EP1576196A1 - Verfahren zur herstellung eines synthetischen aluminiumgerbmittels - Google Patents

Verfahren zur herstellung eines synthetischen aluminiumgerbmittels

Info

Publication number
EP1576196A1
EP1576196A1 EP02781713A EP02781713A EP1576196A1 EP 1576196 A1 EP1576196 A1 EP 1576196A1 EP 02781713 A EP02781713 A EP 02781713A EP 02781713 A EP02781713 A EP 02781713A EP 1576196 A1 EP1576196 A1 EP 1576196A1
Authority
EP
European Patent Office
Prior art keywords
aluminium
acid
range
tanning
per mole
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.)
Granted
Application number
EP02781713A
Other languages
English (en)
French (fr)
Other versions
EP1576196B1 (de
Inventor
Central Leather Research Inst KANTHIMAHI Mookandi
P. Central Leather Research Inst. THANIKAIVELAN
Jonnalagadda R. Central Leather ResearchInst RAO
Balachandran U. Central Leather ResearchInst NAIR
T. Central Leather Research Institute RAMASAMI
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.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
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Publication date
Application filed by Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Publication of EP1576196A1 publication Critical patent/EP1576196A1/de
Application granted granted Critical
Publication of EP1576196B1 publication Critical patent/EP1576196B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C14C3/18—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
    • 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
    • C14C3/04—Mineral tanning

