SE128178C1 - - Google Patents

Description

Inventors: E. Keller and R. Zweidler.

Priorilet begrin frcin on 31 October 1947 (Switzerland).

The present invention relates to a method of producing whitening enhancers for animal and vegetable fibers which have a more or less white to slightly yellowish appearance. The new whiteness-improving agents or optical brighteners light up separately as an additive to the soap component and pray for vegetable fibers and mark themselves for better properties in comparison with known bleaches, as specified below.

For use as optical brighteners, forefingers of the most diverse chemical amnesic classes have already been proposed, hi. a. also derivatives of 4,4'-diamino stilbene, which are partly of minor importance. Thus, by reacting 4,4'-diaminostilbene-2,2'-disulfonic acid with 2 moles of cyanuric halide and replacing the residual halogen atoms with residues of amines, optical brighteners have been obtained, which are distinguished by bid fluorescence and pronounced noun character, and therefore illuminate much choice for improving the whiteness of cellulose fibers. Even more valuable products are obtained from the mentioned condensation products by treatment with formaldehyde. While these agents are very suitable for the bleaching of bleached webs of cellulosic fibers, their use as an additive to detergents for ordinary household / - \ Y - NH - \ - CH CH- / laundry and to rinsing baths is counteracted by the fact that they Due to its high substantivity and wetness during repeated treatment it is enriched in the fiber and due to the very intense fluorescence it gives it an unpleasant, violet to blue appearance. In addition, they lighten themselves to wool due to the too low affinity. Whiteness-enhancing agents suitable for these fibers are diacylated 4,4'-diaminostilbene-2,2'-disulfonic acids, for example the diacetyl derivative, which, however, exhibits the imperfections of a reddish fluorescence and too little affinity for the cellulosic fiber, or dibenzoyl- or di- (p - amino- or di- (p - amino) ) - the derivatives, which, although they also have an affinity for the cellulose fiber, but unfortunately a markedly poor water solubility and of which the other product in particular acts as poor light fastness. They flock out of the non-breathing bath and produce distinctly flattened white effects. Finally, it has also been proposed to use 4,4'-diphenylureido-stilbene-2,2'-disulfonic acids, the reddish fluorescence of which, however, is satisfactory and the lightness of which leaves much to be desired.

It has now surprisingly been observed that 4,4'-diaminostilbene derivatives of the general formula - NH - CO - X - R SO 31-1 in which X represents a direct carbon bond or a two-membered bridge of the formula - 0 - The NH - or - alkylene-O Y acyl residue of a lower aryloxy fatty acid and R an alkyl or aryl residue, which with the exception of the sulfonic acid group may be arbitrarily substituted, are characterized by good water solubility, good affinity for fibers, blue to greenish bib fluorescence, better and medium water velocity, for which HSO, they are excellent for improving the whiteness of saval wool corn cellulose fibers and blends of these ram fibers. The fibers, which have been improved to their whiteness with these agents, mark themselves with a very beautiful white tone and show good watertightness in mild soapy water, and can nevertheless be largely deducted from the fibers by boiling soapy water, so that flake harmful enrichment on the fiber in multiple use does not to fear. They are therefore excellent, as an additive to detergents for household water 2— - and to school baths for white water, especially they also agree to show good resistance to inorganic persalts.

The new whiteness enhancers are obtained either by aryloxy fatty acid residues monoacylated by aryloxy fatty acid residues 4,4'-diaminostilben disulfonic acids by further acylation by means of an acylating agent introducing an R-XCO residue or by means of a RX-CO residue monoacylated cheese 4,4'-monoacylated cheese -disulfonic acids by continued acylation by a reaction-prone derivative of aryloxy fatty acids.

