EP1421223A1 - Procede de production d'agents de tannage contenant du sulfone - Google Patents

Procede de production d'agents de tannage contenant du sulfone

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Publication number
EP1421223A1
EP1421223A1 EP02794798A EP02794798A EP1421223A1 EP 1421223 A1 EP1421223 A1 EP 1421223A1 EP 02794798 A EP02794798 A EP 02794798A EP 02794798 A EP02794798 A EP 02794798A EP 1421223 A1 EP1421223 A1 EP 1421223A1
Authority
EP
European Patent Office
Prior art keywords
mol
phenol
mixture
component
weight
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Withdrawn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
EP02794798A
Other languages
German (de)
English (en)
Inventor
Gunther Pabst
Gerhard Wolf
Jürgen Kast
Jürgen Werner
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
Publication of EP1421223A1 publication Critical patent/EP1421223A1/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Withdrawn legal-status Critical Current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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • 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
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
    • C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated

Definitions

  • the invention relates to a method for producing a solution of sulfone-containing tannins, the solution itself obtainable by this method, the sulfone-containing tannin isolated from this solution, the use of the solution and the sulfone-containing tannin for tanning leather, a method for tanning leather and the tanned one leather itself.
  • Condensation products based on dihydroxydiphenyl sulfone are known for example from DE-B 11 13 457, EP-A 0 245 205, EP-B 0 428 481, US 4,592,940 and EP-B 0 459 168 and can be prepared by the processes described therein.
  • sulfonated phenols which are free of condensed ring systems are reacted with 1 to 1.5 mol of urea and 1.7 to 2.2 mol of formaldehyde per mol of the sulfonated phenol or phenol mixture and the condensate obtained is reacted with phenol and treated with formaldehyde.
  • EP-A 0 245 205 relates to an aqueous composition containing a reaction product of phenol and a sulfonating agent, the molar ratio of phenol: SO 3 being 1: 1.1-2.2, a water-soluble alkylamine, alkanolamine, alkylenediamine, polyalkylene polyamine or hetrocyclic amine , a water-soluble chromium, aluminum, iron or zirconium tanning salt and optionally an alkali metal salt of ethylenediaminetetraacetic acid or a pyrophosphate.
  • EP-A 0 428 481 discloses an agent for the treatment of leather and furs, containing as component (A) formaldehyde condensation products of 4,4'-dihydroxydiphenyl sulfones with hydroxyarylsulfonic acids or formaldehyde condensation products of diaryl ether sulfonic acids with 4,4'-dihydroxydiphenyl sulfone, and as component (B) a polymer or copolymer of unsaturated C 3 -C 5 mono- or dicarboxylic acids or of their hydroxy compounds.
  • 4,592,940 discloses a process for the dirt-repellent finishing of nylon carpets, in which they are treated with an aqueous solution of a condensation product of formaldehyde with a mixture of diphenyl sulfone and phenol sulfonic acid.
  • EP-A 0 459 168 discloses condensation products of phenol monosulfonic acids, dihydroxydiphenyl sulfones, urea and formaldehyde, which are obtainable by
  • the condensation products are used for tanning animal hides.
  • tanning agents which are produced using dihydroxydiphenyl sulfone (DHDPS) are distinguished by a particularly good tanning action and by particularly good fastness properties.
  • DHDPS dihydroxydiphenyl sulfone
  • negative effects of this tanning effect can also be observed on leather. Too high an astringency can lead to the scars of the leather being stressed too much and therefore being associated with it Scarring is observed. The stress on the grain can lead to breakage of the grain, which causes a significant reduction in the quality of the leather.
  • the superficial deposition of strongly astringent tannins also leads to a reduced penetration not only of the tannins used, but also of all other aids.
  • the strong astringency of sulfone-containing tanning agents leads to a strong bleaching effect, making dark, intensely colored leather in particular difficult to produce.
  • the tanning effect of the synthetic tanning agents can be controlled via their molecular weight, but the more tanning agents with higher molecular weight are a disadvantage of a reduced penetration of the tanning agents into the leather cross-section and thus an undesirable superficial deposition of the tanning agents.
  • the leather treated with tannins with a low DHDPS content generally has less good fastness properties.
  • the object of the invention is to provide new tanning agents with advantageous properties.
  • the object of the invention is in particular to provide tanning agents with a good tanning effect and good penetration, which give leather with good fastness properties, softness and fullness.
  • the object is achieved by a process for producing a solution of sulfone-containing tannins, in which
