DE1231711B - 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 in the German Auslegeschrift 1 088 518 for the production of rubber prints with basic dyes, furthermore it is from 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 80 "C is no longer odor-resistant, so 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, if one can produce reaction products which by reacting phenols or naphthols with formaldehyde or formaldehyde-releasing Compounds in the alkaline aqueous medium at temperatures between 300 C and the boiling point have been obtained in any non-acidic aqueous medium Sequence one after the other or simultaneously with a) amides of aliphatic or aromatic Mono- or dicarboxylic acids with at least one hydrogen atom bonded to amide nitrogen and with up to 8 carbon atoms in the acyl radical and optionally further formaldehyde or their N-hydroxymethyl or N-alkoxymethyl derivatives with up to 5 carbon atoms in the alkoxy radical and b) mononuclear aromatic carboxylic or sulfonic acids, the hydroxyl or may contain amino groups, aryloxy fatty acids or aliphatic hydroxypolycarboxylic acids, at a temperature of about 40 to 100 "C and the solutions obtained in usual way dries.

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, alkoxy phenols, such as 2-, 3- and 4-methoxyphenol, 4,4'-dihydroxydiphenyl sulfone, 4 - hydroxydiphenyl sulfone, Phenylhydroxynaphthylsulfone, 2,2-bis (4-hydroxyphenyl) propane, 2-hydroxydiphenyl, 4-hydroxydiphenyl, 4-hydroxydiphenylmethane, os-naphthol, p-naphthol, isopropyl-p-naphthole, Phenolsulphonic acids and naphtholsulphonic acids. There will be such phenols or naphthols preferred which contain no sulfonic acid groups.

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.

Carboxamides of the type defined under a) are z. B. acetamide, Propionic acid amide, acrylic acid amide, methacrylic acid amide, salicylic acid amide, succinic acid diamide, Phthalic acid imide, benzoic acid amide, caproic acid amide, caprylic acid amide, adipic acid diamide and cork acid diamide. In addition, there are also alkylamides of the aforementioned carboxylic acids into consideration, provided they still have at least one hydrogen atom bonded to the amide nitrogen contain, especially those that have up to 5 carbon atoms in the alkyl radicals included, e.g. B. acetic acid methyl and butyl amide, propionic acid ethyl amide and succinic acid di (monomethyl amide). In addition, the compounds a) include the N-hydroxymethyl and N-alkoxymethyl derivatives said carboxamides with up to 5 carbon atoms in the alkoxy radical, e.g. B. N-methylolacetamide, N-methylolpropionic acid amide, N-methylol acrylic acid amide, N-methoxymethylacrylic acid amide, N-butoxymethyl methacrylic acid amide, N-methylolsalicylic acid amide and N, N'-dimethylol succinic acid diamide. If you use N-hydroxymethyl or N-alkoxymethyl derivatives, you can determine the amount of formaldehyde in the implementation with Phenols or naphthols accordingly to decrease.

If you use the carboxamides yourself, you also have the option of to bring some of the formaldehyde only together with these to implement.

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 Hydroxypolycarboxylic acids, e.g. B. tartaric acid, malic acid and citric acid. Also aryloxy fatty acids, such as phenoxyacetic acid and cresoxyacetic acid can be used. As examples for mononuclear aromatic sulfonic acids with amino groups are sulfanilic acid and called metanilic acid.

In the present process, the starting compounds are reaction products used in a known manner by reacting phenols or naphthols with Formaldehyde or formaldehyde-releasing compounds in an alkaline aqueous medium have been received. The ratio of phenols or naphthols to formaldehyde may have been changed within wide limits. Reaction products have proven to be very useful that of 1 mole of phenol or naphthol and 1 to 8 moles, preferably 1 to 6 moles, of formaldehyde or the equivalent amount of a formaldehyde-releasing substance. The alkaline reaction of the reaction mixture in the preparation of the starting materials can be caused by a variety of alkaline substances, e.g. B. by alkali metal hydroxides, such as sodium and potassium hydroxide, by ammonia or by primary, secondary or tertiary amines, e.g. B. ethylamine, diethylamine, Triethylamine, diethanolamine and triethanolamine. A pH value is preferably set between 7 and 8 a. Organic solvents can also be added to the reaction mixture add that are miscible with water, for example methanol, ethanol, acetone, Tetrahydrofuran, glycol and polyglycols. But you can also in the absence of such Solvent work. The reaction is carried out at temperatures between 300 C and boiling point, preferably between 50 and 100 "C, performed and takes under these circumstances generally 2 to 8 hours. Formed by the alkaline conversion so-called resin oils. They should essentially contain resols; H. Mixtures, the phenols, dihydroxydiphenylmethanes, which mainly carry hydroxymethyl groups and dihydroxydibenzyl ether.