Definitions

  • the present invention relates to a process for the preparation of a novel synthetic aluminium tanning agent. More particularly the present invention provides a process for the preparation of a synthetic organo-aluminum tanning agent without using formaldehyde, which forms an alternative to chrome tanning material.
  • the compound has use as a self- tanning agent for hides and skins. Additionally, it is envisaged to be capable to produce fuller leathers with adequate shrinkage temperature for producing leathers with desirable properties. It is also envisaged that the white base of the leathers enhances dyeability and acts as dye saver apart from ample production of white leathers. Background of the invention
  • chrome tanning has been the most predominant method of tannage for the commercial purpose.
  • the major limitation associated with this is that the chrome tanned leathers are empty in nature and hence need heavy retanning for its final performance.
  • chrome tanned leather does not provide any lubrication among the fibres. Hence strong fatliquoring becomes mandatory for the desired level of softness.
  • chrome tanning practices employ basic chromium sulphate salt, a progenitor of several chromium species, having various charges and degree of polymerisation.
  • the kinetic inertness of certain chromium species lends itself to poor exhaustion (50-70%) of chrome tanning salt.
  • the commercial chrome tanning activities release chromium in the range of 2000-5000 ppm.
  • Aluminum tanning is one of the oldest methods of tanning. An old name 'tawing' has been used for this process, which consists of treating the skin with potassium alum in the form of paste including sodium chloride, egg yolk, flour and water.
  • Aluminum tanned leathers are sensitive to water and heat. Aluminum tanned leather has a shrinkage temperature in the range of 75-82°C depending on the method of tanning used. Its water resistance is unsatisfactory, since even a wash with the cold water slowly removes aluminium compounds from leather.
  • Aluminium being d° element, its complexes are much less stable than those of chromium; and thus their binding to collagen is much weaker. This is the reason why aluminium salts are used in contemporary tarining almost exclusively in combined tannage processes.
  • aluminium tanning is done in floats of zero basicity at high concentrations in the presence of sodium chloride to prevent swelling, because the pH of the float is as low as 2.5 - 3.5. No washing is employed after tanning.
  • the main objective of the invention is to provide a process for the preparation of a novel synthetic aluminium tanning agent, which obviates the drawbacks stated above.
  • Another objective of this invention is to provide an organo aluminium complex for direct tanning of delimed pelts without the conventional pickling process thereby reducing the total dissolved solids in the effluent.
  • Yet another objective of the invention is to provide a method for the preparation of Al(III) tanning salt in homogenous chemical formulation in which Al(III) binds irreversibly with skin/hide matrix and resists washing even at a pH 7.
  • Still another objective of the invention is to provide a method for the preparation of A1(III) tanning salt which when used in tanning gives leathers with shrinkage temperature more than 80°C unlike the conventional aluminum tanned leathers.
  • Still another objective of the invention is to provide a product for the manufacture of white leathers through an eco-friendly application procedure.
  • Yet another objective of the invention is to provide a product, which serves as dye saver and efficient chrome saver.
  • Still another objective of the invention is to provide aluminium based syntan, which offers soft and fuller leathers unlike the conventional chrome tanned leather.
  • the present invention provides a process for the preparation of a novel synthetic aluminium tanning agent, which comprises i) sulfonating an aromatic compound having up to 14 carbon atoms followed by the addition of an aqueous mixture of organic ligands and polyfunctional polymer, ⁇ ) adding trivalent aluminium salt along with water to the reaction mixture formed in step(i) and mixing the reaction mass to form a complex, iii) adding sulfo salicylic acid to the reaction mixture formed in step(ii) to form a slurry, iv) adjusting pH of the slurry formed in step (iii), in range of 2.5-3.0 by alkalinizing agent, v) drying the slurry to obtain the tanning agent in powder form.
  • the sulfonation in step (i) is carried out at a temperature in the range of 25 - 160°C.
  • the aqueous mixture of organic ligands and polyfunctional polymer is added to the sulfonated aromatic compound at a temperature in the range of 60 - 80°C.
  • the addition of trivalent aluminium salt along with water to the reaction mixture formed in step(i) is carried out at a temperature in the range of 60 - 80°C.
  • the addition of sulfosalicylic acid to the reaction mixture formed in step(ii) is done at a temperature in the range of 60 - 80°C.
  • the slurry obtained in step (iv) is aerated for a period of 30 - 60 min before drying at a temperature in the range of 130-260°C to get the tanning agent in powder form.
  • the aromatic compound used is selected from the group consisting of phenol, phenolic acid, naphthol, naphthalene and anthracene.
  • the amount of the aromatic compound used is in the range of 0.5 - 2.0 moles per mole aluminium.
  • sulfonation is carried out using sulfuric acid in an amount in the range of 1 - 5 moles per mole of aluminium.