  • a component is produced by al) phenol with concentrated sulfuric acid, with oleum having an SO 3 content of 20 to 65% by weight or with a mixture of sulfuric acid and oleum having an SO 3 content of 20 to 65% by weight. -%, the molar ratio of total sulfuric acid, calculated as SO 3 , to phenol from 0.7: 1 to 1.5: 1, at a temperature of 100 to 180 ° C to a mixture containing phenolsulfonic acid, dihydroxydiphenyl sulfone and sulfuric acid can react, or by mixing the individual components produces a corresponding mixture, a2) then at 40 to 90 ° C per mole of phenol units present with 0.25 to 4 moles of urea and with 0.5 to 4 moles of an aliphatic aldehyde with 1 to 6 C atoms condense, a3) if necessary by adding a base to a pH of 4 to 5,
  • a component B is prepared by reacting bl) dihydroxydiphenyl sulfone with 0.5 to 5 moles of an aliphatic aldehyde with 1 to 6 carbon atoms and 0.4 to 2 moles of sodium sulfite per mole of dihydroxydiphenyl sulfone at a temperature of 90 to 180 ° C. b2) adjusts a pH of 3.5 to 5.5 if necessary by adding acid,
  • tanning agents with a low DHDPS component component A
  • tanning agents with a high DHDPS component component B
  • the tanning effect of the tanning agents with a high DHDPS component is retained, but at the same time a good penetration of the tanning agent mixture is achieved becomes.
  • This avoids superficial deposition of the tanning agent on the leather.
  • this results in considerable advantages in terms of coloring.
  • the surface is colored more intensely and darker, and at the same time the leather cross-section is well colored. This enables savings to be achieved in the dye used, which also improves economy.
  • a scarring or a scarring of the leather is prevented, and the uniformity of the mill fracture is improved.
  • the process according to the invention starts from starting materials known per se for producing sulfone-containing tanning agents, the new reaction sequence and the new quantitative ratio of the starting materials lead to products with improved performance properties.
  • the invention thus also relates to the solutions of sulfone-containing tannins obtained by the process according to the invention and the sulfone-containing tannins themselves which can be isolated therefrom.
  • the aliphatic aldehydes used in the production of component A and component B generally have 1 to 6, preferably 1 to 4 and particularly preferably 1 or 2, carbon atoms.
  • formaldehyde is used as the aliphatic aldehyde, usually in the form of an aqueous solution, for example in the form of a 30% by weight aqueous solution.
  • phenol is concentrated with concentrated sulfuric acid, preferably 96% by weight, and / or oleum with an SO 3 content of 20 to 65% by weight
  • a correspondingly composed phenol monosulfonic acid / dihydroxydiphenyl sulfone / sulfuric acid mixture can also be prepared by mixing the corresponding components.
  • the exact composition of the reaction mixture obtained in step a1) can be determined, for example, by high pressure liquid chromatography.
  • the amount of dihydroxydiphenyl sulfones formed in situ is influenced in particular by the reaction temperature and by the SO 3 content of the reaction mixture.
  • the reaction is preferably carried out with oleum having an SO 3 content of 20 to 32% by weight at a temperature of 150 to 180 ° C.
  • the acids are expediently continuously dripped into a phenol heated to approximately 60 ° C., heating to approximately 90 to 100 ° C. , If necessary, the temperature can be regulated by cooling.
  • a2) the mixture of phenolsulfonic acid, dihydroxydiphenyl sulfone and sulfuric acid at 40 to 90 ° C, for example at about 80 ° C, with 0.25 to 4 mol, preferably 0.4 to 0.8 mol of urea and 0.5 to 4 moles, preferably 0.75 to 1.5 moles, of an aliphatic aldehyde, in particular formaldehyde, condensed per mole of phenol units present.
  • Urea is usually added as an aqueous solution, for example as a 68% strength by weight aqueous solution, and the aldehyde is then metered in over a period of generally 0.25 to 8, preferably 0.25 to 2, hours.
  • a pH of 3.5 to 5.5, preferably 4 to 5, particularly preferably 4.3 to 4.8 and in particular 4.4 to 4.6 can then be set in step a3).
  • the pH can be adjusted by adding a commercially available base, such as alkali metal hydroxide or ammonia. It can also be neutralized first by adding a base and then by adding a weak acid, for example acetic acid, formic acid, oxalic acid, succinic acid, glutaric acid or citric acid, to adjust the pH to 3.5 to 5.5.
  • Component A thus prepared generally contains 2 to 30, preferably 5 to 15% by weight of dihydroxydiphenyl sulfone in free or bound form, based on the dry weight.
  • di) hydroxydiphenyl sulfone with 0.5 to 5 mol, preferably 1 to 1.4 mol, particularly preferably 1.1 to 1.3 mol and in particular approximately 1.2 mol of an aliphatic aldehyde is used in a step b1) , in particular formaldehyde, per mole of dihydroxydiphenyl sulfone and 0.4 to 2 moles, preferably 0.5 to 0.8 moles, in particular 0.6 to 0.7 moles of sodium sulfite per mole of dihydroxydiphenyl sulfone, at a temperature of 90 to 180 ° C.
