EP0000157B1 - Process for the manufacture of highly concentrated aqueous solutions of salts of dicarboxylic acids with diamines and/of polyamide precondensates and their use - Google Patents
Process for the manufacture of highly concentrated aqueous solutions of salts of dicarboxylic acids with diamines and/of polyamide precondensates and their use Download PDFInfo
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- EP0000157B1 EP0000157B1 EP78100175A EP78100175A EP0000157B1 EP 0000157 B1 EP0000157 B1 EP 0000157B1 EP 78100175 A EP78100175 A EP 78100175A EP 78100175 A EP78100175 A EP 78100175A EP 0000157 B1 EP0000157 B1 EP 0000157B1
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- dicarboxylic acid
- diamine
- salt
- diamines
- aqueous solution
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Definitions
- the invention relates to a process for the preparation of 70 to 90% by weight aqueous solutions of salts from dicarboxylic acids and diamines and polyamide precondensates by reacting alkanedicarboxylic acids with 6 to 12 carbon atoms and alkanediamines with 6 to 12 carbon atoms in water.
- the technical task was to provide starting solutions for the production of polyamides from dicarboxylic acids and diamines that are easy to handle and contain as little water as possible and that the thermal energy contained in the starting solutions can be used.
- This object is achieved in a process for the preparation of 70 to 90% by weight aqueous solutions of salts from dicarboxylic acids and diamines and polyamide precondensates by reacting alkanedicarboxylic acids with 6 to 12 carbon atoms and alkanediamines with 6 to 12 carbon atoms in water, characterized in that 40 to 65% by weight aqueous salt solutions of dicarboxylic acids and diamines from 60 to 110 ° C., which contain a corresponding amount of the respective dicarboxylic acid in excess, with the respective molten diamine in equivalent amounts based on dissolved dicarboxylic acid in a manner known per se implemented, with the proviso that the reaction is carried out under increased pressure and a final temperature of 160 to 200 ° C is maintained during the reaction.
- the new process has the advantage that it immediately leads to highly concentrated aqueous starting solutions for polyamide production, which no longer need to be concentrated.
- the new process also has the advantage that starting solutions are obtained in which the heat of neutralization contained is used for the polycondensation.
- the new process has the advantage that the starting materials can be metered and mixed easily.
- alkane dicarboxylic acids with 6 to 12 carbon atoms are used.
- Straight-chain a-w dicarboxylic acids of the stated carbon number are preferably used.
- Suitable dicarboxylic acids are, for example, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid and dodecanedioic acid. Adipic acid and sebacic acid have acquired particular technical importance.
- alkane diamines with 6 to 12 carbon atoms are used.
- Straight-chain a-w-alkanediamines having 6 to 12 carbon atoms are particularly preferably used.
- Suitable diamines are, for example, hexamethylene diamine. Octamethylene diamine, decamethylene diamine or dodecamethylene diamine.
- the starting point is an aqueous salt solution of dicarboxylic acids and diamines of 40 to 65 percent by weight, which contains a corresponding amount of the respective dicarbon contains acid dissolved in excess. Solutions which contain 50 to 65 percent by weight of the respective salts, based on the sum of salt and water, are advantageously used. The amount of dissolved dicarboxylic acid depends on the desired final concentration of the highly concentrated aqueous solutions to be prepared.
- solid dicarboxylic acid is dissolved in a salt solution of lower concentration. Temperatures of 60 to 110 ° C are observed. Salt solution thus obtained containing free dicarboxylic acid is then reacted with molten diamine in equivalent amounts based on the dissolved dicarboxylic acid. It is advantageous to ensure that the pH value for the equivalence point of the salt to be produced is observed.
- the equivalence point for hexamethylene diammonium adipate is pH 7.62 and for hexamethylene diammonium sebacate pH 7.5 measured in 10 percent aqueous solution at 25 ° C.
- the reaction is advantageously carried out in a mixing section, first adding a small deficit of molten diamine and then carrying out the precise adjustment by adding molten diamine again.
- diamines are generally used in excess, e.g. 1.5 mole percent.
- Solve according to another preferred embodiment first solid dicarboxylic acid in an aqueous solution of diamine in deficit. This gives a salt solution of dicarboxylic acid and diamine, which contains an excess amount of dicarboxylic acid in solution. It is understood that the proportions are chosen so that a salt solution of the aforementioned concentration is obtained and the excess amount of dicarboxylic acid corresponds to the desired final concentration of the aqueous solution.
- the diearbonic acid is dissolved at temperatures of 60 to 110 ° C, usually keeping atmospheric pressure.
- the salt solution thus obtained containing free dicarboxylic acid is then reacted with molten diamine in equivalent amounts based on the dissolved dicarboxylic acid. This implementation is advantageously carried out as described in the aforementioned procedure.
