KR20110126416A - Acid anhydride compound, method for the preparation thereof and bleaching composition comprising the same - Google Patents

Abstract

PURPOSE: An acid anhydride-based compound is provided to ensure excellent bleaching activity and to enable the application as a bleaching activator to a bleach composition containing inorganic peroxide. CONSTITUTION: An acid anhydride-based compound is represented by chemical formula 1. In chemical formula 1, R is selected from the group consisting of linear or branched C5-15 alkyl, C5-15 alkenyl and a mixture thereof; and M is selected from the group consisting of hydrogen, alkali metal, ammonium and the same equivalent of alkaline earth metal. A method for preparing the acid anhydride-based compound comprises the steps of: (i) sulfonating acrylate with sodium bisulfate; and (ii) reacting the compound prepared in step (i) with acyl chloride.

Description

Acid anhydride compound, preparation method thereof, and bleaching composition comprising the same {ACID ANHYDRIDE COMPOUND, METHOD FOR THE PREPARATION THEREOF AND BLEACHING COMPOSITION COMPRISING THE SAME}

The present invention relates to an acid anhydride compound, a preparation method thereof and a bleaching composition comprising the same.

Bleaching contaminants such as fruit juice, coffee, wine, and grass juices are being used, with washing methods using inorganic peroxides such as sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate, urea peroxohydrate, and sodium peroxide. Can be removed more easily. However, since sodium perborate exhibits an effective bleaching performance at 80 ° C. or higher and sodium percarbonate at 60 ° C. or higher, the bleaching effect is performed under cold water conditions of 20 to 25 ° C. in summer and even 5 ° C. in winter. It's very hard to get. Therefore, a bleach activator has been introduced so that the inorganic peroxide can exhibit good bleaching power even in low temperature water.

As a general bleaching activator, tetra acetylethylene diamine (TAED) is most commonly used, but there is a limit in removing oily stains such as sebum. In addition, the bleach activator using an acyl compound described in US Patent Nos. 4,412,934, 4,483,778, 4,606,838, and 4,671,891 has a problem in that the economic efficiency is lowered.

In addition, the carbonate derivative-based bleach activators described in US Pat. Nos. 4,686,061 and 5,043,089, and European Patents 210,674 and the like have a problem of generating a bleach odor as the molecular structure is changed in the wash water.

U.S. Patent Nos. 4,179,390, 4,259,201, 5,098,598, 5,520,844, and 5,575,947 describe a number of organic peroxycarboxylic acids as bleach for detergents, but they lose their active oxygen due to heat instability. Tend to. In order to solve this problem, a method of coating and granulating organic peroxycarboxylic acid (see European Patent Nos. 396,341 and 256,443, etc.) has been introduced. There is a disadvantage that the residual phenomenon occurs.

Accordingly, esters capable of releasing bleaching active peroxycarboxylic acid only in low temperature washing water together with inorganic peroxides, are easy to be stored for a long time, have excellent bleaching power against hydrophilic and hydrophobic contamination, and rarely generate bleach odors. Although bleach activators are preferred (see US Pat. No. 5,705,091), the preparation method of such ester bleach activators is carried out by adding phosgene using argon gas, and controlling the reaction temperature to a low temperature of about -78 ° C. In addition, the production process is very complicated and the yield is low (about 50%) such as hydroxybenzene, a hydroxybenzene derivative or a salt thereof reacted under an organic solvent such as methyl cyanide (CH ₃ CN). . In addition, the method (Korean Patent No. 593,529) developed to alleviate these shortcomings is also complicated in the process, long manufacturing period, and economical.

Accordingly, the present inventors have made a thorough study to develop a bleach activator to improve the above-mentioned shortcomings, and thus, the present invention has been completed by finding a novel acid anhydride compound having a very simple and economical process and excellent bleaching activity.

It is therefore an object of the present invention to provide novel acid anhydride compounds.

Another object of the present invention is to provide a method for preparing the acid anhydride compound.

Still another object of the present invention is to provide a bleaching composition comprising the acid anhydride compound as a bleach activator.

