JPH0248541B2 - ANTEIKASHITAFUENOORURUIETOKISHISARUFUEETONOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to stabilized phenol ethoxysulfates that generate very little odor due to changes over time. More specifically, it relates to stabilized phenol ethoxysulfate, which is obtained by adding a specific neutralizing agent to phenol ethoxylate obtained by reacting phenols with ethylene oxide, and then sulfating the resulting product, which exhibits very little change in quality over time. It is something. Phenol ethoxysulfate, which is obtained by sulfating phenol ethoxylate obtained by reacting phenols with ethylene oxide, is used in a wide range of fields as a surfactant. For example, (1) Textile-related polyester, cotton, raw wool washing, wetting agents, dyeing aids, textile bleaching, finishing agents, antistatic agents, textile oils, emulsifiers. (2) Paper and pulp related Wetting agents, finishing, deinking agents, bleaching, resin removal agents, sizing agents (3) Metal related Degreasing and cleaning agents, rust removal and rust prevention agents, machining, lubricant plating, quenching For tempering agent and penetrant testing liquid. (4) Agriculture and forestry-related agricultural chemicals emulsifiers, spreading agents, and various cleaning agents. (5) Leather-related For chromic acid tanning, dyeing, and finishing. (6) Detergent-related industrial use, liquid household use, powder household use, residential use,
For cleaning and automobile use. (7) Cosmetics: For ointments, emulsifiers, and shampoos. (8) Others Used as dustproofing agent, spilled oil treatment agent, oil separation agent, etc. (Prior art) Generally, phenol ethoxylates obtained by reacting phenols with ethylene oxide are prepared using alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alkoxide, boron trifluoride, boron trifluoride-complexes, etc. It is produced by adding ethylene oxide to phenols in the presence of an acidic catalyst such as antimony pentachloride or tin tetrachloride. Phenol ethoxylates obtained by this method not only contain unreacted phenols, but also contain small amounts of catalysts, aldehydes, free acids, peroxides, and other impurities that may cause bad odors or coloration. Contains. Phenol ethoxylates containing these impurities are purified by methods such as neutralization with acid or alkali, washing with aqueous alkaline solution, distillation, reduction, adsorption, and filtration. Alkaline catalysts are usually purified by adding mineral acids such as sulfuric acid or phosphoric acid or acetic acid to neutralize them. The phenol ethoxy sulfate obtained by further sulfating the phenol ethoxylate thus obtained contains other impurities that cause odor, and has the problem of generating a bad odor as it ages. Particularly in recent years, there has been an increasing demand for odorless raw materials for industrial or household detergents. Furthermore, when phenol ethoxylates that have changed over time are sulfated with a sulfating agent such as sulfur trioxide or chlorosulfonic acid, there is a problem in that the odor and color of the produced phenol ethoxysulfates deteriorate significantly. As mentioned above, when the desired phenol ethoxysulfate product is made using the phenol ethoxylate obtained by the conventional technology, there is a problem that the quality of the phenol ethoxysulfate product deteriorates due to changes over time. Undesirable. Alkali catalysts such as sodium hydroxide, potassium hydroxide, and sodium alkoxide used when producing phenol ethoxylates by reacting phenols with ethylene oxide are usually treated with mineral acids such as sulfuric acid, phosphoric acid, or acetic acid. It is purified by adding a neutralizing agent such as
When producing phenol ethoxylates by reacting phenols with ethylene oxide, if a conventional neutralizing agent is used to sulfate phenols to produce phenol ethoxysulfates, the odor caused by the change over time of phenols ethoxysulfates will be reduced. There was a problem. (Problems to be Solved by the Invention) It is an object of the present invention to eliminate odor caused by changes over time in phenol ethoxysulfate obtained by further sulfating phenol ethoxylate obtained by reacting phenols with ethylene oxide. An object of the present invention is to provide phenol ethoxy sulfate with extremely low generation of. (Means for Solving the Problems) The present invention provides stabilization characterized by sulfating a phenol ethoxylate obtained by adding ethylene oxide to a phenol and containing lactic acid and/or a lactate. The present invention relates to phenolic ethoxysulfate. The lactic acid used in the present invention may be produced by either a fermentation method or a synthetic method, and the purity of the lactic acid is not particularly limited. Either can be used. The lactate salts used in the present invention are alkali metal salts of lactic acid such as sodium lactate, potassium lactate, and lithium lactate, alkaline earth metal salts of lactic acid such as calcium lactate, magnesium lactate, and barium lactate, aluminum lactate, zinc lactate, and silver lactate. , copper lactate, iron lactate, manganese lactate, ammonium lactate, etc.
