DE3335845A1 - LUBRICANT FOR LEATHER AND FUR - Google Patents

Description

_nn 3 HENKELKGaA

Henkelstrasse 67 ZR-FE / Patents

4ooo Düsseldorf, September 29, 1983

Dr. Bz / Im

Patent application D 6826

Fatliquor for leather and furs

DE-PS 22 45 077 discloses 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, which are characterized in that they are made from such sulfonated chlorination products consist, which by chlorination of higher fatty acids or of esters of higher fatty acids of chain lengths C "to C _? . up to a chlorine content of 20 to 45 percent by weight, the chlorination products essentially no longer containing any olefinic double bonds, and subsequent sulfonation with SCL up to a content of 40 to 100 mol percent SCu, based on the chlorination product, have been obtained.

DE-OS 3o 18 176 also discloses 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, which are characterized in that they are essentially composed of such sulfonated chlorination products exist, which by sulfochlorination of higher fatty acids or of esters of higher fatty acids of chain lengths C_ to C ₂₄ using chlorine and SO _2, possibly under UV radiation at 2o - 9o ° C up to a content of combined chlorine of 5'- 3o percent by weight and a content of SO ₂ Cl groups of 1 to 2o percent by weight, the ratio of chlorine atoms to S0 ₂ Cl groups being 0.7: 1 to 70: 1, and subsequent saponification have been obtained.

Patent application HENKEL KGaA

ZR-FE / patents

D 6826 -Jt-

It has now been found that the known processes for the preparation of such petting agents can be further improved, provided that higher fatty acid triglycerides are used as a starting point in the preparation of the sulfonated chlorination products. The sulfochlorination of fatty acid triglycerides is possible according to the known process. However, it is slowed down considerably in the course of the reaction due to the rapidly increasing viscosity of the reaction products and ultimately becomes uneconomical because chlorine and SOi no longer react sufficiently in the absence of adequate mixing. This disadvantage is remedied according to the invention characterized in that the higher fatty acid triglycerides C -C before sulfochlorination C, -C -Fett- · säureester monovalent C -C alcohols or mineral oils having boiling points above 200 ⁰ C in the weight ratio 1: 0.2 - 1.2 admixes. These esters or mineral oils act as viscosity-reducing diluents for the higher fatty acid triglycerides. Some of them are also reacted in the sulfochlorination reaction and do not need to be removed from the mixture after the reaction.

The invention thus relates to fatliquoring agents 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 such sulfonated chlorination products, which have been obtained by sulfochlorination of, if appropriate, to the saturation of the double bonds pre-chlorinated mixtures of higher C -C, fatty acid

Patent application HENKEL KGaA

ZR-FE / patents

D 6826 -JB-

triglycerlden and Cg-C ^ o-Fettsäureestern monovalent C ^ - -C alcohols or mineral oils having boiling points above 200 ⁰ C in a weight ratio of 1: 0.2 to 1.2 by means of chlorine and SCU, optionally under UV irradiation, at 20 -90 ⁰ C up to a content of organically bound chlorine of 5-30 percent by weight and a content of SO Cl groups of 1-20 percent by weight, the ratio of chlorine atoms to SOj Cl groups being 0.7: 1-70: 1 and subsequent saponification.

The invention also relates to a process for the production of such fatliquoring agents among those above specified conditions. The new process leads to a better utilization of the gases used, i. H. to lower consumption of chlorine and SCu. If the higher fatty acid triglycerides contain unsaturated fractions, it may be appropriate to first carry out a chlorination until the double bonds are saturated and only then then carry out the sulfochlorination.

In the production of the claimed fatliquoring agents, naturally occurring fats or are preferably used oils that may contain a proportion of monounsaturated or polyunsaturated fatty acids. Examples of this are coconut oil, soybean oil, palm kernel oil, cottonseed oil, rapeseed oil, Linseed oil, castor oil, sunflower oil, olive oil, neat oil, peanut oil, herring oil, cod oil, shark oil, whale oil, Tallow fats or lard. Appropriate synthetically produced triglycerides are also used as starting materials into consideration.

