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

Info

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
Authority
WO
Grant status
Application
Patent type
Prior art keywords
polycondensate
reaction
end
melt
reactor
Prior art date
Application number
PCT/EP2002/005441
Other languages
German (de)
French (fr)
Inventor
Karlheinz Wiltzer
Original Assignee
Polymer Engineering Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/46Post-polymerisation treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053Details of the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/2455Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/2465Stationary 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/247Suited for forming thin films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04Preparatory processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14Lactams
    • C08G69/16Preparatory processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14Lactams
    • C08G69/16Preparatory processes
    • C08G69/18Anionic polymerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00164Controlling or regulating processes controlling the flow
    • B01J2219/00166Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00182Controlling or regulating processes controlling the level of reactants in the reactor vessel

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

A process for producing high-viscosity or highly stabilized polycondensates and entmonomerisiertem PA6

The invention relates to a method for the production of high-viscosity or highly stabilized polycondensates and entmonomerisiertem PA6 of the type mentioned in the preamble of claim 1 and to an apparatus for performing the method.

For the polycondensation it is known to increase the viscosity to perform a degassing in Doppelschneckenextrudem. However, such twin-screw extruder set-consuming and prone to wear components are, and the extent of degassing hereby achievable is limited.

It is also known to carry out after-condensation in an approximately horizontally-arranged after-condensers. The polycondensation melt is continuously exposed to a level by rotating inner mechanical devices, the atmosphere situated above the melt level and thus degassed. The degassed product is discharged to the outside. In this method, however, sufficient exact product residence time is saved, thereby loss of quality of the finished polycondensate occur. Never remove the chemical balance is adjusted at the end of the polycondensation. Moreover, the devices used for this are complicated, in particular the seal to the outside atmosphere is not sufficiently solved problem, whereby oxygen-prone polycondensates are damaged.

The invention has for its object to provide a method of the type mentioned at the outset and a device for carrying out the method, which allows diebei little effort and a strong increase in viscosity.

This object is achieved by the features indicated in claims 1 and 4 Characteristics.

Advantageous embodiments and developments of the invention result from the

Dependent claims. By backfeeding a part of the polycondensate melt located at the lower end of the vertically arranged reaction stage and a pumping a portion of this melt an increase in viscosity and / or a Laktamreduzierung is achieved in a simple manner, since the melt is repeatedly conducted over a range with intensive degassing to remove Polykondensationsabprodukte effective. The residence time in the reaction step is in this case, are respectively set so that sufficient satabprodukt simulated polycondensates and can be removed in the degassing chamber above the melt level in order to achieve the chemical Polykondensatgleichgewichts. The removal of the can by means of Polykondensatabprodukts

Inert gas or carried out in a vacuum.

At the confluence of the polycondensate of the precursor and of the return result is a not building under chemical equilibrium polycondensate, since the amount of Abproduktreaktionspartners is established below the chemical equilibrium of Vorstufenpolykondensats. Here, therefore, finds a place polycondensation reaction. The viscosity of the polycondensation melt thus increases after the confluence not only due to the mix, but also because a polycondensation reaction takes place, provided there is sufficient residence time right after the confluence available. It may therefore be advantageous to

Nachkondensationsreaktionsstufe to create pipe expansion after the confluence additional residence.

An embodiment of the invention is illustrated in the accompanying drawing, which shows a preferred embodiment of the reaction step for carrying out the method according to the invention.

The reaction stage shown in the drawing comprises a vertical reactor 1, which has at the upper end of an inlet pipe 7 for supplying the polycondensate melt supplied from a precursor, which in the course of said feeding line 7 a

Pump P1 may be located.

In the reactor 1 oberflächenvergrößemde elements 3 are arranged, above which a manifold 2 for supplying the polycondensate melt is arranged on the elements 3, whose input is connected to the inlet conduit. 7 At the lower end of the reactor 1 two series connected metering devices P2, P3, for example in the form of controllable pumps are mounted, between which one end of a recirculation line 6 is connected, whose other end is connected to the input of the distributor 2, wherein said compound preferably can also take place at a junction 9 to the inlet conduit. In exit

The direction of flow P3 rear metering device could also be formed by a control valve.

