DE1082050B - Process for the production of water-soluble, metal-containing higher molecular weight organic nitrogen compounds - Google Patents

Description

Process for the production of water-soluble, metal-containing, higher molecular weight organic nitrogen compounds It has already been proposed, e.g. Am British Patent 522 539, the wet fastness of dyeings on various Yarns and fabrics by treatment with a solution of a condensation product to increase that obtained by reacting dicyandiamide with a polyalkylene polyamine will. Furthermore, the use of metal salts of such products is also possible known from US Pat. No. 2,622,075.

It has now been found that dyeings are even more fastidious compared to wet treatment can be achieved by using metal complexes of condensation products which are derived from N-substituted dicyandiamides.

According to the invention, water-soluble, metal-containing, higher molecular weight organic nitrogen compounds made by standing in the absence of water an N-substituted dicyandiamide of the general formula] A. [XN-C (NH) - NHCN] ,, in which A is an alkyl, alkylene, aralkyl, aryl or arylene radical, the one or can have several simple, neutral or basic substituents, and in X is hydrogen or an alkyl radical and p is 1 or 2, with one optionally linear polyalkylenepolyamine of the structural formula Y in salt form. [(CH2) n NH] m (CH2) n NH2 in which Y is NH2, OH or a halogen atom, n is 2, 3, 4, 5 or 6 and m is an integer greater than zero, and the condensation product, if appropriate, is heated as a salt, in aqueous solution with a water-soluble heavy metal salt. The product is then optionally isolated from the solution.

Suitable starting materials N-substituted dicyandiamides are, for. B. ethylene-bis-dicyandiamide, p-chlorophenoldicyandiamide, hexamethylene - bis - dicyandiamide and phenyl dicyandiamide. Manufacturing process for these N-substituted dicyandiamides are, inter alia, in British patents 576401, 599713 and 599 722 described.

Polyalkylenepolyamines suitable as starting materials are, for. B. diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, bishexamethylenetriamine, 1,2 - bis (w-amino-hexylamino) -ethane or polyethylene polyamines obtained by initiating the polymerization of ethylene amine can be represented with hydrochloric acid.

Salts thereof can be used in place of the polyalkylenepolyamines that react in the same way, e.g. B. the carbonates.

The N-substituted dicyandiamide and the polyalkylene polyamine or their mixtures are heated to temperatures of 70 to 200 ° C. Preferably is heated until the initial development of ammonia practically ceases Has. This usually takes 1 to 20 hours.

Optionally, solvents such as. B. hydroxyl-containing solvents, such as butanol, ß-ethoxyethanol or ß-butoxyethanol, can be used.

The organic nitrogen-containing condensation products thus obtained are strongly basic viscous liquids.

To metal salts of these organic nitrogen-containing condensation products it is in itself sufficient to produce the nitrogenous condensation product, optionally in salt form, to be dissolved in water, the calculated amount of the metal salt and then optionally adding a mild alkali. The so educated Metal complex solutions, e.g. B. copper complexes can be used for post-treatment more directly Dyes can be applied to cotton to improve the fastness of the dye. However, it is usually more convenient to isolate the metal complexes prior to use.

As salts of the organic nitrogen-containing condensation product the hydrochlorides, sulfates or acetates come into consideration.

Particularly valuable metal salts for the production of those containing metal Nitrogen compounds are copper salts such as chloride, sulfate, formate or acetate. It can also be other metal salts, such as. B. chromium acetate, chromium chloride, nickel nitrate or cobalt nitrate can be used.

The conversion of the metal salt and the nitrogen-containing condensation product takes place when they are mixed in aqueous solution and can be removed by heating accelerate. The product can easily be isolated by evaporating the solution and contains the metal in non-cationic form, which is evident from the fact that the common inorganic reagents such as hydrogen sulfide or ammonium sulfide, no precipitations of the corresponding sulfides result.

The metal-containing organic nitrogen compounds are special favorable for fixing dyes which contain metallizable groups.

The following examples in which the parts are based on quantities by weight refer to explain the invention in more detail.

Example 1 44 parts of ethylene-bis-dicyandiamide, which by reacting of 1 mole of ethylenediamine dihydrochloride with 2 moles of the sodium salt of cyano-cyanamide is prepared, 43 parts of tetraethylene pentamine are added with stirring. The mixture is heated to 110 to 120 ° C., whereupon ammonia is developed with foaming begins. The temperature is then raised after the initially violent reaction subsides has, carefully increased to 150 to 1600C and is on for 8 to 12 hours kept this height. As condensation progresses, so will The reaction mixture becomes more viscous and becomes increasingly difficult to stir. The product will dissolved in water and mixed with an aqueous solution of a copper salt.

This solution can be used for the aftertreatment of cellulose fabrics dyed with substantive dyes to improve the wet fastness of the dye to improve.

