EP0418661B1 - Use of copolymerisates based on long chain unsaturated esters and ethylenically unsaturated carbonic acids for hydrophobing of leather and fur pelts - Google Patents

Use of copolymerisates based on long chain unsaturated esters and ethylenically unsaturated carbonic acids for hydrophobing of leather and fur pelts Download PDF

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Publication number
EP0418661B1
EP0418661B1 EP90117145A EP90117145A EP0418661B1 EP 0418661 B1 EP0418661 B1 EP 0418661B1 EP 90117145 A EP90117145 A EP 90117145A EP 90117145 A EP90117145 A EP 90117145A EP 0418661 B1 EP0418661 B1 EP 0418661B1
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copolymers
monoethylenically unsaturated
carboxylic acids
acid
copolymer
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German (de)
French (fr)
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EP0418661A1 (en
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Ortwin Dr. Schaffer
Herbert Dr. Bay
Karl Dr. Stork
Norbert Dr. Greif
Knut Dr. Oppenlaender
Walter Denzinger
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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    • 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

  • aqueous polyacrylate dispersions in which the copolymer is predominantly composed of acrylic or methacrylic acid esters of alcohols having 1 to 8 carbon atoms for dressing leather is known from DE-OS 33 44 354 and EP-PS 0 065 253 known.
  • emulsifiers are always required to prepare the aqueous polymer dispersions.
  • the present invention has for its object to provide emulsifier-free agents for the hydrophobization of leather and fur.
  • the copolymers are known for example from DE-OS 38 17 000. They are prepared by copolymerizing the group a) monomers with the group b) monomers. If monoethylenically unsaturated dicarboxylic acid anhydrides are used as monomers of group b) and the copolymerization is carried out with the exclusion of water, the anhydride groups contained in the copolymer are solvolysed after the copolymerization. The solvolysis of the anhydride groups of the copolymers can simultaneously be combined with a partial or complete neutralization of the carboxyl groups by treating the copolymers with bases. If ammonia, primary or secondary amines are used as bases, the copolymers can also be partially amidated.
  • Suitable monomers of group a) for the preparation of the copolymers are C8 to C40 alkyl acrylates and C8 to C40 alkyl methacrylates.
  • Suitable compounds of this type are, for example, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-decyl acrylate, n-decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, isotridecyl acrylate, isotridecyl methacrylate, tetradecyl acrylate, cetyl C-acrylate, C1-methacrylate, C1-methacrylate Palmityl acrylate, palmityl methacrylate, n-eicosyl acrylate, n-eicosyl methacrylate, n-docosyl acrylate, n-docosyl methacrylate, tetracosyl acrylate,
  • acrylates are also suitable. Such mixtures can be prepared, for example, by esterifying alcohols, either using the oxo process or are available using the Ziegler process.
  • the acrylic acid esters and methacrylic acid esters derived from alcohols having 16 to 28 carbon atoms are preferably used.
  • component a) are vinyl esters of carboxylic acids having 8 to 40 carbon atoms.
  • examples of such compounds are vinyl 2-ethylhexanoate, vinyl laurate, vinyl palmitate, vinyl tallow fatty acid esters, vinyl myristate, vinyl stearate, vinyl oleate and mixtures of the vinyl esters mentioned or mixtures of at least one vinyl ester with at least one of the alkyl (meth) acrylates in question.
  • the monomers of group a) are present in the copolymers in amounts of 50 to 90, preferably 65 to 85% by weight in copolymerized form.
  • the monomers of group b) include monoethylenically unsaturated C3 to C12 carboxylic acids and monoethylenically unsaturated dicarboxylic anhydrides.
  • Suitable monoethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, vinyl lactic acid, allylacetic acid, propylidene acetic acid, ethyl acrylic acid, dimethylacrylic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, methylene malonic acid, citric acid and tetrahydrophthalic acid.
  • Examples of ethylenically unsaturated dicarboxylic acid anhydrides which contain a total of 4 to 12 carbon atoms per molecule, are maleic anhydride, itaconic anhydride, citric acid anhydride, methylene malonic acid anhydride and tetrahydrophthalic anhydride.
  • monomers of group b) are monoesters of dicarboxylic acids and alcohols with 1 to 40 carbon atoms, for example monomethyl maleate, monobutyl maleate, monododecyl maleate, monooctadecyl maleate, monotetracosyl maleate, monooctadecyl fumarate, monooctadecohexyl compounds and monoethyl hexacetate compounds, monohexadecyl hexaconate compounds,.
  • acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride are preferred.
  • the group b) monomers also include amides of monoethylenically unsaturated monocarboxylic acids and the half-amides of monoethylenically unsaturated dicarboxylic acids, e.g. Amides and half-amides, each derived from the underlying carboxylic acids and ammonia or amines having 1 to 40 carbon atoms, for example N-isotridecylacrylamide, N-di- (isotridecyl) acrylamide, N-stearylacrylamide, N-stearylmethacrylamide, maleic acid monoisotridecylamide, maleic acid diisotridecylamide , Maleic acid monostearylamide and maleic acid distearylamide.
  • amides of monoethylenically unsaturated monocarboxylic acids and the half-amides of monoethylenically unsaturated dicarboxylic acids e.g. Amides and half-amides, each derived from the underlying
  • the copolymers contain the monomers of group b) in amounts of 10 to 50, preferably 15 to 35,% by weight.
  • the copolymers from the monomers of group a) and b) can optionally also be modified by copolymerization in the presence of monomers from group c).
  • the monomers of group c) include, for example, styrene, methylstyrene, ethylstyrene, butylstyrene, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, methyl acrylate , ethyl acrylate, propyl acrylate, butyl acrylate, Acrylklarehexylester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Methacrylklahexylester, hydroxyethyl acrylate, hydroxypropyl acrylate
  • the copolymerization of the monomers of groups a) and b) and optionally c) takes place by all known batch or continuous polymerization processes, such as bulk, suspension, precipitation and solution polymerization.
  • the copolymerization is preferably carried out in the presence of radical-forming compounds. Up to 10, preferably 0.2 to 5% by weight, based on the monomers used in the copolymerization, are required. All of the polymerization processes mentioned are carried out in the absence of oxygen, preferably in a stream of nitrogen.
  • the usual equipment is used, for example autoclaves and boilers, which are equipped, for example, with anchor, blade, impeller or multi-stage impulse countercurrent stirrers.
  • Bulk polymerization of the monomers of groups (a) and (b) is particularly preferred. It is carried out at temperatures from 80 to 300, preferably from 120 to 200 ° C., the lowest polymerization temperature to be chosen preferably being at least about 20 ° C. above the glass transition temperature of the polymer formed. Depending on the molecular weight that the copolymers should have, the polymerization conditions are chosen. Polymerization at high temperatures produces copolymers with low molecular weights, while polymers with higher molecular weights are formed at lower polymerization temperatures. The amount of the polymerization initiator also has an influence on the molecular weight.
  • the monomers (a) and (b) can be copolymerized at temperatures above 200 ° C even in the absence of polymerization initiators, ie the use of initiators is not absolutely necessary because the monomers (a) and (b) at temperatures above 200 ° C free-radically polymerize even in the absence of initiators.
  • Suitable polymerization initiators are, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexylperoxidicarbonat, tertiary-butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), tertiary-butyl perpivalate, tertiary-butyl-2-ethyl- hexanoate, tertiary-butyl permaleinate, 2,2'-azobis (isobutyronitrile), bis- (tertiary-butylperoxy) cyclohexane, tertiary-butylperoxyisopropyl carbonate, tertiary-butylperacetate, di-tertiary-butylperoxide, diterti
  • the initiators can be used alone or as a mixture with one another. In bulk polymerization, they are preferably introduced into the polymerization reactor separately or in the form of a solution or dispersion in the monomer of component (a).
  • Redox coinitiators can of course also be used in the copolymerization, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium.
  • the use of redox coinitiators allows the polymerization to be carried out at a lower temperature.
  • the amounts of redox coinitiators usually used are about 0.1 to 2000, preferably 0.1 to 1000 ppm, based on the amounts of monomers used.
  • regulators In order to produce low molecular weight polymers, it is often expedient to carry out the copolymerization in the presence of regulators.
  • Common controllers can be used for this, e.g. C1 to C4 aldehydes, allyl alcohol, buten-1-ol-3, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-dodecyl mercaptan and tertiary dodecyl mercaptan .
  • the polymerization regulators are generally used in amounts of 0.1 to 10% by weight, based on the monomers.
  • a pressure vessel with a downstream reaction tube which is provided with a static mixer, can be used with particular advantage.
  • the monomers are preferably polymerized from (meth) acrylic esters, vinyl esters and monoethylenically unsaturated compounds containing acid groups in at least 2 polymerization zones connected in series.
  • One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%.
  • a copolymer of stearyl acrylate and acrylic acid can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a cascade of stirred tanks, and the reaction product after a residence time of 2 to 60, preferably 5 to 30 Minutes, continuously discharged from the reaction zone at temperatures between 200 and 400 ° C.
  • the polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar.
  • the copolymers obtained with solids contents of over 99% can then be further converted to the corresponding alkali and alkaline earth metal salts or amides and ammonium salts.
  • Another preferred embodiment for the preparation of the copolymers is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents that meet this requirement and that do not react with the monomers are suitable for this. For example, these are acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, aliphatic, cycloaliphatic and aromatic hydrocarbons such as n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane, xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane being particularly suitable for achieving low mole
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvents and (meth) acrylic esters or vinyl esters can also be placed in the polymerization reactor and then, after the polymerization temperature has been reached, the monomer containing acid groups, if appropriate dissolved in the solvent, and the initiator, and, if appropriate, coinitiator and regulator, can be metered in.
  • concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 and 70% by weight.
  • the solid copolymer can easily be isolated by evaporating the solvent.
  • Another method for the simple preparation of the copolymers is precipitation polymerization.
  • solvents are used in which the monomers are soluble and the copolymer formed is insoluble and fails.
  • solvents are ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another.
  • ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another.
  • Suitable protective colloids are polymeric substances which are readily soluble in the solvents and which do not react with the monomers.
  • Suitable are, for example, copolymers of maleic anhydride with vinyl alkyl ethers and / or olefins with 8 to 20 carbon atoms, and corresponding copolymers of the monoesters of maleic acid with C10 to C20 alcohols or the mono- and diamides of maleic acid with C10- to C20-alkylamines and polyalkyl vinyl ethers , whose alkyl group contains 1 to 20 carbon atoms, such as polymethyl, polyethyl, polyisobutyl and polyoctadecyl vinyl ether.
  • the amounts of protective colloid added are usually 0.05 to 4% by weight (based on the monomers used), preferably 0.1 to 2% by weight, it often being advantageous to combine several protective colloids.
  • the feed times for the monomer and initiator are generally between 1 and 10 hours, preferably 2 and 5 hours. It is also possible to initially charge all the starting materials in a reactor and to polymerize them, however, heat dissipation problems may occur, making such an operation less convenient.
  • the concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 to 70% by weight.
  • the polymers can be isolated from the polymer suspensions, for example by distilling off the suspension medium of the polymer suspensions in evaporators, for example belt dryers, paddle dryers, spray dryers and fluidized bed dryers.
  • the monomers of groups a) and b) and, if appropriate, c) are copolymerized in accordance with the above-described processes in such a way that copolymers with molar masses of 500 to 30,000, preferably 1,000 to 20,000 g, per mol are retained.
  • Copolymers of stearyl acrylate and maleic anhydride or maleic acid preferably contain the monomers copolymerized in a molar ratio of 1: 1.
  • copolymers obtained in the polymerization processes described above are initially largely freed of volatile components for the preparation of ready-to-use aqueous preparation solutions or aqueous dispersions.
  • the copolymers are preferably heated to temperatures of up to 150 ° C. under reduced pressure. Volatile components distilled off under these conditions.
  • a low-boiling regulator can be removed from copolymers that are produced by bulk polymerization.
  • the solvent used in the polymerization is advantageously distilled off before the preparation of aqueous preparation solutions.
  • Copolymers containing maleic anhydride groups can, however, be converted into the corresponding half-amide groups in the form of the solution in an organic solvent by reacting them with ammonia or amines.
  • the reaction of copolymers containing anhydride groups with alcohols, ammonia or amines is preferably carried out in the absence of solvents.
  • copolymers obtainable by the polymerization processes described above are dissolved or dispersed in water and at least partially neutralized.
  • the copolymers can also, provided that they are monoethylenically unsaturated in the copolymerization as monomers of group b)
  • Carboxylic acids or monoethylenically unsaturated dicarboxylic anhydrides are used, are converted into the corresponding amides or half-amides. For example, ammonia, primary and / or secondary amines are added to a melt of the copolymers from which the volatile constituents have been removed.
  • the reaction is carried out to such an extent that 20 to 50% of the carboxyl groups of the polymerized monoethylenically unsaturated carboxylic acids or 20 to 50% of the carboxyl groups obtainable from the copolymerized monoethylenically unsaturated dicarboxylic acid anhydrides are amidated and at least 10% of the total carboxyl groups present in the copolymer are neutralized.
  • Ready-to-use solutions for the hydrophobization of leather and fur are obtained if the copolymers are neutralized after cooling to room temperature or preferably in the form of a melt which has a temperature in the range from 80 to 180, preferably 90 to 150 ° C., or as already described above - partially amidated by adding ammonia, primary and / or secondary amines.
  • the amounts of water and neutralizing agent are chosen so that 10 to 60, preferably 20 to 55% by weight solids-containing dispersions or polymer solutions are formed which are brought onto the market. Preparation solutions with solids contents of 0.5 to 50% by weight are then prepared from this by dilution with water.
  • Solvolysis can also be carried out with aminocarboxylic acids and salts of aminocarboxylic acids, preferably the alkali metal salts.
  • Alkali metal salts of ⁇ -aminocarboxylic acids are particularly preferably used, the alkali metal salts of sarcosine being particularly advantageous.
  • the solvolysis using salts of aminocarboxylic acids is advantageously carried out in an aqueous medium.
  • the solvolysis is carried out with such amounts of aminocarboxylates that 20 to 50% of the carboxyl groups of the polymerized monoethylenically unsaturated carboxylic acids or 20 to 50% of the carboxyl groups obtainable from the polymerized monoethylenically unsaturated dicarboxylic acid anhydrides are amidated by hydrolysis. After the formation of half-amide groups in the copolymer, neutralization takes place. It is carried out so far that at least 10% of the carboxyl groups of the copolymer obtained in bulk polymerization are neutralized.
  • the copolymers containing acid or anhydride groups obtained during the copolymerization can also be esterified by reaction with alcohols.
  • the esterification is carried out only to an extent that 10 to 50% of the acid groups of the copolymer are esterified.
  • the partially esterified copolymers are then neutralized, in which at least 10% of the carboxyl groups be neutralized.
  • the neutralization of the copolymers containing anhydride or acid groups is carried out at least to such an extent that copolymers which are dispersible in water are obtained. This degree of neutralization is at least 10% of the carboxyl groups of the copolymer or at least 10% of the total carboxyl groups resulting from the anhydride groups of the copolymer.
  • the degree of neutralization also depends on the chain length of the alkyl acrylate or alkyl methacrylate or vinyl ester used.
  • a copolymer of a C30-alkyl acrylate and maleic acid is neutralized to at least 75%, for example a copolymer of a C20-alkyl acrylate and maleic anhydride at a degree of neutralization of 50% of this Copolymer resulting carboxyl groups are already well dispersible in water.
  • a degree of neutralization of 20% of the carboxyl groups resulting from the copolymerized maleic anhydride is sufficient for dispersing the copolymer in water.
  • copolymers which contain copolymerized as an monomer of group b) an ethylenically unsaturated carboxylic acid or preferably a monoethylenically unsaturated dicarboxylic anhydride
  • Suitable primary and secondary amines can have 1 to 40, preferably 3 to 30 carbon atoms.
  • Such substances are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, dimethylamine, diethylamine Di-n-propylamine, di-isopropylamine, di-n-butylamine, diisobutylamine, dihexylamine, dicyclohexylamine, dimethylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, diisotridecylamine, ditallow fatty amine, di-stearylamine, di-oleylamine, ethanol Diethanol
  • the copolymers can be neutralized with the amines or ammonia specified above and with alkali metal and / or alkaline earth metal bases, for example sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium carbonate, magnesium hydroxide, calcium hydroxide and barium hydroxide.
  • Ready-to-use solutions or are preferably produced Dispersions by adding an aqueous base to a melt of the copolymer.
  • the pH of the ready-to-use agents for hydrophobizing is in the range from about 4 to 10.
  • the aqueous solution or dispersion can also be obtained by introducing the copolymer into an aqueous solution of the alkali metal and / or alkaline earth metal base, preferably at temperatures from 20 to 150 ° C.
  • the aqueous copolymer dispersions or solutions obtainable in this way are stable and stable in storage. They are ideally suited for finishing leather and fur skins because they have a particularly pronounced hydrophobic effect and also have a greasy and retanning effect.
  • the leather and fur material treated with these copolymer dispersions shows only a low level of water absorption and water permeability.
  • the dispersions have a softening effect at the same time, so that in most cases no additional fatliquor based on natural or synthetic licker oils is required.
  • the dispersions give the goods a high level and high tensile and tear strength, so that additional treatment with commercially available tanning agents, for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products, in most cases does not more is needed.
  • commercially available tanning agents for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products, in most cases does not more is needed.
  • aqueous dispersions or polymer solutions to be used according to the invention contain no additional emulsifiers. It is known that leather and fur skins that have been treated with products containing emulsifiers have to undergo complex processes after treatment with these agents, e.g. Subsequent treatment with polyvalent metal salts are subjected in order to render the emulsifiers in the leather or in the fur skins ineffective.
  • copolymer dispersions or copolymer solutions are suitable for the treatment of all customary tanned hides, in particular with mineral tanning agents, such as tanned hides containing chromium III salts.
  • the tanned hides are usually deacidified before treatment. They may have been stained before treatment. However, coloring can also only be carried out after the hydrophobization according to the invention has taken place.
  • the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the copolymer dispersions or solutions with water, at pH values from 4 to 10. preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C, for a period of 0.1 to 5, in particular 0.5 to 2 hours, treated. This treatment takes place, for example, by drumming in a barrel.
  • the amount of copolymer dispersion or solution required, 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 liquor length ie the percentage weight ratio of the treatment liquor to the goods, based on the fold weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, and 50 to 500% for fur skins.
  • the pH of the treatment 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.
  • the treatment with the aqueous dispersions or solutions to be used according to the invention can be carried out before or after the retanning step or else in several stages, the aqueous dispersions or solutions being used in part before, during and after the retanning step .
  • the aqueous dispersions or solutions to be used as hydrophobizing agents can also be used together with conventional leather and fur finishing agents, such as hydrophobics based on paraffin. In some cases, this improves the water repellent, oiling and retanning effects.
  • the percentages in the examples are percentages by weight.
  • the molecular weights of the copolymers were determined by gel permeation chromatography before neutralization, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.
  • the treated leather was tested for water absorption and water permeability using the Bally penetrometer in accordance with measurement method IUP 10 of the International Union of Leather Chemists' Associations, Commission for Physical Leather Testing, cf. The leather, volume 12, 36 to 40 (1961).
  • the reaction mixture was then heated for a further 2 hours with stirring and refluxing, and the xylene was then distilled off. The remaining xylene was removed in vacuo (40 millibars) and a temperature of 125 ° C. 79.9 g of morpholine were then added over the course of half an hour and the reaction mixture was heated to a temperature of 130 ° C. with stirring for 2 hours. All of the copolymer's anhydride groups were converted into monoamide groups. The reactor was then closed in a pressure-tight manner. At a temperature of the polymer melt of 125 ° C., 73.5 g of a 50% strength aqueous sodium hydroxide solution and 1130 g of water were then added within 1 h.
  • the reaction mixture was then stirred for a further 2 hours at a temperature of 125 ° C. and cooled to room temperature. A dispersion which was slightly viscous at room temperature and had a solids content of 25.8% was obtained. The molecular weight of the copolymer was 6400 g per mole.
  • a solution of 75 g of acrylic acid in 15 g of o-xylene and then a solution of 9 g of ditertiary butyl peroxide in 31 g of o-xylene were then uniformly added to the refluxing solution over the course of 2 hours.
  • the reaction mixture was then heated under reflux for a further 2 hours, and then the o-xylene was distilled off. Residual xylene was removed from the polymer melt at a temperature of 140 ° C and a pressure of 40 mbar.
  • the polymer melt was then cooled to a temperature of 125 ° C. and the reactor was closed in a pressure-tight manner.
  • the reaction mixture was stirred under reflux for a further 1 h.
  • the unpolymerized buten-1-ol-3 was then distilled off under a pressure of 40 mbar and a temperature of 125.degree.
  • the reactor was then sealed pressure-tight.
  • 125 g of 50% strength aqueous sodium hydroxide solution and 1173 g of water were added under pressure to the melt heated to 140 ° C. in the course of 1 h.
  • the mixture was then stirred at 120 ° C. for 1 h.
  • An emulsion which was viscous at room temperature and had a solids content of 30.6% was obtained.
  • the molecular weight of the copolymer was 3600 g per mole. 90% of the carboxyl groups of the copolymer were in the form of the sodium salt.
  • Chrome-tanned cowhide with a fold thickness of 1.8 mm which had been deacidified to a pH of 5.0 and dyed with 0.7% by weight of a conventional anionic aniline dye, was mixed with 20% of dispersion I, based on the fold weight , tumbled for one and a half hours at 40 ° C in the tanning drum. Following this treatment, the leather was brought to a pH of 3.6 with formic acid. It was then washed, mechanically stretched and dried.
  • the leather thus obtained was very soft and easy to grip and had a high dynamic water resistance.
  • the test with the Bally penetrometer showed a value of 24.7% by weight for a water absorption after 24 h at 15% compression and showed no water penetration during this period.
  • the leather was then dyed with 1% by weight of a conventional anionic aniline dye. Then it was adjusted to a pH of 3.8 with formic acid. Including washing, mechanical stretching and drying.
  • the leather obtained was very soft, supple, well filled, evenly colored and had excellent dynamic water resistance.
  • the test with the Bally penetrometer showed a value of 22.9% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.
  • the leather obtained was extremely soft and pleasant to the touch and showed a high water resistance.
  • the test with the Bally penetrometer showed a value of 19.5% by weight for 15% compression for the water absorption after 24 h and showed no water penetration during this period.

