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

Definitions

• the present invention relates to a process for the aftertreatment of tanned leather and furs, the agent used for this process, a process for producing this agent and the leather or fur material aftertreated by the present process.
• the polymers according to the invention are new.
• the invention also relates to the new polymers, in particular within the scope of the preferred embodiment mentioned above.
• monethylenically unsaturated polymerizable dicarboxylic anhydride there are e.g. Maleic anhydride, citraconic anhydride, methylene malonic anhydride and mixtures of these compounds. Of the anhydrides mentioned, maleic anhydride is preferably used.
• Suitable C1-C30 alcohols as component (b1) are e.g. Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, cyclohexanol, n-hexanol, onanthal alcohol, n-octanol, 2-ethyl hexanol, pelargon alcohol, decanol, dodecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, Arachidyl alcohol, behenyl alcohol, ceryl alcohol, cerotyl alcohol, myricyl alcohol, C9-C11 oxo alcohol, tridecyl alcohol, isotridecanol or mixtures of linear primary alcohols (®Alfole) with 8 to 18 carbon atoms.
• Some representatives of these alfoles are Alfol (8-10), Alfol (9-11
• a cetyl / oleyl alcohol mixture is preferably used as component (b 1).
• Preferred compounds for the optional partial amidation with amines are ammonia, mono- or di-C1-C5-alkylamine, phenyl-C1-C5-alkylamine, mono- or di-C5-C7-cycloalkylamine or morpholine.
• C1-C5-alkylamines used are monomethyl, dimethyl, monoethyl, diethyl, mono-n-propyl, di-n-propyl, monoisopropyl, diisopropyl, mono-n-butyl, di -n-butyl, mono-sec-butyl, di-sec-butyl, mono-tert. Butyl, di-tert.
• Ammonia and morpholine are very particularly preferred.
• Suitable unsaturated or saturated C8-C22 fatty acids which can be considered as component ( ⁇ ) are e.g. Caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, oleic, linoleic, linolenic, arachidonic or coconut fatty acids or the decene, dodecene, teradecene, hexadecene - or ricinoleic acid.
• An example of the adduct of a fatty acid with an alkylene oxide is the adduct of 2 to 15 moles of ethylene oxide and 1 mole of a C8-C22 fatty acid.
• Reaction products of fatty amines and ethylene oxide or propylene oxide such as e.g. Fatty acid alkanolamides with 8 to 22 carbon atoms in the fatty acid residue and 2 to 18 carbon atoms in the alkanol residue.
• Fatty acid alkanolamides with 8 to 22 carbon atoms in the fatty acid residue and 2 to 18 carbon atoms in the alkanol residue.
• This is e.g. to fatty acid-alkanolamine reaction products which are prepared from C8-C22 fatty acids, preferably C8-C18 fatty acids and C2-C6-alkanolamines such as ethanolamine, diethanolamine, isopropanolamine or diisopropanolamine, diethanolamine being preferred.
• C8-C18 fatty acid diethanolamides are particularly preferred.
• Preferred examples of such reaction products are the coconut fatty acid diethanolamide and the lauric acid or stearic acid diethanolamide.
• Preferred compounds which can be considered as component ( ⁇ ) are C8-C22 fatty acids.
• Aqueous bases for partial neutralization and hydrolysis are, in particular, aqueous solutions of NaOH or KOH (sodium hydroxide solution, potassium hydroxide solution), but also aqueous solutions of amines, such as e.g. Ammonia.
• polymers are used in which e.g. 5 to 40, preferably 25 to 35%, based on the amounts of monomers, are esterified and / or amidated.
• the process according to the invention is suitable for the aftertreatment of all customary tanned leather hides, in particular hides tanned with mineral tanning agents, such as chromium III salts. These are usually deacidified before the aftertreatment. They can be colored before the aftertreatment. However, coloring can also take place only after the aftertreatment carried out according to the invention.
• mineral tanning agents such as chromium III salts.
• the tanned and optionally colored skins are expediently mixed with the aqueous polymer solution in an aqueous liquor, which can be obtained by diluting the polymer solution with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 ° to 50 °, preferably 30 to 50 ° C for a period of 0.1 to 5, preferably 0.2 to 2 hours, aftertreated.
• This aftertreatment is carried out, for example, by milling in a barrel.
• the required amount of polymer solution, based on the shaved weight of the leather or the wet weight of the fur skins is 0.1 to 30, preferably 1 to 20,% by weight.
