DE1278681B - Fats of leather or fur - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Irt. α .:

C14c

German classes: 28 a -9

Number: 1278 681

File number: P 12 78 681.1-43 (B 72557)

Filing date: Wed 5, 1963

Opening day: September 26, 1968

Water-emulsifiable leather and fur fatliquors are generally made by sulfating unsaturated, natural and / or synthetic fats, oils or waxes with common sulfating agents such as z. B. technical sulfuric acid produced. This 5 is the sulfation, which is mainly on the double bonds attacks, usually only until sufficient emulsifiability is achieved in Water driven, so that the sulfation products obtained usually still have a considerable residual ίο own iodine value. Due to the resulting unsaturated character, both the oxidation stability (shelf life) of the fatliquoring agent and also has an unfavorable effect on the light resistance of the leathers greased with it.

From the German patent specification 640 791 is a process for the production of sulfuric acid compounds of linseed oil, with linseed oil or linseed oil fatty acid or mixtures of these two substances partially chlorinated and then sulphated in the usual way are known. The chlorination is only carried out up to a chlorine content of 3 to 4%. Furthermore, with a relatively large Sulfated amount of about 70% sulfuric acid. The high proportion of sulfuric acid ester groups has an effect detrimental to the properties of the products with regard to their use as fatliquoring agents. On the other hand, a reduction in the sulfuric acid ester residues at a low degree of chlorination is guaranteed insufficient resistance to yellowing.

It is also from the German patent specification 942 889 and the French patent specification 1 304 908 known, hydrocarbons produced by halogenation or sulfohalogenation or subsequent Saponification of the sulfohalogenation products have been modified to use for leather oiling.

With such fatliquoring agents, however, it is not possible to achieve fatliquoring effects that are as good as they obtained with natural fats and oils or conversion products of natural fats and oils will. In particular, natural fat products can be used to make them much more pleasant and softer Produce grip properties as well as more elastic and stretchable leather, which is particularly suitable for clothing leather, Glove leather, handbag leather and other finer types of leather are suitable. For these purposes as well can also be used for the production of soft and elastic shoe upper leathers from the above mentioned patents known halogenated or sulfohalogenated synthetic fatliquoring agents do not use.

Fats of leather or furs

Applicant:

Bohemian chemistry

Company with limited liability,

4000 Düsseldorf-Holthausen, Henkelstr. 67

Named as inventor:

Dr. Werner Stein, 4000 Düsseldorf-Holthausen;

Dr. Jürgen Plapper, 4000 Düsseldorf

It has now been found that water-emulsifiable materials can advantageously be used for greasing leather or furs chlorine-containing sulfation products of unsaturated organic compounds containing lipophilic radicals Compounds, which by partial chlorination of the unsaturated starting materials up to a chlorine content from 3 to 15%, preferably 5 to 10%, calculated on the starting material, the iodine number of the starting materials has been reduced by 20 to 70%, preferably by 30 to 50%, and then Sulphation in the usual way with 10 to 30%, preferably with 12 to 20%, technical sulfuric acid, calculated on the material to be sulfated.

This advantage is particularly evident in the light and storage stability of the using these Fatliquor produced very soft and supple leather.

The starting materials for the sulfation products to be used according to the invention are higher molecular weight, Unsaturated hydrocarbons, alcohols, ethers, carboxylic acids, esters and the like are considered, z. B. olefins such as dodecane, octadecene or squalene, esters of unsaturated, higher molecular weight alcohols with 12 to 20 carbon atoms, in particular of oleyl alcohol or others singly or multiply unsaturated alcohols with any low or high molecular weight monobasic or polybasic carboxylic acids or ethers of such alcohols. Esters of unsaturated higher molecular weight are also suitable Fatty acids or their mixtures, such as naturally occurring glycerides, one or more of their fatty acid content polyunsaturated, such as soybean oil, cottonseed oil, rapeseed oil, linseed oil, castor oil, sunflower

