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WO2007023108A1 - Procede pour preparer des polyamides - Google Patents

Procede pour preparer des polyamides Download PDF

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Publication number
WO2007023108A1
WO2007023108A1 PCT/EP2006/065321 EP2006065321W WO2007023108A1 WO 2007023108 A1 WO2007023108 A1 WO 2007023108A1 EP 2006065321 W EP2006065321 W EP 2006065321W WO 2007023108 A1 WO2007023108 A1 WO 2007023108A1
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WIPO (PCT)
Prior art keywords
reactor
liquid
chamber
chambers
heat exchanger
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PCT/EP2006/065321
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German (de)
English (en)
Inventor
Motonori Yamamoto
Jürgen Deininger
Oliver SÖTJE
Gad Kory
Peter Eibeck
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BASF SE
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BASF SE
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Publication of WO2007023108A1 publication Critical patent/WO2007023108A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/16—Fractionating columns in which vapour bubbles through liquid
    • B01D3/18—Fractionating columns in which vapour bubbles through liquid with horizontal bubble plates
    • B01D3/20—Bubble caps; Risers for vapour; Discharge pipes for liquid
    • B01D3/205—Bubble caps
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes

Definitions

  • the present invention relates to a process for the preparation of polyamides, their oligomers or mixtures thereof, optionally with further reaction products, by reacting aminonitriles or dinitriles and diamines or a mixture containing aminonitrile, dinitiril and diamine and optionally further polyamide-forming monomers and / or oligomers Water.
  • WO-A-2004/085512 is already a process for the preparation of polyamides, their oligomers or mixtures thereof, optionally with further reaction products, by reacting aminonitriles or dinitriles and diamines or a mixture containing aminonitrile, dinitiril and diamine and optionally further polyamide-forming monomers and / or oligomers with water.
  • the polyamides described therein have e.g. Insufficient impact strength in the heat storage and a not sufficiently rapid rate of molecular weight build-up in the solid phase condensation at a gentle temperature.
  • the present invention was therefore based on the object to remedy the aforementioned disadvantages.
  • a new and improved process for the preparation of polyamides, their oligomers or mixtures thereof, optionally with further reaction products by reacting aminonitriles or dintriles and diamines or a mixture containing aminonitrile, dinitrile and diamine, and optionally other polyamide-forming monomers and / or Oligomers with water in a reactor (1) with vertically oriented longitudinal axis, in which in the reactor (1) the reaction product discharged from the bottom and resulting ammonia and optionally further resulting low molecular weight compounds and water are removed overhead, and the reactor (1) at least two chambers (4) arranged one above the other in the longitudinal direction, the chambers (4) being separated from each other by liquid-tight trays (5), each chamber (4) being connected to the immediately underlying chamber (4) by a respective liquid overflow (6) is and about the fluid overflow
  • the gas space (7) above the liquid level in each chamber (4) with the respectively immediately above the chamber (4) is connected by one or more guide tubes (8), in each case opening into a gas distributor (9) with openings (11) for the gas outlet below the liquid level, and with at least one guide plate (12) arranged vertically around each gas distributor (9), whose upper end is below the liquid level and whose lower end terminates above the liquid-tight bottom (5) of the chamber (4) and which separates each chamber (4) into one or more fumigations (13) and into one or more unfatted (14) spaces,
  • the process can preferably be carried out continuously.
  • the residence times are 2 to 8 hours, preferably 3 to 7 hours, more preferably 4 to 6 hours.
  • the process can advantageously be carried out adiabatically via reactor (1), preferably via the chambers (4), in particular via the chambers (4) with the exception of the lowermost chamber (4).
  • Reactor (1) represents an apparatus that guarantees without moving parts of the apparatus, by an air-lift circulation of the liquid, an excellent phase mixing in multi-phase reactions and a nearly constant composition of the reaction mixture over the entire volume in each chamber, that is both on the cross section and in particular on the liquid level, at the same time simple separation between liquid and gaseous phase after the reaction.
  • the hydrostatic pressure in this liquid space is lowered relative to the non-fumigated liquid space, resulting in a pressure gradient which is converted into kinetic energy.
