SU1263694A1 - Method of producing surface-active substances - Google Patents

Abstract

The invention relates to the class of sulfonated ethoxylated alkyl benzenes (CO EAB), in particular to the preparation of substances of the general formula I R OCH 2 CH j) -CgH2- (R,) (), where R, is Cg-C, o-alkyl or nonylphenyl; K - H, C - C - alkyl; R „- H, bottom. alkyl; n 2-14; A - alkali metal or NH, which can be used as solubilizers, emulsifiers, dispersants and household and technical detergents. In order to simplify the process of obtaining new substances, the class SOEAB is derived from another raw material of general formula II, R, (OCH, jCH) - CgH, (R) (R.J). Sulfonation is carried out by SO with its molar ratio to compound II,

Description

The invention relates to the class of sulfonated ethoxylated alkyl benzenes, in particular, to a method for producing new surfactants (surfactants) of the formula H2 Rl (OCH2. CH2) n Hc C-Cdd alkyl or nonylphenyl hydrogen or C-alkyl; hydrogen or lower alkyl; .2-14, A - alkali metal or ammonium group, which can be used as solubilizers, emulsifiers, dispersants and household and technical detergents. The purpose of the invention is to simplify the process, which is achieved mainly by using the compound of the formula R i (OCH 2 CH 2) n as the starting product, where R, G and P have the indicated values. Example 1. A volumetric reenactor of intensive mixing with a jacket, a stirrer, a device for temperature measurement with nozzles for loading a liquid raw material, gaseous sulphide) and removal of flue gases load 155 g (0.367 mol) of dodecylpolyethoxybenzene with an average molecular weight of 422, including an average of four hydroxyethyl groups. At 20 ° C, sulfur trioxide vapor (1.31 g / min), diluted with dry air to 5% by volume, is continuously fed to the organic raw material. Air flow is 7 l / min. As the reaction proceeds, the temperature is elevated up to and maintained at the end of peak of g for 24.7 minutes, 32.4 g (0.405 mol) of sulfur trioxide is added. The molar ratio of sulfur trioxide: dodecylpolyethoxybenzene is 1.1: 1. 183.7 g of the reaction mass, containing 98% of anionic surfactant, 0.7% of unconverted compounds, is obtained as a result of the interaction of the sulfur trioxide with dodecylpolyethoxybenzene. 1.3% sulfur trioxide (in terms of sulfuric acid). The degree of use of 94 2 and sulfur trioxide is 89, the resulting reaction mass is neutralized with a 15% aqueous solution of sodium hydroxide (19.44 g) until neutral. After neutralization, a paste is obtained with a 60.8% content of anionic surfactants 0.5 % unconverted compounds, 1.1% sodium sulphate. The color on the iodine scale is 80 .. The substance in aqueous solution reduces the tension to 36 surface Дж 10 J / m2. Example 2. Under the conditions of Example 1, 305 g (0.702 mol) of dodecyl polyethoxydiethyl benzene, average molecular weight 434, comprising on average three hydroxyethyl groups, is reacted with sulfur trioxide. For 30 minutes, 62 g / CO, 776 mol) of sulfur trioxide were continuously fed into the reactor at a flow rate of 2.07 g / min, maintaining a sulfur trioxide concentration of 10% by volume and an air flow rate of 5.18 l / min. The temperature during the addition of sulfur trioxide is maintained at 55 ° C. The molar ratio of sulfur trioxide:: dodecyl polyethoxydistilbenzene is 1.1: 1.0. As a result of the reaction, 354 g of the reaction mass is obtained, comprising 98% of anionic surfactants, 1.4% of unconverted compounds, 0.6% of sulfur trioxide (calculated on sulfuric acid). The use of sulfur trioxide is 87.4%. The resulting reaction mass is neutralized with a 25% aqueous solution of ammonium hydroxide (29.76 g) and a paste is obtained containing 77.2% anionic surfactant, 1.1% unconverted compounds and 71% ammonium sulfate. Color 89. The substance in aqueous solution reduces the surface tension to 31 PO J / m2. In an example 1, sulfur trioxide is reacted with 100 g (0.203 mol) of alkyl polyphenylbenzenes in an average molecular weight of 493, iodine number 15 g of g, including 3 average of four oxysthyl groups. Within 3-4 minutes, 24.2 g (0.303 mol) of sulfur trioxide diluted with dry air to 2 vol.