EP0628085B1 - Use of reaction products of homo- or copolymerisates based on monoethylenically unsaturated dicarboxylic acid anhydrides with amines or alcohols for stuffing and fulling leathers and fur pelts - Google Patents

Use of reaction products of homo- or copolymerisates based on monoethylenically unsaturated dicarboxylic acid anhydrides with amines or alcohols for stuffing and fulling leathers and fur pelts Download PDF

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EP0628085B1
EP0628085B1 EP93903970A EP93903970A EP0628085B1 EP 0628085 B1 EP0628085 B1 EP 0628085B1 EP 93903970 A EP93903970 A EP 93903970A EP 93903970 A EP93903970 A EP 93903970A EP 0628085 B1 EP0628085 B1 EP 0628085B1
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mol
reaction products
monoethylenically unsaturated
alcohols
unsaturated dicarboxylic
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EP0628085A1 (en
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Hermann Birkhofer
Peter Danisch
Walter Denzinger
Heinrich Hartmann
Norbert Greif
Knut Oppenlaender
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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

  • the present invention relates to the use of reaction products of homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides with certain amines and alcohols for greasing and filling leather and fur skins.
  • aqueous fat emulsions are used, which are generally based on petrochemically produced or natural oils and fats. These are usually made water-emulsifiable by partial sulfonation or with the help of emulsifiers. Incomplete drainage of the liquor, relatively easy extraction with solvents or water, the occurrence of migration phenomena and unsatisfactory authenticity profiles all turn out to be disadvantages of this class of greasing agents.
  • Polymeric products for example based on unsaturated dicarboxylic acid derivatives and long-chain olefins with lubricating properties for leather and fur skins, are known and are used as water repellents for leather and fur skins.
  • EP-A 412 389 describes copolymers of C8- to C40-monoolefins and ethylenically unsaturated C4- to C8-dicarboxylic acid anhydrides which, following their preparation by solvolysis of the anhydride groups, for example with bases such as amines or partial esterification of the anhydride groups with alcohols and at least partial neutralization of the carboxyl groups formed with bases in an aqueous medium can be converted to aqueous solutions or dispersions which are recommended as water repellents for leather and furskins.
  • EP-A 418 661 also discloses water repellents for leather and furskins, which are copolymers of C8 to C40 alkyl (meth) acrylates or vinyl esters of C8 to C40 carboxylic acids with, inter alia, monoethylenically unsaturated C4 to C12 dicarboxylic acid anhydrides. These copolymers can be reacted with amines after their preparation.
  • US Pat. No. 2,452,536 discloses the use of sulfonated reaction products of copolymers obtained by free radical polymerization based on styrene and maleic anhydride with lauryl or stearyl alcohol for filling and greasing leather.
  • DE-B 26 29 748 describes the use of copolymers of C10- to C30 monoolefins and maleic anhydride, which may have been saponified with amine after their preparation, for filling and greasing leather and furskins.
  • Such polymeric leather greasing agents do have a certain greasing effect, but this is still not entirely satisfactory, especially for soft types of leather.
  • an additional fatty agent based on a native or synthetic Lickers are used, which complements the effect with the polymeric fatliquor.
  • the object of the invention was therefore to provide an improved agent for greasing and filling leather and fur skins, which no longer has the disadvantages of the prior art.
  • Maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, methylene malonic anhydride and mixtures thereof are particularly suitable as monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 10 carbon atoms (a). Maleic anhydride is particularly preferred.
  • the radical R1 is preferably hydrogen or methyl
  • Particularly suitable vinyl aromatics (b) are styrene or ⁇ -methylstyrene or a mixture thereof.
  • vinyl esters (c) come e.g. Vinyl formate, vinyl propionate, vinyl butyrate or in particular vinyl acetate into consideration. Mixtures of such vinyl esters can also be used.
  • Suitable C2 to C6 olefins (d) are, in particular, straight-chain or branched monoolefins, in particular ⁇ -olefins, e.g. Ethylene, propylene, 1-butene, isobutene, 1-pentene or 1-hexene, and also 2-butene, 2-pentene, 2-hexene or 3-hexene. Isobutene is particularly preferred.
  • conjugated dienes such as butadiene or isoprene can also be used. Mixtures of the olefins mentioned can also be used.
  • Suitable monoethylenically unsaturated carboxylic acids (E) are especially C3- to C bis-carboxylic acids, e.g. Crotonic acid or especially acrylic acid and methacrylic acid.
  • Homopolymers A from one monomer (a), copolymers A from two or more monomers (a) and copolymers A from monomers (a) to (e) are used, the copolymer, however, at least 30 mol% of monoethylenically unsaturated dicarboxylic anhydride (a ) must contain.
  • a copolymer of 60 mol% styrene, 30 mol% maleic anhydride and 10 mol% acrylic acid or another copolymer of 50 mol% maleic anhydride, 25 mol% styrene and 25 mol% vinyl acetate can be used.
  • a homopolymer of a monoethylenically unsaturated dicarboxylic anhydride having 4 to 10 carbon atoms (a) is used as component A in the preparation of the reaction products used according to the invention.
  • polymers A it is also possible to use small amounts of further monomers which are copolymerizable with the monomers (a) to (e), in particular monoethylenically and polyethylenically unsaturated compounds.
  • N-vinyl amides such as N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl piperidine, N-vinyl caprolactam and N-vinyl succinimide, N-vinylphthalimide, N-vinyloxazolone, N-vinylformamide and N-vinylimidazole and alkyl vinyl ethers having 1 to 18 carbon atoms in the alkyl radical, for example methyl vinyl ether, ethyl vinyl ether or stearyl vinyl ether, and C8- to C30-olefins, in particular C10- to C20 ⁇ -olefins, for example 1-dodecene, 1-hexadecene or 1-octadecene.
  • N-vinyl amides such as N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl piperidine, N-vinyl caprol
  • methylenebisacrylamide esters of acrylic acid, methacrylic acid and maleic acid with polyhydric alcohols such as, for example, glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • polyhydric alcohols such as, for example, glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose as well as glycol diacrylates of polyethylene glycols with molecular weights up to 3000.
  • the polymers A can be prepared by conventional free radical polymerization methods. The techniques of suspension, solution and bulk polymerization can be used in particular. Organic solvents such as toluene, xylene, ethylbenzene, isopropylbenzene, tetrahydrofuran, dioxane, cyclohexane, petroleum ether or ligroin can be used, for example, as diluents or solvents for the polymerization. One works at normal pressure or under increased pressure.
  • Suitable radical initiator systems are all which form free radicals under the desired polymerization conditions, for example di-tert-butyl peroxide, tert-butyl perbenzoate or tert-butyl perethyl hexanoate.
  • Protective colloids such as polyvinyl vinyl ether, can be added, particularly in the case of suspension polymerization.
  • the K values of the polymers A are generally between 6 and 200, in particular between 8 and 100. According to Fikentscher, the K values of the copolymers were based on 1% by weight solutions in cyclohexanone and the K values of the homopolymers (a ) determined in dimethylformamide as solvent at 25 ° C.
  • the polymers A can be isolated in solid form and, if desired, dried and then reacted with component B. However, the polymers A can also be reacted directly with component B in solution.
  • Primary, secondary and tertiary alcohols having 1 to 30 carbon atoms are to be mentioned as suitable alcohols for component B for the reaction with the polymers A.
  • suitable alcohols for component B for the reaction with the polymers A Both saturated aliphatic alcohols and unsaturated alcohols, such as oleyl alcohol, can be used.
  • Primary or secondary alcohols are preferably used, for example amyl alcohol, n-hexanol, n-octanol, 2-ethylhexanol, n-nonanol, iso-nonanol, n-decanol, n-dodecanol, n-tridecanol, iso-tridecanol, cyclohexanol, of course occurring fatty alcohols such as tallow fatty alcohol or stearyl alcohol as well as the alcohols or alcohol mixtures with 9 to 19 C-atoms, which are technically easily accessible through oxosynthesis, such as C 9/10 -oxoalcohol, C 13/15 -oxoalcohol, and Ziegl alcohols with 12 to 24 C-atoms, e.g. C 12/14 or C 16/18 cuts.
  • fatty alcohols such as tallow fatty alcohol or stearyl alcohol as well as the alcohols or alcohol mixtures with 9 to 19 C
  • the alcohols of component B can also be oxyalkylated, i.e. have been reacted with a C2 to C wie alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
  • alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
  • Tetramethylene can also be present as a polytetrahydrofuran structure as an alkylene building block for such a block.
  • ether alcohols and polyether diols such as ethylene glycol monobutyl ether, di- and triethylene glycol monobutyl ether, polytetrahydrofuran as well as polyethylene glycols and polypropylene glycols.
  • component B in the preparation of the reaction products used according to the invention alcohols in which the radical R6 is C1- to C22-alkyl or C10- to C22-alkenyl, m and n each represent a number from 2 to 4 and p and q each denote a number from 0 to 35.
  • Suitable primary or secondary amines of component B for reaction with the polymers A are n-hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, n-tridecylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, di-n-hexylamine , Dicyclohexylamine, di- (methylcyclohexyl) amine, di- (2-ethylhexyl) amine, di- (n-octyl) amine, di- (isotridecyl) amine, di-tallow fatty amine, di-stearylamine, diolelylamine, diethanolamine, di- To name n-propanolamine or di-iso-propanolamine.
  • the polymers A are reacted with the amines or alcohols B by known methods.
  • carboxylic acid ester or carboxamide functions are incorporated into the polymers A.
  • Amines are advantageously reacted with the polymers A in bulk or in inert organic solvents such as toluene, xylene, cyclohexane, petroleum ether or ligroin, which usually result from the preparation of the polymers A themselves, at atmospheric pressure or elevated pressure at about 60 to 130 ° C. .
  • reaction of the alcohols with the polymers A is advantageously also carried out in bulk or, preferably, in inert organic solvents, as mentioned above, in the presence of acidic catalysts such as p-toluenesulfonic acid under atmospheric pressure or elevated pressure at about 100 to 150 ° C.
  • acidic catalysts such as p-toluenesulfonic acid under atmospheric pressure or elevated pressure at about 100 to 150 ° C.
  • the ratio of components A and B in the reaction is usually chosen so that 0.2 to 1.0 mol of amine or alcohol B or a mixture thereof is used per mole of monomer a) in polymer A.
  • any organic solvent which is present is generally removed, preferably by distillation, and the product is usually dispersed in an aqueous solution of a base, preferably an alkali metal hydroxide such as sodium or potassium hydroxide or ammonia, to remove the remaining anhydride Functions to partially or completely hydrolyze and partially or completely neutralize the functions of the partially esterified or partially amidated polymers.
  • a base preferably an alkali metal hydroxide such as sodium or potassium hydroxide or ammonia
  • the polymer dispersions obtainable in this way are suitable for the treatment of all customary tanned hides.
  • the tanned hides are usually deacidified before treatment. They may have been stained before treatment. Coloring can, however, also be carried out only after the lubrication that takes place according to the invention.
  • the tanned skins are expediently mixed with the aqueous dispersions in an aqueous liquor at pH values of 4 to 10, preferably 5 to 8, and temperatures of 20 to 60 ° C., preferably 30 to 50 ° C., for a period of 0.1 up to 5 hours, in particular 0.5 to 2 hours, treated.
  • This treatment takes place, for example, by drumming in a barrel.
  • the amount of reaction product from A and B required, based on the shaved weight of the leather or the wet weight of the fur file, is 0.1 to 30% by weight, 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 dispersions of the reaction products from A and B used generally have no additional emulsifiers.
  • 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.
  • treatment with the reaction products from A and B to be used according to the invention can take place before or after the retanning step.
  • reaction products to be used according to the invention it is possible to produce very soft leather without the addition of conventional licker. This advantage is reflected in simple and short application formulations.
  • these polymeric greasing agents significantly increase the authenticity profile of the leather.
  • the lightfastness and heat yellowing resistance of such leathers are influenced very positively.
  • the good fixation in the leather results in great resistance to extractability with solvent or water. This leads to so-called washable leathers, i.e. leather that does not lose its properties such as softness, strength and suppleness after washing, in contrast to leather that has been greased with conventional licker.
  • hydrophobic properties of these polymeric greasing agents can be varied so that the leather can also be given a certain water resistance by a suitable selection from the special alcohols and amines of component B in the reaction products used according to the invention.
  • reaction products used according to the invention are not require any additional emulsifiers when applied to leather or fur skins.
  • leather and furs made with emulsifier Products that have been treated often have to be subjected to complex processes, such as aftertreatment with polyvalent metal salts, after the treatment with these agents, in order to render the emulsifiers in the leather or in the fur skins ineffective.
  • the percentages in the examples relate to the weight.
  • the molecular weights of the copolymers were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.
  • the K values according to Fikentscher of the copolymers and of the auxiliaries were determined in 1% strength by weight solutions in cyclohexanone at 25 ° C., in the homopolymers of monomers (a) dimethylformamide was used as the solvent instead of cyclohexanone.
  • the preparation is carried out analogously to Example 2, except that 264.6 g (2.7 mol) of maleic anhydride and 655.2 g (6.3 mol) of styrene were used.
  • the K value of the polymer obtained was 16.0, the molar mass was 9000.
  • the fine, light brown polymer suspension could be processed further directly to give a leather greasing agent.
  • Example 2 In a reactor as in Example 1, 1750 g of maleic anhydride and 1165 g of o-xylene were heated to boiling and a solution of 262 g of tert-butyl perethylhexanoate in 190 g of o-xylene was metered in uniformly over 5 hours while boiling. The mixture was then reheated for an hour and then the o-xylene was decanted over the melt, the melt was applied to an aluminum sheet and cooled. The resin was crushed and the remaining solvent was distilled off in vacuo. The polymer had a K value of 10, the molar mass was 1000.
  • the copolymer obtained was a fine powder with a K value of 25 and its molar mass was 8000.
  • reaction products from polymers A and amines B were prepared by adding the amines shown in the table to the polymers shown in the table in xylene at 120 to 130 ° C. in the molar ratio of amine: maleic anhydride (MA) in the polymer shown in the table. After distilling off of the xylene after the reaction, the product was dispersed with an Ultraturax stirrer in aqueous sodium hydroxide solution in the molar ratio NaOH: MSA given in the table in the polymer, so that a 20 to 25% dispersion with a pH of 7 to 8 resulted.
  • MA maleic anhydride
  • reaction products from polymers A and alcohols B were prepared by reacting the alcohols listed in the table with the polymers listed in the table in xylene at 120 to 130 ° C. in the presence of catalytic amounts of p-toluenesulfonic acid for 3 to 5 hours in the The molar ratio of alcohol: MSA in the polymer indicated in the table.
  • MSA molar ratio of alcohol
  • the product was dispersed in the polymer using an Ultaturax stirrer in aqueous sodium hydroxide solution in the NaOH: MSA molar ratio given in the table, so that a 20 to 25% strength dispersion having a pH of 7 to 8 resulted.
  • Example 9 The product from Example 9 was used analogously to the procedure given in Example 21.
  • the leather thus obtained showed soft and round grip properties.
  • Example 10 The product from Example 10 was used analogously to the procedure given in Example 23.
  • the leather thus obtained was characterized by a round, soft handle.