  • the organic ligand used is selected from the group consisting of formic acid, citric acid, phthalic acid, poly carboxylic acid, oxalic acid, salicylic acid, sodium salts thereof and any mixture thereof.
  • the amount of organic ligands used is in the range of 0.001 - 0.05 mole per mole of aluminium.
  • the polyfunctional polymer used is selected from the group consisting of polyacrylic acid, polyacryl amide, polymethacrylic acid, and any mixture thereof.
  • the amount of the polyfunctional polymer used is in the range of 0.0001 - 0.001 mole per mole of aluminium.
  • the trivalent aluminium salt is selected from the group consisting of aluminium sulfate, aluminium chloride, aluminium ammonium sulfate and aluminium potassium sulfate.
  • the amount of water added to the reaction mixture is in the range of 5 - 30 moles per mole of aluminium.
  • the amount of sulfosalicylic acid used is in the range of 0.001 - 0.01 moles per mole of aluminium. In yet another embodiment of the invention, the amount of sulfuric acid used for sulfonating aromatic compound is in the range of 0.001 - 0.01 moles per mole of aluminium.
  • drying of the slurry is done by drum drying or spray drying.
  • An aromatic hydrocarbon having up to 14 carbon atoms, calculated as 0.5-2.0 moles per mole of aluminium to be used, is sulfonated by known method using 1 to 5 moles sulphuric acid per mole of aluminium for a period of not less than 60 minutes at a temperature in the range 25-160°C.
  • An aqueous mixture of 0.001 - 0.05 mole of organic ligand per mole of aluminium is then added to the sulfonated mass along with 0.0001 - 0.001 moles polyfunctional polymer per mole of aluminium at a temperature of 60 - 80°C with continuous stirring whereby the organic matrix is built up.
  • Trivalent aluminium salt is then added to the resulting mixture along with 5 - 30 moles of water per mole of aluminium while maintaining the temperature in the range of 60 —
  • A1(III) being a d° non-transition element needs a critical additive that is capable of converting it to a pseudo-transition element by transferring the electrons to 3 s, 3p and 3d orbitals. Hence, the reaction is continued for a period of 60 minutes.
  • a critical additive in the range of 0.001 - 0.01 mole per mole of aluminium is sulfonated by known method using 0.001 - 0.01 moles sulphuric acid per mole of aluminium for a period of not less than 3 hours at a temperature in the range 25 - 28°C. The sulfonated critical additive is then added to the reaction mixture. The heating and stirring was continued for another 30 min.
  • the resulting mixture is then adjusted to a pH of 2.5 - 3.0 by conventional method.
  • the slurry is dried conventionally at a temperature range of 130 - 260°C to obtain the organo aluminium complex as a white powder.
  • the novelty and non obviousness of the present development lies in using polyfunctional polymer for providing a polymeric matrix without methylene bridge with suitable critical additive that is capable of anchoring a d° non-transition element, Al(III), by charge transfer mixing of 3s, 3p and 3d orbitals.
  • suitable critical additive that is capable of anchoring a d° non-transition element, Al(III), by charge transfer mixing of 3s, 3p and 3d orbitals.
  • the irreversible binding of aluminium to the organic matrix is achieved by using organic ligands in combination with critical additive having ligating sites capable of anchoring trivalent aluminium ion.
  • Example 1 The invention is described in the following examples, which are provided for illustration only and should not be construed to limit the scope of the present invention.
  • Example 1 The invention is described in the following examples, which are provided for illustration only and should not be construed to limit the scope of the present invention.
  • the naphthalene sulfonic acid, prepared in flask was allowed to cool down to 60°C and 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 60°C with the help of the thermostat.
  • a rnixture of 0.2 gm poly acrylic acid, 0.25 gm phthalic acid, 1 gm citric acid and 0.14 gm salicylic acid was dissolved in 10 ml water in a beaker and the same was added to the reaction mass in the reactor through the dropping funnel. The mixture was heated at 65°C for 20 min.
  • the product was used for tanning the delimed goat skins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leather was left over night and the shrinkage temperature was found to be 85°C exhibiting 80-82% exhaustion of aluminium.
  • Example 2 70 gms of anthracene and 50 ml of cone, sulfuric acid were taken into a 500 ml round bottomed flask fitted with a stirrer. The contents of the flask were heated to 140°C for one hr. with continuous stirring. 1 ml of the resulting mass was taken in a beaker and 3 ml water was added to the same beaker with shaking. It was observed to form a clear solution, confirming the completion of sulfonation. In another beaker 0.3 gms salicylic acid was sulfonated simultaneously by adding 0.3ml cone, sulfuric acid and stirred thoroughly at 28°C. This mass was kept aside for 4 hrs with occasional stirring.
  • the anthracene sulfonic acid was cooled to 60°C and transferred to the reactor fitted with a condenser, stirrer and a dropping funnel.
  • the reactor was fitted into a thermo stated water bath and the sulfonated mass was stirred for 10 min. at a temperature of 60°C.
