Method for preparing sodium dodecanoyloxybenzenesulfonate

Abstract

The present invention relates to a method for synthesizing dodecanoyloxybenzenesulfonate, a bleaching activator, in an aqueous solution at a low temperature. By performing the synthesis in an aqueous solution containing acetone at a low temperature, both purity and yield can be simultaneously increased, thereby reducing production costs and enabling the environmentally friendly preparation of dodecanoyloxybenzenesulfonate, a bleaching activator. Specifically, the purity and yield of dodecanoyloxybenzenesulfonate can be improved by reacting dodecanoyl chloride with sodium phenolsulfonate in a reaction solvent comprising water and acetone mixed at a weight ratio of 7:3 to 5:5, while maintaining the reaction temperature at a low temperature of 0°C to 10°C.

Description

Method for preparing sodium dodecanoyloxybenzenesulfonate

[0001] The present invention relates to a method for producing a sodium dodecanoyloxybenzenesulfonate compound in an aqueous solution with high purity and high yield.

[0002]

[0003] The method for manufacturing sodium dodecanoyloxybenzenesulfonate is known to involve synthesis primarily in hazardous solvents such as toluene or xylene, and actual commercialization techniques also involve synthesis in hazardous solvents.

[0004] U.S. Patent 6,822,113B2 discloses a method for preparing sodium dodecanoyloxybenzene sulfonate by reacting sodium para-phenol sulfonate (SPS) with an anhydride and a carboxylic acid derivative in an isopar G solvent at 120 to 130°C at 220°C.

[0005] U.S. Patent 4,537,724 discloses a method for producing acyloxybenzenesulfonate by reacting a hydroxybenzene sulfonate salt and an aryl ester with an organic solvent at 200 to 350°C.

[0006] Korean Patent Publication No. 10-2013-0086553 discloses a method for synthesizing the bleaching agent 4-dodecanoyloxybenzenesulfonate sodium by adding dehydrated sodium 4-hydroxybenzenesulfonate and lauric acid chloride dropwise at 50°C in an N, N-dimethylformamide (DMF) solution, reacting for 3 hours, removing the solvent, washing with acetone, recrystallizing in a water / acetone (1 / 1 mol) solvent, and purifying. However, it has the disadvantage of using a toxic solvent called N, N-dimethylformamide.

[0007] Korean registered patent No. 10-0423965 discloses a method of synthesizing dehydrated sodium 4-hydroxybenzenesulfonate and dodecanoyl chloride in a heptane solution at 98°C and recovering them by precipitation in methanol, but this also has the problem of using methanol, a harmful solvent.

[0008] Meanwhile, these inventions involve production under organic solvent conditions, resulting in high production costs and harm to the human body and the environment. Therefore, there is a need for the development of an eco-friendly manufacturing process that is easy to produce and economical.

[0009]

[0010] Accordingly, the inventors of the present invention have made efforts to develop an easy-to-produce and environmentally friendly process, and have confirmed that the target compound can be obtained with high yield and high purity even when reacted in an aqueous solution at low temperatures, thereby completing the present invention.

[0011]

[0012] One object of the present invention is to provide a method for producing an acyloxybenzenesulfonate represented by Formula 1, comprising the step of reacting dodecanoyl chloride and sodium phenolsulfonate in a reaction solvent containing water and acetone at a temperature of 10°C or lower.

[0013]

[0014] The present invention relates to a method for synthesizing dodecanoyloxybenzenesulfonate, a bleaching active agent, in an aqueous solution at low temperature. Since it is manufactured in an aqueous solution at low temperature, production costs can be reduced, and dodecanoyloxybenzenesulfonate, a bleaching active agent, can be manufactured in an environmentally friendly manner.

[0015]

[0016] Figure 1 shows the correlation between the yield and the ratio of solvents (purified water and acetone) and the reaction temperature (synthesis temperature).

[0017] Figure 2 shows the purity according to synthesis conditions and purification.

[0018]

[0019] To achieve the above objective, the present invention provides a method for producing an acyloxybenzenesulfonate represented by Formula 1, comprising the step of reacting dodecanoyl chloride and sodium phenolsulfonate in a reaction solvent containing water and acetone at a temperature of 10°C or lower.

[0020] [Chemical Formula 1]

[0021]

[0022] In the above Chemical Formula 1, R is C6 to C 22 The proportion of the compound having R = 11, which is a straight-chain or branched saturated alkyl group, is 60% by weight or more of the total alkyl group, and the reaction solvent is characterized by being a mixture of water and acetone in a weight ratio of 7:3 to 5:5.

[0023] The acyloxybenzenesulfonate represented by the above chemical formula 1 is a compound represented by chemical formula 2, which is sodium dodecanoyloxybenzenesulfonate.

