DE1236193B - Process for the production of nitrogen-containing condensation products - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08g

German KX: 39 C-5

Number: 1236193

File number: B 74696IV d / 39 c

Filing date: December 17, 1963

Opened on: March 9, 1967

From the German patent specification 693 770 it is known to use aromatic hydroxysulfones with formaldehyde and aromatic hydroxycarboxylic acids or aryloxy fatty acids zj alkali-soluble condensation products, which are used in textile and leather Industry can be used. These products are particularly recommended as a substitute for tannins Dyeing and printing works, e.g. according to the information in the German Auslegeschrift 1 088 518, for production of rubber prints with basic dyes. It is also from the German Auslegeschrift 1124 959 known to produce similar condensation products which contain phenols as a further component. These condensation products are also used in a variety of ways, also as auxiliaries in rubber printing with basic dyes, as can be seen from the German Auslegeschrift 1 128 446.

However, the known agents of this type are no longer odor-resistant at temperatures above 80 ° C, so that they are only conditional for the modern methods of rubber printing, which are geared towards speed are suitable.

Furthermore, from the German patent 827 799 certain condensation products from urea or Urea derivatives, aromatic oxy compounds, organic acids or oxy acids and aldehydes known, which are recommended as tanning agents, but which are not picked, especially in the case of tanning Naked goods do not meet all requirements.

It has now been found that nitrogen-containing condensation products can be used with excellent performance Properties obtained when one

a) Condensates obtained by reacting 1 to 5 molar equivalents of one of carboxyl groups free aromatic hydroxyl compound with 5 to 11 molar equivalents of formaldehyde or one Formaldehyde-releasing compound have been produced in an acidic aqueous medium, at the same time or in any order with

b) 0.1 to 5 molar equivalents of lower alkyl ethers of dimethylolurea or the dimethylol compounds of aliphatic linear ones or cyclic urea derivatives and

c) 1 to 6 molar equivalents of an aromatic hydroxycarboxylic acid, an aliphatic dicarboxylic acid or an aryloxy fatty acid

converts or 1 to 5 molar equivalents of an aromatic hydroxy compound free of carboxyl groups, 5 to 11 molar equivalents of formaldehyde Process for the preparation of nitrogenous Condensation products

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Otto Hertel,

Dr. Walter Hensel, Ludwigshafen / Rhine;

Dr. Hans Burkhardt, Limburgerhof

or a formaldehyde-releasing compound and the reactants listed under b) to c) at the same time reacted in an acidic aqueous medium.

Particularly good results are achieved when the amount of formaldehyde is 38 to 50 mol percent.

Suitable aromatic hydroxy compounds are, for. B. Phenol, the cresols, 4-tert.-butylphenol, thymol, α-naphthol, ^ -naphthol, pyrocatechol, resorcinol, Hydroquinone, 2-hydroxydiphenyl, 4-hydroxydiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylpropane- (2 ", 2 ") and, in particular, mono- and dihydroxy compounds of diarylsulfones, such as 4,4'-dihydroxydiphenylsulfone, 4-hydroxydiphenylsulfone and phenylhydroxynaphthyl sulfones. These compounds, which can also be used in mixtures can also be substituted by non-reactive groups, e.g. by chlorine or by alkyl groups. The dialkyl ethers, in particular, are used as the starting compound of group b) the dimethyl ethers of dimethylolurea, dimethylolmethylurea, dimethylol - N, N '- dimethylurea, Dimethyloläthylenurea, Dimethylolpropylenurea, Dimethylolglyoxalmonourein and Dimethylolglyoxaldiurein into consideration.

Starting compounds of group c) are aromatic hydroxycarboxylic acids, such as the hydroxybenzoic acids, in particular salicylic acid and gallic acid, and also aliphatic dicarboxylic acids such as malonic acid and glutaric acid, and further aryloxy fatty acids such as phenoxyacetic acid.

The formaldehyde can either be in free form, e.g. in aqueous solution, or in the form of its formaldehyde releasing derivatives, such as 1,3,5-trioxane, paraformaldehyde and hexamethylenetetramine,

709 518/530

be set. It is preferable to work in the strongly acidic range at condensation temperatures between 30 ^° C. and boiling point. Under these conditions, the condensation takes about 3 to 6 hours. The end of the reaction can be recognized by the so-called fracture sample, ie it is reached when a sample of the cooled process product such as glass breaks.

The products of the process dissolve in aqueous alkalis, but practically not in neutral water and in acids, so that they can easily be separated from the acidic aqueous medium. For further work-up, it is expedient to wash it a few times with hot water and then dry it in a vacuum at about 60 ^° C.

The resins obtainable in this way dissolve not only in alkalis and other basic media, but also in many organic solvents, including ethanol and acetone. Depending on their composition, they generally have an acid ao number between 5 and 20. The partly colorless, partly light-colored and especially odorless process products, which even at temperatures above 100 ° C, such as up to 130 ⁰ C, are odor stable, can Among other things, they are used in the paint, textile and paper industries, but primarily as tanning agents, as they give the leather a great deal of body.

