JPS58131963A - Preparation of sulfonated compound - Google Patents

Abstract

PURPOSE:To obtain a sulfonated compound giving extremely low irritation to the skin and eye mucosa, having extremely low toxicity to fish and high biodegradability, and useful as a surface active agent for cosmetics, in high yield, by reacting an unsaturated dibasic acid monoester with a sulfurous acid salt in the presence of a specific amount of water. CONSTITUTION:The sulfonated product of an unsaturated dibasic acid monoester can be prepared by reacting the monoester with a sulfurous acid salt at 40- 90 deg.C, preferably 50-80 deg.C under weakly acidic condition (5-6pH) in the presence of a limited amount of water to enable the dissolution of a part of the sulfurous acid salt (<=95%, preferably 65-90%) at the reaction temperature. The ester is e.g. the monoester of an unsaturated dibasic acid (e.g. maleic acid, fumaric acid, etc.) with straight- or branched-chain (un)saturated monohydric alcohol, aliphatic monoalkanol amide or an alkylene oxide adduct of a monofunctional active hydrogen-containing compound. USE:Foaming agent for shampoo and cleansing foam, soap modifier, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing sulfonated products. More specifically, the present invention relates to a method for producing a sulfonated product of an unsaturated dibasic acid monoester using a sulfite salt in a high yield and with high purity.

Sulfonated products of unsaturated dibasic acid monoesters have extremely low skin irritation, making them useful compounds as surfactants for cosmetics such as shampoos, shaving foams, and foaming agents for cleansing foams. is desired to have high purity.

Conventionally, its production method involves adding sodium sulfite dissolved in water to an unsaturated dibasic acid monoester and adding 40 to 10
The reaction is carried out at 0°C, or a method is used in which a sufficient amount of water to dissolve sodium sulfite, sodium sulfite and an unsaturated dibasic acid monoester are charged, and the reaction is carried out at 40 to 100°C. However, these methods have the disadvantage that hydrolysis of the ester moiety occurs during sulfonation, making it impossible to obtain a sulfonated product of a highly pure unsaturated dibasic acid monoester. In JP-A No. 54-25286, the pH at the time of preparation was adjusted to 55±α2, and the temperature was 80°C.
Although the reaction is carried out below, even this method cannot sufficiently increase the sulfonation rate.

The present inventors have conducted repeated research to improve these drawbacks, and as a result, have arrived at the present invention. That is, in the present invention, when producing a sulfonated product by reacting an unsaturated dibasic acid monoester with a sulfite in the presence of water, the reaction temperature is in the presence of an amount of water that can dissolve only a portion of the sulfite at the reaction temperature. Examples of the unsaturated dibasic acid monoester used in the present invention include monoesters of unsaturated dibasic acids and some alcohols. It will be done. Examples of unsaturated dibasic acids include maleic acid, methylmaleic acid, tuma μ acid, methylfumaric acid, muconic acid, methylmuconic acid, glutaconic acid, and itaconic acid, with maleic acid being useful. These acids are usually used in the form of acid anhydrides to obtain unsaturated dibasic acid monoesters.

Some alcohols include straight chain or branched saturated or unsaturated alcohols having 1 to 36 carbon atoms.
7 For example, methanol, ethanol propanol, hexyl alcohol, octyl alcohol, deciμ alcohol, dodecyl alcohol, hexadecyl alcohol,
Octadecyl alcohol, dodecyl alcohol, tetracosyl alcohol; branched saturated alcohols such as isopropanol, isobutyl alcohol, 2-ethyl lehexanol, 2-hequinyl alcohol, 2-octyl dodecanol, 2-tetradecyl octadecanol , 2-isohebuty to isoundecoalcohol; unsaturated alcohols such as allyl alcohol.

Oleyl alcohol; synthetic alcohol having 7 to 22 carbon atoms, such as oxo alcohol, secondary alcohol;
Alcohol obtained from natural oils and fats! (Lanolin Alcohol, /l/, Cholestero-IV).

Fatty acid alkaturamides (monoalkano-μ amides of fatty acids having 8 or more carbon atoms, such as lauric acid monoethanolamide, lauric acid monoisopropanolamide, myristic acid monoethano-μ amide, myristic acid monoisopropano-μ amide).