Particularly preferred are sodium lactate and potassium lactate. The amount of lactic acid and/or lactate used in the present invention is 5 to 0.001 parts by weight, preferably 1 to 0.05 parts by weight, per 100 parts by weight of phenol ethoxylate.
Parts by weight. When adding, the pH of the aqueous solution should be 4~
9, preferably in the range of 5 to 7. The method of adding lactic acid and/or lactate of the present invention is to add lactic acid to unneutralized phenol ethoxylate obtained by reacting phenols and ethylene oxide in the presence of an alkali catalyst, or to neutralize the catalyst. There is a method of adding lactic acid and/or lactate to a phenol ethoxylate in which the catalyst has been removed by a known method such as filtration or the like. When adding lactic acid and/or lactate, it is preferable to add lactic acid and/or lactate to phenol ethoxylate as is or as a solution, and stir for about 30 minutes to completely dissolve. The phenol ethoxylates used in the present invention include the phenols and an alkali catalyst such as sodium hydroxide, potassium hydroxide, and sodium alkoxide, or boron trifluoride, boron trifluoride-complex, antimony pentachloride, tin tetrachloride, etc. Examples include those obtained by addition reaction of ethylene oxide in the presence of an acidic catalyst. The reaction temperature of the phenol ethoxylate obtained by reacting the phenols of the present invention with ethylene oxide is preferably in the range of 100 to 200°C, particularly 130 to 170°C. The addition of ethylene oxide to phenols is 0.1 ethylene oxide per mole of phenol.
~100 mol, preferably 1-50 mol. For the sulfation of the phenol ethoxylate of the present invention, a sulfating agent such as sulfur trioxide, chlorosulfonic acid, sulfamic acid, or fuming sulfuric acid can be used. In the sulfation of phenol ethoxylates of the present invention, the amount of the sulfating agent relative to the phenol ethoxylate is not limited, but is in the range of 0.5 to 2.0 mol, preferably 0.8 to 1.5 mol. The reaction temperature for the sulfation of phenol ethoxylates of the present invention is preferably in the temperature range of 50°C or lower, particularly 40°C or lower. Examples of phenols include phenol, bisphenol, ortho-cresol, metacresol, para-cresol, 2,4-dialkylphenol,
2,5-dialkylphenol, 2,6-dialkylphenol, nonylphenol, octylphenol, orthochlorophenol, metachlorophenol, parachlorophenol, paramethoxyphenol, paraaminophenol, orthophenylphenol, t-butyl-paracresol , hydroquinone, catechol, resorcinol, pyrogallol, 1-naphthol, 2-naphthol,
4-chloro-2-nitrophenol, para-t-
Butylphenol, orthoaminophenol, dodecylphenol, octylcresol, dioctylcresol, dinonylphenol, 2,5-
Examples include dichlorophenol. The phenol ethoxylate used in the present invention is prepared by adding alkali catalysts such as sodium hydroxide, potassium hydroxide and sodium alkoxide to phenols, or boron trifluoride, boron trifluoride-complexes, antimony pentachloride, tin tetrachloride, etc. Examples include those obtained by addition reaction of ethylene oxide in the presence of an acidic catalyst. Although the number of moles of ethylene oxide added is not particularly limited, it is usually in the range of 0.1 to 100 moles in terms of average number of moles added, particularly 1 to 50 moles.
