WO2002096975A1 - Method for producing high-viscosity or highly-stable polycondensates and demonomerized pa6 - Google Patents

Method for producing high-viscosity or highly-stable polycondensates and demonomerized pa6 Download PDF

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Publication number
WO2002096975A1
WO2002096975A1 PCT/EP2002/005441 EP0205441W WO02096975A1 WO 2002096975 A1 WO2002096975 A1 WO 2002096975A1 EP 0205441 W EP0205441 W EP 0205441W WO 02096975 A1 WO02096975 A1 WO 02096975A1
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reaction stage
polycondensate
reactor
distributor
reaction
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PCT/EP2002/005441
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German (de)
French (fr)
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Karlheinz Wiltzer
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Polymer Engineering Gmbh
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Application filed by Polymer Engineering Gmbh filed Critical Polymer Engineering Gmbh
Priority to EP02738083A priority Critical patent/EP1406948A1/en
Priority to UA20031212941A priority patent/UA76471C2/en
Publication of WO2002096975A1 publication Critical patent/WO2002096975A1/en

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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
    • C08G69/46—Post-polymerisation treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/247—Suited for forming thin films
    • 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
    • C08G69/04—Preparatory processes
    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel

Definitions

  • the invention relates to a method for producing highly viscous or highly stabilized polycondensates and demonomerized PA6 of the type mentioned in the preamble of claim 1 and to an apparatus for carrying out the method.
  • twin-screw extruders For polycondensation, it is known to increase the viscosity by performing degassing in twin-screw extruders.
  • twin-screw extruders represent complex and wear-prone components, and the extent of the degassing that can be achieved with them is limited.
  • the invention has for its object to provide a method of the type mentioned and an apparatus for carrying out the method, which or with little effort enables a strong increase in viscosity.
  • the reaction stage shown in the drawing comprises a vertical reactor 1 which has an inlet line 7 at the upper end for supplying the polycondensate melt supplied by a preliminary stage, with one in the course of the supply line 7
  • Pump P1 can be arranged.
  • a distributor 2 for supplying the polycondensate melt to the elements 3 is arranged, the inlet of which is connected to the inlet line 7.
  • metering devices P2, P3 connected in series, for example in the form of controllable pumps, between which one end of a return line 6 is connected, the other end of which is connected to the inlet of the distributor 2, this connection can preferably also take place at a connection point 9 with the inlet line.
  • Flow direction rear metering device P3 could also be formed by a control valve.
  • connection point 9 it is expedient to use a static mixer 10 in the inlet line and to dimension the static mixer 10 including the line after the static mixer 10 up to a maximum of the distributor 2 such that the residence time for a viscosity increase due to polycondensation increases.
  • the cross-sectional area of the line 7 after the connection point 9 is therefore larger than the sum of the cross sections of the line 7 before the connection point 9 plus the cross section of the return line 6.
  • connection point 9 which is completely filled with polycondensate and through which the product flows through the connection point 10 until it enters the polycondensation stage.
  • the inlet line 7 at the reactor discharge then ends before the distributor
  • the reactor 1 further has at least one gas outlet 4 at the upper end and a level measuring device 5 in the sump, the output signal of which can be used to control the metering device P3 or alternatively the pump P1.
  • the return line 6 enables a portion of the polycondensate melt located at the lower end of the reactor 1 to be recirculated and thus a portion of this melt to be pumped around, thereby increasing the viscosity and / or reducing the lactam in a simple manner since the melt is repeated several times via the surface-enlarging elements 3 is conducted and degassed intensively to effectively remove polycondensation waste products.
  • the residence time in the reactor 1 is set to achieve the chemical polycondensate equilibrium and / or in the case of the production of PA 6 polycondensate or copolyamide polycondensates based on PA 6 to achieve a reduction in lactam, so that sufficient polycondensate product is simulated and in the degassing space above of the melt level can be removed via the gas outlet 4.
  • the polycondensate product can be removed by introducing an inert gas via a line 8 into the vicinity of the surface of the melt or in a vacuum.
  • the residence time of the melt in the reactor can be 3 hours, with a pumped amount of 50% of the throughput through the reactor 1 being able to be set via the control of the metering devices P2, P3 as an example.
  • Useful volume can be increased by an increase of the fill level measured by the level measuring device 5 by 50%.
  • Stabilizers can be added in the preliminary stage to obtain more stabilized polycondensate.
  • the level is not raised and about 4.5% lactam reduction can be achieved by pumping 100% of the throughput.
  • the gas outlet 4 can be connected to devices for the recovery of monomer, the inert gas and water, which are only indicated schematically.