% Was continuously fed to the reactor. The consumption of sulfur trioxide is 0.712 g / min, air -.9.8 l / min. The temperature is maintained at 50 The molar ratio of alkylpolyethox benzenes: sulfur trioxide is 1: 1.49. After reacting the reactants, 119 g of the reaction mass containing 96.5% of anionic surfactant, 2% of unconverted compounds, 1.7% sulfur trioxide (calculated on sulfuric acid) are obtained. The use of sulfur trioxide is 76.2%. The resulting reaction mass is neutralized with triethanol amine (43.7 g) until neutral, and a paste containing 92.8% anionic surfactant, 1.9% unchanged, and 5.9% triethanolamine sulfate is obtained, the color is 120 surface tension of the solution to Example4. Under the conditions of the example, 81.2 g (0.292 mol) of alkylpolyoxybenzenes of the C .. -C fraction are reacted. an average molecular weight of 278 containing an average of two oxysthyl groups. Within 20 minutes, 28 g (0.35 mol) of sulfur trioxide diluted with air to 7 vol.% Was added, maintaining the temperature at 30 ° C and the molar ratio of sulfur trioxide: alkyl polyethoxybenzene 1.2: 1. The sulfur trioxide consumption is 1.4 g / min, the air consumption is 5.2 l / min. After reacting the reactants, 104 g of the reaction mass containing 91% anionic surfactants, 7.5% unconverted compounds, 1.5% sulfur trioxide (calculated on sulfuric acid) are obtained. The use of sulfur trioxide is 76%. The resulting reaction mass is neutralized with a 20% aqueous solution of potassium hydroxide (20.56 g) to a neutral reaction and a paste containing 38.4% of anionic surfactants, 3.1 unconverted compounds, 0.7% of potassium sulfate, color 90 is obtained. Substance. in aqueous solution, it reduces the surface tension to j / m. Example 5 Under the conditions of Example 1 with 14 g (0.175 mol) of sulfur trioxide, the reaction is subjected to 146.4 (0.2 mol) alkylpolytoxybenzenes of the-SzO fraction with an average molecular weight of 732, including an average of ten hydroxyethyl groups . The reaction was carried out at 70 ° C for 14 minutes, maintaining the molar ratio of alkyl polyethoxybenzenes: sulfur trioxide 1: 0.877, sulfur trioxide consumption 36 g / min, air consumption 5.3 l / min, sulfur trioxide concentration 5% by volume . After reacting the reagents, 149 g of the reaction mass containing 87.4% of anionic surfactants, 11.9% of unconverted sulfur trioxide compounds (calculated as sulfuric acid) are obtained. The degree of use of sulfur trioxide is 91.5%. The resulting reaction mass is neutralized with a 10% aqueous solution of sodium hydroxide (8.14 g) until neutral, and a paste is obtained containing 58.1% anionic surfactant, 7.9% unconverted compounds. O, sodium sulfate, chromaticity 50. In aqueous sodium, chromaticity 50. In solution, the resulting surfactant reduces the surface tension to 35-10 D s / m. Example Under the conditions of Example 1, 87.4 g (0.2 mol) of the dodecyl polyethoxymethyl benzene fraction C of average molecular weight 43 7, comprising an average of four hydroxyethyl groups, are reacted with 16 g (0.2 mol) of sulfur trioxide. The reaction was carried out at 54 ° C for 40 minutes, maintaining the molar ratio of reagents 1: 1, sulfur trioxide consumption 0.4 g / min, air consumption 5.2 l / min, sulfur trioxide concentration 2% by volume. After reacting the reactants, 102 g of the reaction mixture are obtained, including 93.4% of anionic surfactant sulfonic acids, 5.4% of unconverted compounds, 0.2% of sulfur trioxide (calculated on sulfuric acid). The use of sulfur trioxide is 92%. After neutralizing the reaction mixture with a 25% aqueous solution of ammonium hydroxide (7.77 g), a paste containing 76% of anionic surfactants, 4.3% of unconverted compounds, 0.3% of ammonium sulfate is obtained. Color 60. In an aqueous solution, the resulting surfactant reduces the surface tension to ZMO J / m2. Example 7. Under the conditions of Example 1, the interaction with 12.8 g (0.16 mol) of sulfur trioxide is subjected to 67.6 g (0.15 mol) of the dodecyl polymethyloxymethyl benzene fraction C. The average molecular weight is 451, including an average of the oxityl group. The interaction is carried out at a molar ratio of single polypoly carbon and thrombolite: sulfur trioxide 1: 1.07, temperature 60 ° C for 20 min, maintaining the sulfur trioxide consumption 0.64 g / min, air flow 2.3 l / min, the concentration of trioxide 7 vol.