DE1298996B - Process for the production of quaternary ammonium peroxysulphates - Google Patents

Description

The invention relates to a process for the production of quaternary ammonium peroxymonosulphates (hereinafter referred to as peroxysulphates).

The compounds obtained by the process of the invention are effective agents for Bleach fabrics and have good storage stability.

It has also been found that these quaternary ammonium compounds act as fabric softeners act and can be used to soften fabrics during bleaching.

When washing textiles and clothes in household washing machines is common Besides a detergent a bleach is used to restore the original whiteness of the garments after washing. Commonly used bleaches include compounds, such as sodium hypochlorite, chlorinated isocyanuric acids and potassium peroxymonosulfate.

It has been found that these bleaching agents have certain disadvantages. For example, tend Sodium hypochlorite and chlorinated isocyanuric acids add measurable properties to the fabric during bleaching Extent to decompose or degrade and can cause a local overbleaching by direct Cause the bleach to come into contact with the fabric. The bleaching with potassium peroxymonosulfate reduces tissue degradation, but the bleaching effect is inferior to that of sodium hypochlorite. In addition, potassium peroxymonosulfate is not very stable in storage and therefore loses its bleaching effectiveness for long periods of storage.

The invention relates to a process for the preparation of quaternary ammonium peroxymonosulphates the general formula

R ¹

R ² —N —R ⁴ HSO,

wherein at least two of the radicals R ¹ , R ² , R ³ and R ^{4 denote} to 18 carbon atoms, these

Alkyl groups with 1 to 4 carbon atoms represent groups that cannot be oxidized by peroxysulfates

and at least one of the radicals R ¹ , R ² , R ³ and via a carbon atom to the nitrogen atom

and R ^{4 is} a saturated aliphatic group with 12-30 attached.

The process is characterized in that a quaternary is used in a manner known per se Ammonium compound of the formula

R ¹

R ² -N-R ⁴ R ³

in which X is a hydroxyl group or a halogen atom and R ¹ , R ² , R ³ and R ^{4 have} the meanings given above, is reacted with an inorganic peroxysulphate.

In the above formulas, the aliphatic groups can be straight-chain, branched-chain or lower Be linked to form a heterocyclic group.

The quaternary ammonium peroxymonosulphates are made by reacting a quaternary ammonium salt (suitably one in which the anion of the salt is a halogen) with an inorganic one Peroxymonosulfate produced. Typical conversions proceed according to the following equation:

R ¹

R ² -N-R ⁴ R ³

Cl + KHSO ₅

R ² -N-R ⁴

HSO ₅ + KCl

wherein R ¹ , R ² , R ³ and R ^{4 have} the meaning given above. An alternative process for the production of peroxymonosulphates consists in the reaction of quaternary ammonium hydroxides with solutions of Caro's acid (H2SO5).

Examples of quaternary ammonium salt precursors are dodecyltrimethylammonium chloride and quaternary Dimethyl di (hydrogenated tallow) ammonium chloride.

Most of the inorganic ammonium peroxysulphates can be used to produce the quaternary ammonium peroxysulphates Peroxysulfate reagents can be used, but for economic reasons those are generally available Peroxysulphates, for example the ammonium, potassium and sodium peroxymonosulphates, preferred. The potassium peroxymonosulfate (potassium karoate) has proven to be the most suitable.

To prepare the quaternary ammonium peroxymonosulphates, low reaction ^{temperatures should be used, advantageously not above 20 °} C. Low temperatures are necessary because these compounds are so active that they react at higher temperatures with the salt generated in situ to form free chlorine

convert the peroxysulphate compounds into a sulphate. Generally, the reaction temperatures are between about 0 and about 2O ⁰ C.

