EP0000142B1 - Process for the preparation of polyamides - Google Patents
Process for the preparation of polyamides Download PDFInfo
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- EP0000142B1 EP0000142B1 EP78100150A EP78100150A EP0000142B1 EP 0000142 B1 EP0000142 B1 EP 0000142B1 EP 78100150 A EP78100150 A EP 78100150A EP 78100150 A EP78100150 A EP 78100150A EP 0000142 B1 EP0000142 B1 EP 0000142B1
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- solutions
- dicarboxylic acid
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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
Definitions
- the invention relates to a process for the preparation of polyamides by heating aqueous solutions of salts from dicarboxylic acids and diamines to polyamide-forming temperatures under increased pressure and removal of water.
- aqueous solutions of such salts are generally used.
- aqueous solutions of such salts are usually 45 to 70 weight percent aqueous salt solutions.
- the excess water must be largely removed from such solutions by a pre-evaporator stage, e.g. except for a remainder of 30 to 10 weight percent water. This means that the aqueous salt solutions used must first be heated and excess water must be evaporated, which requires considerable amounts of energy, and only then can the actual condensation be carried out.
- the technical task was therefore to avoid the evaporation of large amounts of water in the production of polyamides and, on the other hand, to avoid the metering difficulties of molten liquid starting materials.
- This object is achieved in a process for the preparation of polyamides by heating aqueous solutions of salts from alkanedicarboxylic acids with 6 to 12 carbon atoms and diamines of the formula NH 2 RNH 2 , in which R denotes an alkylene radical with 6 to 12 carbon atoms to elevated temperatures at polyamide-forming temperatures Pressure and removal of water, starting from 75 to 90 weight percent aqueous solutions of salts of dicarboxylic acids and diamines, by neutralization of 40 to 65 wt .-% saline solutions at a temperature of 60 to 110 ° C, the corresponding amount of each Contained dicarboxylic acid dissolved in excess, were obtained with the corresponding diamines under increased pressure while maintaining end temperatures of 140 to 210 ° C.
- the new process has the advantage that much less water has to be evaporated during the polycondensation, which includes the advantage of smaller devices.
- a concentrated solution of such salts is easier to handle compared to molten starting materials.
- Alkane dicarboxylic acids with 6 to 12 carbon atoms are used as starting materials.
- ⁇ , ⁇ -straight-chain alkanedicarboxylic acids of the stated carbon number are particularly suitable.
- Suitable dicarboxylic acids are, for example, adipic acid, suberic acid, azelaic acid, decanedioic acid or dodecanedioic acid. Adipic acid, sebacic acid and dodecanedioic acid have acquired particular technical importance.
- Alkane diamines of the formula NH 2 RNH 2 in which R is an alkylene radical having 6 to 12 carbon atoms, in particular ⁇ , ,- straight-chain alkane diamines, are used as diamines.
- Suitable diamines are, for example, hexamethylene diamine, octamethylene diamine, decamethylene diamine and dodecamethylene diamine. Hexamethylenediamine has gained particular technical importance.
- dicarboxylic acid is additionally dissolved in such a salt solution in an amount which is necessary to achieve the desired final concentration of salt.
- the dicarboxylic acid is dissolved at temperatures of 60 to 110 ° C.
- the salt solution thus obtained, containing free dicarboxylic acids, is then neutralized with the corresponding diamine, advantageously in molten form.
- crystalline dicarboxylic acid is mixed with an aqueous solution of diamine, but using the dicarboxylic acid in excess.
- the neutralization takes place e.g. in mixing sections which contain internals for rapid mixing, it being advantageous not to initially add the entire amount of diamine required for neutralization, and only after a first mixing operation and determination of the pH value is the final adjustment carried out with a further addition of diamine.
- neutralization means reaching the equivalence point for the respective salts of diamines and dicarboxylic acids.
- This is, for example, pH 7.62 for hexamethylene diammonium adipate and pH 7.5 for hexamethylene diammonium sebazate (measured after dilution in 10% by weight aqueous solution at 25 ° C.).