  • a mixture of 1 gm citric acid, 0.06 gm oxalic acid, 0.01 gm phthalic acid, 0.03 gm sodium formate and 0.1 gm poly acrylic acid was dissolved in 15 ml water and added to the reaction mixture keeping the temperature at 60°C. The mass was heated at 65°C for 40 minutes.
  • the product was used for tanning the delimed goat skins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leather was left over night and the shrinkage temperature was found to be 84°C, exhibiting an uptake of 80% aluminium.
  • Example 3 50 gms of phenol and 100 gms of concentrated sulfuric acid were taken into a 500 ml round bottomed flask fitted with a stirrer. The contents of the flask were heated to 120°C for 1 hr. with continuous stirring. 1 ml of the resulting mass was taken in a beaker and 3 ml of water was added. On shaking, a clear solution was obtained confirming the completion of sulfonation. Simultaneously, 0.04 gms of salicylic acid was sulfonated using 0.05 ml concentrated sulfuring acid at 26°C. The contents were stirred occasionally and left aside for 3 hrs.
  • the phenol sulfonic acid prepared in the flask was allowed to cool down to 60°C and transferred to the reactor fitted with a thermostat, stirrer and a dropping funnel. The mass was stirred for 10 min. at 60°C. A mixture of 0.6 gm poly acrylic acid, 0.05 gm of phthalic acid in 2 ml water was added to the reactor through the dropping funnel. The rnixture was stirred for 30 min. maintaining the temperature at 60°C. 136 gms of ammonium aluminium sulfate was added to the above mass along with 100 ml water with vigorous stirring. The temperature of the bath was gradually raised to 70°C and heating continued for 1 hr.
  • the pre made sulfo salicylic acid was added to the reactor and the heating was continued for 1 hour.
  • the reaction mixture was transferred to a bucket and the pH was adjusted to 3.0 using sodium bicarbonate.
  • the solution was filtered and dried using a spray drier at a temperature of 260°C.
  • the dried product was packed in a plastic container. This product was used for tanning the delimed goatskins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leathers were aged for one day and the shrinkage temperature of the tanned leather was found to be 85°C, exhibiting 78% exhaustion of aluminium.
  • Example 4 73 gms of phenolic acid and 100 gms of concentrated sulfuric acid were taken into a
  • the mass was stirred for 10 min. at 60°C.
  • a mixture of 0.6 gmpoly acrylic acid, 0.05 gm of phthalic acid in 2 ml water was added to the reactor through the dropping funnel.
  • the mixture was stirred for 30 min. maintaining the temperature at 60°C.
  • 72 gms of aluminium chloride was added to the above mass along with 100 ml water with vigorous stirring.
  • the temperature of the bath was gradually raised to 70°C and heating continued for 1 hr.
  • the pre made sulfo salicylic acid was added to the reactor and the heating was continued for 1 hour.
  • the reaction mixture was transferred to a bucket and the pH was adjusted to 3.0 using sodium bicarbonate.
  • the solution was filtered and dried using a spray drier at a temperature of 260°C.
  • the dried product was packed in a plastic container.
  • This product was used for tanning the delimed goatskins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leathers were aged for one day and the shrinkage temperature of the tanned leather was found to be 84°C, exhibiting 78% exhaustion of aluminium.
  • the naphthol sulfonic acid prepared in the flask was allowed to cool down to 60°C and transferred to the reactor fitted with a thermostat, stirrer and a dropping funnel. The mass was stirred for 10 min. at 60°C. A mixture of 0.6 gm poly acrylic acid, 0.05 gm of phthalic acid in 2 ml water was added to the reactor through the dropping funnel. The mixture was stirred for 30 min. maintaining the temperature at 60°C. 136gms of ammonium aluminium sulfate was added to the above mass along with 100ml water with vigorous stirring. The temperature of the bath was gradually raised to 70°C and heating continued for 1 hr.
  • the pre made sulfo salicylic acid was added to the reactor and the heating was continued for 1 hour.
  • the reaction mixture was transferred to a bucket and the pH was adjusted to 3.0 using sodium bicarbonate.
  • the solution was filtered and dried using a spray drier at a temperature of 260°C. The dried product was packed in a plastic container.
  • This product was used for tanning the delimed goatskins at an offer of 1.5% as Al 2 O 3 on pelt weight.
  • the tanned leathers were aged for one day and the shrinkage temperature of the tanned leather was found to be 85°C, exhibiting 80% exhaustion of aluminium.
  • the resulting product is pure white powder, freely soluble in water ensuring its potential use as a tanning agent.
  • the process ensures the metal ion in complex form as it resists hydrolysis up to a pH in the range of 5.5-7.0.
  • Syntan moiety is a polymeric matrix, which is built up without the use of formaldehyde, ensuring that the process of the present invention results in an eco-friendly product.
  • the product of the present invention contains 10-12% Al 2 O 3 and has application as a self tanning agent for delimed pelts, apart from serving as dye saver and chrome exhaust aid. 7.
  • the product produces white and soft leathers.
  • the product can be used as self-tanning agent, co-tanning agent along with BCS to improve chromium exhaustion and as retanning agent.
  • the shelf life of the product is about 1.5-2 years
  • the product has aluminium as cation with high positive charge, it can also be used as dye saver in post tanning.

