DE1142173B - 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 Processes have become known according to which tanning agents are produced from phenolsulfonic acids, phenols, urea and formaldehyde can. In the German patent specification 687 066, based on the German patent specification 684 240, recommended, phenols or naphthols or their sulfonic acids with formaldehyde and, if necessary, to implement sulfonating agents, the water-soluble ones thus obtainable Post-treatment of products with phenols and formaldehyde and before, during or after urea and formaldehyde take effect during this aftertreatment allow.

From the German patent specification 701563 is a modification of this Process known in which one is exposed to the action of urea and formaldehyde the production of water-soluble products from phenols or naphthols or their Sulphonic acids, formaldehyde and optionally sulphonating agents connects and only then can the aftertreatment with phenols and formaldehyde follow.

The tannins obtainable by the known processes are if they are not made with naphthols, relatively resistant to Exposure, and leathers made with them have a light color of considerable Lightfastness, but they meet the very high demands of today's fashion on the White effect and extreme resistance to yellowing even with long exposure not fair.

It has now been found that phenolsulfonic acids, phenols, Urea and formaldehyde contain excellent lightfast condensation products, if you use sulfonic acids or sulfonic acid salts of phenols or phenol mixtures, which are free of condensed rings, in acidic aqueous solution with preformed ones water-soluble, optionally partially etherified urea-formaldehyde condensates converts and the products obtained in a conventional manner in acidic aqueous Solution treated with phenols and formaldehyde.

As phenols, their sulfonation products individually or in the form of technical mixtures are used, for example. B. mononuclear phenols such as halophenols and in particular cresols and the phenol itself, furthermore bis-phenols, such as diphenylolpropane and diphenylene sulfone.

Water-soluble urea-formaldehyde condensates with the sulfonated Phenols are converted, for example, dimethylolurea, tetramethylolurea and methylene-bis-methylol urine material. Derivatives of such compounds in which the Methylol groups are partially etherified with low molecular weight alkyl radicals, such as Dimethoxy-dimethylolurea and dibutoxy-dimethylolurea also come into consideration.

The use of 1 to 1, 5 moles of urea-formaldehyde condensate on 1 mole of sulfonated phenol usually gives good results; However, it is possible, depending on the properties to be achieved, larger or smaller amounts of React methylol compound with the sulfonated phenol. The condensation is carried out preferably in a strongly acidic solution. The reaction temperature can be between 20 and 80 ° C can be selected.

The condensates with phenols produced in this way by post-treatment and formaldehyde obtained products are pronounced white tanning agents. You let meet the requirements in a known manner with inorganic or organic acids adapt to the tanning process. The new tannins provide leather with a whitening effect and lightfastness are considerably superior to those known from tanning agents derived from free urea and formaldehyde were produced. she are made from easily accessible raw materials; besides, they have a relatively high content of tanning ingredients and therefore enable the desired effects in tanning with economically favorable quantities to achieve.

The new condensation products can also be very beneficial Tanning agents are used for chrome retanning; one also receives excellent leather of very light color and excellent fastness to light. To be highlighted is also their good compatibility with other synthetic tanning agents.

The condensation products 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 solid form. The drying of the process products is preferably followed by neutralization with alkaline agents, e.g. B. with ammonia, amines or alkali metal hydroxides, however, performed with acids before setting. After setting with fixed 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 powder 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 the solutions of the neutral tanning powder with Rilssigen inorganic or adjust organic acids.

In addition to being used as tannins, the condensation products can also be valuable Auxiliaries can be used in dyeing. They are also excellent dispersants for all purposes that require particularly high lightfastness.

They can be used in the same way as they are produced during production, in liquid form or use solid form.

By adding acidic or alkaline substances you can find out their properties adapt to the needs of consumers.

The parts and percentages given in the following examples are Weight units.

Example 1 250 parts of phenol are mixed with 270 parts at 100 ° C. for 4 hours 98% sulfuric acid heated. The reaction mixture is cooled to 40 to 60 ° C and carries a prepared from 320 parts of dimethylolurea and 200 parts of water Solution one. As soon as a clear solution has formed, 100 parts are 50% aqueous Sodium hydroxide solution and 180 parts of phenol are added and 150 parts are fed in 30% formaldehyde condenses at 20 to 40 ° C until the formaldehyde odor has disappeared and the reaction product has become clearly soluble in water.

