EP0225491B1 - Tanit et son procédé de fabrication - Google Patents

Tanit et son procédé de fabrication Download PDF

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Publication number
EP0225491B1
EP0225491B1 EP86115504A EP86115504A EP0225491B1 EP 0225491 B1 EP0225491 B1 EP 0225491B1 EP 86115504 A EP86115504 A EP 86115504A EP 86115504 A EP86115504 A EP 86115504A EP 0225491 B1 EP0225491 B1 EP 0225491B1
Authority
EP
European Patent Office
Prior art keywords
caractérisé
formylamino
selon
procédé
acétaldéhyde
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
Application number
EP86115504A
Other languages
German (de)
English (en)
Other versions
EP0225491A3 (en
EP0225491A2 (fr
Inventor
Ulrich Riegel
Fritz Dr. Engelhardt
Kuno Dr. Reh
Helmut Dr. Croon
Hermann Becker
Werner Dr. Lotz
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.)
Sanofi Aventis Deutschland GmbH
Original Assignee
Cassella AG
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 Cassella AG filed Critical Cassella AG
Priority to AT86115504T priority Critical patent/ATE46190T1/de
Publication of EP0225491A2 publication Critical patent/EP0225491A2/fr
Publication of EP0225491A3 publication Critical patent/EP0225491A3/de
Application granted granted Critical
Publication of EP0225491B1 publication Critical patent/EP0225491B1/fr
Expired 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

