EP0136641A2 - Fat-liquoring agent for leather and pelts - Google Patents

Abstract

The fatliquors are based on sulfonated chlorination products of natural or synthetic higher fatty acid trigylcerides in the form of their alkali, ammonium or amine salts. The starting point is products which are obtained by sulfochlorination of mixtures of higher C _12-24 fatty acid triglycerides and C _6-20 fatty acid residues of monohydric C _1-3 alcohols or mineral oils and subsequent saponification which are advantageously chlorinated until the double bonds are saturated. The reaction temperature is 20-90 ° C. The course of the reaction can be promoted by UV radiation until the addition of 5-30% by weight of chlorine and 1-20% by weight of SO ₂ Cl groups. (Ratio Cl- to SO ₂ Cl = 0.7: 1 to 70: 1).

Description

From DE-PS 22 45 o77 fatliquoring agents for leather or furs based on sulfonated chlorination products of natural or synthetic higher fatty acids or fatty acid esters in the form of their alkali, ammonium or amine salts are known, which are characterized in that they are derived from such sulfonated chlorination products exist by chlorinating higher fatty acids or esters of higher fatty acids of chain lengths C ₈ to C ₂₄ up to a chlorine content of 2o to 45 percent by weight, the chlorination products essentially no longer containing olefinic double bonds, and subsequent sulfonation with SO ₃ up to one Content of 40 to loo mole percent 50 ₃ , based on the chlorination product, have been obtained.

From DE-OS 3o 18 176 fatliquoring agents for leather or furs based on sulfonated chlorination products of natural or synthetic higher fatty acids or fatty acid esters in the form of their alkali, ammonium or amine salts are also known, which are characterized in that they consist essentially of Such sulfonated chlorination products consist of sulfochlorination of higher fatty acids or esters of higher fatty acids of chain lengths C ₈ to C ₂₄ using chlorine and SO _2, if necessary with UV radiation at 20 - 90 ° C up to a content of bound chlorine of 5 - 30 percent by weight and a content of SO ₂ Cl groups of 1 to 20 percent by weight, the ratio of chlorine atoms to SO ₂ Cl groups being 0.7: 1 to 7 ₀ : 1, and subsequent saponification having been obtained.

It has now been found that the known processes for the preparation of such fatliquoring agents can be further improved, provided that higher fatty acid triglycerides are used in the production of the sulfooated chlorination products. The sulfochlorination of fatty acid triglycerides is possible using the known method. However, it is considerably slowed down in the course of the reaction by the rapidly increasing viscosity of the reaction products and is ultimately uneconomical in that chlorine and SO ₂ no longer react adequately due to insufficient mixing. This disadvantage is remedied according to the invention in that the higher C ₁₂ -C ₂₄ fatty acid triglycerides before the sulfochlorination of C ₆ -C ₂₀ fatty acid esters of monohydric C -C alcohols or mineral oils with boiling points above 200 ° C in a weight ratio of 1: 0.2-1 , 2 admixes. These esters or mineral oils act as viscosity-reducing diluents for the higher fatty acid triglycerides. They are partly reacted in the sulfochlorination reaction and do not need to be removed from the mixture after the reaction.

The subject of the invention are fat-liquoring agents for leather and fur on the basis of sulfonated chlorination of natural or synthetic higher fatty acid triglycerides in the form of their alkali metal, ammonium or amine salts, characterized in that they consist of such sulfonated chlorination in cozy essential _l, the have been obtained by sulfochlorination of mixtures of higher C ₁₂ -C ₂₄ fatty acid which may have been pre-chlorinated until the double bonds have become saturated triglycerides and C ₆ -C ₂₀ fatty acid esters of monohydric C ₁ -C ₃ alcohols or mineral oils with boiling points above 200 ° C in a weight ratio of 1: 0.2 - 1.2 by means of chlorine and SO ₂ , if necessary with UV radiation 2D - 9D ° C up to a content of organically bound chlorine of 5 - 30 weight percent and a content of SO ₂ Cl groups of 1 - 20 weight percent, the ratio of chlorine atoms to SO ₂ Cl groups 0.7: 1 - 70: 1, and subsequent saponification.

The invention further relates to a process for the preparation of such fatty agents under the conditions specified above. The new process leads to better utilization of the gases used, ie to a lower consumption of chlorine and SO ₂ . If the higher fatty acid triglycerides contain unsaturated components, it may be expedient to first carry out chlorination until the double bonds are saturated and only then to carry out the sulfochlorination.

In the production of the claimed fatliquoring agents it is preferred to start from naturally occurring fats or oils which may contain a proportion of mono- or polyunsaturated fatty acids. Examples include coconut oil, soybean oil, palm kernel oil, cottonseed oil, rapeseed oil, linseed oil, castor oil, sunflower oil, olive oil, claw oil, peanut oil, herring oil, cod oil, shark oil, walnut oil, tallow fat or lard. Corresponding synthetically produced triglycerides are also suitable as starting materials.

