WO2011131542A1 - Produits, procédés pour leur préparation et leur utilisation - Google Patents

Produits, procédés pour leur préparation et leur utilisation Download PDF

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Publication number
WO2011131542A1
WO2011131542A1 PCT/EP2011/055867 EP2011055867W WO2011131542A1 WO 2011131542 A1 WO2011131542 A1 WO 2011131542A1 EP 2011055867 W EP2011055867 W EP 2011055867W WO 2011131542 A1 WO2011131542 A1 WO 2011131542A1
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WO
WIPO (PCT)
Prior art keywords
tanning
process according
products
leather
present
Prior art date
Application number
PCT/EP2011/055867
Other languages
German (de)
English (en)
Inventor
Jochen Ammenn
Sebastien Garnier
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 WO2011131542A1 publication Critical patent/WO2011131542A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • 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 present invention relates to a process for the preparation of products, characterized in that
  • R 1 is selected from hydrogen and C 1 -C 4 -alkyl
  • the present invention relates to products which are obtainable by the process according to the invention, and their use for the production of leather.
  • Syntane This is understood to mean condensation products of sulfonated aromatics with aldehydes and other compounds, for example urea. Processes for the preparation of such condensation products, which are generally not pure substances, but poorly separable mixtures of numerous substances with different ferric molecular weight, different degree of substitution and / or different functionality, are described, for example, in WO 2006/064054.
  • the production process according to the invention comprises several steps, which are referred to below as step (A) or step (A) of the production process according to the invention, step (B) or step (B) of the production process according to the invention, etc.
  • the preparation process according to the invention is based on at least one compound of the general formula (I)
  • R 1 is selected from C 1 -C 4 -alkyl, for example sec-butyl, isobutyl, isopropyl, preferably unbranched, for example methyl, ethyl, n-propyl, n-butyl, more preferably methyl and especially hydrogen.
  • Preferred representatives of compounds of the general formula (I) are ortho-cresol, meta-cresol, para-cresol and in particular phenol.
  • step (A) compound of general formula (I) is reacted with a sulfonating agent such that the molar ratio of compound of general formula (I) and active SO 3 is in the range of 1: 0.8 to 1: 1, 09, preferably 1, 00 - 1, 09.
  • Suitable sulfonating agents are, for example: chlorosulfonic acid, sulfuric acid, disulphuric acid H2S2O7 and in particular oleum.
  • step (A) is carried out at temperatures in the range from 80 to 180.degree. C., preferably in the range from 140 to 170.degree.
  • step (A) is carried out at atmospheric pressure.
  • step (A) may be carried out at elevated pressure, for example in a range from 1, 01 to 10 bar.
  • step (A) is carried out under reduced pressure, for example in a range from 20 to 100 mbar.
  • a solvent may be used to carry out step (A).
  • step (A) of the process according to the invention is carried out without a solvent.
  • the compound of the general formula (I) in cases where the compound of the general formula (I) is solid at room temperature, the compound of the general formula (I) is used in a molten state.
  • the procedure is to initially introduce compound of the general formula (I) in liquid form and to add sulfonating reagent.
  • the reaction in step (A) can be carried out over a period in the range of 10 minutes to 24 hours, preferably 4 to 10 hours.
  • step (A) of the preparation process according to the invention is preferably carried out under protective gas, for example under nitrogen.
  • the reaction in step (A) can also be carried out in the presence of air.
  • step (A) is generally a mixture in the compound of general formula (II)
  • Main component is, i. by weight the most significant component.
  • the intermediate obtained after step (A) may be contaminated with compounds of the general formulas (IIIa), (IIIb), (IV) and / or (V).
  • step (B) the proportion of contamination by compounds of general formula (III a), (III b), (IV) and (V) is in most cases at most 60 wt .-%, based on the total intermediate.
  • step (B) is carried out.
  • the intermediate obtained from step (A) is condensed with at least one aliphatic aldehyde.
  • suitable aliphatic aldehydes are propionaldehyde, acetaldehyde and, in particular, formaldehyde. Mixtures of two different aliphatic aldehydes, for example, acetaldehyde and formaldehyde, are also suitable.
  • Aliphatic aldehyde in particular acetaldehyde, can be used, for example, in aqueous solution or as a trimer.
  • Formaldehyde can be used for example as gas, as polymeric formaldehyde or in aqueous solution, for example as formalin.
  • an intermediate from step (A) is reacted with aliphatic aldehyde in a molar ratio ranging from 1: 0.5 to 1: 4, preferably 1: 0.6 to 1: 3.5.
  • aliphatic aldehyde in a molar ratio ranging from 1: 0.5 to 1: 4, preferably 1: 0.6 to 1: 3.5.
  • step (B) is carried out at temperatures in the range from 50 to 140 ° C, preferably 60 to 120 ° C. In one embodiment of the present invention, step (B) is carried out under atmospheric pressure. In another embodiment, step (B) may be carried out at elevated pressure, for example in a range of 1.01 to 10 bar.
  • step (B) can be carried out without solvent. However, it is preferable to carry out step (B) in aqueous solution.
  • the reaction in step (B) can be carried out over a period in the range of 10 minutes to 24 hours, preferably 20 minutes to 6 hours.
  • step (B) it is possible to add at least one further, preferably aromatic, compound which participates in the condensation reaction, for example 2, 4'-dihydroxydiphenylsulfone or 4,4'-dihydroxydiphenylsulfone. It is preferred to add no further organic compound in step (B). It is particularly preferred to add neither an aromatic compound nor urea in step (B). In one embodiment of the present invention, after performing step (A) and before or after the condensation in step (B), it is possible to neutralize partially or completely.
