol and deionized water is 1:1.

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