[0024] [Chemical Formula 2]

[0025]

[0026] In the above chemical formula 1, R is C6 to C 22The proportion of the compound having a straight-chain or branched saturated alkyl group and a dodecanoyl group having R as 11 as the alkyl group (R) is 60% by weight or more of the total alkyl group, and preferably 60 to 100% by weight.

[0027] In the above chemical formula 1, if the proportion of a compound having an alkyl group shorter than the dodecanoyl group (R=11) as the alkyl group (R) increases, the solubility in water becomes excessively high, making recovery after synthesis difficult; conversely, if the proportion of a compound having an alkyl group longer than the dodecanoyl group (R=11) increases, the melting point becomes excessively high, making it difficult to achieve the original bleaching activation effect. Therefore, the proportion of the compound having R=11 is preferably at least 60 weight%, specifically 60 to 100 weight%.

[0028] The acyloxybenzenesulfonate represented by the above chemical formula 1 may be dodecanoyloxybenzenesulfonate, specifically sodium dodecanoyloxybenzenesulfonate, and the following description will focus on dodecanoyloxybenzenesulfonate.

[0029] The above dodecanoyloxybenzenesulfonate can be prepared by reacting dodecanoyl chloride and sodium phenolsulfonate in a reaction solvent containing water and acetone.

[0030] In an embodiment of the present invention, when a reaction was carried out at 0 to 15°C, preferably 5 to 10°C, using dodecanoyl chloride, sodium phenolsulfonate, and water and acetone as reaction solvents (mixed in a weight ratio of 7:3 to 5:5), the yield of sodium dodecanoyloxybenzenesulfonate was 73% or higher, specifically in the range of 73% to 80%, and the purity was 90% or higher. It was confirmed that the purity could be improved to 95% with only one wash. As shown in Fig. 1, while the yield could be increased to the 75% level by increasing the reaction temperature to 15°C or higher and reducing the acetone content, the purity of the product synthesized was low at the 60-80% level, which had the disadvantage of requiring an increase in the number of washes to increase the purity.

[0031] When the reaction temperature was maintained at a low level of 5 to 10°C, unlike the conditions of 15 to 40°C, the yield of dodecanoyloxybenzenesulfonate produced at a weight ratio of water to acetone exceeding 7:3 and increasing the proportion of water to 8:2 to 10:0 actually decreased, and at a weight ratio of water to acetone exceeding 5:5 and increasing the proportion of acetone to 4:6, the reactivity between dodecanoyl chloride and sodium phenolsulfonate decreased, resulting in a decrease in yield (Fig. 1).

[0032] In addition, referring to Table 3 of the present invention, it was confirmed that sodium dodecanoyloxybenzenesulfonate was synthesized by proceeding the reaction in a reaction solvent with a water-to-acetone mixing ratio of 65:35 to 50:50 at 5 to 10°C, and the yield was 73.2% to 78.5%. Furthermore, it was confirmed that when the reaction was carried out in a reaction solvent with a water-to-acetone mixing ratio of 60:40, the yield was the highest at 77% to 78.5%, and the purity was also relatively high at 91.2% to 91.6% (Examples 1, 3, and 4). This was significantly higher than the yield of 58.2% synthesized by reacting at 30°C when the water-to-acetone ratio was 60:40, and the purity was also significantly higher than 80.9% (Comparative Example 5).

[0033] In the inventor's previous patent application No. 10-2019-0013476, it was confirmed that the yield of dodecanoyloxybenzenesulfonate was highest when reacting at room temperature of 20 to 30°C, specifically 28°C, with a weight ratio of water to acetone of 9:1 to 7:3, and that when the weight ratio of acetone was increased to 6:4 under the same temperature conditions, the yield of dodecanoyloxybenzenesulfonate dropped to 58-60%. However, despite the high yield under these conditions, the purity remained at 80-85%, and there was a problem that washing had to be done three or more times to increase the purity to over 95%. Furthermore, during the washing process, the recovery rate decreased by 3-5% per wash, resulting in economic losses, and environmental problems also arose due to the repeated washing.

[0034] However, in the present invention, even when the reaction was carried out at a low temperature of 5 to 10°C with the mixing ratio of water and acetone increased to 7:3 to 5:5, the yield of the synthesized dodecanoyloxybenzenesulfonate was equivalent to or higher than that of the conventional room temperature reaction, and the purity before washing was 90% or higher, so there was no problem in using it as a bleaching agent even without washing, and a purity of 95% could be secured with only one wash.

