JPH0246578B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing high-purity, high-quality higher secondary alcohol ethoxy sulfate that is free of impurities, has no unpleasant odor, and has extremely low irritation. In recent years, the safety of raw materials for cosmetics, cleaning agents, etc. has been desired, and in particular, sufficient safety tests have been conducted on skin irritation, eye mucous membrane irritation, various sensitization properties, carcinogenicity, and various other safety tests. Ta. As a result, one of the things that greatly influences the results of safety tests is
This may be due to the purity of the raw materials used. The purity of this raw material is affected by the method of manufacturing the raw material. Therefore, raw materials for cosmetics, detergents, etc. are required to be as pure as possible, and in particular, a method for producing high-purity raw materials that can strictly suppress the by-product or contamination of harmful substances is desired. . Higher secondary alcohol ethoxy sulfate is
It is currently used in large quantities as a raw material for industrial and household cleaning agents, and is particularly known for its solubility, low-temperature stability, hard water resistance, foam-breaking properties, good biodegradability, and extremely low skin irritation. From this point of view, it is a detergent base material that is expected to grow more and more. Higher secondary alcohol ethoxy sulfate is
Usually 1 to 1 to a linear secondary alcohol with 8 to 20 carbon atoms
It is obtained by sulfating higher secondary alcohol ethoxylate to which 100 moles of ethylene oxide has been added with sulfur trioxide, chlorosulfonic acid, fuming sulfuric acid, etc. The higher secondary alcohol ethoxy sulfate obtained by these methods has unique properties. It has an odor and
Quality deterioration is also likely to occur. This is thought to be because the sulfating agent is a strong dehydrating agent and oxidizing agent, and the raw material ethoxylate, especially the free alcohol therein, is likely to produce olefins, olefin derivatives, aldehydes, etc. through side reactions. It is being Various methods have been reported on methods to suppress the reactivity of these powerful sulfating agents or to improve quality through post-treatment of the generated sulfates, but none have yet met the high demands of recent years. . Therefore, the inventors of the present invention have conducted intensive research and have arrived at the present invention. That is, the present invention is based on the general formula (However, n=1 to 18, m=1 to 18, n+m=7
~19, p is 1 to 100 on average, and contains 1% by weight or less of unreacted alcohol (those with p = 0). ) and sulfamic acid having a particle size distribution of 60 to 200 mesh in the presence of 0.5 to 5% by weight of urea based on the higher secondary alcohol ethoxylate at temperature.
This is a method for producing high-purity secondary alcohol ethoxy sulfate, which is characterized by carrying out the reaction at 70 to 100°C in an inert gas atmosphere. The higher secondary alcohol ethoxylate used in the present invention has the general formula (However, n=1 to 18, m=1 to 18, n+m=7
~19, p is 1 to 100 on average, and contains 1% by weight or less of unreacted alcohol (those with p = 0). ), and in particular, higher secondary alcohol ethoxylates with an unreacted alcohol content of 1% by weight or less are required. The higher secondary alcohol ethoxylate used is one obtained by adding ethylene oxide to a random secondary alcohol obtained by liquid phase oxidation of a linear paraffin having 8 to 20 carbon atoms. For example, an ethylene oxide adduct of a secondary alcohol having 12 to 14 carbon atoms (trade name: SOFTANOL, manufactured by Nippon Shokubai Chemical Co., Ltd.) is preferable. Specific examples include Softanol-30 (in the general formula, n = 1 to 12, m = 1 to 12, an adduct of 3 moles of ethylene oxide with a secondary alcohol having 12 to 14 carbon atoms), Softanol-50 (in the general formula, n = 1 to 12, m = 1 to 12, carbon number 12 to 14 secondary alcohol adduct with 5 moles of ethylene oxide) Softanol-70 (In the general formula, n = 1 to 12, m = 1 to 12 carbon numbers) Softanol-90 (In the general formula, n = 1 to 12, m = 1 to 12, 9 moles of ethylene oxide adduct of a secondary alcohol having 12 to 14 carbon atoms) Softanol-120 (In the general formula, n = 1 to 12, m = 1 to 12, secondary alcohol with 12 to 14 carbon atoms, ethylene oxide
12 Molar Adduct) As the sulfamic acid used in the present invention, a sulfamic acid having a particle size distribution of 60 to 200 meshes is suitable. The molar ratio of higher secondary alcohol ethoxylate and sulfamic acid is not particularly limited, but in order to reduce unreacted higher secondary alcohol ethoxylate or sulfamic acid and obtain high purity higher secondary alcohol ethoxysulfate. A substantially 1:1 molar ratio is preferred. The amount of urea used is 0.5 to 5% by weight based on the higher secondary alcohol ethoxylate, but according to the method of the present invention, the purpose can be sufficiently achieved even with 1 to 2% by weight, and the quality can be significantly improved. . This urea remains in the product and partially decomposes into ammonia etc. at a pH of 7 or above, but at a pH of below 7 it is stable and not only does not cause any toxicity or irritation, but also has solubilizing ability. Has a positive effect on cleaning agents. The reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen. According to the present invention, sufficient solid-liquid contact conditions can be obtained,
Substantially shortened reaction time and prevention of side reactions are achieved. As a result, high secondary alcohol ethoxy sulfate can be obtained with a selectivity of 99% or higher by reacting sulfamic acid with a reaction rate of 99% or higher, and is highly pure higher secondary alcohol ethoxy sulfate that contains almost no impurities and has no unpleasant odor. You can get sulfate. In addition, the method of the present invention uses raw materials with extremely low toxicity and danger, so it does not require large-scale equipment for safety reasons, and it also does not require post-processing or purification. It is industrially excellent as it can produce high grade secondary alcohol ethoxy sulfate with high purity and high quality. The higher secondary alcohol ethoxy sulfate obtained in this way is obtained as an ammonium salt, but in the weakly acidic region of pH 7.0 or lower, it does not produce any ammonia odor and has excellent low temperature stability and solubility.