- amounts of diamines equivalent to the amounts of dicarboxylic acid optionally in a slight excess, e.g. up to 1 mole percent to compensate for diamine losses in the condensation.
- the neutralization is expediently carried out with the exclusion of molecular oxygen, e.g. under inert gas, by.
- reaction mixture heats up due to the heat released during neutralization.
- Final temperatures during the neutralization 140 to 210 ° C., in particular 170 to 200 ° C., are maintained.
- neutralization is carried out under increased pressure, e.g. 2 to 15 bar.
- the salt solutions obtained from dicarboxylic acids and diamines should have a content of 75 to 90 percent by weight. A content of 80 to 85 percent by weight of the respective salts is particularly preferred. Salt solutions of hexamethylene diammonium adipate of the concentration mentioned have become particularly important.
- the highly concentrated salt solutions of dicarboxylic acids and diamines thus produced are condensed to polyamides in a manner known per se.
- the condensation usually takes place at temperatures of 240 to 300 ° C. Temperatures of 260 to 290 ° C. are particularly preferably used. In general, pressures of up to 100 bar are used, in particular pressures of 20 to 80 bar have proven successful.
- the water still introduced with the salt solution and the water formed during the condensation are removed. This can e.g. happen so that the water is gradually separated during the condensation.
- regulators such as lower fatty acids, stabilizers, antistatic agents and matting agents can be added before, during or after the condensation.
- the condensation process can be carried out batchwise. However, it is advantageous to use continuous working methods. Suitable procedures are described for example in DT-AS 1495087, GB-PS 11 95 151, DT-PS 1060139 and GB-PS 674 or DT-OS 2417 003.
- Polyamides which are produced by the process of the invention are suitable for producing shaped structures 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 90-95 ° 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 from an inlet vessel with nitrogen pressure within 2 minutes while running. Stirrer pressed into the autoclave.
- the Ah salt solution was polycondensed without prior cooling. It was heated to 275 ° C. in the course of 31/2 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 at 275 ° C. for 1 hour.
- the product was removed from the autoclave with nitrogen pressure. pressed out, the melt strand was cooled in a water bath and granulated.
- the polyamide 6.6 obtained had one. relative viscosity of 2.54, measured in 1 percent solution in 96 percent sulfuric acid, and a content of acidic groups of 54 mAq / kg and basic groups of 76 meq / kg.
- Polyamide 6.9 and polyamide 10.6 are obtained in an analogous manner.
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Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Polyamiden durch Erhitzen von Wäßrigen Lösungen von Salzen aus Dicarbonsäuren und Diaminen auf polyamidbildende Temperaturen unter erhöhtem Druck und Entfemen von Wasser.The invention relates to a process for the preparation of polyamides by heating aqueous solutions of salts from dicarboxylic acids and diamines to polyamide-forming temperatures under increased pressure and removal of water.
Bei der in der Technik wohlbekannten Herstellung von Polyamiden durch Kondensation von Salzen aus Diaminen und Dicarbonsäuren, wie Hexamethylendiammoniumadipat geht man in der Regel von wäßrigen Lösungen solcher Salze aus. Wie aus der GB-PS 674954, DT-PS 1060139 oder DT-AS 11 58 257 hervorgeht, verwendet man in der Regel 45 bis 70 gewichtsprozentige wäßrige Salzlösungen. Vor der eigentlichen Polykondensation muß jedoch durch eine Vorverdampferstufe aus solchen Lösungen das überschüssige Wasser zum großten Teil entfernt werden, z.B. bis auf einen Rest von 30 bis 10 Gewichtsprozent Wasser. Dies bedeutet, daß die verwendeten wäßrigen Salzlösungen zunächst aufgeheizt werden müssen und überschüssiges Wasser verdampft werden muß, was erhebliche Mengen an Energie bedarf, und daß erst dann die eigentliche Kondensation durchgeführt werden kann.In the preparation of polyamides, which is well known in the art, by condensation of salts from diamines and dicarboxylic acids, such as hexamethylene diammonium adipate, aqueous solutions of such salts are generally used. As is apparent from GB-PS 674954, DT-PS 1060139 or DT-AS 11 58 257, usually 45 to 70 weight percent aqueous salt solutions are used. Before the actual polycondensation, however, the excess water must be largely removed from such solutions by a pre-evaporator stage, e.g. except for a remainder of 30 to 10 weight percent water. This means that the aqueous salt solutions used must first be heated and excess water must be evaporated, which requires considerable amounts of energy, and only then can the actual condensation be carried out.