  • This pressure gradient initiates the air-lift circulation in the form of a flow which is directed upward in the fumigated space, ie in the space between the gas distributor and the baffle or baffles arranged around the gas distributor - rich above the uppermost end of the baffle (the baffles) and below the liquid level by the baffle (the baffles) is deflected, the non-fumigated liquid space outside the baffle (the baffles) flows from top to bottom and above the liquid-tight bottom of the chamber and un - is deflected again below the lowest end of the baffle (the baffles) in a bottom-up flow, whereby the loop movement is closed.
  • the reactor is an apparatus with vertically aligned longitudinal axis, i. H. a high-standing apparatus with supply of one or more liquid, liquid / solid, gaseous / liquid or gaseous / liquid / solid Eduktströme in its upper part and a gaseous stream - educt and / or inert gas - in its lower region, that is with countercurrent flow of the liquid, liquid / solid and gaseous streams.
  • one or more liquid, liquid / solid, gaseous / liquid or gaseous / liquid / solid streams - educt, intermediate, product or inert gas or mixtures of several or all such substances - in the middle or lower region of reactor (1) are particularly suitable, in particular in the preparation of polyamides from dinitriles and diamines or a mixture containing aminonitrile, dinitrile and diamine.
  • the reactor (1) is made up of several, preferably superimposed chambers.
  • the number of chambers may advantageously be at most 200, preferably at most 50, in particular at most 10.
  • the number of chambers may advantageously be at least 2, in particular at least 3.
  • the geometry of the reactor is often cylindrical, but other geometries are possible.
  • each chamber is connected by a respective liquid overflow with the immediately underlying chamber.
  • the liquid overflow can be formed for example in the form of a tube or a shaft and it can be arranged both inside and outside the reactor.
  • the liquid overflows of two successive chambers can be located opposite each other. be arranged on the sides of the reactor. From the bottom chamber, a liquid product stream is withdrawn via the liquid overflow.
  • the lowest chamber of the reactor (1) the so-called sump area, can be subdivided into at least two chambers. These at least two chambers can be arranged side by side or one above the other or one above the other and next to each other.
  • a part of the product stream taken from the bottom region of the reactor (1) can be supplied in liquid form to a heat exchanger, with the aid of this heat exchanger the water contained in the product stream can be partly or completely converted into the gaseous state and the mixture leaving the heat exchanger Feed reactor (1).
  • reactor (1) according to the method obtained polyamides, oligomers or mixtures thereof as a product liquid, especially in the bottom region, remove.
  • At least one of the chambers located in the bottom region of the reactor (1) can supply product in liquid form to a heat exchanger, with the aid of this heat exchanger convert the water contained in the product stream partially or completely into the gaseous state and transfer the heat exchanger feed the leaving mixture to the reactor (1).
  • reactor (1) according to the method obtained polyamides, oligomers or mixtures thereof as a product liquid, especially in the bottom region, remove.
  • At least one of the chambers located in the bottom region of the reactor (1) can supply product in liquid form to a heat exchanger, with the aid of this heat exchanger convert the water contained in the product stream partially or completely into the gaseous state, the gaseous water feed the reactor (1) and obtain the liquid product leaving the heat exchanger as desired product.
  • the heat exchanger used in these preferred embodiments can be in the reactor (1) or outside the reactor (1) or partially inside, partly outside the reactor (1).
  • the heat exchanger may comprise one or more separate devices.
  • the gas space above the liquid level in each chamber is connected to the immediately above each arranged chamber by one or more guide tubes, each of which opens into a gas distributor with openings for the gas outlet below the liquid level.
  • the guide tubes With regard to the number and arrangement of the guide tubes, there are basically no restrictions: it is equally possible to provide a single central guide tube or else a plurality of guide tubes distributed over the reactor cross section. It is also possible, instead of a single gas distributor per chamber several separate gas distributor, each with gas supply via one or more guide tubes to provide. In the gas distributor of the penultimate chamber of the reactor, a gaseous stream is introduced via one or more guide tubes from outside the reactor and / or from the sump region.