The complex salt formation is also possible in the following way: 14 parts Copper sulfate crystals are dissolved in 100 parts of water and the solution is at 25 to 30 ° C to 75 parts of a 400/0 aqueous solution of the aforementioned condensation product added.

The solution of the copper complex is then evaporated to dryness, whereby a bluish green powder is obtained which, even in small quantities, has the authenticity Substantive colorations significantly improved.

Example 2 39 parts of p-chlorophenyl dicyandiamide, which according to British Patent 599722 from p-chloroaniline hydrochloride and the sodium salt of cyano-cyanamide -was made, and 38 parts of tetraethylene pentamine are mixed and taken Stirring heated to 110 to 1200C. After 15 minutes the p-chlorophenyl dicyandiamide dissolves with foam formation and the beginning of ammonia development. After 45 minutes of heating the contents of the reaction vessel are poured out and allowed to cool. The resulting viscous, syrupy mass dissolves in hot water, and the solution according to the example 1 is mixed with the copper salt solution.

Example 3 25 parts of hexamethylene-bis-dicyandiamide are in 18.9 Parts of tetraethylene pentamine stirred in, and the Mixture is heated. At 120 to 130 "C begins to develop ammonia, which indicates the beginning of condensation. The temperature is increased to 140 to 1500 C and 5 hours at this altitude held. The viscous reaction mixture is allowed to cool to 90 to 100.degree and carefully diluted with 60 to 70 parts of water. The solution thus obtained can further diluted with hot water and according to Example 1 with the copper salt solution be moved.

Example 4 45 parts of phenyl dicyandiamide are dissolved in 53 parts of tetraethylene pentamine stirred in, and the mixture is heated. Once the temperature has risen to 120 to 1300C increases, the vigorous development of ammonia begins.

The temperature is held at this level for 11/2 hours and the resulting viscous base is then removed from the reaction vessel. she is in soluble in hot water, and the solution is processed according to Example 1.

Example 5 A mixture of 33 parts of cyclohexyldicyandiamide and 40 parts of tetraethylene pentamine are heated to 150 to 170 ° C. with stirring At this temperature a vigorous evolution of ammonia begins, and so does the temperature is held at the same level for 6 to 7 hours.

The resulting viscous condensation product is in hot water soluble and is converted into the metal complex in solution according to Example 1.

It can be used in this form.

Example 6 43 parts of polyethyleneimine with a molecular weight in of the order of 900, which because of the terminal NH2 groups as a polyalkylene polyamine is to be understood, 9.5 parts of ethylene-bis-dicyandiamide and 30 parts of ß-ethoxyethanol are together at a temperature of 135 to 150 "C for 22 to 24 hours Stirred reflux cow. There is a slow but steady evolution of ammonia instead of. The solvent is then, preferably by distillation under reduced Pressure, removed from the condensation mixture, and what remains as a residue Condensation product is dissolved in hot water. It will then, as in the example 1, reacted in the form of its aqueous solution together with a copper salt.

Example 7 A mixture of 37 parts of ethylene-bis-dicynadiamide, 20 parts of diethylenetriamine and 40 parts of ß-ethoxyethanol are refluxed heated to 135 to 145 ° C. with stirring. There is lively ammonia development, whereby the ethylene-bis-dicyandiamide dissolves and becomes a homogeneous, viscous one Reaction mixture forms. After 6 to 7 hours, the ß-ethoxyethanol, preferably by distillation under reduced pressure, and removed the condensation product dissolved in hot water. The solution is used according to the example.

Example 8 A blend of 60 parts of polyethylene polyamine with a Boiling point of more than 2100C at 14 mm and 32 parts of phenyldicyandiamide is below Stirring heated to 150 to IG0 ° C. The condensation takes place with development of Ammonia instead. After 2 hours Heating to 150 to 160 "C will die viscous base removed from the reaction vessel. It is soluble in hot water and gives a usable solution as described above.

PATENT CLAIM: 1. Process for the production of water-soluble, metal-containing higher molecular weight organic nitrogen compounds through conversion of amido compounds with polyalkylenepolyamines with elimination of ammonia and subsequent metal complex formation, characterized in that in the absence of water a nitrogen-substituted Dicyanamide of the general formula A [XN - C (NH) - NHCNI ,, in which A an optionally one or more simple neutral or basic substituents having alkyl, Alkylene, aralkyl, aryl or Means arylene radical, and in the X hydrogen atom or an alkyl radical and p is 1 or 2, with one optionally present in salt form linear polyalkylenepolyamine of the general formula Y [(CH2) n - NH] rn - (CH2) nNH2, in the Y N H2, OH group or halogen atom, n 2, 3, 4, 5 or 6 and m a whole Number greater than zero means heated and the condensation product, if appropriate as a salt, in aqueous solution with a water-soluble heavy metal salt.

Claims (1)

2. The method according to claim 1, characterized in that as Heavy metal salt uses a copper salt. Documents considered: German Patent No. 855 001; British Patent No. 571,369; U.S. Patent No. 2,622,075.