- reaction of the dissolved dicarboxylic acid with molten diamine is carried out under increased pressure. Pressures of 2 to 15 bar are advantageously obtained. A corresponding pressure arises automatically due to the autogenous pressure and can be increased by adding a small amount of nitrogen to prevent the solution from boiling. It is also an essential feature of the invention that a final temperature of 160 to 200 ° C is maintained during neutralization.
- Aqueous solutions thus obtained contain salts of dicarboxylic acids and diamines. Due to the beginning of polycondensation, they can also contain polyamide precondensates. The conversion of the amino and carboxyl groups can be up to 50% e.g. 20 to 45%.
- the aqueous solutions produced have a content of 70 to 90 percent by weight, in particular 80 to 90 percent by weight, of salts from dicarboxylic acids and diamines and polyamide precondensates.
- Highly concentrated aqueous solutions of salts and polyamide precondensates prepared according to the invention, which are derived from dicarboxylic acids and diamines, are outstandingly suitable for the production of polyamides by condensation.
- the condensation can be carried out batchwise or continuously. Suitable condensation processes are described, for example, in DT-AS 14 95 087, GB-PS 1 159 151, GB-PS 674 954 or DT-PS 1 060 139 and DT-OS 24 17 003. It is particularly advantageous to use the aqueous solution according to the invention Use solutions for condensation without first removing the heat of neutralization. In this context, heat losses caused by the device are irrelevant.
- Polyamides which are produced from the solutions according to the invention are suitable for the production of masses shaped from the melt, such as threads, fibers, moldings, plates or coatings.
- AH salt hexamethylene diammonium adipate
- AH salt hexamethylene diammonium adipate
- 8025 g of solid adipic acid were gradually added with stirring at 90 to 95 ° C. and dissolved.
- the autoclave was flushed with nitrogen and sealed.
- the contents were heated to 100 ° C, which resulted in a pressure of 2 bar (all pressure values are absolute values).
- 6375 g of molten hexamethylenediamine at 100 ° C. were pressed into the autoclave from a feed vessel with nitrogen pressure within 2 minutes with the stirrer running.
- the example shows the use of part of the heat of neutralization to dissolve the dicarboxylic acid.
- the flask was immersed in a water bath at 75 ° C acting as a protective heater; immediately thereafter, a solution of 75 g of hexamethylenediamine in 92 g of water, kept in the dropping funnel at 90 ° C., was added with stirring within 20 seconds. After 2 minutes a clear solution had formed, the temperature of which was 69 ° C.
- the composition of the solution was 37% AH salt, 43% adipic acid and 20% water.
- the further implementation was carried out analogously to Example 1.
- the AH salt solution obtained in Example 1 was polycondensed without cooling the solution. It was heated to 275 ° C. in the course of 3 1/2 hours, the pressure being kept at 19 bar by blowing off steam. After reaching 275 ° C., the pressure was released to atmospheric pressure within 1 hour and the condensation was continued to 275 ° C. for 1 hour. The product was pressed out of the autoclave under nitrogen pressure, the melt strand being cooled in a water bath and granulated.
- the polyamide 66 obtained had a relative viscosity of 2.54, measured in 1 percent solution in 96 percent sulfuric acid, and a content of acidic groups of 54 meq / kg and of basic groups of 76 meq / kg.
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Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von 70 bis 90 gew.%igen, wäßrigen Lösungen von Salzen aus Dicarbonsäuren und Diaminen sowie Polyamidpräkondensaten durch Umsetzen von Alkandicarbonsäuren mit 6 bis 12 Kohlenstoffatomen und Alkandiaminen mit 6 bis 12 Kohlenstoffatomen in Wasser.The invention relates to a process for the preparation of 70 to 90% by weight aqueous solutions of salts from dicarboxylic acids and diamines and polyamide precondensates by reacting alkanedicarboxylic acids with 6 to 12 carbon atoms and alkanediamines with 6 to 12 carbon atoms in water.
Bei der in der Technik wohl bekannten Herstellung von Pölyamiden aus Dicarbonsäuren und Diaminen geht man in der Regel von wäßrigen Salzlösungen aus Dicarbonsäuren und Diaminen aus. Wie aus der GB-PS 674 954, der DT-PS 1 060 139 und der DT-AS 11 58257 bekannt ist, geht man hierbei im allgemeinen von 45 bis 70 gewichtsprozentigen Salzlösungen aus. Vor der eigentlichen Polykondensation ist es jedoch erforderlich, aus den Salzlösungen das überschüssige Wasser zum großen Teil zu entfernen. Dies hat den Nachteil, daß man große Flüssigkeitsmengen bewegen muß und darüber hinaus erhebliche Mengen an Energie verbraucht, um das Wasser zu entfernen.The production of polyamides from dicarboxylic acids and diamines, which is well known in the art, is generally based on aqueous salt solutions of dicarboxylic acids and diamines. As is known from GB-PS 674 954, DT-PS 1 060 139 and DT-AS 11 58257, generally from 45 to 70 percent by weight salt solutions are used. Before the actual polycondensation, however, it is necessary to remove a large part of the excess water from the salt solutions. This has the disadvantage that large amounts of liquid have to be moved and, moreover, considerable amounts of energy are used to remove the water.
