Classifications

• • C—CHEMISTRY; METALLURGY
  • C14—SKINS; HIDES; PELTS; LEATHER
  • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
  • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
  • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

• 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
• 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.
• 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.
• 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.
• 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.
• 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.
• the claimed products 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the viscosity of the product in the reactor increased without, however, interfering with the course of the reaction.
• 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Applications Claiming Priority (2)

Publications (2)

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Family Applications (1)

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Cited By (1)

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• 1983
  • 1983-10-03 DE DE19833335845 patent/DE3335845A1/de not_active Withdrawn
• 1984
  • 1984-09-24 EP EP84111354A patent/EP0136641A3/fr not_active Ceased
  • 1984-10-02 AR AR84298144A patent/AR241659A1/es active
  • 1984-10-02 ZA ZA847749A patent/ZA847749B/xx unknown
  • 1984-10-02 BR BR8404957A patent/BR8404957A/pt unknown

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