[0035] As such, in the present invention, compared to the prior art, it was confirmed that by lowering the synthesis temperature to a range of 10°C or less and increasing the acetone ratio, the purity before washing increased to 90% or more, and the yield also increased to 73% or more. In other words, it was confirmed that lowering the synthesis temperature increased the purity, thereby reducing the number of washes, and that lowering the synthesis temperature while simultaneously increasing the acetone ratio could increase both the purity and the yield.

[0036] Accordingly, the reaction solvent for the above reaction may be a mixture of water and acetone in a weight ratio of 7:3 to 5:5, specifically in a weight ratio of 65:35 to 50:50. In a low-temperature reaction at a synthesis temperature of 0°C to 10°C, if the weight ratio of water to acetone exceeds 7:3 and the water content increases relative to acetone, there is a problem in that the yield or purity of the resulting dodecanoyloxybenzenesulfonate decreases; and if the weight ratio of water to acetone exceeds 5:5 and the acetone content increases relative to water, the reactivity of dodecanoyl chloride and sodium phenolsulfonate decreases, resulting in a decrease in yield (Figs. 1 and 2).

[0037] The above reaction is carried out at 10°C or lower, preferably at 0°C to 10°C. The synthesis of dodecanoyloxybenzenesulfonate represented by Chemical Formula 1 or Chemical Formula 2 by the above reaction is carried out at 10°C or lower, specifically at 5°C to 10°C. In addition, not only the synthesis of dodecanoyloxybenzenesulfonate represented by Chemical Formula 2 but also the recovery of the synthesized dodecanoyloxybenzenesulfonate can be carried out at 10°C or lower, specifically at 5°C to 10°C.

[0038] If the above reaction proceeds at temperatures below 0°C, there is no effect of increasing the synthesis yield or purity, but there is a problem of increased energy consumption. If the reaction proceeds at temperatures above 10°C, the reaction rate is relatively fast, but the purity of the resulting dodecanoyloxybenzenesulfonate decreases. In addition, washing must be repeated several times to increase purity, and since the yield decreases by 3–5% per wash, the final recovery rate is significantly reduced, making it uneconomical.

[0039] In addition, dodecanoyloxybenzenesulfonate represented by the above chemical formula 1 or chemical formula 2 can be used as a bleaching active substance.

[0040] In the present invention, the step of reacting may include: adding a reaction solvent to a reactor; adding sodium phenolsulfonate; adding an aqueous sodium hydroxide solution; adding a catalyst and stirring; and adding dodecanoyl chloride to carry out the reaction.

[0041] The above dodecanoylic chloride can be added by slowly dropping it into the reactor, and the reaction can be carried out for 0.5 to 4 hours after the dropping is finished.

[0042] In the reaction step above, based on 100 to 200 g of the reaction solvent, 0.05 to 0.15 mol of sodium phenolsulfonate, 0.05 to 0.15 mol of sodium hydroxide aqueous solution, and 0.05 to 0.15 mol of dodecanoyl chloride may be added.

[0043] The above sodium hydroxide aqueous solution may be a 20 to 80% sodium hydroxide aqueous solution.

[0044] The catalyst may be added in an amount of 0.05 to 1.0 weight% based on the total weight of the reaction solvent, sodium phenolsulfonate, sodium hydroxide aqueous solution, and dodecanoyl chloride added in the reaction step.

[0045] When the catalyst is added in an amount of less than 0.05 wt%, the reaction yield decreases and there are many by-products generated, and when the catalyst is added in an amount of more than 1.0 wt%, the reaction yield does not increase significantly and there is a disadvantage of reduced efficiency.

[0046] Accordingly, the reaction step may further include the step of maintaining the temperature inside the reactor, specifically at 10°C or lower, specifically at 0°C to 10°C.

[0047] When the above reactor is operated at a temperature below 0℃, there is no effect of increasing the synthesis yield or purity, but there is a problem of increased energy consumption. When the temperature exceeds 10℃, the reaction rate is fast, but there is a problem of significantly lower purity of dodecanoyloxybenzenesulfonate, and there is a problem of a 3~5% decrease in yield per wash due to additional washing.

[0048] The above reaction step may further include a step of maintaining the pH at 7 to 9.

[0049] In the above reaction step, if the pH becomes less than 7, a small amount of sodium hydroxide is added to maintain the pH at 7 to 9.

[0050] When the pH is less than 7, dodecanoyl chloride is easily decomposed, which can lower the yield, and when the pH is greater than 9, the reaction between dodecanoyl chloride and sodium phenolsulfonate slows down, which increases the number of by-products produced.

[0051] In the above reaction step, the dodecanoylic chloride and sodium phenolsulfonate may be added and reacted in a molar ratio of 1.0:0.8 to 1.2.