The C ₆ -C ₂₀ fatty acid esters of monohydric C ₁ -C ₃ alcohols are the methyl, ethyl, propyl and isopropyl esters of the fatty acids concerned, e.g. B. a C ₆ -C ₁₀ fatty acid methyl ester mixture, or tallow fatty acid methyl ester into consideration.

Suitable mineral oils are essentially paraffinic oils with boiling points above 200 ° C, the boiling range preferably being around 250-410 ° C.

The mixtures of fatty acid triglycerides and fatty acid esters or mineral oils are sulfochlorinated in a manner known per se by simultaneous introduction of C ₁₂ and SO in a molar ratio of 85: 1 to 1.4: 1 temperature is 20 - 90 ° C and is kept at the desired level by cooling if necessary. A reaction temperature of 40-75 ° C. is preferred. The course of the reaction is promoted by irradiation with UV light (mercury vapor lamp). The reaction is complete after about 2 to 10 hours, after which time 5 to 30% by weight of chlorine and 1 to 20% by weight of SO ₂ Cl groups have been added. The ratio of chlorine atoms to 30 ₂ Cl groups is 0.7: 1 to 70: 1. The subsequent hydrolysis is carried out with aqueous, about 3 _0% sodium Matnium- or potassium hydroxide solution at about 5 ₀ ° C, the neutralization is carried out either with an excess of the same alkali hydroxy or with ammonia solution or with an aliphatic or cycloaliphatic amine or an alkanolamine of chain lengths C ₂ to C ₆ , such as triethanolamine. This gives liquid, highly concentrated, water-emulsifiable products with excellent oxidation, light and acid stability, which are ideal for greasing all light, pastel-colored and white leather and for greasing valuable and sensitive furs.

When using dark-colored or more unsaturated starting materials, bleaching of the sulfochlorination products can be recommended. This is carried out in a conventional manner by adding small amounts of about 0.5 to 5%, preferably 1 to 4%, H ₂ O ₂ to the acidic sulfochlorination product, the temperatures being between 20 and 80, preferably between 40 and 60 ° C. With this measure, dark-colored sulfochlorination products can also be brightened to a very large extent.

The products are used in the usual way in the form of aqueous emulsions for leather leakage or for fur treatment. The products are self-emulsifying, so that further additions of emulsifiers are generally not necessary. To achieve special effects, the chlorofluorination products can be combined with corresponding non-sulfonated chlorination products, or other conventional leather treatment agents, such as. B. non-sulfonated oils or fats, such as fish oil, sperm oil, claw oil and the like or synthetic fatliquors, such as chlorinated paraffins, paraffin sulfonates, sulfated native fats or oils or synthetic fatty acid esters, or mineral oils or the like, optionally in conjunction with anionic, nonionic or cationic emulsifiers, such as Ethylene oxide addition products to higher fatty alcohols, alkylphenols or fatty amines with chain lengths C ₁₀ to C ₂₀ . The products can be stabilized by rendering any remaining or newly formed hydrogen chloride residues harmless by means of epoxy compounds in quantities of 0.5 to 5 percent by weight. Examples include: glycide, epichlorohydrin, glycidyl ether of mono- or polyhydric alcohols, such as glycol, glycerin or sorbitol, and epoxidized fatty substances, e.g. B. epoxied soybean oil, linseed oil or oleic acid.

The products are well absorbed by the leather and give excellent greasing and softening effects, which have a remarkable resistance to water and aqueous or organic detergent solutions. Your tendency to hike under thermal stress is very low, so that z. B. bonding processes or let the vulcanization of rubber soles on shoe uppers be carried out without difficulty. Of particular note is the good light, oxidation and acid resistance of the products, which also make them suitable for greasing sensitive and light-colored leather and furs. The treated leather or furs are characterized by a particularly pleasant soft and slimy handle and a beautiful shine of the fur hair.

Compared to the sulfochlorination products of higher fatty acid triglycerides of DE-OS 30 18 176, there are particular advantages in that the claimed products have a lower viscosity and are more homogeneous. They are therefore easier to emulsify and result in more uniform and stable emulsions, which is why they can also be added directly to the licker bath. The increased penetration into the leather layer results in an improved deep greasing, which results in softer and more flexible leather and furs.

• Auf einem 2-1-Rundkolben mit Bodenablaß steht ein Reaktorturm aus Glas, der mit Raschigringen gefüllt ist und der einen Doppelmantel für eine Heiz- bzw. Kühlflüssigkeit besitzt.