Entsprechend dem Verfahren nach der US-PS 3 402 152 werden wäßrige Lösungen von Salzen aus Dicarbonsäuren und Diaminen von z.B. 25 bis 55 Gew.% unter erhöhtem Druck bei 130° bis 165°C in einem Verdampfer auf einen Gehalt bis zu ca. 75 Gew.% gebracht. Hierbei treten immer noch Verluste an Diaminen bis zu 0,15 Gew.% auf, was unerwünscht ist.According to the process of U.S. Patent 3,402,152, aqueous solutions of salts of dicarboxylic acids and diamines of e.g. 25 to 55 wt.% Under increased pressure at 130 ° to 165 ° C in an evaporator to a content up to about 75 wt.%. Losses of diamines of up to 0.15% by weight still occur, which is undesirable.
Um überflüssige Mengen an Wasser zu vermeiden, wurde auch schon versucht, direkt von den flüssigen Ausgangsstoffen z.B. geschmolzener Adipinsäure und geschmolzenem Hexamethylendiamin bei der Polyamidherstellung auszugehen. Solche Verfahren sind beispielsweise aus der GB-PS 1 018 653 und BE-PS 640 369 bekannt. Abgesehen davon, daß sich geschmolzene Adipinsäure verändert, z.B. durch Decarboxylierung und Anhydridbildung, treten erhebliche Probleme bei der genauen Dosierung der Ausgangsstoffe auf. Dies gilt umso mehr als eine genaue Dosierung erforderlich ist, um äquivalente Verhältnisse einzuhalten.In order to avoid unnecessary amounts of water, attempts have already been made to directly extract the liquid starting materials, e.g. melted adipic acid and melted hexamethylenediamine in the polyamide production. Such methods are known for example from GB-PS 1 018 653 and BE-PS 640 369. Apart from the fact that molten adipic acid changes, e.g. Due to decarboxylation and anhydride formation, there are considerable problems with the exact dosage of the starting materials. This is all the more true since an exact dosage is required in order to maintain equivalent ratios.
Aus der DT-OS 2403 178 ist auch schon bekannt, kristalline Salze aus Dicarbonsäuren und Diaminen herzustellen, indem man Dicarbonsäure enthaltende Salzlösungen mit dem jeweiligen Diamin neutralisiert. Hierbei sollten jedoch Temperaturen von 80°C nicht überschritten werden.It is also known from DT-OS 2403 178 to produce crystalline salts from dicarboxylic acids and diamines by neutralizing salt solutions containing dicarboxylic acid with the respective diamine. However, temperatures of 80 ° C should not be exceeded.
Es war die technische Aufgabe gestellt, Ausgangslösungen für die Herstellung von Polyamiden aus Dicarbonsäuren und Diaminen zur Verfügung zu stellen, die leicht handhabbar sind und möglichst wenig Wasser enthalten und die in den Ausgangslösungen enthaltene Wärmeenergie nutzbar zu machen.The technical task was to provide starting solutions for the production of polyamides from dicarboxylic acids and diamines that are easy to handle and contain as little water as possible and that the thermal energy contained in the starting solutions can be used.
Diese Aufgabe wird gelöst in einem Verfahren zur Herstellung von 70 bis 90 gew.%igen wäßrigen Lösungen von Salzen aus Dicarbonsäuren und Diaminen sowie Polyamidpräkondensaten durch Umsetzen von Alkandicarbonsäuren mit 6 bis 12 Kohlenstoffatomen und Alkandiaminen mit 6 bis 12 Kohlenstoffatomen in Wasser, dadurch gekennzeichnet, daß man 40 bis 65 gew.%ige wäßrige Salzlösungen aus Dicarbonsäuren und Diaminen von 60 bis 110°C, die eine entsprechende Menge der jeweiligen Dicarbonsäure in Überschuß gelöst enthalten, mit dem jeweiligen geschmolzenen Diamin in äquivalenten Mengen bezogen auf gelöste Dicarbonsäure in an sich bekannter Weise umsetzt, mit der Maßgabe, daß die Umsetzung unter erhöhtem Druck durchgeführt wird und eine Endtemperatur von 160 bis 200°C bei der Umsetzung eingehalten wird.This object is achieved in a process for the preparation of 70 to 90% by weight aqueous solutions of salts from dicarboxylic acids and diamines and polyamide precondensates by reacting alkanedicarboxylic acids with 6 to 12 carbon atoms and alkanediamines with 6 to 12 carbon atoms in water, characterized in that 40 to 65% by weight aqueous salt solutions of dicarboxylic acids and diamines from 60 to 110 ° C., which contain a corresponding amount of the respective dicarboxylic acid in excess, with the respective molten diamine in equivalent amounts based on dissolved dicarboxylic acid in a manner known per se implemented, with the proviso that the reaction is carried out under increased pressure and a final temperature of 160 to 200 ° C is maintained during the reaction.