[0052] In the present invention, the catalyst may be one or more selected from the group consisting of acid compounds, base compounds, metal compounds, and ammonium salt compounds.

[0053] The acid compound is one or more selected from p-toluenesulfonic acid, phosphoric acid, hypophosphorus acid, sodium hypophosphorus, and sulfuric acid, the base compound is an alkali metal hydroxide, the metal compound is a compound containing one or more metals selected from Fe, Cu, Co, Ti, Sn, and Mn, and the ammonium salt may be a quaternary ammonium salt.

[0054] The above alkali metal may be one or more selected from lithium, sodium, potassium, rubidium, cesium, francium, and ununenumium.

[0055] The above ammonium salt compounds are specifically cetyltrimethylammonium chloride, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, diallyldimethylammonium chloride, didodecyldimethylammonium bromide, dimethyloctadecyl[2-(trimethoxysilyl)propyl]ammonium chloride, (hydrrazinocarbonylmethyl)trimethylammonium chloride, glycidyltrimethylammonium chloride, and hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen. Phosphate (Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate), Hexadecyltrimethylammonium bromide, Myristyltrimethylammonium bromide, Tetrabutylammonium bisulfate, Tetrabutylammonium bromide, Tetrabutylammonium chloride, Tetrabutylammonium hexafluorophosphate, Tetrabutylammonium hydrogensulfate,Tetrabutylammonium perchlorate, Tetrabutylammonium sulfate, Methyltrioctylammonium chloride, Tetrabutylammonium tribromide, Tetraethylammonium acetate, Tetraethylammonium bromide, Tetraethylammonium chloride, Tetraethylammonium iodide, Tetramethylammonium bromide, Tetramethylammonium chloride, Tetramethylammonium formate, Tetramethylammonium iodide, It may be one or more selected from the group consisting of tetramethylammonium silicate, tetrapropylammonium bromide, tribubutylmethylammonium chloride, tribubutylmethylammonium bromide, triethylmethylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium chloride, and (vinylbenzyl)trimethylammonium chloride.

[0056] In one embodiment of the present invention, the presence or absence of a reaction was confirmed using thin layer chromatography (TLC). If no residual sodium phenolsulfonate was present, distilled water (purified water) was introduced into the reactor to remove unreacted materials and soap generated as by-products, and dewatering was performed after stirring for about 30 minutes. The dewatered synthetic material was washed and dewatered repeatedly by adding acetone and drying to obtain sodium dodecanoyloxybenzenesulfonate. The dodecanoyloxybenzenesulfonate produced in the present invention has a purity of 90% or higher, and additional washing can be performed to increase the purity.

[0057] Accordingly, the method of manufacturing according to the present invention may further include the step of obtaining by dewatering.

[0058] The step of obtaining by dewatering refers to obtaining dodecanoyloxybenzenesulfonate by separating the solvent and the solid dodecanoyloxybenzenesulfonate through dewatering of the solution after the reaction step is completed. After dewatering, the wet powder can be transferred to a washing tank for additional washing, and at this time, water, acetone, or a mixed solvent of water and acetone can be used as the washing solution depending on the situation. The washed dodecanoyloxybenzenesulfonate is dewatered again and dried at 70 to 140°C for 0.5 to 4 hours, and a grinding process may be added if necessary.

[0059]

[0060] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0061]

[0062] Experimental Example 1. Comparison of yields according to solvent ratio and reaction temperature

[0063] 1-1. Preparation of Sodium Dodecanoyloxybenzenesulfonate

[0064] In a 5-neck flask reactor equipped with a mechanical stirrer, thermometer, and condenser, (A) 160 g of reaction solvent (purified water:acetone 100:0, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60) was added, (B) 23.2 g of sodium phenolsulfonate (0.1 mol, molecular weight 232.2), (C) 8 g of 50% aqueous sodium hydroxide solution (0.1 mol, molecular weight 40, containing 50 wt% water), and 0.7 g of tetra-n-butylammonium chloride (TBAC) / NaOH catalyst (0.33 wt% of the weight of A+B+C+D) were added, and the mixture was stirred at room temperature for about 1 hour. While slowly stirring, 20.8 g of (D) dodecanoyl chloride (0.095 mol, molecular weight 218.8) was slowly added dropwise. At this time, the internal temperature of the reactor (synthesis temperature) was maintained at 5°C to 40°C (specifically, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, or 40°C) using a condenser. After the addition of chloride was finished, the reaction was carried out for 1 hour at 5°C to 40°C (specifically, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, or 40°C) while maintaining the internal temperature of the reactor at 5°C to 40°C (specifically, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, or 40°C). The pH inside the reactor was checked and maintained so as not to fall below 7, and if the pH fell below 7, a small amount of 50% sodium hydroxide was added to adjust the pH to between 7 and 9.