Definitions

  • trimethylol acetaldehyde for tanning hides, skins and furskins is known from German patent specification 1 154 593 and the associated German additional patent specification.
  • the trimethylol acetaldehyde can be used alone or in combination with other known mineral, synthetic or vegetable tanning agents.
  • the fur skins tanned using trimethylol acetaldehyde are distinguished e.g. due to its softness and particularly light weight.
  • the reaction is preferably catalyzed under alkaline conditions.
  • the formylamino compound can have one, two or more formylamino groups of the formula 1 wherein R 'is hydrogen or -CH 2 0H contain. Hydrogen is preferred for R '.
  • Suitable formylamino compounds with one or two formylamino groups in the molecule have, for example, the formula II wherein R 'has the meaning already given and R is hydrogen, (C 1 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl, - (CH 2 ) m -N (R 1 ) -CHO or -0- (CH 2 ) n denotes -ON (R 1 ) -CHO, where m is an integer from 0 to 8 and n is an integer from 1 to 8.
  • the alkyl and alkenyl radicals which stand for R can be straight-chain or branched.
  • (C 1 -C 6 ) alkyl radicals are preferred and in the case of the alkenyl radicals which are R (C 2 -C 6 ) alkenyl radicals are preferred.
  • the vinyl radical is particularly preferred for the alkenyl radicals.
  • Suitable formylamino compounds can also contain 3 or more formylamino groups of the formula 1 in the molecule.
  • Formylamino compounds of the type mentioned are known or can be synthesized by the processes known for the preparation of formylamino compounds.
  • suitable formylamino compounds are: formamide; Methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, pentyl or i-pentyl formamide; Vinyl, allyl, methallyl, crotyl formamide; N-hydroxymethyl-N-methyl-, -ethyl-, -propyl-formamide; N, N'-bis-formyl hydrazine; Methylene bis-formamide; Methylene bis (N-hydroxymethyl formamide); Ethylene bis-formamide; Trimethylene bis-formamide; Tetramethylene-bis-formamide; Methylene bis (O-form hydroxamic acid) [(H
  • Formylamino compounds suitable as starting products for the preparation of the tanning agent according to the invention are also homopolymers or copolymers which contain building blocks of the formula III in the polymer contain.
  • Such polymers are, for example, homopolymers of vinylformamide, and also copolymers of vinylformamide with, for example, acrylic acid, methacrylic acid, unsaturated sulfonic acids, such as vinylsulfonic acid, acrylamidopropanesulfonic acid, unsaturated phosphonic acids, such as vinylphosphonic acid and esters of unsaturated phosphonic acids, diallyldimethylammonium chloride, vinylamides, such as, for. B. vinyl acetamide, acrylonitrile.
  • Such homo- or copolymers are water-soluble and have an average molecular weight of approximately 5000 to 500,000.
  • a formylamino compound or a mixture of different formylamino compounds can be used in the preparation of the tannins according to the invention.
  • the reaction is generally carried out in the aqueous phase, preferably catalyzed by an alkali.
  • An alkalizing agent is added for alkaline catalysis.
  • alkalizing agents e.g. Alkali hydroxides, e.g. Sodium, potassium or lithium hydroxide
  • alkaline salts such as e.g. Alkali carbonates, e.g. Sodium, potassium or lithium carbonate, or tertiary nitrogen bases, e.g. Pyridine.
  • sodium carbonate is used as the alkalizing agent.
  • 0.008 to 0.3 mol, preferably 0.01 to 0.2 mol, of the alkalizing agent are used per mol of acetaldehyde.
  • the reaction can be carried out batchwise or continuously and is highly exothermic. If the reaction is carried out in batches, it is advisable to place one or two reactants in the aqueous phase with cooling (for example to + 10 ° C.) and to add the remaining reaction component or the remaining reaction components and the alkalizing agent, whereupon the reaction begins immediately with an increase in temperature. With the implementation in batches It is usually also advisable for the reaction not to bring the total amount of the reactants to the reaction at once, but to divide them into two or more portions and to add the remaining portions only after the reaction has subsided.
  • the reaction temperatures are generally between 0 and 140 ° C, preferably 5 and 130 ° C.
  • the first reaction phase is often carried out with cooling at reaction temperatures of up to approximately 60 to 70 ° C., and after the temperature development has subsided, the reaction is completed at an elevated temperature of, for example, 60 ° C. or more.
  • the reaction is carried out at temperatures above the boiling point of the reaction mixture at normal pressure in a pressure reactor at the excess pressure of e.g. 4 to 6 bar. Carrying out the reaction at temperatures above 100 ° C, e.g. 100 to 140 ° C, in particular 100 to 130 ° C, enables short reaction times, which can significantly reduce the thermal load on the manufactured products. This is particularly true when the reaction is carried out continuously, which is preferred.
  • Formaldehyde is usually in the form of the commercially available aqueous solutions, e.g. 39% aqueous solutions used.
  • the solution obtained after the end of the reaction which normally has an active substance content of about 30 to about 70% by weight, is expediently filtered and washed with an alkalizing agent, e.g. of the type already mentioned, set to a neutral or approximately neutral pH.
  • an alkalizing agent e.g. of the type already mentioned
  • the liquid products obtained in this way are clear or nearly clear and have a slightly yellowish to brownish color. Under normal conditions they can be kept for at least two years and can be diluted with water as required. They solidify at temperatures below approx. -10 ° C, but are fully usable again after careful thawing.
  • the products according to the invention which can be assumed to contain a mixture of different reaction products, are, as such or in the form of their aqueous solutions, outstandingly suitable as tanning agents for hides, skins and furskins, either alone or in combination with mineral, vegetable or others synthetic tanning agents. They are also excellently compatible with dyes and greasing agents in the various stages of leather and fur production. Compared to the use of trimethylol acetaldehyde, the elasticity, fullness and softness are significantly improved. In addition, the shrinkage temperature is increased and the scar strength is improved. In the case of leather dyeing, inadequate dyeing can be eliminated with the help of the products according to the invention.
  • the softening effect of the fatliquor is increased and the risk of loose grain is reduced by adding the products according to the invention. Since the products according to the invention have a favorable effect on the speed and softness of the leather, they are particularly suitable for the production of white glove leathers and nappa clothing leathers.
  • the products according to the invention have a tanning effect in the pH range from 2 to 9.
  • Examples 1 to 16 relate to the production of products according to the invention by the process according to the invention, and Examples 17 to 23 relate to the use of the products according to the invention in tannery.
  • the 39% strength formaldehyde mentioned in Examples 1 to 4 is a commercially available aqueous solution with a formaldehyde content of 39%.
  • the reaction starts immediately, the temperature rising to about 60 ° C. in the course of 10 minutes.
  • the solution is cooled down to 30 ° C.
  • a further 145 g of 39% strength formaldehyde and 6.5 g of soda are then added in one portion.
  • the temperature then rises again to approx. 40 ° C. in the course of approx. 20 min.
  • the solution is heated and stirred for 1 h at 60 ° C, 70 ° C and 80 ° C, then cooled to room temperature and adjusted to pH 7.0 ⁇ 0.5 with soda. It is filtered off. An almost clear, yellowish solution is obtained.
  • the reaction begins immediately and the temperature rises to about 55 to 60 ° C. in a few minutes, a pressure of 0.9 to 1.1 bar building up.
  • the solution is then heated to 105 to 110 ° C., a pressure of 4.5 to 5 bar being established, and kept at this temperature for 5 to 10 minutes. Then it is cooled to room temperature. After filtration, an almost clear, yellowish brown colored, ready-to-use solution is obtained, which is adjusted if necessary to pH 7.0 ⁇ 0.5 with soda.
  • Metering pumps continuously feed 1 mol of acetaldehyde, 1 mol of formaldehyde, 39% and 2 mol of formamide and small amounts of 10% aqueous soda solution into a pressure vessel equipped with a stirrer, with acetaldehyde, formaldehyde and formamide being premixed in the feed system.
  • the reaction temperature in the pressure vessel is 110 to 115 ° C at a pressure of 4 bar.
  • the reaction mixture is removed from the upper part of the pressure reactor, cooled to room temperature in a cooling tube and filtered off through a filter cartridge. A clear, almost colorless, ready-to-use solution is obtained which, if necessary, is adjusted to a pH of 7.0 ⁇ 0.5 with soda.
  • the semichromgar or purely chromegarden leather which is well rolled on in the usual way, is allowed to run for 15 5 minutes with 1.5 to 2% (based on dry weight) of a product according to the invention (e.g. according to Example 3) and then dyed in the same bath in the usual way. Uniform and deep colorations are obtained.
  • Well-softened fur skins such as Zickel, muskrat, mink or the like are tanned after pickling and possibly thin cutting as follows: 800% liquor 28 to 30 ° C., 2 g / liter liquor of a product according to the invention (eg according to Example 3) in 2 portions with a 20 minute interval, 2 hours.
  • the fur is very soft and the hair has an excellent shine and stand.