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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)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Use of copolymers that contain as copolymerised units   a) from 50 to 90 % by weight of C8-C40-alkyl (meth)acrylates, vinyl esters of C8-C40-carboxylic acids or mixtures thereof and   b) from 10 to 50 % by weight of monoethylenically unsaturated C3-C12-carboxylic acids, monoethylenically unsaturated dicarboxylic anhydrides, monoesters or monoamides of monoethylenically unsaturated C4-C12-dicarboxylic acids, amides of C3-C12-monocarboxylic acids or mixtures thereof and have molecular weights of from 500 to 30,000 g per mole, in at least partially neutralised form in aqueous solution or in aqueous dispersion for waterproofing leathers and fur pelts.

Description

Aus der DE-OS 38 17 000 sind Kraftstoffe für Otto-Motoren bekannt, die unter anderem geringe Mengen an Copolymerisaten aus

  • a) C₈₋ bis C₄₀-Alkylacrylaten oder den entsprechenden Methacrylaten, Vinylestern von C₈- bis C₄₀-Carbonsäuren und
  • b) monoethylenisch ungesättigten Carbonsäuren mit 3 bis 12 C-Atomen
enthalten. Die Copolymerisate haben eine Molmasse von 500 bis 20.000 g pro Mol. Die Carboxylgruppen der Copolymerisate liegen zumindest teilweise als Alkali- oder Erdalkalimetallsalz vor. Wie darin außerdem angegeben ist, kann ein Teil der Carboxylgruppen der Copolymerisate auch amidiert sein.From DE-OS 38 17 000, fuels for Otto engines are known which, among other things, contain small amounts of copolymers
  • a) C₈₋ to C₄₀ alkyl acrylates or the corresponding methacrylates, vinyl esters of C₈ to C₄₀ carboxylic acids and
  • b) monoethylenically unsaturated carboxylic acids with 3 to 12 carbon atoms
contain. The copolymers have a molecular weight of 500 to 20,000 g per mole. The carboxyl groups of the copolymers are at least partially in the form of an alkali metal or alkaline earth metal salt. As is also indicated therein, some of the carboxyl groups of the copolymers can also be amidated.

Aus der US-PS 4 190 687 ist bekannt, gefärbtes Leder mit Copolymerisaten aus monoethylenisch ungesättigten Carbonsäureestern mit 4 bis 22 C-Atomen und aliphatischen Olefinen mit 3 bis 20 C-Atomen zu behandeln. Die Copolymerisate werden dabei in Form einer Lösung in einem organischen Lösemittel behandelt. Als Lösemittel kommen vorzugsweise aromatische Kohlenwasserstoffe, Chlorkohlenwasserstoffe, Ketone, Ether, Ester und Amide in Betracht. Solche Lösungen sind jedoch aufgrund ihres Gehalts an organischen Lösemitteln für eine Hydrophobierung von Leder und Pelzfellen praktisch nicht brauchbar.From US Pat. No. 4,190,687 it is known to treat dyed leather with copolymers of monoethylenically unsaturated carboxylic esters with 4 to 22 carbon atoms and aliphatic olefins with 3 to 20 carbon atoms. The copolymers are treated in the form of a solution in an organic solvent. Aromatic hydrocarbons, chlorinated hydrocarbons, ketones, ethers, esters and amides are preferably used as solvents. However, because of their organic solvent content, such solutions are practically unusable for waterproofing leather and fur skins.