In contrast to the tanning agents known from German patent specification 827 799, they allow perfect Tanning of unpickled pelts.

The products find a particularly important application as laking agents for basic dyes. Color lacquers, e.g. with auramine dyes, rhodamine dyes, Victoria blue dyes, Methyl violet, crystal violet and malachite green are insoluble in water, but despite their salt character excellent organophilicity, so that they can be used for coloring organic materials, e.g. for the production of carbon paper waxes, lithograph compounds or ballpoint pen pastes; to highlight is here the use of the process products as a laking component in Rubber printing (flexographic). The paints that can be achieved with the process products and their subsequent products, like prints and dyeings, show excellent properties.

The parts and percentages given in the examples are parts by weight.

example 1

It is allowed to 37.5 parts of p-tert-butylphenol, 125 parts of 33% aqueous formaldehyde and 5 parts of concentrated hydrochloric acid at 100 ⁰ C for 6 hours to react for one another, the reaction mixture was added then at 8O ⁰ C with 35 parts of salicylic acid and 3, 7 parts Dimethylolharnstoffdimethyläther, this mixture is heated for a further 2 hours at 100 ⁰ C and evaporate it in a vacuum pan dryer at 8O ⁰ C.

A similar process product is obtained if all components are ^{heated together to 100 °} C. for 6 to 8 hours and the reaction mixture is then evaporated.

In both cases, a white resin with an acid number of 11.8 is obtained. As proof of technical progress a flexographic printing ink was produced using the condensate obtained according to the invention.

30 parts of a styrene-maleic acid diethyl ester copolymer are dissolved in 90 parts of ethanol and 10 parts of ethyl glycol and with 7 parts of rhodamine B and mixed with 14 parts of the process product.

A coating on aluminum foil produced in this way showed excellent results when tested in accordance with DIN 16524 Waterfastness.

Equally good results are achieved with rhodamine BA, auramine benzenesulfonate, Victoria blue B and Malachite green.

Example 2

According to the instructions of Example 1, condensation products are also obtained in a more efficient manner Properties if 33 parts of malic acid are used instead of salicylic acid.

The acid number of the resin is 10.7.

Example 3

A mixture of 125 parts of 4,4'-dihydroxydiphenylsulfone, 50 parts of water, 200 parts of concentrated hydrochloric acid and 50 parts of 33% strength aqueous formaldehyde ^em are heated for 2 hours at 95 to 100 ⁰ C, then at 80 ° C with 7.4 Dimethylolharnstoffdimethyläther parts and, after further 2 hours of heating at 100 ⁰ C with 50 parts of salicylic acid.

The entire reaction mixture is kept at 100 ^° C. for 4 hours and then evaporated in vacuo.

The process product, a yellow one, in an ethanol-glycol monoethyl ether mixture soluble powder, has an acid number of 12.3.

Example 4

37.5 parts of p-tert-butylphenol and 25 parts of 30 ° / _o sodium formaldehyde are maintained for 2 hours at 100 ⁰ C with 5 parts of concentrated hydrochloric acid. After cooling to 8O ⁰ C are employed 20.5 parts of a 50 ° / ₀ aqueous solution of dimethyl ether and 35 parts of Dimethylolglyoxalmonourein to salicylic acid and holds for 4 hours to 8O ⁰ C.

The reaction mixture is brought to dryness and pulverized. A yellowish powder is obtained, which dissolves in acetone and alcohol.

Example 5

37.5 parts of p-tert-butylphenol, 25 parts of 30 ° / _o sodium formaldehyde and 5 parts of concentrated hydrochloric acid is maintained for 2 hours at 100 ⁰ C. After cooling to 60 ° C., 15 parts of dimethylolurea and 38 parts of phenoxyacetic acid are introduced. It is heated to 8O ⁰ C. After 4 hours, the reaction product is concentrated by evaporation in a vacuum pan dryer and pulverized it. 95 parts of a yellowish powder are obtained which dissolve well in acetone and alcohol.

Claims (1)

Claim: Process for the production of nitrogen-containing condensation products, characterized in that that he a) Condensates obtained by reacting 1 to 5 molar equivalents of one of carboxyl groups free, aromatic hydroxyl compound with 5 to 11 molar equivalents of formaldehyde or a formaldehyde-releasing compound have been prepared in an acidic aqueous medium, simultaneously or in any Order with b) 0.1 to 5 molar equivalents of lower alkyl ethers of dimethylolurea or the dimethylol compounds of aliphatic linear or cyclic urea derivatives and c) 1 to 6 molar equivalents of an aromatic hydroxycarboxylic acid, an aliphatic dicarboxylic acid or an aryloxy fatty acid converts or 1 to 5 molar equivalents of an aromatic hydroxy ίο free of carboxyl groups compound, 5 to 11 molar equivalents of formaldehyde or a formaldehyde-releasing compound and the reactants listed under b) to c) simultaneously in an acidic aqueous medium implements. Considered publications:
German Patent No. 827799;
J. Scheiber, Chemistry and Technology
artificial resins (1943), pp. 426 to 428. A test report was displayed when the registration was announced. 709 518/530 2.67 © Bundesdruckerei Berlin