The resin oils are in the process of the invention in one or reacted in several stages with the compounds of groups a) and b). The chronological order these implementations can be chosen at will. So you can either use the resin oils react at the same time in one stage with compounds a) and b); you can but also first with one of the compounds a) or b) and then with the other Implement connection. Products with particularly good properties are obtained when 0.1 to 3, preferably 0.1, are added to 1 mol of the phenol converted to the resin oil to 2 mol of the compound a) and 0.1 to 3, preferably 0.5 to 2 mol of the compound b) used. The further reaction of the resin oil is in a non-acidic, aqueous medium carried out.

In general, there are no additional measures took required as the amount of the alkaline reactant added in the production of the resin oil Substance is usually sufficient to continue implementing under the prescribed Conditions to enable. However, should the pH drop below 7, it must An alkaline compound can be added to the mixture.

The reaction temperature can be in about the same range as for the production of the rosin oil can be chosen. Components a) generally react lighter than components b); therefore, lower levels are often sufficient for implementation with a) Temperatures and shorter reaction times than for the reaction with b). In many The following working conditions have proven effective in cases: Implementation with a) at approximately 40 to 60 "C in about 1 to 4 hours. Reaction with b) at about 70 to 100" C in 5 to 10 hours. With simultaneous implementation with a) and b) one chooses the for b) necessary conditions. The end of the implementation is at the so-called breaking test recognizable, d. That is, it is reached when a sample of the product has cooled down like glass breaks.

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.

It is expedient to wash them a few times for further work-up Paint with water and then dry them in a vacuum at around 600 C. For many purposes but it is also sufficient to use the conversion mixture in its entirety in a simpler manner or after separating the main amount of the aqueous layer in a drying pan, dry on a roller or in a spray dryer. The ones obtainable in this way Resins not only dissolve in alkalis and other basic agents, but also also in many organic solvents, including ethanol, acetone and a mixture from ethanol and ethyl glycol. Depending on their composition, they generally have an acid number between 5 and 20. The partly colorless, partly weakly colored and Especially odorless process products are odor-stable up to 130 "C; they can among other things in the paint, textile and paper industry, z. B. as a dispersant, be used.

The products find a particularly important application as laking agents for basic dyes.

Color lacquers, e.g. B. with auramine dyes, rhodamine dyes, Victoria blue dyes, Methyl violet, crystal violet and malachite green are insoluble in water, but in spite of this their salt character is excellently organophilic, so that they can be used to color organic Can use masses, e.g. B. for the production of carbon paper waxes, lithograph materials and ballpoint pen pastes; What should be emphasized here is the use of the process products as a laking component in rubber printing (flexography). The ones with the process products achievable lacquers and 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-tertiary butylphenol, 0.5 part of 500% sodium hydroxide solution and 15 parts of 330% aqueous formaldehyde are heated to 60 ° C. for 6 hours. Thereafter adds 35 parts of salicylic acid are added and the mixture is heated to 800 ° C. for 10 hours.

After cooling to 20 ° C., 1.5 parts of acetamide and 10 parts are added 330/0 aqueous formaldehyde is added and the mixture is stirred at 20 ° C. for 1 hour 4 hours at 45 ° C. The product is then dried in a spray nozzle dryer 80 parts of a yellowish powder are obtained, which is dissolved in ethanol, acetone and a Ethanol-ethylglycol mixture dissolves very well.

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 Rhodamine FB (C.I.

45170) and 14 parts of the condensation product obtained were added. An aluminum foil coated with this flexographic printing ink on a rotary coating machine had water fastness 4 to 5 according to the test method according to DIN 16524.