Abstract

Use of homo-or copolymerisates based on monoethylenically unsaturated dicarboxylic acid anhydrides which can be obtained through the radically initiated polymerisation of a) 30 - 100 mol.% of one or more monoethylenically unsaturated dicarboxylic acid anhydrides with 4-10 C atoms; b) 0 - 70 mol.% of one or more vinyl aromatics of general formula (I) wherein R?1, R2 and R3¿ represent hydrogen, methyl or ethyl and k has a value of 1 or 2; c) 0 - 70 mol.% of one or more vinyl esters of C¿1?-C8 carboxylic acids; d) 0 - 50 mol.% of one or more C2-C6 olefines; and e) 0 - 30 mol.% of one or more monoethylenically unsaturated C3-C5 carboxylic acids, B) amines or alcohols or mixtures of such amines and alcohols for stuffing and fulling leathers and fur pelts.

Description

Die vorliegende Erfindung betrifft die Verwendung von Umsetzungsprodukten von Homo- oder Copolymerisaten auf Basis monoethylenisch ungesättigter Dicarbonsäureanhydride mit bestimmten Aminen und Alkoholen zum Fetten und Füllen von Leder und Pelzfellen.The present invention relates to the use of reaction products of homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides with certain amines and alcohols for greasing and filling leather and fur skins.

Zur Steuerung der mechanischen Eigenschaften von Leder wie Weichheit, Biegsamkeit oder Geschmeidigkeit werden wäßrige Fettemulsionen (Licker) verwendet, die im allgemeinen auf petrochemisch erzeugten oder auf natürlichen Ölen und Fetten basieren. Diese werden in der Regel durch Teilsulfierung oder mit Hilfe von Emulgatoren wasseremulgierbar gemacht. Unvollständige Flottenauszehrungen, relativ leichte Extraktion durch Lösungsmittel oder Wasser, Auftreten von Migrationsphänomenen und unbefriedigende Echtheitsprofile stellen sich als Nachteile dieser Klasse von Fettungsmitteln heraus.To control the mechanical properties of leather such as softness, flexibility or suppleness, aqueous fat emulsions (licker) are used, which are generally based on petrochemically produced or natural oils and fats. These are usually made water-emulsifiable by partial sulfonation or with the help of emulsifiers. Incomplete drainage of the liquor, relatively easy extraction with solvents or water, the occurrence of migration phenomena and unsatisfactory authenticity profiles all turn out to be disadvantages of this class of greasing agents.

Polymere Produkte beispielsweise auf Basis von ungesättigten Dicarbonsäurederivaten und langkettigen Olefinen mit fettenden Eigenschaften für Leder und Pelzfelle sind bekannt und finden als Hydrophobiermittel für Leder und Pelzfelle Anwendung.Polymeric products, for example based on unsaturated dicarboxylic acid derivatives and long-chain olefins with lubricating properties for leather and fur skins, are known and are used as water repellents for leather and fur skins.