Es wurde auch schon versucht, diesen Nachteilen dadurch zu begegnen, indem man von geschmolzener Adipinsäure und flüssigem Hexamethylendiamin ausgeht wie aus der GB-PS 1 018 653 und BE-PS 640 369 bekannt ist. Die Arbeitsweise mit geschmolzenen Ausgangsstoffen bringt erhebliche Probleme bei der Dosierung und bei der raschen Vermischung mit sich. Darüber hinaus neigt geschmolzene Adiponsäure zur Decarboxylierung und Bildung von Adipinsäureanhydrid.Attempts have also been made to overcome these disadvantages by starting from molten adipic acid and liquid hexamethylenediamine, as is known from GB-PS 1 018 653 and BE-PS 640 369. Working with molten starting materials poses considerable problems with dosing and rapid mixing. In addition, molten adiponic acid tends to decarboxylate and form adipic anhydride.
Es war deshalb die technische Aufgabe gestellt, bei der Herstellung von Polyamiden die Verdampfung großer Wassermengen zu vermeiden und andererseits die Dosierschwierigkeiten von geschmolzenen flüssigen Ausgangsstoffen zu umgehen.The technical task was therefore to avoid the evaporation of large amounts of water in the production of polyamides and, on the other hand, to avoid the metering difficulties of molten liquid starting materials.
Diese Aufgabe wird gelöst in einem Verfahren zur Herstellung von Polyamiden durch Erhitzen von wäßrigen Lösungen von Salzen aus Alkandicarbonsäuren mit 6 bis 12 Kohlenstoffatomen und Diaminen der Formel NH2RNH2, in der R einen Alkylenrest mit 6 bis 12 Kohlenstoffatomen bedeutet auf polyamidbildende Temperaturen unter erhöhtem Druck und Entfernen von Wasser, wobei man von 75 bis 90 gewichtsprozentigen wäßrigen Lösungen von Salzen aus Dicarbonsäuren und Diaminen ausgeht, die durch Neutralisation von 40 bis 65 Gew.%igen Salzlösungen einer Temperatur von 60 bis 110°C, die eine entsprechende Menge der jeweiligen Dicarbonsäure im Überschuß gelöst enthalten, mit den entsprechenden Diaminen unter erhöhtem Druck unter Einhaltung von Endtemperaturen von 140 bis 210°C erhalten wurden.This object is achieved in a process for the preparation of polyamides by heating aqueous solutions of salts from alkanedicarboxylic acids with 6 to 12 carbon atoms and diamines of the formula NH 2 RNH 2 , in which R denotes an alkylene radical with 6 to 12 carbon atoms to elevated temperatures at polyamide-forming temperatures Pressure and removal of water, starting from 75 to 90 weight percent aqueous solutions of salts of dicarboxylic acids and diamines, by neutralization of 40 to 65 wt .-% saline solutions at a temperature of 60 to 110 ° C, the corresponding amount of each Contained dicarboxylic acid dissolved in excess, were obtained with the corresponding diamines under increased pressure while maintaining end temperatures of 140 to 210 ° C.
Das neue Verfahren hat den Vorteil, daß man wesentlich weniger Wasser bei der Polykondensation verdampfen muß, was den Vorteil kleinerer Vorrichtungen beinhaltet. Darüber hinaus ist es möglich, das Verfahren durch Ausnutzen der NeutralJsationwärme energiesparender durchzuführen. Ferner ist eine konzentrierte Lösung von solchen Salzen leichter zu handhaben im Vergleich zu geschmolzenen Ausgangsstoffen.The new process has the advantage that much less water has to be evaporated during the polycondensation, which includes the advantage of smaller devices. In addition, it is possible to carry out the process in a more energy-saving manner by utilizing the neutral heat. Furthermore, a concentrated solution of such salts is easier to handle compared to molten starting materials.
