EP0866879A1 - Utilisation, sous forme de matieres tannantes pour le cuir, de solutions ou dispersions aqueuses de copolymeres constitues de monomeres renfermant des groupes carboxyle, d'acetals, de cetals ou d'esters d'acide orthocarboxylique ethyleniquement insatures et eventuellement d'autres monomeres copolyme - Google Patents

Utilisation, sous forme de matieres tannantes pour le cuir, de solutions ou dispersions aqueuses de copolymeres constitues de monomeres renfermant des groupes carboxyle, d'acetals, de cetals ou d'esters d'acide orthocarboxylique ethyleniquement insatures et eventuellement d'autres monomeres copolyme

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Publication number
EP0866879A1
EP0866879A1 EP96942289A EP96942289A EP0866879A1 EP 0866879 A1 EP0866879 A1 EP 0866879A1 EP 96942289 A EP96942289 A EP 96942289A EP 96942289 A EP96942289 A EP 96942289A EP 0866879 A1 EP0866879 A1 EP 0866879A1
Authority
EP
European Patent Office
Prior art keywords
copolymers
alkyl
monomers
cio
tanning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP96942289A
Other languages
German (de)
English (en)
Inventor
Walter Denzinger
Axel Kistenmacher
Gerhard Wolf
Michael Kneip
Norbert Greif
Knut Oppenländer
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0866879A1 publication Critical patent/EP0866879A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/22—Chemical tanning by organic agents using polymerisation products
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes

Definitions

  • the present invention relates to the use of aqueous solutions or dispersions of copolymers of monomers containing carboxyl groups, ethylenically unsaturated cyclic or semicyclic acetals, ketals or orthocarboxylic acid esters and optionally other copolymerizable monomers as leather tanning agents. Because part of this
  • Copolymers represents new substances, the invention further relates to these copolymers.
  • the main tanning is usually done with mineral tanning agents such as basic chrome,
  • Aluminum and / or zirconium salts carried out alone or in combination with synthetic tanning agents. Subsequent retanning with natural or synthetic tanning agents serves to improve leather properties such as feel, softness, grain and fullness.
  • Syntans i.e. water-soluble condensation products from e.g. Naphthalenesulfonic acid and formaldehyde or from phenolsulfonic acid, formaldehyde and urea, also lignosulfonic acids and also polymers and copolymers based on acrylic acid and other unsaturated polymerizable carboxylic acid, generally in combination with the aforementioned syntanes.
  • the known polymeric retanning agents for leather are still in need of improvement with regard to their fullness and softness, which they lend to the leather, and in terms of their dyeing behavior.
  • the object of the present invention was therefore to provide such retanning agents with corresponding improved properties.
  • R ⁇ R 2 are independently hydrogen
  • R 3, R 4, R 5, R 6, R 8, R 9, R 10, R n are independently hydrogen ⁇ material, Ci- to C 10 alkoxy, amino, Ci to C 4 alkylamino, di-Cj .- to C 4 alkylamino, C ß - to C 14 aryl, C 7 - to C 18 aralkyl, carboxyl, Ci to C 20 alkoxycarbonyl, C 2 interrupted by one to five non-adjacent oxygen atoms - to -C 8 alkyl or sulfo or phosphono groups,
  • R 7 is hydrogen, C x - to C ⁇ 0 alkyl, C 6 - to C ⁇ 4 aryl, C 7 - to C ⁇ 8 aralkyl or
  • Ci to Cio alkoxy, hydroxyl or Ci to Cio acyloxy
  • R 2 and R 4 together also represent a 1,3- or 1,4-alkylene group with 3 to 12 carbon atoms and
  • R 5 and R 7 together can also form a 1,2- or 1,3-alkylene group having 2 to 12 carbon atoms, and
  • tanning agents for single tanning, pretanning and tanning of the bare and fur bare and for retanning leather and fur.
  • Suitable carboxyl group-containing monomers of group A are, in particular, monoethylenically unsaturated mono- or dicarboxylic acids or their corresponding anhydrides with 3 to 6 carbon atoms, such as e.g. Acrylic acid, methacrylic acid, ethyl acrylic acid, allyl acetic acid, crotonic acid, vinyl acetic acid, maleic acid, maleic acid monoalkyl ester, itaconic acid, mesaconic acid, fumaric acid, citraconic acid, methylene malonic acid and their alkali metal, alkaline earth metal or ammonium salts and mixtures thereof.
  • monoethylenically unsaturated mono- or dicarboxylic acids or their corresponding anhydrides with 3 to 6 carbon atoms such as e.g. Acrylic acid, methacrylic acid, ethyl acrylic acid, allyl acetic acid, crotonic acid, vinyl acetic acid, maleic acid, maleic acid monoalkyl
  • dicarboxylic acid monoalkyl esters the number of carbon atoms given relates to the dicarboxylic acid skeleton; the alkyl group in the ester radical can independently have 1 to 20 carbon atoms, in particular 1 to 8 carbon atoms.
  • the corresponding monoethylenically unsaturated dicarboxylic anhydrides are maleic anhydride, itaconic anhydride, citraconic anhydride or their
  • Acrylic acid, methacrylic acid, maleic acid itaconic acid and maleic anhydride are preferred.