[0065] After confirming the presence or absence of reaction by thin layer chromatography (TLC), if there was no residual sodium phenolsulfonate, 300 ml of distilled water (purified water) was added to the reactor and stirred for about 30 minutes, and dewatering was performed. The dewatered synthetic material was washed and dewatered twice by adding 100 g of acetone, and the final product was dried at 105°C for 2 hours to obtain sodium dodecanoyloxybenzenesulfonate.

[0066]

[0067] 1-2. Comparison of Yields According to Solvent Ratio and Reaction Temperature

[0068] Figure 1 shows the correlation between the yield and the ratio of solvents (purified water and acetone) and the reaction temperature (synthesis temperature).

[0069] Referring to Figure 1, the highest yield of sodium dodecanoyloxybenzenesulfonate was observed when the ratio of purified water to acetone was approximately 80:20 during synthesis at room temperature (20–30°C). However, since the purity of the reactant was analyzed to be in the 80% range, a washing process of 2 to 3 was required to increase the purity. Under these conditions, most water-soluble impurities were washed away, but a large amount of water-insoluble impurities remained. Therefore, to increase the purity to over 95%, a separate repeated washing process using a solvent such as acetone was required. However, there was a problem in that the yield decreased by approximately 3–5% per wash when the washing was repeated.

[0070] In order to increase the amount of water-insoluble impurities removed solely through the dewatering process during synthesis, the proportion of acetone must be increased. Referring to Fig. 1, the yield of sodium dodecanoyloxybenzenesulfonate decreased when the proportion of acetone increased to 60:40 or higher at 40°C, including at room temperature (20–30°C). However, as a result of lowering the reaction temperature to 0–10°C and increasing the proportion of acetone to 70:30 to 50:50, the yield increased and the purity also increased (Figs. 1 and 2).

[0071] Under conditions above room temperature, the reaction rate slows down as the proportion of acetone increases, creating an environment where the likelihood of side reactions increases. Conversely, under low-temperature reaction conditions, these side reactions are reduced, improving yield and purity, and the formation of water-insoluble byproducts, such as fatty acids, decreases even when the proportion of acetone increases.

[0072] Referring to Figures 1 and 2, when the reaction was carried out at 0 to 10°C using dodecanoyl chloride, sodium phenolsulfonate, and water and acetone as reaction solvents (mixed in a weight ratio of 7:3 to 5:5), the yield of sodium dodecanoyloxybenzenesulfonate was 75% or higher, specifically in the range of 75% to 80%, and the purity was 90% or higher without additional washing, specifically in the level of 90% to 94%, and a product with a purity of 95% or higher could be obtained with only one wash. However, when the reaction was carried out at 15 to 40°C, the yield of sodium dodecanoyloxybenzenesulfonate was 60% to 76%, and the purity was significantly lower in the level of 80% to 85%. In addition, even when the reaction was carried out at 0 to 10°C, the yield of dodecanoyloxybenzenesulfonate produced in the range of 8:2 to 10:0, where the weight ratio of water to acetone exceeded 7:3, decreased, and in the range of 4:6, where the weight ratio of water to acetone exceeded 5:5, the reactivity between dodecanoyl chloride and sodium phenolsulfonate decreased, resulting in a decrease in yield (Fig. 1).

[0073]

[0074] 1-3. Comparison of yield according to solvent ratio and temperature between the prior art and the present invention

[0075] In Table 1, the yield and purity of sodium dodecanoyloxybenzenesulfonate were specifically compared numerically according to the reaction temperature and the mixing ratio of purified water and acetone. At a reaction temperature of 15–40°C, the yield was highest at 74–78% when the ratio of distilled water (purified water) to acetone was 90:10–70:30 (Figure 1). When the ratio of acetone was increased to 60:40, the effect of removing water-insoluble impurities increased, while the yield decreased to 58–60%.

[0076] However, to overcome this, when the reaction temperature was maintained at 5 to 10°C or lower, the yield and purity were found to be highest when the ratio of purified water to acetone converged to around 60:40.

[0077] Reaction Temperature (Synthesis Temperature) Water / Acetone Yield Purity (Before Washing) Purity (1st Wash) Purity (2nd Wash) Purity (3rd Wash) 15~40℃ 80:20 75~78% approx. 80~85% approx. 90% approx. 93% approx. 96% 15~40℃ 60:40 58~60% approx. 80% approx. 86% approx. 90% approx. 93% 5~10℃ 60:40 77-80% approx. 91.5% approx. 95% approx. 97%-

[0078] In conclusion, the inventors discovered that the reaction temperature and the ratio of purified water (water):acetone affect not only the yield but also the purity of sodium dodecanoyloxybenzenesulfonate. As a result of conducting research to minimize the number of washes, it was confirmed that purity and yield are simultaneously increased under conditions of a low reaction temperature of approximately 5 to 10°C and a water:acetone ratio in the range of 70:30 to 50:50.

