EP0628085B1 - Verwendung von umsetzungsprodukten von homo- oder copolymerisaten auf basis monoethylenisch ungesättigter dicarbonsäureanhydride mit aminen oder alkoholen zum fetten und füllen von leder und pelzfellen - Google Patents

Verwendung von umsetzungsprodukten von homo- oder copolymerisaten auf basis monoethylenisch ungesättigter dicarbonsäureanhydride mit aminen oder alkoholen zum fetten und füllen von leder und pelzfellen Download PDF

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Publication number
EP0628085B1
EP0628085B1 EP93903970A EP93903970A EP0628085B1 EP 0628085 B1 EP0628085 B1 EP 0628085B1 EP 93903970 A EP93903970 A EP 93903970A EP 93903970 A EP93903970 A EP 93903970A EP 0628085 B1 EP0628085 B1 EP 0628085B1
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EP
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Prior art keywords
mol
reaction products
monoethylenically unsaturated
alcohols
unsaturated dicarboxylic
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EP93903970A
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German (de)
English (en)
French (fr)
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EP0628085A1 (de
Inventor
Hermann Birkhofer
Peter Danisch
Walter Denzinger
Heinrich Hartmann
Norbert Greif
Knut Oppenlaender
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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 present invention relates to the use of reaction products of homopolymers or copolymers based on monoethylenically unsaturated dicarboxylic acid anhydrides with certain amines and alcohols for greasing and filling leather and fur skins.
  • aqueous fat emulsions are used, which are generally based on petrochemically produced or natural oils and fats. These are usually made water-emulsifiable by partial sulfonation or with the help of emulsifiers. Incomplete drainage of the liquor, relatively easy extraction with solvents or water, the occurrence of migration phenomena and unsatisfactory authenticity profiles all turn out to be disadvantages of this class of greasing agents.
  • Polymeric products for example based on unsaturated dicarboxylic acid derivatives and long-chain olefins with lubricating properties for leather and fur skins, are known and are used as water repellents for leather and fur skins.
  • EP-A 412 389 describes copolymers of C8- to C40-monoolefins and ethylenically unsaturated C4- to C8-dicarboxylic acid anhydrides which, following their preparation by solvolysis of the anhydride groups, for example with bases such as amines or partial esterification of the anhydride groups with alcohols and at least partial neutralization of the carboxyl groups formed with bases in an aqueous medium can be converted to aqueous solutions or dispersions which are recommended as water repellents for leather and furskins.
  • EP-A 418 661 also discloses water repellents for leather and furskins, which are copolymers of C8 to C40 alkyl (meth) acrylates or vinyl esters of C8 to C40 carboxylic acids with, inter alia, monoethylenically unsaturated C4 to C12 dicarboxylic acid anhydrides. These copolymers can be reacted with amines after their preparation.
  • US Pat. No. 2,452,536 discloses the use of sulfonated reaction products of copolymers obtained by free radical polymerization based on styrene and maleic anhydride with lauryl or stearyl alcohol for filling and greasing leather.
  • DE-B 26 29 748 describes the use of copolymers of C10- to C30 monoolefins and maleic anhydride, which may have been saponified with amine after their preparation, for filling and greasing leather and furskins.
  • Such polymeric leather greasing agents do have a certain greasing effect, but this is still not entirely satisfactory, especially for soft types of leather.
  • an additional fatty agent based on a native or synthetic Lickers are used, which complements the effect with the polymeric fatliquor.
  • the object of the invention was therefore to provide an improved agent for greasing and filling leather and fur skins, which no longer has the disadvantages of the prior art.
  • Maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, methylene malonic anhydride and mixtures thereof are particularly suitable as monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 10 carbon atoms (a). Maleic anhydride is particularly preferred.
  • the radical R1 is preferably hydrogen or methyl
  • Particularly suitable vinyl aromatics (b) are styrene or ⁇ -methylstyrene or a mixture thereof.