Die Verwendung wäßriger Polyacrylatdispersionen, bei denen das Copolymerisat zu einem überwiegenden Anteil aus Acrylsäure- oder Methacrysäureestern von Alkoholen mit 1 bis 8 C-Atomen aufgebaut ist, zum Zurichten von Leder ist aus der DE-OS 33 44 354 und der EP-PS 0 065 253 bekannt. Zur Herstellung der wäßrigen Polymerdispersionen benötigt man jedoch immer Emulgatoren.The use of aqueous polyacrylate dispersions in which the copolymer is predominantly composed of acrylic or methacrylic acid esters of alcohols having 1 to 8 carbon atoms for dressing leather is known from DE-OS 33 44 354 and EP-PS 0 065 253 known. However, emulsifiers are always required to prepare the aqueous polymer dispersions.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, emulgatorfreie Mittel für die Hydrophobierung von Leder und Pelzfellen zur Verfügung zu stellen.The present invention has for its object to provide emulsifier-free agents for the hydrophobization of leather and fur.

Die Aufgabe wird erfindungsgemäß gelöst durch Verwendung von Copolymerisaten, die

  • a) 50 bis 90 Gew.-% C₈- bis C₄₀-Alkylacrylate, C₈- bis C₄₀-Alkylmethacrylate, Vinylester von C₈- bis C₄₀-Carbonsäuren oder deren Mischungen und
  • b) 10 bis 50 Gew.-% monoethylenisch ungesättigte C₃- bis C₁₂-Carbonsäuren, monoethylenisch ungesättigte Dicarbonsäurenanhydride, Halbester oder Halbamide von monoethylenisch ungesättigten C₄- bis C₁₂-Dicarbonsäuren, Amide von monoethylenisch ungesättigten C₃- bis C₁₂-Carbonsäuren oder deren Mischungen
einpolymerisiert enthalten und die Molmassen von 500 bis 30.000 g pro Mol haben, in zumindest partiell neutralisierter oder amidierter Form in wäßriger Lösung oder in wäßriger Dispersion als Mittel zum Hydrophobieren von Leder und Pelzfellen.The object is achieved according to the invention by using copolymers which
  • a) 50 to 90 wt .-% C₈ to C₄₀ alkyl acrylates, C₈ to C₄₀ alkyl methacrylates, vinyl esters of C₈ to C₄₀ carboxylic acids or mixtures thereof and
  • b) 10 to 50 wt .-% monoethylenically unsaturated C₃- to C₁₂-carboxylic acids, monoethylenically unsaturated dicarboxylic anhydrides, half-esters or half-amides of monoethylenically unsaturated C₄- to C₁₂-dicarboxylic acids, amides of monoethylenically unsaturated C₃- to C₁₂-carboxylic acids or mixtures thereof
contain in copolymerized form and have molar masses of 500 to 30,000 g per mole, in at least partially neutralized or amidated form in aqueous solution or in aqueous dispersion as agents for waterproofing leather and fur skins.

Die Copolymerisate sind beispielsweise aus der DE-OS 38 17 000 bekannt. Sie werden durch Copolymerisieren der Monomeren der Gruppe a) mit den Monomeren der Gruppe b) hergestellt. Falls als Monomere der Gruppe b) monoethylenisch ungesättigten Dicarbonsäurenanhydride eingesetzt werden und die Copolymerisation unter Ausschluß von Wasser durchgeführt wird, erfolgt im Anschluß an die Copolymerisation eine Solvolyse der im Copolymerisat enthaltenen Anhydridgruppen. Die Solvolyse der Anhydridgruppen der Copolymerisate kann gleichzeitig mit einer partiellen oder vollständigen Neutralisation der Carboxylgruppen verbunden werden, indem man die Copolymerisate mit Basen behandelt. Falls man als Basen Ammoniak, primäre oder sekundäre Amine verwendet, können die Copolymerisate auch partiell amidiert werden. Als Monomere der Gruppe a) zur Herstellung der Copolymerisate kommen C₈- bis C₄₀-Alkylacrylate und C₈- bis C₄₀-Alkylmethacrylate in Betracht. Geeignete Verbindungen dieser Art sind beispielsweise 2-Ethylhexylacrylat, 2-Ethylhexylmethacrylat, n-Decylacrylat, n-Decylmethacrylat, Dodecylacrylat, Dodecylmethacrylat, Isotridecylacrylat, Isotridecylmethacrylat, Tetradecylacrylat, Tetradecylmethacrylat, C₁₆/C₁₈-Talgfettalkoholacrylat, C₁₆/C₁₈-Talgfettalkoholmethacrylat, Octadecylacrylat, Octadecylmethacrylat, Palmitylacrylat, Palmitylmethacrylat, n-Eicosylacrylat, n-Eicosylmethacrylat, n-Docosylacrylat, n-Docosylmethacrylat, Tetracosylacrylat, Tetracosylmethacrylat, Hexacosylacrylat, Hexacosylmethacrylat, Octocosylacrylat, Octocosylmethacrylat sowie Acrylester und Methacrylester von C₄₀-Alkoholen. Außerdem eignen sich Mischungen von Acrylaten. Solche Mischungen sind beispielsweise durch Verestern von Alkoholen herstellbar, die entweder nach dem Oxoverfahren oder nach dem Ziegler-Verfahren erhältlich sind. Vorzugsweise verwendet man die Acrylsäureester und Methacrylsäureester, die sich von Alkoholen mit 16 bis 28 Kohlenstoffatomen ableiten.The copolymers are known for example from DE-OS 38 17 000. They are prepared by copolymerizing the group a) monomers with the group b) monomers. If monoethylenically unsaturated dicarboxylic acid anhydrides are used as monomers of group b) and the copolymerization is carried out with the exclusion of water, the anhydride groups contained in the copolymer are solvolysed after the copolymerization. The solvolysis of the anhydride groups of the copolymers can simultaneously be combined with a partial or complete neutralization of the carboxyl groups by treating the copolymers with bases. If ammonia, primary or secondary amines are used as bases, the copolymers can also be partially amidated. Suitable monomers of group a) for the preparation of the copolymers are C₈ to C₄₀ alkyl acrylates and C₈ to C₄₀ alkyl methacrylates. Suitable compounds of this type are, for example, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-decyl acrylate, n-decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, isotridecyl acrylate, isotridecyl methacrylate, tetradecyl acrylate, cetyl C-acrylate, C₁-methacrylate, C₁-methacrylate Palmityl acrylate, palmityl methacrylate, n-eicosyl acrylate, n-eicosyl methacrylate, n-docosyl acrylate, n-docosyl methacrylate, tetracosyl acrylate, tetracosyl methacrylate, hexacosyl acrylate, hexacosyl methacrylate, octocosyl acrylate and methacrylic acrylate, and octocyl acrylate methacrylate. Mixtures of acrylates are also suitable. Such mixtures can be prepared, for example, by esterifying alcohols, either using the oxo process or are available using the Ziegler process. The acrylic acid esters and methacrylic acid esters derived from alcohols having 16 to 28 carbon atoms are preferably used.

Als Kombonente a) kommen außerdem Vinylester von Carbonsäuren mit 8 bis 40 C-Atomen in Betracht. Solche Verbindungen sind beispeilsweise Vinyl-2-Ethylhexanoat, Vinyllaurat, Vinylpalmitat, Vinyltalgfettsäureester, Vinylmyristat, Vinylstearat, Vinyloleat sowie Mischungen der genannten Vinylester oder Mischungen mindestens eines Vinylesters mit mindestens einem der in Betracht kommenden Alkyl(meth)acrylate. Die Monomeren der Gruppe a) sind in den Copolymerisaten in Mengen von 50 bis 90, vorzugsweise 65 bis 85 Gew.-% in einpolymerisierter Form enthalten.Also suitable as component a) are vinyl esters of carboxylic acids having 8 to 40 carbon atoms. Examples of such compounds are vinyl 2-ethylhexanoate, vinyl laurate, vinyl palmitate, vinyl tallow fatty acid esters, vinyl myristate, vinyl stearate, vinyl oleate and mixtures of the vinyl esters mentioned or mixtures of at least one vinyl ester with at least one of the alkyl (meth) acrylates in question. The monomers of group a) are present in the copolymers in amounts of 50 to 90, preferably 65 to 85% by weight in copolymerized form.

Zu den Monomeren der Gruppe b) gehören monoethylenisch ungesättigte C₃- bis C₁₂-Carbonsäuren und monoethylenisch ungesättigten Dicarbonsäureanhydride. Geeignete monoethylenisch ungesättigte Carbonsäuren sind beispielsweise Acrylsäure, Methacrylsäure, Crotonsäure, Vinylmilchsäure, Allylessigsäure, Propylidenessigsäure, Ethylacrylsäure, Dimethylacrylsäure, Maleinsäure, Fumarsäure, Itakonsäure, Glutakonsäure, Methylenmalonsäure, Zitrakonsäure und Tetrahydrophthalsäure. Ethylenisch ungesättigte Dicarbonsäureanhydride, die insgesamt 4 bis 12 C-Atome pro Molekül enthalten, sind beispeilsweise Maleinsäureanhydrid, Itakonsäureanhydrid, Zitrakonsäureanhydrid, Methylenmalonsäureanhydrid und Tetrahydrophthalsäureanhydrid. Als Monomere der Gruppe b) kommen außerdem Monoester aus Dicarbonsäuren und Alkoholen mit 1 bis 40 C-Atomen in Betracht, beispielsweise Monomethylmaleinat, Monobutylmaleinat, Monododecylmaleinat, Monooctadecylmaleinat, Monotetracosylmaleinat, Monooctadecylfumarat, Monooctadecylitakonat, Mono-2-ethylhexylitakonat und Mischungen der genannten Verbindungen. Von den Monomeren der Gruppe b) sind Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Itakonsäure und Itakonsäureanhydrid bevorzugt.The monomers of group b) include monoethylenically unsaturated C₃ to C₁₂ carboxylic acids and monoethylenically unsaturated dicarboxylic anhydrides. Suitable monoethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, vinyl lactic acid, allylacetic acid, propylidene acetic acid, ethyl acrylic acid, dimethylacrylic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, methylene malonic acid, citric acid and tetrahydrophthalic acid. Examples of ethylenically unsaturated dicarboxylic acid anhydrides, which contain a total of 4 to 12 carbon atoms per molecule, are maleic anhydride, itaconic anhydride, citric acid anhydride, methylene malonic acid anhydride and tetrahydrophthalic anhydride. Also suitable as monomers of group b) are monoesters of dicarboxylic acids and alcohols with 1 to 40 carbon atoms, for example monomethyl maleate, monobutyl maleate, monododecyl maleate, monooctadecyl maleate, monotetracosyl maleate, monooctadecyl fumarate, monooctadecohexyl compounds and monoethyl hexacetate compounds, monohexadecyl hexaconate compounds,. Of the monomers of group b), acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride are preferred.

Zu den Monomeren der Gruppe b) gehören außerdem Amide der monoethylenisch ungesättigten Monocarbonsäuren sowie die Halbamide von monoethylenisch ungesättigten Dicarbonsäuren, z.B. Amide und Halbamide, die sich jeweils von den zugrunde liegenden Carbonsäuren und Ammoniak oder Aminen mit 1 bis 40 C-Atomen ableiten, beispielsweise N-Isotridecylacrylamid, N-Di-(isotridecyl)acrylamid, N-Stearylacrylamid, N-Stearylmethacrylamid, Maleinsäuremonoisotridecylamid, Maleinsäurediisotridecylamid, Maleinsäuremonostearylamid und Maleinsäuredistearylamid.The group b) monomers also include amides of monoethylenically unsaturated monocarboxylic acids and the half-amides of monoethylenically unsaturated dicarboxylic acids, e.g. Amides and half-amides, each derived from the underlying carboxylic acids and ammonia or amines having 1 to 40 carbon atoms, for example N-isotridecylacrylamide, N-di- (isotridecyl) acrylamide, N-stearylacrylamide, N-stearylmethacrylamide, maleic acid monoisotridecylamide, maleic acid diisotridecylamide , Maleic acid monostearylamide and maleic acid distearylamide.

Die Copolymerisate enthalten die Monomeren der Gruppe b) in Mengen von 10 bis 50, vorzugsweise 15 bis 35 Gew.-% einpolymerisiert.The copolymers contain the monomers of group b) in amounts of 10 to 50, preferably 15 to 35,% by weight.

