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EP0412389A1 - Use of copolymerisates based on long chained olefines and ethylenic unsaturated dicarbonic acid anhydrides for waterproofing of leather and fur pelts - Google Patents

Use of copolymerisates based on long chained olefines and ethylenic unsaturated dicarbonic acid anhydrides for waterproofing of leather and fur pelts Download PDF

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Publication number
EP0412389A1
EP0412389A1 EP90114574A EP90114574A EP0412389A1 EP 0412389 A1 EP0412389 A1 EP 0412389A1 EP 90114574 A EP90114574 A EP 90114574A EP 90114574 A EP90114574 A EP 90114574A EP 0412389 A1 EP0412389 A1 EP 0412389A1
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Prior art keywords
copolymers
carboxyl groups
solvolysis
leather
carried out
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German (de)
French (fr)
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EP0412389B1 (en
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Ortwin 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

  • the invention has for its object to provide an improved agent for the waterproofing of leather and fur.
  • the copolymers are known for example from DE-05 3 730 885. They are obtained in the manner of bulk polymerization by copolymerizing the monomers of group (a) with the monomers of group (b) at temperatures from 80 to 300 ° C.
  • Suitable monoolefins with 8 to 40 carbon atoms are, for example, n-octene-1, 2, 4, 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, diisobutene, which is technically an isomer mixture of approx. 80% by weight 2 , 4,4-trimethylpentene-1 and approx.
  • 2,4,4-trimethylpentene-2 is present, 4,4-dimethylhexene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1 , Octadecen-1, C20-olefin-1, C22-olefin-1, C24-olefin-1, C20- to C24-olefin-1, C24- to C28-olefin-1, C30-olefin-1, C35-olefin -1 and C40-olefin-1.
  • the olefins or mixtures of olefins are commercial products.
  • cyclic olefins such as cyclooctene are also suitable.
  • the olefins may contain small amounts of inert organic hydrocarbons, e.g. up to about 5% by weight.
  • the olefins are usually used in the commercially available quality. You do not need to be subjected to any special cleaning.
  • the preferred olefins are C16 to C30 olefins.
  • Component (b) of the copolymers are monoethylenically unsaturated C4 to C8 dicarboxylic anhydrides, e.g. Maleic anhydride, itaconic anhydride, mesaconic anhydride, citraconic anhydride, methylene malonic anhydride and mixtures with one another. Of the anhydrides mentioned, maleic anhydride is preferably used.
  • the copolymers contain 40 to 60 mol% of monoolefins and 60 to 40 mol% of the dicarboxylic acid anhydrides mentioned and have a molar mass of 500 to 20,000, preferably 800 to 10,000 g / mol.
  • Monomers (a) and (b) are obtainable by polymerizing the monomers (a) and (b) in a molar ratio of 1.1: 1 to 1: 1.
  • Monomers (a) and (b) are preferably polymerized in a molar ratio of 1: 1 or only a 1% by weight excess of monomers of component (a) is used.
  • the monomers of groups (a) and (b) form alternating copolymers which, at high molecular weights, contain the monomers (a) and (b) in copolymerized form in each case at 50 mol%.
  • the bulk polymerization 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.
  • the polymerization conditions are chosen. Polymerization at high temperatures results in copolymers 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.
  • the monomers (a) and (b) can be copolymerized at temperatures above 200 ° C. even in the absence of polymerization initiators. This means that the use of initiators is not absolutely necessary, because the monomers (a) and (b) polymerize radically at temperatures above 200 ° C. even in the absence of initiators.
  • Suitable polymerization initiators are, for example, di-tertiary-butyl peroxide, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, di-2-ethylhexylperoxidicarbonat dicyclohexyl peroxydicarbonate, 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 butyl peroxy) cyclohexane, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peracetate, di-tertiary butyl per
  • 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 monoolefin.
  • 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.
  • the monomer mixture is polymerized at the lower limit of the temperature range that is suitable for the polymerization and then polymerized out at a higher temperature, it is expedient to use at least two different initiators which decompose at different temperatures, so that a sufficient concentration is obtained in each temperature interval of radicals is available.
  • regulators In order to produce low molecular weight polymers, it is often expedient to carry out the copolymerization in the presence of regulators.
  • Conventional regulators can be used for this, such as, for example, C1 to C4 aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tertiary 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.
  • the copolymerization is carried out in customary polymerization apparatus, for example a pressure-tight kettle which is provided with a stirrer, in pressure-tight kettle cascades or in a tubular reactor.
  • customary polymerization apparatus for example a pressure-tight kettle which is provided with a stirrer, in pressure-tight kettle cascades or in a tubular reactor.
  • the olefins and anhydrides are copolymerized in a molar ratio in the absence of solvents.
  • the copolymerization can be carried out continuously or batchwise.
  • the olefin or a mixture of different olefins can be placed in the reactor and heated to the desired polymerization temperature with stirring.
  • the ethylenically unsaturated dicarboxylic anhydride is metered in.
  • an initiator is used, it is metered into the reaction mixture, preferably separately or as a solution in an olefin which undergoes polymerization.
  • the polymerization regulator is added to the polymerizing mixture either separately or also dissolved in an olefin.
  • the acid anhydrides are preferably added to the reaction mixture in the form of a melt. The temperature of the melt is about 70 to 90 ° C. If the olefin is used in excess in the copolymerization, e.g. in a 10% excess, after completion of the copolymerization it can be removed from the reaction mixture without difficulty from the copolymer melt by means of distillation, preferably under reduced pressure. The copolymer melt is then expediently processed further directly.
  • the copolymers thus produced are solvolysed after cooling to room temperature or preferably in the form of the melt, which has a temperature in the range from 80 to 180 ° C., preferably 90 to 150 ° C.
  • the solvolysis of the anhydride groups of the copolymers consists in hydrolysis and subsequent neutralization. It is particularly advantageous to work in pressure-tight apparatus and to convert the anhydride groups into carboxyl groups directly by adding water to a melt of the copolymers obtainable in bulk polymerization and to neutralize at least 10% of the carboxyl groups of the hydrolyzed copolymers by subsequent addition of bases.
  • hydrolysis and neutralization can also be carried out practically simultaneously by adding dilute aqueous bases to the copolymer melt.
  • the amounts of water and neutralizing agent are chosen so that 10 to 60, preferably 20 to 55% by weight solids-containing dispersions or solutions are formed be put on the market. Preparation solutions are then prepared from this by dilution to solids contents of 0.5 to 50% by weight.
  • the copolymers obtainable by bulk polymerization can also be solvolysed by adding primary and / or secondary amines.
  • the solvolysis is carried out with amounts of amines such that 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are amidated upon complete 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.
  • 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 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are amidated upon complete 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.
  • Solvolysis can also be carried out by adding alcohols to a melt of the copolymers obtainable in bulk polymerization.
  • the amounts of alcohol used are such that 10 to 50% of the total carboxyl groups formed from the copolymerized dicarboxylic acid units are esterified. This is followed by neutralization, in which at least 10% of the total carboxyl groups resulting from the copolymer containing anhydride groups are neutralized.
  • Suitable neutralizing agents are, for example, ammonia, amines, alkali metal and alkaline earth metal bases, for example sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, calcium hydroxide, barium hydroxide and all amines which are also used to amidate the copolymers.
  • Neutralization is preferably carried out by adding aqueous sodium hydroxide solution to the copolymer.
  • the neutralization of the copolymers containing anhydride groups is carried out at least to such a degree that copolymers which are dispersible in water are obtained.
  • This degree of neutralization is at least 10% of the total from the anhydride groups emerging carboxyl groups.
  • the degree of neutralization is also dependent on the chain length of the olefin of component (a) used in each case.
  • a copolymer of a C30-olefin and maleic anhydride is neutralized to at least 75%, for example, a copolymer of a C20 / C20-olefin and maleic anhydride at a degree of neutralization of 50% from this copolymer resulting carboxyl groups is already readily dispersible in water.
  • a degree of neutralization of 20% of the carboxyl groups formed from the copolymerized maleic anhydride is sufficient for dispersing the copolymer in water.
  • Ammonia and primary and secondary amines can be used to form the amide.
  • the amide formation is preferably carried out in the absence of water by reaction of the anhydride groups of the copolymer with ammonia or the amines.
  • the primary and secondary amines in question can have 1 to 40, preferably 3 to 30, carbon atoms.
  • Suitable amines 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 Propylamine, di-isopropylamine, di-n-butylamine, di-isobutylamine, dihexylamine, di-cyclohexylamine, di-methylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, di-isotridecylamine, di-tallow fatty amine, di-stearylamine, Di-oleylamine,
  • Suitable alcohols can contain 1 to 40, preferably 3 to 30, carbon atoms.
  • Primary, secondary and tertiary alcohols can be used. Both saturated aliphatic alcohols and unsaturated alcohols, such as oleyl alcohol, can be used.
  • Monohydric, primary or secondary alcohols are preferably used, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isomers, n-hexanol and isomers, n-octanol and isomers, such as 2-ethylhexanol , Nonanols, decanols, dodecanols, tridecanols, cyclohexanol, tallow fatty alcohol, stearyl alcohol and the alcohols or alcohol mixtures with 9 to 19 carbon atoms that are easily accessible technically by oxosynthesis, such as C 9/11 oxo alcohol, C 13/15 oxo alcohol and Ziegleral alcohols , which are known under the name Alfol with 12 to 24 carbon atoms.
  • oxosynthesis such as C 9/11 oxo alcohol, C 13/15 oxo alcohol and
  • Alcohols with 4 to 24 carbon atoms such as n-butanol, isobutanol, amyl alcohol, 2-ethylhexanol, tridecanol, tallow fatty alcohol, stearyl alcohol, C 9/11 oxo alcohol, C 13/15 oxo alcohol, C 12/14, are preferably used -Alfols and C 16/18 -Alfols.
  • the anhydride groups still present in the copolymer are hydrolysed.
  • the hydrolysis of the remaining anhydride groups of the copolymer can also be carried out simultaneously with the partial neutralization still required, by adding an aqueous base to the partially amidated or esterified copolymer which still contains anhydride groups.
  • the amount of water and bases is chosen so that the concentration of the copolymer dispersion or solution is preferably 20 to 55% by weight.
  • the pH of the ready-to-use agents for waterproofing is in the range from about 4 to 10.
  • the aqueous copolymer dispersions obtainable in this way are stable and stable in storage. They are outstandingly suitable for finishing leather and furs 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, does not in most cases 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
  • aqueous dispersions to be used according to the invention contain no additional emulsifiers.
  • Leather and furs, which have been treated with products containing emulsifiers, are known to 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 described above 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 skins will be usually deacidified before treatment. They may have been stained before treatment. However, coloring can also be carried out only 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 with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. during a period of 0.1 to 5, especially 0.5 to 2 hours, treated.
  • This treatment is carried out, for example, by drumming in a barrel.
  • the amount of copolymer dispersion 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 fleet length i.e. the percentage weight ratio of the treatment liquor to the goods, based on the fold weight of the leather, the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.
  • the pH of the treatment liquor is adjusted to a pH of 3 to 5, preferably 3.5 to 4, by adding acids, preferably using organic acids, such as formic acid.
  • the treatment with the aqueous dispersions 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 being used in part before, during and after the retanning step.
  • the aqueous dispersions to be used as hydrophobicizing agents can also be used together with conventional leather and fur finishing agents such as hydrophobic agents 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, 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 Chemist Associations, Commission for Physical Leather Testing, cf. the leather, volume 12, 36 to 40 (1961).
  • the reaction mixture is stirred after 2 hours at 110 ° C. in order to convert the anhydride groups of the copolymer into the corresponding half-amide groups.
  • the reaction mixture is then cooled to 90 ° C. with stirring and, separately from one another, 480 g of a 50% strength aqueous sodium hydroxide solution and 8680 g of water, which has a temperature of 90 ° C., are added over the course of half an hour and the mixture is heated for a further 2 Hrs at 90 ° C.
  • a dispersion which is viscous at room temperature and has a solids content of 25.4% is obtained.
  • the molar mass of the non-solvolysed copolymer was 4800 g / mol, 50 mol% of the total carboxyl groups resulting from the anhydride groups were present as the amide group and 50 mol% were neutralized.
  • 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. It was then washed, mechanically stretched and dried.
  • 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 20.9% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.
  • 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 23.7% by weight for the water absorption after 15 hours at 15% compression 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)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