So werden in der EP-A 412 389 Copolymerisate aus C₈- bis C₄₀-Monoolefinen und ethylenisch ungesättigten C₄- bis C₈-Dicarbonsäureanhydriden beschrieben, die im Anschluß an ihre Herstellung durch Solvolyse der Anhydridgruppen beispielsweise mit Basen wie Aminen oder partielle Veresterung der Anhydridgruppen mit Alkoholen und zumindest partielle Neutralisation der entstandenen Carboxylgruppen mit Basen in wäßrigem Medium zu wäßrigen Lösungen oder Dispersionen umgewandelt werden, welche als Hydrophobiermittel für Leder und Pelzfelle empfohlen werden.For example, EP-A 412 389 describes copolymers of C₈- to C₄₀-monoolefins and ethylenically unsaturated C₄- to C₈-dicarboxylic acid anhydrides which, following their preparation by solvolysis of the anhydride groups, for example with bases such as amines or partial esterification of the anhydride groups with alcohols and at least partial neutralization of the carboxyl groups formed with bases in an aqueous medium can be converted to aqueous solutions or dispersions which are recommended as water repellents for leather and furskins.

Aus der EP-A 418 661 sind ebenfalls Hydrophobiermittel für Leder und Pelzfelle bekannt, die Copolymerisate aus C₈- bis C₄₀-Alkyl(meth)acrylaten oder Vinylestern von C₈- bis C₄₀-Carbonsäuren mit u.a. monoethylenisch ungesättigten C₄- bis C₁₂-Dicarbonsäureanhydriden darstellen. Diese Copolymerisate können im Anschluß an ihre Herstellung mit Aminen umgesetzt werden.EP-A 418 661 also discloses water repellents for leather and furskins, which are copolymers of C₈ to C₄₀ alkyl (meth) acrylates or vinyl esters of C₈ to C₄₀ carboxylic acids with, inter alia, monoethylenically unsaturated C₄ to C₁₂ dicarboxylic acid anhydrides. These copolymers can be reacted with amines after their preparation.

Die US-A 2 452 536 offenbart die Verwendung von sulfonierten Umsetzungsprodukten von durch radikalisch initiierte Polymerisation erhaltenen Copolymeren auf Basis von Styrol und Maleinsäureanhydrid mit Lauryl- oder Stearylalkohol zum Füllen und Fetten von Leder.US Pat. No. 2,452,536 discloses the use of sulfonated reaction products of copolymers obtained by free radical polymerization based on styrene and maleic anhydride with lauryl or stearyl alcohol for filling and greasing leather.

In der DE-B 26 29 748 wird die Verwendung von Copolymerisaten aus C₁₀- bis C₃₀-Monoolefinen und Maleinsäureanhydrid, die gegebenenfalls im Anschluß an ihre Herstellung mit Amin verseift worden sind, zum Füllen und Fetten von Leder und Pelzfellen beschrieben.DE-B 26 29 748 describes the use of copolymers of C₁₀- to C₃₀ monoolefins and maleic anhydride, which may have been saponified with amine after their preparation, for filling and greasing leather and furskins.

Derartige polymere Lederfettungsmittel zeigen zwar einen gewissen fettenden Effekt, der aber insbesondere für weiche Ledersorten noch nicht ganz befriedigend ist. In diesen Fällen muß ein zusätzliches Fettungsmittel auf Basis eines nativen oder synthetischen Lickers eingesetzt werden, welches sich in der Wirkung mit dem polymeren Fettungsmittel ergänzt.Such polymeric leather greasing agents do have a certain greasing effect, but this is still not entirely satisfactory, especially for soft types of leather. In these cases, an additional fatty agent based on a native or synthetic Lickers are used, which complements the effect with the polymeric fatliquor.

Der Erfindung lag daher die Aufgabe zugrunde, ein verbessertes Mittel zum Fetten und Füllen von Leder und Pelzfellen bereitzustellen, welches die Nachteile des Standes der Technik nicht mehr aufweist.The object of the invention was therefore to provide an improved agent for greasing and filling leather and fur skins, which no longer has the disadvantages of the prior art.

Demgemäß wurde die Verwendung von Umsetzungsprodukten von

  • A) Homo- oder Copolymerisaten auf Basis monoethylenisch ungesättigter Dicarbonsäureanhydride mit Ausnahme von sulfonierten Polymerisaten, erhältlich durch radikalisch initiierte Polymerisation von
    • (a) 30 bis 100 mol-% eines oder mehrerer monoethylenisch ungesättigter Dicarbonsäureanhydride mit 4 bis 10 C-Atomen,
    • (b) 0 bis 70 mol-% eines oder mehrerer Vinylaromaten der allgemeinen Formel I
      Figure imgb0001
       in der R¹, R und R³ für Wasserstoff, Methyl oder Ethyl stehen und k 1 oder 2 bedeutet,
    • (c) 0 bis 70 mol-% eines oder mehrerer Vinylester von C₁- bis C₄-Carbonsäuren,
    • (d) 0 bis 50 mol-% eines oder mehrerer C₂- bis C₆-Olefine und
    • (e) 0 bis 30 mol-% eines oder mehrerer monoethylenisch ungesättigter C₃- bis C₅-Carbonsäuren,
    wobei der Monomerenmischung aus (a) bis (e) noch bis zu 10 Gew.-% weiterer copolymerisierbarer Monomerer zugesetzt werden können, mit
  • B) Aminen der allgemeinen Formel R⁴R⁵NH, in der R⁴ Wasserstoff, C₁- bis C₂₀-Alkyl, C₅- bis C₈-Cycloalkyl oder C₂- bis C₄-Hydroxyalkyl und R⁵ C₆- bis C₃₀-Alkyl, C₆- bis C₃₀-Alkenyl, C₅- bis C₈-Cycloalkyl oder C₂- bis C₄-Hydroxyalkyl bezeichnet, oder Alkoholen der allgemeinen Formel R⁶-O-(CmH2mO)p-(CnH2nO)q-H, in der R⁶ C₁- bis C₃₀-Alkyl, C₂- bis C₃₀-Alkenyl, C₅- bis C₈-Cycloalkyl oder für den Fall p+q > 0 für Wasserstoff steht, m und n jeweils eine Zahl von 2 bis 4 bedeuten und p und q jeweils eine Zahl von 0 bis 50 bezeichnen, oder Mischungen aus derartigen Aminen und Alkoholen
zum Fetten und Füllen von Leder und Pelzfellen gefunden.Accordingly, the use of reaction products from
  • A) Homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides with the exception of sulfonated polymers, obtainable by free-radically initiated polymerization of
    • (a) 30 to 100 mol% of one or more monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 10 carbon atoms,
    • (b) 0 to 70 mol% of one or more vinyl aromatics of the general formula I
      Figure imgb0001
       in which R¹, R and R³ are hydrogen, methyl or ethyl and k is 1 or 2,
    • (c) 0 to 70 mol% of one or more vinyl esters of C₁ to C₄ carboxylic acids,
    • (d) 0 to 50 mol% of one or more C₂ to C₆ olefins and
    • (e) 0 to 30 mol% of one or more monoethylenically unsaturated C₃ to C₅ carboxylic acids,
    wherein up to 10% by weight of further copolymerizable monomers can be added to the monomer mixture from (a) to (e) with
  • B) Amines of the general formula R⁴R⁵NH, in which R⁴ is hydrogen, C₁- to C₂₀-alkyl, C₅- to C₈-cycloalkyl or C₂- to C₄-hydroxyalkyl and R⁵ C₆- to C₃₀-alkyl, C₆- to C₃₀-alkenyl, C₅ - to C₈-cycloalkyl or C₂- to C₄-hydroxyalkyl, or alcohols of the general formula R⁶-O- (C m H 2m O) p - (C n H 2n O) q -H, in which R⁶ C₁- to C₃₀ -Alkyl, C₂- to C₃₀-alkenyl, C₅- to C₈-cycloalkyl or if p + q> 0 is hydrogen, m and n each represent a number from 2 to 4 and p and q each represent a number from 0 to 50, or mixtures of such amines and alcohols
found for greasing and filling leather and fur skins.

Als monoethylenisch ungesättigte Dicarbonsäureanhydride mit 4 bis 10 C-Atomen (a) eignen sich vor allem Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid, Mesaconsäureanhydrid, Methylenmalonsäureanhydrid sowie Mischungen hieraus. Besonders bevorzugt wird Maleinsäureanhydrid.Maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, methylene malonic anhydride and mixtures thereof are particularly suitable as monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 10 carbon atoms (a). Maleic anhydride is particularly preferred.

In der allgemeinen Formel I für die Vinylaromaten (b) steht der Rest R¹ vorzugsweise für Wasserstoff oder Methyl, die Reste R und R³ bezeichnen vorzugsweise Wasserstoff und k bedeutet vorzugsweise 1. Steht R³ im Fall k = 1 für Methyl oder Ethyl, liegt eine ortho-, meta- oder vorzugsweise para-Substitution am Phenylkern vor. Steht R³ im Fall k = 2 für Methyl oder Ethyl, ist das Substitutionsmuster am Phenylkern vorzugsweise 2,4.In the general formula I for the vinylaromatics (b) the radical R¹ is preferably hydrogen or methyl, the radicals R and R³ preferably denote hydrogen and k preferably denotes 1. If R³ in the case k = 1 represents methyl or ethyl, there is an ortho -, Meta or preferably para substitution on the phenyl nucleus. If R³ in the case k = 2 is methyl or ethyl, the substitution pattern on the phenyl nucleus is preferably 2.4.

Als Vinylaromaten (b) eignen sich insbesondere Styrol oder α-Methylstyrol oder eine Mischung hieraus.Particularly suitable vinyl aromatics (b) are styrene or α-methylstyrene or a mixture thereof.