Abstract

The invention relates to a method and a device for producing high-viscosity or highly stable polycondensates and demonomerized PA6 using vertical reaction stages. According to said method, the molten polycondensate is fed from a preliminary stage into the upper end of the reaction stage and is distributed by means of distribution devices and elements that increase the surface area. Waste reactant is removed from the flowing molten polycondensate using inert gas or a vacuum and is withdrawn from the reaction stage above the level of the molten polycondensate. The product residence time in the sump is selected in such a way that at the lower end of the reaction stage a polycondensate at chemical equilibrium is produced, part of which is re-supplied to the upper end of the reaction stage, the remaining part being withdrawn from the reaction stage, according to the selected throughput, for further use.

Description

Verfahren zur Herstellung von hochviskosen oder hochstabilisierten Polykondensaten und entmonomerisiertem PA6 Process for the production of highly viscous or highly stabilized polycondensates and demonomerized PA6
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von hochviskosen oder hochstabilisierten Polykondensaten und entmonomerisiertem PA6 der im Oberbegriff des Anspruchs 1 genannten Art sowie auf eine Vorrichtung zur Durchführung des Verfahrens.The invention relates to a method for producing highly viscous or highly stabilized polycondensates and demonomerized PA6 of the type mentioned in the preamble of claim 1 and to an apparatus for carrying out the method.
Für die Polykondensation ist es zur Erhöhung der Viskosität bekannt, eine Entgasung in Doppelschneckenextrudem durchzuführen. Derartige Doppelschneckenextruder stellen jedoch aufwendige und verschleißanfällige Bauteile dar, und das Ausmaß der hiermit erreichbaren Entgasung ist begrenzt.For polycondensation, it is known to increase the viscosity by performing degassing in twin-screw extruders. However, such twin-screw extruders represent complex and wear-prone components, and the extent of the degassing that can be achieved with them is limited.
Ebenso ist es bekannt, Nachkondensationsverfahren in annähernd horizontal angeordneten Nachkondensatoren durchzuführen. Dabei wird die Polykondensationsschmelze laufend aus einem Niveau durch sich drehende innere mechanische Vorrichtungen der oberhalb des Schmelzeniveaus befindlichen Atmosphäre ausgesetzt und so entgast. Das entgaste Produkt wird nach außen abgeführt. Bei diesem Verfahren ist jedoch keine ausreichende exakte Produktverweilzeit gesichert, wodurch Qualitätseinbußen des fertigen Polykondensates eintreten. Auf keinen Fall wird das chemische Gleichgewicht am Ende der Polykondensation eingestellt. Im übrigen sind die dafür verwendeten Vorrichtungen kompliziert, insbesondere die Abdichtung zur Außenatmosphäre ist ein nicht ausreichend gelöstes Problem, wodurch sauerstoffanfällige Polykondensate geschädigt werden.It is also known to carry out post-condensation processes in post-condensers arranged approximately horizontally. The polycondensation melt is continuously exposed from one level to the atmosphere above the melt level by rotating internal mechanical devices and thus degassed. The degassed product is discharged to the outside. However, this method does not ensure a sufficient exact product dwell time, as a result of which the quality of the finished polycondensate is reduced. Under no circumstances will the chemical equilibrium be set at the end of the polycondensation. In addition, the devices used for this are complicated, in particular the sealing to the outside atmosphere is a problem which is not adequately solved, as a result of which oxygen-sensitive polycondensates are damaged.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art sowie eine Vorrichtung zur Durchführung des Verfahrens zu schaffen, das bzw. diebei geringem Aufwand eine starke Erhöhung der Viskosität ermöglicht.The invention has for its object to provide a method of the type mentioned and an apparatus for carrying out the method, which or with little effort enables a strong increase in viscosity.