%. After reacting the reactants, 77 g of the reaction mass containing 91.8% of anionic surfactant sulfonic acids, 6.9% of unconverted compounds, 1.3% of sulfur trioxide (calculated as sulfuric acid) are obtained. The degree of use of sulfur trioxide is 83.4%. After neutralizing the reaction mixture with monoethanolamine (11.08 g), a paste containing 90.3% of anionic surfactant, 6.8% of unconverted compounds, 2.9% of monoethanolamine sulfate is obtained to neutralize it. . Chroma 70. The surfactant obtained reduces the interfacial tension at the aqueous solution – heptane interface to 0.01-10 J / m2. Example 8. Under the conditions of Example 1, interaction with 16 g (0.2 mol of sulfur trioxide is subjected to 91.2 g (0.2 {Sol) alkylphenyl polyethoxybenzenes of the C g fraction of average molecular weight 456, including an average of four hydroxyethyl groups. Interaction t at a molar ratio of alkylphenylpolyethoxybenzenes: sulfur trioxide 1: 1, temperature 65 ° for 30 minutes, maintaining sulfur trioxide consumption 0.53 g / min, air consumption 4.8 l / min, concentration of three sulfur oxides 3%,% After reacting the reactants, 104 g of the reaction mixture containing 92.3% anionic agent are obtained. sulfonic acid surfactants, 6.7% of unconverted compounds, 0.8% of sulfur trioxide (calculated as sulfuric acid). The degree of use of sulfur trioxide is 89.6%. After neutralizing the reaction mixture with a 25% aqueous solution of hydroxide ammonium (8.02 g), a paste is obtained containing 85% ammonium sulfonate surfactants, 6.1% unconverted compounds and 1.2% ammonium sulfate, color 60, An aqueous solution of the resulting surfactant reduces surface tension to 38 MO J / m PRI me R 9, Under the conditions of example 8, the interaction with 12.8 g (0.16 mol) tr subjecting the sulfur oxide is dissolved 117.6 g (0.2 mol) alkilfenilpoli ethoxybenzene fraction Sd average molecular weight of 588 comprising 40 94 6 average seven hydroxyethyl groups. The interaction is carried out at a molar ratio of alkylphenylpolyethoxybenzenes: sulfur trioxide 1: 0.8, temperature 80 ° C for 15 minutes, maintaining air flow 4., 6 l / min, sulfur trioxide concentration 5% by volume, 85 g / min. After reacting the reactants, 130.4 g of the reaction mixture containing 77.5% of anionic surfactant sulfonic acids, 23% of non-ionic compounds, 0.5% of sulfur trioxide (calculated as sulfuric acid) are obtained. The degree of use of sulfur trioxide is 94.8%. After neutralizing the reaction mixture with a 10% ammonium hydroxide solution (6.44 g), a paste containing 54.8% anionic surfactants, 15.6% of unconverted compounds, 0 , 6% ammonium sulfate, chromaticity 5. The resulting surfactant reduces the interfacial tension at the aqueous solution – heptane interface to 0.1–10 J / m2, Example 10, Under the conditions of Example 8, the reaction with 9.58 g (0.12 mol ) sulfur trioxide is subjected to 148 g (0.2 mol) of alkylphenylpolyethoxybenzene fraction Cd average molecular weight 740, including their average ten hydroxyethyl groups. The interaction is carried out at a molar ratio of alkylphenylpolyethoxybenzenes: sulfur trioxide 1: 0.6, temperature 100 ° C for 10 minutes, maintaining air flow 3.6 l / min, sulfur trioxide concentration 7 vol.%, Sulfur trioxide consumption 0.95 g / min After reacting the reactants, 146 g of a reaction mixture containing 65.3% anionic surfactant sulfonic acids, 34.5% non-ionic compounds, 0.2% sulfur trioxide (calculated as sulfuric acid) are obtained. The degree of sulfur trioxide utilization is 97%. After neutralization the reaction mixture with a 25% aqueous solution of ammonium hydroxide (4.75 g) get a paste containing 60% surface-active ammonium sulfonates, 31.7% of unconverted compounds, 3.1% ammonium sulfate, color 80, The resulting product is treated with calcium dichloride and exchange Calcium salts, which are oil-soluble surfactants, are obtained in the reaction. 