  • the reaction is usually carried out in aqueous solution under pressure.
  • dihydroxydiphenyl sulfone and formaldehyde in the form of their aqueous solutions and solid sodium sulfite are placed in a pressure reactor and the mixture is heated to 115.degree. After the reaction has started, the temperature rises to about 150 to 160 ° C. and the pressure to about 4 to 5 bar. The reaction generally takes 2 to 10 hours.
  • Dihydroxydiphenyl sulfone in the sense of this invention means the 4,4'-isomer. This can also be used as technical dihydroxydiphenyl sulfone, ie in a mixture with about 10-15% by weight of the 2,4'-isomer and 0 to 5% by weight of p-phenolsulfonic acid.
  • the pH of component B can then be adjusted to 3.5 to 5.5, preferably 4 to 5, particularly preferably 4.3 to 4.8 and in particular 4.4 to 4.6.
  • the pH can be adjusted by adding acid such as sulfuric acid, formic acid or acetic acid.
  • the content of component B in dihydroxydiphenyl sulfone in free or bound form is from 30 to 100% by weight, preferably from 40 to 70% by weight, particularly preferably from 45 to 55% by weight, based on the dry weight.
  • a step c) 10 to 90% by weight, preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight of component A are mixed with 90 to 10% by weight, preferably 80 to 20% by weight. %, particularly preferably 70 to 30% by weight of component B, the sum of A and B giving 100% by weight. If the pH has not already been set in components A and B, it is now carried out in the mixture of A and B using the acids or bases mentioned above.
  • the solution of the sulfone-containing tanning agents thus obtained can be used directly as a tanning agent.
  • the isolation can be carried out in a manner known per se, for example by precipitation of the tanning agent by adding a water-miscible liquid in which the tanning agent does not dissolve, or preferably by evaporating the liquid reaction medium, for example by spray drying.
  • the tannin is usually isolated for shipping purposes. Before use, the solid sulfonic tanning agent is redissolved in water.
  • the present invention also relates to the use of the solutions according to the invention and the sulfone-containing tannins which can be isolated therefrom for tanning leather.
  • the invention also relates to a process for tanning leather, in which the leather is treated with an aqueous solution of the sulfone-containing tanning agent according to the invention.
  • Commercially available dispersants in particular anionic dispersants, and / or commercially available synthetic, polymeric and / or vegetable tannins can also be used in the application. This creates special effects on the treated leather.
  • the treated leather itself is also an object of the present invention.
  • 40 kmol of phenol heated to 60 ° C. are mixed with 40 kmol of oleum with an SO 3 content of 24% by weight within one hour.
  • the mixture obtained is heated to 160 ° C. and stirred at this temperature for 4 hours.
  • the mixture is then allowed to cool to 80 ° C. and 25 kmol of urea are stirred in as a 68% strength by weight aqueous solution and 40 kmol of formaldehyde are then metered in as a 30% strength by weight aqueous solution within 1 1/2 hours.
  • the mixture obtained is then mixed with about 34 kmol NaOH in the form of a 50% strength by weight aqueous solution, a pH of 4.5 being established.
  • the content of dihydroxydiphenyl sulfone is 10% by weight, based on the dry weight.
  • component A 50 parts by weight of component A, in which the pH has not yet been adjusted by adding sodium hydroxide solution, are mixed with 50 parts by weight of component B, in which the pH has not yet been adjusted by adding formic acid, and 4 hours homogenized for a long time.
  • a pH of 4.5 is then set by adding formic acid and the mixture is diluted with 5 parts by weight of water.
  • the content of dihydroxydiphenyl sulfone is 30% by weight, based on the dry weight.
  • Example 3 The procedure is as in Example 3, but 30 parts by weight of component A are mixed with 70 parts by weight of component B.
  • the content of dihydroxydiphenyl sulfone is 42% by weight, based on the dry weight.
  • a custom-made pickled beef blotch (gap thickness 3 mm) is mixed with 25% tannin in the tanning drum in 75% water and agitated at a pH value between 3.0 and 4.0 for 10 hours in a normal working drum.
  • the liquor is removed and drummed with 50% water and 5% of a commercial fatliquor for 60 minutes.
  • the pH is then adjusted to 3.2-3.5 using dilute formic acid.
  • the leather is stretched, dried, conditioned and stabled.
  • the mixtures C and D are superior to the starting components A and B in terms of the entirety of the properties evaluated. In particular, they lead to good coloring in combination with good surface coloring (color depth). This is surprising since the latter two properties are usually opposed. With the mixtures C and D a better fullness and softness are achieved than with the starting components A and B.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