Example 2 37.5 parts of p-tertiary-butylphenol along with 0.5 500/0 parts but sodium hydroxide solution and 15 parts 330/0 in aqueous formaldehyde at 60 "C. heated and held at this temperature for 6 hours.

Then 35 parts of salicylic acid are added and the mixture is heated for 10 hours to 800 C.

After the mixture has cooled to 20 ° C., 4.4 parts are added Add N-methylolacetamide and heat the mixture to 45 ° C. After 2 hours steams the reaction mixture is brought to dryness in vacuo at 800 C and pulverized, 82 parts of a yellowish powder are obtained, which dissolves very well in ethanol or acetone and a mixture of ethanol and ethyl glycol dissolves.

The application test was carried out as indicated in Example 1, only auramine FA (C.I. 41000) was used instead of rhodamine FB.

Water fastness: 4 to 5, Example 3 62.5 parts of dihydroxydiphenyl sulfone, 25 parts of water, 20 parts of formaldehyde (3301% strength) and 10 parts 500% strength sodium hydroxide solution are heated to 100 "C for 2 hours.

After the mixture has cooled to 400 ° C., 2.2 parts of N-methylolacetamide are added and 20 parts of methanol are added and the mixture is stirred at this temperature for 2 hours.

25 parts of salicylic acid are then added to the reaction mixture and heated for 4 hours to 800 C.

The product is evaporated to dryness and pulverized. You get 84 parts of a yellowish powder, which is in ethanol, acetone and an ethanol-ethylglycol mixture is readily soluble.

The application test was carried out as indicated in Example 1, only malachite green (C. 1. 42000) was used instead of Rhodamine FB.

Water fastness: 4.

Example 4 27 parts of pyrogenic oil, 20 parts of 3301 strength formaldehyde, 0.5 Parts of 50% sodium hydroxide solution and 20 parts of methanol are heated to 60 ° C. for 6 hours. Then 35 parts of salicylic acid and 20 parts of methanol are added to the mixture and keeps the mixture for 10 hours at 800 C.

After the reaction mixture has cooled to 400.degree. C., it is mixed with 4.4 parts of N-methylolacetamide and held at this temperature for 2 hours.

The work-up is carried out as in Example 1.

61 parts of a yellow powder are obtained, which is dissolved in acetone and ethanol is readily soluble.

Example 5 37.5 parts of p-tert-butylphenol, 20 parts of formaldehyde (330%) and 0.5 parts of 500% sodium hydroxide solution are heated to 600 ° C. for 6 hours.

After 35 parts of anthranilic acid and 40 parts of methanol have been added the mixture is heated to 80 ° C. and this temperature is maintained for 10 hours.

The mixture is then allowed to cool to 200 ° C. and the reaction mixture is added 2.2 parts of N-methylolacetamide are added and the mixture is heated to 45 ° C. for 2 hours. The product will dried on a roller, 69 parts of a yellow powder are obtained which are dissolved in ethanol and acetone is soluble.

The application-related test followed as in example 1. Water fastness: 4th

Example 6 37.5 parts of p-tertiary-butylphenol, 0.5 part of 5001 sodium hydroxide solution and 20 parts of 3301, its own aqueous formaldehyde, is heated to 60 ° C. and maintained at this Temperature 6 hours. 24.3 parts of malic acid are then added to the mixture and 40 parts of methanol, heated to 80 "C for 10 hours and then cooled to 20" C.

2.2 parts of N-methylolacetamide are then added to the reaction mixture and heated to 45 "C for 2 hours.

The product is evaporated in vacuo at 80 "C and then pulverized. 60 parts of a pale yellow powder are obtained, which is dissolved in ethanol and Acetone is soluble.

Example 7 37.5 parts of p-tert-butylphenol, 0.5 part of 5001, ige Sodium hydroxide solution and 15 parts of 3301 aqueous formaldehyde are heated for 6 hours 60 "C. Then 35 parts of salicylic acid are added and the mixture is heated to 80" C for 10 hours. After cooling to 20 ° C., 4.4 parts of N-methylolphthalic acid imide are added and heated to 45 ° C for 2 hours.

The reaction product is worked up as in Example 2.

73 parts of a yellowish, ethanol- and acetone-soluble one are obtained Powder.