  • the gas distributor which can be used in the present case, there are no fundamental restrictions: it is essential that the gas distributor exits the gas supplied to it via the guide tube (s) from the gas space of the immediately underlying chamber below the liquid level of the chamber in which the gas distributor is arranged leaves.
  • the gas outlet should preferably be as uniform as possible.
  • a gas distributor can in principle a commercial gassing be used, for example, gas distributor in the form of tubes which are equipped with outlet openings for the gas and, for example horizontally, that can be arranged in a plane parallel to the liquid-tight bottom of the chamber. It is also possible to provide annular gas distributors.
  • the openings for the gas outlet must always be located below the liquid level in the chamber, preferably at a distance from the liquid level of at least 10% of the total liquid level in the chamber, preferably at least 30%, particularly preferably at least 50%. It has been found that a particularly favorable immersion depth of the openings for the gas outlet below the liquid level in the chamber is at least 50 mm.
  • the gas distributor (the gas distributor) is formed phonon-like, in the form of an upwardly closed hood with openings for the gas outlet in the lower part.
  • the hood can be completely closed, except for the passage openings for the guide tube or tubes for the gas feed and the gas outlet openings in its lower part.
  • hood open in the lower part.
  • the upper closed end of the hood may terminate below the liquid level, but may also extend beyond the liquid level into the gas space.
  • the hood of the siphon-like gas distributor can basically have any geometric shape; It is for example possible that it consists of a plurality of interconnected parts, which are preferably arranged in cross-section cross-shaped and / or parallel or concentric or radial.
  • the openings for the gas outlet are preferably formed with respect to number, cross section and distance from the liquid level in the chamber in such a way that the pressure drop of the gaseous stream in the gas distributor in the range of 0.1 to 50 mbar.
  • the openings for the gas distributor are preferably arranged at the same height to each other.
  • they can have any desired geometric shape, for example circular, triangular or slot-shaped.
  • the center line of the openings is preferably at a distance of about 1 cm to 15 cm from the lower end of the hood.
  • the arrangement of the openings at different heights may be advantageous for operation with two or more load ranges.
  • the height of the openings for the gas outlet is selected as needed, depending on the specific reaction to be carried out in the reactor so that on the one hand sufficient mass transfer area for the specific gas / liquid or gas / liquid / solid reaction is offered and on the other sufficient drive for the air-lift circulation of the liquid is provided.
  • At least one vertical baffle is arranged around each gas distributor in the reactor according to the invention, the upper end of which ends below the liquid level in the chamber, is spaced from the bottom of the chamber and which gasses each chamber into one or more and separates one or more unfavorable spaces.
  • the baffle may be formed in a preferred embodiment as a cylinder jacket-shaped insertion tube. Likewise, however, is also possible, for example, the shape of a simple flat sheet.
  • the at least one baffle is spaced from the liquid level and from the bottom of the chamber, preferably such that there is substantially no throttling of the liquid flow through the baffle.
  • the distances between the guide plate or the baffles to the liquid surface and to the bottom of the chamber are thus preferably set in such a way that the flow rate of the liquid does not change or only slightly during the deflection by the baffle.
  • a solid catalyst in one or more, preferably in all chambers of the reactor, may be introduced, in particular as a solid bed or in the form of catalyst-coated ordered packings, for example monoliths.
  • an ion exchange resin may be introduced.
  • the reactor thus has the advantage that, for gas / liquid or gas / liquid / solid reactions, it ensures a very good phase mixing and thus a high degree of conversion and, after thorough mixing and reaction, a substantial separation of gaseous and liquid phases. Since it is only necessary for the drive of the air-lift circulation that the gas outlet from the gas distributor takes place below the liquid level in the chamber, wherein the distance of the gas outlet to the liquid level can generally vary within very wide limits, is with the reactor of the invention Apparatus provided in which remplisstechniksverweilzeit and gas pressure loss are largely decoupled.