It also has the characteristics of good foam removal and easy rinsing. In recent years, the importance of safety in detergents has been emphasized, and weakly acidic detergents that are less irritating to the skin and eye mucous membranes are desired, especially in fields that come into direct contact with the skin, and weakly acidic shampoos are being sought after. High purity, high quality higher secondary alcohol ethoxy sulfate is extremely suitable as a base material for dishwashing detergents and shampoos. In addition, by adding alkali metal hydroxide such as NaOH or KOH and removing ammonia as required, high purity and high quality higher alcohol ethoxysulfate alkali metal salts can be easily obtained. . The present invention will be specifically explained below with reference to examples. Example 1 An average of 3 moles of ethylene oxide was added to a mixture of secondary alcohols having 12 to 14 carbon atoms to prepare a 3 mole ethylene oxide adduct of the secondary alcohol (trade name: Softanol) containing 0.5% by weight of unreacted alcohol.
-30 manufactured by Nippon Shokubai Chemical Co., Ltd.) and 1 mole of sulfamic acid (60 to 100 mesh (Note)) as a sulfating agent to 3.33 g of urea (based on the raw material ethoxylate).
1.0% by weight) under a nitrogen atmosphere at 100°C with vigorous stirring. A reaction solution was taken at every predetermined reaction time, and the yield of higher secondary alcohol ethoxysulfate was measured by potentiometric titration. The results were as shown in Table 1. After the reaction is complete, add water and a small amount of ammonia water to adjust the pH.
It was made into a 30% aqueous solution of 6.0 to 6.5. (Note) 60 to 100 mesh refers to material that passes through a 60 mesh sieve but does not pass through a 100 mesh sieve. The same method of expression will be used below. Example 2 The same procedure as in Example 1 was carried out except that the reaction temperature was changed to 95°C. The results were as shown in Table 1. Examples 3 to 4 In Example 1, the amount of urea added was 2% by weight,
The same procedure as in Example 1 was carried out except that sulfamic acid of 60 to 100 mesh and 150 to 200 mesh was used. The results were as shown in Table 1. Comparative Example 1 The same procedure as in Example 1 was carried out except that the experiment was carried out under an air atmosphere. The results were as shown in Table 1. Comparative Examples 2 to 3 The same procedure as in Example 1 was carried out except that the reaction temperature was changed to 120°C and 140°C. The results were as shown in Table 1. Comparative Example 4 The same procedure as in Example 1 was carried out except that urea was not added. The results were as shown in Table 1. Comparative Example 5 The same procedure as in Example 3 was carried out except that 20 to 60 meshes of sulfamic acid were used.
The results were as shown in Table 1. Example 5 A 40% by weight aqueous solution of caustic soda containing an equivalent amount of caustic soda was added to the 30% by weight aqueous solution of the secondary alcohol ethoxysulfate ammonium salt obtained in Example 4, and the mixture was heated at 100°C for 2 hours to remove ammonia. Further water was added to obtain a 30% by weight aqueous solution of soda salt. Comparative Example 6 In Example 1, commercially available sulfamic acid
The same procedure as in Example 1 was carried out except that the width of 200 mesh and the particle size distribution as shown in Table 2 were used. The results were as shown in Table 1. Comparative Example 7 1 mole of the secondary alcohol ethylene oxide adduct (trade name, Softanol-30, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) used in Example 1 was placed in a flask No. 2, and the sulfating agent was added with vigorous stirring under a nitrogen atmosphere. Then, 1.05 mol of chlorosulfonic acid was added dropwise over 60 minutes. The reaction was carried out under ice cooling, and the reaction temperature was maintained at 5 to 10°C. After the dropwise addition was completed, nitrogen was flowed into the solution to remove hydrogen chloride for 60 minutes. After the reaction is complete, add water and aqueous caustic soda solution while cooling in a water bath until the pH is 7.0 to 7.5.
A 30% aqueous solution of sodium sulfate ester was obtained. The results were as shown in Table 1. Table 1 shows the reaction conditions, yield, and product quality (hue, odor) for Examples 1 to 5 and Comparative Examples 1 to 6. The odor was judged as follows. ◎: Almost no odor ○: Slight odor △: Slightly unpleasant odor ×: Obviously unpleasant odor The results of changes over time of the products obtained in Examples 3 and 5 and Comparative Example 6 are shown in Table 3. It was as shown in.
The samples were left in thermostats at 25°C and 40°C for 60 days, and the decomposition rate was measured by the Epton method. Hue (30% aqueous solution APHA NO): Pt-Co hue standard (Chromaticity based on hue indication of ASTM: D1209-54)

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Claims (1)

[Claims] 1. General formula (However, n=1~18, m=1~18, n+m=7
~19, p is 1 to 100 on average, and contains 1% by weight or less of unreacted alcohol (those with p = 0). ) and sulfamic acid having a particle size distribution of 60 to 200 mesh in the presence of 0.5 to 5% by weight of urea based on the higher secondary alcohol ethoxylate at temperature.
A method for producing high purity higher secondary alcohol ethoxy sulfate, which comprises reacting at 70 to 100°C under a nitrogen gas atmosphere with stirring.