DE1768548A1 - Process for the preparation of sulfonation products - Google Patents

Description

Henkel & Cie GmbH Düsseldorf, the 22nd time in 1968

Patent department at Henkelstrasse 67

Dr. Bz / Et

Patent application
D 3593

Process for the preparation of sulfonation products

The invention relates to a method for producing · ^ j Sulphonation products of unsaturated, higher molecular weight aliphatic Alcohols or carboxylic acids, as well as their ethers, esters or amides by means of sulfites or bisulfites, the under mild reaction conditions and relatively little time to products with good water emulsifiability and a relatively high degree of sulfonation.

Water-emulsifiable leather and fur fatliquors generally become more natural through sulfonation of unsaturated ones or synthetic fatty acids, fats, oils or waxes with conventional sulphonation agents, such as. B. technical sulfuric acid or air / bisulfite.

Sulfation with technical sulfuric acid primarily produces sulfuric acid esters, which has the disadvantage have that they are relatively unstable to acids.

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BATH ORIGINAL

In the so-called sulfation, ie the reaction with air / bisulfite, genuine sulfonic acid salts are formed which are not subject to hydrolysis. The addition of the sulfonic acid group to the double bonds occurs - as is known - only in connection with activation by means of oxygen or air, which means that very different, oxidative side reactions take place depending on the air distribution and temperature. In addition, such a reaction only leads to a degree of sulfonation of usually not more than 20 % of the unsaturated compounds used in a relatively long time of 2 to 15 days.

The invention thus provides a process for the preparation of sulfonation products, which is characterized in that is that one has higher molecular weight alcohols or carboxylic acids and / or their ethers, esters or amides, the at least contain an unsaturated aliphatic radical with 8-22 carbon atoms, by means of sulfites and / or bisulfites in the presence of formaldehyde or formaldehyde-releasing substances.

The process is carried out at temperatures below 100.degree. The reaction proceeds relatively quickly and leads to water-emulsifiable products with a high degree of sulfation, which, depending on the starting compounds used and the reaction conditions, can be between 20% and over 90 %.

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Suitable starting materials for the process according to the invention are primarily unsaturated fats and oils, such as those obtained from natural animal and vegetable starting materials. Furthermore, the unsaturated fatty alcohols or fatty acids produced therefrom, as well as their ethers, esters and amides, can be used as starting compounds. The products mentioned can contain proportions of saturated compounds, but the amount of unsaturated compounds in the mixture should be at least 5o - 7o mol percent. Examples of compounds of the type mentioned are: olive oil, neat oil, corn oil, rice oil, castor oil, cottonseed oil, tea seed oil; Marine oils, e.g. B. sperm oil, Waaltran, fish oil; Oleic acid oleyl esters, oleic acid mono-, di- or triglycerol esters, oleyl alcohol, sperm oil alcohols with an iodine number of 70-90> ricinoleic acid, oleic acid and technical mixtures of unsaturated fatty acids, e.g. B. coconut fatty acid mixtures of chain lengths Cp - C ^ o with a proportion of at least Jo mole percent of unsaturated fatty acids having an iodine value of 7 Talgfettsäuregemische ο 9o, butyl oleate, ölsäuremonoäthanolamid, linoleic acid. Instead of the products obtained from naturally occurring raw materials, corresponding synthetically produced unsaturated carboxylic acids or alcohols and their derivatives can also be used as starting materials.

The sulfites or bisulfites are used in the form of their alkali or ammonium salts. You will be the starting materials

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added preferably in the form of concentrated aqueous solutions with a content of 10 to about 35 % of sulfite or bisulfite. A mixture of equivalent amounts of sulfite and bisulfite is preferred. Unreacted amounts of sulfite or bisulfite can oxidatively after the end of the reaction, ζ. Β. by air bubbles.

The formaldehyde is also expediently added in the form of concentrated aqueous solutions with a formaldehyde content of about J> o - 35 %. However, formaldehyde-releasing substances such as paraformaldehyde or formaldehyde-bisulfite addition compounds can also be used. The process according to the invention is preferably carried out in such a way that a molar ratio of unsaturated compounds to formaldehyde to sulfite and / or bisulfite such as 1: 0.8 to 1.3: 0.8 to 1.3 is maintained. It is particularly advantageous if an equimolar ratio of formaldehyde to sulfite and / or bisulfite is maintained.

The reaction takes place without the usual activation by air bubbles at relatively low temperatures, preferably at temperatures below 100 ° C. at a relatively high rate away. The temperature range between 7 o and 85 ° C has proven to be particularly favorable. Depending on the raw materials and the desired degree of conversion, a sulfonation time between 7 and 20 hours is required. The water content of the

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The reaction mixture should be at least about 20 percent by weight or not during the course of the reaction this value will decrease.