  • FIG. 1 shows a longitudinal section through a first embodiment of a chamber (4) of a reactor (1), with a cross section in Fig. 1a and 2 shows a longitudinal section through a chamber (4) of a second embodiment of a reactor (1), with a cross section in Figure 2a and
  • FIG. 3 shows a longitudinal section through a chamber (4) of a third embodiment of a reactor (1), with a cross section in FIG. 3a
  • FIG. 1 shows by way of example one of a plurality of longitudinally stacked chambers 4 of a reactor 1 with feed 2 of a liquid or liquid / solid educt stream in the upper region and a gaseous stream 3 in the lower region of the reactor 1, each with a bottom 5 per Chamber 4, liquid overflows 6, which are exemplarily shown inside the reactor 1, each with a gas space 7 above the liquid level in each chamber 4, which is exemplified by a guide tube 8 with the respective overlying chamber 4 and in a siphon-like gas distributor 9 in Form of a top closed hood 10 opens, with openings 11 for the gas outlet in the lower part.
  • baffles 12 are arranged, which are each spaced from the liquid level and the bottom of the chamber 4 and the chamber 4 in a plurality of fumigated spaces 13 and a plurality of unbegaste spaces 14 separates.
  • hood 10 of the gas distributor 9 is illustrated, in the present example, as formed of parallel parts.
  • the introduced catalyst 15 is characterized in the region of the unfavorable space 14
  • hood 10 of the gas distributor 9 is illustrated, in the present example, as formed of parallel parts.
  • 3a illustrates the exemplary radial arrangement of the parts of the hood 10 of the siphon-type gas distributor 9.
  • aminonitrile or dinitrile and diamine or a mixture containing aminonitrile, dinitrile and diamine, and water in the upper half of reactor (1) are fed.
  • the low boilers (ammonia and water) produced during the reaction can then be enriched in the top of reactor (1) and discharged. while the desired product of oligomers and polyamide as heavies in the bottom is obtained.
  • nitrile group-containing compounds in particular aminonitrile or dinitrile or a mixture containing amino nitrile and dinitrile, and water in the upper half of reactor (1) are fed and nitrile-free compounds, especially diamines , fed to the middle or lower part of reactor (1).
  • the low boilers (ammonia and water) formed in the reaction can then be enriched and removed in the top of reactor (1), while the desired product of oligomers and polyamide is obtained as heavies in the bottom.
  • any catalysts can be used which accelerate the hydrolysis and / or condensation. Preference is given to those catalysts which are either introduced in solid form and consequently can be easily separated off from the desired product or are present as a coating on reactor parts.
  • the invention relates to a, preferably continuous, process for the hydrolytic reaction of aminonitriles or dinitriles and diamines or a mixture containing aminonitrile, dinitrile and diamine, to polyamide and / or its precursors and optionally further polyamide-forming mono- and oligomers to polyamide.
  • aminonitrile or dinitrile and diamine or a mixture containing aminonitrile, dinitrile and diamine is added to an intermediate bottom in the upper part of the reaction mixture.
  • Aminonitrile or dinitrile and diamine or a mixture containing aminonitrile, dinitrile and diamine then flows through the apparatus due to gravity and continuously reacts with water. The resulting ammonia continuously rises due to its volatility and can be separated at the top.
  • nitrile group-containing compounds in particular aminonitrile or dinitrile or a mixture containing aminonitrile and dinitrile
  • nitrile-group-free compounds in particular diamines
  • the educts can be preheated via the optional top condenser.
  • FIG. 4 Such a schematic diagram of the method according to the invention is shown in the drawing in FIG. 4:
  • Fig. 4a Process outline of a reaction of dinitrile and diamine to polyamide by the use of a reactor (1).
  • A1 dinitrile
  • A2 diamine
  • D steam
  • N ammonia
  • P polyamide prepolymer.
  • the ammonia reduction in the melt can be additionally supported by stripping with inert gases (such as nitrogen) or water vapor.
  • amino nitriles ie compounds which have both at least one amino and at least one nitrile group
  • aminonitriles can be used as the aminonitrile.
  • ⁇ -aminonitriles are preferred, among the latter in particular ⁇ -aminoalkyl nitriles having 4 to 12 C atoms, more preferably 4 to 9 C atoms in the alkylene radical, or an aminoalkylaryl nitrile having 8 to 13 C atoms are used, where there are such preferred are those which have between the aromatic unit and the amino and nitrile group an alkyl spacer having at least one carbon atom.