The 4,4'-diaminostilbene compounds monoacylated according to the invention can be easily obtained from the corresponding 4-nitro-4'-acylaminostilbene compounds by reduction of the nitro group. For example, the anhydrides or acid halides are used as derivative derivatives of aryloxy fatty acids, of which only lower molecular weight ones are used. Phenoxyacetyl and cresoxyacetyl derivatives are particularly suitable. As the RX-CO residue introducing acylating agents, if X represents the direct carbon bond: anhydrides of lure fatty acids, such as acetic anhydride, propionic anhydride, etc., or halides of these fatty acids, such as acetyl chloride, f-bromopropionyl chloride, hydrochloric acid, hydrochloric acid, hydrochloric acid halides of aryl substituted fatty acids, such as phenyl acetic acid chloride, etc., aryl carboxylic acid halides, such as benzoyl chloride, p-chlorobenzoyl chloride, 2-naphthoyl chloride, 1-naphthoyl chloride, etc. and -phenyl ester, etc. if X represents an NH group: aliphatic isocyanate, such as methyl isocyanate, or aromatic isocyanate, such as phenyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, naphthyl isocyanate and etc. if X represents an -alkyl group : alkoxy fatty acid anhydrides or halides, such as methoxy-acetic anhydride, ethoxy-acetic acid; anhydride, butoxy-acetic acid chloride, etc. -phenoxy-propionyl chloride, fl-phenoxy-propionyl chloride, etc., whereby, as already mentioned above, phenyloxide derivatives of lower fatty acids come into question as being particularly valuable.

Of course, in the case where Y is identical to R-X-CO-, it is obvious that the monoacyl compound of the 4,4'-diamino-stilbene derivative joke needs to be prepared separately, without suitably directly acylating the 4,4'-diamino-stilbene compound twice. The acylation can take place in aqueous medium but also with good stirring in a two-phase system, for example in a benzene-water mixture, whereby optionally an addition of acid-binding agents, such as sodium acetate, sodium carbonate, calcium or magnesium carbonate, magnesium oxide, etc., is advantageous.

Savida in the preparation of the new compounds nitro group-containing residues are introduced during the aylation with an aroylating agent, the nitro groups may be reduced and the amino groups formed may also be acylated.

The new whiteness-improving agents are characterized in that they contain at least once an aryloxy fatty acid acyl residue, while the second acyl group may either be identical with the first or vary widely from it. In addition to those on the grand of its beautiful, 'green-blue. fluorescence particularly suitable di-aryloxy-'acyl compounds are the new compound groups particularly valuable, which in addition to an aryloxy-acylamino residue on. the other stalls contain an arylureido group or a urethane group, they are distinguished by weak fluorescence, good light fastness and good attractiveness both on wool and on. cellulose.

The. new bleaches agora faintly yellowish, watery powder. In the form of their soluble salts, they can be mixed into any detergent in dry form, or it can also be transferred by evaporation and grinding or by spray-drying into a ready-to-use powder to an aqueous solution which also contains the components of the detergent.

The following examples obscure the manufacturing process and the use of the new optical blue means, without limiting the invention in any way thereto. The parts are, unless otherwise stated, parts by weight, and the temperatures are given in degrees Celsius.

Example 1. 37 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid are dissolved neutrally in 2,000 parts of water, and in the presence of sodium acetate 42 parts of phenoxyacetic acid chloride, 16th, in 250 parts of benzene are added with rapid stirring. Towards the end of the reaction, the reaction mixture is advantageously made neutral by the addition of soda or sodium hydroxide solution. After the acylation is completed, the reaction product is salted out and isolated. It may be dissolved in water and treated in and for purification by such means as absorbing or enlarging any contaminants present. In dried form, the sodium salt of 4,4'-diphenoxy-acetaminostilbene-2,2'-disulfonic acid is a white powder. The same solution dissolves in water and can be used in the form of water solution with the addition of glauber salt to improve the whiteness of cellulose fibers, such as cotton, cellulose, linen, etc. In weakly acidic baths, whiteness is also significantly improved. The whiteness-improved fibers Aga good light, acid and alkali accuracy. The moisture content of cellulose fibers, on the other hand, is more moderate, which is why it is easily possible that e.g. a normal household wash to remove the whiteness-enhancing agent.