The reaction medium used depends to a large extent on the solubility of the final product in the reaction medium. It is chosen so that the end product in the reaction medium is proportionate is insoluble, while the added starting materials remain dissolved therein. For example, will in the production of the quaternary ammonium peroxymonosulphates with higher molecular weight Water is preferred because the end product is relatively insoluble in an aqueous reaction medium is, while the starting products and the by-products are sufficiently soluble to be to be dissolved in the reaction medium. In the case of the quaternary ammonium peroxymonosulphates of lower Molecular weight, a selective organic solvent medium is preferred because the End product in water has a high solubility and the recovery of the end product from one aqueous medium would be extremely difficult. Suitable organic reaction media are, for example, aqueous ones Methanol, dimethylformamide, mixtures thereof and mixtures of isopropyl alcohol and Water.

As bleaching agents according to the invention, those peroxysulfates are suitable which are on the nitrogen atom Wear groups that cannot be oxidized by any peroxysulphate. These groups associated with the nitrogen atom Connected via a carbon atom can be unsubstituted or contain substituents that cannot be oxidized by peroxysulphates. Examples of substituents that cannot be oxidized, are carboxyl, alkoxy, ester, amido and nitro groups. The aliphatic groups can also Have phenyl substituents which cannot be oxidized and which may be unsubstituted or contain substituents can, such as B. carboxyl, alkoxy, ester, amide, nitro and halogen groups. The aromatic Group can also carry aliphatic substituents which are not oxidizable and which have the above correspond to the specified requirements for aliphatic groups. Substituents attached to an aromatic Group can be oxidized and which are therefore unsuitable are, for example, amino, hydroxy, Keto and aldehyde groups. Substituents that can be oxidized on an aliphatic group and which are therefore unsuitable are, for example, amino, hydroxyl, cyano, keto, halogen (except Fluorine) and aldehyde groups.

Examples of suitable quaternary ammonium peroxymonosulfates are

2-ethyllauryl-trimethyl-ammonium peroxy-

monosulfate,
2-ethyl-lauryl-stearyl-dimethyl-ammonium per-

oxymonosulfate,
12-benzylstearyl-trimethyl-ammonium peroxy-

monosulfate,
2-Phenylpalmityllauryl-dimethyl-ammonium-

peroxymonosulfate,
10-m-chlorophenyl stearyl trimethyl ammonium

peroxymonosulfate,
2-nitrostearyl-trimethyl-ammonium peroxy-

monosulfate,
2-methoxystearyl lauryl dimethyl ammonium peroxymonosulfate,

10-cyclohexyl-stearyl-ethyl-dimethyl-

ammonium peroxymonosulfate,
2-carboxypalmityl lauryl dimethyl ammonium peroxymonosulfate,
2-acetoxy-stearylpropyl-dimethyl-ammonium-

peroxymonosulfate,
Di-2-nitro-stearyl-dimethyl-ammonium peroxymonosulfate,

Phenyl stearyl dimethyl ammonium peroxymonosulfate,

Di-p-nitrophenyl-dimethyl-ammonium peroxy-

monosulfate,

p-methoxyphenyl-palmityl-dimethylammonium peroxymonosulfate and
p-carboxyphenyl-diethyl-methyl-ammonium-

peroxymonosulfate.

The effectiveness of one of these peroxysulphates, namely dimethyl di (hydrogenated tallow) ammonium peroxymonosulphate (DDTAM) as a bleaching agent compared to a common bleaching agent, namely potassium peroxymonosulfate, is illustrated in the drawing.

The drawing shows the increase in the whiteness of samples with tea stains (increase in reflection) plotted against the active oxygen content of the bleaching solutions used. As can be seen from the drawing, the bleaching agent according to the invention is in terms of the reflection increase and therefore more effective than potassium peroxymonosulphate (KHSO5) in bleaching the sample. That used to determine these values exact procedure is given in Comparative Example A.