Im Hinblick auf die DT-OS 24 03 178, Seite 4, schien es nicht angezeigt, von sehr hoch konzentrierten Salzen aus Dicarbonsäuren und Diaminen auszugehen, da hierbei Schwierigkeiten, z.B. durch Abbau des Salzes zu erwarten waren.With regard to DT-OS 24 03 178, page 4, it did not seem appropriate to start from very highly concentrated salts of dicarboxylic acids and diamines, since difficulties, e.g. were expected from mining the salt.
Als Ausgangsstoffe verwendet man Alkandicarbonsäuren mit 6 bis 12 Kohlenstoffatomen. Besonders geeignet sind α,ω-geradkettige Alkandicarbonsäuren der genannten Kohlenstoffzahl. Geeignete Dicarbonsäuren sind beispielsweise Adipinsäure, Korksäure, Azelainsäure, Dekandisäure, oder Dodecandisäure. Besondere technische Bedeutung haben Adipinsäure, Sebazinsäure und Dodecandisäure erlangt.Alkane dicarboxylic acids with 6 to 12 carbon atoms are used as starting materials. Α, ω-straight-chain alkanedicarboxylic acids of the stated carbon number are particularly suitable. Suitable dicarboxylic acids are, for example, adipic acid, suberic acid, azelaic acid, decanedioic acid or dodecanedioic acid. Adipic acid, sebacic acid and dodecanedioic acid have acquired particular technical importance.
Als Diamine verwendet man Alkandiamine der Formel NH2RNH2, in der R einen Alkylenrest mit 6 bis 12 Kohlenstoffatomen, insbesondere α,∞- geradkettige Alkandiamine. Geeignete Diamine sind beispielsweise Hexamethylendiamin, Octamethylendiamin, Decamethylendiamin und Dodecamethylendiamin. Besondere technische Bedeutung hat Hexamethylendiamin erlangt.Alkane diamines of the formula NH 2 RNH 2 in which R is an alkylene radical having 6 to 12 carbon atoms, in particular α, ,- straight-chain alkane diamines, are used as diamines. Suitable diamines are, for example, hexamethylene diamine, octamethylene diamine, decamethylene diamine and dodecamethylene diamine. Hexamethylenediamine has gained particular technical importance.
Zunächst geht man von weniger konzentrierten wäßrigen Salzlösungen aus Dicarbonsäure und Diaminen aus. Solche Salzlösungen haben einen Gehalt von 40 bis 65 Gewichtsprozent an den entsprechenden Salzen. Nach einer bevorzugten Arbeitsweise löst man in einer solchen Salzlösung zusätzlich Dicarbonsäure in einer Menge, die erforderlich ist, um die gewünschte Endkonzentration an Salz zu erreichen. Die Lösung der Dicarbonsäure erfolgt bei Temperaturen von 60 bis 110°C. Die so erhaltene, freie Dicarbonsäuren enthaltende, Salzlösung wird dann mit dem entsprechenden Diamin, vorteilhaft in geschmolzener Form, neutralisiert.First of all, less concentrated aqueous salt solutions of dicarboxylic acid and diamines are assumed. Such salt solutions have a content of 40 to 65 percent by weight of the corresponding salts. According to a preferred procedure, dicarboxylic acid is additionally dissolved in such a salt solution in an amount which is necessary to achieve the desired final concentration of salt. The dicarboxylic acid is dissolved at temperatures of 60 to 110 ° C. The salt solution thus obtained, containing free dicarboxylic acids, is then neutralized with the corresponding diamine, advantageously in molten form.
