DE1231712B - Process for the production of alkali-soluble condensation products - Google Patents

Description

Process for the production of alkali-soluble condensation products From the German patent specification 693 770 it is known aromatic hydroxysulfones with formaldehyde and aromatic hydroxycarboxylic acids or aryloxy fatty acids to form alkali-soluble ones Implement condensation products used in the textile and leather industries can be. These products are particularly recommended as a substitute for tannins Dyeing and printing, e.g. B. according to the information of the German Auslegeschrift 1088 518 for the production of rubber prints with basic dyes. Furthermore, it is over the German Auslegeschrift 1 124 959 known to produce similar condensation products, which contain phenols as an additional component. Also find these condensation products manifold use, such. B. also as an aid 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 at temperatures above 800 C is no longer odor-resistant, so that it is for the modern, on speed The deactivated methods of rubber printing are only suitable to a limited extent.

It has now been found that alkali-soluble condensation products, which do not have this disadvantage, can be prepared if reaction products obtained by reacting phenols or naphthols with formaldehyde or formaldehyde-releasing compounds in an alkaline, acidic or neutral aqueous medium at temperatures between 300 ° C. and the boiling point have been obtained, in an alkaline, acidic or neutral aqueous medium in any order, one after the other or simultaneously with a) thioureas of the general formulas or in which Rl is a hydrogen atom, an alkyl radical with up to 4 carbon atoms or a radical of the formula -CS-N (R5) -R2, R2 is a hydrogen atom or an alkyl radical with up to 4 carbon atoms, Ra is an alkyl radical with up to 3 carbon atoms, the hydroxyl groups carry or can be interrupted by -0-, - NH - or - N (R -, R4 a hydrogen atom or an alkyl or hydroxyalkyl radical with up to 4 carbon atoms and R5, which can be identical or different, hydrogen atoms, hydroxymethyl groups or alkoxymethyl groups means up to 5 carbon atoms in the alkoxy radical and optionally further formaldehyde and b) mononuclear aromatic carboxylic or sulfonic acids which can contain hydroxyl or amino groups, aryloxy fatty acids or aliphatic polycarboxylic acids which can contain hydroxyl groups, likewise at temperatures between 30 "C and the boiling point and the solutions obtained are dried in the usual manner.

Examples of phenols and naphthols include phenol itself, cresols, p-tertiary-butylphenol, catechol and its homologues, such as methyl, Ethyl catechols, propyl catechols and their technical mixtures known as fuel oils, Octylphenols, nonylphenols, 1,3- and 1,4-dihydroxybenzene, alkoxyphenols such as 2-, 3- and 4-methoxyphenol, 4,4'-dihydroxydiphenylsulfone, 4-hydroxydiphenylsulfone, phenylhydroxynaphthylsulfone, 2,2-bis (4-hydroxyphenyl) propane, 2-hydroxydiphenyl, 4-hydroxydiphenyl, 4-hydroxydiphenylmethane, α-naphthol, p-naphthol, isopropyl-B-naphthols, phenolsulphonic acids and naphtholsulphonic acids. Phenols or naphthols which do not contain sulfonic acid groups are preferred contain.

The formaldehyde can either be in free form, preferably as aqueous Solution, or in the form of Formaldehyde-releasing compounds, such as Paraformaldehyde, trioxymethylene or hexamethylenetetramine can be used.

Thioureas of the type defined under a) are z. B. the unsubstituted Thiourea, monoalkyl and symmetrical dialkylthiourea with up to 4 carbon atoms in the alkyl radicals, such as N-methylthiourea, N, N'-dimethylthiourea and N, N'-dibutylthiourea, N, N'-alkylene thioureas, such as N, N '- ethylene thiourea, N, N' -1,2 - propylene thiourea and N, N'-1,3-propylene thiourea. In addition, the compounds a) include the methylol and methylol ether derivatives of said thioureas.

Preferred compounds a) are thiourea, mono- and symmetrical Dialkylthioureas and N, N'-alkylenethioureas and their methylol and methylol ether derivatives. If you use the corresponding methylols or methylol ethers, you can determine the amount reduce formaldehyde accordingly.

If you use the thioureas yourself, you can get some of the formaldehyde only to be implemented together with these.

Starting compounds of group b) are preferably mononuclear aromatic Carboxylic acids which may contain hydroxyl or amino groups, e.g. B. benzoic acid, Phthalic acid, salicylic acid, o-cresotinic acid, gallic acid and aminobenzoic acids. Further preferred compounds of group b) are aliphatic polycarboxylic acids, the hydroxyl groups may contain, e.g. B. malonic acid, succinic acid, adipic acid, tartaric acid, malic acid and citric acid. Also aryloxy fatty acids, such as phenoxyacetic acid and cresoxyacetic acids, can be used.

As examples of mononuclear aromatic sulfonic acids with amino groups sulfanilic acid and metanilic acid may be mentioned.