[0079]

[0080] Experimental Example 2. Comparison of Yield and Purity of Dodecanoyloxybenzenesulfonate

[0081] 2-1. Preparation of Sodium Dodecanoyloxybenzenesulfonate

[0082] Example 1.

[0083] In a 5-neck flask reactor equipped with a mechanical stirrer, thermometer, and condenser, 160 g of (A) purified water:acetone 60:40 was added as a reaction solvent, 23.2 g of (B) sodium phenolsulfonate (0.1 mol, molecular weight 232.2), 8 g of (C) 50% aqueous sodium hydroxide solution (0.1 mol, molecular weight 40, containing 50 wt% water), and 0.7 g of tetra-n-butylammonium chloride (TBAC) / NaOH catalyst (0.33 wt% of the weight of A+B+C+D) were added, and the mixture was stirred at room temperature for about 1 hour. While stirring slowly, 20.8 g of (D) dodecanoyl chloride (0.095 mol, molecular weight 218.8) was slowly added dropwise. At this time, the internal temperature of the reactor was maintained at 5°C using a cooler. After the dropwise addition of dodecanoyl chloride was finished, the reaction was carried out at 5°C for 1 hour while maintaining the internal temperature of the reactor at 5°C. The pH inside the reactor was checked and maintained so as not to fall below 7, and if the pH fell below 7, a small amount of 50% sodium hydroxide was added to adjust the pH to between 7 and 9.

[0084] After confirming the presence or absence of reaction by thin layer chromatography (TLC), if no residual sodium phenolsulfonate was found, 300 ml of distilled water (purified water) was added to the reactor and stirred for about 30 minutes, and dewatering was performed. The dewatered synthetic material was washed and dewatered twice by adding 100 g of acetone, and the final product was dried at 105°C for 2 hours to obtain the sodium dodecanoyloxybenzenesulfonate of Example 1.

[0085]

[0086] Examples 2 to 7.

[0087] Sodium dodecanoyloxybenzenesulfonate of Examples 2 to 7 was obtained by reacting under the conditions of Table 2, except that the ratio of purified water to acetone and / or the reaction temperature (synthesis temperature) were different, in the same manner as in Example 1.

[0088]

[0089] Comparative Example 1.

[0090] 98.08 g (0.5 mol) of sodium 4-phenolsulfonate and 25.30 g (0.25 mol) of triethylamine were added to 300 g of heptane, and 109.39 g (0.5 mol) of dodecanoyl chloride was added dropwise over 30 minutes while stirring under a nitrogen atmosphere, then the temperature was raised to 98°C and the reaction was carried out under reflux for 3 hours.

[0091] The reaction mixture was cooled to 50°C and the heptane was removed by reducing the pressure. Subsequently, 300g of methanol was added, and the pH was adjusted to 8.0 with a 25% NaOH aqueous solution. After filtering the mixture and drying it in a 60°C oven for 12 hours, 151.37g of sodium 4-dodecanoyloxybenzenesulfonate powder with a purity of 90% was obtained.

[0092]

[0093] Comparative Example 2.

[0094] A 2L three-necked round flask was equipped with a mechanical stirrer, a reflux condenser, and a gas inlet tube. The flask was filled with dodecanoyl chloride (2, Aldrich, 96 g, 0.44 mol), toluene (500 mL), and anhydrous phenol sulfonate (3, 78 g, 0.40 mol), and the reaction mixture was heated and refluxed for 16 hours while stirring under argon.

[0095] After cooling to room temperature, the mixture was diluted with diethyl ether (500 mL), the precipitated solid was filtered and collected, washed with additional diethyl ether, and air-dried.

[0096] The dried solid was purified by refluxing with methanol (750 mL), cooled to room temperature, filtered, and dried to obtain 125 g of dodecanoyloxybenzenesulfonate (LOBS) (83% of the theoretical value).

[0097]

[0098] Comparative Examples 3 to 10.

[0099] Sodium dodecanoyloxybenzenesulfonate of Comparative Examples 3 to 10 was obtained by reacting under the conditions of Table 2, with the same procedure as in Example 1, but with only the ratio of purified water to acetone and / or the reaction temperature (synthesis temperature) being different.