  • aminoalkylarylnitriles preference is given in particular to those which have the amino and nitrile groups in the 1, 4 position relative to one another.
  • ⁇ -aminoalkylnitrile it is further preferred to use linear ⁇ -aminoalkylnitriles, where the alkylene radical (-CH 2 -) preferably contains 4 to 12 C atoms, more preferably 4 to 9 C atoms, such as 6-amino-1-cyanopentane (US Pat. 6-aminocapronitrile), 7-amino-1-cyanohexane, 8-amino-1-cyanoheptane, 9-amino-1-cyanooctane, 10-amino-1-cyanononane, most preferably 6-aminocapronitrile.
  • 6-amino-1-cyanopentane US Pat. 6-aminocapronitrile
  • 7-amino-1-cyanohexane 8-amino-1-cyanoheptane
  • 9-amino-1-cyanooctane 10-amino-1-cyanononane
  • 10-amino-1-cyanononane most
  • 6-aminocapronitrile is usually obtained by hydrogenating adiponitrile by known processes, for example described in DE-A 836, 938, DE-A 848, 654 or US Pat. No. 5,151,543.
  • mixtures of a plurality of aminonitriles or mixtures of an aminonitrile with further comonomers for example caprolactam or the mixture defined in greater detail below.
  • all dinitriles ie compounds which have at least two nitrile groups, can be used as dinitrile.
  • ⁇ , ⁇ -dinitriles among which ⁇ , ⁇ -dinitriles having 4 to 12 C atoms, more preferably 4 to 9 C atoms in the alkylene radical, or a cyanoalkylarylnitrile having 7 to 12 C atoms are used , where there are preferred those which have between the aromatic unit and the two nitrile an alkyl spacer having at least one carbon atom.
  • the Cyanoalkylarylnitrilen are particularly preferred those having the two nitrile groups in 1, 4-position to each other.
  • diamines that is to say compounds which have at least two amino groups
  • ⁇ , ⁇ -diamines are preferred, among the latter in particular ⁇ , ⁇ -diamines having 4 to 14 C-atoms, more preferably 4 to 10 C-atoms in the alkylene radical, or an aminoalkylarylamine having 7 to 12 C-atoms are used, where there are those which have between the aromatic unit and the two nitrile an alkyl spacer having at least one carbon atom.
  • aminoalkylarylamines preference is given in particular to those which have the two amino groups in the 1, 4 position relative to one another.
  • ⁇ , ⁇ -alkylenediamine it is further preferred to use linear ⁇ , ⁇ -alkylenediamines, where the alkylene radical (-CH 2 -) preferably contains 3 to 12 C atoms, more preferably 3 to 8 C atoms, such as 1, 4- Diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane (hexamethylenediamine), 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, more preferably hexamethylenediamine.
  • the alkylene radical (-CH 2 -) preferably contains 3 to 12 C atoms, more preferably 3 to 8 C atoms, such as 1, 4- Diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane (hexamethylenediamine), 1, 7-d
  • diamines, dinitriles and aminonitriles derived from branched alkylene- or arylene- or alkylarylenes such as 2-methyl-glutarodinitrile or 2-methyl-1,5-diaminopentane.
  • nitrile groups present in the starting materials are used, then a molar ratio of the nitrile groups present in the starting materials to the polyamide-forming nitrile groups is possible for the polyamide formation present in the starting materials - Amino groups in the range of 0.9 to 1, 1, preferably 0.95 to 1, 05, in particular 0.99 to 1.01, particularly preferably of 1, proved to be advantageous.
  • Examples of further polyamide-forming monomers are dicarboxylic acids, such as alkanedicarboxylic acids having 6 to 12 carbon atoms, in particular 6 to 10 carbon atoms, such as adipic acid, pimelic acid, suberic acid or sebacic acid, and terephthalic acid, isophthalic acid and cyclohexanedicarboxylic acid, or amino acids, such as alkane Amino acids having 5 to 12 carbon atoms, in particular ⁇ , ⁇ -C5-Ci2-amino acids use.