A molar range is practical. (Function) Phenol ethoxysulfate obtained by reacting phenols and ethylene oxide to contain lactic acid and/or lactate and then sulfating the phenol ethoxysulfate is as follows:
It was found that this product has the effect of extremely reducing the occurrence of odor due to changes over time. (Example) Hereinafter, embodiments of the present invention will be specifically illustrated and described with reference to Examples. The invention is not limited to the following embodiments. The test methods used in the examples are as follows. ≪Time change test≫ A 500ml transparent glass bottle containing 250g of sample was heated to
It was placed in an air circulation constant temperature bath adjusted to 50°C and subjected to a time change test. (1) PH 5% by weight aqueous solution (2) Odor 50 ml of water was added to 0.5 ml of the sample and judged at a temperature of 50°C. The odor was judged as follows. A: Slight odor B: Slight odor C: Stimulating odor Example 1 Nonylphenol (molecular weight
221) 200g, 0.6g of sodium hydroxide as a catalyst,
400 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. To the resulting nonylphenol adduct with ethylene oxide on average of 10 moles,
2.7 g of 50% by weight aqueous lactic acid solution was added and stirred well. Obtained nonylphenol ethoxylate 1
A mole of chlorsulfonic acid was placed in a stirring tank, and the temperature was maintained at 30 to 35° C., and 1 mole of chlorosulfonic acid was dropped into the stirred tank over about 1 hour to cause a reaction while stirring vigorously. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then 40
The reaction solution was neutralized by pouring it into an aqueous sodium hydroxide solution while maintaining the temperature below .degree. C. to obtain an aqueous solution of nonylphenol ethoxy sulfate. Ethylene oxide average of obtained nonylphenol 10.0
A test on changes over time was conducted on an aqueous solution of morsulfate. The results were as shown in Table 1. Comparative Example 1 Nonylphenol (molecular weight
221) 200g, 0.6g of sodium hydroxide as a catalyst,
400 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. 0.9 g of acetic acid was added to the obtained adduct of nonylphenol with ethylene oxide on average of 10 moles, and the mixture was thoroughly stirred. One mole of the obtained nonylphenol ethoxylate was placed in a stirring tank 1, and the temperature was maintained at 30 to 35°C, and while stirring vigorously, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, An aqueous solution of nonylphenol ethoxy sulfate was obtained. The obtained nonylphenol ethylene oxide sulfate aqueous solution with an average of 3.0 mol was tested for changes over time. The results were as shown in Table 1. Comparative Example 2 Nonylphenol (molecular weight
221) 200g, 0.6g of sodium hydroxide as a catalyst,
400 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. To the resulting nonylphenol adduct with ethylene oxide on average of 10 moles,
0.9 g of 85% by weight aqueous phosphoric acid solution was added and stirred well. One mole of the obtained nonylphenol ethoxylate was placed in a stirring tank 1, and the temperature was maintained at 30 to 35°C, and while stirring vigorously, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then 40
The reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature below .degree. C. to obtain an aqueous solution of nonylphenol ethoxy sulfate. Ethylene oxide average of the obtained nonylphenol: 10.0
A test on changes over time was conducted on an aqueous solution of morsulfate. The results were as shown in Table 1.

[Table] Example 2 Nonylphenol (molecular weight
221) 376g, 0.6g of sodium hydroxide as a catalyst,
224 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. 2.7 g of a 50% by weight aqueous lactic acid solution was added to the obtained nonylphenol adduct with ethylene oxide of 3.0 moles on average, and the mixture was thoroughly stirred. One mole of the obtained nonylphenol ethoxylate was placed in a stirring tank 1, and the temperature was maintained at 30 to 35°C, and while stirring vigorously, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then 40
The reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at a temperature below .degree. C. to obtain an aqueous solution of nonylphenol ethoxy sulfate. Ethylene oxide average of obtained nonylphenol 3.0
A test on changes over time was conducted on an aqueous solution of morsulfate. The results were as shown in Table 2. Comparative Example 3 Nonylphenol (molecular weight
221) 376g, 0.6g of sodium hydroxide as a catalyst,
224 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. 0.9 g of acetic acid was added to the obtained adduct of nonylphenol with ethylene oxide on average of 3.0 mol, and the mixture was thoroughly stirred. 1 mol of the obtained nonylphenol ethoxylate
The mixture was placed in a stirred tank, and the temperature was maintained at 30 to 35°C, and 1 mole of chlorosulfonic acid was dropped into the tank over about 1 hour to cause a reaction while stirring vigorously. After the supply of chlorosulfonic acid is completed, nitrogen gas is supplied into the stirring tank,
By-product hydrogen chloride gas was removed, and then the reaction solution was neutralized in an aqueous sodium hydroxide solution while maintaining the temperature at 40° C. or lower to obtain an aqueous nonylphenol ethoxy sulfate solution. The obtained nonylphenol ethylene oxide sulfate aqueous solution with an average of 3.0 mol was tested for changes over time. The results were as shown in Table 2. Comparative Example 4 Nonylphenol (molecular weight
221) 376g, 0.6g of sodium hydroxide as a catalyst,
224 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. 0.9 g of an 85% by weight aqueous phosphoric acid solution was added to the obtained adduct of nonylphenol with ethylene oxide of 3.0 mol on average, and the mixture was thoroughly stirred. 1 mol of the obtained nonylphenol ethoxylate was placed in a stirring tank 1 and maintained at a temperature of 30 to 35°C.