7 Example 11 Under the conditions of Example 1, 198 g (0.2 mol) are reacted with 12.8 g (0.16 mol) of sulfur trioxide. alkylpolyethoxy alkylbenzenes of the CjoCj fraction, average molecular weight 540, comprising on average three hydroxyethyl groups. The interaction is carried out at a molar ratio of alkyl polyethoxy alkyl benzene sulfur sulfur dioxide 1: 0.8, temperature for 10 minutes, maintaining air consumption 4.7 l / m sulfur trioxide consumption 1.28 g / min, sulfur trioxide concentration of 7 vol.%. After the reaction, 120 g of the reaction mixture are obtained, containing 81.0% anionic surfactant sulfonic acids, 18.8% unconverted compounds, 0.2% sulfur trioxide (calculated as sulfuric acid). The degree of use of sulfur trioxide is 98%. After neutralizing the reaction mass with a 25% aqueous solution of ammonium hydroxide (4.5 g), a paste containing 67.4% of surface-active ammonium sulfonates, 15.7% of unconverted compounds, 0.3% of ammonium sulfate, 50 color, is obtained. the product under conditions of example 10 is treated with calcium dichloride and low-soluble sulphonates are obtained. Example 12. Under the conditions of example 1, 138 g (0.15 mol) of alkyl condensate oxyalkyl benzenes of gas condensate of an average molecular weight 920, including fourteen hydroxyethyl groups, are reacted with 8 g (0.1 mol) of sulfur trioxide. The interaction is carried out at a molar ratio of alkylpolyoxoxyalkylbenzene and sulfur trioxide 1: 0.668, temperature 58 ° C for 20 min, maintaining air flow 2.1 l / min, sulfur trioxide consumption 0.4 g / min, sulfur trioxide concentration 5 vol. % After the reaction, 145 g of the reaction mixture containing 67% anionic sulfonic acids, 32.8% unconstituted compounds, P, 2% sulfur trioxide (calculated as sulfuric acid) are obtained. The degree of use of sulfur trioxide is 98%. After neutralizing the reaction mixture with a 25% aqueous solution of ammonium hydroxide (3.94 g), a paste is obtained containing 62.6% of surface-active ammonium sulfonates, 948 unconverted compounds; 0.25% ammonium sulfate, 40 color. The product obtained is an oil-soluble surfactant, since it is soluble in a hydrocarbon. Example 13. In a film reactor, which is a tube f with an inner diameter of 5 mm and a length of 800 mm, equipped with a jacket, pipes for supplying sulfogent gas and liquid raw materials, 6.73 g / min (0.017 mol) of alkylpolyethoxybenzenes C - C, with an average molecular weight of 396, including three hydroxyethyl groups. Through the device, which provides a film flow of the liquid, gaseous sulfoagent, which represents a mixture of dry air and sulfur trioxide vapor, is continuously fed through a tube located in the center of the axis of the reactor, with a flow rate of sulfur trioxide of 1.07 g / min (0.0136 mol / min ) and by air 7 l / min, maintaining the molar ratio of alkylpolyethoxybenzene and sulfur trioxide 1: 0.8, the concentration of sulfur trioxide 4% by volume and temperature. Contact time is 1 s. After separation of the gas phase, 7.78 g / min of the reaction mixture is obtained, comprising 79.5% anionic surfactant sulfonic acids, 20.2% unconverted compounds, 0.3% sulfur trioxide (calculated as sulfuric acid). The degree of use of sulfur trioxide is 95.6%. After neutralizing the reaction solution with a 10% aqueous solution of sodium hydroxide (0.64 g), a paste is obtained containing 48.9% surfactant sodium sulfonates, 12.5% unconverted compounds, 0.2% sodium sulfate, chroma 40. The resulting the sulfonate reduces the surface tension to 31 10 J / m. Example 14. Under the conditions of Example 1, the reaction was carried out at 120 ° C. for 60 minutes at a molar ratio of alkylphenylpolyethoxybenzenes: sulfur trioxide 1: 1.8, sulfur trioxide concentration 1%. 140 g of the reaction mixture containing 66.8% of coke-like products are obtained and non-convertible substances, 26% anionic surface-active sulfonic acids, 7.2% sulfur oxides (calculated on sulfuric acid). Chromaticity 200. The degree of use of sulfur trioxide is 13%.