Coconut oil fatty acid monoethanolamide, coconut oil fatty acid monoisopropanolamide, oleic acid monoethanolamide, oleic acid monoisopropanolamide) 7 Monofunctional active hydrogen-containing compounds [the above alcohols, fatty acid alkanolamides, octiμphenolμ, Examples include alkyl oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) of alkyl p (C1 ~, 6] phenol and fatty acids (C1 ~, s) such as lauric acid, myristic acid, etc.) such as noniμ phenol. . The number of moles of alkylene oxide added is usually 1 to 2
0. Preferably it is 2-10. When the number of moles of alkylene oxide added is greater than 20, the foaming power decreases.

Specific examples of the unsaturated dibasic acid monoester include the following.

(1) Monoesters of unsaturated dibasic acids and linear or branched saturated or unsaturated alcohols Monoesters of saturated alcohols, monoesters of evamaleic acid and dodecyl alcohol, maleic acid and octadecyl alcohols Coff & to monoester, maleic acid,! = Monoester with 2-ethylhexanol μ, maleic acid and 2-octyldodecanol ester; monoester with unsaturated alcohol-p, e.g. monoester with maleic acid and allyl alcohol-μ /L/, maleic acid Monoester with tooleyl alcohol, etc. (2) Monoester with unsaturated dibasic acid and fatty acid monoalkano-μ amide Monoester with maleic acid and lauric acid monoethanolamide μ, maleic acid and lauric acid monoisopropano-amide
Monoester with μ amide, monoester with maleic acid tomyristic acid monoethanolamide, monoester with maleic acid and myristic acid monoisopropano-μ amide, monoester with maleic acid and coconut oil fatty acid monoethanolamide μ .

Monoesters of maleic acid and coconut oil fatty acid monoisopropano-amide, monoesters of maleic acid tooleic acid monoethanolamide, monoesters of maleic acid and oleic acid monoisopropano-μ amide, etc.

(3) Monoester of unsaturated dibasic acid and alkylene oxide adduct of monofunctional active hydrogen-containing compound. Monoester of maleic acid and polyoxyethylene (p=5) and secondary alcohol (C12-14).

Monoester of maleic acid and polyoxyethylene (p=4) with noniμ phenol, monoester of maleic acid and polyoxyethylene (p=2) coconut oil fatty acid monoethanolamide, maleic acid and polyoxypropylene (
p=3) monoester with lauric acid isopropano-μ amide, tophoryoxyethylene maleate (p=10)
Among these monoesters of lanolin alcohol, preferable monoesters are monoesters of maleic acid and noalkano μamide on fatty acids or alkylene oxide adducts thereof when used in shampoos and the like, in view of foaming power.

Examples of sulfites include sulfite alkali metal (sodium, potassium, etc.) salts, ammonium sulfite, etc.
Sodium sulfite is preferred. Sodium sulfite can be used as an anhydrous salt or a superhydrate salt, but an anhydrous salt is preferred.

In the production of sulfonated products, the molar ratio of unsaturated dibasic acid monoester to sulfite is usually 1:L2 to L2:1, preferably substantially equimolar μ.

In the present invention, the amount of water during the reaction is such that only a portion of the sulfite can be dissolved at the reaction temperature. The amount of water that can dissolve up to 95% of the sulfite is preferred, usually 55-95%,
Particularly preferably 65 to 90%. If it is less than 55%, the reaction system will usually solidify, and if it exceeds 95%, the sulfonation rate will not increase.

The solubility of sodium sulfite at 84°C is 2 &
3t, and the above 55-95% corresponds to 59-218t of 5L of sodium sulfite per 100f of water. As for the charging method, the sulfite may be added after being dispersed in water, or it may be charged separately.

Reaction of unsaturated dibasic acid monoester in the presence of water. If the reaction temperature is less than 40°C, the reaction will be slow; if it exceeds 90°C, hydrolysis of the sulfonated product will occur, resulting in a low sulfonation rate. Use one reaction time. The reaction pressure is usually 1 to 10 hours, preferably 2 to 6 hours, although it can be varied depending on the type of unsaturated dibasic acid ester. The reaction can be carried out at either atmospheric pressure or pressurized pressure, and the reaction can also be carried out by adding a solvent such as ethanol-μ, propylene glyco-μ, or glycerin together with water.Furthermore, in order to prevent coloring of the reaction product, It is preferable to carry out the reaction in an inert gas atmosphere such as nitrogen gas.