Landscapes

  • 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)
  • Tea And Coffee (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Ceramic Products (AREA)
  • Carbon And Carbon Compounds (AREA)

Claims (10)

1. Procédé de préparation d'un tanin, caractérisé en ce qu'on fait réagir, en phase aqueuse, de l'acétaldéhyde, du formaldéhyde et un composé formylamino.
2. Procédé selon la revendication 1, caractérisé en ce que le rapport molaire acétaldéhyde : formaldéhyde : composé formylamino au cours de la réaction est de 1 : (0,4 à 4) : (0,1 à 3).
3. Procédé selon la revendication 1, caractérisé en ce que le rapport molaire acétaldéhyde : formaldéhyde : composé formylamino lors de la réaction est de 1 : (0,5 à 3,1) : (0,2 à 2,2).
4. Procédé selon la revendication 1, caractérisé en ce que le rapport molaire acétaldéhyde : formaldéhyde : composé formylamino au cours de la réaction est de 1 : (0,5 à 3) : (0,2 à 2).
5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'il est exécuté à des températures réactionnelles de 0 à 140°C.
6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'il est exécuté à des températures réactionnelles de 5 à 130°C.
7. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'il est exécuté à des températures réactionnelles de 100 à 140°C.
8. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce qu'il est effectué à des températures réactionnelles de 110 à 130°C.
9. Procédé selon une ou plusieurs des revendications 1 à 8, caractérisé en ce qu'on effectue la réaction en la catalysant par un agent alcalin.
10. Procédé pour tanner le cuir, caractérisé en ce qu'on traite les peaux par un produit de réaction qui peut être obtenu par le procédé selon une ou plusieurs des revendications 1 à 9.
EP86115504A 1985-11-13 1986-11-08 Tanit et son procédé de fabrication Expired EP0225491B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86115504T ATE46190T1 (de) 1985-11-13 1986-11-08 Gerbstoff und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3540211 1985-11-13
DE19853540211 DE3540211A1 (de) 1985-11-13 1985-11-13 Gerbstoff und verfahren zu seiner herstellung

