EP0225491B1 - Tanning agent and method for its manufacture - Google Patents
Tanning agent and method for its manufacture Download PDFInfo
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- 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
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- caractérisé
- formylamino
- selon
- procédé
- acétaldéhyde
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- 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.
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Abstract
Description
Aus der deutschen Patentschrift 1 154 593 und der zugehörigen deutschen Zusatzpatentschrift ist die Verwendung von Trimethylolacetaldehyd zum Gerben von Häuten, Fellen und Pelzfellen bekannt. Der Trimethylolacetaldehyd kann dabei allein oder in Kombination mit anderen bekannten mineralischen, synthetischen oder vegetabilischen Gerbstoffen eingesetzt werden. Bei der Gerbung von Häuten und Fellen mit Trimethylolacetaldehyd werden weiche Leder mit geschmeidigen Narben erhalten. Die unter Verwendung von Trimethylolacetaldehyd gegerbten Pelzfelle zeichnen sich z.B. durch Weichheit und ein besonders leichtes Gewicht aus.The use of 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. When tanning hides and skins with trimethylol acetaldehyde, soft leathers with smooth scars are obtained. The fur skins tanned using trimethylol acetaldehyde are distinguished e.g. due to its softness and particularly light weight.
Es wurde nun gefunden, daß sich die durch Trimethylolacetaldehyd erzielbaren Ergebnisse bei der Gerbung von Häuten, Fellen und Pelzfellen, allein oder in Kombination mit anderen Gerbstoffen, durch die Verwendung der erfindungsgemäßen Gerbstoffe weiter verbessern lassen.It has now been found that the results which can be achieved by trimethylol acetaldehyde in the tanning of hides, skins and fur skins, alone or in combination with other tanning agents, can be further improved by using the tanning agents according to the invention.
Der erfindungsgemäße Gerbstoff wird durch Umsetzung von Acetaldehyd, Formaldehyd und einer Formylamino-Verbindung, insbesondere im Molverhältnis Acetaldehyd : Formaldehyd : Formylamino-Verbindung = 1 : (0,4 bis 4) : (0,1-3), vorzugsweise 1 : (0, 5 bis 3,1): (0,2 bis 2,2), ganz besonders bevorzugt 1 : (0,5 bis 3) : (0,2 bis 2), erhalten. Die Umsetzung wird vorzugsweise alkalisch katalysiert.The tanning agent according to the invention is obtained by reacting acetaldehyde, formaldehyde and a formylamino compound, in particular in a molar ratio of acetaldehyde: formaldehyde: formylamino compound = 1: (0.4 to 4): (0.1-3), preferably 1: (0 , 5 to 3.1): (0.2 to 2.2), very particularly preferably 1: (0.5 to 3): (0.2 to 2). The reaction is preferably catalyzed under alkaline conditions.
Die Formylamino-Verbindung kann eine, zwei oder mehrere Formylamino-Gruppen der Formel 1
Die für R stehenden Alkyl- und Alkenyl-Reste können geradkettig oder verzweigt sein. Bei den für R stehenden Alkylresten sind (C1-C6)Alkylreste und bei den für R stehenden Alkenylresten sind (C2-C6)Alkenylreste bevorzugt. Bei den für R stehenden Alkenylresten ist der Vinylrest besonders bevorzugt.The alkyl and alkenyl radicals which stand for R can be straight-chain or branched. In the case of the alkyl radicals which are R, (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.
Die Zahl m bedeutet insbesondere 0 oder 1, und die Zahl n bedeutet insbesondere 1.The number m in particular denotes 0 or 1, and the number n in particular denotes 1.