Use of copolymers obtainable by free-radical copolymerisation of (a) C8-C40-monoolefins with (b) ethylenically unsaturated C4-C8-dicarboxylic anhydrides in the manner of a mass polymerisation at from 80 to 300 DEG C to form copolymers having molecular weights of from 500 to 20,000 g/mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralisation in an aqueous medium with bases of the carboxyl groups formed in the course of the solvolysis and which are present in the form of aqueous dispersions or solutions, as agents for waterproofing leathers and pelt furs.

Description

Aus der DE-OS 3 730 885 sind Kraftstoffe für Ottomotoren bekannt, die u.a. geringe Mengen an Copolymerisaten enthalten, die Olefine mit 2 bis 40 C-Atomen und Maleinsäureanhydrid einpolymerisiert enthalten, eine Molmasse von 500 bis 20 000 g/Mol aufweisen und bei denen die Anhydrid­gruppen der Copolymerisate ganz oder teilweise mit wäßrigen Alkalimetall- oder Erdalkalimetallbasen umgesetzt sind und der Rest der Carboxylgruppen mit Alkoholen und/oder Aminen in die entsprechenden Ester- und/oder Amid­gruppen und/oder Ammoniumsalze umgesetzt ist.From DE-OS 3 730 885 fuels for gasoline engines are known, which among other things. contain small amounts of copolymers which contain copolymerized olefins with 2 to 40 carbon atoms and maleic anhydride, have a molar mass of 500 to 20,000 g / mol and in which the anhydride groups of the copolymers are completely or partially reacted with aqueous alkali metal or alkaline earth metal bases and the rest of the carboxyl groups with alcohols and / or amines has been converted into the corresponding ester and / or amide groups and / or ammonium salts.

Aus der DE-PS 2 629 748 ist die Verwendung von mit Alkalimetallbasen oder Aminen verseiften Copolymerisaten aus C₁₀- bis C₃₀-Olefinen und Malein­säureanhydrid zum Füllen und Fetten von Leder und Pelzfellen bekannt. Die hydrolysierten Copolymerisate können noch mit Alkalibisulfit umgesetzt werden. Da die Copolymerisate in organischen Lösemitteln hergestellt und die Lösemittel nicht entfernt werden, enthalten die daraus hergestellten wäßrigen Copolymerisatdispersionen beträchtliche Mengen organischer Löse­mittel, beispielsweise Xylol oder Dodecylbenzol. Solche Dispersionen eignen sich zwar zum Fetten von Leder und Pelzfellen, sie sind jedoch aufgrund ihres Gehalts an organischen Lösemitteln für eine Hydrophobierung von Leder und Pelzfellen praktisch nicht brauchbar.From DE-PS 2 629 748 the use of saponified with alkali metal bases or amines copolymers of C₁₀ to C₃₀ olefins and maleic anhydride for filling and greasing leather and fur skins is known. The hydrolyzed copolymers can also be reacted with alkali bisulfite. Since the copolymers are prepared in organic solvents and the solvents are not removed, the aqueous copolymer dispersions prepared therefrom contain considerable amounts of organic solvents, for example xylene or dodecylbenzene. Although such dispersions are suitable for greasing leather and fur, they are practically unusable due to their content of organic solvents for hydrophobizing leather and fur.

Der Erfindung liegt die Aufgabe zugrunde, ein verbessertes Mittel für die Hydrophobierung von Leder und Pelzfellen zur Verfügung zu stellen.The invention has for its object to provide an improved agent for the waterproofing of leather and fur.