  • the group B monomers are monoethylenically unsaturated acetals, ketals or orthocarboxylic acid esters with a cyclic or semicyclic structure.
  • the variables R 1 and R 2 are preferably independently of one another, hydrogen, Ci to C4 alkyl, especially methyl and ethyl, Ci to C 4 alkoxy, especially methoxy and ethoxy, N- (C ⁇ - to C4 alkyl ) ammo, especially N-methylammo and N-ethylamino, and N, N- (di-C 1 -C 4 -alkyl) amino, in particular N, N-dimethylamino and N, N-diethylamino.
  • R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 preferably independently denote hydrogen, C 1 -C 4 -alkyl, in particular methyl and ethyl, C 1 -C 4 -alkoxy, in particular methoxy and ethoxy, N- (C 1 -C 4 -alkyl) amino, in particular N-methylamino and N-ethylamino, N, N- (di-C 1 -C 4 -alkyl) amino, in particular N , N-dimethylamino and N, N-diethylamino, phenyl, tolyl, benzyl, carboxyl,
  • Ci to C 4 alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl, and groupings of the formula -CH 2 OCH 3 , -CH 2 OCH 2 CH 3 , -CH 2 CH 2 OCH 3 , CH 2 CH 2 OCH 2 CH 3 , -CH 2 0 (C 2 H 4 0) m CH 3 , -CH 2 0 (C 3 H 6 0) n CH 3 and -CH 2 0 (C 4 H 8 0) P CH 3 (m, n, p 2 to 4) .
  • the variable R 7 preferably represents hydrogen, Ci to C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, see. -Butyl and tert. -Butyl, phenyl, tolyl, C 7 - to -C 2 aralkyl such as benzyl and 2 -phenylethyl and Ci- to C 4 -acyl such as formyl, acetyl, propionyl and butyryl.
  • the variable R 12 is preferably hydrogen, Ci to C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, see. -Butyl and tert-butyl, Ci to C 4 alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, see. -Butoxy and tert. -Butoxy, hydroxyl and Ci- to C 4 -acyloxy such as acetoxy, propionyloxy and butyryl - oxy.
  • R 12 is particularly preferably hydrogen.
  • 1,3- or 1,4-alkylene groups formed together by R 2 and R 4 are especially -CH 2 CH 2 CH 2 , -CH (CH 3 ) CH 2 CH 2 -, -CH (CH 3 ) CH 2 CH (CH 3 ) - , -CH 2 CH (CH 3 ) CH 2 -, -CH (C 4 H 9 ) CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH (CH 3 ) CH 2 CH 2 - and -CH (C 4 H9) CH 2 CH 2 CH 2 -.
  • 1,2- or 1,3-alkylene groups formed together by R 5 and R 7 are especially -CH 2 CH 2 -, -CH (CH 3 ) CH 2 -, -CH (CH 3 ) CH (CH 3 ) -, -CH (C 2 H 5 ) CH 2 -, -CH (C 4 H 9 ) CH 2 -, -CH 2 CH 2 CH 2 -, -CH (CH 3 ) CH 2 CH 2 -, -CH (CH 3 ) CH 2 CH (CH 3 ) -, -CH 2 CH (CH 3 ) CH 2 - and -CH (C 4 H 9 ) CH 2 CH 2 -.
  • the copolymers contain as monomers B 5, 6-dihydro-4H-pyrans of the general formula Ia
  • the preferably carboxyl group-free monomers of group C include, for example:
  • Ci to C 3 o esters of acrylic acid or methacrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate and phenoxyethyl 1-acrylate;
  • Hydroxyalkyl esters of acrylic acid or methacrylic acid e.g. Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and butanediol-1,4-monoacrylate;
  • C 3 - to Cicrmono- or -dicarboxylic acids such as, for example, methyl diglycol acrylate and methyl pentaglycol methacrylate;
  • linear and branched-chain ⁇ -olefins or mixtures thereof such as e.g. Ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, cyclohexene, octene, 2, 4, 4-trimethyl-1-pentene, optionally in a mixture with 2,4,4-trimethyl-2-pentene, 1- Octene,
  • Acrylamides and alkyl substituted acrylamides such as e.g. Acrylamide, methacrylamide and N-tert. -Butyl acrylamide;
  • monomers containing sulfo groups such as e.g. Allylsulfonic acid, methallylsulfonic acid, styrene sulfonate, vinyl sulfonic acid,
  • Acrylamides or (meth) acrylates which have tertiary amino groups, e.g. 2- (N, N-Dimethyla ⁇ uno) ethyl (meth) acrylate, 2- (N, N-diethylammo) ethyl (meth) acrylate, 2 dimethylaminoethyl (meth) acrylamide and 3-dimethylammopropyl (meth) acrylamide, respectively their salts formed with mineral acids or their quaternization products with alkyl halides or alkyl sulfates;
  • Vinyl esters of ci- to C 2 o-carboxylic acids such as, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate and vinyl laurate;
  • N-vinyl carboxamides of carboxylic acids with 1 to 8 carbon atoms such as e.g. N-Vmylformamide, N-Vinyl-N-methylformamide and N-Vmylacetamide;
  • comonomers e.g. Styrene, ⁇ -methylstyrene, butadiene, N-methylpyrrolidone, N-methylimidazole, acrolein, methacrolein, acrylonitrile, 4-methylpyridm, indene and diallyl-dimethylammonium chloride.