Geeignete Formylamino-Verbindungen können auch 3 oder mehr Formylamino-Gruppen der Formel 1 im Molekül enthalten. Formylamino-Verbindungen der genannten Art sind bekannt oder können nach den für die Herstellung von Formylamino-Verbindungen bekannten Verfahren synthetisiert werden. Beispiele für geeignete Formylamino-Verbindungen sind: Formamid; Methyl-, Ethyl-, Propyl-, i-Propyl-, Butyl-, i-Butyl-, sec.-Butyl-, Pentyl- oder i-Pentyl-formamid; Vinyl-, Allyl-, Methallyl-, Crotyl-formamid; N-Hydroxymethyl-N-methyl-, -ethyl-, -propyl-formamid; N,N'-Bis-formyl-hydrazin; Methylen-bis-formamid; Methylen-bis-(N-hydroxymethyl-formamid); Ethylen-bis-formamid; Trimethylen-bis-formamid; Tetramethylen-bis-formamid; Methylen-bis-(O-form-hydroxamsäure) [(H-CO-NH-O)2CH2], Ethylen-bis-(O-formhydroxamsäure) (H-CO-NH-O-CH2CH2-O-NH--CO-H).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. Examples of 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-CO-NH-O) 2 CH 2 ], ethylene bis (O-form hydroxamic acid) (H-CO-NH-O-CH 2 CH 2 -O -NH - CO-H).
Als Ausgangsprodukt für die Herstellung des erfindungsgemäßen Gerbstoffs geeignete Formylamino-Verbindungen sind darüber hinaus auch Homo- oder Copolymerisate, die im Polymerisat Bausteine der Formel III
Bei der Herstellung der erfindungsgemäßen Gerbstoffe kann neben Acetaldehyd und Formaldehyd eine Formylamino-Verbindung oder ein Gemisch verschiedener Formylamino-Verbindungen eingesetzt werden. Die Umsetzung wird in der Regel in wäßriger Phase, vorzugsweise alkalisch katalysiert, durchgeführt. Für die alkalische Katalysierung wird ein Alkalisierungsmittel zugegeben. Als Alkalisierungsmittel sind z.B. Alkalihydroxide, wie z.B. Natrium-, Kalium-oder Lithiumhydroxid, alkalisch reagierende Salze, wie z.B. Alkalicarbonate, wie z.B. Natrium-, Kalium-oder Lithiumcarbonat, oder tertiäre Stickstoffbasen, wie z.B. Pyridin, geeignet. In der Regel wird als Alkalisierungsmittel Natriumcarbonat verwendet. Pro mol Acetaldehyd kommen normalerweise 0,008 bis 0,3 mol, vorzugsweise 0,01 bis 0,2 mol, des Alkalisierungsmittels zum Einsatz.In addition to acetaldehyde and formaldehyde, 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. As 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. As a rule, sodium carbonate is used as the alkalizing agent. Usually 0.008 to 0.3 mol, preferably 0.01 to 0.2 mol, of the alkalizing agent are used per mol of acetaldehyde.
Die Reaktion kann absatzweise oder kontinuierlich durchgeführt werden und verläuft stark exotherm. Bei einer absatzweisen Durchführung der Reaktion ist es empfehlenswert, einen oder zwei Reaktionspartner in der wäßrigen Phase unter Kühlung (z.B. auf +10°C) vorzulegen und die restliche Reaktionskomponente oder die restlichen Reaktionskomponenten und das Alkalisierungsmittel zuzugeben, worauf die Reaktion sofort unter Temperatursteigerung einsetzt. Bei der absatzweisen Durchführung der Reaktion ist es normalerweise auch empfehlenswert, die Gesamtmenge der Reaktionspartner nicht auf einmal zur Reaktion zu bringen, sondern in zwei oder mehr Teilmengen aufzuteilen und die restlichen Teilmengen erst nach Abklingen der Reaktion zuzusetzen. Die Reaktionstemperaturen liegen im allgemeinen zwischen 0 und 140°C, vorzugsweise 5 und 130°C. Bei der absatzweisen Durchführung der Reaktion wird die erste Reaktionsphase häufig unter Kühlung bei Reaktionstemperaturen bis ca. 60 bis 70°C durchgeführt, und nach Abklingen der Temperaturentwicklung wird die Reaktion bei erhöhter Temperatur von z.B. 60°C oder mehr zu Ende geführt.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. When the reaction is carried out batchwise, 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.