  • dicarboxylic acids such as alkanedicarboxylic acids having 6 to 12 carbon atoms, in particular 6 to 10 carbon atoms, such as adipic acid, pimelic acid, suberic acid or sebacic acid, and terephthalic acid, isophthalic acid and cyclohexanedicarboxylic acid
  • amino acids such as alkane Amino acids having 5 to 12 carbon atoms, in particular ⁇
  • ⁇ -C5-Ci2-amino acid can be 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, preferably 6-aminohexanoic acid, or their inner amides, called lactams, in particular caprolactam, use.
  • R 1 for -OH, -OCi-12-alkyl or -NR 2 R 3, independently of one another, are hydrogen, C 1-12 -alkyl and C 5-8 -cycloalkyl, and m is 3, 4, 5, 6, 7, 8 , 9, 10, 11 or 12.
  • Particularly preferred aminocarboxylic acid compounds are those in which R 1 OH, -O-Ci -4 alkyl, such as -O-methyl, -O-ethyl, -On-propyl, -Oi-propyl, -On-butyl, -O-sec. Butyl, -O-tert.-butyl and -NR 2 R 3, such as -NH 2 , -NHMe, -NHEt, -NMe 2 and -NEt 2 , and m is 5.
  • 6-aminocaproic acid very particular preference is given to 6-aminocaproic acid, 6-aminocaproic acid methyl ester, 6-aminocaproic acid ethyl ester, 6-aminocaproic acid methylamide, 6-aminocaproic acid dimethylamide, 6-aminocaproic acid ethylamide, 6-aminocaproic acid diethylamide and 6-aminocaproic acid amide.
  • the starting compounds are commercially available or, for example, according to EP-A 0 234 295 and Ind. Eng. Chem. Process Des. Dev. 17 (1978) 9-16.
  • the polyamide-forming monomers used are preferably aminonitriles or dinitriles and diamines or mixtures containing aminonitrile, dinitrile and diamine, together with water, more preferably in a molar ratio in the range from 1: 1 to 1:20, based on the overall process.
  • Particularly preferred is amino capronitrile, at a molar ACN: water ratio in the overall process of 1: 1 to 1: 10.
  • Further particularly preferred is a mixture of adiponitrile and hexamethylenediamine, at a molar ratio of the sum of adiponitrile and Hexamethylenediamine: water in the overall process from 1: 1 to 1:10.
  • suitable polyamide-forming monomers besides aminocapronitrile are caprolactam and / or hexamethylenediammonium adipate ("AH salt").
  • caprolactam and / or hexamethylenediammonium adipate are preferably used as polyamide-forming monomers in addition to adiponitrile and hexamethylenediamine.
  • heterogeneous catalysts are generally suitable catalysts.
  • Brönsted acid catalysts selected from a zeolite beta-layer, layered silicate catalyst or a fixed bed catalyst, which are essentially from OO2 with 70 to 100 anatase and O to 30% rutile, in which up to 40% of O2 can be replaced by tungsten oxide.
  • TiO 2 modifications such as FINNTi S150 (Kemira Pigments Oy, Finland), can be used.
  • the heterogeneous catalysts can be, for example, as a suspension, sintered on filler or introduced as an optionally coated catalyst packing or - summarizeung or internals in the apparatus. They can also be present in the apparatus as wall covering or filling, so that a separation of the reaction mixture is easy.
  • the water concentration on the majority of the chambers of reactor (1) which are below the feed point of the aminonitriles or dinitriles and diamines or of the mixture containing dinitrile, diamine and aminonitrile, reaches very high concentrations (molar ratio of lower boilers: water about 1: 4 to 1:50, preferably 1:10 to 1:40) so that, even if the components are metered stoichiometrically into the apparatus, water may be stoichiometrically present in the apparatus itself, shifting the reaction equilibrium to the product side and increasing the rate of equilibration can.
  • the temperature for the reaction should in the reaction part of reactor (1), ie below the educt feed, depending on the water concentration, the residence time, the use of catalysts and the feedstock or concentration concentration about 18O 0 C to 300 0 C, preferably 200 to 28O 0 C and particularly preferably 220 to 27O 0 C.