  • Preferred comonomers of the group C include methyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, butene, isobutene, 2,4,4 trimethyl-1-pentene, 1 octene, C 8-0 0 -olefin, 1 Dodecene, C ⁇ 2 - ⁇ 4 -01efin, C 20 - 24 -olefin, oligopropene, oligohexene, oligo-octadecene, reactive polyisobutene, methyl stearate, 2-acrylamido-2-methylpropane sulfonic acid, ethylhexyl methyl ether, styrene, acrolein and acrylonitrile.
  • the group A and C monomers are generally customary polymer building blocks and are readily accessible.
  • the group B monomers described by the general formula I can be obtained by various preparation methods. Examples include: Production from halogen / O-alkyl acetals with alcohols, production from aldehydes or ketones with hydroxy compounds, production from enol ethers with alcohols, production from enones and enol ethers according to a [4 + 2] cycloaddition or from ethers through electrolysis. These and other manufacturing methods are summarized in general form, for example in: Houoen-Weyl, Methods of Organic Chemistry, Vol. E14a / 1, ed. K. Hage ⁇ mann, Thieme-Verlag 1991.
  • the described copolymers of the present invention are preferably composed of 10 to 90 mol% of the monomers A and 10 to 90 mol% of the monomers B. Become
  • Monomers C co-polymerized in, their proportion is preferably 10 to 70 mol%.
  • the polymerization can be carried out in the presence or absence of inert solvents or inert diluents as bulk polymerization. It is advantageous when using solvents or diluents that both good dissipation of the heat of polymerization and low viscosity ensure smd.
  • solvents or diluents can be used which are able to dissolve both the monomers and the resulting polymer. In this case it is a solution polymerization.
  • the method of precipitation polymerization can also be used advantageously.
  • the monomers are at least partially soluble in the solvent, but not the resulting polymer. The product therefore fails in the course of the polymerization. This ensures a low viscosity during the polymerization and enables the solid product to be easily separated if necessary.
  • Emulsion and suspension polymerization are further polymerization methods which can advantageously be used to prepare the copolymers described.
  • the monomers are present in dispersed form in a continuous phase.
  • Water is usually used as the continuous phase, but hydrocarbons or other solvents can also be used.
  • the advantage of these methods is that the polymerization can be carried out at low viscosities and the products, in particular when water is used as the continuous phase, can usually be used directly for their intended use.
  • emulsifiers or protective colloids can be advantageous for stabilizing the droplets or particles.
  • emulsifiers that can be used are: alkylphenol ethoxylates, primary alcohol ethoxylates, linear
  • Alkylbenzenesulfonates alkyl sulfates, ethylene oxide / propylene oxide block copolymers or alkyl polyglucosides.
  • Protective colloids that can be used are, for example: cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, polyvinyl alcohol, polyvinyl ether, starches and starch derivatives, dextran, polyvinyl pyrrolidone, polyvinyl pyridine, polyethylene imine, polyvinyl imidomolezole, polyimide imidazole -methylsuccinimide, Polyvmyl -1, 3 -oxazoli - don-2, polyvinyl-2-methylimidazole and copolymers containing maleic acid or maleic anhydride.
  • the emulsifiers or protective colloids are usually used in concentrations of 0.05 to 15% by weight, based on the monomers.
  • the method of precipitation or solution polymerization is preferably used to prepare the polymers described.
  • Suitable solvents or diluents for example toluene, o-xylene, p-xylene, ethylbenzene, technical mixtures of alkylaromatics, cyclohexane, technical aliphatic mixtures, acetone, cyclohexanone, tetrahydrofuran, dioxane, glycols and glycol derivatives, polyalkylene glycols and their derivatives , Diethyl ether, tert.
  • the polymerization can be carried out continuously or batchwise.
  • the polymerization temperature can be selected in the range from 20 ° C. to 250 ° C., preferably in the temperature range from 50 ° C. to 160 ° C.
  • the polymerization is preferably carried out in such a way that at least some of the monomers and the initiator are metered into the reaction vessel during the polymerization.
  • the inflow time can be chosen arbitrarily, as a result of which the heat released during the polymerization is released over a defined period of time.
  • the amount of monomers flowing into the reactor per unit of time can be kept constant; however, it is also possible to adjust the monomer flow or
  • the copolymers described are generally prepared using free-radical initiators.
  • Suitable radical initiators are preferably all those compounds which, at the polymerization temperature chosen in each case, have a half-life in the range from 1 minute to 10 hours. If the polymerization is first started at a lower temperature and ends at a higher temperature, it is expedient to work with at least two initiators which disintegrate at different temperatures, namely initially an initiator which disintegrates even at a lower temperature for starting the polymerization to use and then to complete the main polymerization with an initiator which decomposes at a higher temperature. As a rule, an initiator which is soluble in the particular solvent or diluent is used. In the case of polymerization in the dispersed phase, it is also possible to use initiators which are soluble only in the phase.