Die Aufgabe wird erfindungsgemäß gelöst durch die Verwendung von Copoly­merisaten, die durch radikalische Copolymerisation von

  • (a) C₈- bis C₄₀-Monoolefinen mit
  • (b) ethylenisch ungesättigten C₄- bis C₆-Dicarbonsäureanhydriden
nach Art einer Substanzpolymerisation bei Temperaturen von 80 bis 300°C zu Copolymerisaten mit Molmassen von 500 bis 20 000 g/Mol, anschließende Solvolyse der Anhydridgruppen der Copolymerisate und zumindest partielle Neutralisation der bei der Solvolyse entstehenden Carboxylgruppen in wäßrigem Medium mit Basen erhältlich sind und die in Form von 0,5 bis 50 gew.-%igen wäßrigen Dispersionen vorliegen, als Mittel zum Hydro­phobieren von Leder und pelzfellen.The object is achieved by the use of copolymers by free radical copolymerization of
  • (a) C₈ to C₄₀ monoolefins with
  • (b) ethylenically unsaturated C₄ to C₆ dicarboxylic acid anhydrides
after a type of bulk polymerization at temperatures from 80 to 300 ° C to copolymers with molecular weights of 500 to 20,000 g / mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed during solvolysis in an aqueous medium with bases and are available are in the form of 0.5 to 50% by weight aqueous dispersions, as agents for waterproofing leather and furskins.

Die Copolymerisate sind beispielsweise aus der DE-05 3 730 885 bekannt. Sie werden nach Art einer Substanzpolymerisation durch Copolymerisieren der Monomeren der Gruppe (a) mit den Monomeren der Gruppe (b) bei Tempera­turen von 80 bis 300°C erhalten. Geeignete Monoolefine mit 8 bis 40 Kohlenstoffatomen sind beispielsweise n-Octen-1, 2, 4, 4-Trimethyl­penten-1, 2,4,4-Trimethylpenten-2, Diisobuten, das technisch als Isomeren­gemisch aus ca. 80 Gew.-% 2,4,4-Trimethylpenten-1 und ca. 20 Gew.-% 2, 4, 4-Trimethylpenten-2 vorliegt, 4,4-Dimethylhexen-1, Decen-1, Dodecen-1, Tetradecen-1, Hexadecen-1, Octadecen-1, C₂₀-Olefin-1, C₂₂-Olefin-1, C₂₄-Olefin-1, C₂₀- bis C₂₄-Olefin-1, C₂₄- bis C₂₈-Olefin-1, C₃₀-Olefin-1, C₃₅-Olefin-1 und C₄₀-Olefin-1. Die Olefine bzw. Mischungen von Olefinen sind Handelsprodukte. Außer den geradkettigen Olefinen kommen auch cyclische Olefine in Betracht wie Cycloocten. Die Olefine können von der Herstellung her geringe Mengen an inerten organischen Kohlenwasserstoffen enthalten, z.B. bis zu etwa 5 Gew.-%. Die Olefine werden üblicherweise in der im Handel erhältlichen Qualität eingesetzt. Sie brauchen keiner besonderen Reinigung unterworfen zu werden. Die bevorzugten Olefine sind C₁₆- bis C₃₀-Olefine.The copolymers are known for example from DE-05 3 730 885. They are obtained in the manner of bulk polymerization by copolymerizing the monomers of group (a) with the monomers of group (b) at temperatures from 80 to 300 ° C. Suitable monoolefins with 8 to 40 carbon atoms are, for example, n-octene-1, 2, 4, 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, diisobutene, which is technically an isomer mixture of approx. 80% by weight 2 , 4,4-trimethylpentene-1 and approx. 20% by weight 2,4,4-trimethylpentene-2 is present, 4,4-dimethylhexene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1 , Octadecen-1, C₂₀-olefin-1, C₂₂-olefin-1, C₂₄-olefin-1, C₂₀- to C₂₄-olefin-1, C₂₄- to C₂₈-olefin-1, C₃₀-olefin-1, C₃₅-olefin -1 and C₄₀-olefin-1. The olefins or mixtures of olefins are commercial products. In addition to straight-chain olefins, cyclic olefins such as cyclooctene are also suitable. The olefins may contain small amounts of inert organic hydrocarbons, e.g. up to about 5% by weight. The olefins are usually used in the commercially available quality. You do not need to be subjected to any special cleaning. The preferred olefins are C₁₆ to C₃₀ olefins.

Als Komponente (b) der Copolymerisate kommen monoethylenisch ungesättigte C₄- bis C₈-Dicarbonsäureanhydride in Betracht, z.B. Maleinsäureanhydrid, Itaconsäureanhydrid, Mesaconsäureanhydrid, Citraconsäureanhydrid, Methy­lenmalonsäureanhydrid und Mischungen untereinander. Von den genannten Anhydriden wird vorzugsweise Maleinsäureanhydrid verwendet. Die Copoly­merisate enthalten 40 bis 60 mol-% Monoolefine und 60 bis 40 mol-% der genannten Dicarbonsäureanhydride einpolymerisiert und haben eine Molmasse von 500 bis 20 000, vorzugsweise 800 bis 10 000 g/Mol. Sie sind dadurch erhältlich, daß man die Monomeren (a) und (b) im Molverhältnis 1,1:1 bis 1:1 polymerisiert. Vorzugsweise polymerisiert man die Monomeren (a) und (b) im Molverhältnis 1:1 oder verwendet lediglich einen 1 gew.-%igen Überschuß an Monomeren der Komponente (a). Die Monomeren der Gruppen (a) und (b) bilden bekanntlich alternierende Copolymerisate, die bei hohen Molekulargewichten die Monomeren (a) und (b) zu jeweils 50 mol-% einpoly­merisiert enthalten. Bei sehr niedrigen Molekulargewichten der Copoly­merisate kann je nach Art der Endgruppen eine Abweichung vom molaren Verhältnis in dem oben angegebenen Rahmen vorliegen, wenn beispielsweise die Copolymerisatkette mit dem Monomeren (a) startet und auch mit dem Monomeren (a) abbricht.Component (b) of the copolymers are monoethylenically unsaturated C₄ to C₈ dicarboxylic anhydrides, e.g. Maleic anhydride, itaconic anhydride, mesaconic anhydride, citraconic anhydride, methylene malonic anhydride and mixtures with one another. Of the anhydrides mentioned, maleic anhydride is preferably used. The copolymers contain 40 to 60 mol% of monoolefins and 60 to 40 mol% of the dicarboxylic acid anhydrides mentioned and have a molar mass of 500 to 20,000, preferably 800 to 10,000 g / mol. They are obtainable by polymerizing the monomers (a) and (b) in a molar ratio of 1.1: 1 to 1: 1. Monomers (a) and (b) are preferably polymerized in a molar ratio of 1: 1 or only a 1% by weight excess of monomers of component (a) is used. As is known, the monomers of groups (a) and (b) form alternating copolymers which, at high molecular weights, contain the monomers (a) and (b) in copolymerized form in each case at 50 mol%. In the case of very low molecular weights of the copolymers, depending on the type of end groups, there may be a deviation from the molar ratio within the range given above, for example if the copolymer chain starts with the monomer (a) and also breaks off with the monomer (a).

Die Substanzpolymerisation 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. Geeignete Polymerisationsinitiatoren sind beispielsweise Di-tertiär-butylperoxid, 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-tertiär­butylperoxid, 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 Monoolefin 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.The bulk polymerization 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 results in copolymers 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. This means that the use of initiators is not absolutely necessary, because the monomers (a) and (b) polymerize radically at temperatures above 200 ° C. even in the absence of initiators. Suitable polymerization initiators are, for example, di-tertiary-butyl peroxide, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, di-2-ethylhexylperoxidicarbonat dicyclohexyl peroxydicarbonate, 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 butyl peroxy) cyclohexane, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peracetate, di-tertiary butyl peroxyhydro peryl peroxide, di peroxide peroxide peroxide. 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 monoolefin. 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 is polymerized at the lower limit of the temperature range that is suitable for the polymerization and then polymerized out at a higher temperature, it is expedient to use at least two different initiators which decompose at different temperatures, so that a sufficient concentration is obtained in each temperature interval of radicals is available.

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, 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. Conventional regulators can be used for this, such as, for example, C₁ to C₄ aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tertiary 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.

