EP1656460B1 - Verfahren zur herstellung eines synthetischen gerbstoffs - Google Patents

Verfahren zur herstellung eines synthetischen gerbstoffs Download PDF

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Publication number
EP1656460B1
EP1656460B1 EP03817975A EP03817975A EP1656460B1 EP 1656460 B1 EP1656460 B1 EP 1656460B1 EP 03817975 A EP03817975 A EP 03817975A EP 03817975 A EP03817975 A EP 03817975A EP 1656460 B1 EP1656460 B1 EP 1656460B1
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EP
European Patent Office
Prior art keywords
reaction mixture
aromatic compound
acid
range
tanning agent
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.)
Expired - Fee Related
Application number
EP03817975A
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English (en)
French (fr)
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EP1656460A1 (de
Inventor
Mookandi Kanthimathi
Palanisamy Thanikaivelan
Jonnalagadda Rao
Balachandran Unni Nair
Thirumalachari Ramasami
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Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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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
    • 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 a synthetic tanning agent. More particularly the present invention provides a process for the preparation of a organo-polymeric substance, which is free from formaldehyde, using for tanning leather. This polymeric substance has enormous potential application as pretanning as well as retanning agent in leather processing industry.
  • Synthetic tanning agents are conventionally prepared by the condensation of naphthalene/phenol sulphonic acid or urea with formaldehyde as reported by Sharphouse (Leather Technicians Handbook, Vernon Lock Ltd., London, 1983 ).
  • the phenolformaldehyde condensed product which is essentially a low molecular weight resinous material, has always a possibility of eliminating unreacted phenol or formaldehyde, thereby posing a risk of adding to toxicity.
  • Denzinger et al (U.S. Patent 5,425,784 , 1995 ) have prepared water-soluble graft polymers of monosaccharides, oligosaccharides, polysaccharides and derivatives with crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, C 1 -C 8 -alkyl- and hydroxyalkyl esters of acrylic acid, methacrylic acid or crotonic acid, mono- and di- C 1 -C 8 -alkyl and -hydroxyalkyl esters of maleic acid, fumaric acid and citraconic acid, acrylamide, methacrylamide, methacrolein, acrylamido-methylpropanesulfonic acid, N-vinylimidazole and mixtures, and used as a tanning agent for the self-tanning, pretanning, simultaneous tanning and retanning of pelts and skins. But these polymers do not
  • Lakshminarayana et al (Journal of the American Leather Chemists Association, 85, 425, 1990 ) recommends an acrylic acid based syntan as retanning agent for chrome tanned leathers, which is prepared by the graft copolymerization of acrylic ester and methacrylic acid onto a mixture of sulfated fish oil and alginic acid using free radical polymerization.
  • the major limitation associated with this product is that it leads to poor light fastness and heat resistance.
  • the acrylic syntans which are generally attached to the protein through weak linkage, result in either low exhaustion in processing bath or more leaching out during subsequent wet operations. Christner et al (U.S.
  • patent No 4,961,750 , 1990 have reported the preparation of thio containing chromium poly acrylate tanning agents by complexing the chromium ion and an acrylate polymer together with a heterocycle containing nitrogen, oxygen, or sulfur atom, having a molecular weight between 200 and 30,000, which can be offered to prickled skins or hides.
  • the main disadvantage in this tanning agent is the slow release of oxides of sulphur, which is carcinogenic.
  • the main objective of the present invention is to provide a process for the preparation of a synthetic tanning agent, which obviates the drawbacks as detailed above.
  • Another objective of the present invention is to prepare a chromium exhaust aid, which can be offered to delimed pelts along with commercial BCS thus avoiding pickling process thereby reducing the total dissolved solids in the effluent.