• the fleet length i.e. the percentage weight ratio of the aftertreatment liquor to the goods, based on the shaved weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.
• the pH of the liquor is adjusted to a pH of 3 to 5, preferably 3.5 to 4 by adding acids, preferably organic acids such as formic acid, and the leather is finished in the customary manner .
• the leather or furs aftertreated by the process according to the invention are distinguished by a good fullness and an exceptionally smooth feel.
• the polymerization of the ethylenically unsaturated anhydrides is carried out according to known batch or continuous processes, such as bulk, suspension, precipitation and solvent polymerization.
• the monomeric ethylenically unsaturated dicarboxylic anhydrides serving as starting compounds are preferably used as uniform compounds in technical purity. Mixtures of different dicarboxylic acid anhydrides can also be used, so that copolymers are formed. The homopolymers are preferred.
• the polymerization of the anhydrides is e.g. at temperatures of 80 to 300, preferably 120 to 200 ° C, the lowest polymerization temperature to be selected is preferably about at least 20 ° C above the glass transition temperature of the polymer formed.
• the polymerization conditions are chosen. Polymerization at a higher temperature results in polymers with a low molecular weight, while polymers with a higher molecular weight are formed at low polymerization temperatures.
• the conditions for the composition according to the invention are selected such that polymers with molar masses of 500 to 30,000 g per mol, preferably 500 to 2000 g per mol, are formed.
• a simple method for the preparation of the polymers is precipitation polymerization.
• This method uses solvents in which the monomers are soluble and the polymer formed is insoluble and precipitates.
• solvents are e.g. aromatic compounds, preferably toluene, xylene, benzene or cumene and their mixtures with one another.
• the preferred method is solvent polymerization. It is carried out in solvents in which both the monomers and the polymers formed are soluble. All solvents which meet these conditions and are inert to the acid anhydrides are suitable for this, such as Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and aliphatic hydrocarbons such as n-octane, isooctane, cyclohexane or methylcyclohexane.
• polymerization is carried out with the aid of compounds which decompose into free radicals, such as, for example, peroxides, hydroperoxides, redox initiators and azo compounds.
• Suitable polymerization initiators are, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, tertiary butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvalerionitrile), tertiary-butylpermalobitrile (2,2'-bis-azalobitrate), (tertiary-butylperoxy) cyclohexane, tertiary-butylperoxyisopropyl carbonate, tertiary-butylperacetate, di-tertiary-butylperoxide, di-tertiaryamyl
• the reaction is carried out in an inert atmosphere, preferably in the absence of oxygen, in particular in an inert gas stream such as Nitrogen or argon.
• an inert gas stream such as Nitrogen or argon.
• the usual equipment is used for all polymerization reactions, e.g. Autoclaves and kettles equipped with, for example, anchor, blade, impeller or multi-stage impulse countercurrent stirrers.
• the polymers obtainable in this way are then partially esterified and hydrolyzed in a next reaction step, so that the anhydride groups are converted into carboxyl groups. It is also possible to hydrolyze the polymers containing anhydride groups first, so that all of the anhydride groups are in the form of carboxyl groups, and then to carry out the esterification by known methods. However, the procedure is preferred in which the carboxylic anhydride groups of the polymer are first partially esterified.
• the partial esterification can in the presence of solvents which are inert to the anhydride groups and dissolve or swell both the starting materials and the esterified copolymers, e.g. Toluene, xylene, ethylene benzene, aliphatic hydrocarbons and ketones such as acetone and methyl ketone can be carried out.
• solvents which are inert to the anhydride groups and dissolve or swell both the starting materials and the esterified copolymers, e.g. Toluene, xylene, ethylene benzene, aliphatic hydrocarbons and ketones such as acetone and methyl ketone can be carried out.
• the proportions of the reactants are chosen so that only a partial esterification of the anhydride groups occurs.
• Based on the hydrolyzed partially esterified polymer 5 to 75, preferably 5 to 50% of the carboxyl groups are esterified.
• the esterification itself is usually carried out at higher temperatures,
• esterification reaction is complete after about 0.5 to 20, preferably 1 to 10 hours.
• solvents are removed from the reaction mixture, e.g. by distillation, if appropriate under reduced pressure, and the remaining partially esterified polymers are dissolved in water with the addition of alkalis.
• alkalis are e.g. Sodium hydroxide solution, potassium hydroxide solution, ammonia, amines and alkanolamines.