Die Durchführung der Reaktion bei Temperaturen, die über dem Siedepunkt des Reaktionsgemisches bei Normaldrück liegen, erfolgt in einem Druckreaktor bei dem sich einstellenden Überdruck von z.B. 4 bis 6 bar. Die Durchführung der Reaktion bei Temperaturen über 100°C, z.B. 100 bis 140°C, insbesondere 100 bis 130°C, ermöglicht kurze Reaktionszeiten, wodurch die thermische Belastung der hergestellten Produkte erheblich herabgesetzt werden kann. Dies gilt insbesondere auch bei einer kontinuierlichen Durchführung der Reaktion, die bevorzugt ist. Formaldehyd wird in der Regel in Form der handelsüblichen wäßrigen Lösungen, z.B. 39% wäßrigen Lösungen, eingesetzt.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.
Die nach der Beendigung der Umsetzung erhaltene Lösung, die normalerweise einen Wirkstoffgehalt von ca. 30 bis ca. 70 Gew.-% besitzt, wird zweckmäßigerweise filtriert und mit einem Alkalisierungsmittel, z.B. der bereits genannten Art, auf einen neutralen oder annähernd neutralen pH-Wert eingestellt. Die so erhaltenen flüssigen Produkte sind klar oder annähernd klar und besitzen eine schwach gelbliche bis bräunliche Farbe. Sie sind unter normalen Bedingungen mindestens zwei Jahre haltbar und beliebig mit Wasserverdünnbar. Sie erstarren bei Temperaturen unter ca. -10°C, sind jedoch nach vorsichtigem Auftauen wieder voll verwendbar.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. 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.
Die erfindungsgemäßen Produkte, von denen angenommen werden kann, daß sie ein Gemisch verschiedener Umsetzungsprodukte enthalten, sind als solche oder in Form ihrer wäßrigen Lösungen hervorragend als Gerbstoffe für Häute, Felle und Pelzfelle geeignet, und zwar allein oder in Kombination mit mineralischen, pflanzlichen oder anderen synthetischen Gerbstoffen. Sie sind auch mit Farbstoffen und fettungsmitteln in den verschiedenen Stadien der Leder- und Pelzfellherstellung ausgezeichnet verträglich. Im vergleich zu der Verwendung von Trimethylolacetaldehyd wird die Elastizität, Fülle und Weichheit deutlich verbessert. Außerdem wird die Schrumpfungstemperatur erhöht und die Narbenfestigkeit verbessert. Bei der Lederfärbung können ungenügende Durchfärbungen mit Hilfe der erfindungsgemäßen Produkte beseitigt werden. Bei der Lederfettung wird durch Zugabe der erfindungsgemäßen Produkte die weichmachende Wirkung der Fettungsmittel erhöht und die Gefahr der Losnarbigkeit vermindert. Da die erfindungsgemäßen Produkte die Zügigkeit und Weichheit der Leder günstig beeinflussen, sind sie besonders für die Herstellung von weißen Handschuhledern und Nappabekleidungsledern geeignet. Die erfindungsgemäßen Produkte sind im pH-Bereich von 2 bis 9 gerbwirksam.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. In leather greasing, 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.
In den nachfolgenden Beispielen sind Temperaturen in °C und prozente, soweit nichts anderes erwähnt ist, als Gewichtsprozente angegeben.In the following examples, temperatures in ° C. and percentages, unless stated otherwise, are given as percentages by weight.
Die Beispiele 1 bis 16 betreffen die Herstellung erfindungsgemäßer Produkte nach dem erfindungsgemäßen Verfahren, und die Beispiele 17 bis 23 betreffen die Anwendung der erfindungsgemäßen Produkte in der Gerberei. Bei dem in den Beispielen 1 bis 4 erwähnten Formaldehyd, 39%ig, handelt es sich um eine handelsübliche wäßrige Lösung mit einem Formaldehydgehalt von 39%.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%.