Die Copolymerisation wird in üblichen Polymerisationsapparaturen, bei­spielsweise einem druckdichten Kessel, der mit einem Rührer versehen ist, in druckdichten Rührkesselkaskaden oder in einem Rohrreaktor durchgeführt. Bei der Substanzpolymerisation erfolgt die Copolymerisation der Olefine und der Anhydride im molaren Verhältnis in Abwesenheit von Lösemitteln. Die Copolymerisation kann kontinuierlich oder diskontinuierlich durchge­führt werden. Beispielsweise kann man das Olefin oder ein Gemisch verschiedener Olefine im Reaktor vorlegen und unter Rühren auf die gewünschte Polymerisationstemperatur erhitzen. Sobald das Olefin die Polymerisationstemperatur erreicht hat, dosiert man das ethylenisch unge­sättigte Dicarbonsäureanhydrid zu. Falls ein Initiator eingesetzt wird, wird er dem Reaktionsgemisch, vorzugsweise separat oder gelöst in einem zur Polymerisation gelangenden Olefin, zudosiert. Der Polymerisations­regler wird, sofern er eingesetzt wird, entweder separat oder ebenfalls in einem Olefin gelöst der polymerisierenden Mischung zugefügt. Die Säure­anhydride, insbesondere Maleinsäureanhydrid, werden vorzugsweise in Form einer Schmelze dem Reaktionsgemisch zugegeben. Die Temperatur der Schmelze beträgt etwa 70 bis 90°C. Falls man bei der Copolymerisation das Olefin im Überschuß anwendet, z.B. in einem 10 %igen Überschuß, so kann es nach Abschluß der Copolymerisation ohne Schwierigkeit vom Reaktionsgemisch mit Hilfe einer Destillation, vorzugsweise unter vermindertem Druck, aus der Copolymerisatschmelze entfernt werden. Die Copolymerisatschmelze wird anschließend zweckmäßigerweise direkt weiter verarbeitet.The copolymerization is carried out in customary polymerization apparatus, for example a pressure-tight kettle which is provided with a stirrer, in pressure-tight kettle cascades or in a tubular reactor. In bulk polymerization, the olefins and anhydrides are copolymerized in a molar ratio in the absence of solvents. The copolymerization can be carried out continuously or batchwise. For example, the olefin or a mixture of different olefins can be placed in the reactor and heated to the desired polymerization temperature with stirring. As soon as the olefin has reached the polymerization temperature, the ethylenically unsaturated dicarboxylic anhydride is metered in. If an initiator is used, it is metered into the reaction mixture, preferably separately or as a solution in an olefin which undergoes polymerization. If used, the polymerization regulator is added to the polymerizing mixture either separately or also dissolved in an olefin. The acid anhydrides, in particular maleic anhydride, are preferably added to the reaction mixture in the form of a melt. The temperature of the melt is about 70 to 90 ° C. If the olefin is used in excess in the copolymerization, e.g. in a 10% excess, after completion of the copolymerization it can be removed from the reaction mixture without difficulty from the copolymer melt by means of distillation, preferably under reduced pressure. The copolymer melt is then expediently processed further directly.

Die so hergestellten Copolymerisate werden nach dem Abkühlen auf Raumtem­peratur oder vorzugsweise in Form der Schmelze, die eine Temperatur in dem Bereich von 80 bis 180°C, vorzugsweise 90 bis 150°C hat, solvolysiert. Die Solvolyse der Anhydridgruppen der Copolymerisate besteht im einfachsten Fall in einer Hydrolyse und anschließender Neutralisation. Es ist besonders vorteilhaft, in druckdichten Apparaturen zu arbeiten und darin direkt durch Zugabe von Wasser zu einer Schmelze der bei der Substanz­polymerisation erhältlichen Copolymerisate die Anhydridgruppen in Carboxylgruppen zu überführen und durch anschließende Zugabe von Basen mindestens 10 % der Carboxylgruppen der hydrolysierten Copolymerisate zu neutralisieren. Hydrolyse und Neutralisation können jedoch auch praktisch gleichzeitig durch Zugabe verdünnter wäßriger Basen zur Copolymerisat­schmelze vorgenommen werden. Die Mengen an Wasser und an Neutralisations­mittel werden dabei so gewählt, daß 10 bis 60, vorzugsweise 20 bis 55 Gew.-% Feststoffe enthaltende Dispersionen oder Lösungen entstehen, die in den Handel gebracht werden. Daraus werden dann Präparationslösungen durch Verdünnen auf Feststoffgehalte von 0,5 bis 50 Gew.-% hergestellt.The copolymers thus produced are solvolysed after cooling to room temperature or preferably in the form of the melt, which has a temperature in the range from 80 to 180 ° C., preferably 90 to 150 ° C. In the simplest case, the solvolysis of the anhydride groups of the copolymers consists in hydrolysis and subsequent neutralization. It is particularly advantageous to work in pressure-tight apparatus and to convert the anhydride groups into carboxyl groups directly by adding water to a melt of the copolymers obtainable in bulk polymerization and to neutralize at least 10% of the carboxyl groups of the hydrolyzed copolymers by subsequent addition of bases. However, hydrolysis and neutralization can also be carried out practically simultaneously by adding dilute aqueous bases to the copolymer melt. The amounts of water and neutralizing agent are chosen so that 10 to 60, preferably 20 to 55% by weight solids-containing dispersions or solutions are formed be put on the market. Preparation solutions are then prepared from this by dilution to solids contents of 0.5 to 50% by weight.

Die durch Substanzpolymerisation erhältlichen Copolymerisate können auch durch Zugabe von primären und/oder sekundären Aminen solvolysiert werden. Die Solvolyse wird dabei mit solchen Mengen an Aminen durchgeführt, daß 10 bis 50 % der aus den einpolymerisierten Monomeren (b) insgesamt bei einer vollständigen Hydrolyse entstehenden 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 Copolymerisates neutralisiert werden. Ferner kann auch mit Aminocarbonsäuren sowie Salzen von Amino­carbonsäuren, vorzugsweise den Alkalimetallsalzen, 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 10 bis 50 % der aus den einpolymerisierten Monomeren (b) insgesamt bei einer vollständigen Hydrolyse entstehenden 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.The copolymers obtainable by bulk polymerization can also be solvolysed by adding primary and / or secondary amines. The solvolysis is carried out with amounts of amines such that 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are amidated upon complete 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. 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 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are amidated upon complete 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 Solvolyse kann auch durch Zugabe von Alkoholen zu einer Schmelze der bei der Substanzpolymerisation erhältlichen Copolymerisate vorgenommen werden. Man setzt dabei solche Mengen an Alkohol ein, daß 10 bis 50 % der aus den einpolymerisierten Dicarbonsäureeinheiten insgesamt entstehenden Carboxylgruppen verestert werden. Anschließend erfolgt eine Neutralisa­tion, bei der mindestens 10 % der insgesamt aus dem Anhydridgruppen ent­haltenden Copolymerisat entstehenden Carboxylgruppen neutralisiert sind.Solvolysis can also be carried out by adding alcohols to a melt of the copolymers obtainable in bulk polymerization. The amounts of alcohol used are such that 10 to 50% of the total carboxyl groups formed from the copolymerized dicarboxylic acid units are esterified. This is followed by neutralization, in which at least 10% of the total carboxyl groups resulting from the copolymer containing anhydride groups are neutralized.