After the junction 9, it is expedient to use in the inlet duct a static mixer 10 and to dimension the static mixer 10 including the line to the static mixer 10 to a maximum of the manifold 2 so that the residence time increases for an increase in viscosity through polycondensation. The cross-sectional area of ​​the conduit 7 to the connection point 9 is therefore greater 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

It is also possible to incorporate another (not shown) reactor according to the connection point 9, which is completely filled with the polycondensate and flows through the junction 10 to the entry into the polycondensation stage of the product. The inlet duct 7 at reactor then ends before distribution

2 and is integrated with any diameter in the manifold. 2

The reactor 1 further comprises at the upper end at least one gas outlet 4 and in the bottom a ride level measuring device 5, the output signal for controlling the metering device P3 or alternatively, the pump P1 may be used.

The return line 6 allows the backfeeding of a part of the polycondensate melt located at the lower end of the reactor 1 so umd, recirculation of a portion of this melt, thereby achieving an increase in viscosity and / or a Laktamreduzierung in a simple manner, since the melt several times over the surface enlarging elements 3 directed and intense degassing wird.um polycondensation densationsabprodukte effectively remove. The residence time in the reactor 1 is in this case 6, is set so that reproduced sufficiently Polykondensatabprodukt and in the degassing chamber above the in each case to achieve a Laktamreduzierung to achieve the chemical Polykondensatgleichgewichts and / or in the production of PA 6 or polycondensate Copolyamidpolykondensaten based on PA case melt level can be removed via the gas outlet. 4

The removal of the Polykondensatabprodukts can be done by introducing an inert gas through a line 8 into the vicinity of the surface of the melt or in a vacuum.

For a polycondensation for increasing the viscosity of the melt residence time in the reactor can be from 3 hours to give as an example a circulation rate of 50% of the throughput through the reactor 1 via control of the metering devices P2, P3 can be set. It should the

Useful volume can be increased through an increase in the measured by the level measuring filling level 5 to 50%.

For the production of higher stabilized polycondensate stabilizers can be added in the precursor.

If the method of Entlactamisierung of PA6 is used, the level is not raised, and it can be achieved by the pumping of 100% of the throughput of a Lactamreduzierung about 4.5%.

The gas outlet 4 may be associated with only schematically indicated equipment for the recycling of monomer, the inert gas and water.

Claims

claims:
1. A process for the production of high-viscosity or highly stabilized polycondensates and entmonomerisiertem PA6 using vertical reaction stages, characterized in that the polycondensate melt is fed from a precursor in the upper end of the reaction stage and is distributed via distributor devices and surface-increasing elements, that the means of inert gas or vacuum from are flowing polycondensate Abproduktionsreaktionspartner away and removed from above the level of the polycondensate from the reaction stage, that the product residence time is selected in the bottom so that at the lower end of the reaction stage a work in chemical equilibrium polycondensate is present, a portion of which is fed back into the upper end of the reaction stage , while the remaining part is discharged according to the selected flow rate for further use in the reaction stage.
2. The method of claim 1, characterized in that the fed back portion corresponds to 50% of the flow rate of the reaction stage.
3. The method according to claim 1 or 2, characterized, in that the that the
Product residence time for polycondensation for increasing the viscosity is up to 5 hours and the product residence after the confluence of fresh product is fed back with the product up to 1 hour.
4. An apparatus for implementing the method, characterized by a reactor (1), in the surface-enlarging elements (3) are arranged, above which a manifold (2) for supplying the polycondensate of the elements (3) is arranged, wherein the reactor ( comprising 1) at the upper end at least one gas outlet 4 and in the bottom a ride level measuring device (5) and at the lower end of the
Reactor (1) two series-dosing (P2, P3) are mounted, between which one end of a return line (6) is connected, whose other end is connected to the input of the distributor (2) is connected.
5. The device according 'to claim 4, characterized in that at least one of
Metering means is formed by a pump (P2, P3).
6. Device according to claim 4 or 5, characterized in that the polycondensate melt from the precursor to the manifold (2) via a pump (P1) is supplied, which for regulating the flow rate through the reactor (1) is controllable.
7. Device according to one of claims 4 to 6, characterized in that the return line (6) downstream of the pump (P1) at a junction (9) in the inlet conduit (7) opens out, and behind the connecting point (9) in the inlet conduit (7) upstream of the distributor (2), a static mixer (10) and / or provided with inlet and discharge reactor is located.
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)