Diese Aufgabe wird durch die im Anspruch 1 bzw. 4 angegebenen Merkmale gelöst.This object is achieved by the features specified in claims 1 and 4, respectively.
Vorteilhafte Ausgestaltungen und Weiterbildungen der Erfindung ergeben sich aus denAdvantageous refinements and developments of the invention result from the
Unteransprüchen. Durch die Zurückspeisung eines Teils der am unteren Ende der vertikal angeordneten Reaktionsstufe befindlichen Polykondensatschmelze und damit ein Umpumpen eines Teils dieser Schmelze wird in einfacher Weise eine Erhöhung der Viskosität und/oder eine Laktamreduzierung erreicht, da die Schmelze mehrmals über einen Bereich mit intensiver Entgasung geleitet wird, um Polykondensationsabprodukte wirksam zu entfernen. Die Verweilzeit in der Reaktionsstufe wird dabei jeweils zur Erreichung des chemischen Polykondensatgleichgewichts eingestellt, damit ausreichend Polykonden- satabprodukt nachgebildet und im Entgasungsraum oberhalb des Schmelzeniveaus entfernt werden kann. Die Entfernung des Polykondensatabprodukts kann mittelsDependent claims. By feeding back part of the polycondensate melt located at the lower end of the vertically arranged reaction stage and thus pumping around part of this melt, an increase in viscosity and / or a lactam reduction is achieved in a simple manner, since the melt is passed several times over an area with intensive degassing to effectively remove polycondensation wastes. The residence time in the reaction stage is adjusted in each case in order to achieve the chemical polycondensate equilibrium so that sufficient polycondensation product can be simulated and removed in the degassing space above the melt level. Removal of the polycondensate product can be done using
Inertgas oder im Vakuum erfolgen.Inert gas or in a vacuum.
Am Zusammenfluß von Polykondensat aus der Vorstufe und aus der Rückführung entsteht ein nicht im chemischen Gleichgewicht befindliches Polykondensat, da die Menge des Abproduktreaktionspartners sich unterhalb des chemischen Gleichgewichts des Vorstufenpolykondensats einstellt. Hier findet deshalb eine Polykondensations- reaktion statt. Die Viskosität der Polykondensationsschmelze steigt demzufolge nach dem Zusammenfluß nicht nur wegen der Mischung an, sondern auch weil eine Polykondensationsreaktion stattfindet, sofern ausreichend Verweilzeit direkt nach dem Zusammenfluß zur Verfügung steht. Es kann deshalb von Vorteil sein, durchAt the confluence of the polycondensate from the precursor and from the recycle, a polycondensate which is not in chemical equilibrium is formed, since the amount of the product reaction partner is below the chemical equilibrium of the precursor polycondensate. A polycondensation reaction therefore takes place here. The viscosity of the polycondensation melt consequently increases after the confluence not only because of the mixture, but also because a polycondensation reaction takes place, provided there is sufficient dwell time directly after the confluence. It can therefore be beneficial to
Rohrerweiterung nach dem Zusammenfluß bis zur Nachkondensationsreaktionsstufe zusätzliche Verweilzeit zu schaffen.Pipe extension after the confluence to the post-condensation reaction stage to create additional residence time.
Ein Ausführungsbeispiel der Erfindung ist in der beigefügten Zeichnung dargestellt, die eine bevorzugte Ausführungsform der Reaktionsstufe zur Durchführung des erfindungsgemäßen Verfahrens zeigt.An embodiment of the invention is shown in the accompanying drawing, which shows a preferred embodiment of the reaction stage for performing the method according to the invention.