In the process of the invention, the starting compounds are reaction products used by reacting phenols or naphthols with formaldehyde or Formaldehyde-releasing compounds in alkaline, acidic or neutral aqueous Funds have been received. The ratio of phenol or naphthol to formaldehyde can be changed within wide limits. It has proven very useful to use 1 mole Phenol or naphthol 1 to 8 moles, preferably 1 to 6 moles, formaldehyde or the to use an equivalent amount of a formaldehyde-releasing substance. The alkaline The reaction mixture can react with a variety of alkaline reactions Substances are caused, e.g. B. by alkali metal hydroxides, such as sodium and Potassium hydroxide, by ammonia or by primary, secondary or tertiary amines, z. B. ethylamine, diethylamine, triethylamine, diethanolamine and triethanolamine. the Reactions in acidic agents are preferably carried out with mineral acid, e.g. B salt or Sulfuric acid. Medium-strength inorganic acids such as phosphoric acid, acid salts such as sodium hydrogen sulfate and organic acids, especially aliphatic Carboxylic acids that are free from hydroxyl groups, such as formic acid, acetic acid, oxalic acid and trichloroacetic acid, come into consideration.

You can also add organic solvents to the reaction mixture, which are miscible with water, for example methanol, ethanol, acetone, tetrahydrofuran, Glycol and polyglycols. But you can also in the absence of such solvents work. the The reaction is preferably carried out at temperatures between 30 ° C. and the boiling point between 50 and 100 "C, and generally decreases under these circumstances 2 to 8 hours to complete.

The reaction products obtained are then according to the method of Invention in one or more stages with the starting materials of groups a) and b) implemented. The order of these conversions can be chosen at will. So you can either use the reaction products at the same time in one stage with the Implement compounds a) and b); but you can also start with one of the connections a) or b) and then implement with the other connection. Products with special good properties are obtained if 0.1 to 1 mole of the converted phenol is used 3, preferably 0.1 to 2 mol of compound a) and 0.1 to 3, preferably 0.5 up to 2 moles of compound b) are used. The implementation with the compounds a) and b) is carried out in an acidic, alkaline or neutral aqueous medium. In general no additional measures are required, as the amount of the implementation of phenol or naphthol with formaldehyde added alkaline or acidic reacting Substance is mostly sufficient to further implement under the prescribed Conditions to enable.

The reaction temperature will be in the same range as that for Implementation of phenols or naphthols with formaldehyde is chosen. The connections a) generally react more easily than compounds b); therefore suffice for the Implementation with a) often lower temperatures and shorter reaction times than for the implementation with b). In many cases the following working conditions have been found proven; Reaction with a) at about 40 to 60 "C in 1 to 4 hours. Reaction with b) at about 70 to 100 "C in 4 to 10 hours. With simultaneous reaction with a) and b) one selects the conditions required for b). The end of implementation can be recognized by the so-called fracture test, d. i.e. it is reached when a Sample of the cooled process product breaks like glass.

The products of the process do, however, not dissolve in aqueous alkalis in neutral water and in acids, making them out of an acidic or neutral aqueous Funds can be easily separated. They are washed for further work-up expediently a few times with water and then dry them in a vacuum at about 60 "C. For many purposes, however, it is also sufficient to reduce the conversion mixture to simpler Way in its entirety or after separation of the main amount of aqueous layer to dry, for example in a drying pan, on a roller or in a Spray dryer. The resins obtainable in this way do not only dissolve in alkalis and other basic agents, but also in many organic solvents, including ethanol, acetone and a mixture of ethanol and ethyl glycol. Depending on Their composition generally has an acid number between 5 and 20. The partly colorless, partly weakly colored and, above all, odorless process products are odor-stable up to 130 ° C; they can be used in the paint, textile and paper industries, z. B. can be used as a dispersant.

The products find a particularly important application as laking agents for basic dyes. Color varnish, e.g. B. with Auramill dyes, Rhodamine dyes, Victoria dyes, methyl violet, crystal violet and malachite green, are insoluble in water, however, despite their salt character, excellently organophilic, so that you can use them for coloring organic materials, e.g. B. for production of carbon paper waxes, lithography compounds and ballpoint pen pastes; to highlight is here the use of the process products as a laking component in Rubber printing (flexography). The paints that can be achieved with the process products as well their subsequent products, such as prints and dyeings, show excellent properties.

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

Example 1 37.5 parts of p-tert-butylphenol are heated to 70 "C, sets at this temperature 0.5 parts 500 /, igc sodium hydroxide solution and within half a Hour 8.3 parts of paraformaldehyde added.

The reaction mixture is now kept at 70 ° C. for 2 hours and afterwards 35 parts of salicylic acid and 2 parts of thiourea are added. Then heated the reaction product is heated to 100 ° C. for 6 hours. The product is evaporated to dryness and pulverized.

79 parts of a pale yellow powder are obtained which are dissolved in an ethylglycol-ethanol mixture is readily soluble.

A flexographic printing ink is obtained from the process product in the following way: 30 parts of a styrene-maleic acid ester copolymer were dissolved in 90 parts of ethanol and 10 parts of ethyl glycol dissolved and 7 parts of auramine FA (C. 1.

