DE1122542B - Process for the production of lightfast condensation products by reacting sulfonated phenols which are free from condensed rings with urea and formaldehyde - Google Patents

Description

Process for the production of lightfast condensation products Conversion of sulfonated phenols, which are free of condensed rings, with urea and formaldehyde The patent application B 53374 IVb / 12 q (German Auslegeschrift 1 113 457) relates to a process for the production of lightfast condensation products, by converting sulfonated phenols that are free from condensed ring systems, with urea and formaldehyde and aftertreatment of the condensates obtained with phenols and formaldehyde, which is characterized in that in the first process stage 1 mole each of a sulfonated phenol or phenol mixture with 1 to 1.5 moles of urea and 1.7 to 2.2 moles of formaldehyde converts.

It has now been found that a modification of this procedure also lightfast condensation products are obtained if the in the first process stage obtained condensates instead of phenols and formaldehyde with sulfonated or sulfomethylated Phenols and formaldehyde aftertreated. Those to be used in the second condensation stage Amounts of phenol derivatives and formaldehyde can, depending on the intended use of the condensation products, can be varied within wide limits. For production of Tanning agents are used for 1 mole of the phenolsulfonic acid condensed in the first stage usually 0.5 to 1.5 moles of phenol derivative and 0.3 to 2 moles of formaldehyde, while good dispersants can be obtained by post-condensation with 0.5 to 5 moles of phenol derivative and 0.3 to 7 moles of formaldehyde, based on 1 mole of phenolsulfonic acid originally used, receives.

The phenol derivatives mentioned can be carried out by known processes Sulfonation or sulfomethylation of phenols can be obtained which did not condense Contain 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'-dioxydiphenyl sulfone, called. Sulfonation or sulfomethylation products can be used Use from pure phenols or from technical phenol mixtures.

The condensation products obtained by the novel process are just like the products obtained using the main patent application process 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 dye preparations. They prevent that when dyeing pigment migration from fibrous material. With plastic dispersions are the new ones Products very well tolerated. They are excellent dispersants for all purposes, which require particularly high lightfastness. You can do it like that they accrue during production, use them in liquid or solid form. By Adding acidic or alkaline substances can change their properties according to the needs adapt to the consumer.

The parts and percentages given in the examples are units of weight. Example 1 250 parts of phenol are mixed with 270 parts of 98% sulfuric acid for 4 hours heated to 100 ° C. The mixture is cooled to 50 ° C. and the reaction mixture is added 100 parts of water and 176 parts of urea. At 40 to 60 ° C you give it gradually 475 parts of 30% formaldehyde were added. 190 parts of 50% aqueous sodium hydroxide solution are used and 374 parts of phenolsulfonic acid, which has been prepared as described above, and condenses with the slow addition of 150 parts of formaldehyde at 25 to 45 ° C, until the formaldehyde odor has disappeared and the reaction product is clearly soluble in water has become. Then it is neutralized with 245 parts of 500% aqueous sodium hydroxide solution and drying the reaction solution into powder by a spray nozzle dryer.

1210 parts of a colorless powder are obtained which are dissolved in water is easily and clearly soluble. Example 2 As described in Example 1, 250 Parts of phenol sulfonated with 270 parts of 98% sulfuric acid and, after cooling, and Addition of 100 parts of water at 40 to 60 ° C with 160 parts of urea and 460 parts Formaldehyde condenses. After adding 80 parts of 50% aqueous sodium hydroxide solution and 1100 parts of an aqueous solution of phenol methanesulfonic acid are added to the mixture at 25 to 45 ° C. 150 parts of formaldehyde were slowly added. Then the liquid Reaction mixture neutralized with 319 parts of 50% aqueous sodium hydroxide solution and by a spray nozzle dryer to 1280 parts of a colorless, in water easily and dried to clear soluble powder.

The phenol methanesulfonic acid can, for. B. be prepared in a conventional manner by refluxing 94 parts of phenol, 113 parts of sodium sulfite, 150 parts of 30% aqueous formaldehyde and 500 parts of water for 4 hours and, after cooling, from the reaction mixture with 100 parts of water and 158 parts conc. Reacts sulfuric acid with cooling. Example 3 As stated in Example 1, 250 parts of phenol are sulfonated with 270 parts of 98% sulfuric acid and the phenolsulfonic acid thus obtained is cooled and diluted with 100 parts of water with 160 parts of urea and 450 parts of 30% formaldehyde at 40 to 60 ° C condensed. 90 parts of 50% sodium hydroxide solution and 720 parts of an aqueous solution of sulfomethylated 4,4'-dioxydiphenylsulfone are then added and the mixture is condensed with 150 parts of 30% formaldehyde, as described in Example 1. The reaction solution is dried on a double drum dryer to give 927 parts of a colorless powder which is clear and easily soluble in water.

The solution of sulfomethylated 4,4'-dioxydiphenyl sulfone can, for. B. be prepared in a conventional manner by 180 parts of 4,4'-dioxydiphenyl sulfone, 85 parts of sodium sulfite, 115 parts of aqueous 30% formaldehyde and 340 parts of water Heated to 150 ° C. for 10 hours in a stirred autoclave. After cooling down to about At 80 to 90 ° C., 28 parts of 98% sulfuric acid are added with stirring.

Example 4 286 parts of a commercial, technical mixture of phenol and cresol, which can also contain small amounts of xylenol, are used 300 parts of 98% sulfuric acid heated to 100 ° C. for 4 hours. Staggered at 50 ° C one with 100 parts of water and 200 parts of urea and allowed to slowly at 30.degree. to 50.degree 530 parts of 30% formaldehyde run in. After completing the implementation one adds 189 parts of 50% aqueous sodium hydroxide solution and 205 parts of the sulfonic acid mixture to, which was prepared as described above, and condensed at 20 to 40 ° C with the slow addition of 85 parts of 30% formaldehyde until it disappears the formaldehyde odor and the achievement of clear water solubility of the reaction product. After neutralization with 190 parts of 50% aqueous sodium hydroxide solution the reaction solution is on a double drum dryer to 1108 parts of a pale pink, slightly water-soluble powder dried.

Claims (1)

PATENT CLAIM: Modification of the process for producing lightfast Condensation products from the conversion of sulfonated phenols that have condensed free Rings are, with urea and formaldehyde, according to patent application B 53374 IVb / 12 q (German Auslegeschrift 1 113 457), characterized in that the aftertreatment of the condensates obtained in the first process stage instead of with phenols and formaldehyde with sulfonated or sulfomethylated phenols and formaldehyde.