Als Vinylester (c) kommen z.B. Vinylformiat, Vinylpropionat, Vinylbutyrat oder insbesondere Vinylacetat in Betracht. Auch Mischungen solcher Vinylester können eingesetzt werden.As vinyl esters (c) come e.g. Vinyl formate, vinyl propionate, vinyl butyrate or in particular vinyl acetate into consideration. Mixtures of such vinyl esters can also be used.

Als C₂- bis C₆-Olefine (d) eignen sich vor allem geradkettige oder verzweigte Monoolefine, insbesondere α-Olefine, z.B. Ethylen, Propylen, 1-Buten, Isobuten, 1-Penten oder 1-Hexen, weiterhin auch 2-Buten, 2-Penten, 2-Hexen oder 3-Hexen. Besonders bevorzugt wird Isobuten. Daneben können aber auch noch konjugierte Diene wie Butadien oder Isopren verwendet werden. Auch Mischungen der genannten Olefine können eingesetzt werden.Suitable C₂ to C₆ olefins (d) are, in particular, straight-chain or branched monoolefins, in particular α-olefins, e.g. Ethylene, propylene, 1-butene, isobutene, 1-pentene or 1-hexene, and also 2-butene, 2-pentene, 2-hexene or 3-hexene. Isobutene is particularly preferred. In addition, conjugated dienes such as butadiene or isoprene can also be used. Mixtures of the olefins mentioned can also be used.

Als monoethylenisch ungesättigte Carbonsäuren (e) kommen vor allem C₃- bis C₄-Carbonsäuren in Betracht, z.B. Crotonsäure oder insbesondere Acrylsäure und Methacrylsäure.Suitable monoethylenically unsaturated carboxylic acids (E) are especially C₃- to C bis-carboxylic acids, e.g. Crotonic acid or especially acrylic acid and methacrylic acid.

Verwendung finden Homopolymerisate A aus einem Monomer (a), Copolymerisate A aus zwei oder mehreren Monomeren (a) und Copolymerisate A aus den Monomeren (a) bis (e), wobei das Copolymerisat jedoch mindestens 30 mol-% an monoethylenisch ungesättigtem Dicarbonsäureanhydrid (a) enthalten muß. So kann beispielsweise ein Copolymerisat aus 60 mol-% Styrol, 30 mol-% Maleinsäureanhydrid und 10 mol-% Acrylsäure oder ein anderes Copolymerisat aus 50 mol-% Maleinsäureanhydrid, 25 mol-% Styrol und 25 mol-% Vinylacetat eingesetzt werden.Homopolymers A from one monomer (a), copolymers A from two or more monomers (a) and copolymers A from monomers (a) to (e) are used, the copolymer, however, at least 30 mol% of monoethylenically unsaturated dicarboxylic anhydride (a ) must contain. For example, a copolymer of 60 mol% styrene, 30 mol% maleic anhydride and 10 mol% acrylic acid or another copolymer of 50 mol% maleic anhydride, 25 mol% styrene and 25 mol% vinyl acetate can be used.

In einer bevorzugten Ausführungsform wird als Komponente A bei der Herstellung der erfindungsgemäß verwendeten Umsetzungsprodukte ein Homopolymerisat aus einem monoethylenisch ungesättigten Dicarbonsäureanhydrid mit 4 bis 10 C-Atomen (a) eingesetzt.In a preferred embodiment, a homopolymer of a monoethylenically unsaturated dicarboxylic anhydride having 4 to 10 carbon atoms (a) is used as component A in the preparation of the reaction products used according to the invention.

In einer weiteren bevorzugten Ausführungsform wird als Komponente A bei der Herstellung der erfindungsgemäß verwendeten Umsetzungsprodukte ein Copolymerisat aus

  • (a) 30 bis 99 mol-% eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 10 C-Atomen und
  • (b) 1 bis 70 mol-% eines oder mehrerer Vinylaromaten I
eingesetzt.In a further preferred embodiment, a copolymer is used as component A in the preparation of the reaction products used according to the invention
  • (a) 30 to 99 mol% of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 10 carbon atoms and
  • (b) 1 to 70 mol% of one or more vinyl aromatics I
used.

In einer weiteren bevorzugten Ausführungsform wird als Komponente A bei der Herstellung der erfindungsgemäß verwendeten Umsetzungsprodukte ein Copolymerisat aus

  • (a) 30 bis 99 mol-% eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 10 C-Atomen und
  • (c) 1 bis 70 mol-% eines oder mehrerer Vinylester von C₁- bis C₄-Carbonsäuren
eingesetzt.In a further preferred embodiment, a copolymer is used as component A in the preparation of the reaction products used according to the invention
  • (a) 30 to 99 mol% of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 10 carbon atoms and
  • (c) 1 to 70 mol% of one or more vinyl esters of C₁ to C₄ carboxylic acids
used.

In einer weiteren bevorzugten Ausführungsform wird als Komponente A bei der Herstellung der erfindungsgemäß verwendeten Umsetzungsprodukte ein Copolymerisat aus

  • (a) 50 bis 99 mol-% eines monoethylenisch ungesättigten Dicarbonsäureanhydrids mit 4 bis 10 C-Atomen und
  • (d) 1 bis 50 mol-% eines oder mehrerer C₂- bis C₆-Olefine
eingesetzt.In a further preferred embodiment, a copolymer is used as component A in the preparation of the reaction products used according to the invention
  • (a) 50 to 99 mol% of a monoethylenically unsaturated dicarboxylic acid anhydride with 4 to 10 carbon atoms and
  • (d) 1 to 50 mol% of one or more C₂ to C₆ olefins
used.

Zur weiteren Modifizierung der Eigenschaften der Polymerisate A können noch geringe Mengen weiterer mit den Monomeren (a) bis (e) copolymerisierbare Monomerer, insbesondere monoethylenisch und mehrfach ethylenisch ungesättigter Verbindungen zum Einsatz gelangen. Dies sind beispielsweise Hydroxyalkylester mit 2 bis 6 C-Atomen im Alkylrest und die entsprechenden Nitrile der bisher schon genannten Mono- und Dicarbonsäuren, N-Vinyiamide wie z.B. N-Vinylacetamid, N-Vinylpyrrolidon, N-Vinylpiperidin, N-Vinylcaprolactam, N-Vinyl-succinimid, N-Vinylphthalimid, N-Vinyloxazolon, N-Vinylformamid und N-Vinylimidazol sowie Alkylvinylether mit 1 bis 18 C-Atomen im Alkylrest, z.B. Methylvinylether, Ethylvinylether oder Stearylvinylether, und C₈- bis C₃₀-Olefine, insbesondere C₁₀- bis C₂₀-α-Olefine, z.B. 1-Dodecen, 1-Hexadecen oder 1-Octadecen. Weiter sind geeignet Methylenbisacrylamid, Ester von Acrylsäure, Methacrylsäure und Maleinsäure mit mehrwertigen Alkoholen wie z.B. Glykoldiacrylat, Glycerintriacrylat, Glykoldimethacrylat, Glycerintrimethacrylat, sowie mindestens zweifach mit Acrylsäure oder Methacrylsäure veresterte Polyole wie Pentaerythrit und Glucose. Außerdem sind geeignet Divinylbenzol, Divinyldioxan, Pentaerythrittriallylether und Pentaallylsucrose sowie Glykoldiacrylate von Polyethylenglykolen mit Molgewichten bis zu 3000. Diese zur Modifizierung der Polymerisate A einsetzbaren Monomeren werden der Monomerenmischung aus (a) bis (e) in Mengen von bis zu 10 Gew.-%, vorzugsweise bis zu 5 Gew.-%, zugesetzt.To further modify the properties of the polymers A, it is also possible to use small amounts of further monomers which are copolymerizable with the monomers (a) to (e), in particular monoethylenically and polyethylenically unsaturated compounds. These are, for example, hydroxyalkyl esters with 2 to 6 carbon atoms in the alkyl radical and the corresponding nitriles of the mono- and dicarboxylic acids already mentioned, N-vinyl amides such as N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl piperidine, N-vinyl caprolactam and N-vinyl succinimide, N-vinylphthalimide, N-vinyloxazolone, N-vinylformamide and N-vinylimidazole and alkyl vinyl ethers having 1 to 18 carbon atoms in the alkyl radical, for example methyl vinyl ether, ethyl vinyl ether or stearyl vinyl ether, and C₈- to C₃₀-olefins, in particular C₁₀- to C₂₀ α-olefins, for example 1-dodecene, 1-hexadecene or 1-octadecene. Also suitable are methylenebisacrylamide, esters of acrylic acid, methacrylic acid and maleic acid with polyhydric alcohols such as, for example, glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose. Also suitable are divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose as well as glycol diacrylates of polyethylene glycols with molecular weights up to 3000. These monomers which can be used to modify the polymers A are added to the monomer mixture from (a) to (e) in amounts of up to 10% by weight, preferably up to 5% by weight.

