EP2190891A1 - Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation - Google Patents

Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation

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Publication number
EP2190891A1
EP2190891A1 EP08786866A EP08786866A EP2190891A1 EP 2190891 A1 EP2190891 A1 EP 2190891A1 EP 08786866 A EP08786866 A EP 08786866A EP 08786866 A EP08786866 A EP 08786866A EP 2190891 A1 EP2190891 A1 EP 2190891A1
Authority
EP
European Patent Office
Prior art keywords
ethylenically unsaturated
aqueous
comonomer
solution
per molecule
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.)
Withdrawn
Application number
EP08786866A
Other languages
German (de)
English (en)
Inventor
Markus Brym
Stephan Hüffer
Audrey Renoncourt
Ulrike Mahn
Franz Glocknitzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08786866A priority Critical patent/EP2190891A1/fr
Publication of EP2190891A1 publication Critical patent/EP2190891A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • the present invention relates to a process for the preparation of aqueous formulations, characterized in that
  • the present invention relates to aqueous formulations containing at least one copolymer (D) obtainable by copolymerization of
  • the present invention relates to the use of aqueous formulations according to the invention for the production of leather and leather produced according to the invention, which are particularly suitable for the production of shoe upper leather, clothing and furniture. Furthermore, the present invention relates to copolymers
  • soft leathers which are leathers that feel soft and full, but nevertheless have sufficient strength.
  • copolymerization is carried out with one another free-radically in preferably aqueous medium:
  • Carboxylic acid for example (E) - or (Z) - crotonic acid or in particular methacrylic acid or acrylic acid, or at least one ethylenically unsaturated C4-Cio-dicarboxylic acid or its anhydride, for example maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, metaconic acid, metaconic anhydride and citraconic acid. Preference is given to itaconic anhydride and in particular maleic anhydride,
  • comonomers with at least one permanent cationic charge per molecule (B) are those ethylenically unsaturated compounds which, independent of the pH, have at least one cationic charge per molecule exhibit. Accordingly, comonomers having exactly one permanent cationic charge per molecule are to be understood as meaning those ethylenically unsaturated compounds which, independently of the pH, have exactly one cationic charge per molecule.
  • Comonomer (B) may be selected from heterocyclic comonomers having at least one permanent cationic charge per molecule, hereinafter also referred to as heterocyclic comonomers (B) for short, or from noncyclic comonomers having at least one permanent cationic charge per molecule, hereinafter also referred to briefly as non-cyclic comonomers (B).
  • Heterocyclic comonomer (B) or non-cyclic comonomer (B) preferably has exactly one permanent cationic charge per molecule.
  • heterocyclic comonomers (B) are with C 1 -C 4 -alkyl, preferably with primary or secondary C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or sec. Butyl quaternized olefins with nitrogen-containing heterocycle.
  • counterion to the neutralization of the positive charge can generally serve anions which are inert to free-radical reactions, for example carboxylates without ethylenic double bonds. Examples which may be mentioned are acetates, benzoates and propionates. Furthermore, mention may be made of halide ions, for example bromide and, in particular, chloride as the counterion, furthermore tetrafluoroborate, hydrogensulfate, C 1 -C 4 -alkylsulfate, in particular ethylsulfate and methylsulfate, and also sulfate.
  • halide ions for example bromide and, in particular, chloride as the counterion, furthermore tetrafluoroborate, hydrogensulfate, C 1 -C 4 -alkylsulfate, in particular ethylsulfate and methylsulfate, and also sulfate.
  • heterocyclic comonomers (B) are comonomers of the general formulas I a to I c
  • R 2 is, if possible, different or preferably the same and selected from preferably primary C 1 -C 10 -alkyl, for example methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n Octyl, n-nonyl, n-decyl, preferably from primary C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, n-butyl and especially methyl,
  • y is an integer and selected from 1, 2 or 3.
  • E is selected from nitrogen and CH, wherein at least one E is a nitrogen, and it is preferred that in formula Ia a maximum of two adjacent positions in the ring are nitrogen.
  • olefins of the general formula I a may be preferred:
  • G is selected from N and CH with the proviso that for the case that G is equal to N, the G in question is not substituted by R 2 .