In order to achieve the above object, the present invention provides an acid anhydride compound of Formula 1 below:

[Formula 1]

Where

R may be selected from the group consisting of straight or branched C _5-15 alkyl, C _5-15 alkenyl and mixtures thereof;

M can be selected from the group consisting of hydrogen, alkali metals, ammonium and an equivalent of alkaline earth metals.

The present invention to achieve the above another object,

1) sulfonating acrylate with sodium bisulfite; And

2) It provides a method for producing an acid anhydride-based compound of Formula 1 comprising the step of reacting the compound prepared in step 1) with acyl chloride.

In order to achieve the above another object, the present invention provides a bleaching composition comprising the compound of Formula 1 as a bleach activator.

The acid anhydride-based compound of the present invention is very simple, economical, and excellent in bleaching activity, and thus can be usefully used as a bleach activator in bleaching compositions containing inorganic peroxides.

Hereinafter, the present invention will be described in more detail.

The present invention provides an acid anhydride compound of Formula 1:

Where

R may be selected from the group consisting of straight or branched C _5-15 alkyl, C _5-15 alkenyl and mixtures thereof;

M can be selected from the group consisting of hydrogen, alkali metals, ammonium and an equivalent of alkaline earth metals.

In the general formula (1), a compound characterized in that R is linear or branched C _8-12 alkyl.

In addition, the present invention is 1) to sulfonate acrylate salts with sodium bisulfite step; And 2) reacting the compound prepared in step 1) with acyl chloride, to provide an acid anhydride compound of Chemical Formula 1.

Specifically, in step 1), 1.0 to 1.1 equivalents of sodium bisulfite powder is gradually added to the acrylate, and then sulfonated for 10 to 100 minutes at a temperature of 40 ° C. to 80 ° C. Prepare the phonated compound.

The acrylate may be prepared by neutralizing acrylic acid using a caustic soda in a solvent such as water. The water used for the neutralization reaction may be used in an amount of 4 to 10 times based on the weight of caustic soda. At this time, if the amount of water used is less than 4 times the viscosity of the final reactant is high, the reaction does not proceed well, if the amount of water exceeds 10 times the production efficiency is lowered and the reaction product may be lost. The caustic soda may be used in an amount of 1.0 to 1.1 equivalents based on acrylic acid, and since the exothermic phenomenon occurs during the neutralization reaction, caustic soda is slowly added to the aqueous acrylic acid solution.

In step 2), acyl chloride is added to the sulfonated compound prepared in step 1) and reacted at a temperature of 50 ° C to 90 ° C for 10 to 100 minutes. The acid anhydride compound of the present invention can then be prepared by filtering or spraying the resulting reaction precipitate to remove and dry the solvent.

The acyl chloride is octanoyl chloride (octanoyl chloride), decanoyl chloride (decanoyl chloride), dodecanoyl chloride (dodecanoyl chloride), neodecanoyl chloride (neodecanoyl chloride), ethylhexanoyl chloride (ethylhexanoyl chloride) and isononano One chloride (isononanoyl chloride; 3,5,5-trimethylhexanoyl chloride) may be selected from the group consisting of 0.7 to 1.0 equivalents based on the acrylate. At this time, when the amount of acyl chloride is less than 0.7 equivalent, the unreacted two-stage reactant increases, and when it exceeds 1.0 equivalent, the odor is severe due to unreacted acyl chloride, and filtration becomes difficult.

     In addition, the present invention provides a bleaching composition comprising the acid anhydride compound of Formula 1 and an inorganic peroxide. The bleaching composition may be, for example, a synthetic bleach for clothing, a bleach for clothing, or a bleach for textiles.