Die Copolymerisate aus dem Monomeren der Gruppe a) und b) können noch gegebenenfalls durch Copolymerisieren in Gegenwart von Monomeren der Gruppe c) modifiziert werden. Zu den Monomeren der Gruppe c) gehören beispielsweise Styrol, Methylstyrol, Ethylstyrol, Butylstyrol, N-Vinylpyrrolidon, N-Vinylcaprolactam, N-Vinylformamid, N-Vinyl-N-methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, Acrylsäuremethylester, Acrylsäureethylester, Acrylsäurepropylester, Acrylsäurebutylester, Acrylsäurehexylester, Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäurepropylester, Methacrylsäurebutylester, Methacrylsäurehexylester, Hydroxiethylacrylat, Hydroxipropylacrylat, Hydroxibutylacrylat, Hydroxiethylmethacrylat, Hydroxipropylacrylat, Hydroxibutylacrylat, Maleinsäuremonomethylester, Maleinsäuredimethylester, Maleinsäuremonoethylester, Maleinsäurediethylester, Maleinsäuremonopropylester, Maleinsäuredipropylester, Maleinsäuremonobutylester, Maleinsäuredibutylester, Maleinsäuremonohexylester, Maleinsäuredihexylester, Fumarsäuremonomethylester, Fumarsäuredimethylester, Fumarsäuremonoethylester, Fumarsäurediethylester, Fumarsäuremonopropylester, Fumarsäuredipropylester, Fumarsäuremonobutylester, Fumarsäuredibutylester, Fumarsäuremonohexylester, Fumarsäuredihexylester, Vinylformiat, Vinylacetat, Vinylpropionat, Vinylbutyrat, Acrylnitril, Methacrylnitril, Dimethylaminoethylacrylat, Diethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Diethylaminoethylmethacrylat, Dimethylaminopropylacrylat, Diethylaminopropylacrylat, Dimethylaminopropylmethacrylat, Diethylaminopropylmethacrylat, Dimethylaminopropylacrylamid, 1-Vinylimidazol, 1-Vinyl-2-methylimidazol, 1-Vinyl-4-methylimidazol, 1-Vinyl-5-methylimidazol, Vinylsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Acrylamidomethylpropansulfonsäure, Styrolsulfonsäure, Acrylsäure-(3-sulfopropylester), Vinylphosphonsäure, Allylphosphonsäure sowie Mischungen untereinander.The copolymers from the monomers of group a) and b) can optionally also be modified by copolymerization in the presence of monomers from group c). The monomers of group c) include, for example, styrene, methylstyrene, ethylstyrene, butylstyrene, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, methyl acrylate , ethyl acrylate, propyl acrylate, butyl acrylate, Acrylsäurehexylester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Methacrylsäurehexylester, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, Maleinsäuremonopropylester, Maleinsäuredipropylester, monobutyl maleate, dibutyl maleate, Maleinsäuremonohexylester, Maleinsäuredihexylester , Monomethyl fumarate, Dimethyl fumarate, Monoethyl fumarate, Diethyl fumarate, Fumars äuremonopropylester, Fumarsäuredipropylester, Fumarsäuremonobutylester, dibutyl fumarate, Fumarsäuremonohexylester, Fumarsäuredihexylester, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminopropyl acrylamide, 1-vinylimidazole, 1-vinyl- 2-methylimidazole, 1-vinyl-4-methylimidazole, 1-vinyl-5-methylimidazole, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, acrylamidomethylpropanesulfonic acid, styrenesulfonic acid, acrylic acid (3-sulfopropyl ester), vinylphosphonic acid, allylphosphonic acid and mixtures with one another.

Die Monomeren der Gruppe c) sind, sofern sie für die Modifizierung der Copolymerisate aus a) und b) eingesetzt werden, darin in Mengen von 1 bis 20 Gew.-% in einpolymerisierter Form enthalten.The monomers of group c), provided they are used for the modification of the copolymers from a) and b), are present in them in amounts of from 1 to 20% by weight in copolymerized form.

Die Copolymerisation der Monomeren der Gruppen a) und b) sowie gegebenenfalls c), erfolgt nach allen bekannten diskontinuierlichen oder kontinuierlichen Polymerisationsverfahren, wie Masse-, Suspensions-, Fällungs- und Lösungspolymerisation. Die Copolymerisation wird vorzugsweise in Gegenwart von Radikale bildenden Verbindungen durchgeführt. Man benötigt davon bis zu 10, vorzugsweise 0,2 bis 5 Gew.-%, bezogen auf die bei der Copolymerisation eingesetzten Monomeren. Bei allen genannten Polymerisationsverfahren wird unter Ausschluß von Sauerstoff gearbeitet, vorzugsweise in einem Stickstoffstrom. Für alle Polymerisationsmethoden werden die üblichen Apparaturen verwendet, z.B. Autoklaven und Kessel, die beispielsweise mit Anker-, Blatt-, Impeller- oder Mehrstufenimpuls-Gegenstrom-Rührern ausgestattet sind. Besonders bevorzugt ist die Substanzpolymerisation der Monomeren der Gruppen (a) und (b). Sie wird bei Temperaturen von 80 bis 300, vorzugsweise von 120 bis 200°C durchgeführt, wobei die niedrigste zu wählende Polymerisationstemperatur vorzugsweise etwa mindestens 20°C über der Glastemperatur des gebildeten Polymeren liegt. Je nach Molekulargewicht, das die Copolymerisate haben sollen, werden die Polymerisationsbedingungen gewählt. Polymerisation bei hohen Temperaturen ergibt Copolymerisate mit niedrigen Molekulargewichten, während bei niedrigeren Polymerisationstemperaturen Polymerisate mit höheren Molekulargewichten entstehen. Auch die Menge des Polymerisationsinitiators hat einen Einfluß auf das Molekulargewicht. Man benötigt im allgemeinen 0,01 bis 5 Gew.-%, bezogen auf die bei der Polymerisation eingesetzten Monomeren, an Radikale bildenden Polymerisationsinitiatoren. Höhere Initiatormengen führen hierbei zu Copolymerisaten mit niedrigeren Molekulargewichten. Die Monomeren (a) und (b) können bei Temperaturen von oberhalb 200°C auch in Abwesenheit von Polymerisationsinitiatoren copolymerisiert werden, d.h. ein Einsatz von Initiatoren ist nicht unbedingt erforderlich, weil die Monomeren (a) und (b) bei Temperaturen von oberhalb 200°C auch in Abwesenheit von Initiatoren bereits radikalisch polymerisieren.The copolymerization of the monomers of groups a) and b) and optionally c) takes place by all known batch or continuous polymerization processes, such as bulk, suspension, precipitation and solution polymerization. The copolymerization is preferably carried out in the presence of radical-forming compounds. Up to 10, preferably 0.2 to 5% by weight, based on the monomers used in the copolymerization, are required. All of the polymerization processes mentioned are carried out in the absence of oxygen, preferably in a stream of nitrogen. For all polymerization methods the usual equipment is used, for example autoclaves and boilers, which are equipped, for example, with anchor, blade, impeller or multi-stage impulse countercurrent stirrers. Bulk polymerization of the monomers of groups (a) and (b) is particularly preferred. It is carried out at temperatures from 80 to 300, preferably from 120 to 200 ° C., the lowest polymerization temperature to be chosen preferably being at least about 20 ° C. above the glass transition temperature of the polymer formed. Depending on the molecular weight that the copolymers should have, the polymerization conditions are chosen. Polymerization at high temperatures produces copolymers with low molecular weights, while polymers with higher molecular weights are formed at lower polymerization temperatures. The amount of the polymerization initiator also has an influence on the molecular weight. In general, 0.01 to 5% by weight, based on the monomers used in the polymerization, of polymerization initiators which form free radicals is required. Higher amounts of initiator lead to copolymers with lower molecular weights. The monomers (a) and (b) can be copolymerized at temperatures above 200 ° C even in the absence of polymerization initiators, ie the use of initiators is not absolutely necessary because the monomers (a) and (b) at temperatures above 200 ° C free-radically polymerize even in the absence of initiators.

Geeignete Polymerisationsinitiatoren sind beispielsweise Acetylcyclohexansulfonylperoxid, Diacetylperoxidicarbonat, Dicyclohexylperoxidicarbonat, Di-2-ethylhexylperoxidicarbonat, Tertiär-butylperneodecanoat, 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitril), Tertiär-butylperpivalat, Tertiär-butylper-2-ethyl-hexanoat, Tertiär-butylpermaleinat, 2,2'-Azobis-(isobutyronitril), Bis-(tertiär-butylperoxi)cyclohexan, Tertiär-butylperoxiisopropylcarbonat, Tertiär-butylperacetat, Di-tertiär-butylperoxid, Ditertiäramylperoxid, Cumolhydroperoxid und Tertiär-butylhydroperoxid. Die Initiatoren können allein oder in Mischung untereinander angewendet werden. Sie werden bei der Substanzpolymerisation vorzugsweise separat oder in Form einer Lösung oder Dispersion in dem Monomer der Komponente (a) in den Polymerisationsreaktor eingebracht. Bei der Copolymerisation können selbstverständlich auch Redox-Coinitiatoren mitverwendet werden, z.B. Benzoin, Dimethylanilin, Ascorbinsäure sowie organisch lösliche Komplexe von Schwermetallen, wie Kupfer, Cobalt, Eisen, Mangan, Nickel und Chrom. Die Mitverwendung von Redox-Coinitiatoren gestattet es, die Polymerisation bei tieferer Temperatur durchzuführen. Die üblicherweise verwendeten Mengen an Redox-Coinitiatoren betragen etwa 0,1 bis 2000, vorzugsweise 0,1 bis 1000 ppm, bezogen auf die eingesetzten Mengen an Monomeren. Falls das Monomergemisch an der unteren Grenze des für die Polymerisation in Betracht kommmenden Temperaturbereiches anpolymerisiert und anschließend bei einer höheren Temperatur auspolymerisiert wird, ist es zweckmäßig, mindestens zwei verschiedene Initiatoren zu verwenden, die bei unterschiedlichen Temperaturen zerfallen, so daß in jedem Temperaturintervall eine ausreichende Konzentration an Radikalen zur Verfügung steht.Suitable polymerization initiators are, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexylperoxidicarbonat, tertiary-butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), tertiary-butyl perpivalate, tertiary-butyl-2-ethyl- hexanoate, tertiary-butyl permaleinate, 2,2'-azobis (isobutyronitrile), bis- (tertiary-butylperoxy) cyclohexane, tertiary-butylperoxyisopropyl carbonate, tertiary-butylperacetate, di-tertiary-butylperoxide, ditertiary tertiaryhydroperoxide, butyl tertiaryhydroperoxide. The initiators can be used alone or as a mixture with one another. In bulk polymerization, they are preferably introduced into the polymerization reactor separately or in the form of a solution or dispersion in the monomer of component (a). Redox coinitiators can of course also be used in the copolymerization, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium. The use of redox coinitiators allows the polymerization to be carried out at a lower temperature. The amounts of redox coinitiators usually used are about 0.1 to 2000, preferably 0.1 to 1000 ppm, based on the amounts of monomers used. If the monomer mixture at the lower limit of that is considered for polymerization Coming polymerized temperature range and then polymerized at a higher temperature, it is advantageous to use at least two different initiators, which disintegrate at different temperatures, so that a sufficient concentration of radicals is available in each temperature interval.

Um niedrigmolekulare Polymerisate herzustellen, ist es oft zweckmäßig, die Copolymerisation in Gegenwart von Reglern durchzuführen. Hierfür können übliche Regler verwendet werden, wie z.B. C₁- bis C₄-Aldehyde, Allylalkohol, Buten-1-ol-3, Ameisensäure und organische SH-Gruppen enthaltende Verbindungen, wie 2-Mercaptoethanol, 2-Mercaptopropanol, Mercaptoessigsäure, Mercaptopropionsäure, tertiär-Butylmercaptan, n-Dodecylmercaptan und tertiär-Dodecylmercaptan. Die Polymerisationregler werden im allgemeinen in Mengen von 0,1 bis 10 Gew.-%, bezogen auf die Monomeren, eingesetzt.In order to produce low molecular weight polymers, it is often expedient to carry out the copolymerization in the presence of regulators. Common controllers can be used for this, e.g. C₁ to C₄ aldehydes, allyl alcohol, buten-1-ol-3, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-dodecyl mercaptan and tertiary dodecyl mercaptan . The polymerization regulators are generally used in amounts of 0.1 to 10% by weight, based on the monomers.