  • A- is an anion which is inert to radical reactions, for example carboxylates without ethylenic double bonds. Examples include acetates, benzoates and propionates. Also to be mentioned as anion halide ions, such as bromide and in particular chloride, also tetrafluoroborate, hydrogen sulfate and sulfate. Very particularly preferred is A " selected from Ci-C4-alkyl sulfate, for example, methyl sulfate or ethyl sulfate.
  • heterocyclic comonomers (B) are ortho, meta or para-vinyl-n-Ci-C4-alkyl-pyridinium or N-vinyl- quaternized with Ci-C 4 -AlkVl, preferably with primary or secondary CrC 4 -AlkVl.
  • Very particular preference is given to 3-methyl-N-vinylimidazolium.
  • Examples of preferred non-cyclic comonomers (B) are olefins of the general formula [(R 3 ) X N (R 4 ) 4 -X ] + A-, the variables being chosen as follows:
  • R 4 is, if possible, different or preferably the same and selected from preferably primary C 1 -C 10 -alkyl, for example methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , n-nonyl, n-decyl, preferably from primary C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, n-butyl and especially methyl.
  • x is an integer and selected from 1, 3, and preferably 2.
  • Another comonomer is at least one ethylenically unsaturated carboxylic acid amide (C).
  • ethylenically unsaturated carboxylic acid amide (C) is one which does not carry a permanent cationic charge.
  • Preference is given to methacrylamide and in particular acrylamide.
  • copolymerization is carried out in an aqueous medium, preferably in aqueous solution.
  • peroxides or hydroperoxides there may be di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permalate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-chlorobenzoyl peroxide and Dicyclohexylperoxiddicarbonat exemplified.
  • peroxides or hydroperoxides there may be di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permalate, tert-butyl perisobutyrate, benzoyl peroxid
  • inorganic radical initiators are alkali metal peroxodisulfate, in particular sodium peroxodisulfate and potassium peroxodisulfate. Also the use of alkali metal peroxodisulfate, in particular sodium peroxodisulfate and potassium peroxodisulfate. Also the use of alkali metal peroxodisulfate, in particular sodium peroxodisulfate and potassium peroxodisulfate. Also the use of
  • Redox initiators is suitable, for example combinations of hydrogen peroxide or sodium peroxodisulfate or one of the abovementioned peroxides with at least one reducing agent.
  • Suitable reducing agents are, for example, ascorbic acid, tartaric acid, Fe (II) salts such as FeSO 4 , sodium bisulfite, potassium bisulfite.
  • Fe (II) salts such as FeSO 4
  • copper (II) salts such as copper sulfate
  • Suitable radical initiators are also azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride (2,2'-azobis (2-methylpropionamidine) dihydrochloride) and 2,2'-azobis (2-aminopropionamidine dihydrochloride). Azobis (4-methoxy-2,4-dimethylvaleronitrile).
  • the copolymerization can be carried out at pressures in the range of 1, 1 to 10 bar. However, it is preferred to carry out the copolymerization at atmospheric pressure.
  • the copolymerization is carried out at temperatures in the range of 65 to 120 0 C, preferably 80 to 115 ° C. In one embodiment of the present invention, the copolymerization is carried out over a period of time ranging from 30 minutes to 10 hours.
  • the copolymerization is carried out at a pH in the range from 1 to 10, preferably from 1 to 7.
  • Some of the comonomers can be very acidic, in which case one can adjust the pH with the aid of base, or one can neutralize partially or completely. In another embodiment of the present invention, the neutralization is omitted before or during the copolymerization and copolymerized at a strongly acidic pH.
  • Examples of basic alkali metal compounds are carbonates, bicarbonates and in particular hydroxides of alkali metals, in particular of potassium or sodium. Particularly preferred are potassium hydroxide and sodium hydroxide.
  • the comonomers are used in the following weight ratios: in the range from 1 to 30% by weight, preferably from 5 to 20% by weight, of ethylenically unsaturated mono- or dicarboxylic acid or its anhydride (A), in the range from 5 to 60 wt .-%, preferably 10 to 45 wt .-% comonomer (B), in the range of 30 to 80 wt .-%, preferably 40 to 60 wt .-% ethylenically unsaturated carboxylic acid (C).