Die Polymerisate A können nach hierfür üblichen Methoden der radikalischen Polymerisation hergestellt werden. Dabei können insbesondere die Techniken der Suspensions-, Lösungs- und Massepolymerisation angewandt werden. Als Verdünnungs- bzw. Lösungsmittel für die Polymerisation können beispielsweise organische Lösungsmittel wie Toluol, Xylol, Ethylbenzol, Isopropylbenzol, Tetrahydrofuran, Dioxan, Cyclohexan, Petrolether oder Ligroin eingesetzt werden. Man arbeitet bei Normaldruck oder unter erhöhtem Druck. Als radikalische Initiatorsysteme eignen sich alle, die unter den gewünschten Polymerisationsbedingungen Radikale bilden, beispielsweise Di-tert.-butylperoxid, tert.-Butylperbenzoat oder tert.-Butylperethylhexanoat. Es können, besonders bei der Suspensionspolymerisation, Schutzkolloide wie Polyethylvinylether zugesetzt werden.The polymers A can be prepared by conventional free radical polymerization methods. The techniques of suspension, solution and bulk polymerization can be used in particular. Organic solvents such as toluene, xylene, ethylbenzene, isopropylbenzene, tetrahydrofuran, dioxane, cyclohexane, petroleum ether or ligroin can be used, for example, as diluents or solvents for the polymerization. One works at normal pressure or under increased pressure. Suitable radical initiator systems are all which form free radicals under the desired polymerization conditions, for example di-tert-butyl peroxide, tert-butyl perbenzoate or tert-butyl perethyl hexanoate. Protective colloids, such as polyvinyl vinyl ether, can be added, particularly in the case of suspension polymerization.

Die K-Werte der Polymerisate A liegen in der Regel zwischen 6 und 200, insbesondere zwischen 8 und 100. Die K-Werte der Copolymerisate wurden nach Fikentscher an 1 gew.-%igen Lösungen in Cyclohexanon und die K-Werte der Homopolymerisate (a) in Dimethylformamid als Lösungsmittel bei 25°C bestimmt.The K values of the polymers A are generally between 6 and 200, in particular between 8 and 100. According to Fikentscher, the K values of the copolymers were based on 1% by weight solutions in cyclohexanone and the K values of the homopolymers (a ) determined in dimethylformamide as solvent at 25 ° C.

Die Polymerisate A können nach der Polymerisation in fester Form isoliert und gewünschtenfalls getrocknet und danach mit der Komponente B umgesetzt werden. Die Polymerisate A können aber auch direkt in Lösung mit der Komponente B umgesetzt werden.After the polymerization, the polymers A can be isolated in solid form and, if desired, dried and then reacted with component B. However, the polymers A can also be reacted directly with component B in solution.

Als zur Umsetzung mit den Polymerisaten A geeignete Alkohole der Komponente B sind in erster Linie primäre, sekundäre und tertiäre Alkohole mit 1 bis 30 C-Atomen zu nennen. Man kann sowohl gesättigte aliphatische Alkohole als auch ungesättigte Alkohole, wie beispielsweise Oleylalkohol, einsetzen. Vorzugsweise werden primäre oder sekundäre Alkohole verwendet, z.B. Amylalkohol, n-Hexanol, n-Octanol, 2-Ethylhexanol, n-Nonanol, iso-Nonanol, n-Decanol, n-Dodecanol, n-Tridecanol, iso-Tridecanol, Cyclohexanol, natürlich vorkommende Fettalkohole wie Talgfettalkohol oder Stearylalkohol sowie die technisch durch Oxosynthese leicht zugänglichen Alkohole bzw. Alkoholgemische mit 9 bis 19 C-Atomen wie z.B. C9/10-Oxoalkohol, C13/15-Oxoalkohol, sowie Ziegleralkohole mit 12 bis 24 C-Atomen, z.B. C12/14- oder C16/18-Schnitte.Primary, secondary and tertiary alcohols having 1 to 30 carbon atoms are to be mentioned as suitable alcohols for component B for the reaction with the polymers A. Both saturated aliphatic alcohols and unsaturated alcohols, such as oleyl alcohol, can be used. Primary or secondary alcohols are preferably used, for example amyl alcohol, n-hexanol, n-octanol, 2-ethylhexanol, n-nonanol, iso-nonanol, n-decanol, n-dodecanol, n-tridecanol, iso-tridecanol, cyclohexanol, of course occurring fatty alcohols such as tallow fatty alcohol or stearyl alcohol as well as the alcohols or alcohol mixtures with 9 to 19 C-atoms, which are technically easily accessible through oxosynthesis, such as C 9/10 -oxoalcohol, C 13/15 -oxoalcohol, and Ziegl alcohols with 12 to 24 C-atoms, e.g. C 12/14 or C 16/18 cuts.

Die Alkohole der Komponente B können auch oxalkyliert vorliegen, d.h. mit einem C₂- bis C₄-Alkylenoxid wie Ethylenoxid, Propylenoxid oder Butylenoxid umgesetzt worden sein. Hierbei können im Molekül ein oder zwei verschiedene Alkylenoxid-Blöcke vorhanden sein. Als Alkylen-Baustein für einen derartigen Block kann auch Tetramethylen als Polytetrahydrofuran-Struktur vorliegen.The alcohols of component B can also be oxyalkylated, i.e. have been reacted with a C₂ to C wie alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide. One or two different alkylene oxide blocks can be present in the molecule. Tetramethylene can also be present as a polytetrahydrofuran structure as an alkylene building block for such a block.

Weiterhin in Betracht kommen als Alkohole der Komponente B Etheralkohole und Polyetherdiole wie Ethylenglykolmonobutylether, Di- und Triethylenglykolmonobutylether, Polytetrahydrofuran sowie Polyethylenglykole und Polypropylenglykole.Also suitable as alcohols of component B are ether alcohols and polyether diols such as ethylene glycol monobutyl ether, di- and triethylene glycol monobutyl ether, polytetrahydrofuran as well as polyethylene glycols and polypropylene glycols.

In einer bevorzugten Ausführungsform werden als Komponente B bei der Herstellung der erfindungsgemäß verwendeten Umsetzungsprodukte Alkohole, bei denen der Rest R⁶ für C₁- bis C₂₂-Alkyl oder C₁₀- bis C₂₂-Alkenyl steht, m und n jeweils eine Zahl von 2 bis 4 bedeuten und p und q jeweils eine Zahl von 0 bis 35 bezeichnen, eingesetzt.In a preferred embodiment, as component B in the preparation of the reaction products used according to the invention, alcohols in which the radical R⁶ is C₁- to C₂₂-alkyl or C₁₀- to C₂₂-alkenyl, m and n each represent a number from 2 to 4 and p and q each denote a number from 0 to 35.

Als zur Umsetzung mit den Polymerisaten A geeignete primäre oder sekundäre Amine der Komponente B sind beispielsweise n-Hexylamin, Cyclohexylamin, Methylcyclohexylamin, 2-Ethylhexylamin, n-Octylamin, n-Tridecylamin, Isotridecylamin, Talgfettamin, Stearylamin, Oleylamin, Di-n-Hexylamin, Dicyclohexylamin, Di-(methylcyclohexyl)amin, Di-(2-ethylhexyl)-amin, Di-(n-octyl)amin, Di-(isotridecyl)amin, Di-Talgfettamin, Di-stearylamin, Diolelylamin, Diethanolamin, Di-n-propanolamin oder Di-iso-propanolamin zu nennen.Examples of suitable primary or secondary amines of component B for reaction with the polymers A are n-hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, n-tridecylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, di-n-hexylamine , Dicyclohexylamine, di- (methylcyclohexyl) amine, di- (2-ethylhexyl) amine, di- (n-octyl) amine, di- (isotridecyl) amine, di-tallow fatty amine, di-stearylamine, diolelylamine, diethanolamine, di- To name n-propanolamine or di-iso-propanolamine.

In einer bevorzugten Ausführungsform werden als Komponente B bei der Herstellung der erfindungsgemäß verwendeten Umsetzungsprodukte Amine, bei denen der Rest R⁴ Wasserstoff und der Rest R⁵, C₁₀- bis C₂₂-Alkyl oder C₁₀- bis C₂₂-Alkenyl bezeichnet, eingesetzt.In a preferred embodiment, amines in which the radical R der is hydrogen and the radical R Am, C₁₀- to C₂₂-alkyl or C₁₀- to C₂₂-alkenyl referred to.

Der Umsetzung der Polymerisate A mit den Aminen oder Alkoholen B erfolgt nach bekannten Methoden. Hierbei werden in der Regel Carbonsäureester- bzw. Carbonsäureamid-Funktionen in die Polymerisate A eingebaut. Amine werden zweckmäßigerweise mit den Polymerisaten A in Substanz oder in inerten organischen Lösungsmitteln wie Toluol, Xylol, Cyclohexan, Petrolether oder Ligroin, welche üblicherweise von der Herstellung der Polymerisate A selbst herrühren, unter Normaldruck oder erhöhtem Druck bei ca. 60 bis 130°C umgesetzt. Die Umsetzung der Alkohole mit den Polymerisaten A erfolgt zweckmäßigerweise ebenfalls in Substanz oder bevorzugt in inerten organischen Lösungsmitteln, wie sie oben genannt sind, in Gegenwart von sauren Katalysatoren wie p-Toluolsulfonsäure unter Normaldruck oder erhöhtem Druck bei ca. 100 bis 150°C.The polymers A are reacted with the amines or alcohols B by known methods. As a rule, carboxylic acid ester or carboxamide functions are incorporated into the polymers A. Amines are advantageously reacted with the polymers A in bulk or in inert organic solvents such as toluene, xylene, cyclohexane, petroleum ether or ligroin, which usually result from the preparation of the polymers A themselves, at atmospheric pressure or elevated pressure at about 60 to 130 ° C. . The reaction of the alcohols with the polymers A is advantageously also carried out in bulk or, preferably, in inert organic solvents, as mentioned above, in the presence of acidic catalysts such as p-toluenesulfonic acid under atmospheric pressure or elevated pressure at about 100 to 150 ° C.