  • vinyl esters (c) come e.g. Vinyl formate, vinyl propionate, vinyl butyrate or in particular vinyl acetate into consideration. Mixtures of such vinyl esters can also be used.
  • Suitable C2 to C6 olefins (d) are, in particular, straight-chain or branched monoolefins, in particular ⁇ -olefins, e.g. Ethylene, propylene, 1-butene, isobutene, 1-pentene or 1-hexene, and also 2-butene, 2-pentene, 2-hexene or 3-hexene. Isobutene is particularly preferred.
  • conjugated dienes such as butadiene or isoprene can also be used. Mixtures of the olefins mentioned can also be used.
  • Suitable monoethylenically unsaturated carboxylic acids (E) are especially C3- to C bis-carboxylic acids, e.g. Crotonic acid or especially acrylic acid and methacrylic acid.
  • Homopolymers A from one monomer (a), copolymers A from two or more monomers (a) and copolymers A from monomers (a) to (e) are used, the copolymer, however, at least 30 mol% of monoethylenically unsaturated dicarboxylic anhydride (a ) must contain.
  • a copolymer of 60 mol% styrene, 30 mol% maleic anhydride and 10 mol% acrylic acid or another copolymer of 50 mol% maleic anhydride, 25 mol% styrene and 25 mol% vinyl acetate can be used.
  • a homopolymer of a monoethylenically unsaturated dicarboxylic anhydride having 4 to 10 carbon atoms (a) is used as component A in the preparation of the reaction products used according to the invention.
  • polymers A it is also possible to use small amounts of further monomers which are copolymerizable with the monomers (a) to (e), in particular monoethylenically and polyethylenically unsaturated compounds.
  • N-vinyl amides such as N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl piperidine, N-vinyl caprolactam and N-vinyl succinimide, N-vinylphthalimide, N-vinyloxazolone, N-vinylformamide and N-vinylimidazole and alkyl vinyl ethers having 1 to 18 carbon atoms in the alkyl radical, for example methyl vinyl ether, ethyl vinyl ether or stearyl vinyl ether, and C8- to C30-olefins, in particular C10- to C20 ⁇ -olefins, for example 1-dodecene, 1-hexadecene or 1-octadecene.
  • N-vinyl amides such as N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl piperidine, N-vinyl caprol
  • methylenebisacrylamide esters of acrylic acid, methacrylic acid and maleic acid with polyhydric alcohols such as, for example, glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • polyhydric alcohols such as, for example, glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose as well as glycol diacrylates of polyethylene glycols with molecular weights up to 3000.
  • the polymers A can be prepared by conventional free radical polymerization methods. The techniques of suspension, solution and bulk polymerization can be used in particular. Organic solvents such as toluene, xylene, ethylbenzene, isopropylbenzene, tetrahydrofuran, dioxane, cyclohexane, petroleum ether or ligroin can be used, for example, as diluents or solvents for the polymerization. One works at normal pressure or under increased pressure.
  • Suitable radical initiator systems are all which form free radicals under the desired polymerization conditions, for example di-tert-butyl peroxide, tert-butyl perbenzoate or tert-butyl perethyl hexanoate.
  • Protective colloids such as polyvinyl vinyl ether, can be added, particularly in the case of suspension polymerization.
  • the K values of the polymers A are generally between 6 and 200, in particular between 8 and 100. According to Fikentscher, the K values of the copolymers were based on 1% by weight solutions in cyclohexanone and the K values of the homopolymers (a ) determined in dimethylformamide as solvent at 25 ° C.
  • the polymers A can be isolated in solid form and, if desired, dried and then reacted with component B. However, the polymers A can also be reacted directly with component B in solution.
  • Primary, secondary and tertiary alcohols having 1 to 30 carbon atoms are to be mentioned as suitable alcohols for component B for the reaction with the polymers A.
  • suitable alcohols for component B for the reaction with the polymers A Both saturated aliphatic alcohols and unsaturated alcohols, such as oleyl alcohol, can be used.
  • Primary or secondary alcohols are preferably used, for example amyl alcohol, n-hexanol, n-octanol, 2-ethylhexanol, n-nonanol, iso-nonanol, n-decanol, n-dodecanol, n-tridecanol, iso-tridecanol, cyclohexanol, of course occurring fatty alcohols such as tallow fatty alcohol or stearyl alcohol as well as the alcohols or alcohol mixtures with 9 to 19 C-atoms, which are technically easily accessible through oxosynthesis, such as C 9/10 -oxoalcohol, C 13/15 -oxoalcohol, and Ziegl alcohols with 12 to 24 C-atoms, e.g. C 12/14 or C 16/18 cuts.