Bei der Substanzpolymerisation kann mit besonderem Vorteil ein Druckkessel mit einem nachgeschalteten Reaktionsrohr, das mit einem statischen Mischer versehen ist, verwendet werden. Vorzugsweise polymerisiert man die Monomeren aus (Meth)acrylestern, Vinylestern und säuregruppenhaltigen monoethylenisch ungesättigten Verbindungen in mindestens 2 hintereinander geschalteten Polymerisationszonen. Dabei kann die eine Reaktionszone aus einem druckdichten Kessel, die andere aus einem beheizbaren statischen Mischer bestehen. Man erhält dabei Umsätze von mehr als 99 %. Ein Copolymerisat aus Stearylacrylat und Acrylsäure kann beispielsweise dadurch hergestellt werden, daß man die Monomeren und einen geeigneten Initiator einem Reaktor oder zwei hintereinandergeschalteten Reaktionszonen, beispielsweise einer Rührkesselkaskade, kontinuierlich zuführt, und das Reaktionsprodukt nach einer Verweilzeit von 2 bis 60, vorzugsweise von 5 bis 30 Minuten, bei Temperaturen zwischen 200 und 400°C kontinuierlich aus der Reaktionszone ausschleust. Die Polymerisation wird zweckmäßig bei Drücken von mehr als 1 bar, vorzugsweise zwischen 1 und 200 bar, durchgeführt. Die erhaltenen Copolymeren mit Feststoffgehalten von über 99 % können dann weiter zu den entsprechenden Alkali- und Erdalkalisalzen bzw. Amiden und Ammonsalzen umgesetzt werden.In the case of bulk polymerization, a pressure vessel with a downstream reaction tube, which is provided with a static mixer, can be used with particular advantage. The monomers are preferably polymerized from (meth) acrylic esters, vinyl esters and monoethylenically unsaturated compounds containing acid groups in at least 2 polymerization zones connected in series. One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%. A copolymer of stearyl acrylate and acrylic acid can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a cascade of stirred tanks, and the reaction product after a residence time of 2 to 60, preferably 5 to 30 Minutes, continuously discharged from the reaction zone at temperatures between 200 and 400 ° C. The polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar. The copolymers obtained with solids contents of over 99% can then be further converted to the corresponding alkali and alkaline earth metal salts or amides and ammonium salts.

Eine weitere bevorzugte Ausführungsform für die Herstellung der Copolymeren ist die Lösungspolymerisation. Sie wird in Lösemitteln durchgeführt, in denen die Monomeren und die gebildeten Copolymeren löslich sind. Es sind hierfür alle Lösemittel geeignet, die diese Vorgabe erfüllen und die mit den Monomeren keine Reaktionen eingehen. Beispielsweise sind dies Aceton, Methylethylketon, Diethylketon, Methylisobutylketon, Ethylacetat, Butylacetat, aliphatische, cycloaliphatische und aromatische Kohlenwasserstoffe wie n-Oktan, Isooktan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol, Ethylbenzol, Cumol, Tetrahydrofuran und Dioxan, wobei zur Erzielung niedermolekularer Copolymerer Xylol, Ethylbenzol, Cumol, Tetrahydrofuran und Dioxan besonders gut geeignet sind. Wie bei der Masse- und Fällungspolymerisation ist es auch hier zweckmäßig, das Lösemittel und einen Teil der Monomerenmischung (z.B. ca. 5 bis 20 %) vorzulegen und den Rest der Monomerenmischung mit dem Initiator und gegebenenfalls Co-Initiator und Regler zuzudosieren. Es können auch Lösemittel und (Meth)acrylester oder Vinylester im Polymerisationsreaktor vorgelegt und nach Erreichen der Polymerisationstemperatur dann das säuregruppenhaltige Monomere, gegebenenfalls gelöst im Lösemittel, und der Initiator sowie gegebenenfalls Coinitiator und Regler zudosiert werden. Die Konzentrationen der zu polymerisierenden Monomeren liegen zwischen 20 und 80 Gew.%, bevorzugt 30 und 70 Gew.%. Das feste Copolymer kann problemlos durch Verdampfen des Lösemittels isoliert werden.Another preferred embodiment for the preparation of the copolymers is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents that meet this requirement and that do not react with the monomers are suitable for this. For example, these are acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, aliphatic, cycloaliphatic and aromatic hydrocarbons such as n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane, xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane being particularly suitable for achieving low molecular weight copolymers. As with bulk and precipitation polymerization, it is also expedient here to introduce the solvent and part of the monomer mixture (for example about 5 to 20%) and to meter in the rest of the monomer mixture with the initiator and, if appropriate, co-initiator and regulator. Solvents and (meth) acrylic esters or vinyl esters can also be placed in the polymerization reactor and then, after the polymerization temperature has been reached, the monomer containing acid groups, if appropriate dissolved in the solvent, and the initiator, and, if appropriate, coinitiator and regulator, can be metered in. The concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 and 70% by weight. The solid copolymer can easily be isolated by evaporating the solvent.

Eine weitere Methode zur einfachen Herstellung der Copolymeren ist die Fällungspolymerisation. Bei der Fällungspolymerisation werden solche Lösemittel eingesetzt, in denen die Monomeren löslich und das gebildete Copolymere unlöslich ist und ausfällt. Solche Lösemittel sind beispielsweise Ether, wie Diethylether, Dipropylether, Dibutylether, Methyl-tert.-butylether, Diethylenglykoldimethylether und Mischungen untereinander. Bei der Durchführung der Fällungspolymerisation ist es zweckmäßig, besonders wenn bei Konzentrationen von über 40 Gew.% gearbeitet wird, zur Verhinderung der Aggregatbildung in Gegenwart eines Schutzkolloids zu polymerisieren. Als Schutzkolloide sind polymere Stoffe geeignet, die in den Lösemitteln gut löslich sind und keine Reaktion mit den Monomeren eingehen. Geeignet sind beispielsweise Copolymere des Maleinsäureanhydrids mit Vinylalkylethern und/oder Olefinen mit 8 bis 20 C-Atomen sowie entsprechende Copolymere der Monoester der Maleinsäure mit C₁₀- bis C₂₀-Alkoholen oder der Mono- und Diamide der Maleinsäure mit C₁₀- bis C₂₀-Alkylaminen sowie Polyalkylvinylether, deren Alkylgruppe 1 bis 20 C-Atome enthält, wie beispielsweise Polymethyl-, Polyethyl-, Polyisobutyl- sowie Polyoktadecylvinylether. Die zugesetzten Mengen an Schutzkolloid liegen üblicherweise bei 0,05 bis 4 Gew.% (berechnet auf eingesetzte Monomere), vorzugsweise 0, 1 bis 2 Gew.%, wobei es oftmals von Vorteil ist, mehrere Schutzkolloide zu kombinieren. Bei der Polymerisation ist es zweckmäßig, das Lösemittel, das Schutzkolloid und einen Teil der Monomermischung im Reaktor vorzulegen und bei gewählter Polymerisationstemperatur unter intensivem Rühren den Rest der Monomerenmischung und den Initiator sowie gegebenenfalls den Coinitiator und Regler zuzudosieren. Die Zulaufzeiten für Monomer und Initiator sind im allgemeinen zwischen 1 und 10 Std., vorzugsweise 2 und 5 Std. Es ist auch möglich, alle Einsatzstoffe gemeinsam in einem Reaktor vorzulegen und darin zu polymerisieren, wobei jedoch Probleme mit der Wärmeabführung auftreten können, so daß eine solche Arbeitsweise weniger zweckmäßig ist. Die Konzentrationen der zu polymerisierenden Monomeren liegen zwischen 20 und 80 Gew.%, bevorzugt 30 bis 70 Gew.%. Die Polymeren können aus den Polymerisatsuspensionen isoliert werden, z.B. durch Abdestillieren des Suspensionsmittels der Polymerisatsuspensionen in Verdampfern, beispielsweise Bandtrocknern, Schaufeltrocknern, Sprühtrocknern und Wirbelbett-Trocknern.Another method for the simple preparation of the copolymers is precipitation polymerization. In the case of precipitation polymerization, solvents are used in which the monomers are soluble and the copolymer formed is insoluble and fails. Examples of such solvents are ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another. When carrying out the precipitation polymerization, it is expedient, particularly when working at concentrations of more than 40% by weight, to polymerize in the presence of a protective colloid to prevent the formation of aggregates. Suitable protective colloids are polymeric substances which are readily soluble in the solvents and which do not react with the monomers. Suitable are, for example, copolymers of maleic anhydride with vinyl alkyl ethers and / or olefins with 8 to 20 carbon atoms, and corresponding copolymers of the monoesters of maleic acid with C₁₀ to C₂₀ alcohols or the mono- and diamides of maleic acid with C₁₀- to C₂₀-alkylamines and polyalkyl vinyl ethers , whose alkyl group contains 1 to 20 carbon atoms, such as polymethyl, polyethyl, polyisobutyl and polyoctadecyl vinyl ether. The amounts of protective colloid added are usually 0.05 to 4% by weight (based on the monomers used), preferably 0.1 to 2% by weight, it often being advantageous to combine several protective colloids. In the case of the polymerization, it is expedient to put the solvent, the protective colloid and part of the monomer mixture in the reactor and to meter in the rest of the monomer mixture and the initiator and, if appropriate, the coinitiator and regulator at the chosen polymerization temperature with vigorous stirring. The feed times for the monomer and initiator are generally between 1 and 10 hours, preferably 2 and 5 hours. It is also possible to initially charge all the starting materials in a reactor and to polymerize them, however, heat dissipation problems may occur, making such an operation less convenient. The concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 to 70% by weight. The polymers can be isolated from the polymer suspensions, for example by distilling off the suspension medium of the polymer suspensions in evaporators, for example belt dryers, paddle dryers, spray dryers and fluidized bed dryers.

Die Monomeren der Gruppe a) und b) sowie gegebenenfalls c) werden in der Weise nach den oben beschriebenen Verfahren copolymerisiert, daß man Copolymerisate mit Molmassen von 500 bis 30.000, vorzugsweise 1.000 bis 20.000 g pro Mol behält. Vorzugsweise eignen sich für die erfindungsgemäße Verwendung Copolymerisate aus Stearylacrylat und Maleinsäureanhydrid bzw. Maleinsäure, Copolymerisate aus C₁₈- bis C₂₂-Alkylmethacrylaten und Acrylsäure oder Methacrylsäure, Copolymerisate aus Octadecylacrylat und Acrylsäure, Maleinsäure oder Maleinsäureanhydrid sowie Copolymerisate aus Vinyl-2-Ethylhexaonat oder Vinylstearat und Maleinsäureanhydrid. Die Copolymerisate aus den langkettigen Vinylestern und Maleinsäureanhydrid enthalten die Monomeren vorzugsweise im Molverhältnis 1:1 einpolymerisiert.The monomers of groups a) and b) and, if appropriate, c) are copolymerized in accordance with the above-described processes in such a way that copolymers with molar masses of 500 to 30,000, preferably 1,000 to 20,000 g, per mol are retained. Copolymers of stearyl acrylate and maleic anhydride or maleic acid, copolymers of C₁₈- to C₂₂-alkyl methacrylates and acrylic acid or methacrylic acid, copolymers of octadecyl acrylate and acrylic acid, maleic acid or maleic anhydride and copolymers of vinyl 2-ethylhexanate and vinyl stearate or vinyl stearate or vinyl stearate or vinyl stearate or vinyl stearate or vinyl stearate or vinyl stearate are preferably suitable for the use according to the invention . The copolymers of the long-chain vinyl esters and maleic anhydride preferably contain the monomers copolymerized in a molar ratio of 1: 1.

Die bei den oben beschriebenen Polymerisationsverfahren anfallenden Copolymerisate werden für die Herstellung gebrauchsfertiger wäßriger Präparationslösungen bzw. wäßriger Dispersionen zunächst weitgehend von flüchtigen Anteilen befreit. Hierzu werden die Copolymerisate vorzugsweise unter vermindertem Druck auf Temperaturen von bis zu 150°C erwärmt. Unter diesen Bedingungen destillierten flüchtige Anteile ab. So kann ein beispielsweise niedrig siedender Regler aus Copolymerisaten entfernt werden, die durch Substanzpolymerisation hergestellt werden. Bei Polymerisaten, die durch Lösungspolymerisation erhalten werden, destilliert man vorteilhafter Weise vor der Herstellung wäßriger Präparationslösungen das bei der Polymerisation verwendete Lösemittel ab. Maleinsäureanhydridgruppen enthaltende Copolymerisate können jedoch in Form der Lösung in einem organischen Lösemittel in die entsprechenden Halbamidgruppierungen überführt werden, indem man sie mit Ammoniak oder Aminen zur Reaktion bringt. Die Umsetzung von Anhydridgruppen enthaltenden Copolymerisaten mit Alkoholen, Ammoniak oder Aminen erfolgt vorzugsweise in Abwesenheit von Lösemitteln.The copolymers obtained in the polymerization processes described above are initially largely freed of volatile components for the preparation of ready-to-use aqueous preparation solutions or aqueous dispersions. For this purpose, the copolymers are preferably heated to temperatures of up to 150 ° C. under reduced pressure. Volatile components distilled off under these conditions. For example, a low-boiling regulator can be removed from copolymers that are produced by bulk polymerization. In the case of polymers which are obtained by solution polymerization, the solvent used in the polymerization is advantageously distilled off before the preparation of aqueous preparation solutions. Copolymers containing maleic anhydride groups can, however, be converted into the corresponding half-amide groups in the form of the solution in an organic solvent by reacting them with ammonia or amines. The reaction of copolymers containing anhydride groups with alcohols, ammonia or amines is preferably carried out in the absence of solvents.