  • A ethylenically unsaturated mono- or dicarboxylic acid or its anhydride
  • B ethylenically unsaturated mono- or dicarboxylic acid or its anhydride
  • B ethylenically unsaturated mono- or dicarboxylic acid or its anhydride
  • B ethylenically unsaturated mono- or dicarboxylic acid or its anhydride
  • B
  • data in% by weight are based on the total copolymer according to the invention.
  • Alkyl esters or ⁇ -hydroxy-Ci-C3-alkyl esters of (meth) acrylic acid are suitable comonomers.
  • suitable comonomers are acrylonitrile and vinyl aromatics such as styrene. It is preferred that the proportion of further comonomers does not exceed 50 parts by weight, based on the sum of ethylenically unsaturated mono- or dicarboxylic acid or its anhydride (A), comonomer (B) and ethylenically unsaturated carboxylic acid amide (C).
  • the proportion of further comonomers should be 5 parts by weight, based on the sum of ethylenically unsaturated mono- or dicarboxylic acid or its anhydride (A), comonomer (B) and ethylenically unsaturated carboxylic acid amide (C).
  • no further comonomers are polymerized, in particular none of the comonomers mentioned in the preceding paragraph.
  • An aqueous formulation prepared by the production process of the present invention may have a solids content in the range of 1 to 80%, preferably 10 to 50%.
  • copolymer (D) prepared by the production method of the present invention has a K value in the range of 10 to 80, preferably 20 to 60, determined by Fikentscher on a 1 wt% aqueous solution at room temperature.
  • Aqueous formulations prepared by the preparation process according to the invention can be used for the production of leather, preferably for tanning and in particular for retanning.
  • an aqueous formulation prepared by the production process according to the invention is mixed with at least one polymeric tanning or retanning agent (E).
  • Polymeric tanning and retanning agents (E) are known as such. Examples are the homopolymers and copolymers mentioned in EP 1 335 029 A1 as tanning agents A) to L) and N) and the copolymers mentioned in WO 2004/070063, in WO 2005/019480 and in WO 2006/015745, where terpolymers with are included.
  • polymeric tanning or retanning agent (E) is selected from homopolymers and copolymers of ethylenically unsaturated carboxylic acids (A), in particular of (meth) acrylic acid. Particular preference is given to the homopolymers and copolymers mentioned in EP 1 335 029 A1 as tanning agents A) to D) and the copolymers mentioned in WO 2005/019480 and in WO 2006/015745, in which terpolymers are included.
  • Very particularly preferred polymeric tanning and retanning agents (E) are homopolymers of (meth) acrylic acid, in particular having a molecular weight M w in the range from 1,000 to 200,000 g / mol.
  • Very particularly preferred polymeric tanning and retanning agents (E) are homopolymers of (meth) acrylic acid having a Fikentscher K value in the range from 10 to 120, preferably from 60 to 100, determined on the basis of 1% by weight with NaOH neutralized aqueous solution (pH 7) at 23 ° C.
  • copolymer (D) according to the invention for example in aqueous formulation, is mixed with so much polymeric tanning or retanning agent (E) to give an aqueous formulation which, based on its total amount, contains from 5 to 50% by weight. , preferably 15 to 30% by weight of copolymer (D), a corresponding amount of ethylenically unsaturated dicarboxylic acid (C-P2) or its anhydride and 1 to 30% by weight, preferably 5 to 15% by weight of polymeric tanning or retanning agent ( E) contains.
  • copolymer (D) according to the invention is mixed with so much polymeric tanning or retanning agent (E) to give an aqueous formulation which, based on its total amount, contains from 5 to 50% by weight. , preferably 15 to 30% by weight of copolymer (D), a corresponding amount of ethylenically unsaturated dicarboxylic acid (C-P2) or its anhydride and 1 to 30%
  • aqueous formulation prepared by the production process of the present invention and polymeric tanning or retanning agent (E) is arbitrary.
  • polymeric tanning or retanning agent (E) as a solid or, preferably, as an aqueous solution or dispersion.
  • a further subject of the present invention are aqueous formulations obtainable by mixing aqueous formulations obtainable by the preparation process according to the invention with at least one polymeric tanning or retanning agent (E).