Die in der Zeichnung gezeigte Reaktionsstufe umfaßt einen vertikalen Reaktor 1 , der am oberen Ende eine Einlaßleitung 7 zur Zuführung der von einer Vorstufe gelieferten Polykondensatschmelze aufweist, wobei im Verlauf der Zuführungsleitung 7 eineThe reaction stage shown in the drawing comprises a vertical reactor 1 which has an inlet line 7 at the upper end for supplying the polycondensate melt supplied by a preliminary stage, with one in the course of the supply line 7
Pumpe P1 angeordnet sein kann.Pump P1 can be arranged.
In dem Reaktor 1 sind oberflächenvergrößemde Elemente 3 angeordnet, über denen ein Verteiler 2 zur Zuführung der Polykondensatschmelze an die Elemente 3 angeordnet ist, dessen Eingang mit der Einlaßleitung 7 verbunden ist. Am unteren Ende des Reaktors 1 sind zwei in Reihe geschaltete Dosiereinrichtungen P2, P3, beispielsweise in Form von steuerbaren Pumpen, angebaut, zwischen denen ein Ende einer Rückführleitung 6 angeschlossen ist, deren anderes Ende mit dem Eingang des Verteilers 2 verbunden ist, wobei diese Verbindung vorzugsweise auch an einer Verbindungsstelle 9 mit der Einlaßleitung erfolgen kann. Die in Austritts-In the reactor 1, surface-enlarging elements 3 are arranged, above which a distributor 2 for supplying the polycondensate melt to the elements 3 is arranged, the inlet of which is connected to the inlet line 7. At the lower end of the reactor 1 there are two metering devices P2, P3 connected in series, for example in the form of controllable pumps, between which one end of a return line 6 is connected, the other end of which is connected to the inlet of the distributor 2, this connection can preferably also take place at a connection point 9 with the inlet line. The in exit
Strömungsrichtung hintere Dosiereinrichtung P3 könnte auch durch ein Regelventil gebildet sein.Flow direction rear metering device P3 could also be formed by a control valve.
Nach der Verbindungsstelle 9 ist es zweckmäßig, in die Einlaßleitung einen statischen Mischer 10 einzusetzen und den statischen Mischer 10 einschließlich der Leitung nach dem statischen Mischer 10 bis maximal zum Verteiler 2 so zu dimensionieren, daß die Verweilzeit für einen Viskositätsanstieg durch Polykondensation ansteigt. Die Querschnittsfläche der Leitung 7 nach der Verbindungsstelle 9 ist deshalb größer als die Summe der Querschnitte der Leitung 7 vor der Verbindungsstelle 9 plus dem Querschnitt der Rückführleitung 6.After the connection point 9, it is expedient to use a static mixer 10 in the inlet line and to dimension the static mixer 10 including the line after the static mixer 10 up to a maximum of the distributor 2 such that the residence time for a viscosity increase due to polycondensation increases. The cross-sectional area of the line 7 after the connection point 9 is therefore larger than the sum of the cross sections of the line 7 before the connection point 9 plus the cross section of the return line 6.
Es ist auch möglich, nach der Verbindungsstelle 9 noch einen (nicht gezeigten) Reaktor einzubauen, der vollständig mit Polykondensat gefüllt ist und von der Verbindungsstelle 10 bis zum Eintritt in die Polykondensationsstufe von dem Produkt durchströmt wird. Die Einlaßleitung 7 am Reaktoraustrag endet dann vor dem VerteilerIt is also possible to install a reactor (not shown) after the connection point 9, which is completely filled with polycondensate and through which the product flows through the connection point 10 until it enters the polycondensation stage. The inlet line 7 at the reactor discharge then ends before the distributor
2 und ist mit beliebigem Durchmesser in den Verteiler 2 eingebunden.2 and is integrated with any diameter in the distributor 2.