Application Number Priority Date Filing Date Title
DE2001126133 DE10126133B4 (en) 2001-05-29 2001-05-29 Method and apparatus for producing high-viscosity or highly stabilized polycondensates and entmonomerisiertem PA 6
DE10126133.0 2001-05-29

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20020738083 EP1406948A1 (en) 2001-05-29 2002-05-17 Method for producing high-viscosity or highly-stable polycondensates and demonomerized pa6

Publications (1)

Publication Number Publication Date
WO2002096975A1 true true WO2002096975A1 (en) 2002-12-05

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ID=7686512

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/005441 WO2002096975A1 (en) 2001-05-29 2002-05-17 Method for producing high-viscosity or highly-stable polycondensates and demonomerized pa6

Country Status (5)

Country Link
EP (1) EP1406948A1 (en)
CN (1) CN1249125C (en)
DE (1) DE10126133B4 (en)
RU (1) RU2295545C2 (en)
WO (1) WO2002096975A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US7872090B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Reactor system with optimized heating and phase separation
US7872089B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Multi-level tubular reactor with internal tray
US7943094B2 (en) 2006-12-07 2011-05-17 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313592A (en) * 1970-04-28 1973-04-11 Toray Industries Method and apparatus of a continuous polymerization
EP0792672A2 (en) * 1996-02-29 1997-09-03 Wiltzer, Karl-Heinz Process and apparatus for the continuous extraction of polymer granules
US5973105A (en) * 1995-08-30 1999-10-26 Polymer Engineering Gmbh Process for continuously preparing a polyamide 6 with a low dimer content

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2461902A1 (en) * 1974-12-31 1976-07-08 Zimmer Ag Removing volatile components from molten polyamides - by subjecting polyamide to turbulent treatment with gas stream at subatmospheric pressure
DE4039857C2 (en) * 1990-10-19 1993-08-19 Ems-Inventa Ag, Zuerich, Ch
DE19506407B4 (en) * 1995-02-23 2006-08-10 Peter Lausmann Method and apparatus for producing high-viscosity or stabilized highly reactive polyamides stable and continuous demonomerization of polyamides
DE19841376A1 (en) * 1998-09-10 2000-03-16 Lurgi Zimmer Ag A process for feeding additives into a polymer melt stream

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313592A (en) * 1970-04-28 1973-04-11 Toray Industries Method and apparatus of a continuous polymerization
US5973105A (en) * 1995-08-30 1999-10-26 Polymer Engineering Gmbh Process for continuously preparing a polyamide 6 with a low dimer content
EP0792672A2 (en) * 1996-02-29 1997-09-03 Wiltzer, Karl-Heinz Process and apparatus for the continuous extraction of polymer granules

Cited By (15)

* Cited by examiner, † Cited by third party
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
US8114954B2 (en) 2000-12-07 2012-02-14 Grupo Petrotemex, S.A. De C.V. Polyester process using a pipe reactor
US7842778B2 (en) 2000-12-07 2010-11-30 Eastman Chemical Company Polyester process using a pipe reactor
US7649109B2 (en) 2006-12-07 2010-01-19 Eastman Chemical Company Polyester production system employing recirculation of hot alcohol to esterification zone
US7943094B2 (en) 2006-12-07 2011-05-17 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel
US8470250B2 (en) 2006-12-07 2013-06-25 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel
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
US7847053B2 (en) 2007-07-12 2010-12-07 Eastman Chemical Company Multi-level tubular reactor with oppositely extending segments
US7868129B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Sloped tubular reactor with spaced sequential trays
US7872090B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Reactor system with optimized heating and phase separation
US7872089B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Multi-level tubular reactor with internal tray
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
US7868130B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Multi-level tubular reactor with vertically spaced segments

Also Published As

Publication number Publication date Type
RU2003137774A (en) 2005-05-20 application
CN1535291A (en) 2004-10-06 application
RU2295545C2 (en) 2007-03-20 grant
DE10126133A1 (en) 2003-01-02 application
CN1249125C (en) 2006-04-05 grant
DE10126133B4 (en) 2007-03-29 grant
EP1406948A1 (en) 2004-04-14 application

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