[0100] Classification Reactant Reaction Solvent (Ratio) Synthesis Temperature (°C) Dodecanoyl Chloride Sodium Phenol Sulfonate Purified Water Acetone Example 1 23.220.860405 Example 2 23.220.855455 Example 3 23.220.860408 Example 4 23.220.8604010 Example 5 23.220.8653510 Example 6 23.220.865355 Example 7 23.220.850508 Comparative Example 1 - Comparative Example 2 - Comparative Example 3 23.220.8802030 Comparative Example 4 23.220.8703030 Comparative Example 5 23.220.8604030 Comparative Example 623.220.8802020Comparative Example 723.220.8703020Comparative Example 823.220.810005Comparative Example 923.220.8901010Comparative Example 1023.220.880205

[0101]

[0102] 2-2. Comparison of Yield and Purity According to Solvent Ratio and Temperature

[0103] The yield and purity of the dodecanoyloxybenzenesulfonates prepared in Examples 1 to 7 and Comparative Examples 1 to 10 were specifically compared in Table 3.

[0104] The synthesis yield of Examples 1 to 7, in which the reaction was carried out at a synthesis temperature of 5 to 10°C in a reaction solvent with a ratio of purified water to acetone of 65:35 to 50:50, was 73.2% to 78.5%, and the purity was high at 90.5% to 94.2% even before washing. In addition, the purity was very high at over 95% after one wash, so the number of washes could be reduced.

[0105] In addition, Comparative Examples 1 and 2 were synthesized using a known method, and the yield was 78.2% to 83%, and the purity before washing was significantly low at 78% to 88.8%. Furthermore, even after washing twice, the purity was low at 92% to 94%.

[0106] Comparative Examples 3 to 7, in which the reaction was carried out at a synthesis temperature of 20 to 30°C under a reaction solvent with a ratio of purified water to acetone of 80:20 to 60:40, were synthesized by varying only the ratio of purified water to acetone and / or the synthesis temperature compared to Examples 1 to 7. Except for Comparative Example 5 (58.2%), the synthesis yield was at the level of 75.5% to 78.2%, but the purity before washing was at the level of 80.9% to 85.4%, which was significantly lower than that of Examples 1 to 7. In addition, the purity was less than 95% even after one and two washes, which was lower than that of Examples 1 to 7. In the case of dodecanoyloxybenzenesulfonate synthesized at a reaction temperature of 30°C with a water-to-acetone ratio of 8:2 in Comparative Example 3, the purity was 96.5% after three washes, indicating that at least three washes are required to secure a purity of 95% or higher. Additionally, Comparative Example 5 showed the lowest yield among Comparative Examples 3 to 7, with a yield of 58.2% and a purity of 80.9%. In the case of Comparative Example 5, although the reaction solvent was the same as in Examples 1, 3, and 4, the purity and yield were significantly lower because the synthesis was carried out at a temperature of 30°C.

[0107] In addition, it can be seen that Comparative Examples 8 to 10, in which the reaction was carried out at a water-to-acetone ratio of 100:0 to 80:20 even when the reaction was carried out at a synthesis temperature of 5 to 10°C, had a low synthesis yield and low purity before washing as well as low purity after the first and second washes. The higher the ratio of water to acetone, the lower the synthesis yield and purity before washing, and the purity after the first and second washes was also low.

[0108] In the present invention, it was confirmed that by lowering the synthesis temperature to a range of 5°C to 10°C and increasing the acetone ratio to a level of 70:30 to 50:50, the purity before washing increased to over 90%, and the yield also increased to over 73%. That is, as a result of lowering the synthesis temperature, the purity increased, which could reduce the number of washes, and by lowering the synthesis temperature while simultaneously increasing the acetone ratio, both the purity and the yield were increased.

[0109] Even if the synthesis yield is high, if the purity is low, the number of washing cycles required to increase purity may increase, leading to higher costs and environmental burdens. Furthermore, there is a problem where the final recovery rate decreases due to product loss during the washing process. However, the present invention has the advantage of simultaneously increasing both purity and yield by controlling the synthesis temperature and the acetone ratio.

[0110] Classification Synthetic Yield (%) Purity (%) Before Washing (%) 1st Wash (%) 2nd Wash (%) 3rd Wash (%) Example 1 78.59 1.69 7.49 8.1 Example 2 77.29 0.59 6.39 7.8 Example 3 77.89 1.59 7.69 7.9 Example 4 77.91.29 7.49 7.6 Example 5 75.91.69 5.95 5.4 Example 6 77.89 2.19 6.69 8.8 Example 7 77.29 4.29 6.89 9.1 Comparative Example 1 78.28 8.89 0.94 Comparative Example 2 83.78 88 92 Comparative Example 3 78.28 5.49 294.59 6.5 Comparative Example 47884.490.994.8 Comparative Example 558.280.986.390.5 Comparative Example 677.481.588.993.2 Comparative Example 775.581.587.892.2 Comparative Example 862.166.569.173.2 Comparative Example 970.277.780.288.3 Comparative Example 1072.980.988.389.8

[0111]

[0112] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims also fall within the scope of the present invention.