  • Another object of the present invention are aqueous formulations containing (D) at least one copolymer obtainable by copolymerization of
  • aqueous formulations defined above are also referred to as aqueous formulations according to the invention.
  • Polymeric tanning and retanning agents (E) are known as such. Examples are the homopolymers and copolymers mentioned in EP 1 335 029 A1 as tanning agents A) to L) and N) and the copolymers mentioned in WO 2004/070063, in WO 2005/019480 and in WO 2006/015745, where terpolymers with are included.
  • polymeric tanning or retanning agent (E) is selected from homopolymers and copolymers of ethylenically unsaturated carboxylic acids (A), in particular of (meth) acrylic acid. Particular preference is given to the homopolymers and copolymers mentioned in EP 1 335 029 A1 as tanning agents A) to D) and the copolymers mentioned in WO 2005/019480 and in WO 2006/015745, in which terpolymers are included.
  • Very particularly preferred polymeric tanning and retanning agents (E) are homopolymers of (meth) acrylic acid, in particular having a molecular weight M w in the range from 1,000 to 200,000 g / mol.
  • Very particularly preferred polymeric tanning and retanning agents (E) are homopolymers of (meth) acrylic acid having a Fikentscher K value in the range from 10 to 120, preferably from 60 to 100, determined on the basis of 1% by weight with NaOH neutralized aqueous solution (pH 7) at 23 ° C.
  • Ethylenically unsaturated mono- or dicarboxylic acid or its anhydride (A), comonomer (B), ethylenically unsaturated dicarboxylic acid (C-P1) or its anhydride and also ethylenically unsaturated dicarboxylic acid (C-P2) or its anhydride are described above ,
  • Aqueous formulations according to the invention may have a solids content in the range from 1 to 80%, preferably 10 to 50%.
  • Aqueous formulations according to the invention may have a pH in the range from 5.5 to 11, preferably from 7 to 9.
  • Another object of the present invention is the use of aqueous formulations according to the invention for the production of leather.
  • a further subject of the present invention is a process for the production of leather using aqueous formulations according to the invention.
  • Another object of the present invention is leather, prepared using at least one aqueous formulation according to the invention.
  • the process according to the invention for producing leather is used as a tanning process, hereinafter also referred to as Tanning process according to the invention, preferably referred to as retanning process, hereinafter also referred to as nachgerb vide invention.
  • the tanning process according to the invention is generally carried out by adding at least one aqueous formulation according to the invention in one portion or in several portions immediately before or else during the tanning step.
  • the tanning process according to the invention is preferably carried out at a pH of from 2.5 to 1 l, preferably to 4, it being frequently observed that the pH increases by about 0.3 to three units during the performance of the tanning process according to the invention.
  • the novel tanning process is generally carried out at temperatures of 10 to 45 ° C, preferably at 20 to 30 0 C. Has proven useful a duration of 10 minutes to 12 hours, preferably one to three hours.
  • the tanning process according to the invention can be carried out in any conventional tanning vessel, for example by walking in barrels or in rotated drums.
  • a total of 0.01 to 10% by weight of aqueous formulation according to the invention is used, based on the solids content of aqueous formulation according to the invention on the one hand and on the shaved weight on the other hand, preferably 0.5 to 5% by weight. %.
  • an aqueous formulation according to the invention is used together with one or more conventional tanning substances, for example with chrome tanning agents, mineral tannins, syntenes, polymer tanning agents or vegetable tanning agents, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A15, pages 259 to 282 and in particular page 268 ff., 5th edition, (1990), Verlag Chemie Weinheim.
  • the weight ratio of aqueous formulation according to the invention: conventional tanning agent or sum of conventional tanning agents is suitably from 0.01: 1 to 100: 1 (based in each case on the solids contents).
  • only a few ppm of conventional tanning agent are added to the aqueous formulation according to the invention.
  • an aqueous formulation according to the invention is used together with one or more fatliquoring agents or oleophilic components.
  • an aqueous formulation according to the invention is added in one portion or in several portions before or during pre-tanning.
  • An addition in the pimple is conceivable.
  • To carry out the Nachgerbvons invention is based on conventionally, ie, for example, with chrome tanning agents, mineral tannins, polymer tanning agents, aldehydes, syntans or resin tanning tanned semi-finished or inventively prepared as described above semifinished products.
