DE1164424B - Process for the production of lightfast condensation products from phenolsulfonic acids, phenols, urea and formaldehyde - Google Patents

Description

Process for the production of lightfast condensation products from phenolsulfonic acids, Phenols, urea and formaldehyde German patent 1,142,173 relates to a process for the production of lightfast condensation products from phenolsulfonic acids, phenols, Urea and formaldehyde, which is characterized by the fact that one has sulfonic acids or sulfonic acid salts of phenols or phenol mixtures that are free from condensed Rings are, in acidic aqueous solution with pre-formed water-soluble, optionally partially etherified urea-formaldehyde condensates and the resulting Products in a manner known per se in acidic aqueous solution with phenols and formaldehyde post-treated.

It has now been found that this process is particularly valuable lightfast condensation products are obtained if the in sulfonated or sulfomethylated condensates obtained in the first process stage, at most binuclear phenols and formaldehyde containing no condensed rings used. The amounts of phenol derivatives to be used in the second condensation stage and formaldehyde can, depending on the intended use of the condensation products, can be varied within wide limits. One uses for the production of tanning agents to 1 mole of the phenolsulfonic acid condensed in the first stage is usually 0.5 up to 1.5 moles of phenol derivative and 0.3 to 2 moles of formaldehyde; good dispersant by post-condensation with 0.5 to 5 moles of phenol derivative and 0.3 to 7 moles of formaldehyde, based on 1 mol of phenolsulfonic acid originally used.

The phenol derivatives mentioned can be carried out by known processes Sulfonation or sulfomethylation of at most binuclear phenols are obtained, which do not contain any condensed ring systems. Examples are low molecular weight Phenols, such as halophenols and in particular cresols and the phenol itself, also Bis-phenols, such as 4,4'-dioxydiphenylpropane- (2,2) and 4,4'-dioxydiphenylsulfone, called. You can sulfonation or sulfomethylation products from pure phenols or Use from technical phenol mixtures.

The condensation products obtained by the new process are just like the products obtained by the process of the main patent White tannins. They can be combined in a known way with inorganic or organic Adapt acids to the requirements of the tanning process. The new condensation products deliver white leathers of excellent lightfastness during tanning.

They can also be very useful as tanning agents for chrome retanning be used; excellent leather of very light color is also obtained Color and excellent lightfastness. Their good tolerance should also be emphasized with other synthetic tanning agents.

The condensation products obtainable according to the invention are temperature-resistant and can be stored indefinitely; they do not tend to crystallize and can be without reducing their valuable properties through known drying processes, such as evaporation in a vacuum or roller or spray drying, converted into the solid form. The products of the process are preferably dried after they have been neutralized with alkaline agents, e.g. B. with ammonia or alkali metal hydroxides, however performed with acids before setting. After adjusting with solid acids or acid donors, e.g. B. with sodium bisulfate, oxalic acid, adipic acid, citric acid or mixtures of such acidic substances do not result in powdery form hygroscopic tannins that are easily and clearly soluble in cold water and which have the same excellent properties as the liquid products. One can also use solutions of neutral tannin powder with liquid inorganic ones or adjust organic acids.

The new condensation products are of particular importance as auxiliaries for pigment preparations. They prevent this when dyeing fiber material disturbing pigment migration. With plastic dispersions, the new products are great well tolerated. They are excellent dispersants for everyone Purposes that require particularly high lightfastness. You can do it as they are used in production, in liquid or solid form. By adding acidic or alkaline substances you can adjust their properties to suit your needs adapt to the consumer.

The parts and percentages given in the examples are weight units. Example 1 94 parts of phenol are mixed with 102 parts of 98% strength sulfuric acid for 4 hours heated to 100 ° C. The reaction mixture is cooled to 40 to 60 ° C. and carried a solution prepared from 120 parts of dimethylolurea and 150 parts of water. As soon as a clear solution has formed, 40 parts of 50% sodium hydroxide solution are used and 150 parts of phenolsulfonic acid were added and 75 parts of 30% strength were added Formaldehyde condenses at 20 to 40 ° C, but the formaldehyde odor has disappeared and the reaction product has become clearly soluble in water. After neutralization with 120 parts of 50% aqueous sodium hydroxide solution is the condensation product dried in a drying pan to 500 parts of a colorless powder. example 2,188 parts of phenol are mixed with 204 parts of 980/0 sulfuric acid at 100 ° C. in 4 hours sulfated. After cooling to 40 to 60 ° C, a solution of 160 parts of dimethylolurea entered in 200 parts of water and the mixture until it becomes clear Solution condenses. There are then 90 parts of 500 /, aqueous sodium hydroxide solution and 234 parts of sulfomethylated phenol are added and 100 parts are added 30% formaldehyde at 20 to 40 ° C until the formaldehyde odor disappears condensed.