Das Verhältnis der Komponenten A und B bei der Umsetzung wird üblicherweise so gewählt, daß pro Mol des Monomeren a) im Polymerisat A 0,2 bis 1,0 mol Amin oder Alkohol B oder einer Mischung hieraus eingesetzt wird.The ratio of components A and B in the reaction is usually chosen so that 0.2 to 1.0 mol of amine or alcohol B or a mixture thereof is used per mole of monomer a) in polymer A.

Nach erfolgter Umsetzung der Komponenten A und B wird in der Regel eventuell vorhandenes organisches Lösungsmittel entfernt, vorzugsweise durch Destillation, und das Produkt üblicherweise in einer wäßrigen Lösung einer Base, vorzugsweise eines Alkalimetallhydroxids wie Natrium- oder Kaliumhydroxid oder Ammoniak, dispergiert, um die restlichen Anhydrid-Funktionen der teilveresterten oder teilamidierten Polymerisate teilweise oder vollständig zu hydrolysieren und teilweise oder vollständig zu neutralisieren.After the reaction of components A and B, any organic solvent which is present is generally removed, preferably by distillation, and the product is usually dispersed in an aqueous solution of a base, preferably an alkali metal hydroxide such as sodium or potassium hydroxide or ammonia, to remove the remaining anhydride Functions to partially or completely hydrolyze and partially or completely neutralize the functions of the partially esterified or partially amidated polymers.

Die so erhältlichen Polymerisatdispersionen eignen sich zur Behandlung von allen üblichen 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 Fettung vorgenommen werden.The polymer dispersions obtainable in this way are suitable for the treatment of all customary tanned hides. The tanned hides are usually deacidified before treatment. They may have been stained before treatment. Coloring can, however, also be carried out only after the lubrication that takes place according to the invention.

Die gegerbten Häute werden mit den wäßrigen Dispersionen zweckmäßigerweise in wäßriger Flotte bei pH-Werten von 4 bis 10, vorzugsweise von 5 bis 8, und Temperaturen von 20 bis 60°C, vorzugsweise 30 bis 50°C, während eines Zeitraumes von 0,1 bis 5 Stunden, insbesondere 0,5 bis 2 Stunden, behandelt. Diese Behandlung erfolgt beispielsweise durch Walken in einem Faß. Die benötigte Menge an Umsetzungsprodukt aus A und B beträgt, bezogen auf das Falzgewicht des Leders oder das Naßgewicht der Pelzfeile, 0,1 bis 30 Gew.-%, 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 überlicherweise 10 bis 1000 %, vorzugsweise 30 bis 150 %, bei Pelzfellen 50 bis 500 %. Die eingesetzten Dispersionen der Umsetzungsprodukte aus A und B weisen in der Regel keine zusätzlichen Emulgatoren auf.The tanned skins are expediently mixed with the aqueous dispersions in an aqueous liquor at pH values of 4 to 10, preferably 5 to 8, and temperatures of 20 to 60 ° C., preferably 30 to 50 ° C., for a period of 0.1 up to 5 hours, in particular 0.5 to 2 hours, treated. This treatment takes place, for example, by drumming in a barrel. The amount of reaction product from A and B required, based on the shaved weight of the leather or the wet weight of the fur file, is 0.1 to 30% by weight, 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 dispersions of the reaction products from A and B used generally have no additional emulsifiers.

Nach der Behandlung mit der beschriebenen wäßrigen Flotte wird der pH-Wert der Behandlungsflotte durch Zusatz von Säuren, vorzugsweise von organischen 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, 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 der Mitverwendung von üblichen Nachgerbstoffen beim Veredlungsprozeß des Leders und der Pelzfelle kann die Behandlung mit den erfindungsgemäß zu verwendenden Umsetzungsprodukten aus A und B vor oder nach dem Nachgerbschritt erfolgen.If customary retanning agents are also used in the finishing process of the leather and the fur skins, treatment with the reaction products from A and B to be used according to the invention can take place before or after the retanning step.

Mit den erfindungsgemäß zu verwendenden Umsetzungsprodukten ist es möglich, sehr weiche Leder ohne Zusatz herkömmlicher Licker herzustellen. Dieser Vorteil spiegelt sich in einfachen und kurzen Applikationsrezepturen wider.With the reaction products to be used according to the invention, it is possible to produce very soft leather without the addition of conventional licker. This advantage is reflected in simple and short application formulations.

Neben einer Verbesserung der mechanischen Eigenschaften wie Reißfestigkeit bewirken diese polymeren Fettungsmittel eine deutliche Steigerung im Echtheitsprofil des Leders. So werden die Lichtechtheit und Wärmevergilbungsresistenz solcher Leder sehr positiv beeinflußt. Neben der praktisch quantitativen Flottenauszehrung bewirkt die gute Fixierung im Leder eine große Resistenz gegenüber der Extrahierbarkeit mit Lösungsmittel oder Wasser. Dies führt zu sogenannten waschbaren Ledern, d.h. Ledern, die nach dem Waschen ihre Eigenschaften wie Weichheit, Festigkeit und Geschmeidigkeit nicht verlieren, im Gegensatz zu Ledern, die mit konventionellen Lickern gefettet wurden.In addition to an improvement in mechanical properties such as tear resistance, these polymeric greasing agents significantly increase the authenticity profile of the leather. The lightfastness and heat yellowing resistance of such leathers are influenced very positively. In addition to the practically quantitative exhaustion of the liquor, the good fixation in the leather results in great resistance to extractability with solvent or water. This leads to so-called washable leathers, i.e. Leather that does not lose its properties such as softness, strength and suppleness after washing, in contrast to leather that has been greased with conventional licker.

Durch geeignete Auswahl unter den speziellen Alkoholen und Aminen der Komponente B in den erfindungsgemäß verwendeten Umsetzungsprodukten lassen sich die hydrophoben Eigenschaften dieser polymeren Fettungsmitel so variieren, daß dem Leder auch eine gewisse Wasserbeständigkeit verliehen werden kann.The hydrophobic properties of these polymeric greasing agents can be varied so that the leather can also be given a certain water resistance by a suitable selection from the special alcohols and amines of component B in the reaction products used according to the invention.

Ein weiterer Vorteil der erfindungsgemäß verwendeten Umsetzungsprodukte besteht darin, daß aus ihnen hergestellte Dispersionen bei der Applikation auf Leder oder Pelzfellen keine zusätzlichen Emulgatoren benötigen. Leder und Pelze, die mit emulgatorhaltigen Produkten behandelt worden sind, müssen in vielen Fällen 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 reaction products used according to the invention is that dispersions prepared from them do not require any additional emulsifiers when applied to leather or fur skins. Leather and furs made with emulsifier Products that have been treated often have to be subjected to complex processes, such as aftertreatment with polyvalent metal salts, after the treatment with these agents, in order to render the emulsifiers in the leather or in the fur skins ineffective.

BeispieleExamples

Die Prozentangaben in den Beispielen beziehen sich, falls nicht anders angegeben, auf das Gewicht. Die Molmassen der Copolymerisate wurden durch Gelpermationschromatographie bestimmt, wobei als Elutionsmittel Tetrahydrofuran und zur Eichung eng verteilte Fraktionen von Polystyrol eingesetzt wurden. Die K-Werte nach Fikentscher der Copolymerisate und der Hilfsstoffe wurden an 1 gew.-%igen Lösungen in Cyclohexanon bei 25°C bestimmt, bei den Homopolymerisaten der Monomeren (a) wurde Dimethylformamid anstelle von Cyclohexanon als Lösungsmittel eingesetzt.Unless stated otherwise, the percentages in the examples relate to the weight. The molecular weights of the copolymers were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration. The K values according to Fikentscher of the copolymers and of the auxiliaries were determined in 1% strength by weight solutions in cyclohexanone at 25 ° C., in the homopolymers of monomers (a) dimethylformamide was used as the solvent instead of cyclohexanone.

Herstellung der Polymerisate APreparation of the polymers A Beispiel 1example 1

In einem beheizbaren Reaktor, der mit Rührer, Rückflußkühler, Thermometer, Zulaufvorrichtungen, Stickstoffeinlaß und -auslaß versehen war, wurden 1600 g technisches Xylol, 392 g (4,0 mol) Maleinsäureanhydrid und 7 g Polyethylvinylether mit einem K-Wert von 50 bis zum Sieden erhitzt und innerhalb von 2 Stunden wurden 344 g (4,0 mol) Vinylacetat und eine Lösung von 4 g Di-tert.-butylperoxid in 200 g technischem Xylol unter Siedebedingungen gleichmäßig zudosiert. Anschließend wurde noch eine Stunde unter Rückfluß gerührt, abgekühlt und das als feine Suspension vorliegende Polymerisat abfiltriert und der Filterkuchen bei 80°C im Vakuum getrocknet. Der K-Wert des in Form eines weißen Pulvers vorliegenden Copolymerisats betrug 15,9, die Molmasse lag bei 7000.In a heatable reactor, which was provided with a stirrer, reflux condenser, thermometer, feed devices, nitrogen inlet and outlet, 1600 g of technical xylene, 392 g (4.0 mol) of maleic anhydride and 7 g of polyvinyl vinyl ether with a K value of 50 to Boiling heated and within 2 hours 344 g (4.0 mol) of vinyl acetate and a solution of 4 g of di-tert-butyl peroxide in 200 g of technical xylene were metered in uniformly under boiling conditions. The mixture was then stirred under reflux for a further hour, cooled and the polymer present as a fine suspension was filtered off and the filter cake was dried at 80 ° C. in vacuo. The K value of the copolymer in the form of a white powder was 15.9 and the molar mass was 7000.