Der Reaktor 1 weist weiterhin am oberen Ende mindestens einen Gasaustritt 4 und im Sumpf eine Niveaumeßeinrichtung 5 auf, deren Ausgangssignal zur Steuerung der Dosiereinrichtung P3 oder alternativ auch der Pumpe P1 verwendet werden kann.The reactor 1 further has at least one gas outlet 4 at the upper end and a level measuring device 5 in the sump, the output signal of which can be used to control the metering device P3 or alternatively the pump P1.
Die Rückführleitung 6 ermöglicht die Zurückspeisung eines Teils der am unteren Ende des Reaktors 1 befindlichen Polykondensatschmelze umd damit ein Umpumpen eines Teils dieser Schmelze, wodurch in einfacher Weise eine Erhöhung der Viskosität und/oder eine Laktamreduzierung erreicht wird, da die Schmelze mehrmals über die oberflächenvergrößernden Elemente 3 geleitet und intensiv entgast wird.um Polykon- densationsabprodukte wirksam zu entfernen. Die Verweilzeit in dem Reaktor 1 wird dabei jeweils zur Erreichung des chemischen Polykondensatgleichgewichts und/oder im Fall der Produktion von PA 6-Polykondensat bzw. Copolyamidpolykondensaten auf der Basis von PA 6 zur Erreichung einer Laktamreduzierung eingestellt, damit ausreichend Polykondensatabprodukt nachgebildet und im Entgasungsraum oberhalb des Schmelzeniveaus über den Gasaustritt 4 entfernt werden kann.The return line 6 enables a portion of the polycondensate melt located at the lower end of the reactor 1 to be recirculated and thus a portion of this melt to be pumped around, thereby increasing the viscosity and / or reducing the lactam in a simple manner since the melt is repeated several times via the surface-enlarging elements 3 is conducted and degassed intensively to effectively remove polycondensation waste products. The residence time in the reactor 1 is set to achieve the chemical polycondensate equilibrium and / or in the case of the production of PA 6 polycondensate or copolyamide polycondensates based on PA 6 to achieve a reduction in lactam, so that sufficient polycondensate product is simulated and in the degassing space above of the melt level can be removed via the gas outlet 4.
Die Entfernung des Polykondensatabprodukts kann mittels Einleitung eines Inertgases über eine Leitung 8 in die Nähe der Oberfläche der Schmelze oder im Vakuum erfolgen.The polycondensate product can be removed by introducing an inert gas via a line 8 into the vicinity of the surface of the melt or in a vacuum.
Für eine Polykondensation zur Erhöhung der Viskosität kann die Verweilzeit der Schmelze in dem Reaktor 3 Stunden betragen, wobei als Beispiel eine Umpumpmenge von 50% des Durchsatzes durch den Reaktor 1 über die Steuerung der Dosiereinrichtungen P2, P3 eingestellt werden kann. Hierbei sollte dasFor a polycondensation to increase the viscosity, the residence time of the melt in the reactor can be 3 hours, with a pumped amount of 50% of the throughput through the reactor 1 being able to be set via the control of the metering devices P2, P3 as an example. Here, that should
Nutzvolumen über eine Erhöhung des durch die Niveaumeßeinrichtung 5 gemessenen Füllstandes um 50% erhöht werden.Useful volume can be increased by an increase of the fill level measured by the level measuring device 5 by 50%.
Zur Gewinnung von höher stabilisiertem Polykondensat können Stabilisatoren in der Vorstufe zugesetzt werden.Stabilizers can be added in the preliminary stage to obtain more stabilized polycondensate.
Wenn das Verfahren zur Entlactamisierung von PA6 verwendet wird, wird das Niveau nicht angehoben, und es kann durch Umpumpen von 100% des Durchsatzes eine Lactamreduzierung von etwa 4,5% erreicht werden.When the PA6 deactamization process is used, the level is not raised and about 4.5% lactam reduction can be achieved by pumping 100% of the throughput.
Der Gasaustritt 4 kann mit nur schematisch angedeuteten Einrichtungen zur Rückgewinnung von Monomerem, des Inertgases und Wasser verbunden sein. The gas outlet 4 can be connected to devices for the recovery of monomer, the inert gas and water, which are only indicated schematically.