After the reaction, water may be removed by vacuum distillation or the like, or it may be diluted with water or a solvent to facilitate handling.

The present invention can produce a sulfonated product of an unsaturated dibasic acid monoester with a high sulfonation rate. The obtained sulfonated product is highly pure. This sulfonated product has good foaming power, good foaming ability, and moderate detergency, and has extremely low skin irritation, eye mucous membrane irritation, and fish toxicity, and has good biodegradability. Since it has the above characteristics, the sulfonated product according to the present invention is a shampoo.

It is useful for uses such as foaming agent for shaving foam and cleansing foam, soap modifier, and kitchen detergent base.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Maleic acid and polyoxyethylene (p=5) 2nd
Class alcohol/' (C12-14) monoester)v
1 mo/L/(519t) and sodium sulfite 1 mo/L/
(12alf) and water were reacted at 80 to 85°C in a nitrogen atmosphere to produce a sulfonated product by changing the amount of water and the pH at the time of charging the raw materials. The sulfonation rate was determined by the nibton method.

The results are shown in Table 1 (the same applies to the following examples), and it can be seen that the sulfonation rate of the sulfonated product in the present invention is particularly excellent.

`` Ike Shiji 2 -qv Inic acid and polyoxyethylene (p = 2) Coconut oil fatty acid monoethanolamide g Noeste / l / 1 mo /
1z (439 ft) and sodium sulfite 1 mozL/(
12alP) and water were reacted at 55 to 60° C. with stirring under a nitrogen atmosphere while changing the amount of water as shown in Table 1 to produce a sulfonated product. The sulfonation rate of the sulfonated product is shown in Table 1, and it can be seen that the sulfonation rate of the sulfonated product in the present invention is particularly excellent. In addition, the pH at the time of raw material preparation is δ
It was set to 5-aO.

Table-2 Example 3 7L/monoester with tophoryoxyethylene (p=4) nonylphenol 1 mo/l/(494f)
and sodium sulfite l/1/(12alf) and water 42
0t was reacted at 60 to 65° C. for 4 hours with stirring in a nitrogen atmosphere to produce a sulfonated product. The sulfonation rate at this time was 989%.

Example 4 Monoeste of qv inic acid and polyoxypropylene (p=3) lauric acid monoisopropaturamide/1/
1 mo/I/(529#) and sodium sulfite 1 mo/L/
(12al#) and 435f of water under stirring in a nitrogen atmosphere.
A sulfonated product was produced by reacting at 0 to 65°C for 5 hours.

The sulfonation rate at this time was 9% and 3%.

Example 5

Claims (1)

[Scope of Claims] Unsaturated dibasic acid monoester/l/Th An amount capable of dissolving only a portion of the sulfite at the reaction temperature when reacting with sulfite to produce a sulfonate in the presence of water. 1. A method for producing a sulfonated product of an unsaturated dibasic acid monoester P, which comprises reacting in the presence of water. 2. The method according to claim 1, wherein the two reactions are carried out in the presence of water in an amount capable of dissolving up to 95% of the sulfite. (a) The manufacturing method according to claim 1 or 2, wherein the reaction temperature is 40 to 90°C. The unsaturated dibasic acid monoester is a monoester of an unsaturated dibasic acid and a linear or branched saturated or unsaturated alcohol, a monoester of an unsaturated dibasic acid and an aliphatic nokanolamide, and/or a monoester of an unsaturated dibasic acid and a linear or branched saturated or unsaturated alcohol. or a monoester of an unsaturated dibasic acid and an alkylene oxide adduct of a monofunctional active hydrogen-containing compound.
The manufacturing method described in any of paragraphs. &Unsaturated dibasic acids are maleic acid, methyl cimaleic acid,
5. The production method according to claim 4, wherein the compound is a compound selected from the group consisting of fumaric acid, methymuconic acid, muconic acid, methylmuconic acid, glutaconic acid, and itaconic acid.