41000) and 14 parts of the condensation product obtained were added. The flexographic printing ink is coated onto aluminum foil on a rotary coating machine.

A coating produced in this way had, tested according to DIN 16524, the Water fastness 4.

Example 2 One works under the same conditions and with the the same amounts as in Example 1. Used instead of the 2 parts of thiourea However, 2.6 parts of N-ethylthiourea are used. The reaction mixture is according to the information of Example 1 worked up and the reaction product tested from an application point of view.

The yield is 79 parts. Water fastness: 4.

Example 3 One works under the same conditions as in the example 1. Instead of the 8.3 parts of paraformaldehyde, however, 25 parts of its own 330/0 are used aqueous formaldehyde and instead of the thiourea 3 parts of N-methyl-N'-ethylthiourea. The reaction mixture is worked up according to the information in Example 1 and that Product received application-technically tested.

The yield is 80 parts. Water fastness: 3 to 4.

Example 4 62.5 parts of dihydroxydiphenyl sulfone, 50 parts of water, 25 Parts of 330% strength aqueous formaldehyde and 5 parts concentrated hydrochloric acid is heated to 100'C and maintains this temperature for 2 hours. The mixture is then allowed to reach 800 To cool C, 25 parts of S-alicylic acid and 2.6 parts of N-ethylthiourea are added and reheat the mixture to 100aug. After having the reaction mixture 8 hours has kept at this temperature, it is washed acid-free with water.

The product is dried in vacuo at 80 ° C. and in a ball mill ground. The yellow powder dissolves in alcohol, acetone and a mixture of ethanol and jithyl glycol. The application test is carried out as in Example 1.

The yield is 86 parts. Water fastness: 3 to 4.

Example 5 One works under the same conditions and with the same Amounts as in Example 4. Used in place of the 2.6 parts of N-ethylthiourea but 3.5 parts of N, N-diethylthiourea. The reaction mixture is after Details of Example 1 worked up and the product was tested in terms of its application.

The yield is 87 parts. Water fastness: 3 to 4.

Example 6 One works under the same conditions as in the example 1. Instead of the 2 parts of thiourea, however, 3.5 parts of dithio-allophanoic acid ethylamide are used. The reaction mixture is worked up according to the information in Example 1 and that Reaction product tested from an application point of view.

The yield is 81 parts. Water fastness: 3 to 4.

Example 7 One works under the same conditions and with the the same amounts as in Example 1. Instead of the 0.5 part of 500% sodium hydroxide solution however, 5 parts of concentrated hydrochloric acid are used. The reaction mixture is worked up according to the information in Example 1 and the product obtained from an application point of view checked.

The yield is 78 parts. Water fastness: 4.

Example 8 One works under the same conditions and with the the same amounts as in Example 1. Used instead of the 2 parts of thiourea However, one 2.6 parts of ethylidene thiourea. The reaction mixture is after Details of Example 1 worked up and the product obtained from an application point of view checked.

The yield is 80 parts. Water fastness: 3 to 4.

Example 9 One works under the same conditions as in the example 1. Instead of salicylic acid, however, 43 parts of sulfanilic acid are used. You get 86 parts of a pale yellow powder, which is in ethanol, acetone and a mixture dissolves well from ethanol and ethyl glycol.

The application-related test of the product obtained is carried out as in example 1. Water fastness: 4.

Claims (1)

Claim: Process for the preparation of alkali-soluble condensation products from phenols, formula aldehyde and nitrogen-containing organic compounds, characterized in that reaction products obtained by reacting phenols or naphthols with formaldehyde or formaldehyde-releasing compounds in an alkaline, acidic or neutral aqueous medium at temperatures between 30 "C and the boiling point have been obtained, in an alkaline, acidic or neutral aqueous medium in any order, one after the other or simultaneously with a) thioureas of the general formulas or in which R1 is a hydrogen atom, an alkyl radical with up to 4 carbon atoms or a radical of the formula -CS-N (R5) -R2, R2 is a hydrogen atom or an alkyl radical with up to 4 carbon atoms, R3 is an alkyl radical with up to 3 carbon atoms, the hydroxyl groups or can be interrupted by - 0-, - NH - or - N (R4) -, R4 is a hydrogen atom or an alkyl or hydroxyalkyl radical with up to 4 carbon atoms and R5, which can be identical or different, hydrogen atoms, Hydroxymethyl groups or alkoxymethyl groups with up to 5 carbon atoms in the alkoxy radical and optionally further formaldehyde and b) mononuclear aromatic carboxylic or sulfonic acids which can contain hydroxyl or amino groups, aryloxy fatty acids or aliphatic polycarboxylic acids which can contain hydroxyl groups, also at temperatures between 30 ° C and the boiling point and the resulting solutions are dried in the usual way. Considered publications: German Patent Specifications No. 693 923, 696 869; J. S c h e i b e r, Chemistry and Technology of Artificial Resins, 1943, pp. 426 to 432.