Das neue Verfahren hat den Vorteil, daß man unmittelbar zu hochkonzentrierten wäßrigen Ausgangslösungen für die Polyamidherstellung gelangt, die nicht mehr weiter konzentriert werden müssen. Weiter hat das neue Verfahren den Vorteil, daß man Ausgangslösungen erhält, in denen die enthaltene Neutralisationswärme für die Polykondensation genutzt wird. Schließlich hat das neue Verfahren den Vorteil, daß die Dosierung der Ausgangsstoffe und deren Vermischung einfach zu bewerkstelligen ist.The new process has the advantage that it immediately leads to highly concentrated aqueous starting solutions for polyamide production, which no longer need to be concentrated. The new process also has the advantage that starting solutions are obtained in which the heat of neutralization contained is used for the polycondensation. Finally, the new process has the advantage that the starting materials can be metered and mixed easily.
Im Hinblick auf die DT-OS 2 403 178 war es nicht angezeigt, bei der Neutralisation von Dicarbonsäuren mit Diaminen Temperaturen von 80°C zu überschreiten, da bei höheren Temperaturen für die Polykondensation unbrauchbare Produkte zu erwarten waren.With regard to DT-OS 2 403 178, it was not appropriate to exceed temperatures of 80 ° C. in the neutralization of dicarboxylic acids with diamines, since products which were unusable for polycondensation were to be expected at higher temperatures.
Erfindungsgemäß geht man von Alkandicarbonsäuren mit 6 bis 12 Kohlenstoffatomen aus. Bevorzugt verwendet man geradkettige a-w-Dicarbonsäuren der genannten Kohlenstoffzahl. Geeignete Dicarbonsäuren sind beispielsweise Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Dekandisäure und Dodecandisäure. Besondere technische Bedeutung haben Adipinsäure und Sebacinsäure erlangt.According to the invention, alkane dicarboxylic acids with 6 to 12 carbon atoms are used. Straight-chain a-w dicarboxylic acids of the stated carbon number are preferably used. Suitable dicarboxylic acids are, for example, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid and dodecanedioic acid. Adipic acid and sebacic acid have acquired particular technical importance.
Ferner geht man von Alkandiaminen mit 6 bis 12 Kohlenstoffatomen aus. Besonders bevorzugt verwendet man geradkettige a-w-Alkandiamine mit 6 bis 12 Kohlenstoffatomen. Geeignete Diamine sind beispielsweise Hexamethylendiamin. Octamethylendiamin, Decamethylendiamin oder Dodecamethylendiamin.Furthermore, alkane diamines with 6 to 12 carbon atoms are used. Straight-chain a-w-alkanediamines having 6 to 12 carbon atoms are particularly preferably used. Suitable diamines are, for example, hexamethylene diamine. Octamethylene diamine, decamethylene diamine or dodecamethylene diamine.
Besondere technische Bedeutung hat Hexamethylendiamin erlangt. Demzufolge sind auch Lösungen von Salzen und Polyamidpräkondensaten, die sich von Adipinsäure oder Sebacinsäure und Hexamethylendiamin ableiten, bevorzugte Verfahrensprodukte.Hexamethylenediamine has gained particular technical importance. Accordingly, solutions of salts and polyamide precondensates which are derived from adipic acid or sebacic acid and hexamethylenediamine are also preferred process products.
Man geht zunächst von einer wäßrigen Salzlösung aus Dicarbonsäuren und Diaminen von 40 bis 65 Gewichtsprozent aus, die eine entsprechende Menge der jeweiligen Dicarbonsäure im Überschuß gelöst enthält. Vorteilhaft verwendet man Lösungen, die 50 bis 65 Gewichtsprozent an den jeweiligen Salzen, bezogen auf die Summe von Salz und Wasser, enthalten. Die Menge an gelöster Dicarbonsäure richtet sich nach der gewünschten Endkonzentration der herzustellenden hochkonzentrierten wäßrigen Lösungen.The starting point is an aqueous salt solution of dicarboxylic acids and diamines of 40 to 65 percent by weight, which contains a corresponding amount of the respective dicarbon contains acid dissolved in excess. Solutions which contain 50 to 65 percent by weight of the respective salts, based on the sum of salt and water, are advantageously used. The amount of dissolved dicarboxylic acid depends on the desired final concentration of the highly concentrated aqueous solutions to be prepared.