Nach einer anderen bevorzugten Arbeitsweise mischt man kristalline Dicarbonsäure mit einer wäßrigen Lösung von Diamin, wobei man jedoch die Dicarbonsäure im Überschuß verwendet. Hierdurch erhält man zunächst eine Salzlösung niederer Konzentration, z.B. 40 bis 65 Gewichtsprozent, bezogen auf Salz und Wasser, die zusätzlich überschüssige Dicarbonsäure gelöst enthält. Hierbei hält man in der Regel Temperaturen von 60 bis 110°C ein. Die so erhaltene Lösung wird, wie oben beschrieben, dann mit flüssigem Diamin neutralisiert.According to another preferred procedure, crystalline dicarboxylic acid is mixed with an aqueous solution of diamine, but using the dicarboxylic acid in excess. This initially gives a salt solution of low concentration, for example 40 to 65 percent by weight, based on salt and water, which additionally contains excess dicarboxylic acid in solution. Temperatures of 60 to 110 ° C are generally maintained. The the solution thus obtained is then, as described above, neutralized with liquid diamine.
Die Neutralisation erfolgt z.B. in Mischstrecken, die Einbauten zur raschen Durchmischung enthalten, wobei man vorteilhaft zunächst nicht die gesamte zur Neutralisation notwendige Diaminmenge zugibt und erst nach einem ersten Mischvorgang und Ermittlung des pH-Wertes die Endeinstellung mit einer weiteren Diaminzugabe bewerkstelligt.The neutralization takes place e.g. in mixing sections which contain internals for rapid mixing, it being advantageous not to initially add the entire amount of diamine required for neutralization, and only after a first mixing operation and determination of the pH value is the final adjustment carried out with a further addition of diamine.
Als Neutralisation sei erfindungsgemäß die Erreichung ders Äquivalenzpunktes für die jeweiligen Salze aus Diaminen und Dicarbonsäuren verstanden. Für Hexamethylendiammoniumadipat ist dies beispielsweise pH 7,62, für Hexamethylendiammoniumsebazat pH 7,5 (gemessen nach Verdünnung in 10 gewichtsprozentiger wäßriger Lösung bei 25°C). Es versteht sich, daß man den Dicarbonsäuremengen äquivalente Mengen an Diaminen, gegebenenfalls in geringem Überschuß, z.B. bis 1 Molprozent zum Ausgleich von Diaminverlusten bei der Kondensation, zusetzt.According to the invention, neutralization means reaching the equivalence point for the respective salts of diamines and dicarboxylic acids. This is, for example, pH 7.62 for hexamethylene diammonium adipate and pH 7.5 for hexamethylene diammonium sebazate (measured after dilution in 10% by weight aqueous solution at 25 ° C.). It is understood that amounts of diamines equivalent to the amounts of dicarboxylic acid, optionally in a slight excess, e.g. up to 1 mole percent to compensate for diamine losses in the condensation.
Zweckmäßig führt man die Neutralisation unter Ausschluß von molekularem Sauerstoff, z.B. unter Inertgas, durch.The neutralization is expediently carried out with the exclusion of molecular oxygen, e.g. under inert gas, by.
Durch die bei der Neutralisation freiwerdende Wärme erhitzt sich das Reaktionsgemisch. Man hält Endtemperaturen bei der Neutralisation von 140 bis 210°C, insbesondere 170 bis 200°C ein. In der Regel wird die Neutralisation unter erhöhtem Druck, z.B. 2 bis 15 bar, durchgeführt.The reaction mixture heats up due to the heat released during neutralization. Final temperatures during the neutralization of 140 to 210 ° C., in particular 170 to 200 ° C., are maintained. As a rule, neutralization is carried out under increased pressure, e.g. 2 to 15 bar.
Die so erhaltenen Salzlösungen aus Dicarbonsäuren und Diaminen sollen einen Gehalt von 75 bis 90 Gewichtsprozent haben. Besonders bevorzugt wird ein Gehalt von 80 bis 85 Gewichtsprozent an den jeweiligen Salzen. Besondere Bedeutung haben Salzlösungen von Hexamethylendiammoniumadipat der genannten Konzentration erlangt.The salt solutions obtained from dicarboxylic acids and diamines should have a content of 75 to 90 percent by weight. A content of 80 to 85 percent by weight of the respective salts is particularly preferred. Salt solutions of hexamethylene diammonium adipate of the concentration mentioned have become particularly important.