  • fatty alcohols such as tallow fatty alcohol or stearyl alcohol as well as the alcohols or alcohol mixtures with 9 to 19 C
  • the alcohols of component B can also be oxyalkylated, i.e. have been reacted with a C2 to C wie alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
  • alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
  • Tetramethylene can also be present as a polytetrahydrofuran structure as an alkylene building block for such a block.
  • ether alcohols and polyether diols such as ethylene glycol monobutyl ether, di- and triethylene glycol monobutyl ether, polytetrahydrofuran as well as polyethylene glycols and polypropylene glycols.
  • component B in the preparation of the reaction products used according to the invention alcohols in which the radical R6 is C1- to C22-alkyl or C10- to C22-alkenyl, m and n each represent a number from 2 to 4 and p and q each denote a number from 0 to 35.
  • Suitable primary or secondary amines of component B for reaction with the polymers A are n-hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, n-tridecylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, di-n-hexylamine , Dicyclohexylamine, di- (methylcyclohexyl) amine, di- (2-ethylhexyl) amine, di- (n-octyl) amine, di- (isotridecyl) amine, di-tallow fatty amine, di-stearylamine, diolelylamine, diethanolamine, di- To name n-propanolamine or di-iso-propanolamine.
  • the polymers A are reacted with the amines or alcohols B by known methods.
  • carboxylic acid ester or carboxamide functions are incorporated into the polymers A.
  • Amines are advantageously reacted with the polymers A in bulk or in inert organic solvents such as toluene, xylene, cyclohexane, petroleum ether or ligroin, which usually result from the preparation of the polymers A themselves, at atmospheric pressure or elevated pressure at about 60 to 130 ° C. .
  • reaction of the alcohols with the polymers A is advantageously also carried out in bulk or, preferably, in inert organic solvents, as mentioned above, in the presence of acidic catalysts such as p-toluenesulfonic acid under atmospheric pressure or elevated pressure at about 100 to 150 ° C.
  • acidic catalysts such as p-toluenesulfonic acid under atmospheric pressure or elevated pressure at about 100 to 150 ° C.
  • the ratio of components A and B in the reaction is usually chosen so that 0.2 to 1.0 mol of amine or alcohol B or a mixture thereof is used per mole of monomer a) in polymer A.
  • any organic solvent which is present is generally removed, preferably by distillation, and the product is usually dispersed in an aqueous solution of a base, preferably an alkali metal hydroxide such as sodium or potassium hydroxide or ammonia, to remove the remaining anhydride Functions to partially or completely hydrolyze and partially or completely neutralize the functions of the partially esterified or partially amidated polymers.
  • a base preferably an alkali metal hydroxide such as sodium or potassium hydroxide or ammonia
  • the polymer dispersions obtainable in this way are suitable for the treatment of all customary tanned hides.
  • the tanned hides are usually deacidified before treatment. They may have been stained before treatment. Coloring can, however, also be carried out only after the lubrication that takes place according to the invention.
  • the tanned skins are expediently mixed with the aqueous dispersions in an aqueous liquor at pH values of 4 to 10, preferably 5 to 8, and temperatures of 20 to 60 ° C., preferably 30 to 50 ° C., for a period of 0.1 up to 5 hours, in particular 0.5 to 2 hours, treated.
  • This treatment takes place, for example, by drumming in a barrel.
  • the amount of reaction product from A and B required, based on the shaved weight of the leather or the wet weight of the fur file, is 0.1 to 30% by weight, preferably 1 to 20% by weight.
  • the liquor length ie the percentage weight ratio of the treatment liquor to the goods, based on the fold weight of the leather or the wet weight of the fur skins, is usually 10 to 1000%, preferably 30 to 150%, and 50 to 500% for fur skins.
  • the dispersions of the reaction products from A and B used generally have no additional emulsifiers.
  • the pH of the treatment liquor is adjusted to a pH of 3 to 5, preferably 3.5 to 4, by adding acids, preferably organic acids such as formic acid.