  • at least one aqueous formulation according to the invention is allowed to act on semi-finished products, ie, it is treated with at least one aqueous formulation according to the invention.
  • the retanning process according to the invention can be carried out under otherwise customary conditions. It is expedient to choose one or more, ie 2 to 6, action steps and to be able to rinse with water between the interaction steps.
  • the temperature during the individual treatment steps is in each case from 5 to 60 0 C, preferably 20 to 45 ° C. It is expedient to use one or more further agents customarily used during the retanning, for example fatliquors, polymer tanning agents and acrylate- and / or methacrylate-based fatliquoring agents, tanning agents based on vegetable tanning agents, fillers, leather dyes or emulsifiers.
  • fatliquors for example fatliquors, polymer tanning agents and acrylate- and / or methacrylate-based fatliquoring agents, tanning agents based on vegetable tanning agents, fillers, leather dyes or emulsifiers.
  • Has proven useful for the Nachgerb compiler invention a duration of 10 minutes to 12 hours, preferably one to three hours.
  • the retanning process according to the invention can be carried out in any conventional tanning vessel, for example by walking in barrels or in rotated drums.
  • a total of 0.01 to 10% by weight of aqueous formulation according to the invention is used, based on the solids content of inventive aqueous formulation on the one hand and on the shaved weight on the other hand, preferably 0.5 to 5% by weight.
  • Another object of the present invention is leather, prepared by the method according to the invention.
  • leather according to the invention is characterized by good fullness, softness and intensity and washing resistance of the dyeing and further good use properties.
  • leather according to the invention is suitable, for example, for producing shoe upper leather, items of clothing such as, for example, jackets, coats or trousers, and furthermore furniture.
  • Copolymers (D) Another object of the present invention are copolymers, referred to in the context of the present invention as copolymers (D).
  • Copolymers (D) according to the invention contain polymerized in:
  • Copolymers of the invention (D) may be partially or completely neutralized with ammonia, basic amine or basic alkali metal compound, in particular with potassium hydroxide or sodium hydroxide.
  • copolymers (D) according to the invention comprise, in copolymerized form, in the range from 1 to 30% by weight, preferably from 5 to 20% by weight, of ethylenically unsaturated monocarboxylic or dicarboxylic acid or its anhydride (A) in the range from 5 to 60 wt .-%, preferably 10 to 45 wt .-% comonomer (B), in the range of 30 to 80 wt .-%, preferably 40 to 60 wt .-% ethylenically unsaturated carboxylic acid (C).
  • A ethylenically unsaturated monocarboxylic or dicarboxylic acid or its anhydride
  • B ethylenically unsaturated monocarboxylic or dicarboxylic acid or its anhydride
  • B ethylenically unsaturated monocarboxylic or dicarboxylic acid or its anhydride
  • C ethylenically unsaturated carb
  • copolymer (D) according to the invention has a K value in the range from 10 to 80, preferably from 20 to 60, determined according to Fikentscher on a 1% by weight aqueous solution at room temperature.
  • copolymers (D) according to the invention have an average molecular weight M w in the range from 2,000 to 100,000 g / mol, preferably in the range from 9,000 to 15,000 g / mol. In another embodiment of the present invention, copolymers (D) according to the invention have an average molecular weight M w in the range of more than 100,000 g / mol up to 500,000 g / mol, in each case measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Another object of the present invention are mixtures of inventive copolymer (D) with at least one polymeric tanning or retanning agent (E).
  • inventive copolymer (D) with at least one polymeric tanning or retanning agent (E).
  • polymeric tanning and retanning agents (E) are described above.
  • copolymer (D) according to the invention If mixtures according to the invention or copolymer (D) according to the invention are to be prepared anhydrous, it is possible, for example, to prepare an aqueous formulation of copolymer (D) according to the invention as described above and optionally ethylenically unsaturated dicarboxylic acid (CP-2) or its anhydride or optionally polymeric tanning or retanning (D) is added and then removed by known methods, the water. It is preferred to remove the water by evaporation, in particular by spray drying.
  • the weight ratio of copolymer (D) according to the invention to polymeric tanning agent (E) is in the range from 50: 1 to 1: 6, preferably 3: 1 to 1: 3.