Die so hergestellten hochkonzentrierten Salzlösungen aus Dicarbonsäuren und Diaminen werden in an sich bekannter Weise zu Polyamiden kondensiert. Die Kondensation erfolgt in der Regel bei Temperaturen von 240 bis 300°C. Besonders bevorzugt werden Temperaturen von 260 bis 290°C angewandt. Im - allgemeinen wendet man hierbei Drücke bis zu 100 bar an, insbesondere haben sich Drücke von 20 bis 80 bar bewährt. Während der Kondensation wird das noch mit der Salzlösung eingebrachte Wasser, sowie das bei der Kondensation entstehende Wasser entfernt. Dies kann z.B. so geschehen, daß das Wasser während der Kondensation stufenweise abgetrennt wird. Es ist aber auch möglich, insbesondere bei kontinuierlichen Verfahren, das Wasser nach der Kondensation in der Endstufe abzutrennen. Zusätzlich können Regler, wie niedere Fettsäuren, Stabilisatoren, Antistatikmittel und Mattierungsmittel vor, während oder nach der Kondensation zugegeben werden.The highly concentrated salt solutions of dicarboxylic acids and diamines thus produced are condensed to polyamides in a manner known per se. The condensation usually takes place at temperatures of 240 to 300 ° C. Temperatures of 260 to 290 ° C. are particularly preferably used. In general, pressures of up to 100 bar are used, in particular pressures of 20 to 80 bar have proven successful. During the condensation, the water still introduced with the salt solution and the water formed during the condensation are removed. This can e.g. happen so that the water is gradually separated during the condensation. However, it is also possible, particularly in the case of continuous processes, to remove the water after the condensation in the final stage. In addition, regulators such as lower fatty acids, stabilizers, antistatic agents and matting agents can be added before, during or after the condensation.
Das Kondensationsverfahren kann diskontinuierlich durchgeführt werden. Vorteilhaft wendet man jedoch kontinuierliche Arbeitsweisen an. Geeignete Arbeitsweisen werden beispielsweise beschrieben in der DT-AS 1495087, GB-PS 11 95 151, DT-PS 1060139 und GB-PS 674 oder DT-OS 2417 003.The condensation process can be carried out batchwise. However, it is advantageous to use continuous working methods. Suitable procedures are described for example in DT-AS 1495087, GB-PS 11 95 151, DT-PS 1060139 and GB-PS 674 or DT-OS 2417 003.
Polyamide, die nach dem Verfahren der Erfindung hergestellt werden, eignen sich zur Erzeugung geformter Gebilde aus der Schmelze, wie Fäden, Fasern, Formteilen, Platten oder Überzügen.Polyamides which are produced by the process of the invention are suitable for producing shaped structures from the melt, such as threads, fibers, moldings, plates or coatings.
Das Verfahren nach der Erfindung sei an folgendem Beispiel veranschaulicht.The method according to the invention is illustrated by the following example.
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 90-95°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 wurden aus einem Zulaufgefäß mit Sickstoffdruck innerhalb von 2 Minuten bei laufendem. Rührer in den Autoklaven gedrückt. In der so erhaltenen 85 prozentigen 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 ser 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 90-95 ° 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 from an inlet vessel with nitrogen pressure within 2 minutes while running. Stirrer pressed into the autoclave. In the thus obtained 85 percent AH salt solution, the temperature rose due to the released heat of neutralization, reaching 2 minutes after addition of the Hexameth y lendiamins 162 ° C. During the addition of the hexamethylenediamine, the pressure rose temporarily to 4 bar and fell to 3 bar until the end of the addition.