Specifically, the acid anhydride-based compound of the present invention may be usefully used as a bleach activator added to a bleaching composition containing an inorganic peroxide to help their bleaching function. In consideration of the activating effect and decomposition rate on the inorganic peroxide, the content of the bleaching activator is preferably 0.01 to 40% by weight based on the total weight of the composition. If the content of the bleaching activator is less than 0.01% by weight, the effect of activating the inorganic peroxide may not be sufficient. If the amount of the bleaching activator exceeds 40% by weight, the activation rate of the inorganic peroxide may be too high. The acid anhydride-based compound of the present invention has an effect of reducing electric energy and reducing the amount of detergent due to the advantage of having an excellent bleaching activating function even in cold water, compared to tetraacetylethylenediamine which is commonly used.

In the bleaching composition comprising the acid anhydride compound and the inorganic peroxide of the present invention, the inorganic peroxide may be selected from the group consisting of percarbonate salt, perborate salt, and mixtures thereof, The content is preferably 1 to 40% by weight of the total weight of the bleach in the composition, in consideration of the bleaching effect and economy.

The bleaching composition of the present invention may be blended using an appropriate amount of the component commonly used according to the type and purpose of the bleaching composition in addition to the compound of formula 1 and the inorganic peroxide, and a surfactant, a builder, and the like may be used.

Anionic surfactants or nonionic surfactants may be used as the surfactant, and the content thereof is not particularly limited, but is preferably 5 to 40% by weight based on the total weight of the composition. As the anionic surfactant, for example, alkylbenzene sulfonate, fatty acid salt, alkyl monosulfonate salt or alpha olefin sulfonate salt can be used. As the nonionic surfactant, oxo alcohol polyethylene glycol, fatty acid polyoxyethylene glycol, alkylphenyl polyoxyethylene glycol or polyoxyethylene glycol may be used.

In addition, builders are alkali metal salt additives for improving the cleaning ability of surfactants, for example, alkali metal salts of polyphosphates such as sodium tripolyphosphate, aluminosilicates such as zeolites, polyacetal carboxylates, polycarboxylates, sodium carbonate, carbonate It may be used, such as silicates, such as the α-Na ₂ SiO ₃ or β-Na ₂ SiO ₃ carbonates, such as sodium, layered crystalline (layered crystalline). The builder is preferably added in an amount of 30 to 95% by weight based on the total weight of the composition in consideration of the aspect of improving the detergent power of the surfactant.

The bleaching composition of the present invention may include other additives such as inorganic salts such as sodium carbonate and sodium sulfate, fluorescent dyes, enzymes, fragrances, etc., which are commonly used in detergents, in addition to the above-described ingredients.

[Example]

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1 Preparation of Acid Anhydride Compound-1

230 g of distilled water and 72 g of acrylic acid were added to a five-necked flask equipped with a mechanical stirrer, a thermometer, a condenser, and a distillation apparatus at room temperature under a nitrogen atmosphere, followed by neutralization while slowly adding 80 g of a 50% caustic soda solution. 104 g of sodium bisulfite powder was slowly added thereto, the temperature was maintained at 50 to 60 ° C. for about 30 minutes, and the reaction was terminated. The reaction was confirmed by thin layer chromatography (TLC).

Subsequently, 171.5 g of decanoyl chloride (Sigma Aldrich) was added to the compound and reacted for 1 hour with vigorous stirring to terminate the reaction. After the reaction was completed, the viscosity was increased, and after cooling, the solvent was filtered and the solvent and salt were removed and dried to obtain 280 g of an acid anhydride compound.

Quantification of the final anionized compound was performed using the Epson method, which is a general quantification method of anionic surfactants, and measured using a METTLER DP-5 (automatic Epson titration instrument). The sampling amount was 0.5 ml, the molecular weight of the sample was 330, and measured using hyamine 1622 (benzetonium chloride) as a titrant to calculate the amount of the final product subjected to anionization. At this time, since the side reaction in the anionization process has a very low probability, it was assumed that all the final products subjected to anionization were converted to the desired output structure.

Example 2: Preparation of Acid Anhydride Compound-2

280 g of an acid anhydride compound was obtained in the same manner as in Example 1, except that neodecanoyl chloride (BASF) was used instead of decanoyl chloride.