• the pH of the aqueous, partially esterified polymer solution thus obtained is 4 to 10, preferably 6 to 8.
• Example 1 240 g of maleic anhydride and 240 g of technical xylene are placed in a polymerization reactor provided with stirrer, cooler, nitrogen inlet and outlet and with metering devices and heated to about 140 ° C. until boiling. 80 g of di-tert are added to the low-boiling solution within 2 hours. Butyl peroxide and the reaction mixture is heated for 2 hours after addition of the initiator with stirring and reflux, 2 phases forming. The polymer thus produced with a molar mass of approximately 4000 g per mol is then partially esterified with 230 g of a cetyl / oleyl alcohol mixture in the presence of 1 g of p-toluenesulfonic acid at 130 ° C. within 2 hours with stirring. The remaining xylene is distilled off under reduced pressure.
• the reaction mixture is cooled to a temperature of 100 ° C and, by simultaneously adding 384 ml of water and 180 g of 30% aqueous sodium hydroxide solution, processed into a stable, yellowish emulsion which has a solids content of approx. 55% and a pH of 6 , 8 has. Approx. 45 mol% of the total carboxyl groups resulting from the anhydride groups have been esterified and approximately 55 mol% have been neutralized.
• Example 2 560 g of the polymer prepared in Example 1 in xylene are mixed with 200 g of a cetyl / oleyl alcohol mixture and 200 g of an adduct of 6 moles of ethylene oxide with 1 mole of a C16 / C18 oxo alcohol in the presence of 2 g of p-toluenesulfonic acid within 3 Partially esterified for hours at 130 ° C. The remaining xylene is distilled off under reduced pressure. The reaction mixture is cooled to a temperature of 100 ° C. and processed into a low-viscosity emulsion by simultaneously adding 800 ml of water and 106 g of 30% strength aqueous sodium hydroxide solution. The pale yellowish emulsion thus obtained has a solids content of approximately 40% and a pH of 6.8.
• Example 3 560 g of the polymer prepared in Example 1 in xylene are partially esterified with 192 g of a cetyl / oleyl alcohol mixture in the presence of 1 g of p-toluenesulfonic acid within 2 hours with stirring. The remaining xylene is distilled off under reduced pressure. 161 g of morpholine are then added over the course of half an hour and the reaction mixture is heated to a temperature of 130 ° C. within 2 hours with stirring. Thereby, further, still existing anhydride groups of the copolymer converted into monoamide groups. The reaction mixture is cooled to 80 ° C.
• EXAMPLE 5 If the procedure is as described in Example 1, but instead of 230 g of the cetyl / oleyl alcohol mixture, 1505 g of the cetyl / oleyl alcohol mixture and 92 g of laurylamine are used, a dispersion which is viscous at room temperature and has a solids content of about 55% is obtained. .
• EXAMPLE 6 If the procedure is as described in Example 1, but instead of 230 g of the cetyl / oleyl alcohol mixture, 250 g of the adduct of 8 mol of ethylene oxide and 1 mol of stearic acid are used, a dispersion which is viscous at room temperature and has a solids content of approx. 52 is obtained %.
• EXAMPLE 7 If the procedure is as described in Example 1, but instead of 230 g of the cetyl / oleyl alcohol mixture, 240 g of the adduct of 4 moles of ethylene oxide and 1 mole of oleylamine are used, a dispersion which is viscous at room temperature and has a solids content of about 50 is obtained %.
• EXAMPLE 8 If the procedure is as described in Example 1, but 230 g of the adduct of 6 mol of ethylene oxide and 1 mol of lauric acid amide are used instead of 230 g of the cetyl / oleyl alcohol mixture, a dispersion which is viscous at room temperature and has a solids content of approximately 49 is obtained %.
• Example 9 Chrome-tanned, to a pH value of 5.2 deacidified leather had a shaved thickness of 1.8 mm is in a conventional manner with 1%, based on the weight of the leather, the dye of the formula colored. The leather is then aftertreated with 8% of the product produced according to Example 1, based on the shaved weight. The total fleet length is 100%. Then it is adjusted to a pH of 3.8 with formic acid. The leather is then washed, mechanically stretched and dried.
• the leather obtained is very soft, supple to the touch and shows a brilliant and level coloring.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1993
  • 1993-06-01 EP EP93810396A patent/EP0574351B1/fr not_active Expired - Lifetime
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• 1994
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