Vorzugsweise werden jeweils 25 bis 50 % der aus den einpolymerisierten Dicarbonsäureanhydriden insgesamt entstehenden Carboxylgruppen amidiert oder verestert. Als Neutralisationsmittel eignen sich beispielsweise Ammoniak, Amine, Alkalimetall- und Erdalkalimetallbasen, z.B. Natronlauge, Kalilauge, Magnesiumhydroxid, Calciumhydroxid, Bariumhydroxid sowie sämt­liche Amine, die auch zur Amidierung der Copolymerisate eingesetzt werden. Vorzugsweise erfolgt die Neutralisation durch Zugabe von wäßriger Natron­lauge zum Copolymerisat. Die Neutralisation der Anhydridgruppen enthalten­den Copolymerisate wird mindestens bis zu einem solchen Grad durchgeführt, daß man in Wasser dispergierbare Copolymerisate erhält. Dieser Neutralisa­tionsgrad liegt bei mindestens 10 % der insgesamt aus den Anhydridgruppen entstehenden Carboxylgruppen. Der Neutralisationsgrad ist außerdem von der Kettenlänge des jeweils verwendeten 0lefins der Komponente (a) abhängig. Um gut in Wasser dispergierbare bzw. kolloidal lösliche Copolymerisate zu erhalten, wird ein Copolymerisat aus einem C₃₀-Olefin und Maleinsäure­anhydrid zu mindestens 75 % neutralisiert, während beispielsweise ein Copolymerisat aus einem C₂₀/C₂₄-Olefin und Maleinsäureanhydrid bei einem Neutralisationsgrad von 50 % der aus diesem Copolymerisat entstehenden Carboxylgruppen bereits gut in Wasser dispergierbar ist. Bei einem Copoly­merisat aus einem C₁₂-Olefin und Maleinsäureanhydrid reicht bereits ein Neutralisationsgrad von 20 % der aus dem einpolymerisierten Maleinsäure­anhydrid entstehenden Carboxylgruppen für das Dispergieren des Copolymeri­sats in Wasser aus.In each case, preferably 25 to 50% of the total carboxyl groups resulting from the copolymerized dicarboxylic acid anhydrides are amidated or esterified. Suitable neutralizing agents are, for example, ammonia, amines, alkali metal and alkaline earth metal bases, for example sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, calcium hydroxide, barium hydroxide and all amines which are also used to amidate the copolymers. Neutralization is preferably carried out by adding aqueous sodium hydroxide solution to the copolymer. The neutralization of the copolymers containing anhydride groups is carried out at least to such a degree that copolymers which are dispersible in water are obtained. This degree of neutralization is at least 10% of the total from the anhydride groups emerging carboxyl groups. The degree of neutralization is also dependent on the chain length of the olefin of component (a) used in each case. To obtain water-dispersible or colloidally soluble copolymers, a copolymer of a C₃₀-olefin and maleic anhydride is neutralized to at least 75%, for example, a copolymer of a C₂₀ / C₂₀-olefin and maleic anhydride at a degree of neutralization of 50% from this copolymer resulting carboxyl groups is already readily dispersible in water. In a copolymer of a C₁₂ olefin and maleic anhydride, a degree of neutralization of 20% of the carboxyl groups formed from the copolymerized maleic anhydride is sufficient for dispersing the copolymer in water.

Zur Amidbildung kann man Ammoniak und primäre und sekundäre Amine ein­setzen. Die Amidbildung erfolgt vorzugsweise in Abwesenheit von Wasser durch Reaktion der Anhydridgruppen des Copolymerisats mit Ammoniak oder den Aminen. Die in Betracht kommenden primären und sekundären Amine können 1 bis 40, vorzugsweise 3 bis 30 Kohlenstoffatome aufweisen. Geeignete Amine sind beispielsweise 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, Di-Isobutylamin, Dihexylamin, Di-Cyclo­hexylamin, Di-Methylcyclohexylamin, Di-2-Ethylhexylamin, Di-n-Octylamin, Di-Isotridecylamin, Di-Talgfettamin, Di-Stearylamin, Di-Oleylamin, Ethanolamin, Di-Ethanolamin, n-Propanolamin, Di-n-Propanolamin und Morpholin. Vorzugsweise wird Morpholin verwendet.Ammonia and primary and secondary amines can be used to form the amide. The amide formation is preferably carried out in the absence of water by reaction of the anhydride groups of the copolymer with ammonia or the amines. The primary and secondary amines in question can have 1 to 40, preferably 3 to 30, carbon atoms. Suitable amines 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 Propylamine, di-isopropylamine, di-n-butylamine, di-isobutylamine, dihexylamine, di-cyclohexylamine, di-methylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, di-isotridecylamine, di-tallow fatty amine, di-stearylamine, Di-oleylamine, ethanolamine, di-ethanolamine, n-propanolamine, di-n-propanolamine and morpholine. Morpholine is preferably used.

Um die bei der Substanzpolymerisation erhaltenen Anhydridgruppen aufwei­senden Copolymerisate partiell zu verestern, werden sie mit Alkoholen umgesetzt. Auch die Veresterung erfolgt vorzugsweise unter Ausschluß von Wasser. Geeignete Alkohole können 1 bis 40, vorzugsweise 3 bis 30 C-Atome enthalten. Es können primäre, sekundäre und tertiäre Alkohole Verwendung finden. Man kann sowohl gesättigte aliphatische Alkohole als auch unge­sättigte Alkohole, wie beispielsweise Oleylalkohol einsetzen. Vorzugsweise werden einwertige, primäre oder sekundäre Alkohole verwendet, z.B. Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, n-Pentanol und Isomere, n-Hexanol und Isomere, n-Octanol und Isomere, wie z.B. 2-Ethylhexanol, Nonanole, Decanole, Dodecanole, Tridecanole, Cyclohexanol, Talgfettalkohol, Stearylalkohol sowie die technisch durch Oxosynthese leicht zugänglichen Alkohole bzw. Alkoholgemische mit 9 bis 19 C-Atomen, wie z.B. C9/11-Oxoalkohol, C13/15-Oxoalkohol sowie Ziegler­alkohole, die unter den Namen Alfol bekannt sind mit 12 bis 24 C-Atomen. Vorzugsweise verwendet man Alkohole mit 4 bis 24 C-Atomen, wie z.B. n-Butanol, Isobutanol, Amylalkohol, 2-Ethylhexanol, Tridecanol, Talgfett­alkohol, Stearylalkohol, C9/11-Oxoalkohol, C13/15-Oxoalkohol, C12/14-Alfole und C16/18-Alfole.In order to partially esterify the copolymers containing anhydride groups obtained in bulk polymerization, they are reacted with alcohols. The esterification is also preferably carried out with the exclusion of water. Suitable alcohols can contain 1 to 40, preferably 3 to 30, carbon atoms. Primary, secondary and tertiary alcohols can be used. Both saturated aliphatic alcohols and unsaturated alcohols, such as oleyl alcohol, can be used. Monohydric, primary or secondary alcohols are preferably used, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isomers, n-hexanol and isomers, n-octanol and isomers, such as 2-ethylhexanol , Nonanols, decanols, dodecanols, tridecanols, cyclohexanol, tallow fatty alcohol, stearyl alcohol and the alcohols or alcohol mixtures with 9 to 19 carbon atoms that are easily accessible technically by oxosynthesis, such as C 9/11 oxo alcohol, C 13/15 oxo alcohol and Ziegleral alcohols , which are known under the name Alfol with 12 to 24 carbon atoms. Alcohols with 4 to 24 carbon atoms, such as n-butanol, isobutanol, amyl alcohol, 2-ethylhexanol, tridecanol, tallow fatty alcohol, stearyl alcohol, C 9/11 oxo alcohol, C 13/15 oxo alcohol, C 12/14, are preferably used -Alfols and C 16/18 -Alfols.

Nach der partiellen Umwandlung der Anhydridgruppen in Halbamid- oder Halbester-Gruppen erfolgt die Hydrolyse der noch vorhandenen Anhydrid­gruppen des Copolymerisats. Die Hydrolyse der restlichen Anhydridgruppen des Copolymerisats kann auch gleichzeitig mit der noch erforderlichen partiellen Neutralisation vorgenommen werden, indem man eine wäßrige Base zu dem partiell amidierten bzw. veresterten und noch Anhydridgruppen enthaltenden Copolymerisat zusetzt. Die Menge an Wasser und Basen wird so gewählt, daß die Konzentration der Copolymerisatdispersion oder Lösung vorzugsweise 20 bis 55 Gew.-% beträgt. Der pH-Wert der gebrauchsfertigen Mittel zum Hydrophobieren liegt in dem Bereich von etwa 4 bis 10.After the partial conversion of the anhydride groups into half-amide or half-ester groups, the anhydride groups still present in the copolymer are hydrolysed. The hydrolysis of the remaining anhydride groups of the copolymer can also be carried out simultaneously with the partial neutralization still required, by adding an aqueous base to the partially amidated or esterified copolymer which still contains anhydride groups. The amount of water and bases is chosen so that the concentration of the copolymer dispersion or solution is preferably 20 to 55% by weight. The pH of the ready-to-use agents for waterproofing is in the range from about 4 to 10.