Example 8 One works under the same conditions and with the same Quantities as in Example 7, except that 4.4 parts of N-methylolphthalimide are used 4.2 parts of N-methylol salicylamide.

Work-up is carried out as in Example 2. 71 parts of one are obtained pale yellow powder in ethanol, acetone and in an ethanol-ethylglycol mixture is soluble.

Example 9 The reaction is carried out as in Example 7.

Instead of the 4.4 parts of N-methylolphthalic acid amide, 3.7 parts are used N, N'-dimethylol succinic acid amide.

Work-up is carried out as described in Example 2. The yield is 72 parts.

Example 10 36 parts of jB-naphthol, 75 parts of water, 1 part of 50% Sodium hydroxide solution and 22.8 parts 330/0 but aqueous formaldehyde are heated to 80 ° C. for 6 hours heated.

Then 50 parts of salicylic acid and 20 parts are added to the mixture Methanol is added and the temperature is kept at sOOC for 10 hours.

The reaction mixture is then cooled to 450 ° C. and 4.4 Divide N-methylolacetamide. After 2 hours, the mixture is evaporated and pulverized it.

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

Example 11 Regarding the reaction product prepared according to Example 1, paragraph 1 one adds 115 parts of a 400% alcoholic solution at a temperature of 45C of N-methylol methacrylic acid amide and maintains this temperature for 2 hours.

The work-up is carried out as in Example 2. The yield is 76 pieces.

The product dissolves in an ethanol-ethylglycol mixture.

Example 12 27 parts of pyrogenic oil, 15 parts of 330% aqueous formaldehyde, 1 part of 50% sodium hydroxide solution and 20 parts of methanol are heated to 600 for 6 hours C.

Then 35 parts of salicylic acid and 20 parts of methanol are added and heated to 80 "C for 10 hours.

The mixture is then allowed to cool to 45 ° C. and 2.1 parts are added Methacrylic acid amide and 10 parts 33010eigen aqueous formaldehyde and keeps that Mixture for 2 hours at this temperature.

The reaction product is evaporated and pulverized in vacuo.

66 parts of a yellow powder are obtained, which dissolves well in ethanol, Acetone and dissolves in an ethanol-ethylglycol mixture.

Example 13 37.5 parts of p-tert-butylphenol, 0.5 part of 500 ml Sodium hydroxide solution and 15 parts of 3301, its own aqueous formaldehyde, are heated for 6 hours 60 "C. Then 43 parts of sulfanilic acid are added and the mixture is heated for 10 hours to 800 C.

After cooling to 200 ° C., 1.5 parts of acetamide are added to the mixture and 10 parts of 33010 own aqueous formaldehyde and the mixture is stirred at 20 ° C. for 1 hour 4 hours at 45 ° C. The product is then dried in a spray can dryer.

89 parts of a yellowish powder are obtained, which dissolves in ethanol and acetone dissolves very well.

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 Rhodamine FB (C.I.

45170) and 14 parts of the condensation product obtained were added. An aluminum foil coated with this flexographic printing ink on a rotary coating machine had water fastness 4 to 5 according to the test method according to DIN 16524.

Claims (1)

Claim: Process for the production of alkali-soluble condensation products from organic compounds containing phenols, formaldehyde and nitrogen, d a marked e t that reaction products obtained by reacting phenols or naphthols with formaldehyde or formaldehyde-releasing compounds in the alkaline aqueous agent has been obtained at temperatures between 300 C and the boiling point are, in the non-acidic aqueous agent in any order one after the other or simultaneously with a) amides of aliphatic or aromatic mono- or dicarboxylic acids with at least one hydrogen atom bonded to the amide nitrogen and with up to 8 carbon atoms in the acyl radical and optionally further formaldehyde or their N-hydroxymethyl or N-alkoxymethyl derivatives with up to 5 carbon atoms in the Alkyl radical and b) mononuclear aromatic carboxylic or sulfonic acids, the hydroxyl or may contain amino groups, aryloxy fatty acids or aliphatic hydroxypolycarboxylic acids at a temperature between about 40 and 1000 C and the solutions obtained dries in the usual way. Publications considered: J. 5 c h r e i b e r, Chemie and Artificial Resin Technology, 1943, pp. 429-432.