  • Peroxides or azo compounds are usually used as polymerization initiators, such as, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxydicarbonate, tert.
  • acetylcyclohexanesulfonyl peroxide diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxydicarbonate, tert.
  • -butyl-perneodecanoate 2,2'-azobis- (4-methoxy-2, 4-dimethylvalero-nitrile), 2, 2'-azobis- (2-methyl N-phenylpropionamide) dihydrochloride, tert.
  • salts or complexes of heavy metals e.g. Copper, cobalt, manganese, iron, vanadium, cerium, nickel or chromium salts or organic compounds such as benzom, dimethylaniline or ascorbic acid
  • the half-value tents of the radical initiators indicated can be reduced. So you can, for example, tert.
  • the reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine.
  • a polymerization initiator or a mixture of several polymerization initiators 0.01 to 30% by weight of the reducing compounds are added as redox components.
  • Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often advantageous to use a combination of peroxide, reducing agent and heavy metal as the redox catalyst.
  • the polymerization is expediently carried out in m
  • regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan, n-dodecyl mercaptan or tert. Dodecyl mercaptan. Also suitable as controllers,
  • the Copolymers have a number average molecular weight of 500 to 1,000,000, preferably 800 to 150,000.
  • the polymerization is carried out as bulk polymerization, the polymer must be converted into an aqueous solution or dispersion in order to obtain a usable product.
  • the polymer can, for example, after the end of the polymerization water to admit polymer and the mixture be solved i emer ge ⁇ suitable temperature or disperse.
  • the polymer can also be added as a melt or solid, with stirring, to a stirred tank charged with water.
  • the cyclic and semicyclic acetals polymerized as monomers B can be saponified to the corresponding aldehydes in a polymer-analogous manner. May continue to einpolymeri ⁇ overbased ketals or Orthocarbonklareester be converted into the corresponding ⁇ ketones or carboxylic acids.
  • the presence of free or hydrated aldehyde groups, ketone groups or carboxyl groups in the polymers can increase both the water solubility of the products and their effectiveness.
  • the formation of aldehyde, ketone or Orthocar- bonsaure philosophy favor, heating the aqueous polymer solution or dispersion over a longer time ⁇ space.
  • the aldehyde-containing polymers obtained after the acetals have been opened can, if appropriate, also be converted in a polymer-analogous manner.
  • these can be converted to alcohols to give hemiacetals or acetals, to mercaptans to thioacetals, to ammonia or primary amines to Schiff bases, to hydroxylamines to oximes, to hydrazines to hydrazone, to secondary amines to enamines and with sodium bisulfite to bisulfite addition compounds put.
  • the aldehyde groups can be reductively converted to alcohols or amines.
  • ketone or carboxyl groups obtainable by hydrolysis can be implemented in a polymer-analogous manner by methods known per se.
  • a group A comonomer is a monoethylenically unsaturated dicarboxylic acid anhydride, such as e.g. Malemsaure ⁇ anhydride used, this anhydride group can be implemented in a polymer analog. The prerequisite for this is that the
  • Suitable alcohols can contain 1 to 40, preferably 3 to 30, carbon atoms. Primary, secondary and tertiary alcohols 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, for example, 2-ethylhexanol ;
  • Alcohols are preferably used with 3 to 30 C-atoms, such as n-butanol, isobutanol, Amyl ⁇ alcohol, 2-ethylhexanol, tridecanol, tallow fatty alcohol, stearyl alcohol, C9 / u-oxo, C 13/15 -oxo alcohol, C ⁇ 2 / ⁇ 4 -Al - fole ® and C ⁇ 6 / ⁇ e-Alfoie.
  • the esterification can optionally be accelerated by a catalyst such as p-toluenesulfonic acid.
  • the copolymers containing anhydride groups can also be amidated or imidized by adding primary or secondary amines.
  • the amidation / imidization is carried out with amounts of amines such that 10 to 70% of the total carboxyl groups resulting from the copolymerized dicarboxylic acid anhydride units are amidated or 10 to 70% of the polymerized dicarboxylic acid anhydride units are imidized.
  • Ammonia and primary and secondary nurse 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-ethylhexylamm, n-octylamine, isotridecylamm, tallow fatty amine, stearylamm, oleylamine, dimethylamm, diethyl n-propylamine, di-isopropylamine, di-n-butylamm, di-isobutylamine, dihexylamine, di-cyclohexylamine, di-methylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, di-isotridecylamm, di- Tallow fat amine, di-stearylamm, di-oleyl
  • the remaining anhydride groups of the polymer can be hydrolysed.
  • the hydrolysis of further of the anhydride groups still present in the copolymer can also be carried out simultaneously with the partial neutralization still required, by adding an aqueous base to the partially esterified, amidated or imidized copolymer which still contains anhydride groups.
  • a suitable catalyst such as 4-dimethylaminopyridine, can optionally also be added to accelerate the hydrolysis of the anhydride groups.
  • the copolymers containing carboxyl groups are generally converted into a neutralized form. 10 to 95% of the carboxyl groups are preferably neutralized.