Beispiel 2Example 2

In einem Reaktor wie in Beispiel 1 wurden 1960 g o-Xylol, 441 g (4,5 mol) Maleinsäureanhydrid und 45 g Polyethylvinylether mit einem K-Wert von 50 zum Sieden erhitzt und innerhalb von 3 Stunden wurden 468 g (4,5 mol) Styrol und eine Lösung von 18,2 g tert.-Butylperbenzoat in 162 g o-Xylol gleichmäßig unter Sieden zudosiert. Anschließend wurde noch 2 Stunden nacherhitzt und dann abgekühlt. Der K-Wert des erhaltenen Polymerisats betrug 14,6, die Molmasse lag bei 5000. Die hellbraune, feine Suspension mit einem Polymerisatgehalt von 29,5 % konnte direkt zu einem Lederfettungsmittel weiterverarbeitet werden.In a reactor as in Example 1, 1960 g of o-xylene, 441 g (4.5 mol) of maleic anhydride and 45 g of polyethyl vinyl ether with a K value of 50 were heated to boiling and within 3 hours, 468 g (4.5 mol ) Styrene and a solution of 18.2 g of tert-butyl perbenzoate in 162 g of o-xylene are metered in evenly while boiling. The mixture was then heated for a further 2 hours and then cooled. The K value of the polymer obtained was 14.6, the molar mass was 5000. The light brown, fine suspension with With a polymer content of 29.5%, it could be processed directly into a leather greasing agent.

Beispiel 3Example 3

Die Herstellung erfolgt analog zu Beispiel 2, nur wurden hier 264,6 g (2,7 mol) Maleinsäureanhydrid und 655,2 g (6,3 mol) Styrol eingesetzt. Der K-Wert des erhaltenen Polymerisats betrug 16,0, die Molmasse lag bei 9000. Die feine, hellbraune Polymerisatsuspension konnte direkt weiter zu einem Lederfettungsmittel weiterverarbeitet werden.The preparation is carried out analogously to Example 2, except that 264.6 g (2.7 mol) of maleic anhydride and 655.2 g (6.3 mol) of styrene were used. The K value of the polymer obtained was 16.0, the molar mass was 9000. The fine, light brown polymer suspension could be processed further directly to give a leather greasing agent.

Beispiel 4Example 4

In einem Reaktor wie in Beispiel 1 wurden 1750 g Maleinsäureanhydrid und 1165 g o-Xylol bis zum Sieden erhitzt und innerhalb von 5 Stunden wurde unter Sieden eine Lösung von 262 g tert.-Butylperethylhexanoat in 190 g o-Xylol gleichmäßig zudosiert. Anschließend wurde noch eine Stunde nacherhitzt und dann das o-Xylol über der Schmelze abdekantiert, die Schmelze auf ein Aluminiumblech aufgebracht und abgekühlt. Das Harz wurde zerkleinert und das restliche Lösungsmittel im Vakuum abdestilliert. Das Polymerisat besaß einen K-Wert von 10, die Molmasse lag bei 1000.In a reactor as in Example 1, 1750 g of maleic anhydride and 1165 g of o-xylene were heated to boiling and a solution of 262 g of tert-butyl perethylhexanoate in 190 g of o-xylene was metered in uniformly over 5 hours while boiling. The mixture was then reheated for an hour and then the o-xylene was decanted over the melt, the melt was applied to an aluminum sheet and cooled. The resin was crushed and the remaining solvent was distilled off in vacuo. The polymer had a K value of 10, the molar mass was 1000.

Beispiel 5Example 5

In einem Druckreaktor mit Aufbauten wie in Beispiel 1 beschrieben wurden 1210 g o-Xylol, 636 g (6,5 mol) Maleinsäureanhydrid und 6 g Polyethylvinylether mit einem K-Wert von 50 vorgelegt. Der Reaktor wurde dicht verschlossen, dreimal mit je 3 bar Stickstoff abgepreßt und wieder entspannt, evakuiert und auf 120°C erhitzt. Danach wurden innerhalb von 4 Stunden gleichmäßig 364 g (6,5 mol) Isobuten und eine Lösung von 30 g tert.-Butylperethylhexanoat in 250 g o-Xylol bei 120°C zudosiert. Anschließend wurde noch 2 Stunden bei 120°C nacherhitzt. Dann wurde der aufgebaute Druck von 3 bar entspannt und der Reaktor abgekühlt. Die viskose, feinkörnige Suspension des Copolymerisats wurde im Vakuum bei 80°C vom Lösungsmittel befreit. Das erhaltene Copolymerisat war ein feines Pulver mit einem K-Wert von 25, seine Molmasse lag bei 8000.1210 g of o-xylene, 636 g (6.5 mol) of maleic anhydride and 6 g of polyvinyl vinyl ether with a K value of 50 were placed in a pressure reactor with structures as described in Example 1. The reactor was tightly sealed, pressed three times with 3 bar of nitrogen each time and relaxed again, evacuated and heated to 120 ° C. 364 g (6.5 mol) of isobutene and a solution of 30 g of tert-butyl perethylhexanoate in 250 g of o-xylene were then metered in uniformly at 120 ° C. in the course of 4 hours. The mixture was then reheated at 120 ° C. for 2 hours. Then the pressure built up of 3 bar was released and the reactor was cooled. The viscous, fine-grained suspension of the copolymer was freed from the solvent in vacuo at 80 ° C. The copolymer obtained was a fine powder with a K value of 25 and its molar mass was 8000.

Herstellung der Dispersionen der Umsetzungsprodukte aus A und BPreparation of the dispersions of the reaction products from A and B.

Die Herstellung der Umsetzungsprodukte aus Polymerisaten A und Aminen B erfolgte durch Zugabe der in der Tabelle angegebenen Amine zu den in der Tabelle angegebenen Polymerisaten in Xylol bei 120 bis 130°C in dem in der Tabelle angegebenen Molverhältnis Amin:Maleinsäureanhydrid (MSA) im Polymerisat. Nach Abdestillieren des Xylols nach erfolgter Umsetzung wurde das Produkt mit einem Ultraturax-Rührer in wäßriger Natronlauge in dem in der Tabelle angegebenen Molverhältnis NaOH:MSA im Polymerisat dispergiert, so daß eine 20 bis 25%ige Dispersion mit einem pH-Wert von 7 bis 8 resultierte.The reaction products from polymers A and amines B were prepared by adding the amines shown in the table to the polymers shown in the table in xylene at 120 to 130 ° C. in the molar ratio of amine: maleic anhydride (MA) in the polymer shown in the table. After distilling off of the xylene after the reaction, the product was dispersed with an Ultraturax stirrer in aqueous sodium hydroxide solution in the molar ratio NaOH: MSA given in the table in the polymer, so that a 20 to 25% dispersion with a pH of 7 to 8 resulted.

Die Herstellung der Umsetzungsprodukte aus Polymerisaten A und Alkoholen B erfolgte durch Reaktion der in der Tabelle angegebenen Alkohole mit den in der Tabelle angegebenen Polymerisaten in Xylol bei 120 bis 130°C in Gegenwart katalytischer Mengen p-Toluolsulfonsäure während 3 bis 5 Stunden in dem in der Tabelle angegebenen Molverhältnis Alkohol:MSA im Polymerisat. Nach Abdestillieren des Xylols nach erfolgter Umsetzung wurde das Produkt mit einem Ultaturax-Rührer in wäßriger Natronlauge in dem in der Tabelle angegebenen Molverhältnis NaOH:MSA im Polymerisat dispergiert, so daß eine 20 bis 25%ige Dispersion mit einem pH-Wert von 7 bis 8 resultierte.

Figure imgb0002
Figure imgb0003
 The reaction products from polymers A and alcohols B were prepared by reacting the alcohols listed in the table with the polymers listed in the table in xylene at 120 to 130 ° C. in the presence of catalytic amounts of p-toluenesulfonic acid for 3 to 5 hours in the The molar ratio of alcohol: MSA in the polymer indicated in the table. After the xylene had been distilled off after the reaction had taken place, the product was dispersed in the polymer using an Ultaturax stirrer in aqueous sodium hydroxide solution in the NaOH: MSA molar ratio given in the table, so that a 20 to 25% strength dispersion having a pH of 7 to 8 resulted.
Figure imgb0002
Figure imgb0003

Anmerkung:Annotation:

C₄H₈O in Beispiel 14, 15, 17, 18 und 19 bezeichnet Oxybutylen, erhalten durch Umsetzung von Methanol mit ButylenoxidC₄H₈O in Example 14, 15, 17, 18 and 19 denotes oxybutylene, obtained by reacting methanol with butylene oxide

AnwendungsbeispieleExamples of use Beispiel 21Example 21

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert worden war, wurde mit 15 % des Produktes aus Beispiel 6, bezogen auf das Falzgewicht, 2 Stunden bei 40°C im Gerbfaß gewalkt. Die Gesamtflottenlänge betrug 150 %. Das Leder wurde anschließend mit 1 % eines üblichen anionischen Anilinfarbstoffes gefärbt. Danach wurde es mit Ameisensäure auf einen pH-Wert von 3,8 eingestellt. Es wurde abschließend gewaschen, mechanisch ausgereckt und getrocknet. Das erhaltene Leder war sehr weich, geschmeidig, gut gefüllt und gleichmäßig gefärbt.Chrome-tanned cowhide with a fold thickness of 1.8 mm, which had been deacidified to a pH of 5.0, was drummed with 15% of the product from Example 6, based on the fold weight, in the tanning drum at 40 ° C. for 2 hours. The total fleet length was 150%. The leather was then dyed with 1% of a common anionic aniline dye. Then it was adjusted to a pH of 3.8 with formic acid. It was then washed, mechanically stretched and dried. The leather obtained was very soft, supple, well filled and evenly colored.