The reaction is accelerated and the degree of sulfonation is improved if the phases are mixed intensively by vigorous stirring. A further acceleration can be achieved if, at the beginning of the sulfonation, small amounts of an emulsifier or a portion of a sulfonation product prepared according to the invention are added, as a result of which a significantly better phase mixing is achieved. In general, 3-5 % of an emulsifier is required for this, for which known emulsifiers, such as fatty alcohol sulfates or alkylbenzenesulfonates, ethylene oxide adducts with higher fatty alcohols, fatty acids and the like come into consideration. However, it is particularly advantageous to use portions of a sulfonation product prepared according to the invention instead, with somewhat higher amounts, for example 5-10 %, having to be used depending on the degree of sulfonation End product that is not contaminated by foreign matter.

The products according to the invention are relatively lighter Color and are easily emulsified in water. You can

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Depending on the degree of sulfonation as a wetting, dispersing and finishing agent for the textile and paper industry, as well as for metalworking, z. B. can be used as cutting and drilling oils .

However, the products according to the invention are very particularly suitable as fatliquoring agents for leather fatliquoring. They differ in an advantageous manner from the suIfi erungsprodukte previously used for leather fatigue by their relatively high affinity for the leather fiber. This is noticeable in the significantly lower solvent extractability from the greased leathers. In addition, the products according to the invention give the leather better water behavior, ie lower absorbency and lower water absorption. At the same time, you get a full, soft leather handle and a noticeably firm and smooth grain.

The properties mentioned are particularly valuable for pettling modern upper leathers that are to be glued or vulcanized , since a higher content of extractable fat components has a considerable disruptive effect. Such a low extractable fat content also has a favorable effect in terms of good fastness to dry cleaning in the case of clothing suede.

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17685A8

The very low water absorbency of the inventive Leather greased products is particularly advantageous in the manufacture of all sports and waterproof leathers, as well in clothing leathers.

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Example 1a

415 g of a 8 ° C filtered Spermölfiltrates (JZ: 86, VZ: 157) are heated with stirring to 85 c ^0th To this end, 126 g of sodium sulfite, dissolved in 49o g of water, and then 86 g of formaldehyde solution (55%) are added at the same temperature and the entire batch is stirred at 85 ° C. for 20 hours. The water content of the reaction mixture should not fall below 20-25 % .

A light brown, viscous, readily water-emulsifiable sperm oil sulfonate with an emulsifier content of 20 % is obtained.

Example 1b

Chrome-tanned shoe upper leathers retanned with synthetic or resin tanning agents are licked at 60 ° C. for 45 minutes with 250 % liquor and 4.5-5> 5% fatty substance of a mixture of 80 % of the sulfonation product from Example 1a and 20 % hoof oil. The leathers, which are dried and finished in the usual way, are distinguished by a particularly light color and a soft and supple handle.

Example 2a

445 g of triolein are heated ^{to 85 ° C. with stirring.} Then 189 g of sodium sulfite in 730 g of water and 129 g of formaldehyde solution (55%) are added at the same temperature

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admitted. The batch is then stirred at 85 ° C until about 20 hours have elapsed. The water content of the reaction product should not fall below 20-25 % . A light yellow product which is readily emulsifiable in water and has an emulsifier content of 19 % is obtained.

Example 2b

Chrome-tanned and dyed leather clothing are gelickert at 6o C "M 45 min 250% float and 6 - 8% oily substance of a mixture of

77 % of the sulfonation product according to Example 2a and 2o % sperm oil filtrate.

3 % of a mixture of technical fatty alcohols ethoxylated with 8 moles of ethylene oxide with chain lengths of C ₁₂ - C ₁ Q.

The finished leathers are distinguished by their light color (| and smooth grip.

Example 3a

450 g of a Trangemisches from herring and cod oil (JZ SZ 125 * 15) are added at 85 ⁰ C with a solution of 32 g sodium sulfite and 26 g of sodium bisulfite in 19o g of water and then added 43 g of formaldehyde solution (35 $ strength). The mixture is naehgerUhrt 7 hours at 85 ⁰ C. It should

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the water content of the reaction product does not fall below 2o % . A water-emulsifiable transulfonate with approx. 31 % emulsifier content is obtained.

Example? B

Combined tanned vachettes are licked at 60 ° C. for 45 minutes with 250 % liquor and 5 % fatty substance of the transulfonation product according to Example J3a.

The leathers, dried and finished in the usual way, have a full and supple feel.

Example 4a

450 g of ricinoleic acid at 80 ° - 85 ° C under stirring with a solution of 94.5 g of sodium sulfite and 78.0 g Natriumbisulf it in 565 g water and 129 g of formaldehyde solution (35 #ig added The mixture is at the same temperature approx. . stirred for 7 hours, the water content should not fall below 2o%.

