EP1656460B1 - Procede de preparation d'un agent de tannage synthetique - Google Patents

Procede de preparation d'un agent de tannage synthetique 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
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Expired - Lifetime
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EP03817975A
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German (de)
English (en)
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EP1656460A1 (fr
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. Procédé pour la préparation d'un agent de tannage organopolymère et synthétique qui est exempt de formaldéhyde et qui est utilisable pour le tannage de cuir, ledit procédé comprenant :
    (a) la réaction d'un composé aromatique avec de l'acide sulfonique à une température dans l'intervalle de 40 à 60°C pour obtenir un composé aromatique sulfoné ;
    (b) l'addition d'un ou plusieurs ligands organiques au composé aromatique sulfoné obtenu dans l'étape (a) et le chauffage du mélange à une température dans l'intervalle de 60 à 80°C ;
    (c) l'addition d'un ou plusieurs polymères multifonctionnels au mélange de l'étape (b) et le chauffage de ceux-ci à une température dans l'intervalle de 40 à 100°C pour obtenir un mélange réactionnel ;
    (d) l'addition d'eau au mélange réactionnel de l'étape (c) et l'ajustement de la valeur du pH de celui-ci dans l'intervalle de 3,0 à 3,5 ; et
    (e) l'aération facultative du mélange réactionnel et le séchage du mélange réactionnel de l'étape (d) pour obtenir l'agent de tannage organopolymère synthétique.
  2. Procédé selon la revendication 1, dans lequel dans l'étape (a), le composé aromatique utilisé contient jusqu'à 14 atomes de carbone.
  3. Procédé selon la revendication 1 ou 2, dans lequel dans l'étape (a), le composé aromatique réagit avec de l'acide sulfurique sur une durée dans l'intervalle de 50 à 250 min.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (a), de 1 à 5 mol d'acide sulfurique sont utilisées par mole de composé aromatique.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (a), le composé aromatique utilisé est choisi parmi le naphtène, l'anthracène ou le phénol.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (b), le ligand organique utilisé est choisi parmi l'acide formique, l'acide citrique, l'acide phtalique, l'acide salicylique, l'acide oxalique ou leurs sels de sodium soit individuellement, soit en combinaison.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (b), de 0,01 à 0,1 mol de ligand organique est utilisée par mole du composé aromatique.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (c), le polymère multifonctionnel est choisi parmi le poly(acide acrylique), l'acide méthacrylique et des mélanges de ceux-ci.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (c), de 0,001 à 0,01 mol de polymère multifonctionnel est utilisée par mole du composé aromatique.
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (d), de 5 à 25 mol d'eau par mole du composé aromatique sont ajoutées au mélange réactionnel.
  11. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (d), le pH du mélange réactionnel est ajusté par addition d'une solution de bicarbonate de sodium ou d'hydroxyde de sodium.
  12. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (e), le mélange réactionnel est aéré en faisant passer de l'air/un gaz inerte à travers celui-ci.
  13. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (e), le mélange réactionnel est aéré sur une durée dans l'intervalle de 30 à 60 minutes.
  14. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (e), le mélange réactionnel est séché soit par séchage en tambour, soit par séchage par pulvérisation.
  15. Procédé selon l'une quelconque des revendications précédentes, dans lequel dans l'étape (e), le mélange réactionnel est séché à une température dans l'intervalle de 130 à 260°C.
  16. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'agent de tannage organopolymère synthétique ainsi obtenu présente une libération de chrome dans l'intervalle de 90 à 99 %.
  17. Utilisation d'un agent de tannage pouvant être obtenu par un procédé selon l'une quelconque des revendications précédentes dans le tannage de cuir.
  18. Procédé pour la préparation de cuir tanné, lequel comprend :
    - la préparation d'un agent de tannage par un procédé selon l'une quelconque des revendications 1 à 16 ; et
    - le tannage de cuir utilisant l'agent de tannage ainsi obtenu en présence de BCS.
EP03817975A 2003-08-12 2003-08-12 Procede de preparation d'un agent de tannage synthetique Expired - Lifetime EP1656460B1 (fr)

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PCT/IB2003/003592 WO2005014865A1 (fr) 2003-08-12 2003-08-12 Procede de preparation d'un agent de tannage synthetique

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

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

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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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ES2066189T3 (es) * 1989-11-13 1995-03-01 Ciba Geigy Ag Procedimiento para la preparacion de cueros y pieles.
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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Publication number Publication date
AU2003250493B2 (en) 2009-05-28
AU2003250493A1 (en) 2005-02-25
CN100535126C (zh) 2009-09-02
EP1656460A1 (fr) 2006-05-17
WO2005014865A1 (fr) 2005-02-17
DE60327001D1 (de) 2009-05-14
CN1839207A (zh) 2006-09-27

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