Claims

1. A method for preparing an acyloxybenzenesulfonate represented by Chemical Formula 1, comprising the step of reacting dodecanoyl chloride and sodium phenolsulfonate in a reaction solvent containing water and acetone at a temperature of 10°C or lower; [Chemical Formula 1] In the above chemical formula 1, R is C6 to C 22 It is a straight-chain or branched saturated alkyl group, and The proportion of compounds where R is 11 is 60 weight percent or more of the total alkyl groups, and The above reaction solvent is a mixture of water and acetone in a weight ratio of 7:3 to 5:

5.

2. In Paragraph 1, A method for manufacturing the above acyloxybenzenesulfonate, wherein the acyloxybenzenesulfonate is a compound represented by Chemical Formula 2. [Chemical Formula 2] 3. In Paragraph 1, The above reaction step is, Step of adding a reaction solvent to the reactor; Step of adding sodium phenolsulfonate; Step of adding an aqueous sodium hydroxide solution; Step of adding and stirring a catalyst; and A method of manufacturing comprising the step of carrying out a reaction by adding dodecanoyl chloride.

4. In Paragraph 3 A method of preparation comprising adding 0.05 to 0.15 mol of sodium phenolsulfonate, 0.05 to 0.15 mol of sodium hydroxide aqueous solution, and 0.05 to 0.15 mol of dodecanoyl chloride to 100 to 200 g of the above reaction solvent.

5. In Paragraph 3 A method of preparation in which the catalyst is added in an amount of 0.05 to 1.0 weight% based on the total weight of the reaction solvent, sodium phenolsulfonate, sodium hydroxide aqueous solution, and dodecanoyl chloride added in the reaction step.

6. In Paragraph 3, A method of manufacturing, wherein the above reaction step further includes the step of maintaining the internal temperature of the reactor at 10℃ or lower.

7. In Paragraph 3, A method of manufacturing, wherein the above reaction step further includes a step of maintaining the pH at 7 to 9.

8. In Paragraph 1, A method of manufacturing in which the above reaction is carried out at 10℃ or lower.

9. In Paragraph 1, A method for manufacturing, wherein in the above reaction step, the dodecanoylic chloride and sodium phenolsulfonate are added and reacted in a molar ratio of 1.0:0.8 to 1.

2.

10. In Paragraph 3, A method for manufacturing the above catalyst, wherein the catalyst is one or more selected from the group consisting of acid compounds, base compounds, metal compounds, and ammonium salt compounds.

11. In Paragraph 10, A method for manufacturing, wherein the acid compound is one or more selected from p-toluenesulfonic acid, phosphoric acid, hypophosphoric acid, sodium hypophosphorus, and sulfuric acid, the base compound is an alkali metal hydroxide, the metal compound is a compound containing one or more metals selected from Fe, Cu, Co, Ti, Sn, and Mn, and the ammonium salt is a quaternary ammonium salt.

12. In Paragraph 10, The above ammonium salt compounds are cetyltrimethylammonium chloride, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, diallyldimethylammonium chloride, didodecyldimethylammonium bromide, dimethyloctadecyl[2-(trimethoxysilyl)propyl]ammonium chloride, (hydrrazinocarbonylmethyl)trimethylammonium chloride, glycidyltrimethylammonium chloride, and hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen. Phosphate (Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate), Hexadecyltrimethylammonium bromide, Myristyltrimethylammonium bromide, Tetrabutylammonium bisulfate, Tetrabutylammonium bromide, Tetrabutylammonium chloride, Tetrabutylammonium hexafluorophosphate, Tetrabutylammonium hydrogensulfate, Tetrabutylammonium perchlorate,Tetrabutylammonium sulfate, Methyltrioctylammonium chloride, Tetrabutylammonium tribromide, Tetraethylammonium acetate, Tetraethylammonium bromide, Tetraethylammonium chloride, Tetraethylammonium iodide, Tetramethylammonium bromide, Tetramethylammonium chloride, Tetramethylammonium formate, Tetramethylammonium iodide, Tetramethylammonium silicate, A method of manufacturing, wherein one or more selected from the group consisting of tetrapropylammonium bromide, tribubutylmethylammonium chloride, tribubutylmethylammonium bromide, triethylmethylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium chloride, and (vinylbenzyl)trimethylammonium chloride.

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