Die so erhältlichen wäßrigen Copolymerisatdispersionen sind beständig und lagerstabil. Sie eignen sich in hervorragender Weise zur Veredlung von Leder und Pelzen, 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 obtainable in this way are stable and stable in storage. They are outstandingly suitable for finishing leather and furs 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, does not in most cases more is needed.

Ein weiterer Vorteil der erfindungsgemäß zu verwendenden wäßrigen Dis­persionen besteht darin, daß sie keine zusätzlichen Emulgatoren enthalten. Leder und Pelze, 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 to be used according to the invention is that they contain no additional emulsifiers. Leather and furs, which have been treated with products containing emulsifiers, are known to 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 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 copolymer dispersions described above 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 skins will be usually deacidified before treatment. They may have been stained before treatment. However, coloring can also be carried out only 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 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 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, 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 with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. during a period of 0.1 to 5, especially 0.5 to 2 hours, treated. This treatment is carried out, for example, by drumming in a barrel. The amount of copolymer dispersion 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 fleet length, i.e. the percentage weight ratio of the treatment liquor to the goods, based on the fold weight of the leather, the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.

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 using 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 vor oder nach dem Nachgerbeschritt oder auch mehrstufig erfolgen, wobei die wäßrigen Dispersionen anteilsweise vor, während und nach dem Nachgerbungsschritt eingesetzt werden. Die als Hydrophobierungsmittel zu verwendenden wäßrigen Dispersionen 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 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 being used in part before, during and after the retanning step. The aqueous dispersions to be used as hydrophobicizing agents can also be used together with conventional leather and fur finishing agents such as hydrophobic agents 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 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, 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 Chemist 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 für Polymerisationen ausgerüsteten Reaktor aus Stahl, der mit einem Rührer und Dosierungsvorrichtungen versehen ist, werden 1195 g eines C₂₀- bis C₂₄-Olefin-1-gemisches (Gulftene 20-24, Handelsprodukt der Firma Gulf Oil Chemical Company, USA) vorgelegt und unter Rühren in einem schwachen Stickstoffstrom auf 190°C erhitzt. Sobald diese Temperatur erreicht ist, fügt man gleichmäßig 392 g auf 70°C erhitztes Maleinsäure­anhydrid und separat davon 16 g Ditertiärbutylperoxid innerhalb von 4 Stunden zu. Anschließend wird das Reaktionsgemisch 2 Stunden bei 190°C gerührt und unter Rühren auf 90°C abgekühlt. Innerhalb einer halben Stunde gibt man dann jeweils getrennt voneinander 320 g einer 50 %igen wäßrigen Natronlauge und 3909 g Wasser zu, das auf 90°C erwärmt ist. Das Reaktions­gemisch wird 4 Stunden in dem Temperaturbereich von 90 bis 95°C gerührt und danach auf Umgebungstemperatur abgekühlt. Man erhält auf diese Weise eine schwachviskose wäßrige Dispersion mit einem Feststoffgehalt von 30,2 %. Die Molmasse des nicht hydrolysierten Copolymerisats aus Olefin und Maleinsäureanhydrid betrug 8900 g/Mol, 50 mol-% der insgesamt entstehenden Carboxylgruppen waren neutralisiert.In a steel reactor equipped for polymerizations, which is provided with a stirrer and metering devices, 1195 g of a C₂ C- to C₂₄-olefin-1 mixture (Gulftene 20-24, a commercial product of the Gulf Oil Chemical Company, USA) are introduced and heated to 190 ° C. with stirring in a weak stream of nitrogen. As soon as this temperature has been reached, 392 g of maleic anhydride heated to 70 ° C. and 16 g of di-tert-butyl peroxide separately are added within 4 hours. The reaction mixture is then stirred at 190 ° C. for 2 hours and cooled to 90 ° C. with stirring. Within half an hour, 320 g of a 50% aqueous sodium hydroxide solution and 3909 g of water, which has been heated to 90 ° C., are then added separately. The reaction mixture is stirred for 4 hours in the temperature range from 90 to 95 ° C. and then cooled to ambient temperature. A weakly viscous aqueous dispersion with a solids content of 30.2% is obtained in this way. The molar mass of the non-hydrolyzed copolymer of olefin and maleic anhydride was 8900 g / mol, 50 mol% of the total carboxyl groups formed were neutralized.

Dispersion IIDispersion II

In dem Reaktor, in dem die Dispersion I hergestellt wurde, werden 1500 g Octadecen-1 vorgelegt und unter Rühren in einer Stickstoffatmosphäre auf 190°C erhitzt. Sobald diese Temperatur erreicht ist, gibt man getrennt voneinander und jeweils innerhalb von 2 Stunden 588 g einer Schmelze von Maleinsäureanhydrid und eine Lösung von 27 g Ditertiärbutylperoxid in 42,8 g Octadecen-1 zu. Das Reaktionsgemisch wird nach Zugabe des Maleinsäureanhydrids und des Peroxids noch 2 Std. bei 190°C nacherhitzt, dann auf 110°C abgekühlt. Dann dosiert man innerhalb von 1 Stunde 522 g Morpholin zu. Die Umsetzungstemperatur wird bei 110°C gehalten. Nach Beendigung der Morpholinzugabe wird das Reaktionsgemisch nach 2 Stunden bei 110°C gerührt, um die Anhydridgruppen des Copolymerisats in die entsprechenden Halbamidgruppen umzuwandeln. Man kühlt das Reaktionsgemisch dann unter Rühren auf 90°C ab und fügt, getrennt voneinander, 480 g einer 50 %igen wäßrigen Natronlauge und 8680 g Wasser, das eine Temperatur von 90°C hat, innerhalb von einer halben Stunde zu und erhitzt noch 2 Std. bei 90°C. Man erhält eine bei Raumtemperatur viskose Dispersion mit einem Feststoffgehalt von 25,4 %. Die Molmasse des nicht solvolysierten Copoly­merisats betrug 4800 g/Mol, 50 mol-% der ingesamt aus den Anhydridgruppen entstehenden Carboxylgruppen lagen als Amidgruppe vor und 50 mol-% waren neutralisiert.1500 g of octadecene-1 are placed in the reactor in which dispersion I was prepared and heated to 190 ° C. with stirring in a nitrogen atmosphere. As soon as this temperature has been reached, 588 g of a melt of maleic anhydride and a solution of 27 g of ditertiary butyl peroxide in 42.8 g of octadecene-1 are added separately and in each case within 2 hours. After the addition of the maleic anhydride and the peroxide, the reaction mixture is heated for a further 2 hours at 190 ° C., then cooled to 110 ° C. Then 522 g of morpholine are metered in over the course of 1 hour. The reaction temperature is kept at 110 ° C. After the addition of morpholine has ended, the reaction mixture is stirred after 2 hours at 110 ° C. in order to convert the anhydride groups of the copolymer into the corresponding half-amide groups. The reaction mixture is then cooled to 90 ° C. with stirring and, separately from one another, 480 g of a 50% strength aqueous sodium hydroxide solution and 8680 g of water, which has a temperature of 90 ° C., are added over the course of half an hour and the mixture is heated for a further 2 Hrs at 90 ° C. A dispersion which is viscous at room temperature and has a solids content of 25.4% is obtained. The molar mass of the non-solvolysed copolymer was 4800 g / mol, 50 mol% of the total carboxyl groups resulting from the anhydride groups were present as the amide group and 50 mol% were neutralized.

Beispiel 1example 1

Chromgegerbtes Rindleder mit einer Falzstärke von 1,8 mm, das auf einen pH-Wert von 5,0 entsäuert worden war, wurde mit 15 der Dispersion I, 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 of 5.0, was drummed with 15 of the dispersion I, based on the fold weight, in a tanning drum at 40 ° C. for 2 hours. 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 abschließend 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. It was then washed, mechanically stretched and dried.