  • Another object of the present invention are aqueous formulations containing at least one inventive copolymer (D).
  • Another object of the present invention are aqueous formulations containing at least one of the mixtures described above.
  • aqueous formulations according to the invention may have a solids content in the range from 1 to 80%, preferably 10 to 50%.
  • Copolymers of the invention and mixtures according to the invention are very well suited, in particular in the form of aqueous formulations, for the production of leather.
  • Solution 1.1.1 2.5 g of a 50% by weight aqueous solution of H2O2
  • Butyl hydroperoxide solution too It was then cooled to room temperature and 7.9 g of a 10 wt .-% aqueous solution of disodium 2-hydroxysulfinatoacetat, Na2C2H4 ⁇ 5S. Subsequently, a biocide was added, namely 2.16 g of a 20 wt .-% solution of 1, 2-benzisothiazolin-3-one ("BIT") in propylene glycol.
  • BIT 2-benzisothiazolin-3-one
  • Aqueous formulation WF.1 according to the invention having a pH of 7 and a solids content of 28.3% was obtained which contained copolymer (D.1) according to the invention.
  • the K value (according to Fikentscher), measured at room temperature on an aqueous formulation WF.1 diluted to a solids content of 1% by weight, was 22.7.
  • the mean molecular weight M w was 11,700 g / mol, determined by gel permeation chromatography.
  • Solution 1.2.1 17.7 g of a 7% by weight aqueous solution of Na 2 SO 2.
  • Solution 1.2.3 172.1 g of a 7% by weight aqueous solution of Na 2 S 2 Os.
  • Aqueous formulation WF.2 according to the invention having a pH of 7.5 and a solids content of 31.5% was obtained which contained copolymer (D.2) according to the invention.
  • the K value (according to Fikentscher), measured at room temperature on an aqueous formulation WF.2 diluted to a solids content of 1% by weight, was 52.5.
  • Solution 1.3.1 2.4 g of a 50% by weight aqueous solution of H2O2.
  • Aqueous formulation WF.3 according to the invention having a pH of 7.2 and a solids content of 29.3% was obtained which contained copolymer (D.3) according to the invention.
  • the K value (according to Fikentscher), measured at room temperature on an aqueous formulation WF.3 diluted to a solids content of 1% by weight, was 47.6.
  • Solution 1.6.3 188 g of a 7% by weight aqueous solution of Na 2 SO 2.
  • a 2-liter stirred vessel with several feeds, reflux condenser and gas inlet tube, 51, 7 ml of distilled water and 128.6 g of solution 1.6.2 were introduced. Nitrogen was bubbled through the template (15 minutes) and heated to 85 ° C with stirring. As soon as the internal temperature had reached 70 ° C., that is still during the heating, solution 1.6.1 was rapidly added.
  • Aqueous formulation WF.6 according to the invention having a pH of 8.2 and a solids content of 31.1% was obtained which contained copolymer (D.6) according to the invention.
  • the molecular weight M w of copolymer (D.6) according to the invention was 102,000 g / mol, determined by GPC.
  • the Walk barrels were 1 to 15 at 25 to 35 ° C with 4% of inventive copolymer D.1 to D.3 or comparison copolymer V-CP.4 or V-CP.5 is moved to Table 1.
  • Table 1 After a walk time of 20 minutes, in each case 4% of sulfone tanning agent from EP-B 0 459 168, Example K1, and 0.7% formic acid were dosed.
  • Example A 4% of a fat-liquoring agent according to WO 03/023069, Example A were metered in 100% water (50 0 C). After 20 minutes, acidified with 1% formic acid to the pH of 3.8.
  • the leather thus obtainable were washed, dried, staked, 30 sec treated in a vacuum dryer at 60 0 C and evaluated according to the conditions specified in Table 1 test criteria.
  • the leathers L.1 to L.9 according to the invention and the comparative leathers VL.10 to VL.15 were obtained.
  • the rating was based on a grading system from 1 (very good) to 5 (poor).
  • Comparative copolymer V-CP.4 was an acrylic acid-acrylamide random copolymer having a Fikentscher K value of 70 (1 wt% solution in water), comonomer ratio in mol%: (acrylic acid: acrylamide) 90 : 10th
  • V-CP.5 was a random terpolymer made from acrylic acid, acrylamide and DMAPMAM (N, N-dimethylaminopropylmethacrylamide), Fikentscher K value of 60 (1 wt% solution in water).