The condensation product formed is 50% strength with 144 parts aqueous sodium hydroxide solution and neutralized for use as a tanning agent by adding 48 parts of 80% formic acid and 14 parts of glacial acetic acid to one pH from 3.2 to 3.5 adjusted.

A light yellow, clearly water-soluble syrup is obtained, its analysis delivers the following values: Tanning agent .. 39.6% non-tanning tone \ .... 13.1% number of parts ..... 75, 1 Example 2 250 parts of phenol are mixed with 270 parts of 98% strength sulfuric acid in Sulphonated at 100 ° C for 4 hours.

The reaction mixture is cooled to 40 to 60 ° C and with a mixed from 525 parts of dimethylolurea and 500 parts of water prepared solution. As soon as a clear solution has formed, 50 parts of 50% strength aqueous sodium hydroxide solution are added and 125 parts of phenol are added and 100 parts of 30% formaldehyde are added condensed at 20 to 40 ° C until the reaction mixture became clear water-soluble is. The reaction solution is mixed with 196 parts of 50% strength aqueous sodium hydroxide solution neutralized and dried to powder in a spray nozzle dryer. The received Powder is clearly soluble in water. 200 parts are required for use as a tanning agent Powder with the addition of 1.5 parts of sodium bisulfate and 0.8 parts of oxalic acid as above adjusted that a 10% aqueous solution of the mixture has a pH of 3.2 to 3, 5 has. The product has the following analysis values: Tannin ......... 75.2% Non-tanning agent ..... 18.6% number of parts ...... 80.2 Example 3 250 parts of phenol are, as described in Example 1, sulfonated with 270 parts of 98% sulfuric acid. In the reaction mixture at a temperature between 40 and 60 ° C is a 525 parts of dimethylolurea and 500 parts of water prepared solution entered. As soon as a clear solution has formed, 57 parts of 50% aqueous sodium hydroxide solution are added and 75 parts of 4,4'-dioxydiphenylsulfone added; one condenses with the addition of 75 parts of 30% formaldehyde at 20 to 45 ° C until the mixture is clearly water-soluble has become. The condensation product is mixed with 200 parts of 50% strength aqueous sodium hydroxide solution neutralized and dried to powder on a double drum dryer. The received Powder is clearly soluble in water. 200 parts of powder are intended for use as a Tanning material with 1.6 parts of sodium bisulfate and 0.8 parts of oxalic acid so adjusted that the 10% aqueous solution of the mixture has a pH of 3.2 to 3.5. The analysis of the product gives the following values: tanning agent ..... 67.8% non-tanning agent ..... 25, 7% number of shares ..... 72, 7 Example 4 108 parts of o-cresol become 112 Share 98% sulfuric acid heated to 100 ° C for 4 hours. Added after cooling the reaction mixture is mixed with 100 parts of water and 90 parts are left at 30.degree. to 60.degree a 75% solution of tetramethylolurea in water. One sets 48 parts of 25% strength ammonia and 77 parts of o-cresol are added and condensed with the addition of 50 parts of 30% formaldehyde at 20 to 45 ° C until the formaldehyde odor disappears. The condensation product is mixed with 10 parts of 50% strength aqueous sodium hydroxide solution and 54 parts of 25% ammonia neutralized and for use as a tanning agent by adding 20 parts of 80% formic acid and 5 parts of glacial acetic acid adjusted to a pH of 3.2 to 3.5.

It becomes a slightly pink, clear water-soluble syrup with the following analysis values were obtained: tanning agent ............ 43.1% non-tanning agent ............ 8.3% number of parts ..... 83.7 Example 5 108 parts of o-cresol are combined with 112 parts 98% sulfuric acid heated to 100 ° C for 4 hours. It is allowed to cool, mixed with 100 parts of water and at 30 to 80 ° C carries 90 parts of a 70% aqueous paste of dimethylolurea, in which 25% of the methylol groups are etherified with methanol, a.

50 parts of 25% ammonia and 54 parts of o-cresol are added and condensed with the addition of 50 parts of 30% formaldehyde at 20 to 45 ° C, to the formaldehyde has disappeared. The reaction mixture is 60 parts of 25% Ammonia neutralized and for use as a tanning agent with 18 parts 80 "/ piger Formic acid and 5 parts of glacial acetic acid were adjusted to a pH of 3.2 to 3.5.

The product obtained is syrupy and pale pink in color, good pourable and easily soluble in water.