The class of peroxysulfates obtainable according to the invention can be used in amounts in washing solutions sufficient to contain up to about 30 ppm active oxygen by weight the bleach solution. Larger amounts may be used for economic reasons however, these are undesirable. In addition, the bleaching effect is sufficient at this concentration, to meet household linen requirements. The exact amounts that are used depend on the particular chosen Peroxysulphate. For example, a low molecular weight alkyl quaternary ammonium peroxysulfate chosen, which mainly serve as a bleaching agent with no fabric softening effect is to be added, this is added in amounts sufficient to add about 30 ppm of active oxygen deliver. On the other hand, a long chain quaternary ammonium peroxysulfate is used to provide a To obtain fabric-softening effect, it can be used in amounts of about 0.1 to 0.15 percent by weight, based on the tissue. When using low concentrations of these compounds for the purpose of fabric softening, the bleaching effect is not as pronounced as when higher Concentrations of the quaternary ammonium peroxysulfate are applied. But also at low Concentrations, the bleaching effect supports the preservation of the original whiteness of the Fabric, with a softening effect is obtained at the same time. This is important as it is common subsequent yellowing of fabrics treated with chemical softeners as a result of chemical changes occurring in the plasticizer itself.

The following examples illustrate the invention. example 1

44 g of a 75 weight percent solution of dimethyl di (hydrogenated tallow) ammonium chloride in aqueous isopropanol were dissolved in 150 ml of methanol and poured into a 400 ml beaker. The fatty alkyl groups in this mixture contain about 65% Ci ₈ -, 30 ° / ,, Cw- and 5% Cw-alkyl chains. The solution was cooled to 5 ° C. A solution was then added to it which had been prepared from 15 g of 88% strength Ka humperoxymonosulfate (potassium caroate) dissolved in 150 ml of distilled water. The reaction mixture was stirred and further cooled to OC. A colorless solid product crystallized out of the reaction mixture and was filtered off from the mother liquor. The solids obtained were washed twice with 100 ml each time of a cold (-5 ^C C) methanol-water mixture and dried under reduced pressure in a rotary evaporator. The resulting white solid weighed 36 g and had an active oxygen content of 2.20 percent by weight. A sample of the product was purified by recrystallization from methylene chloride and analyzed.

20th

Calculated Found C. 67.45%
2.16%
11.98%
4.90%
2.47% 67.39%
2.16%
11.90%
4.82%
2.20% N H S. Active sour
material

The product obtained was found to be dimethyl di- (hydrogenated Sebum) ammonium peroxymonosulfate identified.

Example 2

The procedure described in Example 1 was repeated, but 11.8 g a 50 weight percent solution of palmityltrimethylammonium chloride in aqueous isopropanol and 4.5 g of potassium peroxymonosulfate used. The resulting colorless product weighed 5 g and had a active oxygen content of 3.05 percent by weight. It was called palmityl trimethyl ammonium peroxymonosulfate identified.

Example 3

The procedure of Example 1 was repeated except that 13.9 g of a 50% strength were used as reagents Solution of stearyl trimethyl ammonium chloride in aqueous isopropanol and 4.5 g of potassium peroxymonosulfate used. The resulting colorless solid product weighed 5.8 g and had an active oxygen content of 3.01 percent by weight. The product was called stearyl trimethyl ammonium peroxymonosulfate identified.

Example 4

The procedure of Example 1 was repeated, except that 23.5 g of distearyldimethylammonium chloride were used as reagents and 6.0 g of potassium peroxymonosulfate used. The resulting colorless solid product weighed 20 g and had an active oxygen content of 2.02 percent by weight. The product was called dis-stearyl-dimethyl-ammonium peroxymonosulfate identified.

Example 5

The procedure of Example 1 was repeated, except that 5.6 g of dilauryl-dimethylammonium chloride were used as reagents and 1.75 g of potassium peroxymonosulfate used. The resulting colorless solid product weighed 3.5 g and contained active Oxygen of 2.41 weight percent. The product was called dilauryl dimethyl ammonium peroxymonosulfate identified.

Example 6

The procedure of Example 1 was repeated, but 10.6 g of lauryl trimethyl were used as reagents - ammonium chloride and 3.2 g of potassium peroxymonosulphate are used. The resulting colorless Product had an active oxygen content of 4.35 percent by weight. The product was sold as a Lauryl trimethyl ammonium peroxymonosulfate identified.