Patent application, HENKEL KGaA

• ZR-FE / patents

D 6826

The C -C fatty acid esters are monohydric C -C alcohols

6 20 13

the methyl, ethyl, propyl and isopropyl esters of the respective Fatty acids, e.g. B. the "methyl ester forerun" designated C -C fatty acid methyl ester mixture, or TaIg-

6 10
fatty acid methyl ester into consideration.

Suitable mineral oils are paraffin consisting of copolyamide in essential oils having boiling points above 200 ⁰ C, the boiling range, preferably at about 250 - 410 ⁰ C lie.

The mixtures of fatty acid triglycerides and fatty acid esters or mineral oils are made in a manner known per se sulfochlorinated by the simultaneous introduction of Cl and

SO in a molar ratio of 85: 1 to 1.4: 1. The reaction 2

Sd 23OM38539 4 04 83

Patent application D6826 ~ ß ~ HENKELKGaA

ZR-FE / patents

temperature is 20-90 ⁰ C, and optionally by cooling at the desired level. A reaction temperature of 40-75 ° C. is preferred. Irradiation with UV light (mercury vapor lamp) promotes the course of the reaction. The reaction is complete after about 2-10 hours, after which time 5-30% by weight of chlorine and 1-20% by weight of SO — Cl groups have been added on. The ratio of chlorine atoms to ί GOjCl groups is 0.7: 1 to 70: 1. The subsequent saponification is carried out with an aqueous, approximately 30% sodium or potassium hydroxide solution at approximately 50 ° C carried out, the neutralization takes place either with an excess of the same alkali metal hydroxide or with 'ammonia solution or with an aliphatic or cyclo-, aliphatic amine or an alkanolamine of chain lengths Cp to C, -, or triethanolamine. Liquid, highly concentrated, water-emulpable products are obtained with excellent oxidation, light and acid stability, which are ideally suited for the fatliquoring of all light-colored, pastel-colored and white leathers as well as for the fatliquoring of valuable and sensitive furs.

If dark-colored or more unsaturated raw materials are used, the sulfochlorination products may be bleached recommend. This is usually achieved by adding small amounts of about 0.5 to 5%, preferably 1 to 4 2 ILO carried out to the acidic sulfochlorination product, the temperatures between 20 and 80, preferably between 40 and 60 ° C. By this measure, dark-colored sulfochlorination products can also be removed can be brightened very largely.

Patent application D6826 - / 6 - HENKELKGaA

ZR-FE / patents

The products are used in the customary manner in the form of aqueous emulsions for licking leather or for treating fur. The products are self-emulsifying, so that further emulsifiers are generally not necessary. To achieve special effects, the sulfochlorination 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, neat oil and the like or synthetic fatliquors such as chlorinated paraffins, paraffinsulfonates, 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 with higher fatty alcohols, alkylphenols or fatty amines with chain lengths of C ₁₀ to C ₂₀ . A stabilization of the products can be achieved by rendering any existing or newly formed hydrogen chloride residues harmless by means of epoxy compounds in amounts of 0.5 to 5 percent by weight. Examples include: glycide, epichlorohydrin, glycidyl ethers of mono- or polyhydric alcohols, such as glycol, glycerol or sorbitol, and epoxidized fatty substances, e.g. B. epoxy soybean oil, linseed oil or oleic acid butyl ester.

The products are well absorbed by leather and give excellent fatliquoring and softening effects have a remarkable resistance to water and aqueous or organic detergent solutions. Your tendency to wander under thermal stress is very low, so that z. B. Adhesion

Sd 230/438539 4 04 83

Patent application HENKEL KGaA

O ZR-FE / patents

D 6826 -ST-

or let the vulcanization of rubber soles on shoe uppers be carried out without difficulty. Particularly What should be emphasized is the good light, oxidation and acid resistance of the products that they are used for Suitable for petting sensitive and light-colored leathers and furs do. The treated leather or furs are characterized by a particularly pleasant soft and greasy handle and a beautiful shine of the fur hair.

There are advantages over the sulfochlorination products of higher fatty acid triglycerides in DE-OS 30 18 176 in particular that the claimed products have a lower viscosity and are more homogeneous are. They can therefore be emulsified more easily and result in more uniform and more stable emulsions, which is why they can also be added directly to the liquor bath. As a result of the increased penetration into the The leather layer results in improved deep fatigue, which results in softer and more flexible leather and furs will.