  • a base e.g. Alkali or alkaline earth metal hydroxides, e.g. Sodium hydroxide, potassium hydroxide or magnesium hydroxide, alkali or alkaline earth metal carbonates, such as e.g. Sodium carbonate or potassium carbonate, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, dimethylethanolamine, triethanolamine or morpholine can be used.
  • Alkali or alkaline earth metal hydroxides e.g. Sodium hydroxide, potassium hydroxide or magnesium hydroxide
  • alkali or alkaline earth metal carbonates such as e.g. Sodium carbonate or potassium carbonate, ammonia, methylamine, dimethylamine, trimethylamine, ethyl
  • the neutralization can either already take place during the polymerization, for example by using partially neutralized monomers, or can be carried out after the polymerization and, if appropriate, after the hydrolytic opening of the acetal, ketal or orthocarboxylic acid ester structures.
  • copolymer solutions or dispersions obtainable in this way can be used excellently as tanning agents in leather and fur production.
  • the copolymers used according to the invention can be used for the sole tanning or pre-tanning of pelts and pelts in aqueous liquors.
  • the procedure is expediently such that the speckled pelts, for example cowhide pelts with a gap thickness of 1.5 to 4 mm, or pelts, for example sheepskin pelts, at a pH of 2 to 7, in particular 2.5 to 4.5 and a temperature of 15 to 40 ° C., in particular 20 to 35 ° C., are treated with an aqueous solution or dispersion of the copolymers used according to the invention for a period of 2 to 20 hours the.
  • the treatment takes place, for example, by drumming in the barrel.
  • the required amounts of copolymers used according to the invention are normally 2 to 30% by weight, in particular 5 to 25% by weight, based on the pelt weight.
  • the fleet length, i.e. the percentage weight ratio of the treatment liquor to the goods is usually
  • the leather or fur is usually adjusted to a pH of 2 to 8, in particular 3 to 5, for which purpose, for example, magnesium oxide, sodium carbonate, sodium hydrogen carbonate or an organic acid such as formic acid or its salts, optionally treated with other tanning agents and, if desired, colored and greased towards the end or after the end of the tanning process.
  • a pH of 2 to 8, in particular 3 to 5, for which purpose, for example, magnesium oxide, sodium carbonate, sodium hydrogen carbonate or an organic acid such as formic acid or its salts optionally treated with other tanning agents and, if desired, colored and greased towards the end or after the end of the tanning process.
  • the copolymers used according to the invention can be used for tanning pelts and pale skin together with the tanning agents of the main tanning, which can be, for example, chrome, aluminum, titanium or zircon tanning.
  • the working conditions with regard to pH, temperature and duration of the treatment are adjusted to the requirements of the main components of the tanning, the same applies to the treatment apparatus and the liquor length as well as to the aftertreatment.
  • the amount of copolymer used according to the invention is normally 0.1 to 20% by weight, in particular 0.5 to 14% by weight, based on the pale weight.
  • the copolymers used according to the invention can be used for retanning leather and fur which have already been tanned, for example chrome leather ("wet blue"), "wet white” (with, for example, aldehydes or pelts or pelts pretanned with synthetic tanning agents) or vegetable tanned leather or fur, be used in aqueous liquor.
  • Chrome leather is preferably retanned.
  • the procedure is generally such that the pickled pelts and skins, for example round pelts with gap thicknesses of 1.5 to 4 mm, with, for example, a chromium-containing tannin such as a chromium III salt, e.g.
  • the pre-tanned skin thus obtained is deacidified and at a pH of 2 to 7, in particular 2.5 to 6, and at temperatures of 15 to 60 ° C., in particular at 25 to 45 ° C. for a period of 0.25 to 12 hours are treated with an aqueous solution or dispersion of the copolymers used according to the invention.
  • This treatment takes place, for example, by drumming in a barrel.
  • the amount of copolymers used according to the invention is normally 2 to 30% by weight, in particular 5 to 25%, based on the shaved weight of the leather.
  • the liquor length is usually 30 to 200% for bare and
  • the leather or fur is usually adjusted to a pH of 3 to 5, for which purpose magnesium oxide or an organic acid such as formic acid or its salts is used, for example. and colors and greases towards the end or after treatment if desired.
  • the thus retanned leather or skin tanning can before the disadvantages with the inventively used copolymers additionally ä suddenly with other tanning agents as other Polymergerb S toffen, synthetic or vegetable tanning agents be ⁇ concerns have been.
  • inventively USAGE ⁇ Deten copolymers can be used simultaneously with such additional tanning agents.
  • tanning agents for example m Ullmann Enzyklopä ⁇ of Industrial Chemistry, 3rd Edition, 11.Band, S.585 to 612 (1960).
  • Tannin classes to be mentioned individually are the mineral tannins, for example chromium, aluminum, titanium and zirconium salts, the synthetic tannins, the vegetable tannins and the polymer tannins.
  • D i e leather produced with the inventively used copolymers provide excellent results posted L i chtechtheit and Warmestabilitat. This is particularly noticeable on chrome-pretanned leather.
  • the copolymers used according to the invention have very good fullness, high softness and good solid grain even when used in quantities. With large quantities, the leather does not get stuck.