Nach einer bevorzugten Ausführungsform löst man in einer Salzlösung geringerer Konzentration feste Dicarbonsäure auf. Hierbei hält man Temperaturen von 60 bis 110°C ein. So erhaltene freie Dicarbonsäure enthaltende Salz- lösung wird dann mit geschmolzenem Diamin in äquivalenten Mengen bezogen auf die gelöste Dicarbonsäure umgesetzt. Vorteilhaft achtet man darauf, daß man den pH-Wert für den Äquivalenzpunkt des jeweils herzustellenden Salzes einhält. Beispielsweise ist der Äquivalenzpunkt für Hexamethylendiammoniumadipat pH 7,62 und für Hexamethylendiammoniumsebacat pH 7,5 gemessen in 10 prozentiger wäßriger Lösung bei 25°C. Vorteilhaft führt man die Umsetzung in einer Mischstrecke durch, wobei man zunächst einen geringen Unterschuß an geschmolzenem Diamin zugibt und dann die präzise Einstellung durch eine weitere Zugabe vom geschmolzenen Diamin durchführt. Um den bei der Polykondensation eintretenden Verlust an Diaminen auszugleichen, verwendet man Diamine in der Regel im Überschuß z.B. 1,5 Molprozent.According to a preferred embodiment, solid dicarboxylic acid is dissolved in a salt solution of lower concentration. Temperatures of 60 to 110 ° C are observed. Salt solution thus obtained containing free dicarboxylic acid is then reacted with molten diamine in equivalent amounts based on the dissolved dicarboxylic acid. It is advantageous to ensure that the pH value for the equivalence point of the salt to be produced is observed. For example, the equivalence point for hexamethylene diammonium adipate is pH 7.62 and for hexamethylene diammonium sebacate pH 7.5 measured in 10 percent aqueous solution at 25 ° C. The reaction is advantageously carried out in a mixing section, first adding a small deficit of molten diamine and then carrying out the precise adjustment by adding molten diamine again. In order to compensate for the loss of diamines which occurs during the polycondensation, diamines are generally used in excess, e.g. 1.5 mole percent.
Nach einer anderen bevorzugten Ausführungsform lösn. man zunächst feste Dicarbonsäure in einer wäßrigen Lösung von Diamin im Unterschuß. Hierbei erhält man eine Salzlösung aus Dicarbonsäure und Diamin, die eine überschüssige Menge an Dicarbonsäure gelöst enthält. Es versteht sich, daß man die Mengenverhältnisse so wählt, daß man eine Salzlösung der vorgenannten Konzentration erhält und die überschüssige Menge an Dicarbonsäure der gewünschten Endkonzentration der wäßrigen Lösung entspricht. Das Lösen der Diearbonsäure erfolgt bei Temperaturen von 60 bis 110°C, wobei man in der Regel atmosphärischen Druck einhält. Die so erhaltene freie Dicarbonsäure enthaltende Salzlösung wird dann mit geschmolzenem Diamin in äquivalenten Mengen bezogen auf gelöste Dicarbonsäure umgesetzt. Diese Umsetzung erfolgt vorteilhaft wie bei der vorgenannten Arbeitsweise beschrieben.Solve according to another preferred embodiment. first solid dicarboxylic acid in an aqueous solution of diamine in deficit. This gives a salt solution of dicarboxylic acid and diamine, which contains an excess amount of dicarboxylic acid in solution. It is understood that the proportions are chosen so that a salt solution of the aforementioned concentration is obtained and the excess amount of dicarboxylic acid corresponds to the desired final concentration of the aqueous solution. The diearbonic acid is dissolved at temperatures of 60 to 110 ° C, usually keeping atmospheric pressure. The salt solution thus obtained containing free dicarboxylic acid is then reacted with molten diamine in equivalent amounts based on the dissolved dicarboxylic acid. This implementation is advantageously carried out as described in the aforementioned procedure.
Es ist ein wesentliches Merkmal der Erfindung, daß die Umsetzung der gelösten Dicarbonsäure mit geschmolzenem Diamin unter erhöhtem Druck durchgeführt wird. Vorteilhaft erhält man Drücke von 2 bis 15 bar ein. Ein entsprechender Druck stellt sich durch den autogenen Druck von selbst ein und kann noch durch geringe Stickstoffzugaben erhöht werden, um ein Sieden der Lösung zu verhindern. Ferner ist es ein wesentliches Merkmal der Erfindung, daß man bei der Neutralisation eine Endtemperatur von 160 bis 200°C einhält.It is an essential feature of the invention that the reaction of the dissolved dicarboxylic acid with molten diamine is carried out under increased pressure. Pressures of 2 to 15 bar are advantageously obtained. A corresponding pressure arises automatically due to the autogenous pressure and can be increased by adding a small amount of nitrogen to prevent the solution from boiling. It is also an essential feature of the invention that a final temperature of 160 to 200 ° C is maintained during neutralization.