  • at least one further, preferably aromatic, compound which participates in the condensation reaction for example 2, 4'-dihydroxydiphenylsulfone or 4,4'-dihydroxydiphenylsulfone. It is preferred to add no further organic compound in step (B). It is particularly preferred to add neither an aromatic compound nor urea in step (B).
  • organic amines for neutralizing it is possible to use, for example, organic amines, ammonia or, preferably, basic alkali metal compounds.
  • organic amines are ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, N, N-diethanolamine, ethanolamine, N-methylethanolamine, ⁇ , ⁇ -dimethylethanolamine, N-methyl-N, N-diethanolamine, N - (n-propyl) -ethanolamine, N- (n-butyl) -ethanolamine and N- (n-butyl) -N, N-diethanolamine.
  • 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.
  • Basic alkali metal compound can be used preferably in aqueous solution.
  • partial or complete neutralization is carried out at temperatures in the range of zero to 90 ° C, preferably 20 to 30 ° C.
  • the intermediate of step (A) can be purified. However, it is preferred to carry out no purification and to use the intermediate from step (A) either immediately in step (B) or to use it after partial or complete neutralization in step (B).
  • a product according to the invention is obtained which can be used, for example, for the production of leather.
  • the product according to the invention is to be understood as meaning the organic fractions, ie free acids or even salts.
  • Inventive product can be used in aqueous formulation or initially isolated, for example by evaporation or, in particular, by spray-drying the reaction mixtures obtainable according to step (B).
  • the product according to the invention may have an average molecular weight M w in the range from 1,000 to 10,000 daltons, preferably from 2,000 to 5,000 daltons.
  • the average molecular weight can be determined, for example, by gel permeation chromatography (GPC), for example a syntan can be used as standard.
  • Suitable solvent is, for example, water.
  • Another object of the present invention is the use of inventive product for the production of leather.
  • Another object of the present invention is a process for the production of leather using inventive product.
  • Another object of the present invention is leather, prepared using inventive product.
  • the process according to the invention for producing leather is used as a tanning process, hereinafter also referred to as the tanning process according to the invention, and preferably as a post-tanning process, hereinafter also referred to as retanning process according to the invention.
  • the tanning process according to the invention is generally carried out by adding the product 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 2.5 to 1 1, preferably up to 5, wherein it is frequently observed that the pH during the performance of the tanning process according to the invention increases by about 0.3 to three units.
  • the tanning process according to the invention is generally carried out at temperatures of from 10 to 45.degree. C., preferably at from 20 to 30.degree. 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 product according to the invention is used, based on the solids content of the product 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 the product according to the invention: conventional tanning agent or sum of the conventional tanning agents is advantageously from 0.01: 1 to 100: 1 (based in each case on the solids contents).
  • the product according to the invention is used together with one or more fatliquoring agents or oleophilic components.
  • the product according to the invention is added in one portion or in several portions before or during pre-treatment. An addition in the pimple is conceivable.
  • the retanning process according to the invention can be carried out under otherwise customary conditions. It is convenient to choose one or more, i. 2 to 6 action steps and can rinse with water between the interaction steps.
  • the temperature in the individual reaction steps is in each case from 5 to 60.degree. C., preferably from 20 to 45.degree.
  • 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.
  • the retanning process according to the invention is carried out at a pH in the range from 4 to 9.
  • 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 product according to the invention is used, based 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 good heat yellowing properties, ie a low tendency to heat yellowing, and further good use properties.
  • leather according to the invention is suitable, for example, for producing shoe upper leather, clothing such as jackets, coats or trousers, and furniture.
  • step (B.2) 300 g of a solution of 1.1 were added, corresponding to about 0.57 mol of the compound of the formula (IIa.1) or its isomers, and the mixture was cooled to 0 ° C. Within 13 minutes was added under cooling 95.7 g of a 50 wt .-% aqueous sodium hydroxide solution, the temperature at 0 ° C remained. The pH was 8.1. Within 18 minutes were added 181 g of a 30 wt .-% aqueous formaldehyde solution, corresponding to 1, 8 moles of formaldehyde. The temperature rose to 18 ° C during the addition.
  • a commercially available bovine wet blue (Packer, USA) was folded to a thickness of 1, 5 to 1, 8 mm. The core area was cut into three strips of approx. 1700 g each. The strips were then mixed in a drum (50 l) and a liquor length of 200% (based on shaved weight) at intervals of 10 minutes with 1.5% by weight of sodium formate and 0.5% sodium bicarbonate and 1% of a naphthalenesulfonic acid Formaldehyde condensation product, prepared according to US 5,186,846, example "Dispersant 1.” After 70 minutes, the liquor was drained off and the strips were then distributed to separate walk-drums 1 to 3.
  • the leathers thus obtained were washed, dried, staked, treated for 30 seconds in a vacuum dryer at 60 ° C. and evaluated according to the test criteria specified in Table 1.
  • the leathers L.1 and L.2 according to the invention and the comparison leather V-L.3 were obtained.
  • the rating was based on a grading system from 1 (very good) to 5 (poor).