  • Em particular advantage of the inventively copolymers used is the fact that they can, in contrast to herk ö mmlichen syntans no health hazard Denden unsulfo- i Erten phenols n as residual monomers contained and Ver ⁇ gle i ch to herk ö mmlichen polymer tanning by the increased React i v i t t ä the aldehyde functions latently present in the copolymer t i ons a better exhaustion of the tanning liquors ore i elen and so that a lower pollution of the wastewater with organic substances is observed.
  • R L , R 2 are independently hydrogen
  • Ci to Cio alkyl Ci to Cirj alkoxy, Ammo, Ci to C 4 alkylamino, or
  • R 7 is hydrogen, C x - to C ⁇ 0 alkyl
  • Ri 2 is hydrogen, C x - to C ⁇ 0 alkyl
  • Ci to Cio alkoxy, hydroxyl or Ci to Cio acyloxy
  • R 2 and R 4 together also represent a 1,3- or 1,4-alkylene group with 3 to 12 carbon atoms and
  • R 5 and R 7 together can also form a 1,2- or 1,3-alkylene group having 2 to 12 carbon atoms, and
  • the K values of the copolymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932) in aqueous solution on the sodium salts of the copolymers at a concentration of 1% by weight, a pH Value of 7 and a temperature of 25 ° C determined.
  • the solids contents were determined by drying at 2 hours / 80 ° C. in vacuo.
  • Feed 1 consisting of 200.0 g of methacrylic acid, was metered in uniformly into this solution over 2 hours.
  • feed 2 consisting of 4.0 g of 2,2'-azoisobutyronitrile and
  • Feed 1 consisting of a mixture of 137.1 g of 6-methoxy-5, 6-dihydro-4H-pyran and 33.7 g of 1-octene, was metered in uniformly into this solution over 3 hours.
  • feed 2 consisting of 22.6 g of tert was added over 4 hours.
  • the reaction mixture was then polymerized for a further 2 hours at 110 ° C. After the end of the polymerization, a yellow, low-viscosity suspension was obtained.
  • a yellow, low-viscosity suspension was obtained.
  • 318 g of demineralized water were added to the reaction mixture.
  • the solvent toluene was then distilled off azeotropically by introducing steam.
  • the solution was cooled and neutralized with 155.0 g sodium hydroxide solution (50%). A red-brown, clear solution with pH 7.1 and a solids content of 39.1% was obtained.
  • the K value of a 1% strength aqueous solution of the copolymer (pH 7) was 13.8.
  • feed 1 consisting of 129.0 g of 6-methoxy-5, 6-dihydro-4H-pyran
  • feed 2 consisting of 36.5 g of methacrylic acid
  • feed 3 consisting of 22.6 g of tert, was added over 4 hours.
  • Feed 1 consisting of 171.0 g of 6-methoxy-5, 6-dihydro-4H-pyran, was metered in uniformly into this solution over 5 hours.
  • feed 2 consisting of 22.6 g, was tert during 6 hours.
  • the reaction mixture was then polymerized at 95 ° C. for a further 2 hours.
  • feed 1 consisting of a mixture of 130.2 g of 6-methoxy-5, 6-dihydro-4H-pyran and 48.0 g of 1-dodecene, was metered in uniformly over 3 hours.
  • feed 2 consisting of 22.6 g of tert was added over 4 hours.
  • the reaction mixture was then polymerized for a further 2 hours at 110 ° C. After the end of the polymerization, a two-phase mixture consisting of an upper yellow, clear phase and a lower brown phase was obtained. At an internal temperature of 90 ° C, 318 g of demineralized water were added to the reaction mixture given. The toluene solvent was then distilled off azeotropically by introducing steam. The solution was cooled and neutralized with 148.0 g sodium hydroxide solution (50%). A red-brown, clear solution with pH 7.1 and a solids content of 33.1% was obtained. The K value of 1% aqueous solution of the copolymer (pH 7) was 14.4.
  • feed 1 consisting of 240.8 g of 6-methoxy-5, 6-dihydro-4H-pyran and feed 2, consisting of 48.0 g of 1 dodecene
  • feed 3 consisting of 3.2 g of tert was added over 4 hours.
  • the reaction mixture was then polymerized for a further 2 hours at 70.degree. After the end of the polymerization, the solvent was distilled off and then 318 g of demineralized water were added to the reaction mixture and the batch was heated to 100.degree. The solution was cooled and adjusted to pH 7 with sodium hydroxide solution. A brown solution with a solids content of 42.1% was obtained. The K value of a 1% strength aqueous solution of the copolymer (pH 7) was 36.
  • Feed 1 consisting of 294.7 g of 2,5-dimethoxy-2,5-dihydrofuran, was metered in uniformly into this solution over 3 hours.
  • feed 2 consisting of 6.4 g of 2,2-azo-bis (2,4-dimethylvalerontrium) and 50 g of tetrahydrofuran, was metered in uniformly over 4 hours. The reaction mixture was then polymerized for a further 2 hours at 67.degree.
  • the internal temperature was lowered to 90 ° C. and 320 g of demineralized water were added to the reaction mixture.
  • the toluene solvent was then distilled off azeotropically by introducing steam.