Example 15. Under the conditions of Example 10, the reaction was carried out at 8 minutes at a molar ratio of alkylphenyl polyethoxybenzenes: sulfur trioxide 1: 0.4, sulfur trioxide concentration of 25 vol.%. After the reaction, 148.3 g of the reaction mixture containing 3.5% anionic surface-active sulfonic acids, 0.1% sulfur trioxide (calculated as sulfuric acid), 96.4% of the unconverted compounds are obtained. Color 20. The degree of use of sulfur trioxide 31%.

Example 16. Under conditions of example 13, a mixture of 6.73 g / min of the mixture is subjected to 4 g / min of alkylpolyethoxybenzene fractions of a molecular weight of 396, including three hydroxyethyl groups, and 2.73 g / min of alkylphenylpolyethoxybenzene of a fraction of Cd average molecular weight of 456, including four hydroxyethyl groups, maintaining the molar ratio of organic raw materials: sulfur trioxide 1: 0.84 and temperature. After separating the prepared medium, 7.77 g / min of the reaction mixture comprising 80% anionic surfactant sulfonic acids, E9.7% unconverted compounds and 0.3% sulfur trioxide (calculated as sulfuric acid), which is treated with the basic reagent (0 , 64 g) according to example 13. Color 50. The degree of use of sulfur trioxide is 95.5%. The surface tension of aqueous solutions using this surfactant is reduced to 32-10 n / m.

In tab. 1 shows the characteristics of the feedstock, and table. 2 the results obtained by the proposed method, in comparison with the prototype and the basic object.

The sulfonates obtained by the inventive method can be used as the basis for the preparation of micellar dispersions. Micelle dispersions

are multi-component stable systems. As such components there can be various hydrocarbons or their derivatives, water, electrolytes, auxiliary substances, on the ratio of which the stability of the micellar dispersion depends. For each substance or group of substances there will be its component compositions, which limit the stability of dispersions. Stability depends not only on the surfactant, but also on the excipient and electrolyte. The stability of the compositions for the sulfonates of examples 2 and 7 is more than 10, and in example 12 is less than 10.

For the sulfonates of example 2, the composition of the micellar dispersion was selected, which includes, in wt%: sulfonate 6.5; hydrocarbons 27.7; water 65.3; isopropanol 2, and an oil displacement capacity of 91% is determined.

Claims (1)

Invention Formula The method of producing surfactants by sulfonating the ethoxylated alkyl benzenes with gaseous sulfuric anhydride under heating followed by neutralization of the sulfomass by the main reagent, characterized in that, in order to simplify the process, compounds of the general formula I I are used as ethoxylated alkyl benzenes H1 (OCH2CH2) p-h3 3 de R - Cg-C, 2 o-alkyl or nonylphenyl; R. hydrogen or alkyl; • hydrogen or lower alkyl; 2-14, P and sulfonation is carried out at a molar ratio of the compound of formula 1 and sulfuric anhydride 1: (O, 6-1.2) and a temperature of 40-80 ° C. j th eat oo g ts g vO with p g with oo 1L Yu g 4t sh in a: cJ about U) TO ABOUT 1L w and l and TO E and about and S and 00 about (Tt Yu The radio is not installed, moreover, the baa oSect does not receive sulphonatm. Tablts "2