Herstellung eines Umsetzungsprodukts aus Acetaldehyd, Formaldehyd und Formamid im Molverhältnis 1 : 2,68 : 0,46.Preparation of a reaction product from acetaldehyde, formaldehyde and formamide in a molar ratio of 1: 2.68: 0.46.
In einem 1-I-Reaktionskolben, der mit Rührer. Thermometer und Rückflußkühler ausgerüstet ist, werden unter Rühren 50 g Trinkwasser, 440 g Formaldehyd, 39%ig, und 58,5 g Formamid vorgelegt und mittels eines Kühlbades auf 10°C abgekühlt. Nacheinander werden dann in jeweils einer Portion 125 g Acetaldehyd sowie eine Lösung aus 1,1 g Soda in 16 g Trinkwasser zugegeben.In a 1 liter reaction flask equipped with a stirrer. Equipped thermometer and reflux condenser, 50 g of drinking water, 440 g of formaldehyde, 39%, and 58.5 g of formamide are introduced with stirring and cooled to 10 ° C. by means of a cooling bath. 125 g of acetaldehyde and a solution of 1.1 g of soda in 16 g of drinking water are then added in succession in one portion.
Die Reaktion setzt sofort ein, wobei die Temperatur im Verlauf von 10 min bis auf ca. 60°C ansteigt. Wenn die Temperatur von allein abfällt, wird die Lösung auf 30°C heruntergekühlt. In einer Portion werden dann nochmals 145 g Formaldehyd, 39%ig, und 6,5 g Soda zugegeben. Im Verlauf von ca. 20 min steigt die Temperatur dann wieder bis auf ca. 40°C an. Wenn die Temperatur wieder abfällt, wird die Lösung angeheizt und je 1 h bei 60°C, 70°C und 80°C nachgerührt, dann auf Raumtemperatur abgekühlt und mit Soda auf einem pH 7,0 ± 0,5 eingestellt. Es wird abfiltriert. Man erhält eine nahezu klare, gelblich gefärbte Lösung.The reaction starts immediately, the temperature rising to about 60 ° C. in the course of 10 minutes. When the temperature drops by itself, 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. When the temperature drops again, 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.
Herstellung eines Umsetzungsprodukts aus Acetaldehyd, Formaldehyd und Bis-formyl-hydrazin im Molverhältnis 1 : 3 : 0,1.Preparation of a reaction product from acetaldehyde, formaldehyde and bis-formyl hydrazine in a molar ratio of 1: 3: 0.1.
In einem Druckreaktor werden bei Raumtemperatur unter Rühren über eine Druckbürette nacheinander zugegeben: 655 g Formaldehyd, 39%ig, 25 g Bis-formyl-hydrazin, 125 g Acetaldehyd und 80 g 10%ige wäßrige Sodalösung.In a pressure reactor at room temperature with stirring using a pressure burette are added in succession: 655 g of formaldehyde, 39%, 25 g of bis-formyl hydrazine, 125 g of acetaldehyde and 80 g of 10% aqueous sodium carbonate solution.
Die Reaktion setzt sofort ein, und die Temperatur steigt in wenigen Minuten bis auf ca. 55 bis 60°C an, wobei sich ein Druck von 0,9 bis 1,1 bar aufbaut. Die Lösung wird nun auf 105 bis 110°C angeheizt, wobei sich ein Druck von 4,5 bis 5 bar einstellt, und 5 bis 10 min bei dieser Temperatur gehalten. Dann wird dieser auf Raumtemperatur abgekühlt. Nach der Filtration erhält man eine nahezu klare, gelblich braun gefärbte, gebrauchsfertige Lösung, die gegebenenfalls mit Soda auf einen pH von 7,0 ± 0,5 nachgestellt wird.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.
Herstellung eines Umsetzungsprodukts aus Acetaldehyd, Formaldehyd und Formamid im Molverhältnis 1 : 1 : 2.Preparation of a reaction product from acetaldehyde, formaldehyde and formamide in a molar ratio of 1: 1: 2.