  • the solution was cooled and adjusted to pH 7 with sodium hydroxide solution. A red-brown solution with a solids content of 40.8% was obtained.
  • the K value of a 1% strength aqueous solution of the copolymer (pH 7) was 25.5.
  • feed 3 consisting of a solution of 3.2 g of 2,2'-azobis-2-methylpropionamidine dihydrochloride in 50 g of deionized water, was metered in uniformly over 4 hours.
  • the reaction mixture was then polymerized at 80 ° C. for a further 2 hours. After the end of the polymerization, the internal temperature was lowered and the reaction mixture was adjusted to pH 7 with dilute sodium hydroxide solution. A clear solution with a solids content of 25.8% was obtained.
  • the K value of a 1% strength aqueous solution of the copolymer (pH 7) was 70.8.
  • the reaction mixture was then polymerized at 110 ° C. for a further 2 hours. After the end of the polymerization, the internal temperature was lowered to 90 ° C. and 320 g of completely demineralized water were added to the reaction mixture. The toluene solvent was then distilled off azeotropically by introducing steam. The solution was cooled and adjusted to pH 7.1 with sodium hydroxide solution. A red-brown solution with a solids content of 40.8% was obtained. The K value of a 1% strength aqueous solution of the copolymer (pH 7) was 31.5.
  • feed 1 consisting of 171.0 g of 6-methoxy-5, 6-dihydro-4H-pyran, was metered in uniformly over 3 hours.
  • feed 2 consisting of 22.6 g of tert-butyl per-2-ethylhexanoate and 80 g of toluene, was metered in uniformly over 4 hours.
  • the reaction mixture was then polymerized at 110 ° C. for a further 2 hours. After the end of the polymerization, a light brown, low-viscosity suspension was obtained. 200 g of demineralized water were added to the reaction mixture and the organic solvent was distilled off azeotropically by introducing steam. After the steam distillation had ended, a slightly cloudy, brown solution was present. The solution was cooled and neutralized with 158.0 g sodium hydroxide solution (50%). A dark brown, clear solution with pH 7.1 and a solids content of 32.7% was obtained. The K value of a 1% strength aqueous solution of the copolymer (pH 7) was 13.9.
  • Feed 3 consisting of 171.0 g of 6-methoxy-5, 6-dihydro-4H-pyran and 16.0 g of n-dodecyl mercaptan was metered in uniformly into this solution over 3 hours.
  • inlet 2 consisting of 22.6 g of tert was added over 4 hours.
  • the reaction mixture was then polymerized at 110 ° C. for a further 2 hours. After the end of the polymerization, a light brown, low-viscosity suspension is obtained.
  • a cowhide blue with a fold thickness of 1.2 mm was first washed with 300% water at 30 ° C and then in 100%
  • Example 24 3%, based on the solids content of the products, of the copolymers from Examples 3 and 4 were used for retanning chrome bovine leather into furniture leather. In both cases, very full and soft leathers were obtained, which were particularly spectacular due to their good depth of color with good color throughout and a uniform mill grain.
  • Comparative example A (retanning from chrome leather to furniture leather)
  • the leather thus obtained showed less fullness and, with the same amount of dye, a lighter color both on the surface and in the cut.
  • Example 27 (retanning from chrome leather to upper leather with a high amount of polymer used)
  • a 1.5 mm thick beef wet blue was rinsed in the usual manner, washed and then deacidified in 100% liquor with sodium formate at 30 ° C. to a pH of 4.5. After washing, it was drummed in 100% liquor with 5%, based on the solids content, of the copolymer from Example 1, 90 mm at a temperature of 40 ° C.
  • the leather was then washed again and dyed in 100% liquor at 50 ° C. with 1% of a commercially available leather dye within 20 minutes. This was followed by greasing in the same liquor with 4% of a commercially available fat liquor.
  • the pH was then adjusted to 3.6 with formic acid. After a short rinse, the leather was stretched out, dried, machined, and stolled. Leather was obtained with good fullness and firm grain, a round, supple handle and a very level, deep color.
  • Example 27 Analogously to Example 27, 5%, based on the solids content, of the copolymers from Examples 2 to 22 were used as retanning agents. In all cases, very full and deep-colored leather was obtained, which varied in softness depending on the comonomer. Commercially available polymers based on acrylic acid compared to the same procedure The above examples are too hard, rough leather with an uncomfortable grip.
  • Example 49 (retanning from chrome leather to upper leather with a low amount of polymer tanning agent)
  • a 1.8 mm thick fold was rinsed in the usual way, washed and then deacidified in 100% liquor with sodium formate to a pH of 4.4. After a new wash, drumming in 100% liquor at 30 ° C. was first carried out for 30 minutes with 1.0% of a commercial dispersant (phenolsulfonic acid-formaldehyde condensation product). The copolymer from Example 1 was then retanned at 30 ° C. in the same liquor with 1%, based on the solids content. After 90 mm of flexing, the leather was rewound again.
  • a commercial dispersant phenolsulfonic acid-formaldehyde condensation product
  • the dyeing was carried out in 200% liquor with 1% of a commercially available leather dye at 40 ° C., the greasing was carried out with 4% of a commercially available fat liquor.
  • the pH was then adjusted to 3.6 with formic acid.