So erhaltene wäßrige Lösungen enthalten Salze aus Dicarbonsäuren und Diaminen. Sie können durch beginnende Polykondensation auch Polyamidpräkondensate enthalten. Der Umsatz der Amino- und Carboxylgruppen kann bis zu 50% z.B. 20 bis 45% betragen.Aqueous solutions thus obtained contain salts of dicarboxylic acids and diamines. Due to the beginning of polycondensation, they can also contain polyamide precondensates. The conversion of the amino and carboxyl groups can be up to 50% e.g. 20 to 45%.
Die erzeugten wäßrigen Lösungen haben einen Gehalt von 70 bis 90 Gewichtsprozent, insbesondere 80 bis 90 Gewichtsprozent an Salzen aus Dicarbonsäuren und Diaminen und Polyamidpräkondensaten.The aqueous solutions produced have a content of 70 to 90 percent by weight, in particular 80 to 90 percent by weight, of salts from dicarboxylic acids and diamines and polyamide precondensates.
Erfindungsgemäß hergestellte hochkonzentrierte wäßrige Lösungen von Salzen und Polyamidpräkondensaten, die sich von Dicarbonsäuren und Diaminen ableiten eignen sich in hervorragender Weise zur Herstellung von Polyamiden durch Kondensation. Die Kondensation kann absatzweise oder kontinuierlich durchgeführt werden. Geeignete Kondensationsverfahren werden beispielsweise beschrieben in der DT-AS 14 95 087, GB-PS 1 159 151, GB-PS 674 954 oder DT-PS 1 060 139 und DT-OS 24 17 003. Besonders vorteilhaft ist es, die erfindungsgemäßen, wäßrigen Lösungen für die Kondensation zu verwenden, ohne vorher die Neutralisationswärme abzuführen. Unbeachtlich sind in diesem Zusammenhang apparativ bedingte Wärmeverluste.Highly concentrated aqueous solutions of salts and polyamide precondensates prepared according to the invention, which are derived from dicarboxylic acids and diamines, are outstandingly suitable for the production of polyamides by condensation. The condensation can be carried out batchwise or continuously. Suitable condensation processes are described, for example, in DT-AS 14 95 087, GB-PS 1 159 151, GB-PS 674 954 or DT-PS 1 060 139 and DT-OS 24 17 003. It is particularly advantageous to use the aqueous solution according to the invention Use solutions for condensation without first removing the heat of neutralization. In this context, heat losses caused by the device are irrelevant.
Es ist auch möglich, einen Teil der Neutralisationswärme zum Lösen der Dicarbonsäuren in den Salzlösungen geringerer Konzentration zu verwenden.It is also possible to use part of the heat of neutralization to dissolve the dicarboxylic acids in the salt solutions of lower concentration.
Polyamide, die aus den erfindungsgemäßen Lösungen hergestellt werden, eignen sich zur Erzeugung von aus der Schmelze geformten Massen, wie Fäden, Fasern, Formteile, Platten oder Überzügen.Polyamides which are produced from the solutions according to the invention are suitable for the production of masses shaped from the melt, such as threads, fibers, moldings, plates or coatings.
Das Verfahren nach der Erfindung sei in folgenden Beispielen veranschaulicht.The method according to the invention is illustrated in the following examples.
5250 g AH-Salz (Hexamethylendiammoniumadipat) wurden in einem 40-1-Rührautoklaven in 3450 g Wasser unter Erwärmen auf 95°C gelöst. Zu der so erhaltenen 60,3 prozentigen AH-Salz-Lösung wurden 8025 g feste Adipinsäure allmählich unter Rühren bei 90 bis 95°C zugegeben und gelöst. Der Autoklav wurde mit Stickstoff gespült und verschlossen. Der Inhalt wurde auf 100°C erhitzt, wobei sich ein Druck von 2 bar einstellte (alle Druckangaben sind Absolutwerte). 6375 g geschmolzenes Hexamethylendiamin von 100°C wurde aus einem Zulaufgefäß mit Stickstoffdruck innerhalb von 2 Minuten bei laufendem Rührer in den Autoklaven gedrückt. In der so erhaltenen 85 gewichtsprozentigen AH-Salz-Lösung stieg die Temperatur durch die freiwerdende Neutralisationswärme an und erreichte 2 Minuten nach Zugabe des Hexamethylendiamins 162°C. Während der Zugabe des Hexamethylendiamins stieg der Druck vorübergehend auf 4 bar und fiel bis zum Ende der Zugabe auf 3 bar.5250 g of AH salt (hexamethylene diammonium adipate) were dissolved in 3450 g of water in a 40 l stirred autoclave while heating to 95 ° C. To the 60.3 percent AH salt solution thus obtained, 8025 g of solid adipic acid were gradually added with stirring at 90 to 95 ° C. and dissolved. The autoclave was flushed with nitrogen and sealed. The contents were heated to 100 ° C, which resulted in a pressure of 2 bar (all pressure values are absolute values). 6375 g of molten hexamethylenediamine at 100 ° C. were pressed into the autoclave from a feed vessel with nitrogen pressure within 2 minutes with the stirrer running. In the 85% by weight AH salt solution thus obtained, the temperature rose due to the heat of neutralization released and reached 162 ° C. 2 minutes after the addition of the hexamethylenediamine. During the addition of the hexamethylenediamine, the pressure rose temporarily to 4 bar and fell to 3 bar by the end of the addition.
