DE961351C - Process for the production of water-soluble, tanning condensation products - Google Patents

Description

Process for the production of water-soluble, tanning condensation products The invention relates to a method for the production of new tanning agents Condensation products using mixtures of oxy-polyaryl-sulfone-sulfonic acids and polyoxy-polyaryl-polysulfones as starting materials.

It has now been found that water-soluble, tanning condensation products can be obtained obtained when one, mixture of oxy-polyaryls: ulfone-sulfonic acids, which per Phenyl radical contain at most one nucleus-bound oxy group and from phenolsulfonic acids with at least one replaceable hydrogen atom in the o- or p-position to the hydroxyl group by heating in a vacuum to temperatures exceeding 150 ° with at most the equimolecular Amount of sulfonic acids from the benzene and naphthalene series that are still used as substituents May contain hydroxyl, halogen and / or methyl groups, has been prepared are, and polyoxy-polya.ryl-polysulfones, which are obtained from the above oxy-polyaryl-sulfone-sulfonic acids by heating in a vacuum to 14o ° exceeding temperature * n with the existing one Sulphonic acid groups calculated amount of a phenol with at least one replaceable Hydrogen atom in o- or p-position to the hydroxyl group have been produced, Formaldehyde or formaldehyde emitting Compounds in aqueous alkaline Allow agent to act at elevated temperature and the condensation products obtained optionally with soluble salts of sulphurous acid and / or with aromatic salts Aftertreated sulfonic acids or their soluble condensation products.

The new condensation products deliver white, very lightfast leather of excellent abundance. The method according to the invention enables use of various raw materials and consequently the production of tannins with the most varied of properties, according to the previously known methods of manufacture of tannins was not possible.

From the Swiss patent zag 76a a process for the production of condensation products with a tanning effect is known. that consists of a mixture of 4 4 @ -dioxy-diphenylsulfone and 4, 4'-dioxydiphenylsulfone-sulfonic acid, the latter obtainable by sulfonating 4,4'-diaxydiphenylsulfone with equimolecular amounts of sulfuric acid monohydrate at about 150 °, condensed in an alkaline medium with formaldehyde. In contrast, in the process according to the invention, polysulfones and not monosulfones are condensed with sulfonic acids, and the tanning agents obtained produce fuller and softer leathers in comparison with the condensation products mentioned.

It is not necessary to use the oxy-polyaryl-sulfonsulfonic acids and the To produce polyoxy-polyaryl-polysulfones in separate operations. One technically Rather, a very simple and therefore preferred embodiment consists in the fact that phenolsulfonic acids or the mixture of phenolsulfonic acids with -. at most the equivalent amount, but preferably less, another aromatic sulforic acid in a vacuum 15o to igo °, preferably at 16o to 18o °, a few hours, for example 8 to 10 hours are heated, whereupon the still present in the condensation product Sulphonic acid groups, for example, determined electrometrically, and then one the existing sulfonic acid groups only partially adds a corresponding amount of a phenol and in the reaction mass in a vacuum at iSo to igo °, preferably at 16o to iSo °, carries out the further condensation to polyoxy-polyaryl-polysulfones. So direct obtained technical mixture of oxy-polyaryl-sulfone-sulfonic acids and of polyoxy-polyaryl-polysulfones is then advantageously in an aqueous alkaline solution at a pH of 7.5 up to 9 and in as concentrated a solution as possible with formaldehyde or formaldehyde releasing Connections by heating, e.g. B. at reflux at 100 to 10 ° to the water-soluble End products condensed.

The preparation of the used as starting materials according to the process Oxy-polyaryl-sulfonsulfonic acids and polyoxy-polyaryl-polysulfones. Belongs, however not the subject of the invention.

The water solubility of the end product depends on the degree of sulfonation addicted'; as readily water-soluble tannins can be obtained directly if in the preferred execution of the process 25 to 5o% that after the first condensation stage any sulfonic acid groups that are still present are further condensed with phenols. Predominates on the other hand, in the mixture of oxypolyaryl-s, ulfon-sulfonic acids which condenses with formaldehyde and the latter component of polyoxypolyaryl polysulfones. so z. B. 50 to 80% or even more of that still present after the first condensation in the vacuum Sulphonic acid groups condensed further with phenols, this can result in end products, whose water solubility is too low for practice. Those that are too insoluble in water Condensation products can easily be treated with water-soluble Salts of sulphurous acid, which are in aqueous solution or suspension in the heat can be carried out at ordinary or under increased pressure without loss the tanning properties can be converted into sufficiently soluble products. Included must be emphasized -, verden that, in contrast to known processes, the condensation with Formaldehyde and treatment with salts of sulphurous acid are not carried out at the same time can be carried out. A second method, the solubility of too little To increase water-soluble condensation products consists in treating them Products after the formaldehyde condensation with aromatic sulfonic acids or their soluble condensation products.