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

Patent application D 6826-4 ? - HENKELKGaA

ZR-FE / patents

A reactor tower stands on a 2 l round bottom flask with a bottom drain made of glass, which is filled with Raschig rings and a double jacket for a heating or cooling liquid owns.

The feed is drawn through the bottom drain of the round bottom flask pumped by means of a peristaltic pump through a heated 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 Do-. sizing is carried out by means of rotameters. The flow velocity of the gases is between 25 and i2o l / h for chlorine and between k and 50 i / _{n for SO 2} .

The resulting HCl gas is not converted with the rest of the Starting gases taken from the top of the reaction tube via a washing bottle system. The glass reaction column can be irradiated from the outside with a mercury vapor lamp will.

Sd2M / 438S39 4 04 83

Patent application D6826 - 9} - / f / HENKELKGaA

* 7D.CC/Dof saidnte

ZR-FE / patents

Example 1 a

A mixture of 800 g of tallow and 200 g of Cg-C _1Q fatty acid methyl ester ("methyl ester forerun") was pumped around in the apparatus described at a rate of 1 l / min and 50 l of chlorine at 40 ^° C. over the course of about one hour initiated, which rose towards the substrate flowing under in the trickle tower. After the chlorination had ended (about 45 minutes), the mixture was sulfochlorinated for 3 hours with 50 l / h of chlorine and 12.5 l / h of SO ^{2 under UV radiation at 50-55 ° C.} The implementation went smoothly. A build-up of congestion in the reaction tower as a result of an increase in viscosity was not observed. The circulation rate could be maintained until the end of the reaction.

The following were obtained: ''

1338 g of sulfochlorination product containing

20.7 wt. 55 chlorine (48.8 % of consumption) 4.7 wt. 55 SO ₂ (65.4 % of consumption)

Example Ib ■

A mixture of 600 g of tallow and 400 g of Cg-C ^ fatty acid methyl ester j was implemented as described in Example la. The reaction went! without interference.

The following were obtained:

1252 g of sulfochlorination product containing

18.8% by weight of chlorine (42.2% of consumption) 3.5% by weight of SO ₂ (46.ο % of consumption)

Patent application HENKEL KGaA

! y ^ ZR-FE / Patents

D 6826 - yd Example Ic

For comparison, 1000 g of tallow were _{reacted without the addition of Cg-C 10} fatty acid methyl ester in the manner described in Example 1a, the introduction of chlorine being carried out at a rate of 1 l / min. After a reaction time of 45 minutes, congestion occurred in the packed column as a result of the increase in viscosity, so that the circulation rate had to be reduced to 0.75 l / min. After heating to 60 ^° C., sulfochlorination was carried out under UV irradiation, as indicated in Example 1a. As early as 10 minutes after the start of the sulfochlorination, congestion occurred again, which is why the circulation speed had to be reduced to 0.5 l / min.

After a further 2 hours, the circulation speed had to be reduced further to 0.3 l / min. the total reaction time was 6 hours. The experiment could not end because of the high viscosity be guided. The reaction product obtained was found to be insufficiently sulfochlorinated and suitable not suitable for the production of emulsifiable leather fatliquors

Example 2a

A mixture of 500 g of soybean oil and 500 g of Ci - C ₁ Q fatty acid methyl ester was in the described apparatus at a speed of 1 l / min. 60 minutes at 25 ° C with 50 l / h and 12.5 l / h SO., Sulfochlorinated. The reaction proceeded without any problems and without obscuration.

Sd 230 / -433539 4 04 83

Patent application HENKEL KGaA

/ Ζ ZR-FE / Patents

D 6826-3 »The following were obtained:

Containing 1360 g of sulfochlorination products

21.4 wt -.% Of chlorine (48.4% of consumption) 2.2 wt .-% Sa (29.6% of consumption)

Example 2b

For comparison, 1000 g of soybean oil without the addition of C-C-

-Fatty acid methyl ester implemented as described in Example 2a. Already 20 minutes after the sulfochlorination began there was a build-up of congestion in the reaction column, which led to a reduction in the circulation speed to 0.75 l / min, force. The orbital speed then had to be several times be reduced, finally down to 0.3 l / min. To achieve a reasonably adequate sulfochlorination, the total reaction time had to be extended to 6 hours.