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 Stunden einen Wert von 20,9 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 20.9% by weight for the water absorption after 15 hours 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 und mit 0,7 Gew.-% eines üblichen anionischen Anilinfarbstoffs gefärbt worden war, wurde mit 20 % der Dispersion II, 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 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 and dyed with 0.7% by weight of a conventional anionic aniline dye, was mixed with 20% of dispersion II, based on the fold weight , tumbled for one and a half 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.

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 Stunden einen Wert von 23,7 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 23.7% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.

Claims (5)

1. Verwendung von Copolymerisaten, die durch radikalische Copolymeri­sation von
(a) C₈- bis C₄₀-Monoolefinen mit
(b) ethylenisch ungesättigten C₄- bis C₈-Dicarbonsäureanhydriden
nach Art einer Substanzpolymerisation bei Temperaturen von 80 bis 300°C zu Copolymerisaten mit Molmassen von 500 bis 20 000 g/Mol, anschließende Solvolyse der Anhydridgruppen der Copolymerisate und zumindest partielle Neutralisation der bei der Solvolyse entstehenden Carboxylgruppen in wäßrigem Medium mit Basen erhältlich sind und die in Form von wäßrigen Lösungen oder Dispersionen vorliegen, als Mittel zum Hydrophobieren von Leder und Pelzfellen.1. Use of copolymers by radical copolymerization of
(a) C₈ to C₄₀ monoolefins with
(b) ethylenically unsaturated C₄ to C₈ dicarboxylic acid anhydrides
after a type of bulk polymerization at temperatures from 80 to 300 ° C to copolymers with molecular weights of 500 to 20,000 g / mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed during solvolysis in an aqueous medium with bases and are available are in the form of aqueous solutions or dispersions, as agents for waterproofing leather and fur. 2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man die Solvolyse durch Zugabe von Wasser zu einer Schmelze der bei der Substanzpolymerisation erhältlichen Copolymerisate durchführt und mindestens 10 % der Carboxylgruppen der hydrolysierten Copolymerisate mit Ammoniak, Aminen, Alkalimetall- oder Erdalkalimetallbasen neutralisiert.2. Use according to claim 1, characterized in that the solvolysis is carried out by adding water to a melt of the copolymers obtainable in bulk polymerization and neutralizing at least 10% of the carboxyl groups of the hydrolyzed copolymers with ammonia, amines, alkali metal or alkaline earth metal bases. 3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man die Solvolyse durch Zugabe von primären und/oder sekundären Aminen zu einer Schmelze der bei der Substanzpolymerisation erhältlichen Copoly­merisate so durchführt, daß 10 bis 50 % der aus den einpolymerisierten Monomeren (b) insgesamt entstehenden Carboxylgruppen amidiert und mindestens 10 % der insgesamt entstehenden Carboxylgruppen neutrali­siert sind.3. Use according to claim 1, characterized in that the solvolysis is carried out by adding primary and / or secondary amines to a melt of the copolymers obtainable in bulk polymerization in such a way that 10 to 50% of the total from the copolymerized monomers (b) Carboxyl groups are amidated and at least 10% of the total carboxyl groups formed are neutralized. 4. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man die Solvolyse der bei der Substanzpolymerisation erhältlichen Copolymeri­sate in wäßrigem Medium durch Zugabe von Salzen von Aminocarbonsäuren so durchführt, daß 10 bis 50 % der aus den einpolymerisierten Mono­meren (b) insgesamt entstehenden Carboxylgruppen amidiert und min­destens 10 % der insgesamt entstehenden Carboxylgruppen neutralisiert sind.4. Use according to claim 1, characterized in that the solvolysis of the copolymers obtainable in bulk polymerization is carried out in an aqueous medium by adding salts of aminocarboxylic acids such that 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are amidated and at least 10% of the total carboxyl groups formed are neutralized. 5. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man die Solvolyse durch Zugabe von Alkoholen zu einer Schmelze der bei der Substanzpolymerisation erhältlichen Copolymerisate so durchführt, daß 10 bis 50 % der aus den einpolymerisierten Monomeren (b) insgesamt entstehenden Carboxylgruppen verestert und mindestens 10 % der insgesamt entstehenden Carboxylgruppen neutralisiert sind.5. Use according to claim 1, characterized in that the solvolysis is carried out by adding alcohols to a melt of the copolymers obtainable in bulk polymerization such that 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are esterified and at least 10 % of the total carboxyl groups formed are neutralized.
EP90114574A 1989-08-08 1990-07-30 Use of copolymerisates based on long chained olefines and ethylenic unsaturated dicarbonic acid anhydrides for waterproofing of leather and fur pelts Revoked EP0412389B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3926167 1989-08-08
DE3926167A DE3926167A1 (en) 1989-08-08 1989-08-08 USE OF COPOLYMERISATS BASED ON LONG-CHAIN OLEFINS AND ETHYLENICALLY UNSATURATED DICARBONIC ACID ANHYDRIDES FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS

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EP0412389A1 true EP0412389A1 (en) 1991-02-13
EP0412389B1 EP0412389B1 (en) 1994-11-30

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EP (1) EP0412389B1 (en)
JP (1) JPH0376800A (en)
KR (1) KR910004817A (en)
AT (1) ATE114727T1 (en)
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CA (1) CA2021758A1 (en)
DE (2) DE3926167A1 (en)
ES (1) ES2064554T3 (en)
NZ (1) NZ234781A (en)
PT (1) PT94915B (en)

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EP0542033A2 (en) * 1991-11-14 1993-05-19 BASF Aktiengesellschaft Use of pigment preparations for the manufacture of pastes, printing inks and paints
DE4214011C1 (en) * 1992-04-29 1993-11-04 Muenzing Chemie Gmbh COPOLYMERISATE
US5266165A (en) * 1991-10-05 1993-11-30 Basf Aktiengesellschaft Paper sizing using copolymers of long-chain olefins and maleic anhydride in the form of the semiamides with morpholine
US5268437A (en) * 1992-01-22 1993-12-07 Rohm And Haas Company High temperature aqueous polymerization process
EP0574351A1 (en) * 1992-06-09 1993-12-15 Ciba-Geigy Ag Process for the after-treatment of tanned leather and furs
EP0583973A2 (en) * 1992-08-18 1994-02-23 Ciba Specialty Chemicals Water Treatments Limited Impregnating composition for leather
WO1994010346A1 (en) * 1992-10-29 1994-05-11 Chemische Fabrik Stockhausen Gmbh Process for softening/stuffing leather and fur skins
WO1995020056A1 (en) * 1994-01-25 1995-07-27 Basf Aktiengesellschaft Aqueous solutions or dispersions of copolymers
EP0682044A1 (en) * 1994-05-10 1995-11-15 Hoechst Aktiengesellschaft Copolymers of ethylenically unsaturated dicarboxylic acid anhydrides, long-chaim olefines and fluoro-olefines
US5489389A (en) * 1992-07-14 1996-02-06 Henkel Kommanditgesellschaft Auf Aktien New leather oiling preparations and their use
US5501707A (en) * 1991-09-03 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Aqueous dispersions of new amphiphilic co-oligomers for the washing- and cleaning-resistant oiling of leather and skins and their use
US5567343A (en) * 1992-07-14 1996-10-22 Henkel Kommanditgesellschaft Auf Aktien New leather oiling preparations and their use
US5683611A (en) * 1994-01-12 1997-11-04 Henkel Kommanditgesellschaft Auf Aktien Preparations for the oiling of leather
WO1998010103A1 (en) * 1996-09-09 1998-03-12 Stockhausen Gmbh & Co. Kg Novel leather-treatment agents, process for their preparation, and their use for producing low-fogging leathers
US5728313A (en) * 1994-02-18 1998-03-17 Henkel Corporation Leather oiling compositions and their use
US6200640B1 (en) 1996-04-01 2001-03-13 Basf Aktiengesellschaft Polymer composition and process for treating leather and fur skins
US6336942B1 (en) 1995-03-12 2002-01-08 Basf Aktiengesellschaft Processes of treating leather and skins employing polymer compositions
WO2003044233A1 (en) * 2001-10-16 2003-05-30 Buckman Laboratories International, Inc. Leather waterproofing formulation and leather goods waterproofed therewith
WO2011050980A2 (en) 2009-10-30 2011-05-05 FLN FEUERLöSCHGERäTE NEURUPPIN VERTRIEBS GMBH Composition suitable for production of foam extinguishants
WO2013110413A1 (en) 2012-01-27 2013-08-01 Evonik Industries Ag Mixture composition containing amino-functional siloxanes, hydrophobic particles and high-molecular silicones as well as the use thereof for leather treatment
US9029310B2 (en) 2008-07-07 2015-05-12 Basf Se Enzyme composition comprising enzyme containing polymer particles