L'invention concerne un procédé de production d'une solution d'agents de tannage contenant du sulfone. Ce procédé consiste à a) produire un composant A au cours d'un processus consistant à : a1) faire réagir du phénol avec de l'acide sulfurique concentré, de l'oléum comportant 20 à 65 % en poids de SO3, ou un mélange d'acide sulfurique et d'oléum comportant 20 à 65 % en poids de SO3, le rapport molaire entre l'acide sulfurique totale sous la forme SO3 et le phénol étant compris entre 0,7 : 1 et 1,5 : 1, à une température comprise entre 100 et 180 DEG C, pour obtenir un mélange contenant de l'acide phénolsulfonique, du sulfone de dihydroxydiphényle et de l'acide sulfurique, ou à mélanger ces composants individuels pour former un mélange correspondant ; a2) puis à condenser ledit mélange à une température comprise entre 40 et 90 DEG C par mole d'unités de phénol présentes avec 0,25 à 4 moles d'urée et 0,5 à 4 moles d'un aldéhyde aliphatique comportant 1 à 6 atome(s) de carbone ; a3) à éventuellement porter le pH à une valeur comprise entre 4 et 5 en ajoutant une base ; b) produire un composant B au cours d'un processus consistant à : faire réagir du sulfone de dihydroxydiphényle avec 0,5 à 5 moles d'un aldéhyde aliphatique comportant entre 1 et 6 atome(s) de carbone avec 0,4 à 2 moles de sulfite de sodium par mole de sulfone de dihydroxydiphényle, à une température comprise entre 90 et 180 DEG C ; b2) à éventuellement porter le pH à une valeur comprise entre 3,5 et 5,5 en ajoutant un acide ; c) mélanger 10 à 90 % en poids du composant A avec 90 à 10 % en poids du composant B (la somme de A et B étant équivalente à 100 % en poids), et si cela n'a pas été effectué lors de l'étape a3) et b2), porter le pH du mélange à une valeur comprise entre 3,5 et 5,5.
EP02794798A 2001-08-17 2002-08-16 Procede de production d'agents de tannage contenant du sulfone Withdrawn EP1421223A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10140551 2001-08-17
DE10140551A DE10140551A1 (de) 2001-08-17 2001-08-17 Verfahren zur Herstellung sulfonhaltiger Gerbstoffe
PCT/EP2002/009186 WO2003016578A1 (fr) 2001-08-17 2002-08-16 Procede de production d'agents de tannage contenant du sulfone