The sulfochlorination reactions described in the following examples were carried out in the following apparatus:

• A glass reactor tower, which is filled with Raschig rings and has a double jacket for a heating or cooling liquid, stands on a 2-1 round-bottom flask with a bottom drain.

The feed material is pumped through the bath drain of the round bottom flask by means of a peristaltic pump through a heatable riser pipe into the head of the reaction tower.

The gases (chlorine and sulfur dioxide) are introduced at the lower end of the tower via needle valves. The metering is carried out by means of rotometers. The flow rate of the gases for chlorine is between 25 and ₁₂₀ 1 / h and for S0 ₂ between 4 and 50 l / h.

The HCl gas formed is removed with the rest of the unreacted starting gases at the top of the reaction tube via a wash bottle system. The glass reaction column can be irradiated from the outside with a mercury vapor lamp.

Example 1 a

A mixture of 800 g of tallow and 200 g of C ₆ -C ₁₀ fatty acid methyl ester was pumped around in the apparatus described at a circulation rate of 1 l / min, and 50 l of chlorine were passed in at about 40 ° C. over the course of about an hour in the trickle tower after ascending under flowing substrate. After the chlorination had ended (about 45 min.), The mixture was sulfochlorinated for 3 hours with 50 l / h chlorine and 12.5 l / h SO ₂ with UV radiation at 50-55 ° C. The implementation went smoothly. No build-up in the reaction tower due to an increase in viscosity was observed. The circulation rate could be maintained until the end of the reaction.

• 1338 g Sulfochlorierungsprodukt, enthaltend 2₀,7 Gew.-% Chlor (48,8 % des Verbrauchs) 4,7 Gew.-% SO₂ (65,4 % des Verbrauchs)

The following were obtained:

• 1338 g Sulfochlorierungsprodukt containing 2 _0, 7 wt .-% chlorine (48.8% of consumption) 4.7 wt .-% SO ₂ (65.4% of consumption)

Example 1b

A mixture of 6 g ₀₀ g tallow and 4oo C ₆ -C ₁₀ fatty acid methyl ester was reacted as described in Example la. The reaction went smoothly.

• 1252 g Sulfochlorierungsprodukt, enthaltend 18,8 Gew.-% Chlor (42,2% des Verbrauchs) 3,5 Gew.-% SO₂ (46,0% des Verbrauchs)

The following were obtained:

• 1252 g sulfochlorination product containing 18.8% by weight chlorine (42.2% of consumption) 3.5% by weight SO ₂ (46.0% of consumption)

Example lc

For comparison, 1000 g of tallow were reacted without the addition of C ₆ -C ₁₀ fatty acid methyl ester in the manner described in Example la, the chlorine being introduced at a circulation rate of 1 l / min. was made. After 45 min. The reaction time already caused jam formation in the packed column due to an increase in viscosity, so that the circulation speed had to be reduced to 0.75 l / min. After heating to 60 ° C., sulfochlorination was carried out under UV radiation, as indicated in Example la. Already 10 min. after the start of the sulfochlorination, there was again formation of jams, which is why the circulation speed to 0.5 1 / min. had to be reduced. After a further 2 hours there was a further reduction in the circulation speed to 0.3 1 / min. required. The total response time was 6 hours. The experiment could not be completed due to the high viscosity. The reaction product obtained was not sufficiently sulfochlorinated and was not suitable for the production of emulsifiable leather greasing agents

Example 2a

A mixture of 500 g soybean oil and 500 g C ₆ -C ₁₀ fatty acid methyl ester was in the apparatus described at a circulation rate of 1 l / min. 60 minutes at 25 ° C with 50 1 / h and 12.5 1 / h SO ₂ sulfochlorinated. The reaction was trouble-free without jamming.

• 1360 g Sulfochlorierungsprodukte, enthaltend 21,4 Gew.-% Chlor (48,4 % des Verbrauchs) 2,2 Gew.-% SO₂ (29,6 % des Verbrauchs)

The following were obtained:

• 1360 g of sulfochlorination products containing 21.4% by weight of chlorine (48.4% of consumption) 2.2% by weight of SO ₂ (29.6% of consumption)

Example 2b

For comparison, 1000 g of soybean oil were reacted as described in Example 2a without the addition of C -C - fatty acid methyl ester. Already 20 min. after the start of the sulfochlorination, there was build-up in the reaction column, which reduced the circulation speed to 0.75 l / min. force. The speed of circulation then had to be reduced several times, finally to 0.3 l / min. In order to achieve a reasonably adequate sulfochlorination, the entire reaction time had to be extended to 6 hours.