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DE4139090A1 (en) * 1991-11-28 1993-06-03 Stockhausen Chem Fab Gmbh USE OF COPOLYMERS WITH POLYSILOXANE UNITS FOR THE TREATMENT OF LEATHER AND FURS
DE4205839A1 (en) * 1992-02-26 1993-09-02 Basf Ag USE OF IMPLEMENTATION PRODUCTS OF HOMO OR COPOLYMERISATS BASED ON MONOETHYLENICALLY UNSATURATED DICARBONIC ACID ANHYDRIDES WITH AMINES OR ALCOHOLS FOR FAT AND FILL LEATHER OR FUR SKINS
DE4242039A1 (en) * 1992-12-12 1994-06-16 Stockhausen Chem Fab Gmbh Copolymers and their use for the treatment of leather
DE19516961A1 (en) * 1995-05-12 1996-11-28 Stockhausen Chem Fab Gmbh Process for waterproofing leather at low pH values and leather produced therewith
ES2276226T3 (en) * 2004-07-13 2007-06-16 ZSCHIMMER & SCHWARZ GMBH & CO KG CHEMISCHE FABRIKEN AGENT FOR LEATHER HYDROFUGO PARESTO.
DE102005029627A1 (en) * 2005-06-23 2007-01-04 Basf Ag Process for the production of leather
JP2008012958A (en) * 2006-07-03 2008-01-24 Fujikura Parachute Co Ltd Anti-g suit
JP5941806B2 (en) * 2012-09-27 2016-06-29 花王株式会社 Method for producing polymer composition
JP6199125B2 (en) * 2013-09-05 2017-09-20 花王株式会社 Aqueous slurry

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DE3730885A1 (en) * 1987-09-15 1989-03-23 Basf Ag Fuel for Otto engines (spark ignition engines)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5501707A (en) * 1991-09-03 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Aqueous dispersions of new amphiphilic co-oligomers for the washing- and cleaning-resistant oiling of leather and skins and their use
US5266165A (en) * 1991-10-05 1993-11-30 Basf Aktiengesellschaft Paper sizing using copolymers of long-chain olefins and maleic anhydride in the form of the semiamides with morpholine
EP0542033A3 (en) * 1991-11-14 1993-06-02 Basf Aktiengesellschaft Use of pigment preparations for the manufacture of pastes, printing inks and paints
EP0542033A2 (en) * 1991-11-14 1993-05-19 BASF Aktiengesellschaft Use of pigment preparations for the manufacture of pastes, printing inks and paints
US5352729A (en) * 1991-11-14 1994-10-04 Basf Aktiengesellschaft Use of pigment formulations for the preparation of pastes, printing inks and coatings
US5412026A (en) * 1992-01-22 1995-05-02 Rohm And Haas Company High temperature aqueous polymerization process
US5268437A (en) * 1992-01-22 1993-12-07 Rohm And Haas Company High temperature aqueous polymerization process
DE4214011C1 (en) * 1992-04-29 1993-11-04 Muenzing Chemie Gmbh COPOLYMERISATE
EP0574351A1 (en) * 1992-06-09 1993-12-15 Ciba-Geigy Ag Process for the after-treatment of tanned leather and furs
US5558675A (en) * 1992-06-09 1996-09-24 Ciba-Geigy Corporation Process for aftertreating tanned leather and pelts
US5741434A (en) * 1992-07-14 1998-04-21 Henkel Kommanditgesellschaft Auf Aktien Leather oiling preparations and their use
US5489389A (en) * 1992-07-14 1996-02-06 Henkel Kommanditgesellschaft Auf Aktien New leather oiling preparations and their use
US5567343A (en) * 1992-07-14 1996-10-22 Henkel Kommanditgesellschaft Auf Aktien New leather oiling preparations and their use
EP0583973A2 (en) * 1992-08-18 1994-02-23 Ciba Specialty Chemicals Water Treatments Limited Impregnating composition for leather
EP0583973A3 (en) * 1992-08-18 1994-04-27 Allied Colloids Ltd
WO1994010346A1 (en) * 1992-10-29 1994-05-11 Chemische Fabrik Stockhausen Gmbh Process for softening/stuffing leather and fur skins
US5683611A (en) * 1994-01-12 1997-11-04 Henkel Kommanditgesellschaft Auf Aktien Preparations for the oiling of leather
WO1995020056A1 (en) * 1994-01-25 1995-07-27 Basf Aktiengesellschaft Aqueous solutions or dispersions of copolymers
US5728313A (en) * 1994-02-18 1998-03-17 Henkel Corporation Leather oiling compositions and their use
AU701756B2 (en) * 1994-05-10 1999-02-04 Clariant Gmbh Copolymers based on ethylenically unsaturated dicarboxylic anhydrides, long-chain olefins and fluoroolefins
EP0682044A1 (en) * 1994-05-10 1995-11-15 Hoechst Aktiengesellschaft Copolymers of ethylenically unsaturated dicarboxylic acid anhydrides, long-chaim olefines and fluoro-olefines
US5534604A (en) * 1994-05-10 1996-07-09 Hoechst Copolymers based on ethylenically unsaturated dicarboxylic anhydrides, long-chain olefins and fluoroolefins
US6336942B1 (en) 1995-03-12 2002-01-08 Basf Aktiengesellschaft Processes of treating leather and skins employing polymer compositions
US6200640B1 (en) 1996-04-01 2001-03-13 Basf Aktiengesellschaft Polymer composition and process for treating leather and fur skins
WO1998010103A1 (en) * 1996-09-09 1998-03-12 Stockhausen Gmbh & Co. Kg Novel leather-treatment agents, process for their preparation, and their use for producing low-fogging leathers
WO2003044233A1 (en) * 2001-10-16 2003-05-30 Buckman Laboratories International, Inc. Leather waterproofing formulation and leather goods waterproofed therewith
US6753369B2 (en) 2001-10-16 2004-06-22 Buckman Laboratories International, Inc. Leather waterproofing formulation and leather goods waterproofed therewith
US9029310B2 (en) 2008-07-07 2015-05-12 Basf Se Enzyme composition comprising enzyme containing polymer particles
WO2011050980A2 (en) 2009-10-30 2011-05-05 FLN FEUERLöSCHGERäTE NEURUPPIN VERTRIEBS GMBH Composition suitable for production of foam extinguishants
WO2013110413A1 (en) 2012-01-27 2013-08-01 Evonik Industries Ag Mixture composition containing amino-functional siloxanes, hydrophobic particles and high-molecular silicones as well as the use thereof for leather treatment
DE102012201167A1 (en) 2012-01-27 2013-08-01 Evonik Industries Ag Mixture composition containing amino-functional siloxanes, hydrophobic particles and high molecular weight silicones and its use for leather treatment

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DE3926167A1 (en) 1991-02-14
CA2021758A1 (en) 1991-02-09
AU628205B2 (en) 1992-09-10
PT94915A (en) 1991-04-18
JPH0376800A (en) 1991-04-02
PT94915B (en) 1997-05-28
ATE114727T1 (en) 1994-12-15
EP0412389B1 (en) 1994-11-30
KR910004817A (en) 1991-03-29
AU6022790A (en) 1991-02-14
ES2064554T3 (en) 1995-02-01
NZ234781A (en) 1991-10-25
DE59007823D1 (en) 1995-01-12

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