  • treatment with the reaction products from A and B to be used according to the invention can take place before or after the retanning step.
  • reaction products to be used according to the invention it is possible to produce very soft leather without the addition of conventional licker. This advantage is reflected in simple and short application formulations.
  • these polymeric greasing agents significantly increase the authenticity profile of the leather.
  • the lightfastness and heat yellowing resistance of such leathers are influenced very positively.
  • the good fixation in the leather results in great resistance to extractability with solvent or water. This leads to so-called washable leathers, i.e. leather that does not lose its properties such as softness, strength and suppleness after washing, in contrast to leather that has been greased with conventional licker.
  • hydrophobic properties of these polymeric greasing agents can be varied so that the leather can also be given a certain water resistance by a suitable selection from the special alcohols and amines of component B in the reaction products used according to the invention.
  • reaction products used according to the invention are not require any additional emulsifiers when applied to leather or fur skins.
  • leather and furs made with emulsifier Products that have been treated often have to be subjected to complex processes, such as aftertreatment with polyvalent metal salts, after the treatment with these agents, in order to render the emulsifiers in the leather or in the fur skins ineffective.
  • the percentages in the examples relate to the weight.
  • the molecular weights of the copolymers were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.
  • the K values according to Fikentscher of the copolymers and of the auxiliaries were determined in 1% strength by weight solutions in cyclohexanone at 25 ° C., in the homopolymers of monomers (a) dimethylformamide was used as the solvent instead of cyclohexanone.
  • the preparation is carried out analogously to Example 2, except that 264.6 g (2.7 mol) of maleic anhydride and 655.2 g (6.3 mol) of styrene were used.
  • the K value of the polymer obtained was 16.0, the molar mass was 9000.
  • the fine, light brown polymer suspension could be processed further directly to give a leather greasing agent.
  • Example 2 In a reactor as in Example 1, 1750 g of maleic anhydride and 1165 g of o-xylene were heated to boiling and a solution of 262 g of tert-butyl perethylhexanoate in 190 g of o-xylene was metered in uniformly over 5 hours while boiling. The mixture was then reheated for an hour and then the o-xylene was decanted over the melt, the melt was applied to an aluminum sheet and cooled. The resin was crushed and the remaining solvent was distilled off in vacuo. The polymer had a K value of 10, the molar mass was 1000.
  • the copolymer obtained was a fine powder with a K value of 25 and its molar mass was 8000.
  • reaction products from polymers A and amines B were prepared by adding the amines shown in the table to the polymers shown in the table in xylene at 120 to 130 ° C. in the molar ratio of amine: maleic anhydride (MA) in the polymer shown in the table. After distilling off of the xylene after the reaction, the product was dispersed with an Ultraturax stirrer in aqueous sodium hydroxide solution in the molar ratio NaOH: MSA given in the table in the polymer, so that a 20 to 25% dispersion with a pH of 7 to 8 resulted.
  • MA maleic anhydride
  • reaction products from polymers A and alcohols B were prepared by reacting the alcohols listed in the table with the polymers listed in the table in xylene at 120 to 130 ° C. in the presence of catalytic amounts of p-toluenesulfonic acid for 3 to 5 hours in the The molar ratio of alcohol: MSA in the polymer indicated in the table.
  • MSA molar ratio of alcohol
  • the product was dispersed in the polymer using an Ultaturax stirrer in aqueous sodium hydroxide solution in the NaOH: MSA molar ratio given in the table, so that a 20 to 25% strength dispersion having a pH of 7 to 8 resulted.
  • Example 9 The product from Example 9 was used analogously to the procedure given in Example 21.
  • the leather thus obtained showed soft and round grip properties.
  • Example 10 The product from Example 10 was used analogously to the procedure given in Example 23.
  • the leather thus obtained was characterized by a round, soft handle.