Die nach den oben beschriebenen Polymerisationsverfahren erhältlichen Copolymerisate werden in Wasser gelöst bzw. dispergiert und zumindest teilneutralisiert. Die Copolymerisate können jedoch auch, sofern bei der Copolymerisation als Monomere der Gruppe b) monoethylenisch ungesättigte Carbonsäuren oder monoethylenisch ungesättigte Dicarbonsäureanhydride eingesetzt werden, in die entsprechenden Amide bzw. Halbamide überführt werden. Hierzu gibt man beispielsweise zu einer Schmelze der Copolymerisate, aus der die flüchtigen Anteile entfernt worden sind, Ammoniak, primäre und/oder sekundäre Amine. Die Umsetzung wird dabei soweit geführt, daß 20 bis 50 % der Carboxylgruppen der einpolymerisierten monoethylenisch ungesättigten Carbonsäuren oder 20 bis 50 % der aus den einpolymerisierten monoethylenisch ungesättigten Dicarbonsäureanhydriden durch Hydrolyse erhältlichen Carboxylgruppen amidiert und jeweils mindestens 10 % der insgesamten vorhandenen Carboxylgruppen im Copolymerisat neutralisiert sind. Für die Hydrophobierung von Leder und Pelzfellen gebrauchsfertige Lösungen werden erhalten, wenn man die Copolymerisate nach dem Abkühlen auf Raumtemperatur oder vorzugsweise in Form einer Schmelze, die eine Temperatur in dem Bereich von 80 bis 180, vorzugsweise 90 bis 150°C aufweist, neutralisiert oder - wie oben bereits beschrieben - partiell durch Zusatz von Ammoniak, primären und/oder sekundären Aminen amidiert. Die Mengen an Wasser und Neutralisationsmittel werden dabei so gewählt, daß 10 bis 60, vorzugsweise 20 bis 55 Gew.-% Feststoffe enthaltende Dispersionen oder Polymerlösungen entstehen, die in den Handel gebracht werden. Daraus werden dann durch Verdünnen mit Wasser Präparationslösungen mit Feststoffgehalten von 0,5 bis 50 Gew.-% hergestellt.The copolymers obtainable by the polymerization processes described above are dissolved or dispersed in water and at least partially neutralized. However, the copolymers can also, provided that they are monoethylenically unsaturated in the copolymerization as monomers of group b) Carboxylic acids or monoethylenically unsaturated dicarboxylic anhydrides are used, are converted into the corresponding amides or half-amides. For example, ammonia, primary and / or secondary amines are added to a melt of the copolymers from which the volatile constituents have been removed. The reaction is carried out to such an extent that 20 to 50% of the carboxyl groups of the polymerized monoethylenically unsaturated carboxylic acids or 20 to 50% of the carboxyl groups obtainable from the copolymerized monoethylenically unsaturated dicarboxylic acid anhydrides are amidated and at least 10% of the total carboxyl groups present in the copolymer are neutralized. Ready-to-use solutions for the hydrophobization of leather and fur are obtained if the copolymers are neutralized after cooling to room temperature or preferably in the form of a melt which has a temperature in the range from 80 to 180, preferably 90 to 150 ° C., or as already described above - partially amidated by adding ammonia, primary and / or secondary amines. The amounts of water and neutralizing agent are chosen so that 10 to 60, preferably 20 to 55% by weight solids-containing dispersions or polymer solutions are formed which are brought onto the market. Preparation solutions with solids contents of 0.5 to 50% by weight are then prepared from this by dilution with water.

Ferner kann auch mit Aminocarbonsäuren sowie Salzen von Aminocarbonsäuren, vorzugsweise die Alkalimetallsalze, solvolysiert werden. Besonders bevorzugt werden Alkalimetallsalze von α-Aminocarbonsäuren eingesetzt, wobei die Alkalimetallsalze des Sarcosins ganz besonders vorteilhaft sind. Die Solvolyse mittels Salzen von Aminocarbonsäuren wird zweckmäßigerweise in wäßrigem Medium ausgeführt. Die Solvolyse wird dabei mit solchen Mengen an Aminocarboxylaten durchgeführt, daß 20 bis 50 % der Carboxylgruppen der einpolymerisierten monoethylenisch ungesättigten Carbonsäuren oder 20 bis 50 % der aus den einpolymerisierten monoethylenisch ungesättigten Dicarbonsäurenanhydriden durch Hydrolyse erhältlichen Carboxylgruppen amidiert sind. Nach der Bildung von Halbamid-Gruppen im Copolymerisat erfolgt die Neutralisation. Sie wird soweit geführt, daß mindestens 10 % der Carboxylgruppen des bei der Substanzpolymerisation anfallenden Copolymerisats neutralisiert werden.Solvolysis can also be carried out with aminocarboxylic acids and salts of aminocarboxylic acids, preferably the alkali metal salts. Alkali metal salts of α-aminocarboxylic acids are particularly preferably used, the alkali metal salts of sarcosine being particularly advantageous. The solvolysis using salts of aminocarboxylic acids is advantageously carried out in an aqueous medium. The solvolysis is carried out with such amounts of aminocarboxylates that 20 to 50% of the carboxyl groups of the polymerized monoethylenically unsaturated carboxylic acids or 20 to 50% of the carboxyl groups obtainable from the polymerized monoethylenically unsaturated dicarboxylic acid anhydrides are amidated by hydrolysis. After the formation of half-amide groups in the copolymer, neutralization takes place. It is carried out so far that at least 10% of the carboxyl groups of the copolymer obtained in bulk polymerization are neutralized.

Die bei der Copolymerisation anfallenden Säure- oder Anhydridgruppen enthaltenden Copolymerisate können auch durch Reaktion mit Alkoholen verestert werden. Die Veresterung wird dabei nur zu einem Anteil durchgeführt, daß 10 bis 50 % der Säuregruppen des Copolymerisates verestert sind. Anschließend erfolgt dann eine Neutralisation der partiell veresterten Copolymerisate, bei der mindestens 10 % der Carboxylgruppen neutralisiert werden. Die Neutralisation der Anhydrid- bzw. Säuregruppen enthaltenden Copolymerisate wird mindestens zu einem solchen Grad durchgeführt, daß man in Wasser dispergierbare Copolymerisate erhält. Dieser Neutralisationsgrad liegt bei mindestens 10 % der Carboxylgruppen des Copolymerisates bzw. mindestens 10 % der insgesamt aus den Anhydridgruppen des Copolymerisates entstehenden Carboxylgruppen. Der Neutralisationsgrad ist außerdem von der Kettenlänge des jeweils verwendeten Alkylacrylats bzw. Alkylmethacrylats oder der Vinylester abhängig. Um gut in Wasser dispergierbare bzw. kolloidal lösliche Copolymerisate zu erhalten, wird beispielsweise ein Copolymerisat aus einem C₃₀-Alkylacrylat und Maleinsäure zu mindestens 75 % neutralisiert, während beispielsweise ein Copolymerisat aus einem C₂₀-Alkylacrylat und Maleinsäureanhydrid bei einem Neutralisationsgrad von 50 % der aus diesem Copolymerisat entstehenden Carboxylgruppen bereits gut in Wasser dispergierbar sind. Bei einem Copolymerisat aus einem C₁₂-Alkylacrylat oder Alkylmethacrylat und Maleinsäureanhydrid oder Maleinsäure reicht bereits ein Neutralisationsgrad von 20 % der aus dem einpolymerisiertem Maleinsäureanhydrid entstehenden Carboxylgruppen für das Dispergieren des Copolymerisats in Wasser aus.The copolymers containing acid or anhydride groups obtained during the copolymerization can also be esterified by reaction with alcohols. The esterification is carried out only to an extent that 10 to 50% of the acid groups of the copolymer are esterified. The partially esterified copolymers are then neutralized, in which at least 10% of the carboxyl groups be neutralized. The neutralization of the copolymers containing anhydride or acid groups is carried out at least to such an extent that copolymers which are dispersible in water are obtained. This degree of neutralization is at least 10% of the carboxyl groups of the copolymer or at least 10% of the total carboxyl groups resulting from the anhydride groups of the copolymer. The degree of neutralization also depends on the chain length of the alkyl acrylate or alkyl methacrylate or vinyl ester used. In order to obtain copolymers which are readily water-dispersible or colloidally soluble, for example a copolymer of a C₃₀-alkyl acrylate and maleic acid is neutralized to at least 75%, for example a copolymer of a C₂₀-alkyl acrylate and maleic anhydride at a degree of neutralization of 50% of this Copolymer resulting carboxyl groups are already well dispersible in water. In a copolymer of a C₁₂-alkyl acrylate or alkyl methacrylate and maleic anhydride or maleic acid, a degree of neutralization of 20% of the carboxyl groups resulting from the copolymerized maleic anhydride is sufficient for dispersing the copolymer in water.

Falls man als Monomere der Gruppe b) bei der Copolymerisation keine Halbamide eingesetzt hat und die Bildung von Halbamidgruppen im Copolymerisat erwünscht ist, kann man Copolymerisate, die als Monomer der Gruppe b) eine ethylenisch ungesättigte Carbonsäure oder vorzugsweise ein monoethylenisch ungesättigtes Dicarbonsäureanhydrid einpolymerisiert enthalten, in Abwesenheit von Wasser mit Ammoniak, primären und/oder sekundären Aminen zu den entsprechenden Halbamiden umsetzen. Geeignete primäre und sekundäre Amine können 1 bis 40, vorzugsweise 3 bis 30 Kohlenstoffatome aufweisen. Bei solchen Stoffen handelt es sich beispielsweise um Methylamin, Ethylamin, n-Propylamin, Isopropylamin, n-Butylamin, Isobutylamin, Hexylamin, Cyclohexylamin, Methylcyclohexylamin, 2-Ethylhexylamin, n-Octylamin, Isotridecylamin, Talgfettamin, Stearylamin, Oleylamin, Dimethylamin, Diethylamin, Di-n-Propylamin, Di-Isopropylamin, Di-n-Butylamin, Diisobutylamin, Dihexylamin, Dicyclohexylamin, Dimethylcyclohexylamin, Di-2-ethylhexylamin, Di-n-Octylamin, Diisotridecylamin, Ditalgfettamin, Di-Stearylamin, Di-Oleylamin, Ethanolamin, Diethanolamin, n-Propanolamin, Di-n-Propanolamin und Morpholin. Vorzugsweise wird Morpholin verwendet.If no half-amides have been used as monomers of group b) in the copolymerization and the formation of half-amide groups in the copolymer is desired, copolymers which contain copolymerized as an monomer of group b) an ethylenically unsaturated carboxylic acid or preferably a monoethylenically unsaturated dicarboxylic anhydride In the absence of water, react with ammonia, primary and / or secondary amines to the corresponding half amides. Suitable primary and secondary amines can have 1 to 40, preferably 3 to 30 carbon atoms. Such substances are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, dimethylamine, diethylamine Di-n-propylamine, di-isopropylamine, di-n-butylamine, diisobutylamine, dihexylamine, dicyclohexylamine, dimethylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, diisotridecylamine, ditallow fatty amine, di-stearylamine, di-oleylamine, ethanol Diethanolamine, n-propanolamine, di-n-propanolamine and morpholine. Morpholine is preferably used.

Die Neutralisation der Copolymerisate kann mit den oben angegebenen Aminen oder Ammoniak sowie mit Alkalimetall- und/oder Erdalkalimetallbasen vorgenommen werden, z.B. Natronlauge, Kalilauge, Natriumbicarbonat, Soda, Kaliumcarbonat, Magnesiumhydroxid, Calciumhydroxid und Bariumhydroxid. Vorzugsweise erfolgt die Herstellung gebrauchsfertiger Lösungen oder Dispersionen durch Zugabe einer wäßrigen Base zu einer Schmelze des Copolymerisats. Der pH-Wert der gebrauchsfertigen Mittel zum Hydrophobieren liegt in dem Bereich von etwa 4 bis 10. Natürlich kann die wäßrige Lösung oder Dispersion auch durch Eintragen des Copolymeren in eine wäßrige Lösung der Alkalimetall- und/oder Erdalkalimetallbase, vorzugsweise bei Temperaturen von 20 bis 150°C, hergestellt werden.The copolymers can be neutralized with the amines or ammonia specified above and with alkali metal and / or alkaline earth metal bases, for example sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium carbonate, magnesium hydroxide, calcium hydroxide and barium hydroxide. Ready-to-use solutions or are preferably produced Dispersions by adding an aqueous base to a melt of the copolymer. The pH of the ready-to-use agents for hydrophobizing is in the range from about 4 to 10. Of course, the aqueous solution or dispersion can also be obtained by introducing the copolymer into an aqueous solution of the alkali metal and / or alkaline earth metal base, preferably at temperatures from 20 to 150 ° C.