Example 2. 40 parts of 4-nitro-4'-amino-stilbene-2,2'-disulfonic acid are acylated with 21 parts of phenoxy-acetic acid chloride with the addition of acid-binding agents, such as sodium acetate, advantageously in a benzene-water system, and nitro is reduced. - - —3 the association according to e.g. Bechamp with jam and hydrochloric acid to 4-amino-4'-phenoxy-acetaminostilben-2,2'-disulfonic acid. 51.4 parts of this amino compound are dissolved in a slightly attic acid reaction in 2,000 parts of water and reacted with good stirring with 14.3 parts of phenyl isocyanate in 250 parts of benzene. The resulting reaction product is dissolved in hot water, Iran is filtered off in a small amount as the by-product formed diphenylurea and further purified as in Example 1, if necessary.

The preparation of 4-phenylureido-4'-phenoxy-acetaminostilben-2,2'-disulfonic acid can, of course, also be carried out so that 4-nitro-4'-aminostilben-2,2'-disulfonic acid is first reacted with phenyl isocyanate, then reduced and finally acylated with phenoxy-acetic acid chloride.

The sodium salt of the new compound is a white powder. On cellulose fibers, a very good whiteness improvement is thus obtained, which is distinguished by good water, acidity and light fastness and for a very beautiful shade, which, compared with the same in the product described in Example 1, appears substantially offset against blue. DA the product, although it has a very good substantivity, shows only a moderate wash rate, so that it can be removed in a strong wash Ater, but at the same time stands out for good perborate rate, it is very v5.1 usable rather than an additive to household detergent or detergent . The same can also be used to improve the whiteness of wool in slightly acidic baths, whereby it again stands out for good whiteness-improving effect.

Example 3. 51.4 parts of it according to e.g. Example 2 prepared 4-amino-4'-phenoxy-acetaminostilben-2,2'-disulfonic acid is reacted in aqueous benzene solution with 26 parts of p-nitrophenoacetic acid doloride. After completion of the reaction, the nitro compound is isolated and reduced with jam and hydrochloric acid to 4 '- (4 "-aminophenoxy-acetamino) -4-phenoxyacetamino-stilbene-2,2'-disulfonic acid. 66.3 parts of this amino compound are reacted, with advantage Ater in two-phase systems. The product obtained is a yellowish powder and, in the form of its aqueous solutions, can be used to improve the whiteness of textile fibers, such as wool, cotton and cellulose, to show the effects obtained. very good light and water fastness as well as good acid and alkali fastness, while the product due to its properties on cellulose fibers is particularly suitable as an additive to detergent, however, it is also possible in two-phase systems instead of p-nitrophenoxy-acetic acid chloride reacted 51.4 parts of the 4-amino-4'-phenoxyacetaminostilbene-2,2'-disulfonic acid with 20 parts of p-toluic acid chloride. etching properties.

Example 4. 40 parts of 4,4'-nitroaminostilbene-2,2'-disulfonic acid are reacted in a phase phase system with 23 parts of 2,5-dichlorophenyl isocyanate, dissolved in benzene. The nitro group is then reduced with iron and hydrochloric acid, and 56 parts of the resulting 4-amino-4 '- (2 ", 5" -dichlorophenylureido) -stilben-2,2'-disulfonic acid are reacted with a benzene solution of 21 parts of phenoxy -acetic acid chloride. The purified product contains a slightly yellowish powder, which on wool and cellulose fibers shows interesting whitening-improving effects. It should be emphasized in particular that very good moisture and an interesting alkali quality are obtained on wool in particular.