Von Dosierpumpen werden kontinuierlich 1 mol Acetaldehyd, 1 mol Formaldehyd, 39%ig, und 2 mol Formamid und kleine Mengen 10%iger wäßriger Sodalösung von unten in ein mit Rührer ausgestattetes Druckgefäß eingespeist, wobei Acetaldehyd, Formaldehyd und Formamid im Zuleitungssystem vorgemischt werden. Die Reaktionstemperatur im Druckgefäß beträgt 110 bis 115°C bei einem Druck von 4 bar. Nach einer mittleren Verweilzeit von 5,5 min wird das Reaktionsgemisch im oberen Teil des Druckreaktors entnommen, in einem Kühlrohr auf Raumtemperatur abgekühlt und über eine Filterpatrone abfiltriert. Man erhält eine klare, nahezu farblose, gebrauchsfertige Lösung, die gegebenenfalls mit Soda auf einen pH von 7,0 ± 0,5 nachgestellt wird.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. After an average residence time of 5.5 min, 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.
Herstellung eines Umsetzungsprodukts aus Acetaldehyd, Formaldehyd und Formamid im Molverhältnis 1 : 0,5 : 2.Preparation of a reaction product from acetaldehyde, formaldehyde and formamide in a molar ratio of 1: 0.5: 2.
In einem 1-I-Reaktionskolben, ausgerüstet mit Rührer, Thermometer und Rückflußkühler werden unter Rühren 50 g Trinkwasser, 109 g Formaldehyd, 39%ig, und 255 g Formamid vorgelegt und mittels eines Kühlbades auf 10°C abgekühlt. Dann werden 125 g Acetaldehyd auf einmal zugegeben und im Verlauf von 5 bis 10 min 40 g einer 10%igen wäßrigen Sodalösung zugetropft. Schon unmittelbar nach der Acetaldehyd-Zugabe steigt die Temperatur bis auf ca. 25°C an, nach der Soda-Zugabe wird eine Temperatur von 35 bis 40°C erreicht. Nach dem Abfallen der Innentemperatur wird langsam auf 70°C angeheizt und 1 h bei 70°C sowie anschließend 2 h bei 80°C nachgerührt, dann auf Raumtemperatur abgekühlt und mit Soda auf einen pH von 7,0 ± 0,5 eingestellt. Man erhält eine nahezu klare, gelblich braun gefärbte Lösung.In a 1 liter reaction flask equipped with a stirrer, thermometer and reflux condenser, 50 g of drinking water, 109 g of formaldehyde, 39% strength and 255 g of formamide are introduced with stirring and cooled to 10 ° C. by means of a cooling bath. Then 125 g of acetaldehyde are added all at once and 40 g of a 10% strength aqueous sodium carbonate solution are added dropwise in the course of 5 to 10 minutes. The temperature rises to approx. 25 ° C immediately after the addition of acetaldehyde, and a temperature of 35 to 40 ° C is reached after the addition of soda. After the internal temperature has dropped, the mixture is slowly heated to 70 ° C. and stirred for 1 hour at 70 ° C. and then for 2 hours at 80 ° C., then cooled to room temperature and adjusted to a pH of 7.0 ± 0.5 with soda. An almost clear, yellowish brown colored solution is obtained.
Analog zu den beispielen 1 bis 4 werden weitere erfindungsgemäße Produkte hergestellt. Die Molverhältnisse und die Struktur der Formylamino-Verbindung sind in der Tabelle 1 angegeben.