809 618/507

3 4

oil, olive oil, neat oil, herring oil, cod oil, shark deodorization. However, other bleaching fish oil or whale oil, as well as unsaturated waxes, medium and bleaching processes, optionally with such as sperm oil, or their reaction products can also be used. other pH values can be used. On the Her-Weiter come as starting materials, ester unsaturation of the fatliquoring agent, as it was previously written with fatty acids with mono- or polyvalent Aiko- 5, no protection is sought,
get the aliphatic, cycloaliphatic, aroma- The water-emulsified or heterocyclic series obtained in this way as well as fat fatliquors are very light- and storage-stable esters of unsaturated carboxylic acids and alcohol- dig, little sensitive to oxidation, solidify when mixed or unsaturated mixed esters from the same to the non-pre-chlorinated sulfation pro polyhydric alcohols and various unsaturated products at lower temperatures and unsaturated carboxylic acids tend. Furthermore, esters are also slower for salt formation and salt excretion,
applicable, in which both the acid and the alcohol content when used according to the invention on leather have a mono- or polyolefinically resulting water-emulsifiable, chlorine-containing suI-unsaturated hydrocarbon radical. Preference products in comparison to the raw materials that are not used in advance represent the natural, untreated sulfation products, surprisingly saturated animal and vegetable fats, oils or considerably softer and more supple waxes, because they are well suited and easily accessible. who are borrowed. Use of the usual release agents only through long-term

The chlorination of the unsaturated starting materials with other combinations that are difficult to test can be carried out in various ways, such as special emulsifiers or new substances. One can join the well-known tralfetten that can be reached.
Use methods of chlorine addition, such as B. The sulfation products described should generally be used alone in the introduction of gaseous chlorine into the chlorine, but they can be used as starting material, which in appropriate cases can also be diluted with solvents in connection with a new batch. Tral oils and synthetic emulsifiers are anionic, but it is also possible, for example, to use the cationic and nonionic type of stored chlorine in the form of a solution in one. Natural inert solvents are added to the material to be chlorinated and synthetic oils, fats or waxes of vegetable origin are added under neutral oils. In any case, it is understood by appropriate animal or mineral origin, cooling to ensure that the heat, which can also be chlorinated,
tint is dissipated to prevent damage. -I ₁
Avoid side reactions. example

The sulfation of the incompletely chlorinated untanned chrome-tanned, with synthetic tanning agents or saturated starting materials are made in the usual way with resin tanning materials with 10 to 30%, preferably 12 to 20%, tech- 35 in the barrel at 60 ° C for 45 minutes using 250% Nical sulfuric acid (98%), calculated on to sul- liquor with 4.5 to 5.5% of the below-described Material below 40 ° C, preferably benen chlorine-containing sulfation product as the fatty one at 15 to 30 ° C. If the substance is reduced to a greater extent, in relation to leather, licked. Those in excess iodine numbers the unsaturated raw materials by the Licher way dried and finished leather incomplete chlorination, e.g. B. below 35, 4 ° are characterized by a full, soft and become usually higher amounts of sulfuric acid pliable handle, good grain firmness and good and with remaining higher iodine numbers, e.g. B. from 50, light resistance.

As a rule, lower amounts of sulfuric acid are used. The chlorine-containing sulfation product used required for sufficient sulfation. In place had been won in the following way: One at of technical sulfuric acid are in principle also 45 8 ° C supercooled and filtered sperm oil with the other known sulfating agents can be used, such as acid number 2.5, saponification number 135 and Chlorosulfonic acid, oleum or sulfur trioxide. The iodine number was 81 in one with a cooling coil Wash and neutralize the recovered sulfa-tipped flasks. While stirring vigorously tation products can be done in the usual way, was slowly introduced chlorine gas, with the Tementneither was kept at 17 ° C by washing at saturated or half-temperature by cooling. That saturated salt solutions and subsequent neutrali- progress of the reaction was determined by weighing sation or by a combined washing neutral, and the chlorination was followed by a chlorination, in which the sulfation product terminated in a 25% uptake of 10.1%. The responsive one Ammonia solution is entered, the approximately 80 product was then mixed with water and verbis 85% of the am- 55 dilute sodium bicarbonate solution required for neutralization was washed and contains amount of monia. After separating off the acid number 1.7, iodine number 38.2, separate salt water layer can neutralize chlorine content 10.1%. This intermediate was to be completed in the usual way. It is then each with 15% technical sulfuric acid but also possible, just a neutralization without (98%) at 28 to 30 ° C by a known method to carry out special washing. 60 sulfated, stirred for 1 hour and then in a