The following were obtained:

1326 g sulfochlorination product, containing:

21.5 GeWw-JK Chlor (48.1 % of consumption)

1.8 wt -.% SO ₂ (27.1% of consumption)

Patent application HENKEL KGaA

ZR-FE / patents

D 6826

Example 3

A mixture of 800 g of tallow and 200 g of mineral oil (boiling point 295-375 ° C.) was prepared as described in Example 1 at a speed of 1.0 l / min. Reacted with 50 liters of chlorine at 25 ° C. for 60 minutes. Thereafter, sulfochlorination was carried out at 60 ^° C. for 3 hours while introducing 50 l / h of chlorine and 12.5 l / h of SO _2. The reaction went without. Disturbance to the end.

The following were obtained:

1282 g SuIfochlorierungsprokukte containing 19.8 wt -.% Of chlorine (47% of consumption) 2.73 wt -.% SO (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 within one hour as described in Example 1. 60 ⁰ C sulfochlorinated 3 hours under introduction of 50 l / h of chlorine and 12.5 l / h SO ₅ - thereafter at 55 was. During the chlorination and sulfochlorination, the viscosity of the product in the reactor increased without, however, interfering with the course of the reaction.

The following were obtained:

1214 g SuIfochlorierungsprodukte containing 21.0 wt -.% Of chlorine (36% of consumption) 5.2 wt .-% SO ₂ (51.5 consumption)

Sd 230/438539 4 04 83

Patent application HENKEL KGaA

ZR-FE / patents

D 6826

The saponification and neutralization of the products according to the above examples took place with about 30% strength NaOH. With the exception of Example 1c, water-emulsifiable products were found in all cases Obtain products that could be used as leather oiling agents. The Products of Examples la, Ib, 2a, 3 and 4 in that they give the leather treated therewith a very pleasant, soft and musky handle conferred. In contrast, product 2b was somewhat dry to the touch.

Claims (8)

Patent application HENKEL KGaA ZR-FE / Patents D 6826 patent claims 1. Fatliquor for leather and fur 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 sulfonating optionally up to saturation of the double bonds pre-chlorinated mixtures of higher C ₁₂ -C ₂ I -fatty acid triglycerides and Cj- -C _pf v fatty acid esters einwer tiger C -C alcohols or mineral oils having boiling points above 200 ⁰ C in a weight ratio of 1: 0.2-1.2 by means of chlorine and SO, optionally under UV irradiation, at 20-90 ⁰ C to a content of SO ₂ Cl -Groups of 1-20 percent by weight, the ratio of chlorine atoms to SO Cl groups being 0.7: 1-70: 1, and subsequent saponification. 2. Fatting agent 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 are. 3. Fatting agent according to claim 1 and 2, characterized in that the fatty acid ester is called a "methyl ester forerun" designated C-C fatty acid methyl ester mixture. Patent application HENKEL KGaA 9. ZR-FE / Patents D 6826 4. Fatliquor according to Claim 1 and 2, characterized in that that the fatty acid esters are a mixture of tallow fatty acid methyl esters " 5 x fatliquoring agent as claimed in claim 1 and 2, characterized in that the mineral oils consist essentially ausparaffinischen proportions and have boiling range of about 250 410 ⁰ C. 6. Fatting agent according to claim 1 and 2, characterized in that the ratio of the chlorine atoms to the SCl 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 emulsifiers for greasing leather and furs in the form of watery emusions. 8. A process for the production of fatliquors according to claims 1 to 6, characterized in that optionally up to the higher C -C fatty acid triglycerides and C £ -C fatty acid esters of monohydric C -C "alcohols or mineral oils with boiling points above 200 ⁰ C im Weight ratio 1: 0.2-1.2 sulfochlorinated by means of chlorine and SO, optionally under UV radiation, at 20-90 ° C up to a content of organically bound chlorine of 5-30 percent by weight and a content of SO Cl groups of 1-20 percent by weight, the ratio of chlorine atoms to SO.Cl groups being 0.7: 1 to 70: 1, and subsequently saponified. Sd 230 «38539 4 04 83