  • the copolymers according to the invention have particular advantages with regard to process stability and breadth of applicability.
  • the leathers according to the invention have excellent process stability over a wide pH window without color shifts and a constant intensity of coloration. Noteworthy is the balance fullness and softness with excellent scar resistance.
  • the copolymers according to the invention enable a very efficient handling of dye.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Procédé de production de formulations aqueuses, caractérisé en ce qu'on copolymérise mutuellement, par polymérisation radicalaire, en milieu aqueux : (A) au moins un acide mono- ou di-carboxylique éthyléniquement insaturé; (B) au moins un comonomère ayant au moins une charge cationique permanente par molécule; et (C-P1) au moins un amide d'un acide carboxylique éthyléniquement insaturé
EP08786866A 2007-09-03 2008-08-05 Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation Withdrawn EP2190891A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08786866A EP2190891A1 (fr) 2007-09-03 2008-08-05 Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP07115518 2007-09-03
EP07115514 2007-09-03
EP07115644 2007-09-04
EP07122718 2007-12-10
EP08101061 2008-01-29
EP08786866A EP2190891A1 (fr) 2007-09-03 2008-08-05 Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation
PCT/EP2008/060255 WO2009030567A1 (fr) 2007-09-03 2008-08-05 Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation

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EP2190891A1 true EP2190891A1 (fr) 2010-06-02

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US (1) US20100192307A1 (fr)
EP (1) EP2190891A1 (fr)
CN (1) CN101809045A (fr)
BR (1) BRPI0816186A2 (fr)
WO (1) WO2009030567A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009030697A1 (fr) 2007-09-04 2009-03-12 Basf Se Procédé de production du cuir, copolymères adaptés à cette fin, et autres utilisations de ces produits
CN103146850B (zh) * 2013-02-01 2014-06-04 四川大学 一种无盐不浸酸两性聚合物无铬鞣剂

Family Cites Families (11)

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Publication number Priority date Publication date Assignee Title
US3163625A (en) * 1960-04-13 1964-12-29 Du Pont Color-forming monomers and polymers of acrylic acid amides of 3-aminopyrazolone
DE3702153A1 (de) * 1987-01-26 1988-08-04 Stockhausen Chem Fab Gmbh Verfahren zum nachgerben
DE4014977A1 (de) * 1990-05-10 1991-11-14 Basf Ag Kondensationsprodukte aus phenolmonosulfonsaeuren, dihydroxydiphenylsulfonen, harnstoff und formaldehyd
DE4018873A1 (de) * 1990-06-13 1991-12-19 Basf Ag Verwendung von kondensaten auf basis von arylsulfonsaeuren und formaldehyd als dispergiermittel
DE19711169A1 (de) * 1997-03-18 1998-09-24 Basf Ag Oligomere Azofarbstoffe
DE10143949A1 (de) * 2001-09-07 2003-03-27 Basf Ag Emulgatorzusammensetzung und fogging-arme, hochauszehrende Fettungsmittel, ihre Herstellung und Verwendung
DE10261197A1 (de) * 2002-12-20 2004-07-08 Basf Ag Wässrige Polymerdispersion
DE10304959A1 (de) * 2003-02-06 2004-08-19 Basf Ag Verfahren zur Herstellung von Leder
DE10333749A1 (de) * 2003-07-23 2005-02-10 Basf Ag Verfahren zur Herstellung von Leder unter Verwendung von Polymerisaten
DE102004038217A1 (de) * 2004-08-05 2006-03-16 Basf Ag Copolymerisate, ihre Herstellung und Verwendung
DE102004042948A1 (de) * 2004-09-02 2006-03-09 Basf Ag Verfahren zur Herstellung von Polymeren durch Sprühpolymerisation

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Title
See references of WO2009030567A1 *

Also Published As

Publication number Publication date
US20100192307A1 (en) 2010-08-05
WO2009030567A1 (fr) 2009-03-12
BRPI0816186A2 (pt) 2015-04-14
CN101809045A (zh) 2010-08-18

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