EP0412389B1 - Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures - Google Patents

Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures Download PDF

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Publication number
EP0412389B1
EP0412389B1 EP90114574A EP90114574A EP0412389B1 EP 0412389 B1 EP0412389 B1 EP 0412389B1 EP 90114574 A EP90114574 A EP 90114574A EP 90114574 A EP90114574 A EP 90114574A EP 0412389 B1 EP0412389 B1 EP 0412389B1
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EP
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Prior art keywords
copolymer
carboxyl groups
solvolysis
groups formed
total amount
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Revoked
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EP90114574A
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German (de)
English (en)
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EP0412389A1 (fr
Inventor
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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Classifications

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

Definitions

  • the 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 peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, tertiary butyl perneodecanoate, 2,2 ′ azobis (4-methoxy-2,4-di-tert-butylperyl peri-butyl peri-peri-butyl peri-per-di-tert-butyl peri-nitro-di-peri-butyl per-iodo-2-di-peri-butyl per-iodo-per-oxy-2-di-peri-butyl per-iodo-2-dimer-butyl peri-t-per-butyl per-iodo-2-peri-tetraperyl per-iodo
  • 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 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 present 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 if used, is added to the polymerizing mixture either separately or also in solution 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 the end 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 a solids content 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 formed 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.
  • the 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 / C24-olefin and maleic anhydride at a degree of neutralization of 50% carboxyl groups resulting from this copolymer are already readily dispersible 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 as well as alcohols or alcohol mixtures with 9 to 19 carbon atoms that are technically easily accessible through oxo synthesis, 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.
  • 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 at the same time as 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 ideal 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, in most cases does not more is needed.
  • commercially available tanning agents for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products, in most cases does not more is needed.
  • aqueous dispersions to be used according to the invention contain no additional emulsifiers. It is known that leather and furs that have been treated with products containing emulsifiers have to undergo complex processes after treatment with these agents, e.g. Subsequent treatment with polyvalent metal salts are subjected in order to render the emulsifiers in the leather or in the fur skins ineffective.
  • copolymer dispersions 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 only be carried out after the hydrophobization according to the invention has taken place.
  • the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the copolymer dispersions 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 takes place, 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 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 Chemists' Associations, Commission for Physical Leather Testing, cf. the leather, volume 12, 36 to 40 (1961).
  • the reaction mixture is stirred at 110 ° C. for 2 hours 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)

Claims (5)

  1. Utilisation, pour l'imperméabilisation de cuirs et de peaux en poils, de copolymères qui sont obtenus par copolymérisation radicalaire de
    a) monooléfines en C₈-C₄₀ avec
    b) des anhydrides d'acides dicarboxyliques en C₄-C₈ à insaturation éthylénique
    à la manière d'une polymérisation en masse à des températures de 80 à 300°C, pour donner des copolymères ayant des masses molaires de 500 à 20 000 g/mole, suivie de solvolyse des groupements anhydride des copolymères et de neutralisation au moins partielle des groupements carboxyle résultant de la solvolyse, en milieu aqueux avec des bases, et qui se présentent sous forme de solutions ou de dispersions aqueuses.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'on effectue la solvolyse par addition d'eau à une masse fondue des copolymères obtenus dans la polymérisation en masse, et en ce qu'on neutralise au moins 10% des groupements carboxyle des copolymères hydrolysés avec de l'ammoniac, des amines, des bases de métaux alcalins ou des bases de métaux alcalino-terreux.
  3. Utilisation selon la revendication 1, caractérisée en ce qu'on effectue la solvolyse par addition d'amines primaires et/ou secondaires à une masse fondue des copolymères obtenus dans la polymérisation en masse, de telle sorte que 10 à 50% des groupements carboxyle provenant au total des monomères (b) contenus en liaison polymère soient amidés et qu'au moins 10% des groupements carboxyle formés au total soient neutralisés.
  4. Utilisation selon la revendication 1, caractérisée en ce qu'on effectue la solvolyse des copolymères obtenus dans la polymérisation en masse, en milieu aqueux, par addition de sels d'acides aminocarboxyliques, de telle sorte que 10 à 50% des groupements carboxyle provenant au total des monomères (b) contenus en liaison polymère soient amidés et qu'au moins 10% des groupements carboxyle formés au total soient neutralisés.
  5. Utilisation selon la revendication 1, caractérisée en ce qu'on effectue la solvolyse par addition d'alcools à une masse fondue des copolymères obtenus dans la polymérisation en masse, de telle sorte que 10 à 50% des groupements carboxyle provenant au total des monomères (b) contenus en liaison polymère soient estérifiés et qu'au moins 10% des groupements carboxyle formés au total soient neutralisés.
EP90114574A 1989-08-08 1990-07-30 Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures Revoked EP0412389B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3926167 1989-08-08
DE3926167A DE3926167A1 (de) 1989-08-08 1989-08-08 Verwendung von copolymerisaten auf basis von langkettigen olefinen und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen

Publications (2)

Publication Number Publication Date
EP0412389A1 EP0412389A1 (fr) 1991-02-13
EP0412389B1 true EP0412389B1 (fr) 1994-11-30

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ID=6386714

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Application Number Title Priority Date Filing Date
EP90114574A Revoked EP0412389B1 (fr) 1989-08-08 1990-07-30 Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures

Country Status (10)

Country Link
EP (1) EP0412389B1 (fr)
JP (1) JPH0376800A (fr)
KR (1) KR910004817A (fr)
AT (1) ATE114727T1 (fr)
AU (1) AU628205B2 (fr)
CA (1) CA2021758A1 (fr)
DE (2) DE3926167A1 (fr)
ES (1) ES2064554T3 (fr)
NZ (1) NZ234781A (fr)
PT (1) PT94915B (fr)

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DE4223111A1 (de) * 1992-07-14 1994-01-20 Henkel Kgaa Neue Lederfettungsmittel und ihre Verwendung
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DE4416415A1 (de) * 1994-05-10 1995-11-16 Hoechst Ag Copolymere auf Basis von ethylenisch ungesättigten Dicarbonsäureanhydriden, langkettigen Olefinen und Fluorolefinen
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NZ234781A (en) 1991-10-25
CA2021758A1 (fr) 1991-02-09
ATE114727T1 (de) 1994-12-15
PT94915A (pt) 1991-04-18
AU628205B2 (en) 1992-09-10
DE3926167A1 (de) 1991-02-14
DE59007823D1 (de) 1995-01-12
EP0412389A1 (fr) 1991-02-13
PT94915B (pt) 1997-05-28
ES2064554T3 (es) 1995-02-01
AU6022790A (en) 1991-02-14
JPH0376800A (ja) 1991-04-02
KR910004817A (ko) 1991-03-29

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