In üblicher Weise für die Gerbung vorbereitete und gepickelte Schafblößen werden mit (% bezogen auf das Pickelgewicht) 100% Wasser von 23°C, 3% Salz, 4% des nach Beispiel 3 hergestellten Reaktionsprodukts 60 min gewalkt. Dann werden durch Zugabe von Natriumbicarbonat in zwei bis drei Raten Flotte und Blößen im Verlauf von 2 Stunden auf einen pH-Wert von 6 bis 6,5 gebracht. Dem gleichen Bad werden anschließend 3 bis 4% eines kationisch emulgierten Fettlickers mit 80 bis 85% Reinfettgehalt, dem noch 0,3 bis 0,5% eines Neutralfettes (Spermöl oder Klauenöl) beigemischt sein können, zugesetzt und noch weitere 2 h gewalkt. Die Leder kommen über Nacht auf den Bock, werden dann kurz gespült und bei Raumtemperatur von 25 ° C getrocknet.Pickled sheep pelts prepared and tipped in the usual way for the tanning are drummed with (% based on the pimple weight) 100% water of 23 ° C., 3% salt, 4% of the reaction product prepared according to Example 3 for 60 min. Then, by adding sodium bicarbonate in two to three installments, the liquor and brine are brought to a pH of 6 to 6.5 in the course of 2 hours. Then 3 to 4% of a cationically emulsified fat licker with 80 to 85% pure fat content, to which 0.3 to 0.5% of a neutral fat (sperm oil or claw oil) can be added, are added to the same bath and drummed for a further 2 hours. The leathers are put on the jack overnight, then rinsed briefly and dried at room temperature of 25 ° C.
Nach dem Einspänen und Stollen wird ein weißes Leder erhalten, das in Fülle und Griff einem in gleicher Weise, aber mit Trimethylolacetaldehyd gegerbten Leder deutlich überlegen ist.After chipping and tunneling, it turns white Obtain leather that is far superior to leather tanned in the same way but with trimethylol acetaldehyde.
In üblicher Weise vorbereitete gepickelte Blößen (Schaf, Ziege oder Pekari) mit einem pH-Wert von 1, bis 3,5 werden mit (% bezogen auf das Pickelblö- ßengewicht) 150% Wasser, 3 bis 5% Salz (je nach pH-Wert der Pickelblößen) 10 Minuten gewalkt. Dann werden dem Bad 4% des Reaktionsproduktes von Beispiel 3 zugesetzt und 30 Minuten gewalkt. Dann werden dem Bad 2% Chromalaun (0/12 bas.) oder Chromacetat zugesetzt und 30 Minuten gewalkt. Dann werden dem Bad 3% eines basischen Aluminiumsalzes als Pulver zugesetzt und 30 Minuten gewalkt. Nach Zusatz von 1 % eines anionischen Fettungsmittels mit ca. 70% Fettgehalt wird nochmals 30 Minuten gewalkt, dann wird mit 2 bis 3% Natriumbicarbonat in 3 bis 4 Raten im Verlauf von 120 Minuten ein pH-Wert von 4 bis 4,5 eingestellt und anschließend im gleichen Bad mit 5% eines anionisch emulgierten Lickeröls (80 bis 85% Reinfettgehalt), dem noch 1 % Spermöl zugemischt wird, gefettet. Die Leder kommen dann über Nacht auf den Bock, werden dann gespült und in üblicher Weise fertiggestellt.Pickled pelts (sheep, goat or peccary) with a pH value of 1 to 3.5 prepared in the usual way are treated with (% based on the pimple block weight) 150% water, 3 to 5% salt (depending on the pH Value of pimple bare feet) tumbled for 10 minutes. Then 4% of the reaction product from Example 3 are added to the bath and drummed for 30 minutes. Then 2% chromium alum (0/12 bas.) Or chromium acetate are added to the bath and drummed for 30 minutes. Then 3% of a basic aluminum salt is added to the bath as a powder and drummed for 30 minutes. After adding 1% of an anionic fatliquor with a fat content of approx. 70%, the drum is drummed again for 30 minutes, then a pH of 4 to 4.5 is set with 2 to 3% sodium bicarbonate in 3 to 4 installments over the course of 120 minutes then greased in the same bath with 5% of an anionically emulsified licker oil (80 to 85% pure fat content), to which 1% sperm oil is added. The leathers are put on the trestle overnight, then rinsed and finished in the usual way.
Es werden weiße, sehr weiche Handschuhleder mit guter Fülle und Zügigkeit erhalten.White, very soft glove leather with good fullness and speed is obtained.