• 1326 g Sulfochlorierungsprodukt, enthaltend: 21,5 Gew.-% Chlor (48,1 % des Verbrauchs) 1,8 Gew.-% SO₂ (27,1 % des Verbrauchs)

The following were obtained:

• 1326 g of sulfochlorination product, containing: 21.5% by weight of chlorine (48.1% of consumption) 1.8% by weight of SO ₂ (27.1% of consumption)

Example 3

A mixture of 800 g of tallow and 200 g of mineral oil (boiling point 295 - 375 ° C) was as described in Example 1 at a circulation speed of 1.0 l / min. Reacted for 60 minutes at 25 ° C. with 50 l of chlorine. The mixture was then sulfochlorated at 60 ° C. for 3 hours while introducing 50 1 / h of chlorine and 12.5 1 / h of SO ₂ . The reaction went to the end without any disturbance.

• 1282 g Sulfochlorierungsprokukte, enthaltend 19,8 Gew.-% Chlor (47 % des Verbrauchs) 2,73 Gew.-% SO₂ (51,7% des Verbrauchs)

The following were obtained:

• 1282 g sulfochlorination products containing 19.8% by weight chlorine (47% of consumption) 2.73% by weight SO ₂ (51.7% of consumption)

Example 4

A mixture of 800 g of purified tallow and 200 g of tallow fatty acid methyl ester was reacted with 50 l of chlorine as described in Example 1 within one hour. The mixture was then sulfochlorinated at 55-60 ° C. for 3 hours while introducing 50 l / h of chlorine and 12.5 1 / h of SO. During the chlorination and sulfochlorination, the viscosity of the product in the reactor increased without, however, interfering with the course of the reaction.

• 1214 g Sulfochlorierungsprodukte, enthaltend 21,0 Gew.-% Chlor (3b % des Verbrauchs) 5,2 Gew.-% SO (51,5 des Verbrauchs)

The following were preserved:

• 1214 g of sulfochlorination products containing 21.0% by weight of chlorine (3b% of consumption) 5.2% by weight of SO (51.5 of consumption)

The saponification and neutralization of the products according to the above examples was carried out with about 30% NaOH. With the exception of Example 1 c, water-emulsifiable products were obtained in all cases, which could be used as leather greasing agents. The products of examples la, lb, 2a, 3 and 4 were distinguished by the fact that they gave the leathers treated with them a very pleasant, soft and slimy feel. In contrast, product 2b was somewhat dry to the touch.

Claims (8)

1. Fatliquor for leather and furs based on sulfonated chlorination products of natural or synthetic higher fatty acid triglycerides in the form of their alkali, ammonium or amine salts, characterized in that they consist essentially of those sulfonated chlorination products which have been obtained by sulfochlorination of optionally up to saturation of the double bonds of pre-chlorinated mixtures of higher C ₁₂ -C ₂₄ fatty acid triglycerides and C ₆ -C ₂₀ fatty acid esters of monohydric C ₁ -C ₃ alcohols or mineral oils with boiling points above 200 ° C in a weight ratio of 1: 0.2 - 1 , 2 using chlorine and SO ₂ , if appropriate with UV radiation, at 20-90 ° C. up to a content of SO ₂ Cl groups of 1–20 percent by weight, the ratio of chlorine atoms to SO Cl groups 0.7: 1 - 70: 1, and subsequent saponification. 2. Fatliquor according to claim 1, characterized in that the higher fatty acid triglycerides are naturally occurring fats and oils with a proportion of mono- or polyunsaturated fatty acids. 3. fatliquor according to claim 1 and 2, characterized in that the fatty acid ester. C ₆ -C ₁₀ fatty acid methyl ester mixture. 4. Fatliquor according to claim 1 and 2, characterized in that the fatty acid esters are a tallow fatty acid methyl ester mixture. 5. fatliquor according to claim 1 and 2, characterized in that the mineral oils consist essentially of Parafflischen proportions and boiling limits of about 250 - 410 ° C. 6. Fatliquor according to claim 1 and 2, characterized in that the ratio of the chlorine atoms to the SO ₂ Cl groups is 2: 1 to 20: 1. 7. Use of fatliquoring agents according to claims 1 to 6 in combination with conventional leather treatment agents and / or anionic, nonionic or cationic enulsifiers for the fatliquoring of leather and furs in the form of aqueous emulsions. 8. A process for the preparation of fatliquoring agents according to claims 1 to 6, characterized in that optionally up to higher C ₁₂ -C ₂₄ fatty acid triglycerides and C ₆ -C ₂₀ fatty acid esters monohydric C ₁ -C ₃ alcohols or mineral oils with boiling points above 200 ° C in a weight ratio of 1: 0.2-1.2 by means of chlorine and SO ₂ sulfochlorinated, optionally under UV radiation, at 20-90 ° C up to a content of organically bound chlorine of 5-30% by weight and a content of SO ₂ Cl groups from 1 to 20 percent by weight, the ratio of chlorine atoms to SO ₂ Cl groups being 0.7: 1 to 70: 1, and then saponified.