  • Still another objective of the present invention is to prepare a formaldehyde free polymeric network, which helps in preventing the precipitation of chromium at lower pH values.
  • Yet another objective of the present invention is to prepare a polymeric product, which can be used as a retanning agent and provides leathers with improved fullness, grain firmness with uniform dyeing.
  • the present invention provides a process for the preparation of synthetic organo-polymeric tanning agent free from formaldehyde used for tanning leather, said process comprising the steps of:
  • the aromatic compound 20 used contains 1-14 carbon atoms.
  • step (a) the aromatic compound is reacted with sulfuric acid for a time period in the range of 50 to 250 minutes.
  • step (a) In yet another embodiment of the present invention wherein in step (a), 1 to 5 moles of sulfuric acid is used per mole of aromatic compound.
  • the aromatic compound used is selected from the group consisting of naphthene, anthracene, or phenol.
  • the organic ligand used is selected from the group consisting of formic acid, citric acid, phthalic acid, salicylic acid, oxalic acid or their sodium salts ether individually or in combination.
  • step (b) 0.01 to 0. mole of organic ligand is used per mole of the aromatic compound.
  • the multi-functional polymer is selected from the group consisting of polyacrylic acid, methacrylic acid or mixture thereof.
  • step (c) 0.001 to 0.01 mole of multi-functional polymer is used per mole of the aromatic compound.
  • step (d) In another embodiment of the present invention wherein in step (d), 5 to 25 moles of 10 water per mole of aromatic compound is added to the reaction mixture.
  • step (d) the pH of the reaction mixture is adjusted by adding sodium bicarbonate or by sodium hydroxide solution.
  • step (e) the reaction mixture is aerated by passing air /inert gas through the same.
  • reaction mixture is aerated for the time period in the range of 30 to 60 minute.
  • reaction mixture is dried either by drum drying or by spray drying.
  • reaction mixture is dried at temperature in the range of 130 to 260°C.
  • the synthetic organo-polymeric tanning agent thus obtained has chromium exhaust in the range of 90 to 99 %.
  • An aromatic compound having up to 14 carbon atoms is sulfonated by known method using 1 - 5 moles sulfuric acid per mole of aromatic compound for a period of not less than 90 min at a temperature in the range of 40 - 160°C.
  • the temperature of the reaction mass is then adjusted in the range of 60 - 80°C and an aqueous mixture of 0.01 - 0.1 mole of organic ligand per mole of aromatic compound is added to the said mass.
  • 0.0001 - 0.01 mole of multi functional polymer per mole of aromatic compound is then added to the said reaction mixture.
  • Heating is allowed to continue for a period not less than 60 minutes at a temperature in the range of 60 - 80°C, pH of the resulting mixture is then adjusted at a range of 3.0 - 3.5 by known method to obtain the synthetic tanning agent in slurry form.
  • the above slurry is subjected, as optional step, to aeration for a period of 30-60 minutes followed by conventional drying at a temperature in the range of 130 - 260°C to obtain the synthetic tanning agent in powder form.
  • the novelty and non-obviousness of the present invention lies in polymerizing the multi functional polymer with sulfonated aromatic compound, pretreated with organic ligand, thereby forming an organo-polymeric matrix, free from formaldehyde, having potential application in leather industry for not only ensuring an eco-friendly approach in chrome tanning by way of eliminating the conventional pickling process and the resulting problem of total dissolved solids (TDS) associated with the effluent, but also suggesting an exhaust aid for chrome because of its multiple carboxyl groups, thereby ensuring an economical eco-benign approach for leather tanning.
  • TDS total dissolved solids
  • the product was offered to delimed goatskins at an offer of 1.5% along with 5% BCS at a float of 20%.