In üblicher Weise vorbereitete gepickelte Blößen (Schaf, Ziege oder Pekari) mit einem pH-Wert von 1, bis 3, werden mit (% bezogen auf das Pickelblö- ßengewicht) 150% Wasser, 3 bis 5% Salz (je nach pH-Wert der Pickelblößen) 10 Minuten gewalkt. Dann werden dem Bad 4% des Reaktionsproduktes von Beispiel 3 zugesetzt und 30 Minuten gewalkt. Dann werden dem Bad 4% eines basischen Aluminiumsalzes zugesetzt und weitere 60 Minuten gewalkt. Dann wird der pH-Wert des Bades im Verlaufe von 120 Minuten durch Zugabe von 2 bis 3% Natriumacetat in 2 bis 4 Raten abgestumpft und gegebenenfalls durch Zugabe von 0,2 bis 0,5% Natriumbicarbonat auf einen pH-Wert von 4,3 bis 4,4 eingestellt. Anschließend wird 90 Minuten mit 3 bis 4% eines anionisch emulgierten Lickeröls (ca. 80% Reinfettgehalt) gefettet. Die Leder kommen dann über Nacht auf den Bock, werden dann gespült und in üblicher Weise fertiggestellt.Pickled pelts (sheep, goat or peccary) with a pH value of 1 to 3 prepared in the usual way are mixed with (% based on the pimple block weight) 150% water, 3 to 5% salt (depending on the pH value of the pimples) tumbled for 10 minutes. Then 4% of the reaction product from Example 3 are added to the bath and drummed for 30 minutes. Then 4% of a basic aluminum salt are added to the bath and drummed for a further 60 minutes. Then the pH of the bath is blunted in 2 to 4 installments over the course of 120 minutes by adding 2 to 3% sodium acetate and, if appropriate, by adding 0.2 to 0.5% sodium bicarbonate to a pH of 4.3 set to 4.4. Then it is greased for 90 minutes with 3 to 4% of an anionically emulsified licker oil (approx. 80% pure fat content). The leathers are put on the trestle overnight, then rinsed and finished in the usual way.
Es werden weiße Handschuhleder mit guter Weichheit, Fülle und Zügigkeit erhalten.White glove leather with good softness, fullness and speed is obtained.
Die in üblicher Weise gut aufgewalkten semichromgaren oder rein chromgaren Leder läßt man mit 1,5 bis 2% (bezogen auf Trockengewicht) eines erfindungsgemäßen Produktes (z.B. gemäß Beispiel 3) 15 5 Minuten vorlaufen und färbt dann im gleichen Bad in üblicher Weise. Man erhält gleichmäßige und tiefe Durchfärbungen.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.
Gut geweichte Pelzfelle, wie z.B. Zickel, Bisam, Nerze oder dergl. werden nach dem Pickeln und eventuellem Dünnschneiden wie folgt gegerbt: 800% Flotte 28 bis 30°C, 2 g/Liter Flotte eines erfindungsgemäßen Produktes (z.B. gemäß Beispiel 3) in 2 Anteilen mit 20 Minuten Abstand, 2 Stunden.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.
Zusatz: 2 g/Liter Flotte Kalialaun, 1 g/Liter Chromalaun oder Chromacetat, 8 bis 10 Stunden Laufzeit. Anschließend wird die Flotte mit Natriumacetat im Laufe von 2 stunden auf pH 4,0 bis 4, eingestellt und im gleichen Bad oder nach dem Abtropfen bzw. Zentrifugieren der Felle durch Streichfettung in üblicher Weise gefettet.Addition: 2 g / liter of potash alum, 1 g / liter of chrome alum or chrome acetate, 8 to 10 hours running time. The liquor is then adjusted to pH 4.0 to 4 over the course of 2 hours and greased in the same bath or after draining or centrifuging the skins in a conventional manner by spreading.
Das Fell ist sehr weich, und die Haare haben einen hervorragenden Glanz und Stand.The fur is very soft and the hair has an excellent shine and stand.