Publications (1)

Publication Number Publication Date
EP1421223A1 true EP1421223A1 (fr) 2004-05-26

Family

ID=7695869

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02794798A Withdrawn EP1421223A1 (fr) 2001-08-17 2002-08-16 Procede de production d'agents de tannage contenant du sulfone

Country Status (6)

Country Link
US (1) US6881356B2 (fr)
EP (1) EP1421223A1 (fr)
CN (1) CN1220781C (fr)
BR (1) BR0211707A (fr)
DE (1) DE10140551A1 (fr)
WO (1) WO2003016578A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004009739A1 (de) 2004-02-25 2005-09-15 Basf Ag Verfahren zur Herstellung von gut in Wasser redispergierbaren Polymerisatpulvern
US20090258074A1 (en) * 2006-05-17 2009-10-15 Basf Se Mixtures of tannins, their production and use in medicaments or as disinfectants
WO2011131542A1 (fr) * 2010-04-21 2011-10-27 Basf Se Produits, procédés pour leur préparation et leur utilisation
CN102943137B (zh) * 2012-09-25 2014-06-04 兴业皮革科技股份有限公司 裂纹软面包袋革的制作方法
CN103255242B (zh) * 2013-05-23 2015-11-18 青岛联康油脂制品有限公司 一种砜桥型合成鞣剂的制备方法
EP3181707A1 (fr) * 2015-12-18 2017-06-21 LANXESS Deutschland GmbH Procede destine a la fabrication de semi-produits en cuir ou en fourrure
US10644342B2 (en) * 2016-03-03 2020-05-05 Lockheed Martin Energy, Llc Coordination complexes containing monosulfonated catecholate ligands and methods for producing the same
EP3625372B1 (fr) * 2017-05-17 2021-04-21 Stahl International B.V. Agent de tannage pour la fabrication de cuir comprenant un polymère à base de phénol sulfoné, urée et formaldéhyde

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB722370A (en) 1951-08-21 1955-01-26 Basf Ag Improvements in the production of condensation products having tanning action
DE1113457B (de) 1959-05-27 1961-09-07 Basf Ag Verfahren zur Herstellung lichtechter Kondensationsprodukte durch Umsetzung sulfonierter Phenole mit Harnstoff und Formaldehyd
US4211856A (en) * 1978-01-05 1980-07-08 Chesnokov Vadim D Process for producing acid agent from sulfonated phenol and formaldehyde
US4592940A (en) 1983-12-16 1986-06-03 Monsanto Company Stain-resistant nylon carpets impregnated with condensation product of formaldehyde with mixture of diphenolsulfone and phenolsulfonic acid
US4830632A (en) 1986-05-05 1989-05-16 Ciba-Geigy Corporation Aqueous composition from a sulfonated phenol, an amine and a tanning salt, process for the production thereof and use thereof as a tanning agent
ES2066189T3 (es) 1989-11-13 1995-03-01 Ciba Geigy Ag Procedimiento para la preparacion de cueros y pieles.
DE4014977A1 (de) 1990-05-10 1991-11-14 Basf Ag Kondensationsprodukte aus phenolmonosulfonsaeuren, dihydroxydiphenylsulfonen, harnstoff und formaldehyd

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03016578A1 *

Also Published As

Publication number Publication date
CN1543511A (zh) 2004-11-03
US20040250353A1 (en) 2004-12-16
DE10140551A1 (de) 2003-02-27
CN1220781C (zh) 2005-09-28
BR0211707A (pt) 2004-09-21
WO2003016578A1 (fr) 2003-02-27
US6881356B2 (en) 2005-04-19

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