Example 5. 40 parts of 4,4'-nitroaminostilben2,2'-disulfonic acid are reacted in two-phase systems with 23 parts of 3,4-dichlorophenyl isocyanate, suitably s5.- as indicated in Example 4, and the nitro compound is reduced with jam and hydrochloric acid. 56 parts of this 4-amino-4 '- (3' ', 4 "-dichlorophenylureido) -stilbene-2,2'-disulfonic acid are acylated with 29 parts of 3,4-dichlorophenoxy-acetic acid chloride, isolated and, if In dried form, this compound is a yellowish powder, the aqueous solutions of which are used to improve the whiteness of cotton, cellulose and wool.Processed cellulosic fibers have excellent washability with generally good care properties.

Example 6. 51.4 parts of the 4-amino-4'-phenoxy-acetaminostilbene-2,2'-disulfonic acid described in Example 2 are reacted in the presence of sodium acetate in aqueous solution with 13.1 parts of chlorocarbyl ethyl ester. The urethane forms a light yellow powder, which in a weak curt bath strongly improves the whiteness of the wool and in a neutral bath the same in cellulose fibers. Products which behave in a rather similar manner are obtained if, instead of chloroacetic acid ethyl ester, equivalent amounts of chlorocarboxylic acid methyl or isopropyl ester are used. These compounds can also be built up in reverse order, first reacting the 4,4'-nitroamino stilbene - 2,2 '- disulfonic acid with the chlorocarbyl alkyl ester, reducing the resulting urethane to the amino compound and then acylating with the phenoxy-acetic acid chloride.

Example 7. 51.4 parts of 4-amino-4'-phenoxy-acetaminostilben-2,2'-disulfonic acid are reacted in aqueous benzene solution with 23 parts of phenyl isoyanate-m-carboxylic acid ethyl ester. After separation of diphenylurea name-dicarboxylic acid ethyl ester and possible purification, a yellowish substance is obtained, the coin being a good whitening agent for wool and cellulose fibers of all kinds.

On cell wool, the resulting whiteness refraction shows excellent alkali and acidity, very good water resistance and good light fastness. Ph ylle is likewise a strong whiteness improvement, which, as on cell wool, shows valuable properties.

Example 8. 40 parts of 4,4'-nitroaminostilben-2,2'-disulfonic acid are reacted in a two-phase system with a benzene solution of 19 parts of hydrochloric acid phenyl ester in the presence of sodium acetate, the nitro group is reduced with jam and hydrochloric acid and 49 parts of the resulting 4-amino acid The 4'-carbonphenoxy-amino-stilbene-2,2'-disulfonic acid is acylated with 21 parts of phenoxy-acetic acid chloride. The same compound is obtained if Ater is reacted in a two-phase system with 51.4 parts of the 4-amino-4 '- (phenoxyacetamino) -stylben-2,2'-disulfonic acid described in Example 2 with 19 parts of 4-chlorochloric acid phenyl ester . The product achieves a strong whiteness improvement on wool and cellulose fibers with very good caution properties.

Example 9. 40 parts of 4,4'-nitroaminostilben-2,2'-disulfonic acid are reacted with 21.6 parts of p-nitrobenzoyl chloride, and the reaction product is reduced with iron and hydrochloric acid to the diamino compound. 48.9 parts of this 4-amino-4 '- (4 "-aminobenzoyl) -amino-stilbene-2,2'-disulfonic acid are acylated, with advantage in two-phase systems, with 42 parts of phenoxy-acetic acid chloride. yellow powder, which is used to improve the whiteness of cellulose fibers and wool.

Of particular interest is its use as an additive in whey powder and other detergents.

Example 10. To a detergent, consisting of parts of whey, 16 parts of calcined soda and 5 parts of water glass, was added 0.01-0.1% of 4-phenoxy-acetamino-4'-phenylureidostilben-2,2'-disulfonic acid.

With this detergent in ordinary household washing, cotton swabs washed out after rinsing and drying for a very beautiful, white tone.

In the following table, a number of additional compounds have been compiled, which can be prepared according to the information given in Examples 1-9. They likewise possess valuable qualities.