Claims

Patentansprüche: claims:
1. Verfahren zur Herstellung von hochviskosen oder hochstabilisierten Polykondensaten und entmonomerisiertem PA6 unter Verwendung von senkrechten Reaktionsstufen, dadurch gekennzeichnet, daß Polykondensatschmelze aus einer Vorstufe in das obere Ende der Reaktionsstufe eingespeist und über Verteilereinrichtungen und oberflächenvergrößernde Elemente verteilt wird, daß mittels Inertgas oder Vakuum aus der fließenden Polykondensatschmelze Abproduktionsreaktionspartner entfernt und oberhalb des Pegels der Polykondensatschmelze aus der Reaktionsstufe entfernt werden, daß die Produktverweilzeit im Sumpf so gewählt wird, daß am unteren Ende der Reaktionsstufe ein im chemischen Gleichgewicht befindliches Polykondensat vorliegt, von dem ein Teil in das obere Ende der Reaktionsstufe zurückgespeist wird, während der verbleibende Teil entsprechend dem gewählten Durchsatz zur weiteren Verwendung aus der Reaktionsstufe ausgetragen wird.1. A process for the preparation of highly viscous or highly stabilized polycondensates and demonomerized PA6 using vertical reaction stages, characterized in that polycondensate melt is fed from a preliminary stage into the upper end of the reaction stage and is distributed via distributor devices and surface-enlarging elements, that by means of inert gas or vacuum from the flowing polycondensate melt production reaction partners are removed and above the level of the polycondensate melt are removed from the reaction stage in such a way that the product residence time in the bottom is chosen so that a polycondensate which is in chemical equilibrium is present at the lower end of the reaction stage, part of which is fed back into the upper end of the reaction stage is discharged from the reaction stage for further use in accordance with the selected throughput.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß der zurückgespeiste Teil 50% der Durchsatzmenge der Reaktionsstufe entspricht.2. The method according to claim 1, characterized in that the recovered part corresponds to 50% of the throughput of the reaction stage.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die daß die3. The method according to claim 1 or 2, characterized in that that
Produktverweilzeit für eine Polykondensation zur Erhöhung der Viskosität bis 5 Stunden beträgt und die Produktverweilzeit nach dem Zusammenströmen von frischen Produkt mit zurückgespeisten Produkt bis 1 Stunde beträgt.Product residence time for a polycondensation to increase the viscosity is up to 5 hours and the product residence time after the confluence of fresh product with the returned product is up to 1 hour.
4. Vorrichtung zur Durchführung des Verfahrens, gekennzeichnet durch einen Reaktor (1), in dem oberflächenvergrößernde Elemente (3) angeordnet sind, über denen ein Verteiler (2) zur Zuführung der Polykondensatschmelze an die Elemente (3) angeordnet ist, wobei der Reaktor (1) am oberen Ende mindestens einen Gasaustritt 4 und im Sumpf eine Niveaumeßeinrichtung (5) aufweist und am unteren Ende des4. Apparatus for carrying out the method, characterized by a reactor (1) in which surface-enlarging elements (3) are arranged, above which a distributor (2) for supplying the polycondensate melt to the elements (3) is arranged, the reactor ( 1) has at least one gas outlet 4 at the upper end and a level measuring device (5) in the sump and at the lower end of the
Reaktors (1) zwei in Reihe geschaltete Dosiereinrichtungen (P2, P3) angebaut sind, zwischen denen ein Ende einer Rückführleitung (6) angeschlossen ist, deren anderes Ende mit dem Eingang des Verteilers (2) verbunden ist.Reactor (1) two metering devices (P2, P3) connected in series, between which one end of a return line (6) is connected, the other end of which is connected to the inlet of the distributor (2).
5. Vorrichtung nach" Anspruch 4, dadurch gekennzeichnet, daß zumindest eine der5. The device according to " claim 4, characterized in that at least one of
Dosiereinrichtungen durch eine Pumpe (P2, P3) gebildet ist. Metering devices is formed by a pump (P2, P3).
6. Vorrichtung nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß Polykondensatschmelze aus der Vorstufe dem Verteiler (2) über eine Pumpe (P1) zugeführt wird, die zur Regelung des Durchsatzes durch den Reaktor (1) steuerbar ist.6. Apparatus according to claim 4 or 5, characterized in that the polycondensate melt is fed from the preliminary stage to the distributor (2) via a pump (P1) which can be controlled to regulate the throughput through the reactor (1).
7. Vorrichtung nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, daß die Rückführleitung (6) in Strömungsrichtung hinter der Pumpe (P1) an einer Verbindungsstelle (9) in die Einlaßleitung (7) mündet, und hinter der Verbindungsstelle (9) in der Einlaßleitung (7) vor dem Verteiler (2) ein statischer Mischer (10) und/oder ein mit Einlaß und Ablaß versehener Reaktor angeordnet ist. 7. Device according to one of claims 4 to 6, characterized in that the return line (6) opens in the flow direction behind the pump (P1) at a connection point (9) into the inlet line (7), and behind the connection point (9) in a static mixer (10) and / or a reactor provided with inlet and outlet is arranged in front of the distributor (2) of the inlet line (7).
PCT/EP2002/005441 2001-05-29 2002-05-17 Method for producing high-viscosity or highly-stable polycondensates and demonomerized pa6 WO2002096975A1 (en)