While vigorously stirring, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, An aqueous solution of nonylphenol ethoxy sulfate was obtained. The obtained nonylphenol ethylene oxide sulfate aqueous solution with an average of 3.0 mol was tested for changes over time. The results were as shown in Table 2.

[Table] Example 3 Octylphenol (molecular weight
206) 191g, potassium hydroxide 0.6g as a catalyst,
409 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. To the obtained adduct of octylphenol with an average of 10 moles of ethylene oxide, 1.9 g of a 50% by weight aqueous lactic acid solution was added and stirred well. One mole of the obtained octylphenol ethoxylate was placed in a stirring tank No. 1, and the temperature was maintained at 30 to 35°C, and while vigorously stirring, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction.
After the supply of chlorosulfonic acid is completed, nitrogen gas is supplied into the stirring tank to remove by-product hydrogen chloride gas, and then
The reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40° C. or lower to obtain an aqueous octylphenol ethoxy sulfate solution. The resulting aqueous solution of octylphenol in ethylene oxide with an average of 10.0 mol of sulfate was tested for changes over time. The results were as shown in Table 3. Comparative Example 5 Octylphenol (molecular weight
206) 191g, potassium hydroxide 0.6g as a catalyst,
409 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. 0.6 g of acetic acid was added to the obtained adduct of octylphenol with ethylene oxide on average of 10 moles, and the mixture was thoroughly stirred. One mole of the obtained octylphenol ethoxylate was placed in a stirring tank No. 1, and the temperature was maintained at 30 to 35°C, and while vigorously stirring, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, An aqueous solution of octylphenol ethoxysulfate was obtained. The resulting aqueous solution of octylphenol in ethylene oxide with an average of 10.0 mol of sulfate was tested for changes over time. The results were as shown in Table 3. Comparative Example 6 Octylphenol (molecular weight
206) 191g, potassium hydroxide 0.6g as a catalyst,
409 g of ethylene oxide was charged and reacted at a temperature of 150° C. and a pressure of 6.0 Kg/cm ² G. 0.65 g of an 85% by weight aqueous phosphoric acid solution was added to the obtained adduct of octylphenol with an average of 10 moles of ethylene oxide, and the mixture was thoroughly stirred. 1 mole of the obtained octylphenol ethoxylate was placed in a stirring tank of 1, maintained at a temperature of 30 to 35°C, and mixed with 1 mole of chlorosulfonic acid while stirring vigorously.
The moles were dropped into a stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, An aqueous solution of octylphenol ethoxysulfate was obtained. The resulting aqueous solution of octylphenol in ethylene oxide with an average of 10.0 mol of sulfate was tested for changes over time. The results were as shown in Table 3.

【table】

[Table] (Effects of the invention) Phenol ethoxy sulfate obtained by reacting phenols with ethylene oxide contains lactic acid and/or lactate, and then sulfates the phenol ethoxy sulfate. It was found that the effect of extremely reducing odor generation due to changes over time was achieved. Furthermore, the obtained phenol ethoxysulfate can be used as a surfactant in a wide range of fields.

Claims (1)

[Claims] 1. A method for producing a stabilized phenol ethoxysulfate, which comprises adding lactic acid and/or a lactate to a phenol ethoxylate obtained by adding ethylene oxide to a phenol, and sulfating the phenol ethoxylate.