Tab ell Y - NH - \\ .— CH = CH —— NH - CO - X - R SO3HHS03 No— X —o - CH, - CO - 0— CH2— CO —0— CH, - CO - OCH3 CI - Cl - Cl CI 6 CH, -— —CO —NH— / - CH, - CO - - CH3 - CI I3 - CH, - CH3 CH, CH, 7 Cl- I— - '0— CH2 — CO —NH— - 0 - CH2— CO —— CH, - 1.281.78 - - X - R 11 12 C1_ \ - 0 - CH2- CO - \ 9 Cl - / \ / \ - 0 - CH, - CO- Cl- \ 0 - CH, - CO \> 0 - CH2- GO - \ 0 - CH, - CO- - 0 - CH, - CO - \ \ \ - 0 - CH2- CO- \ - 0- CH, - CO - \ / 16 \ / \ - 0 - CH, - CO - 17/0 - CH, - CO- \ / 181 <\ 0- CH, - CO - / 19 Cl- \ - 0 - CH2- CO - - CH2- CH, CH2 - CH2 CI-12 / CH, -CH, ___ \ / - / \\ - NH - CO - CH, \ -NH - CO - OC21-1 / '\ H -CO - CH, - 0 - / / NN 13 14 Cl N CI - \; - 0 - CH, - CO -0- C2H 6 - - - X - R - 0 —CH, - / —0— CH, - <CO —NH —— \ CH, - CO —NH— / 0 — CH2 — CO - - 0 — CH. — CO- - 0 - C, H, - 0 - UT, CI N Cl - / \ —0 - CH2 - CO —NH - \\; —0— CH. — CO - // CI - -NH- // \ / \ \\ ./ \ \ 0 - CH, - CO - \ 37 - 0 - CH, - CO - 38 \ - 0 - CH, - CO - \ 39 CH, - 0 - \ _ D-CH, - CO- \\ 0 - CH, - CO - Cl - \ - 0 - CH, - CO - - CO - / \\ - 0 - CH, - CO - - CH, -O- C4H9 - CH, - 0 - C4H, - CH, - O- / \ - CH- 0 - / \ \ CH3 \ -0 -CH, - CH, - CO -I- CH - CH 0 2 --2 - _ - / \ • - 0 - CH, - CO - N - 0 - CH, - CO- N \ - 0 - CH, - CO - 49, / - 0 - CH, - CO - I / 0 - \ -0-CH - / \ N2 \ CH, - 0 - \ / \ - NH-CO -CH2-0 - \ / \ /// -CH, - 0 - / \ / \ -NH- CO -CH \ 2 / -0- / \ - CH CH-01 \ - CH, - 0 - / \ -NH-CO -CH -0 - / \ \ / 2 \ / 41 42 4 44 4 46 47 48 8 - - No —X - R CH (/ 0— CH, - CO —— CH2-0 - / \ —NH — CO — NH— / \ \ CH3 51 \ —0 —CH, —CH, - CH, - CO - - CO - NH - \

Claims (2)

Patent claim: A process for the preparation of whiteness improvers of the general formula Y - —— CH = CH - / - NH - CO - X - R SO, HHSO, in which X represents a direct carbon bond or a double bridge link of the formula -0-, -NH- or -alkylene-O-, Y the acyl radical of a crude aryloxy fatty acid on R is an alkyl or aryl radical which, with the exception of the sulfonic acid group, may be arbitrarily substituted, characterized in that either an aryloxy fatty acid residue is further acylated by means of an aryloxy fatty acid residue , 4'-diaminostilben-disulfonic acid by means of an acylating agent introducing an RX-CO residue or reacting a 4,4'-diaminostilben-disulfonic acid monoacylated with an R-XCO residue with a reaction-prone derivative of an aryloxy fatty acid, wherein sasom oxy fatty acids only qualify as those with lower molecular weight. Modification of the process set according to claim 1, Unsubscribed, that if nitro group-containing residues are introduced during the acylation by means of an aroylating agent, the nitro groups are reduced and the amino groups formed are further acylated. Stockholm 1OO. Kungl. Roktr. P. A. Norstedt & Siiner 500039