Priority Applications (2)

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EP02738083A EP1406948A1 (en) 2001-05-29 2002-05-17 Method for producing high-viscosity or highly-stable polycondensates and demonomerized pa6
UA20031212941A UA76471C2 (en) 2001-05-29 2002-05-17 Method for the preparation of high-viscous or high stable polycondensates, a method for the preparation of demonomerized and delactaminized polyamide -6 , and an apparatus for realizing these methods

Applications Claiming Priority (2)

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DE2001126133 DE10126133B4 (en) 2001-05-29 2001-05-29 Process and apparatus for the preparation of highly viscous or highly stabilized polycondensates and demonomerized PA 6
DE10126133.0 2001-05-29

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US7649109B2 (en) 2006-12-07 2010-01-19 Eastman Chemical Company Polyester production system employing recirculation of hot alcohol to esterification zone
US7718759B2 (en) 2000-12-07 2010-05-18 Eastman Chemical Company Polyester process using a pipe reactor
US7829653B2 (en) 2007-07-12 2010-11-09 Eastman Chemical Company Horizontal trayed reactor
US7842777B2 (en) 2007-07-12 2010-11-30 Eastman Chemical Company Sloped tubular reactor with divided flow
US7847053B2 (en) 2007-07-12 2010-12-07 Eastman Chemical Company Multi-level tubular reactor with oppositely extending segments
US7858730B2 (en) 2007-07-12 2010-12-28 Eastman Chemical Company Multi-level tubular reactor with dual headers
US7863477B2 (en) 2007-03-08 2011-01-04 Eastman Chemical Company Polyester production system employing hot paste to esterification zone
US7868130B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Multi-level tubular reactor with vertically spaced segments
US7868129B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Sloped tubular reactor with spaced sequential trays
US7872089B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Multi-level tubular reactor with internal tray
US7872090B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Reactor system with optimized heating and phase separation
US7943094B2 (en) 2006-12-07 2011-05-17 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel

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Cited By (15)

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Publication number Priority date Publication date Assignee Title
US7718759B2 (en) 2000-12-07 2010-05-18 Eastman Chemical Company Polyester process using a pipe reactor
US7842778B2 (en) 2000-12-07 2010-11-30 Eastman Chemical Company Polyester process using a pipe reactor
US8114954B2 (en) 2000-12-07 2012-02-14 Grupo Petrotemex, S.A. De C.V. Polyester process using a pipe reactor
US8470250B2 (en) 2006-12-07 2013-06-25 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel
US7943094B2 (en) 2006-12-07 2011-05-17 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel
US7649109B2 (en) 2006-12-07 2010-01-19 Eastman Chemical Company Polyester production system employing recirculation of hot alcohol to esterification zone
US7863477B2 (en) 2007-03-08 2011-01-04 Eastman Chemical Company Polyester production system employing hot paste to esterification zone
US7858730B2 (en) 2007-07-12 2010-12-28 Eastman Chemical Company Multi-level tubular reactor with dual headers
US7868130B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Multi-level tubular reactor with vertically spaced segments
US7868129B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Sloped tubular reactor with spaced sequential trays
US7872089B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Multi-level tubular reactor with internal tray
US7872090B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Reactor system with optimized heating and phase separation
US7847053B2 (en) 2007-07-12 2010-12-07 Eastman Chemical Company Multi-level tubular reactor with oppositely extending segments
US7842777B2 (en) 2007-07-12 2010-11-30 Eastman Chemical Company Sloped tubular reactor with divided flow
US7829653B2 (en) 2007-07-12 2010-11-09 Eastman Chemical Company Horizontal trayed reactor

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RU2003137774A (en) 2005-05-20
DE10126133B4 (en) 2007-03-29
DE10126133A1 (en) 2003-01-02
CN1535291A (en) 2004-10-06
CN1249125C (en) 2006-04-05
EP1406948A1 (en) 2004-04-14
RU2295545C2 (en) 2007-03-20
UA76471C2 (en) 2006-08-15

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