Publications (3)

Publication Number Publication Date
EP0225491A2 EP0225491A2 (fr) 1987-06-16
EP0225491A3 EP0225491A3 (en) 1987-11-11
EP0225491B1 true EP0225491B1 (fr) 1989-09-06

Family

ID=6285850

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86115504A Expired EP0225491B1 (fr) 1985-11-13 1986-11-08 Tanit et son procédé de fabrication

Country Status (8)

Country Link
US (1) US4828570A (fr)
EP (1) EP0225491B1 (fr)
JP (1) JPS62115100A (fr)
AT (1) ATE46190T1 (fr)
BR (1) BR8605597A (fr)
DE (2) DE3540211A1 (fr)
ES (1) ES2010502B3 (fr)
PT (1) PT83727B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020109962A1 (fr) 2018-11-28 2020-06-04 Sasib S.P.A. Procédé de prise en charge de changement de configuration d'une zone de fonctionnement d'une machine d'emballage de produits en général

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3030863B2 (ja) * 1990-12-25 2000-04-10 ダイキン工業株式会社 皮革改質剤、皮革の改質方法および改質なめし皮革
DE4102545A1 (de) * 1991-01-29 1992-07-30 Basf Ag Verfahren zum alleingerben, vorgerben und mitgerben von bloessen und fellbloessen und zum nachgerben von leder und fell
US5853427A (en) * 1995-07-12 1998-12-29 The United States Of America As Represented By The Secretary Of Agriculture Use of polymerizable oil for leather fatliquor
DE19815946A1 (de) * 1998-04-09 1999-10-14 Basf Ag N-Vinyleinheiten enthaltende polymere Gerbstoffe
EP2062985A1 (fr) * 2007-11-23 2009-05-27 N-Zyme BioTec GmbH Agent et procédé de tannage de peaux et de pelages

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE918779C (de) * 1942-01-18 1954-10-04 Roehm & Haas G M B H Verfahren zur Herstellung von Faellungsmitteln fuer Farb- und Gerbstoffe mit sauren Gruppen
GB777474A (en) * 1954-07-05 1957-06-26 St Lawrence Corp Ltd Leather making
US3991328A (en) * 1975-06-24 1976-11-09 Rca Corporation Planar transferred electron logic device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020109962A1 (fr) 2018-11-28 2020-06-04 Sasib S.P.A. Procédé de prise en charge de changement de configuration d'une zone de fonctionnement d'une machine d'emballage de produits en général

Also Published As

Publication number Publication date
US4828570A (en) 1989-05-09
EP0225491A3 (en) 1987-11-11
DE3540211A1 (de) 1987-05-14
BR8605597A (pt) 1987-08-18
JPS62115100A (ja) 1987-05-26
PT83727B (de) 1988-02-08
DE3665483D1 (en) 1989-10-12
ES2010502B3 (es) 1989-11-16
EP0225491A2 (fr) 1987-06-16
ATE46190T1 (de) 1989-09-15
PT83727A (de) 1986-12-01

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