  • the leather was stretched out, dried, machined and pounded. A leather with good fullness and softness, very good firm grain and very good dyeing behavior was obtained, both in the surface color and in the penetration of the dye in the leather cross-section.
  • Example 34 Analogously to Example 34, a commercial tanning agent based on acrylic acid was used instead of the product from Example 8. Compared to Example 24, the fullness, softness and color of the leather was much worse.

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Abstract

Copolymères constitués de: A) 5 à 95 % en moles d'acides mono ou dicarboxyliques éthyléniquement insaturés comportant 3 à 10 atomes de carbone, leurs anhydrides, leurs sels alcalins, leurs sels de métaux alcalinoterreux ou d'ammonium, ou leurs mélanges; B) 5 à 95 % en moles d'acétals, de cétals ou d'ester d'acide orthocarboxylique éthyléniquement insaturés, de formule générale (I), dans laquelle les variables ont la signification suivante: R1 à R12 représentent indépendamment l'un de l'autre hydrogène ou un radical organique, et a à d valent indépendamment l'un de l'autre 0 ou 1; et C) 0 à 70 % en moles de monomères copolymérisables. L'invention concerne l'utilisation de solutions ou dispersions aqueuses desdits copolymères ou des produits d'hydrolyse ou produits de réaction analogues à des polymères desdits copolymères, sous forme de matières tannantes pour le tannage seul, le prétannage et le co-tannage de peaux pélanées ou autres ainsi que pour le retannage de cuir et de peaux.
EP96942289A 1995-12-12 1996-12-02 Utilisation, sous forme de matieres tannantes pour le cuir, de solutions ou dispersions aqueuses de copolymeres constitues de monomeres renfermant des groupes carboxyle, d'acetals, de cetals ou d'esters d'acide orthocarboxylique ethyleniquement insatures et eventuellement d'autres monomeres copolyme Withdrawn EP0866879A1 (fr)

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DE19546254A DE19546254A1 (de) 1995-12-12 1995-12-12 Verwendung von wäßrigen Lösungen oder Dispersionen von Copolymerisaten aus carboxylgruppenhaltigen Monomeren, ethylenisch ungesättigten Acetalen, Ketalen oder Orthocarbonsäureestern und gegebenenfalls weiteren copolymerisierbaren Monomeren als Ledergerbstoffe
DE19546254 1995-12-12
PCT/EP1996/005318 WO1997021839A1 (fr) 1995-12-12 1996-12-02 Utilisation, sous forme de matieres tannantes pour le cuir, de solutions ou dispersions aqueuses de copolymeres constitues de monomeres renfermant des groupes carboxyle, d'acetals, de cetals ou d'esters d'acide orthocarboxylique ethyleniquement insatures et eventuellement d'autres monomeres copolymerisables

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US6517990B1 (en) * 2000-01-19 2003-02-11 Samsung Electronics Co., Ltd. Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition containing the same
US6833230B2 (en) 2000-01-19 2004-12-21 Samsung Electronics Co., Ltd. Photosensitive polymers containing adamantylalkyl vinyl ether, and resist compositions including the same
US6673513B2 (en) 2000-01-19 2004-01-06 Samsung Electronics Co., Ltd. Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition containing the same
DE10012722A1 (de) * 2000-03-16 2001-09-20 Basf Ag Mischungen von Halbestern mehrbasiger organischer Säuren und langkettiger Alkanole, ihre Herstellung und Verwendung
JP2002133645A (ja) * 2000-10-20 2002-05-10 Fuji Electric Co Ltd 磁気記録媒体およびその製造方法
US6703469B2 (en) * 2001-03-05 2004-03-09 Specialty Fertilizer Products, Llc Anionic polymers composed of dicarboxylic acids and uses thereof
US20040226331A1 (en) * 2001-03-05 2004-11-18 Sanders John Larry Anionic polymers composed of dicarboxylic acids and uses thereof
US20050210596A1 (en) * 2002-03-15 2005-09-29 Basf Aktiengesellschaft Use of polyelectrolytes in the production of leather
EP1375732A3 (fr) * 2002-06-11 2004-02-04 Car Trim Biermann, Marktfort und Dr. Rau GbR Procédé de fabrication d'un matériau de revêtement pour véhicules, en particulier d'un revêtement pour sièges de véhicules à moteur
EP1590492B1 (fr) * 2003-01-28 2009-04-15 Basf Se Tanins et conservateurs
DE10303311A1 (de) * 2003-01-28 2004-07-29 Basf Ag Addukte auf Basis cyclischer Verbindungen und ihre Verwendung als Gerbstoffe und Konservierungsmittel
CN102517409B (zh) * 2011-11-28 2013-07-24 郑州科信化工有限公司 皮革复鞣方法
CN103276119B (zh) * 2013-05-08 2015-01-28 陕西科技大学 一种两性皮革复鞣剂及其制备方法
EP3529382B1 (fr) 2016-10-18 2020-06-10 Stahl International B.V. Procédé de préparation de cuir
CN112552158B (zh) * 2020-12-09 2023-05-19 南京工业大学 一种含酮羧酸结构的高吸收铬鞣助剂的制备及应用
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