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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)
  • Chemical Treatment Of Metals (AREA)
EP02781713A 2002-12-23 2002-12-23 Verfahren zur herstellung eines synthetischen aluminiumgerbmittels Expired - Lifetime EP1576196B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2002/005611 WO2004057036A1 (en) 2002-12-23 2002-12-23 Process for preparing a synthetic aluminium tanning agent

Publications (2)

Publication Number Publication Date
EP1576196A1 true EP1576196A1 (de) 2005-09-21
EP1576196B1 EP1576196B1 (de) 2008-09-03

Family

ID=32676702

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02781713A Expired - Lifetime EP1576196B1 (de) 2002-12-23 2002-12-23 Verfahren zur herstellung eines synthetischen aluminiumgerbmittels

Country Status (6)

Country Link
EP (1) EP1576196B1 (de)
CN (1) CN100375789C (de)
AT (1) ATE407225T1 (de)
AU (1) AU2002348767B2 (de)
DE (1) DE60228767D1 (de)
WO (1) WO2004057036A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4638558B2 (ja) * 2008-12-22 2011-02-23 パナソニック株式会社 語音明瞭度評価システム、その方法およびそのコンピュータプログラム
CN102719571B (zh) * 2012-06-12 2014-10-29 陕西科技大学 一种含铝单宁的制备方法
CN103757148A (zh) * 2014-01-22 2014-04-30 烟台昊煜标本有限公司 一种制作毛皮动物标本的鞣皮工艺
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
CN113073160A (zh) * 2021-04-29 2021-07-06 陕西科技大学 一种具有稳定框架结构的羧酸配体MOFs纳米鞣剂及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
DE2546166A1 (de) * 1975-10-15 1977-04-28 Behringwerke Ag Gegerbte thrombozyten
GB2068999B (en) * 1980-02-11 1984-02-22 British Leather Mfg Res Tanning leather
FR2476320B1 (fr) * 1980-02-15 1985-10-25 Guffroy Rene Nouveau reactif immunologique pour la detection en tubes du facteur rhumatoide dans un echantillon biologique et procede de preparation de ce nouveau reactif
CH656140A5 (de) * 1983-11-04 1986-06-13 Ciba Geigy Ag Faserreaktive chromkomplexe und deren herstellung.
SU1348372A1 (ru) * 1986-03-07 1987-10-30 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ противоплесневой обработки кожи
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
JPH0488100A (ja) * 1990-08-01 1992-03-19 Yoshikawa Seiyu Kk 鞣剤およびその製造方法

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Also Published As

Publication number Publication date
WO2004057036A1 (en) 2004-07-08
CN1720337A (zh) 2006-01-11
DE60228767D1 (de) 2008-10-16
AU2002348767A1 (en) 2004-07-14
AU2002348767B2 (en) 2006-11-23
CN100375789C (zh) 2008-03-19
ATE407225T1 (de) 2008-09-15
EP1576196B1 (de) 2008-09-03

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