Landscapes

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

Abstract

L'invention concerne un procédé pour la préparation de produits, caractérisé en ce que : (A) on transforme l'un avec l'autre au moins un composé de formule générale (I), R1 étant choisi parmi hydrogène et C1-C4-alkyle, et un agent de sulfonation dans un rapport molaire dans la plage de 1:0,8 à 1:1,09, par rapport au SO3 actif; (B) on condense le produit intermédiaire obtenu avec au moins un aldéhyde aliphatique.
PCT/EP2011/055867 2010-04-21 2011-04-14 Produits, procédés pour leur préparation et leur utilisation WO2011131542A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10160597.0 2010-04-21
EP10160597 2010-04-21

Publications (1)

Publication Number Publication Date
WO2011131542A1 true WO2011131542A1 (fr) 2011-10-27

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5186846A (en) 1990-06-13 1993-02-16 Basf Aktiengesellschaft Dye dispersants: aryl sulphonic acid-formaldehyde condensate or ligninsulfonate
EP0970148B1 (fr) 1997-03-18 2001-06-13 Basf Aktiengesellschaft Colorants azo oligomeriques
WO2003016578A1 (fr) * 2001-08-17 2003-02-27 Basf Aktiengesellschaft Procede de production d'agents de tannage contenant du sulfone
WO2003023069A1 (fr) 2001-09-07 2003-03-20 Basf Aktiengesellschaft Composition emulsifiante et agents de graissage hautement degradables a faible brumisation, sa production et son utilisation
WO2006064054A1 (fr) * 2004-12-17 2006-06-22 Tfl Ledertechnik Gmbh Composition pour le traitement du cuir
WO2007012606A1 (fr) * 2005-07-25 2007-02-01 Tfl Ledertechnik Gmbh Agents de production de cuir

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5186846A (en) 1990-06-13 1993-02-16 Basf Aktiengesellschaft Dye dispersants: aryl sulphonic acid-formaldehyde condensate or ligninsulfonate
EP0970148B1 (fr) 1997-03-18 2001-06-13 Basf Aktiengesellschaft Colorants azo oligomeriques
WO2003016578A1 (fr) * 2001-08-17 2003-02-27 Basf Aktiengesellschaft Procede de production d'agents de tannage contenant du sulfone
WO2003023069A1 (fr) 2001-09-07 2003-03-20 Basf Aktiengesellschaft Composition emulsifiante et agents de graissage hautement degradables a faible brumisation, sa production et son utilisation
WO2006064054A1 (fr) * 2004-12-17 2006-06-22 Tfl Ledertechnik Gmbh Composition pour le traitement du cuir
WO2007012606A1 (fr) * 2005-07-25 2007-02-01 Tfl Ledertechnik Gmbh Agents de production de cuir

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