Die so erhältlichen wäßrigen Copolymerisatdispersionen oder -lösungen sind beständig und lagerstabil. Sie eignen sich in hervorragender Weise zur Veredlung von Leder und Pelzfellen, weil sie eine besonders ausgeprägte hydrophobierende Wirkung aufweisen und darüberhinaus noch eine fettende und nachgerbende Wirkung entfalten. Das mit diesen Copolymerisatdispersionen behandelte Leder- und Pelzmaterial zeigt nur noch eine geringe Wasseraufnahmebereitschaft und Wasserdurchlässigkeit. Die Dispersionen wirken gleichzeitig weichmachend, so daß man in den meisten Fällen keine zusätzlichen Fettungsmittel auf Basis natürlicher oder synthetischer Lickeröle benötigt. Die Dispersionen verleihen der Ware eine hohe Fülle und hohe Zug- und Weiterreißfestigkeiten, so daß eine zusätzliche Behandlung mit handelsüblichen Nachgerbstoffen, beispielsweise mit vegetabilen Gerbstoffen oder synthetischen organischen Gerbstoffen (Synthanen) auf Basis von Phenolsulfonsäure/Phenol/Formaldehyd-Kondensationsprodukten in den meisten Fällen nicht mehr erforderlich ist.The aqueous copolymer dispersions or solutions obtainable in this way are stable and stable in storage. They are ideally suited for finishing leather and fur skins because they have a particularly pronounced hydrophobic effect and also have a greasy and retanning effect. The leather and fur material treated with these copolymer dispersions shows only a low level of water absorption and water permeability. The dispersions have a softening effect at the same time, so that in most cases no additional fatliquor based on natural or synthetic licker oils is required. The dispersions give the goods a high level and high tensile and tear strength, so that additional treatment with commercially available tanning agents, for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products, in most cases does not more is needed.

Ein weiterer Vorteil der erfindungsgemäß zu verwendenden wäßrigen Dispersionen oder Polymerlösungen besteht darin, daß sie keine zusätzlichen Emulgatoren enthalten. Leder und Pelzfelle, die mit emulgatorhaltigen Produkten behandelt worden sind, müssen bekanntlich nach der Behandlung mit diesen Mitteln aufwendigen Prozessen, wie z.B. Nachbehandlung mit mehrwertigen Metallsalzen unterworfen werden, um die Emulgatoren im Leder oder in den Pelzfellen unwirksam zu machen.Another advantage of the aqueous dispersions or polymer solutions to be used according to the invention is that they contain no additional emulsifiers. It is known that leather and fur skins that have been treated with products containing emulsifiers have to undergo complex processes after treatment with these agents, e.g. Subsequent treatment with polyvalent metal salts are subjected in order to render the emulsifiers in the leather or in the fur skins ineffective.

Die oben beschriebenen Copolymerisatdispersionen bzw. Copolymerisatlösungen eignen sich zur Behandlung von allen üblichen gegerbten Häuten, insbesondere mit Mineralgerbstoffen, wie Chrom-III-salzen gegerbten Häuten. Die gegerbten Häute werden üblicherweise vor der Behandlung entsäuert. Sie können bereits vor der Behandlung gefärbt worden sein. Eine Färbung kann jedoch auch erst nach der erfindungsgemäß erfolgenden Hydrophobierung vorgenommen werden.The above-described copolymer dispersions or copolymer solutions are suitable for the treatment of all customary tanned hides, in particular with mineral tanning agents, such as tanned hides containing chromium III salts. The tanned hides are usually deacidified before treatment. They may have been stained before treatment. However, coloring can also only be carried out after the hydrophobization according to the invention has taken place.

Die gegerbten Häute werden mit den wäßrigen Dispersionen zweckmäßigerweise in wäßriger Flotte, die durch Verdünnen der Copolymerisatdispersionen oder -lösungen mit Wasser erhältlich sind, bei pH-Werten von 4 bis 10, vorzugsweise 5 bis 8 und Temperaturen von 20 bis 60, vorzugsweise 30 bis 50°C, während eines Zeitraums von 0,1 bis 5, insbesondere 0,5 bis 2 Stunden, behandelt. Diese Behandlung erfolgt beispielsweise durch Walken in einem Faß. Die benötigte Menge an Copolymerisatdispersion bzw. -lösung beträgt, bezogen auf das Falzgewicht des Leders oder das Naßgewicht der Pelzfelle, 0,1 bis 30, vorzugsweise 1 bis 20 Gew.-%. Die Flottenlänge, d.h. das prozentuale Gewichtsverhältnis der Behandlungsflotte zur Ware, bezogen auf das Falzgewicht des Leders bzw. das Naßgewicht der Pelzfelle, beträgt üblicherweise 10 bis 1000, vorzugsweise 30 bis 150 %, bei Pelzfellen 50 bis 500 %.The tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the copolymer dispersions or solutions with water, at pH values from 4 to 10. preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C, for a period of 0.1 to 5, in particular 0.5 to 2 hours, treated. This treatment takes place, for example, by drumming in a barrel. The amount of copolymer dispersion or solution required, 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 liquor length, ie the percentage weight ratio of the treatment liquor to the goods, based on the fold weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, and 50 to 500% for fur skins.

Nach der Behandlung mit der oben beschriebenen wäßrigen Flotte wird der pH-Wert der Behandlungsflotte durch Zusatz von Säuren, vorzugsweise verwendet man organische Säuren, wie Ameisensäure, auf einen pH-Wert von 3 bis 5, vorzugsweise 3,5 bis 4 eingestellt.After the treatment with the aqueous liquor described above, the pH of the treatment 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.

Bei Mitverwendung von üblichen Nachgerbstoffen beim Veredlungsprozess des Leders und der Pelzfelle kann die Behandlung mit den erfindungsgemäß zu verwendenden wäßrigen Dispersionen oder Lösungen vor oder nach dem Nachgerbeschritt oder auch mehrstufig erfolgen, wobei die wäßrigen Dispersionen oder Lösungen anteilsweise vor, während und nach dem Nachgerbungsschritt eingesetzt werden. Die als Hydrophobierungsmittel zu verwendenden wäßrigen Dispersionen oder Lösungen können auch zusammen mit üblichen Leder- und Pelzveredlungsmitteln, wie Hydrophoblickern auf Paraffinbasis, verwendet werden. Dadurch wird in einigen Fällen die Hydrophobierungs-, Fettungs- und Nachgerbwirkung verbessert.If conventional retanning agents are also used in the finishing process of the leather and the fur skins, the treatment with the aqueous dispersions or solutions to be used according to the invention can be carried out before or after the retanning step or else in several stages, the aqueous dispersions or solutions being used in part before, during and after the retanning step . The aqueous dispersions or solutions to be used as hydrophobizing agents can also be used together with conventional leather and fur finishing agents, such as hydrophobics based on paraffin. In some cases, this improves the water repellent, oiling and retanning effects.

Die Prozentangaben in den Beispielen sind, falls nicht anders angegeben, Gewichtsprozent. Die Molmassen der Copolymeren wurden vor dem Neutralisieren durch Gelpermeationschromatographie bestimmt, wobei als Elutionsmittel Tetrahydrofuran und zur Eichung eng verteilte Fraktionen von Polystyrol eingesetzt wurden. Die Prüfung der behandelten Leder auf Wasseraufnahmebereitschaft und Wasserdurchlässigkeit erfolgte mit dem Bally-Penetrometer gemäß der Meßmethode IUP 10 der Internationalen Union der Leder-Chemiker-Verbände, Kommission für physikalische Lederprüfung, vgl. Das Leder, Band 12, 36 bis 40 (1961).Unless stated otherwise, the percentages in the examples are percentages by weight. The molecular weights of the copolymers were determined by gel permeation chromatography before neutralization, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration. The treated leather was tested for water absorption and water permeability using the Bally penetrometer in accordance with measurement method IUP 10 of the International Union of Leather Chemists' Associations, Commission for Physical Leather Testing, cf. The leather, volume 12, 36 to 40 (1961).

Herstellung der wäßrigen CopolymerisatdispersionenPreparation of the aqueous copolymer dispersions Dispersion IDispersion I

In einem Reaktor aus Edelstahl, der mit einem Rührer, Zulaufvorrichtungen und einer Vorrichtung für das Arbeiten unter Stickstoff ausgestattet war, wurden 90 g Maleinsäureanhydrid und 100 g technisches Xylol vorgelegt und auf ca. 140°C bis zum Sieden erhitzt. Zu der schwach siedenden Lösung gab man gleichzeitig innerhalb von 2 h eine schwach erwärmte Lösung von 210 g Stearylacrylat, 4,5 g Buten-1-ol-3 und 15 g 2-Mercaptoethanol in 200 g technischem Xylol und innerhalb von 3 h eine Lösung von 9 g Ditertiärbutylperoxid in 31 g technischem Xylol zu. Anschließend erhitzte man das Reaktionsgemisch noch 2 h unter Rühren und Rückflußsieden und destillierte dann das Xylol ab. Das restliche Xylol wurde dabei im Vakuum (40 millibar) und einer Temperatur von 125°C entfernt. Man fügte dann 79,9 g Morpholin innerhalb von einer halben Stunde zu und erhitzte das Reaktionsgemisch unter Rühren 2 h auf eine Temperatur von 130°C. Dabei wurden sämtliche Anhydridgruppen des Copolymerisats in Monoamidgruppen umgewandelt. Danach wurde der Reaktor druckdicht verschlossen. Bei einer Temperatur der Polymerschmelze von 125°C fügte man dann innerhalb von 1 h 73,5 g einer 50%igen wäßrigen Natronlauge und 1130 g Wasser zu. Dadurch wurden die restlichen Carboxylgruppen des Copolymerisats neutralisiert. Das Reaktionsgemisch wurde anschließend noch 2 h bei einer Temperatur von 125°C gerührt und auf Raumtemperatur abgekühlt. Man erhielt eine bei Raumtemperatur schwach viskose Dispersion mit einem Feststoffgehalt von 25,8 %. Die Molmasse des Copolymerisats betrug 6400 g pro Mol.90 g of maleic anhydride and 100 g of technical xylene were placed in a reactor made of stainless steel, which was equipped with a stirrer, feed devices and a device for working under nitrogen heated to approx. 140 ° C until boiling. A weakly heated solution of 210 g of stearyl acrylate, 4.5 g of buten-1-ol-3 and 15 g of 2-mercaptoethanol in 200 g of technical grade xylene was added to the low-boiling solution at the same time over the course of 2 hours and a solution was added within 3 hours of 9 g of ditertiary butyl peroxide in 31 g of technical xylene. The reaction mixture was then heated for a further 2 hours with stirring and refluxing, and the xylene was then distilled off. The remaining xylene was removed in vacuo (40 millibars) and a temperature of 125 ° C. 79.9 g of morpholine were then added over the course of half an hour and the reaction mixture was heated to a temperature of 130 ° C. with stirring for 2 hours. All of the copolymer's anhydride groups were converted into monoamide groups. The reactor was then closed in a pressure-tight manner. At a temperature of the polymer melt of 125 ° C., 73.5 g of a 50% strength aqueous sodium hydroxide solution and 1130 g of water were then added within 1 h. This neutralized the remaining carboxyl groups in the copolymer. The reaction mixture was then stirred for a further 2 hours at a temperature of 125 ° C. and cooled to room temperature. A dispersion which was slightly viscous at room temperature and had a solids content of 25.8% was obtained. The molecular weight of the copolymer was 6400 g per mole.