If the sulphation products are dark in color, 5% ammonia solution, the 80% of the total stand, as is the amount of dechlorinated ammonia required sometimes during sulphation, partial neutralization Herringstrane is the case, which can be kept, given the temperature 30 to 40 ° C Sulphation products in the weakly acidic pH range, not exceeded. For the separation of the salt water, for example in connection with the washing neutral layer, the station stood at about 50 ° C overnight left at a pH of 2.5 to 3 with 5 to, then peeled off the salt water layer and 15% (based on sulphation product) 40% pure sulphation product with technical Bleach hydrogen peroxide at about 50 ° C and neutralize ammonia to a final pH of 7.0.

Claims (1)

5 6 sated. It was a clear, yellow oil, which also means 250% liquor with 4 to 6% fatty substance, remained uniform after prolonged storage and none - consisting of a mixture of 60% of the subsequent- For deposits and other changes described in the chlorine-containing sulphation showed received. Product, 20% of the partially chlorinated, but not Beisoiel 2 ^{5 su} i lf ^{at Erten} Trans, 15% paraffin oil of viscosity ^F 50 ° E at 20% C, 5% one with 8 moles of ethylene oxide Chrome-tanned and dyed clothing leather from a converted mixture of technical fatty alcohols from Cattle hides were licked in the barrel at 60 ° C for 45 minutes using chain lengths C ₁₂ to C _{18 and} 250% liquor with 6 to 8% fatty substance, occasionally dried and finished. There were standing from a mixture of 77% of the nach- io particularly soft and supple as well as brisk The chlorine-containing sulfation glove leather described above is of good lightfastness. product, 20% sperm oil filtrate and 3% one with hold. 8 moles of ethylene oxide reacted mixture tech- The used chlorine-containing sulfation product of fatty alcohols of chain lengths C ₁₂ to C ₁₈ was prepared as described below: Licked in the barrel. The conventionally dried A Trangemisch with the key figures acid number and finished leather were characterized by a 17.5, saponification number 186.1 and iodine number 125.4, soft, supple and full handle and by obtaining the key figures acid number 11.9 , Iodine good lightfastness. number 82.4 and chlorine content 10.1% chlorine added. The chlorine-containing sulphate used for leaching - The chlorination product was prepared according to Example 2 The product was made as follows: A 20 sulfated, bleached and deodorized. It became a Cod oil with acid number 8 to 10 obtained light, yellow, clear, water-emulsifiable oil, and iodine number 140 to 150 became long- under cooling. . sam with a 10% chlorine containing tetrachlor example 5 carbon solution added. The speed of addition- chrome-tanned, synthetic or resin-tanned The speed was set so that the temperature was set to 25 fabrics retanned shoe upper leathers 15 ⁰ C was held. After uptake of 9.7% 6O ⁰ C for 45 minutes by means of 250% float with Chlorine was washed with water and the solution was 4.5-5.5% fatty substance of a mixture medium distilled off. The reaction product was 70% that of the chlorine-containing one described below Key figures acid number 9.4, iodine number 99.8, chlorine content of sulfation product and 30% of the partially chlorinated 9.7%. The chlorination product was fermented, but not sulfated, tea seed oil in the barrel game 1 sulphated with 15% technical sulfuric acid, dried and finished. The received and after entering into the 5% ammonia- tene shoe upper leather was characterized by full, Solution with 10% 40% hydrogen peroxide with a soft and supple handle as well as good 50 ° C for 10 to 15 minutes with stirring and light resistance. deodorized. The batch remained standing overnight, 35 The chlorine-containing sulfation product used whereby the sulfation product from the salt