  • the drum was run for 1 hr and 80% water was added. Running was continued for another hr and the penetration was assessed by checking uniform blue color along the cut section. The pH of the solution and the cut section was found to be 4.2.
  • the bath was drained and the wet blue leathers were piled. Next day the leathers were post tanned using a conventional upper leather-processing recipe. The chromium exhaustion of the spent tan liquor was found to be 94%. The fullness of the crust leathers was found to be superior to that of conventional chrome tanned leathers.
  • the prepared syntan was added to the delimed sheepskins at an offer of 1.0% along with 5% BCS at a float of 20%.
  • the drum was run for 1 hr and 80% water was added. Running was continued for another hr and the penetration was assessed by checking uniform blue color along the cut section. The pH of the solution and the cut section was 10 found to be 4.4.
  • the bath was drained and the wet blue leathers were piled. Next day the leathers were post tanned using a conventional garment leather processing recipe. The chromium exhaustion of the spent tan liquor was found to be 95%. The fullness of the crust leathers was found to be superior to that of conventional chrome tanned leathers.
  • the product was offered to delimed cow sides at an offer of 1.5% along with 8% BCS at a float of 20%.
  • the drum was run for 2 hrs and 80% water was added. Running was continued for another 4 hrs and the penetration was assessed by checking uniform blue color along the cut section. The pH of the solution and the cut section was found to be 4.0.
  • the bath was drained and the wet blue leathers were piled. Next day the leathers were post tanned using a conventional upper leather processing recipe. The chromium exhaustion of the spent tan liquor was found to be 92%. The fullness of the crust leathers was found to be superior to that of conventional chrome tanned leathers.
  • 256 gms of naphthalene and 544 ml of concentrated sulfuric acid were taken in a 2 litre round bottom flask fitted with a stirrer. The contents of the flask were heated to 160°C for 90 minutes. 1 ml of the resulting m ass w as taken in a beaker and 2ml water was added to the mass with shaking. It was observed that the solution was clear indicating the completion of sulfonation. The sulfonated mass was transferred to a reactor fitted with a thermometer, stirrer and a dropping funnel. The mass was stirred continuously for a period of 10 min. while maintaining the temperature at 80°C. A mixture of 8.4 gms citric acid, 16.6 gms phthalic acid and 4 gms sodium formate dissolved in 50 ml water was added to the above sulfonated mass and stirring was continued at 80°C.
  • a mixture of 20 gms poly methacrylic acid and 5 gms polyacrylic acid was added to the sulphonic acid mixture and the mixture was heated to 60°C for 1 hour.
  • a small portion of the reaction mixture was taken in a beaker and 2 ml water was added to the mass.
  • the pH of the solution in the beaker was adjusted to 3.5 and a clear solution was obtained indicating the completion of the reaction.
  • About 900 ml of water was added to the mass and is transferred to a bucket after cooling the reaction mass to room temperature.
  • the pH of the mass was raised to 3.5 by adding a solution of 100 gms of sodium hydroxide dissolved in 200 ml water, followed by the addition of a solution of 300 gms sodium bicarbonate dissolved in 600 ml water.
  • the slurry was filtered using a cloth of pore size 5-10 ⁇ .
  • the filtrate was drum dried at 130°C and the white powder was stored in a plastic container.
  • the product was offered to delimed buff calfs at an offer of 1.5% along with 8% BCS at a float of 20%.
  • the drum was run for 2 hrs and 80% water was added. Running was continued for another 4 hers and the penetration was assessed by checking uniform blue color along the cut section. The pH of the solution and the cut section was found to be 4.0.
  • the bath was drained and the wet blue leathers were piled. Next day the leathers were post tanned using a conventional upper leather-processing recipe. The chromium exhaustion of the spent tan liquor was found to be 94%. The fullness of the crust leathers was found to be superior to that of conventional chrome tanned leathers.