The new condensation products are mostly strong. sensitive to electrolytes, which is why they are advantageous by acidification with mineral acid from their aqueous solution precipitated, freed from beige salts by separating the precipitated resins, redissolved in water: and with organic acids to the required pH can be set.

The new condensation products can not only be considered synthetic Tannins, but also as auxiliaries for the textile industry or as components serve for the production of textile auxiliaries.

The following examples explain the process according to the invention. Unless otherwise stated, the parts are to be understood as parts by weight. Example 1 500 parts of molten phenol are slowly mixed with q40 parts of 66% oil at 6o to 70 ° and then sulfonated at 100 ° for f hour. The phenolsulfonic acid formed is then slowly heated in vacuo from about 11 to 13 mm to 160 to 165 °, so that only a little phenol is distilled off, and kept at this temperature until ig of the condensation product 3.5 to 3; 7 ccm i normal caustic soda neutralized against Congo red. The condensation product formed in this way is mixed with up to 100 parts of phenol, and after the phenol has been thoroughly mixed, the reaction mass is again slowly placed under vacuum and heated in vacuo at 65 ° until ig of the condensation product is only -2 , 7 to 2.5 ccm i normal sodium hydroxide solution neutralized against Congo red. Yield about 900 to 940 parts.

100 parts of the condensation product obtained are cautious melted with about 41 parts of 400 per cent. sodium hydroxide solution and with 20 to 22 parts of 37 per cent Formaldehyde solution added and condensed for as long (about 6 hours) at 100 to 10 °, until a sample is diluted with a little water when acidifying with dilute sulfuric acid remains clear. The reaction mass is then diluted with 30 parts of water, the resulting Tannin precipitated with 400 per cent sulfuric acid and Glauber's salt and the precipitated Resin pressed out well. Yield 155 parts. The low-salt Congo-neutral resin is used in Dissolved a little water and acidified with 8 parts of 80% acetic acid.

This tanning agent is particularly suitable for the production of white leather.

Example 2 The phenol produced according to Example i from 500 parts Condensation product with a titre of 3.5 to 3.7 becomes in vacuo at about 150 ° with 100 Implemented up to 130 parts of raw cresol DAB IV. The implementation is so long at 15o ° carried out until i g of the condensation product is only 2.2 to 2.5 ccm 1 normal Sodium hydroxide neutralized against Congo red. Yield 920 to 960 parts.

100 parts of this condensation product are carefully mixed with 40 parts 400% sodium hydroxide solution was melted and mixed with 20 to 22 parts 37% formaldehyde solution 6 hours at i`oo to io @ 5 ° condensed. A sample diluted with water remains clear after acidification with dilute sulfuric acid. The reaction mass is in it in a manner similar to that described in Example i, worked up. One receives a Product with similar properties to the product described in example i. Yield 162 parts.

Instead of raw cresol, either the individual cresols or other substituted phenols that still have at least. one in para or ortho position have replaceable hydrogen atom for the phenolic hydroxyl group, e.g. B. o-chlorophenol, can be used for the implementation described above.

Example 3. The condensation product obtained according to Example i from 500 parts of phenol from the titre 3.5 to 3.7 with zoo to 22o parts phenol in a similar way as in the example i at 165 to i7o ° set by @. After the implementation there are only 1.6 up to 1.7 ccm i normal sodium hydroxide solution necessary to counter i g of the condensation product Congo red to neutralize. Yield about 1,000 parts.

100 parts of the condensation product obtained are carefully melted with 34 parts of 400% sodium hydroxide solution and heated with 23 to 24 parts of 37% formaldehyde solution for 41/2 hours at 100 to 10 °. After this time, 25 parts of 25% sodium bisulfite solution are added and the mixture is heated at 100 to 10 ° for a further 6 hours. A sample diluted with water and acidified with dilute sulfuric acid then remains clear. The resulting product is diluted with 30 parts of water, precipitated with dilute sulfuric acid and sodium sulphate and the resin which has separated out is pressed out thoroughly in order to free the resin from the admixed salts. Yield 165 parts.

The reaction with sodium bisulfite can also be carried out with advantage under pressure be carried out at i 5o '.

The leather made with this product is particularly distinctive characterized by its fullness, softness and lightfastness.

The formaldehyde condensation product obtained can also through subsequent treatment with aromatic sulfonic acids or their soluble condensation products to be made soluble. If you replace the 25 parts bisulfite in the above example with 5o parts of ß-1? Aphthalenesulfonic acid and heated for 11 / z hour to 100 to 105 °, in this way a condensation product which is readily soluble in water is obtained. After treatment the product is diluted with 100 parts of water, the solution with ammonia to one The pH was adjusted to 3.5 and then 10 parts of 8oo /% acetic acid were added. You get in this way a product with good tanning properties.