had been produced in the following way: A tea water mixture separated. After pulling off the suede oil with an initial iodine number of 85 to 90 This fatigue product was partially processed using technical methods until it had an iodine number of 45 Ammonia completely neutralized to pH 7.0. It was chlorinated and treated with 18% technical grade sulfuric acid a light, yellow-brown, clear oil obtained, which measured Example 1 sulfated. After neutralization easily emulsified in water. became a clear, yellow-brown, water-emulsifiable ". . , “Oil won. Example 3 ⁶ A combined tanned shoe upper leather was ^ at 6O ⁰ C for 45 minutes by means of 250% liquor 45 pastel-colored or white clothing leather with 4.5 to 6.0% oily substance of a mixture of an oily substance were Geaus with 6 to 8% 75% of the below-described chlorine--mixture of 70% of the term sulfation product described below and 25% of the partially chlorine-containing sulfation product, 26% of the partially chlorinated but unsulfated trans in the barrel, chlorinated but not sulfated triolein and licked and dried in the usual way and finished 50 4% of one with 4 moles of ethylene oxide implemented. A full, supple shoe coconut fatty acid monoethanolamide was obtained at 60 ° C. while upper leather with a good grain pattern. 45 minutes by means of 250% liquor in the barrel, The chlorine-containing sulfation product used is dried and finished. The received clothing was obtained in the following way: A pudding leather is characterized by good lightfastness. Fish oil with the key figures acid number 0.4, saponification 55 and by being soft, pliable and full number 196, iodine number 181 and OH number 13.5 was made up to handle. to obtain the key figures acid number 5.2, iodine number For the production of the chlorine-containing suI- 130.4, OH number 13.4 and chlorine content 9.0% partially fatierungsprodukts was a technical Triolein the chlorinated. The chlorination product obtained had an iodine number of 85 to 90 except for an iodine number of about with 15% technical sulfuric acid and ammonia 60 50 partially chlorinated, sulfated according to Example 1 and neutralization in conjunction with a bleach and neutralized.
Deodorization process according to Example 2 implemented. It became a light, brown, clear, water-emulsifying patent claims: get real oil. 1. Use of water emulsifiable _R. . . 65 sulfation products containing chlorine unsaturated Example 4 _; ijpophjie containing _residues , organic Pastel-colored, chrome-tanned glove leather compounds, which are partially caused by chlorine from lambskins at 60 ° C 45 minutes with the unsaturated starting materials up to a chlorine content of 3 to 15%, whereby the iodine number of the starting materials is reduced by 20 to 70% has been, and subsequent sulfation with 10 to 30% technical sulfuric acid, calculated on the material to be sulfated, for greasing leather or Furs. 2. Embodiment according to claim 1, characterized in that water-emulsifiable, chlorine-containing sulfation products, which are caused by partial chlorination of the unsaturated, lipophilic Starting materials containing residues up to a chlorine content of 5 to 10%, the iodine number the starting materials have been reduced by 30 to 50%, and subsequent sulfation with 12 to 20% technical sulfuric acid, calculated on the material to be sulfated, has been produced are to be used. 3. Embodiment according to claim 1, characterized in that water-emulsifiable chlorine-containing Sulphation products, which are caused by partial chlorination and subsequent sulphation natural, unsaturated, animal or vegetable fats, oils or waxes are to be used. Considered publications:
German Patent Nos. 640 791, 942 889;
French Patent No. 1,304,908;
U.S. Patent No. 2,469,059. 809 618/507 9.68 © Bundesdruckerei Berlin