Beispiel 22Example 22

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert und mit 0,7 % eines üblichen anionischen Anilinfarbstoffes gefärbt worden war, wurde mit 20 % des Produktes aus Beispiel 7, bezogen auf das Falzgewicht, 1,5 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 und wie üblich fertiggestellt. Das so erhaltene Leder wahr sehr weich und griffig.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% of a conventional anionic aniline dye, was mixed with 20% of the product from Example 7, based on the fold weight , Tumbled for 1.5 hours at 40 ° C in the tanning barrel. Following this treatment, the leather was brought to a pH of 3.6 with formic acid and finished as usual. The leather thus obtained was very soft and easy to grip.

Beispiel 23Example 23

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert und mit 0,7 % eines üblichen anionischen Anilinfarbstoffes gefärbt worden war, wurde mit 15 % des Produktes aus Beispiel 8, bezogen auf das Falzgewicht, 30 Minuten bei 40°C im Gerbfaß gewalkt und anschließend mit 3 % eines üblichen synthetischen Gerbstoffes eine Stunde weiterbehandelt. Dann wurde das Leder mit Ameisensäure auf einen pH-Wert von 3,6 gebracht und wie üblich fertiggestellt. Das so erhaltene Leder fühlte sich angenehm weich und griffig an.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% of a conventional anionic aniline dye, was mixed with 15% of the product from Example 8, based on the fold weight , Tumbled for 30 minutes at 40 ° C. in a tanning drum and then treated further with 3% of a conventional synthetic tanning agent for one hour. Then the leather was brought to a pH of 3.6 with formic acid and finished as usual. The leather thus obtained felt pleasantly soft and easy to grip.

Beispiel 24Example 24

Das Produkt aus Beispiel 9 wurde analog zu der im Beispiel 21 angegebenen Arbeitsweise eingesetzt. Das so erhaltene Leder zeigte weiche und runde Griffeigenschaften.The product from Example 9 was used analogously to the procedure given in Example 21. The leather thus obtained showed soft and round grip properties.

Beispiel 25Example 25

Das Produkt aus Beispiel 10 wurde analog zu der im Beispiel 23 angegebenen Arbeitsweise eingesetzt. Das so erhaltene Leder zeichnete sich durch einen runden, weichen Griff aus.The product from Example 10 was used analogously to the procedure given in Example 23. The leather thus obtained was characterized by a round, soft handle.

Beispiele 26 bis 28Examples 26 to 28

Die Produkte aus den Beispielen 11 bis 13 wurden analog zu der im Beispiel 22 angegebenen Arbeitsweise eingesetzt. Die Ergebnisse waren ähnlich vorteilhaft wie bei den vorigen Beispielen.The products from Examples 11 to 13 were used analogously to the procedure given in Example 22. The results were similarly advantageous as in the previous examples.

Beispiele 29 bis 33Examples 29-33

Die Produkte aus den Beispielen 14 bis 18 wurden anaiog zu der im Beispiel 21 angegebenen Arbeitsweise eingesetzt. Die Ergebnisse waren ähnlich vorteilhaft wie bei den vorigen Beispielen.The products from Examples 14 to 18 were used analogously to the procedure given in Example 21. The results were similarly advantageous as in the previous examples.

Beispiele 34 und 35Examples 34 and 35

Die Produkte aus den Beispielen 19 und 20 wurden analog zu der in Beispiel 23 angegebenen Arbeitsweise eingesetzt. Die Ergebnisse waren ähnlich vorteilhaft wie bei den vorigen Beispielen.The products from Examples 19 and 20 were used analogously to the procedure given in Example 23. The results were similarly advantageous as in the previous examples.

Claims (9)

  1. The use of reaction products of
    A) homo- or copolymers based on monoethylenically unsaturated dicarboxylic anhydrides, with the exception of sulfonated polymers, and obtainable by free radical polymerization of
    a) from 30 to 100 mol% of one or more monoethylenically unsaturated dicarboxylic anhydrides of from 4 to 10 carbon atoms,
    b) from 0 to 70 mol% of one or more aromatic vinyl compounds of the general formula I
    Figure imgb0005
     where R¹, R and R³ are each hydrogen, methyl or ethyl and k is 1 or 2,
    (c) from 0 to 70 mol% of one or more vinyl esters of C₁- to C₄-carboxylic acids,
    (d) from 0 to 50 mol% of one or more C₂- to C₆-olefins, and
    (e) from 0 to 30 mol% of one or more monoethylenically unsaturated C₃- to C₅-carboxylic acids,
    which mixture of monomers (a) to (e) may additionally contain up to 10% by weight of further copolymerizable monomers, with
    B) amines of the general formula R⁴R⁵NH, where R⁴ is hydrogen, C₁- to C₂₀-alkyl, C₅- to C₈-cycloalkyl or C₂- to C₄-hydroxyalkyl and R⁵ is C₆- to C₃₀-alkyl, C₆-to C₃₀-alkenyl, C₅- to C₈-cycloalkyl or C₂- to C₄-hydroxyalkyl, or alcohols of the general formula R₆-O-(CmH2mO)p-(CnH2nO)q-H, where R⁶ is C₁- to C₃₀-alkyl, C₂- to C₃₀-alkenyl, C₅- to C₈-cycloalkyl or - if p+q > 0 - hydrogen, m and n are each from 2 to 4 and p and q are each from 0 to 50, or mixtures of such amines and alcohols,
    for fatliquoring and filling leather and fur skins.
  2. The use of reaction products as set forth in claim 1 prepared using as component A a homopolymer of a monoethylenically unsaturated dicarboxylic anhydride of from 4 to 10 carbon atoms (a), for fatliquoring and filling leather and fur skins.
  3. The use of reaction products as set forth in claim 1 prepared using as component A a copolymer of
    (a) from 30 to 99 mol% of a monoethylenically unsaturated dicarboxylic anhydride of from 4 to 10 carbon atoms, and
    (b) from 1 to 70 mol% of one or more aromatic vinyl compounds I,
    for fatliquoring and filling leather and fur skins.
  4. The use of reaction products as set forth in claim 1 prepared using as component A a copolymer of
    (a) from 30 to 99 mol% of a monoethylenically unsaturated dicarboxylic anhydride of from 4 to 10 carbon atoms, and
    (c) from 1 to 70 mol% of one or more vinyl esters of C₁to C₄-carboxylic acids
    for fatliquoring and filling leather and fur skins.
  5. The use of reaction products as set forth in claim 1 prepared using as component A a copolymer of
    (a) from 50 to 99 mol% of a monoethylenically unsaturated dicarboxylic anhydride of from 4 to 10 carbon atoms, and
    (d) from 1 to 50 mol% of one or more C₂- to C₆-olefins for fatliquoring and filling leather and fur skins.
  6. The use of reaction products as set forth in any of claims 1 to 5 prepared using maleic anhydride as monomer (a) for polymer A, for fatliquoring and filling leather and fur skins.
  7. The use of reaction products as set forth in any of claims 1 to 6 prepared using as component B amines where R⁴ is hydrogen and R⁵ is C₁₀- to C₂₂-alkyl- or C₁₀- to C₂₂-alkenyl, for fatliquoring and filling leather and fur skins.
  8. The use of reaction products as set forth in any of claims 1 to 6 prepared using as component B alcohols where R⁶ is C₁- to C₂₂-alkyl- or C₁₀- to C₂₂-alkenyl, m and n are each from 2 to 4 and p and q are each from 0 to 35, for fatliquoring and filling leather and fur skins.
  9. A process for fatliquoring and filling leather and fur skins, which comprises using reaction products as set forth in any of claims 1 to 8.
EP93903970A 1992-02-26 1993-02-15 Use of reaction products of homo- or copolymerisates based on monoethylenically unsaturated dicarboxylic acid anhydrides with amines or alcohols for stuffing and fulling leathers and fur pelts Expired - Lifetime EP0628085B1 (en)

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DE4205839 1992-02-26
PCT/EP1993/000354 WO1993017130A1 (en) 1992-02-26 1993-02-15 Use of reaction products of homo- or copolymerisates based on monoethylenically unsaturated dicarboxylic acid anhydrides with amines or alcohols for stuffing and fulling leathers and fur pelts

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DE59301646D1 (en) 1996-03-28
EP0628085A1 (en) 1994-12-14
US5433752A (en) 1995-07-18
AU3497393A (en) 1993-09-13
WO1993017130A1 (en) 1993-09-02
DE4205839A1 (en) 1993-09-02
JPH07504217A (en) 1995-05-11
ES2083280T3 (en) 1996-04-01
AU661562B2 (en) 1995-07-27

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