The resulting condensation product is neutralized with 35 parts of 25% strength aqueous ammonia and, for use as a tanning agent, is adjusted to a pH of 3.2 to 3.5 by adding 65 parts of 80% strength formic acid and 12 parts of glacial acetic acid. A light yellow, clearly water-soluble syrup is obtained, the analysis of which gives the following values: Tanning agent. . . . . . . . . . . . . . . 44.3 0/0 Non-tanning agent ........... 15.5% Number of shares. . . . . . . . . . . . . . 74.2 Example 3 125 parts of phenol are sulfated with 135 parts of 98% strength sulfuric acid at 100 ° C. in the course of 4 hours. A solution of 154 parts of dimethylolurea in 200 parts of water is introduced into the sulfonic acid obtained at 40 to 60 ° C. and condensation is carried out until a clear solution has formed. After the addition of 56 parts of 50% aqueous sodium hydroxide solution and a solution of 50 parts of sulfomethylated 4,4'-dioxydiphenylsulfone in 100 parts of water, condensation is carried out at 20 to 40 ° C. with the addition of 75 parts of 30% formaldehyde until the formaldehyde odor disappears . The solution obtained is neutralized with 65 parts of 50% strength aqueous sodium hydroxide solution and, for use as a tanning agent, is adjusted to a pH of 3.2 to 3.5 with 32 parts of 80% strength formic acid and 10 parts of glacial acetic acid. A light yellow, clearly water-soluble syrup is obtained, the analysis of which gives the following values: Tanning agent. . . . . . . . . . . . . . . . . 3004 Non-tanning agent ......... «... 14 ° / o Number of shares .... . . . . . . . . . . . . 68.2 Example 4 108 parts of o-cresol are heated to 100 ° C. with 112 parts of 98% strength sulfuric acid for 4 hours. The reaction mixture is diluted with 70 parts of water; at 30.degree. to 80.degree. C., 90 parts of a 70% strength aqueous paste of dimethylolurea in which 250/0 methylol groups are etherified with methanol are introduced. After adding 50 parts of 50% strength aqueous sodium hydroxide solution and 110 parts of o-cresol sulfonic acid, condensation is carried out with the gradual addition of 50 parts of 30% formaldehyde at 20 ° to 40 ° C. until clear water solubility is achieved. It is neutralized with 100 parts of 50% strength aqueous sodium hydroxide solution and dried to powder in a spray nozzle dryer. 450 parts of a pale pink powder are obtained. Example s 108 parts of a commercially available technical mixture of phenol and cresol, which can also contain small amounts of xylenol, are heated to 100 ° C. with 112 parts of 98% strength sulfuric acid for 4 hours. It is allowed to cool, 70 parts of water are added and 90 parts of a 70% strength aqueous paste of dimethylolurea in which 25% of the methylol groups are etherified with methanol are carried at 30 to 80 ° C .; a. 50 parts of 500% strength aqueous sodium hydroxide solution and 50 parts of o-cresol sulfonic acid are added and the mixture is condensed with the addition of 50 parts of 30% formaldehyde at 20 to 45 ° C. until the formaldehyde odor has disappeared. The resulting solution is neutralized with 40 parts of 50% strength aqueous sodium hydroxide solution and evaporated to dryness. 360 parts of a pale pink powder are obtained.

Example 6 108 parts of a commercially available technical mixture of phenol and cresol, which can also contain small amounts of xylenol, are sulfonated in 4 hours at 100 ° C. with 172 parts of 98% strength sulfuric acid. After cooling, 70 parts of water and 30 parts of methanol are added. At 30 to 60 ° C., 120 parts of a condensation and etherification product made from 24% urea, 30% formaldehyde and 60 % butanol, dissolved in 400% butanol, are then added. 34 parts of 500% strength aqueous sodium hydroxide solution and 50 parts of o-cresol sulfonic acid are added to the reaction mixture, and 30 parts of 30% formaldehyde are added to condense at 20 ° to 45 ° C. until the mixture has become clearly soluble in water.

The resulting condensation product becomes 50% aqueous with 30 parts Sodium hydroxide solution neutralized and evaporated to dryness under reduced pressure. 350 parts of a pale pink powder are obtained.

Example ? 108 parts of o-cresol are mixed with 112 parts of 98% strength sulfuric acid Heated to 100 ° C for 4 hours. After this 70 parts of water are cooled and 30 parts of methanol are added. 120 parts of one are then used at 30 to 60.degree Condensation and etherification product from 240 / (, urea, 300/0 formaldehyde and 6% butanol dissolved in 40% butanol. One adds to the conversion mixture 45 parts of 50% aqueous sodium hydroxide solution and 110 parts of sulfomethylated o-cresol and condensed at 20 to 40 ° C with the gradual addition of 50 parts 30% formaldehyde.

The resulting condensation product, which is clearly soluble in water, is with 35 parts of 50% aqueous sodium hydroxide solution and neutralized to 430 parts of a pale pink colored powder.

Claims (1)

Claim: Further development of the manufacturing process lightfast condensation products from phenolsulfonic acids, phenols, urea and Formaldehyde according to patent 1 142173, d a d u r c h characterized that one for the Aftertreatment stage sulfonated or sulfomethylated, at most binuclear, none phenols and formaldehyde containing condensed rings are used.