Comparative experiment A

The bleaching effect of dimethyl di (hydrogenated tallow) ammonium peroxymonosulphate (DDTAM), prepared according to the method of Example I ₁ , was compared with a standard bleaching agent, namely potassium peroxymonosulphate, according to the following method:

32 cotton sample strips (12.7 χ 12.7 cm cotton fabric with the same number of wefts and warps) were contaminated with tea. The staining was achieved by placing five tea bags in 1 liter of water and boiled for 5 minutes and then dipped the test strips into the tea and boiled for another 5 minutes. The dyed test strips were then squeezed in order to Remove excess liquid, dried, rinsed with cold water and dried.

Three dyed cotton test strips were each placed in a laboratory stainless steel washer Stahl (manufactured by the US Testing Company) brought 1000 ml of a standard 0.2% detergent solution at a temperature of 49 "C. Measured amounts of each bleach that contained Sufficient to match predetermined active oxygen levels were then divided into separate Given vessels. The pH of the solutions in the vessels was determined using sodium hydroxide solution set to 9.5. To achieve a typical household ratio of washing water to clothing of 20: 1 To create, cut pieces of white toweling cloth were added. The washing machine was then operated for 15 minutes at a temperature of 49 ° C. at 72 revolutions per minute. To At the end of the wash cycle, the test strips were removed under cold tap water rinsed and dried in a hot air strand dryer. The experiments were carried out in triplicate including comparative tests with detergent only. The reflection measurements of the Sample strips were made using a reflectometer before and after each wash cycle of the blue filter. Each test strip was made twice (weft and warp) on each side

35

measured against a background of five similarly soiled test strips. At all readings the fluorescence effect was excluded. The increase in reflectance obtained compared to the blanks at different concentrations of active oxygen is shown in the drawing for both DDTAM as well as indicated for potassium peroxymonosulfate.

Comparative experiment B

The softening effect of dimethyl-di- (hydrogenated Tallow) - ammonium peroxymonosulfate (DDTAM), prepared according to that described in Example 1 Procedure, was tested according to the ASTM-D 1175-55 T method. This test is the number of standard flexural wear cycles measured that a garment can withstand until it is worn off. The test was as follows performed: Cotton samples with yarn counts of 80x80 and 136x64 and a Dacron sample were made placed in a household washing machine and a household washing process with a common detergent subject. During the last rinse, 4.72 g of DDTAM (100% active material) added to the 68.11 wash water. The total solids load was 3.4 kg dry laundry. This allowed 0.137% plasticizer solids based on the weight of the solution to be removed from the solution Laundry to knock down on the laundry. A blank test was also carried out in which the No softener has been added to the laundry. The samples so treated were placed on the flexural abrasion tester and the number of cycles of abrasion to rub the cloth was recorded. The results are in the following Table shown.

The softening of the cloth is indicated by the increase in the number of abrasion cycles required for attrition of the cloth are necessary. One treated with a standard amount of a plasticizer Cloth has better flexibility and is more difficult to tear. The stronger the effect of the plasticizer, the greater the increase in the abrasion cycles required.

sample

80 χ 80 cotton cloth.
136 χ 64-cotton cloth
Dacron

Abrasion cycles

DDTAM

681

1235

10 149

comparison

241

328

8 134

Claims (1)

Claim: Process for the preparation of quaternary ammonium peroxymonosulfates of the general formula R ¹ R ² -N-R ⁴
R ³ HSO, wherein at least two of the radicals R ¹ , R ² , R ³ and R ^{4 are} alkyl groups with 1 to 4 carbon atoms and at least one of the radicals R ¹ , R ² , R ³ and R ^{4 is} a saturated aliphatic group with 12 to 18 carbon atoms, These groups cannot be oxidized by peroxysulfates and are bonded to the nitrogen atom via a carbon atom, characterized in that a quaternary ammonium compound of the formula is obtained in a manner known per se R ¹ R ² - N - R ⁴ R ³ wherein X represents a hydroxyl group or a halogen atom and R ¹ , R ² , R ³ and R ^{4 have} the abovementioned meanings, is reacted with an inorganic peroxysulfate. 1 sheet of drawings 909 528/296