Die Ah-Salz-Lösung wurde ohne vorherige Abkühlung polykondensiert. Sie wurde innerhalb von 31/2 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 bei 275°C nachkondensiert. Das Produkt wurde mit Stickstoffdruck aus dem Autoklaven. herausgedrückt, wobei der Schmelzestrang in einem Wasserbad abgekühlt und granuliert wurde. Das erhaltene Polyamid 6,6 hatte eine. relative Viskosität von 2,54, gemessen in 1 prozentiger Lösung in 96 prozentiger Schwefelsäure, und einen Gehalt an sauren Gruppen von 54 mAq/kg und an basischen Gruppen von 76 mÄq/kg.The Ah salt solution was polycondensed without prior cooling. It was heated to 275 ° C. in the course of 31/2 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 at 275 ° C. for 1 hour. The product was removed from the autoclave with nitrogen pressure. pressed out, the melt strand was cooled in a water bath and granulated. The polyamide 6.6 obtained had one. relative viscosity of 2.54, measured in 1 percent solution in 96 percent sulfuric acid, and a content of acidic groups of 54 mAq / kg and basic groups of 76 meq / kg.
In analoger Weise erhält man Polyamid 6,9 und Polyamid 10,6.Polyamide 6.9 and polyamide 10.6 are obtained in an analogous manner.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2728931 | 1977-06-27 | ||
| DE19772728931 DE2728931A1 (en) | 1977-06-27 | 1977-06-27 | METHOD FOR MANUFACTURING POLYAMIDES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000142A1 EP0000142A1 (en) | 1979-01-10 |
| EP0000142B1 true EP0000142B1 (en) | 1980-08-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100150A Expired EP0000142B1 (en) | 1977-06-27 | 1978-06-14 | Process for the preparation of polyamides |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4251653A (en) |
| EP (1) | EP0000142B1 (en) |
| JP (1) | JPS5411999A (en) |
| DE (2) | DE2728931A1 (en) |
| IT (1) | IT1096578B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58205492A (en) * | 1982-05-27 | 1983-11-30 | Q P Corp | Granule for sake(liquor), its preparation, and alcoholic drink using it |
| US4442260A (en) * | 1983-03-14 | 1984-04-10 | E. I. Du Pont De Nemours & Company | Preparation of salt solution useful for making nylon |
| US4617373A (en) | 1985-02-15 | 1986-10-14 | Eastman Kodak Company | Condensation polymers and products therefrom |
| WO1989005171A2 (en) * | 1987-12-03 | 1989-06-15 | University Of Florida | Apparatus for stereotactic radiosurgery |
| DE4403452A1 (en) * | 1993-04-26 | 1994-10-27 | Zimmer Ag | Discontinuous catalytic process for the production of polyamide-6.6 |
| US20070287822A1 (en) * | 2006-06-13 | 2007-12-13 | Eastman Chemical Company | Light absorbing compositions |
| JP2015500360A (en) | 2011-12-05 | 2015-01-05 | インヴィスタ テクノロジーズ エスアエルエル | Preparation method of polyamide |
| CN104130403B (en) * | 2013-05-01 | 2018-05-29 | 英威达纺织（英国）有限公司 | For producing the metering method of the dicarboxylic acid powder of nylon salt solution |
| 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE548810A (en) * | 1955-07-23 | |||
| NL252332A (en) * | 1959-06-06 | |||
| BE640369A (en) | 1963-08-12 | 1964-03-16 | ||
| BE638236A (en) | 1962-10-04 | |||
| 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 DE19772728931 patent/DE2728931A1/en not_active Withdrawn
-
1978
- 1978-06-08 US US05/913,748 patent/US4251653A/en not_active Expired - Lifetime
- 1978-06-14 EP EP78100150A patent/EP0000142B1/en not_active Expired
- 1978-06-14 DE DE7878100150T patent/DE2860225D1/en not_active Expired
- 1978-06-20 IT IT24768/78A patent/IT1096578B/en active
- 1978-06-26 JP JP7659078A patent/JPS5411999A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000142A1 (en) | 1979-01-10 |
| DE2728931A1 (en) | 1979-01-04 |
| DE2860225D1 (en) | 1980-12-04 |
| IT1096578B (en) | 1985-08-26 |
| JPS6315297B2 (en) | 1988-04-04 |
| IT7824768A0 (en) | 1978-06-20 |
| US4251653A (en) | 1981-02-17 |
| JPS5411999A (en) | 1979-01-29 |
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