It has the following analysis values: Tanning agent ............ 39.6% non-tanning agent ............... 13, 5% number of parts ............ 74, 6 Example 6 108 parts of o-cresol are 112 Parts of 98% sulfuric acid heated to 100 ° C for 4 hours. After cooling down 70 parts of water and 30 parts of methanol were added. It is then set at 30 to 60 ° C 120 parts of a condensation and etherification product from 24% urea, 30% Formaldehyde and 6% butanol, dissolved in 40% butanol, too. To the conversion mixture are 50 parts of 50% strength aqueous sodium hydroxide solution and 54 parts of o-cresol and condensed with the addition of 34 parts of 30% formaldehyde at 20 to 45 ° C, bis the mixture has become clearly soluble in water.

The condensation product formed is 50% with 64 parts aqueous sodium hydroxide solution and neutralized for use as a tanning agent by adding 20 parts of 80% formic acid and 4 parts of glacial acetic acid to pH set from 3, 2 to 3, 5.

A slightly pink, clear water-soluble syrup is obtained, which has the following analytical values: tannin. 37.00 / o non-tanning agent .................. 10, zozo number of parts ............. 77, 4 Example 7 352 parts of p, p'-dihydroxydiphenylsulfonic acid Sodium is stirred with 400 parts of water and with 50 parts of concentrated hydrochloric acid acidified. At 60 to 80 ° C you give it gradually 70 parts of a 70% aqueous Paste of dimethylolurea in which 25% of the methylol groups are etherified with methanol are to the solution. After stirring for a further 2 hours, the reaction mixture is added with 60 parts of phenol and condensed at 30 to 50 ° C by adding 60 parts 300% formaldehyde until the product is clearly soluble in water. To The reaction material is neutralized with 40 parts of 50% sodium hydroxide solution in one Drying pan dried to 480 parts of an almost colorless powder. The analysis provides the following values: tanning agent ....... 61.0 "/ o non-tanning agent .... 32, zozo Number of parts ... 65, 2 Example 8 174 parts o-phenolsulfonic acid are in 100 parts Dissolved in water. In this solution at a temperature between 40 and 60 ° C is a solution prepared from 240 parts of dimethylolurea and 240 parts of water gradually registered. As soon as the resulting condensation product is clearly soluble in water has become, 40 parts of phenol are added and by adding 35 parts 30% aqueous formaldehyde is post-condensed at 30 to 35 ° C. The condensation product is neutralized with 80 parts of 50% sodium hydroxide solution and placed in a drying pan dried to 450 parts of a colorless powder. The tannin analysis provided the following values: tanning agent ....... 73.5% non-tanning agent ... 10.8% number of parts .. 78 Example 9 196 parts of sodium o-phenolsulfonate are mixed with a solution of 20 Parts of 98% sulfuric acid are stirred in 150 parts of water. Be in the solution at 30 to 80 ° C gradually 70 parts of a 70% aqueous paste of dimethylolurea, in which 25% of the methylol groups are etherified with methanol, entered. One sets then 40 parts of phenol are added and the mixture is condensed with the addition of 50 parts of 30% strength aqueous Formaldehyde at 20 to 45 ° C until the formaldehyde odor has disappeared and the product has become clearly soluble in water. The product is mixed with 34 parts of 50% sodium hydroxide solution neutralized and dried in a drying pan to 320 parts of a colorless powder. The analysis gives the following values: tanning agent ....... 63, 2% non-tanning agent ... 32, 0% number of parts .... 66.5 Example 10 196 parts of sodium o-phenolsulfonate become stirred with 200 parts of 10% phosphoric acid and the mixture at 30 to 60 ° C mixed with 90 parts of a 75% solution of tetramethylolurea in water. 40 parts of phenol are added to the reaction mixture and the mixture is condensed with the addition of 40 parts of 30 ° / own aqueous formaldehyde at 20 to 45 ° C until the formaldehyde odor ver

Claims (1)

disappeared and the product has become clearly soluble in water. That Product is neutralized with 50 parts of 500 / piger sodium hydroxide solution and placed in a drying pan dried to 330 parts of a colorless powder. The analysis provides the following values : Tanning agent ....... 61, 4% non-tanning agent ... 34, 2 ° lo number of parts ..... 64, 2 PATENT CLAIM : Process for the production of lightfast condensation products from phenolsulfonic acids, Phe- nolen, urea and formaldehyde, characterized in that 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. Considered publications: German Patent Specifications No. 684 240, 687 066, 701 563.