Bei der Wiederholung der Beispiele 17 und 18 mit Umsetzungsprodukten der Beispiele 1, 2, 4 bis 16 werden ähnlich gute Ergebnisse erhalten.When Examples 17 and 18 are repeated with reaction products from Examples 1, 2, 4 to 16, similarly good results are obtained.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86115504T ATE46190T1 (en) | 1985-11-13 | 1986-11-08 | TANNING AND PROCESS FOR ITS PRODUCTION. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3540211 | 1985-11-13 | ||
| DE19853540211 DE3540211A1 (en) | 1985-11-13 | 1985-11-13 | TANNEL AND METHOD FOR THE PRODUCTION THEREOF |
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| Publication Number | Publication Date |
|---|---|
| EP0225491A2 EP0225491A2 (en) | 1987-06-16 |
| EP0225491A3 EP0225491A3 (en) | 1987-11-11 |
| EP0225491B1 true EP0225491B1 (en) | 1989-09-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP86115504A Expired EP0225491B1 (en) | 1985-11-13 | 1986-11-08 | Tanning agent and method for its manufacture |
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| Country | Link |
|---|---|
| US (1) | US4828570A (en) |
| EP (1) | EP0225491B1 (en) |
| JP (1) | JPS62115100A (en) |
| AT (1) | ATE46190T1 (en) |
| BR (1) | BR8605597A (en) |
| DE (2) | DE3540211A1 (en) |
| ES (1) | ES2010502B3 (en) |
| PT (1) | PT83727B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020109962A1 (en) | 2018-11-28 | 2020-06-04 | Sasib S.P.A. | Method for supporting the configuration changeover of an operating area of a machine for packaging products in general |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3030863B2 (en) * | 1990-12-25 | 2000-04-10 | ダイキン工業株式会社 | Leather modifying agent, leather modifying method and modified tanned leather |
| DE4102545A1 (en) * | 1991-01-29 | 1992-07-30 | Basf Ag | METHOD FOR GELING, PRELIMINATING AND GIVING BARE AND FUR BLOSSES AND FOR LEAVING LEATHER AND FUR |
| 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 (en) * | 1998-04-09 | 1999-10-14 | Basf Ag | Polymeric tanning agents containing N-vinyl units |
| EP2062985A1 (en) * | 2007-11-23 | 2009-05-27 | N-Zyme BioTec GmbH | Method and device for tanning hides and pelts |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE918779C (en) * | 1942-01-18 | 1954-10-04 | Roehm & Haas G M B H | Process for the production of coloring agents for dyes and tannins with acidic groups |
| 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 |
-
1985
- 1985-11-12 BR BR8605597A patent/BR8605597A/en unknown
- 1985-11-13 DE DE19853540211 patent/DE3540211A1/en not_active Withdrawn
-
1986
- 1986-10-09 US US06/917,600 patent/US4828570A/en not_active Expired - Fee Related
- 1986-11-08 AT AT86115504T patent/ATE46190T1/en not_active IP Right Cessation
- 1986-11-08 DE DE8686115504T patent/DE3665483D1/en not_active Expired
- 1986-11-08 EP EP86115504A patent/EP0225491B1/en not_active Expired
- 1986-11-08 ES ES86115504T patent/ES2010502B3/en not_active Expired
- 1986-11-12 PT PT83727A patent/PT83727B/en unknown
- 1986-11-12 JP JP61267879A patent/JPS62115100A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020109962A1 (en) | 2018-11-28 | 2020-06-04 | Sasib S.P.A. | Method for supporting the configuration changeover of an operating area of a machine for packaging products in general |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8605597A (en) | 1987-08-18 |
| DE3540211A1 (en) | 1987-05-14 |
| EP0225491A3 (en) | 1987-11-11 |
| ES2010502B3 (en) | 1989-11-16 |
| EP0225491A2 (en) | 1987-06-16 |
| PT83727B (en) | 1988-02-08 |
| PT83727A (en) | 1986-12-01 |
| DE3665483D1 (en) | 1989-10-12 |
| US4828570A (en) | 1989-05-09 |
| ATE46190T1 (en) | 1989-09-15 |
| JPS62115100A (en) | 1987-05-26 |
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