Dispersion IIDispersion II

In dem zur Herstellung der Dispersion I beschriebenen Reaktor legte man 281,25 g einer 80%igen Lösung eines C₁₈- bis C₂₂-Alkylmethacrylats (Methacrylester eines C₁₈-C₂₂-Alkoholgemisches, das unter dem Handelsnamen Alfol 1822 erhältlich ist) in o-Xylol, 9 g Buten-1-ol-3 und 15 g 2-Mercaptoethanol vor und erhitzte die Lösung zum Sieden auf eine Temperatur von etwa 145°C. Zu der unter Rückfluß siedenden Lösung gab man dann innerhalb von 2 h eine Lösung von 75 g Acrylsäure in 15 g o-Xylol und innerhalb von 3 h eine Lösung 9 g Ditertiärbutylperoxid in 31 g o-Xylol gleichmäßig zu. Danach wurde das Reaktionsgemisch noch 2 h unter Rühren am Rückfluß erhitzt und dann das o-Xylol abdestilliert. Restliches Xylol wurde aus der Polymerschmelze bei einer Temperatur von 140°C und einem Druck von 40 mbar entfernt. Die Polymerschmelze wurde dann auf eine Temperatur von 125°C abgekühlt und der Reaktor druckdicht verschlossen. Dann fügte man innerhalb von einer halben Stunde eine Lösung von 78 g 50%iger wäßriger Natronlauge in 586 g Wasser zu. Dadurch erreichte man eine Neutralisationsgrad von 95 % der im Copolymerisat vorhandenen Carboxylgruppen. Das Reaktionsgemisch wurde noch 3 h bei einer Temperatur von 125°C intensiv gerührt. Man erhielt eine viskose Dispersion mit einem Feststoffgehalt von 34,9 %. Die Molmasse des Copolymerisats betrug 4500 g pro Mol.In the reactor described for the preparation of dispersion I, 281.25 g of an 80% strength solution of a C₁₈- to C₂₂-alkyl methacrylate (methacrylic ester of a C₁₈-C₂₂-alcohol mixture, which is available under the trade name Alfol 1822) were placed in o-xylene, 9 g of buten-1-ol-3 and 15 g of 2-mercaptoethanol and heated the solution to a boil at a temperature of about 145 ° C. A solution of 75 g of acrylic acid in 15 g of o-xylene and then a solution of 9 g of ditertiary butyl peroxide in 31 g of o-xylene were then uniformly added to the refluxing solution over the course of 2 hours. The reaction mixture was then heated under reflux for a further 2 hours, and then the o-xylene was distilled off. Residual xylene was removed from the polymer melt at a temperature of 140 ° C and a pressure of 40 mbar. The polymer melt was then cooled to a temperature of 125 ° C. and the reactor was closed in a pressure-tight manner. A solution of 78 g of 50% strength aqueous sodium hydroxide solution in 586 g of water was then added within half an hour. This achieved a degree of neutralization of 95% of the carboxyl groups present in the copolymer. The reaction mixture was stirred vigorously for a further 3 h at a temperature of 125 ° C. A viscous dispersion with a solids content of 34.9% was obtained. The molecular weight of the copolymer was 4500 g per mole.

Dispersion IIIDispersion III

In dem für die Herstellung der Dispersion I beschriebenen Reaktor legte man 50 g Buten-1-ol-3 und 50 g Octadecylacrylat vor und erhitzte die Mischung unter Rühren auf eine Temperatur von 110°C. Durch getrennte Zulaufvorrichtungen dosierte man innerhalb von 5 h jeweils separat voneinander 300 g Octadecylacrylat, das auf eine Temperatur von 70°C erwärmt worden war, 150 g Methacrylsäure und innerhalb von 6 h 15 g Tertiärbutylperethylhexanoat gleichmäßig zu. Die Polymerisation wurde bei Siedetemperatur des Reaktionsgemisches durchgeführt. Die Siedetemperatur steigt langsam auf 132°C an. Nach Zugabe des Peroxids wurde das Reaktionsgemisch noch 1 h unter Rückflußsieden gerührt. Danach destillierte man das nichteinpolymerisierte Buten-1-ol-3 unter einem Druck von 40 mbar und einer Temperatur von 125°C ab. Der Reaktor wurde dann druckdicht verschlossen. Zu der darin auf 140°C erhitzten Schmelze gab man unter Druck 125 g 50%iger wäßriger Natronlauge und 1173 g Wasser innerhalb von 1 h zu. Die Mischung wurde dann noch 1 h bei 120°C gerührt. Man erhielt eine bei Raumtemperatur viskose Emulsion mit einem Feststoffgehalt von 30,6 %. Die Molmasse des Copolymerisats betrug 3600 g pro Mol. 90 % der Carboxylgruppen des Copolymerisats lagen in Form des Natriumsalzes vor.50 g of buten-1-ol-3 and 50 g of octadecyl acrylate were placed in the reactor described for the preparation of dispersion I and the mixture was heated to a temperature of 110 ° C. with stirring. 300 g of octadecyl acrylate, which had been heated to a temperature of 70.degree. C., 150 g of methacrylic acid and 15 g of tertiary butyl perethyl hexanoate were metered in uniformly over a period of 5 hours through separate feed devices. The polymerization was carried out at the boiling point of the reaction mixture. The boiling temperature slowly rises to 132 ° C. After the peroxide had been added, the reaction mixture was stirred under reflux for a further 1 h. The unpolymerized buten-1-ol-3 was then distilled off under a pressure of 40 mbar and a temperature of 125.degree. The reactor was then sealed pressure-tight. 125 g of 50% strength aqueous sodium hydroxide solution and 1173 g of water were added under pressure to the melt heated to 140 ° C. in the course of 1 h. The mixture was then stirred at 120 ° C. for 1 h. An emulsion which was viscous at room temperature and had a solids content of 30.6% was obtained. The molecular weight of the copolymer was 3600 g per mole. 90% of the carboxyl groups of the copolymer were in the form of the sodium salt.

Beispiel 1example 1

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert und mit 0,7 Gew.-% eines üblichen anionischen Anilinfarbstoffs gefärbt worden war, wurde mit 20 % der Dispersion I, bezogen auf Falzgewicht, eineinhalb Stunden bei 40°C im Gerbfaß gewalkt. Im Anschluß an diese Behandlung wurde das Leder mit Ameisensäure auf einen pH-Wert von 3,6 gebracht. Es wurde anschließend gewaschen, mechanisch ausgereckt und getrocknet.Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH of 5.0 and dyed with 0.7% by weight of a conventional anionic aniline dye, was mixed with 20% of dispersion I, based on the fold weight , tumbled for one and a half hours at 40 ° C in the tanning drum. Following this treatment, the leather was brought to a pH of 3.6 with formic acid. It was then washed, mechanically stretched and dried.

Das so erhaltene Leder war sehr weich und griffig und wies eine hohe dynamische Wasserfestigkeit auf. Die Prüfung mit dem Bally-Penetrometer ergab bei 15 % Stauchung für die Wasseraufnahme nach 24 h einen Wert von 24,7 Gew.-% und ließ während dieser Zeitspanne keinen Wasserdurchtritt erkennen.The leather thus obtained was very soft and easy to grip and had a high dynamic water resistance. The test with the Bally penetrometer showed a value of 24.7% by weight for a water absorption after 24 h at 15% compression and showed no water penetration during this period.

Beispiel 2Example 2

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert worden war, wurde mit 12 % der Dispersion II bezogen auf Falzgewicht, 2 Stunden bei 40°C im Gerbfaß gewalkt. Die Gesamt-Flottenlänge betrug 150 %.Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH value of 5.0, was drummed with 12% of dispersion II, based on fold weight, in the tanning drum for 2 hours at 40 ° C. The total fleet length was 150%.

Das Leder wurde anschließend mit 1 Gew.-% eines üblichen anionischen Anilinfarbstoffs gefärbt. Danach wurde es mit Ameisensäure auf einen pH-Wert von 3,8 eingestellt. Es wurde einschließend gewaschen, mechanisch ausgereckt und getrocknet.The leather was then dyed with 1% by weight of a conventional anionic aniline dye. Then it was adjusted to a pH of 3.8 with formic acid. Including washing, mechanical stretching and drying.

Das erhaltene Leder war sehr weich, geschmeidig, gut gefüllt, gleichmäßig gefärbt und hatte eine hervorragende dynamische Wasserfestigkeit. Die Prüfung mit dem Bally-Penetrometer ergab bei 15 % Stauchung für die Wasseraufnahme nach 24 h einen Wert von 22,9 Gew.-% und ließ während dieser Zeitspanne keinen Wasserdurchtritt erkennen.The leather obtained was very soft, supple, well filled, evenly colored and had excellent dynamic water resistance. The test with the Bally penetrometer showed a value of 22.9% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.

Beispiel 3Example 3

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert war, wurde mit 15 % der Polymerdispersion III und gleichzeitig mit 5 % einer 42%igen wäßrigen Dispersion eines handelsüblichen Hydrophoblickers auf Paraffinbasis, jeweils bezogen auf das Falzgewicht des Leders, 2 h bei 40°C im Gerbfaß gewalkt. Die Gesamt-Flottenlänge lag bei 150 %. Im Anschluß an diese Behandlung wurde das Leder mit Ameisensäure auf einen pH-Wert von 3,8 gebracht und wie üblich fertiggestellt.Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH of 5.0, was in each case obtained with 15% of polymer dispersion III and at the same time with 5% of a 42% aqueous dispersion of a commercially available hydrophobic liner based on paraffin on the fold weight of the leather, tumbled for 2 hours at 40 ° C in the tanning drum. The total fleet length was 150%. Following this treatment, the leather was brought to a pH of 3.8 with formic acid and finished as usual.

Das erhaltene Leder war außerordentlich weich und angenehm im Griff und zeigte eine hohe Wasserresistenz. Die Prüfung mit dem Bally-Penetrometer ergab bei 15 % Stauchung für die Wasseraufnahme nach 24 h einen Wert von 19,5 Gew.-%und ließ während dieser Zeitspanne keinen Wasserdurchtritt erkennen.The leather obtained was extremely soft and pleasant to the touch and showed a high water resistance. The test with the Bally penetrometer showed a value of 19.5% by weight for 15% compression for the water absorption after 24 h and showed no water penetration during this period.

Claims (5)

  1. The use of copolymers which contain
    a) from 50 to 90 % by weight of C₈-C₄₀-alkyl acrylates, C₈-C₄₀-alkyl methacrylates, vinyl esters of C₈-C₄₀-carboxylic acids or mixtures thereof and
    b) from 10 to 50 % by weight of monoethylenically unsaturated C₃-C₁₂-carboxylic acids, monoethylenically unsaturated dicarboxylic anhydrides, monoesters or monoamides of monoethylenically unsaturated C₄-C₁₂-dicarboxylic acids, amides of monoethylenically unsaturated C₃-C₁₂-monocarboxylic acids or mixtures thereof
    as copolymerized units, and which have molecular masses of from 500 to 30,000 g per mole, in at least partially neutralized form in aqueous solution or dispersion, as emulsifier-free water repellents for leather and furs.
  2. The use as claimed in claim 1, wherein the copolymers can be obtained by bulk polymerization of monomers a) and b) at from 80 to 300°C and wherein the resulting copolymer melt is at least partially neutralized and, where appropriate, partially amidated by addition of bases.
  3. The use as claimed in claim 1 or 2, wherein water and ammonia, amines, alkali metal or alkaline earth metal bases are added to a melt of the copolymers of a) and b) in amounts such that not less than 10 % of the carboxyl groups in the copolymers are neutralized.
  4. The use as claimed in claim 1 or 2, wherein primary and/or secondary amines are added to a melt or a virtually anhydrous solution of the copolymers of a) and b) in an inert organic solvent so that from 20 to 50 % of the carboxyl groups in the carboxylic acids or from the hydrolysis of the dicarboxylic anhydrides forming copolymerized units are amidated and not less than 10 % of the total of carboxyl groups in the copolymer are neutralized.
  5. The use as claimed in claim 1 or 2, wherein the copolymers are solvolyzed in aqueous medium by adding salts of amino carboxylic acids in amounts such that from 20 to 50 % of the carboxyl groups in the carboxylic acids or from the hydrolysis of the dicarboxylic anhydrides forming copolymerized units are amidated, and subsequently neutralized so that not less than 10 % of the total carboxyl groups present in the copolymer are neutralized.
EP90117145A 1989-09-16 1990-09-06 Use of copolymerisates based on long chain unsaturated esters and ethylenically unsaturated carbonic acids for hydrophobing of leather and fur pelts Revoked EP0418661B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3931039A DE3931039A1 (en) 1989-09-16 1989-09-16 USE OF COPOLYMERISATS BASED ON LONG-CHAIN UNSATURATED ESTERS AND ETHYLENICALLY UNSATURATED CARBONIC ACIDS FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS
DE3931039 1989-09-16

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EP0418661A1 EP0418661A1 (en) 1991-03-27
EP0418661B1 true EP0418661B1 (en) 1994-12-28

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US (1) US5124181A (en)
EP (1) EP0418661B1 (en)
JP (1) JPH03207800A (en)
KR (1) KR910006561A (en)
AT (1) ATE116377T1 (en)
AU (1) AU628646B2 (en)
CA (1) CA2024759A1 (en)
DE (2) DE3931039A1 (en)
ES (1) ES2066068T3 (en)
NZ (1) NZ235305A (en)
PT (1) PT95319B (en)

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CA2024759A1 (en) 1991-03-17
ATE116377T1 (en) 1995-01-15
JPH03207800A (en) 1991-09-11
US5124181A (en) 1992-06-23
AU6252790A (en) 1991-03-21
DE59008123D1 (en) 1995-02-09
ES2066068T3 (en) 1995-03-01
EP0418661A1 (en) 1991-03-27
PT95319B (en) 1997-06-30
NZ235305A (en) 1992-02-25
DE3931039A1 (en) 1991-03-28
PT95319A (en) 1991-05-22
KR910006561A (en) 1991-04-29

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