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

Claims (18)

  1. Verfahren zur Herstellung eines synthetischen, organo-polymeren Gerbstoffes, der frei von Formaldehyd ist und sich zur Verwendung bei der Gerbung von Leder eignet, wobei das Verfahren folgendes umfasst:
    (a) das Umsetzen einer aromatischen Verbindung mit Schwefelsäure bei einer Temperatur im Bereich von 40 bis 60 °C unter Bildung einer sulfonierten, aromatischen Verbindung;
    (b) das Zugeben von einem oder mehreren organischen Liganden zu der in Stufe (a) erhaltenen sulfonierten, aromatischen Verbindung und das Erwärmen des Gemisches auf eine Temperatur im Bereich von 60 bis 80 °C;
    (c) das Zugeben von einem oder mehreren multifunktionellen Polymeren zu dem Gemisch von Stufe (b) und das Erwärmen des Gemisches auf eine Temperatur im Bereich von 40 bis 100 °C unter Bildung eines Reaktionsgemisches;
    (d) das Zugeben von Wasser zum Reaktionsgemisch von Stufe (c) und das Einstellen des pH-Werts des Gemisches auf den Bereich von 3,0 bis 3,5; und
    (e) gegebenenfalls das Belüften des Reaktionsgemisches und das Trocknen des Reaktionsgemisches von Stufe (d) unter Bildung des synthetischen, organo-polymeren Gerbstoffes.
  2. Verfahren nach Anspruch 1, wobei in Stufe (a) die verwendete aromatische Verbindung bis zu 14 Kohlenstoffatome enthält.
  3. Verfahren nach Anspruch 1 oder 2, wobei in Stufe (a) die aromatische Verbindung mit Schwefelsäure für eine Zeitspanne im Bereich von 50 bis 250 Minuten umgesetzt wird.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (a) 1 bis 5 mol Schwefelsäure pro 1 mol der aromatischen Verbindung verwendet werden.
  5. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (a) die verwendete aromatische Verbindung aus Naphthen, Anthracen oder Phenol ausgewählt wird.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (b) der verwendete organische Ligand aus Ameisensäure, Citronensäure, Phthalsäure, Salicylsäure, Oxalsäure oder deren Natriumsalzen entweder einzeln oder in Kombination ausgewählt wird.
  7. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (b) 0,01 bis 0,1 mol des organischen Liganden pro 1 mol der aromatischen Verbindung verwendet wird.
  8. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (c) das multifunktionelle Polymere aus Polyacrylsäure, Methacrylsäure und Gemischen davon ausgewählt wird.
  9. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (c) 0,001 bis 0,01 mol des multifunktionellen Polymeren pro 1 mol der aromatischen Verbindung verwendet wird.
  10. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (d) 5 bis 25 mol Wasser pro 1 mol der aromatischen Verbindung zum Reaktionsgemisch gegeben werden.
  11. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (d) der pH-Wert des Reaktionsgemisches eingestellt wird, indem man eine Natriumbicarbonat- oder Natriumhydroxidlösung zugibt.
  12. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (e) das Reaktionsgemisch belüftet wird, indem man Luft/Inertgas durch das Gemisch leitet.
  13. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (e) das Reaktionsgemisch für eine Zeitspanne im Bereich von 30 bis 60 Minuten belüftet wird.
  14. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (e) das Reaktionsgemisch durch Trommeltrocknung oder Sprühtrocknung getrocknet wird.
  15. Verfahren nach einem der vorstehenden Ansprüche, wobei in Stufe (e) das Reaktionsgemisch bei einer Temperatur im Bereich von 130 bis 260 °C getrocknet wird.
  16. Verfahren nach einem der vorstehenden Ansprüche, wobei der auf diese Weise erhaltene synthetische, organo-polymere Gerbstoff eine Chromerschöpfung (chromium exhaust) im Bereich von 90 bis 99 % aufweist.
  17. Verwendung eines Gerbstoffes, der nach dem Verfahren eines der vorstehenden Ansprüche erhältlich ist, beim Gerben von Leder.
  18. Verfahren zur Herstellung von gegerbtem Leder, umfassend:
    - das Herstellen eines Gerbstoffes durch ein Verfahren nach einem der Ansprüche 1 bis 16; und
    - das Gerben von Leder unter Verwendung des auf diese Weise erhaltenen Gerbstoffes in Gegenwart von BCS.
EP03817975A 2003-08-12 2003-08-12 Verfahren zur herstellung eines synthetischen gerbstoffs Expired - Fee Related EP1656460B1 (de)

Applications Claiming Priority (1)

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PCT/IB2003/003592 WO2005014865A1 (en) 2003-08-12 2003-08-12 A process for the preparation of a synthetic tanning agent

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EP1656460A1 EP1656460A1 (de) 2006-05-17
EP1656460B1 true EP1656460B1 (de) 2009-04-01

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CN (1) CN100535126C (de)
AU (1) AU2003250493B2 (de)
DE (1) DE60327001D1 (de)
WO (1) WO2005014865A1 (de)

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Publication number Priority date Publication date Assignee Title
CN102260763B (zh) * 2011-06-23 2013-09-25 陕西科技大学 一种改性壳聚糖两性聚合物复鞣剂及其制备方法
CN103667544A (zh) * 2013-11-07 2014-03-26 齐河力厚化工有限公司 一种高吸收铬鞣剂及其制备方法
CN104450991B (zh) * 2014-09-26 2017-02-22 山东力厚轻工新材料有限公司 一种不浸酸铬粉及其制备方法
CN107400738B (zh) * 2017-08-15 2019-09-10 陕西科技大学 两性酚类合成鞣剂及其制备方法
CN107619890B (zh) * 2017-08-24 2020-09-29 南通市宏飞橡胶制品有限公司 一种复合鞣剂

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EP0428481B1 (de) * 1989-11-13 1994-12-14 Ciba-Geigy Ag Mittel zur Behandlung von Leder und Pelzen
US5629376A (en) * 1990-10-31 1997-05-13 Peach State Labs, Inc. Polyacrylic acid compositions for textile processing
DE4131202A1 (de) * 1991-09-19 1993-03-25 Bayer Ag Verfahren zur herstellung von chromleder

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WO2005014865A1 (en) 2005-02-17
EP1656460A1 (de) 2006-05-17
AU2003250493B2 (en) 2009-05-28
DE60327001D1 (de) 2009-05-14
CN100535126C (zh) 2009-09-02
CN1839207A (zh) 2006-09-27
AU2003250493A1 (en) 2005-02-25

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