Instead of the phenol, raw cresol, the individual cresol or other substituted phenols that have one in para- or ortho-position to the phenolic Hy droxylgruppe convertible hydrogen atom containing, are used, wherein, depending on the component used, the reaction temperature is lower or higher. Beispie14 300 parts of molten naphthalene become slowly mixed with 264 parts of 66% oleum and sulfonated for 4 hours at 135 °. After this time, the reaction mixture is cooled to 90 ° and first with. 3oo Parts of phenol and then slowly mixed with 264 parts of 66% oleum, then stirred at 100 to 10 ° for an hour. The resulting sulfonic acid mixture is now slowly heated in a vacuum from about i i to i3 mm to 165 ° and so long (about 20 hours) condensed at this temperature until i g of the reaction mass 3.5 to 3.7 ccm i normal sodium hydroxide solution neutralized against Congo red. The condensation mass is then mixed well with 100 to 120 parts of phenol and the further implementation carried out in vacuo at 165 ° until i g of the condensation product 2.5 up to 2.7 ccm i normal sodium hydroxide solution neutralized against Congo red. Yield about 1050 Parts.

100 parts of the above condensation product are carefully melted with about 40 parts of 40% sodium hydroxide solution and refluxed with 18 parts 37% formaldehyde solution (about 7 hours) at 100 to 10 ° until a sample is dissolved in a little water dilute sulfuric acid remains clear. After the condensation, the tanning agent obtained is worked up in the same way as described in Example i. Yield 155 parts.

Toluene can also be used in place of naphthalene. Furthermore, instead of the phenol, crude cresol or other phenols which still contain at least one reactive hydrogen atom in the para or ortho position to the phenolic hydroxyl group can be used to convert the resulting condensation product with a titre of 3.5 to 3.7. EXAMPLE 5 35 parts of a \ taphthyl-oxy-polyphenyl-sulfone - obtained as described in Example 4, by heating equivalent amounts of naphthalene and phenol sulfonic acids in vacuo at 165 ° until the condensation product is about 3.5 liters of normal sodium hydroxide solution Congo red neutralized, and subsequent reaction of the still free sulfonic acid groups with phenol in vacuo at 180 ° until there is no further decrease in acidity, the polysulfone obtained having then been washed acid-free and dried - and 65 parts of an oxy-polyphenyl-sulfone-sulfonic acid, obtained by Heating phenolsulfonic acid, as described in Example i, to a titer of 3.5, is carefully melted together with about qo parts of 400% sodium hydroxide solution and then with 22 parts of 37o% formaldehyde solution (about 7 hours) at 100% Condensed up to 10 ° until a sample, dissolved in a little water, remains clear when acidified with dilute sulfuric acid. The product obtained is then worked up as described in example i and shows similar properties to the product described in this example. Yield 157 parts.

If, in the above example, the sulfone content is increased so that the condensation product is no longer sufficiently soluble in water after the formaldehyde condensation, then as described in Example 3, by an aftertreatment with bisulfite or with aromatic Sulphonic acids or their soluble condensation products greatly improves the solubility will.

Claims (2)

PATENT CLAIMS: i. Process for the preparation of water-soluble, tanning condensation products, characterized in that one is on a. Mixture of oxy-polyaryl-sulfonsulfonic acids, which contain at most one nucleus-bound oxy group per phenyl radical and of phenolsulfonic acids with at least one replaceable hydrogen atom in o- or p-position to the hydroxyl group by heating in vacuo to i 5o 'exceeding temperatures with at most the equimolecular amount of Sulphonic acids of the benzene and naphthalene series, which can also contain hydroxyl, halogen and / or methyl groups as substituents, have been prepared, and polyoxypolyarylpolysulphones, which are obtained from the above oxypolyaryl-sulphone-s, sulphonic acids by heating in vacuo to iao ° Exceeding temperatures with the calculated amount of a phenol with at least one replaceable hydrogen atom in the o- or p-position to the hydroxyl group, calculated on the sulfonic acid groups present, formaldehyde or formaldehyde-releasing compounds in an aqueous alkaline agent at elevated temperature and the condensation products obtained against also aftertreated with soluble salts of sulphurous acid and / or with aromatic sulphonic acids or their soluble condensation products. 2. The method according to claim i, characterized in that .man uses a mixture of oxypolyaryl-sulfone-sulfonic acids and polyoxypolyaryl-polysulfones, which is obtained from the oxy-polyaryl-sulfone-sulfonic acids by heating in vacuo to i5o to igo ° with phenols at least one replaceable hydrogen atom in, o- or p-position to the hydroxyl group in such amounts that the sulfonic acid groups present are partially blocked with oxyphenyl sulfone formation. Publications considered: Swiss patent specification No. 239 762.