In analoger Weise erhält man Nylone 6,9 und Nylone 10,6 Salzlösungen.Analogously, nylons 6.9 and nylons 10.6 salt solutions are obtained.
Das Beispiel zeigt die Ausnutzung eines Teils der Neutralisationswärme zum Lösen der Dicarbonsäure.The example shows the use of part of the heat of neutralization to dissolve the dicarboxylic acid.
In einem Glaskolben mit Rührer, Rückflußkühler, Thermometer und Tropftrichter wurden 292 g feste Adipinsäure bei 20°C vorgelegt.292 g of solid adipic acid were placed at 20 ° C. in a glass flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel.
Der Kolben wurde in ein als Schutzheizung wirkendes Wasserbad von 75°C eingetaucht; sofort danach wurde eine im Tropftrichter auf 90°C gehaltene Lösung von 75 g Hexamethylendiamin in 92 g Wasser innerhalb von 20 Sekunden unter Rühren zugegeben. Nach 2 Minuten war eine klare Lösung entstanden, deren Temperatur 69°C betrug. Die Zusammensetzung der Lösung war 37% AH-Salz, 43% Adipinsäure und 20% Wasser. Die weitere Umsetzung erfolgte analog Beispiel 1.The flask was immersed in a water bath at 75 ° C acting as a protective heater; immediately thereafter, a solution of 75 g of hexamethylenediamine in 92 g of water, kept in the dropping funnel at 90 ° C., was added with stirring within 20 seconds. After 2 minutes a clear solution had formed, the temperature of which was 69 ° C. The composition of the solution was 37% AH salt, 43% adipic acid and 20% water. The further implementation was carried out analogously to Example 1.
Die im Beispiel 1 erhaltene AH-Salz-Lösung wurde ohne Abkühlen der Lösung polykondensiert. Sie wurde innerhalb von 3 1/2 Stunden auf 275°C erhitzt, wobei der Druck durch Abblasen von Wasserdampf auf 19 bar gehalten wurde. Nach Erreichen von 275°C wurde innerhalb von 1 Stunde auf Normaldruck entspannt und 1 Stunde bis 275°C nachkondensiert. Das Produkt wurde mit Stickstoffdruck aus dem Autoklaven herausgedruckt, wobei der Schmelzstrang in einem Wasserbad abgekühlt und granuliert wurde. Das erhaltene Polyamid 66 hatte eine relative Viskosität von 2,54, gemessen in 1 prozentiger Lösung in 96 prozentiger Schwefelsäure, und einen Gehalt an sauren Gruppen von 54 mÄq/kg und an basischen Gruppen von 76 mÄq/kg.The AH salt solution obtained in Example 1 was polycondensed without cooling the solution. It was heated to 275 ° C. in the course of 3 1/2 hours, the pressure being kept at 19 bar by blowing off steam. After reaching 275 ° C., the pressure was released to atmospheric pressure within 1 hour and the condensation was continued to 275 ° C. for 1 hour. The product was pressed out of the autoclave under nitrogen pressure, the melt strand being cooled in a water bath and granulated. The polyamide 66 obtained had a relative viscosity of 2.54, measured in 1 percent solution in 96 percent sulfuric acid, and a content of acidic groups of 54 meq / kg and of basic groups of 76 meq / kg.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772728817 DE2728817A1 (en) | 1977-06-27 | 1977-06-27 | PROCESS FOR THE PRODUCTION OF HIGHLY CONCENTRATED Aqueous SOLUTIONS OF DICARBONIC DIAMINE SALT AND POLYAMIDE PRECONDENSATE |
| DE2728817 | 1977-06-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000157A1 EP0000157A1 (en) | 1979-01-10 |
| EP0000157B1 true EP0000157B1 (en) | 1981-04-01 |
Family
ID=6012415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100175A Expired EP0000157B1 (en) | 1977-06-27 | 1978-06-16 | Process for the manufacture of highly concentrated aqueous solutions of salts of dicarboxylic acids with diamines and/of polyamide precondensates and their use |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4213884A (en) |