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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)
  • Polyethers (AREA)
EP93903970A 1992-02-26 1993-02-15 Verwendung von umsetzungsprodukten von homo- oder copolymerisaten auf basis monoethylenisch ungesättigter dicarbonsäureanhydride mit aminen oder alkoholen zum fetten und füllen von leder und pelzfellen Expired - Lifetime EP0628085B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4205839 1992-02-26
DE4205839A DE4205839A1 (de) 1992-02-26 1992-02-26 Verwendung von umsetzungsprodukten von homo- oder copolymerisaten auf basis monoethylenisch ungesaettigter dicarbonsaeureanhydride mit aminen oder alkoholen zum fetten und fuellen von leder oder pelzfellen
PCT/EP1993/000354 WO1993017130A1 (de) 1992-02-26 1993-02-15 Verwendung von umsetzungsprodukten von homo- oder copolymerisaten auf basis monoethylenisch ungesättigter dicarbonsäureanhydride mit aminen oder alkoholen zum fetten und füllen von leder und pelzfellen

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EP0628085A1 EP0628085A1 (de) 1994-12-14
EP0628085B1 true EP0628085B1 (de) 1996-02-14

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EP93903970A Expired - Lifetime EP0628085B1 (de) 1992-02-26 1993-02-15 Verwendung von umsetzungsprodukten von homo- oder copolymerisaten auf basis monoethylenisch ungesättigter dicarbonsäureanhydride mit aminen oder alkoholen zum fetten und füllen von leder und pelzfellen

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US (1) US5433752A (es)
EP (1) EP0628085B1 (es)
JP (1) JPH07504217A (es)
AU (1) AU661562B2 (es)
DE (2) DE4205839A1 (es)
ES (1) ES2083280T3 (es)
WO (1) WO1993017130A1 (es)

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Publication number Priority date Publication date Assignee Title
DE4236556A1 (de) * 1992-10-29 1994-05-05 Stockhausen Chem Fab Gmbh Verfahren zur Weichmachung/Fettung von Ledern und Pelzen
DE4402029A1 (de) * 1994-01-25 1995-07-27 Basf Ag Wäßrige Lösungen oder Dispersionen von Copolymerisaten
US6004264A (en) 1994-07-04 1999-12-21 Asahi Kogaku Kogyo Kabushiki Kaisha Portable endoscope system
DE19942681B4 (de) * 1999-09-07 2006-04-27 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co Copolymer zur Behandlung von Leder und Pelzfellen
US6753369B2 (en) 2001-10-16 2004-06-22 Buckman Laboratories International, Inc. Leather waterproofing formulation and leather goods waterproofed therewith
DE10304959A1 (de) * 2003-02-06 2004-08-19 Basf Ag Verfahren zur Herstellung von Leder
DE10321628A1 (de) * 2003-05-13 2004-12-02 Basf Ag Verwendung von Copolymerisaten als Hilfsmittel für die Lederherstellung
DE10343904A1 (de) * 2003-09-19 2005-04-21 Basf Ag Verfahren zur Herstellung von Copolymerisaten
AR045605A1 (es) * 2003-09-26 2005-11-02 Basf Ag Dispersiones acuosas de copolimerizados, su preparacion y uso
DE102004031158A1 (de) 2004-06-28 2006-01-19 Basf Ag Verwendung von Ethergruppen enthaltenden Polymeren als Lösungsvermittler
PT2190892E (pt) 2007-09-04 2013-05-03 Basf Se Processo para a produção de couro, copolímeros adequados a esse fim e outras utilizações dos mesmos
GB0810075D0 (en) * 2008-05-03 2008-07-09 Raven Mfg Ltd Satellite date receiving apparatus
DE102009047183A1 (de) 2008-12-19 2010-07-15 Basf Se Farbstoffmischung zum Färben von Leder
US8779069B2 (en) * 2011-12-12 2014-07-15 Axalta Coating Systems Ip Co., Llc Cathodic electrocoating compositions

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
US2452536A (en) * 1944-07-25 1948-11-02 Du Pont Process for impregnating leather with sulfonated polymeric compositions
US2746837A (en) * 1951-12-28 1956-05-22 Gen Aniline & Film Corp Manufacture of leather using a modified vinyl ether-maleic anhydride copolymer, and resulting product
DE2501123C2 (de) * 1975-01-14 1984-02-09 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Suspensions-Copolymerisaten
DE2629748C2 (de) * 1976-07-02 1979-06-07 Zschimmer & Schwarz Chemische Fabriken, 5420 Lahnstein Verwendung von Copolymerisaten aus Monoolefinen und Maleinsäureanhydrid zum Füllen und Fetten von Leder und Pelzfellen
US5279613A (en) * 1989-08-08 1994-01-18 Basf Aktiengesellschaft Copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent
DE3926167A1 (de) * 1989-08-08 1991-02-14 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen olefinen und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen
DE3926168A1 (de) * 1989-08-08 1991-02-14 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen alkylvinylethern und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen
DE3931039A1 (de) * 1989-09-16 1991-03-28 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen

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

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