Example 3: Preparation of Bleaching Composition of the Present Invention-1

After granulating 100 g of alkylbenzenesulfonic acid (AK chemical) in 300 g of sodium carbonate to prepare granular powder, 50 g of Laureth-7 (Green Soft Chem) was added using a Lodige mixer. It was. 270 g of sodium sulfate, 150 g of zeolite 4A and 100 g of percarbonate were added thereto and mixed together. Subsequently, 30 g of the acid anhydride compound prepared in Example 1 was added and mixed to prepare a bleach detergent in powder form.

Example 4: Preparation of Bleaching Composition of the Present Invention-2

Powdered bleach detergent was prepared in the same manner as in Example 3, except that 30 g of the compound prepared in Example 2 was used instead of the compound prepared in Example 1.

Comparative Example 1: Preparation of Bleaching Composition

Powdered bleach detergent was prepared in the same manner as in Example 3, except that 30 g of tetraacetylethylenediamine was used instead of the compound prepared in Example 1.

Experimental Example: Bleaching force evaluation experiment

Bleaching power evaluation experiment was performed according to the water temperature using the bleaching detergent of the powder form prepared in Examples 3 and 4, and Comparative Example 1.

Bleaching power evaluation experiments used internationally standardized test cloths of coffee (WFK BC-2), tea (WFK BC-3) and red pepper (WFK 10P) as standard test cloths of 5 × 5 cm 2. To a tergotometer, a washing power meter, water having a water temperature of 20 ° C. and 40 ° C., and a hardness of 50 ppm, respectively, and a bleach detergent prepared in Examples 3 and 4 and Comparative Example 1 were added at a rate of 1 g / L. Then, each was put in a standard staining cloth, washed for 10 minutes, rinsed for 3 minutes, and dried.

After measuring the whiteness of the cotton cloth before and after the washing using a colorimeter, the decontamination ratio (%) before and after washing was calculated, and the results are shown in Table 1 below.

As shown in Table 1, the bleaching detergent containing the compound according to the present invention as a bleach activator, it can be seen that the effect of bleaching activity against contamination of coffee, tea, and red pepper is excellent even at low temperature compared to tetraacetylethylenediamine there was.

Claims (11)

An acid anhydride compound of Formula 1
[Formula 1]

Where
R may be selected from the group consisting of straight or branched C _5-15 alkyl, C _5-15 alkenyl and mixtures thereof;
M can be selected from the group consisting of hydrogen, alkali metals, ammonium and an equivalent of alkaline earth metals. The method of claim 1,
The acid anhydride compound, wherein R is linear or branched C _8-12 alkyl. 1) sulfonating acrylate with sodium bisulfite step; And
2) reacting the compound prepared in step 1) with acyl chloride
A method for producing the acid anhydride compound of claim 1 comprising a. The method of claim 3, wherein
Said acrylate is prepared by neutralizing acrylic acid in water using caustic soda. The method of claim 4, wherein
Wherein the water is used in an amount of 4 to 10 times based on the weight of caustic soda. The method of claim 3, wherein
The sodium bisulfite manufacturing method, characterized in that used in 1.0 to 1.1 equivalents based on acrylate. The method of claim 3, wherein
The acyl chloride is octanoyl chloride (octanoyl chloride), decanoyl chloride (decanoyl chloride), dodecanoyl chloride (dodecanoyl chloride), neodecanoyl chloride (neodecanoyl chloride), ethylhexanoyl chloride (ethylhexanoyl chloride) and isononano Production method characterized in that it is selected from the group consisting of (isononanoyl chloride; 3,5,5-trimethylhexanoyl chloride). The method of claim 3, wherein
The acyl chloride is 0.7 to 1.0 based on acrylate Production method characterized in that used in the equivalent. Bleaching composition containing the acid anhydride type compound of Claim 1, and an inorganic peroxide. The method of claim 9,
Bleaching composition, characterized in that the acid anhydride-based compound is contained in 0.01 to 40% by weight based on the total weight of the composition. The method of claim 9,
And the inorganic peroxide is selected from the group consisting of percarbonates, perborates and mixtures thereof.