| EP (1) | EP0000157B1 (en) |
| JP (1) | JPS5412316A (en) |
| DE (2) | DE2728817A1 (en) |
| IT (1) | IT1096586B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4442260A (en) * | 1983-03-14 | 1984-04-10 | E. I. Du Pont De Nemours & Company | Preparation of salt solution useful for making nylon |
| JPH0448937U (en) * | 1990-08-24 | 1992-04-24 | ||
| FR2916756B1 (en) * | 2007-06-04 | 2009-07-17 | Rhodia Recherches & Tech | METHOD FOR MANUFACTURING A SOLUTION OF DIACID / DIAMINE SALTS |
| FR2943348B1 (en) * | 2009-03-20 | 2012-12-21 | Rhodia Operations | PROCESS FOR PRODUCING POLYAMIDE |
| FR2981600B1 (en) | 2011-10-25 | 2013-11-15 | Rhodia Operations | PROCESS FOR THE PREPARATION OF POLYAMIDE PELLETS |
| US20140296472A1 (en) | 2011-12-05 | 2014-10-02 | Invista North America S.A R.L. | Process for the preparation of polyamides |
| FR2984332B1 (en) | 2011-12-15 | 2015-12-11 | Rhodia Operations | PROCESS FOR PREPARING POLYAMIDE PELLETS AND USES |
| TW201443103A (en) | 2013-05-01 | 2014-11-16 | Invista Tech Sarl | Nylon salt solution production from a partially balanced acid solution |
| TW201446836A (en) | 2013-05-01 | 2014-12-16 | Invista Tech Sarl | Process for producing a partially balanced acid solution |
| TW201529640A (en) | 2013-12-17 | 2015-08-01 | Invista Tech Sarl | Process for producing partially balanced acid solution with vessel having a disperser head for nylon salt production |
| EP3174917B1 (en) * | 2014-07-29 | 2024-05-01 | DSM IP Assets B.V. | Process for preparing nylon salt and its polymerization |
| TWI787251B (en) | 2017-04-13 | 2022-12-21 | 英商英威達紡織（英國）有限公司 | Monomeric balance control in the preparation of precursors for polyamidation processes |
| EP3842472A1 (en) | 2019-12-23 | 2021-06-30 | Polytechnyl S.A.S. | Process for producing a concentrated aqueous solution of a salt of a diamine and dicarboxylic acid |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE487516A (en) * | 1948-05-01 | |||
| NL102671C (en) * | 1955-07-23 | |||
| NL252332A (en) * | 1959-06-06 | |||
| BE640369A (en) | 1963-08-12 | 1964-03-16 | ||
| NL298696A (en) * | 1962-10-04 | |||
| US3502624A (en) * | 1966-04-04 | 1970-03-24 | Du Pont | Preparation of diamine-dicarboxylic acid salts for polycarbonamides |
| GB1159151A (en) | 1966-04-22 | 1969-07-23 | Ici Ltd | Improvements in or relating to Continuous Polymerisation of Polyamides |
| US3476713A (en) * | 1967-03-13 | 1969-11-04 | Du Pont | Colorimetric indicator control of polyamide salt stoichiometry |
| US3952051A (en) * | 1971-05-08 | 1976-04-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for crystallization of diamine dicarboxylate |
| US4131712A (en) * | 1977-08-10 | 1978-12-26 | E. I. Du Pont De Nemours And Company | Process for preparing polyamide from diacid-rich component and diamine-rich component |
-
1977
- 1977-06-27 DE DE19772728817 patent/DE2728817A1/en not_active Withdrawn
-
1978
- 1978-06-08 US US05/913,641 patent/US4213884A/en not_active Expired - Lifetime
- 1978-06-16 DE DE7878100175T patent/DE2860572D1/en not_active Expired
- 1978-06-16 EP EP78100175A patent/EP0000157B1/en not_active Expired
- 1978-06-20 IT IT24766/78A patent/IT1096586B/en active
- 1978-06-26 JP JP7659178A patent/JPS5412316A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT1096586B (en) | 1985-08-26 |
| DE2860572D1 (en) | 1981-04-23 |
| DE2728817A1 (en) | 1979-01-04 |
| IT7824766A0 (en) | 1978-06-20 |
| EP0000157A1 (en) | 1979-01-10 |
| JPS626534B2 (en) | 1987-02-12 |
| JPS5412316A (en) | 1979-01-30 |
| US4213884A (en) | 1980-07-22 |
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