The result is an almost colorless, pliable, water-soluble paste with an emulsifier content of approx. 95 %, based on the water- and salt-free fatty substance.

Example 4b

A chrome-tanned shoe suede is after the Chromnach

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tanning in the usual way, pre-greased with 1.6-2 % fatty substance of the above sulfonation product, dried, sanded, paperback and dyed as usual, and re-greased with 0.5-1% fatty substance of the same sulfonation product. The finished suede has a soft, supple handle and a good cut.

Example 5

42J g of oleic acid are mixed with a solution of 156 g of sodium bisulfite in 590 g of water and 129 g of formaldehyde solution (35%) at 70-85 ° C. At the same temperature, stirring is continued for about 10 minutes, the water content of the reaction product not falling below 20 % ; excess bisulfite can be removed by blowing in air during the last part of the reaction time. A light yellow, clear, water-emulsifiable oil with an emulsifier content of approx. 51 % is obtained, based on the water- and salt-free fatty substance.

Suede leather can advantageously be treated with this product, as described in Example 4b.

Example 6

450 g of a mixture of herring and cod oil (JZ 125 * SZ 15) with a solution of 32 g of sodium sulfite and

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26 g of sodium bisulfite and 45 g of the sulfonation product according to Example 3a were added to 190 g of water and then 43 g of formaldehyde solution (35%) were added. The batch is stirred vigorously at 85 ° C. for 6 hours. The water content should not drop below 2o%. A water-emulsifiable transulfonate with approx. 35 % emulsifier components is obtained, which can be used in the same way as indicated in Example 3b.

Example 7

450 g ricinoleic at 80-85 ⁰ C under stirring with a solution of 94.5 g of sodium sulfite, 78.0 g sodium bisulfite and 25 g of 8 moles of ethylene oxide with technical ethoxylated fatty alcohol mixture having chain lengths of C ₁₂ - C ₁ O in 565 g water and 129 g formaldehyde solution (35 #) added. The batch is then stirred at the same temperature for about 7 hours, the water content not dropping below 20 % .

An almost colorless, pliable paste is obtained which can be used as in Example 4b.

Example 8

270 g of technical oleyl alcohol (JZ 90-95) are mixed with a solution of 126 g of sodium sulfite in 487 g of water and 86 g of formaldehyde solution (35%) ^{at about 85 ° C. while stirring.}

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The batch is subsequently stirred at the same temperature for 15 hours .

A liquid, light brown reaction mixture is obtained which can be used with advantage for leather oiling according to Example 1b or 2b.

Example 9

37 o g of oleic acid diethanolamide are mixed with a solution of 126 g of sodium sulfite in 487 g of water and 86 g of formaldehyde solution (35%) at 85 ° C. while stirring. The batch is subsequently stirred at the same temperature for about 15 hours. The result is a liquid, homogeneous, light brown reaction product which, when diluted with water, is excellent
results in stable emulsions which can advantageously be used for leather oiling according to Example 2b or hb.

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Claims (1)

- 14 PATENT CLAIMS 1. Process for the production of suIfonierungsprodukte, characterized in that one uses higher molecular weight alcohols or carboxylic acids and / or their ethers, esters or amides which contain at least one unsaturated aliphatic radical Contains 8-22 carbon atoms by means of sulfites and / or bisulfites in the presence of formaldehyde or formaldehyde releasing substances. 2. The method according to claim 1, characterized in that the ratio of unsaturated compounds to formaldehyde to sulfite and / or bisulfite such as 1: 0.8 to 1.3: 0.8 to 1.3. . Process according to claims 1 and 2, characterized in that the reaction was eaten at tempera
wisely carried out at 7o - 85 ° C. that the reaction is carried out at temperatures below 100 ° C., preferably 4. Process according to Claims 1-3 *, characterized in that the reaction mixture contains at least 2o % water. 5. Process according to Claims 1-4, characterized in that the reaction takes place in the presence of 3 - 1o % of an emulsifier is carried out. - 15 1 09847/1 896 17685 ^ 8 6. The method according to claim 5 *, characterized in that as an emulsifier, a sulfonation product prepared according to the invention is used. 7. Process according to claims 1-6, characterized in that that one carries out the reaction with natural unsaturated fats or oils. 8. The method according to claim 1-6, characterized in that the reaction with unsaturated fatty alcohols of chain lengths C ₁₂ - ^c 18 * ^or de ** « ¹ ethers or esters is carried out. 9. Process according to Claims 1-6, characterized in that the reaction is carried out with unsaturated fatty acids of chain lengths C ₁ O - C ₁ O, or their esters or amides. 1o. Sulfonation products of unsaturated compounds according to claims 1-9 11. Use of the sulfonation products prepared according to claims 1-9 as a leather fatliquor. HBNKlL ft CIS .OfflbH. in general, 109847/1896