  • the temperatures in the chambers (4) of reactor (1) should advantageously be within a narrow range, preferably within 15 ° C, preferably within 10 0 C, in particular within 8 0 C.
  • the two-phase mode of operation allows a lowering of the pressure level necessary for the reaction, since gaseous components do not have to be kept in the liquid phase, as in a single-phase mode of operation. It is preferable that only the intrinsic pressure of the system depends on the temperature. This is about 10 to 60 bar. The expenditure on equipment is reduced by the integration of procedural operations such as heat and mass transfer in one and the same apparatus.
  • the flow profile of the liquid phase in the apparatus approaches an ideal plug flow, resulting in a very uniform residence time spectrum in the apparatus.
  • the product of value obtained has, depending on the residence time in reactor (1) the process temperatures, the pressure ratios and other procedural parameters a different, adjustable within wide limits molecular weight and different properties. If desired, after the reaction, further processing of the product for adjustment of desired product properties can take place.
  • the product may be subjected to a polycondensation to increase the molecular weight.
  • a polycondensation can be carried out by processes known per se for the preparation and aftertreatment of polyamides, such as in a fully continuous flow tube ("VK tube").
  • the content of cyclic dimer in the polyamide-6 obtained according to the invention can be further reduced by first extracting the polyamide with an aqueous solution of caprolactam and then with water and / or gas-phase extraction (described, for example, in EP-A 0284968 ) subjects.
  • the resulting in this treatment low molecular weight components such as caprolactam and linear and cyclic oligomers can be attributed to the process of the invention or the upstream reactor.
  • the polyamide obtained after the extraction can generally then be dried in a manner known per se.
  • this can take place with the concomitant use of inert gases, such as nitrogen or superheated steam, as a heat carrier, for example in countercurrent.
  • inert gases such as nitrogen or superheated steam
  • the desired viscosity determined in 1% strength by weight solution in 96% strength
  • the inventive method is characterized by continuous Christsnite- tion, reduced energy and input material costs and a comparatively low expenditure on equipment.
  • the method can thus operate more cost-effectively compared to known methods and provide a higher quality product with improved heat storage stability.
  • hexamethylenediamine and water (molar 1: 1: 12) is prepared at a pressure of 80 bar and a temperature of 250 0 C in analogy to the application EP-B-1 109 491 in a tubular reactor, a prepolymer.
  • the hydrolytic residence time was 2.5 h.
  • the resulting nylon 66 prepolymer is flashed in a separator in analogy to EP-A-1 198 491 to a pressure of 22 bar and thereby volatile components such as water and ammonia separated as a gaseous phase of the molten prepolymer phase.
  • This input stream to reactor (1) has a throughput of 16.5 kg / h and a temperature of 240 0 C.
  • the pressure in the reactor is regulated and is 21 bar overpressure.
  • the sump temperature is regulated and is 275 ° C.
  • the temperature profile in the reactor develops adiabatically, with the outlet temperature from the fifth chamber being 245.5 ° C.
  • the total residence time in the reactor is 5 h, including a residence time in the bottom region of less than 20 minutes.
  • the mixture of precondensate leaving the reactor (1) is flashed into the separator.
  • the melt remains in the separator, which serves as a polycondensation zone, for a further 40 minutes, is then discharged by means of a discharge tamp with evaporation zone in the form of strands, solidified in a water bath and subsequently granulated.
  • VZ viscosity number
  • hexamethylenediamine and water (molar 1: 1: 12) is prepared at a pressure of 80 bar and a temperature of 250 0 C in analogy to the application EP-B-1 109 491 in a tubular reactor, a prepolymer.
  • the hydrolytic residence time was 0.83 h.
  • the resulting nylon 66 prepolymer is flashed in a separator in analogy to EP-A-1 198 491 to a pressure of 22 bar and thereby volatile components such as water and ammonia separated as a gaseous phase of the molten prepolymer phase.
  • This input current to the reactor (1) has a throughput of 48 kg / h and a tem- perature of 240 C. 0
  • the pressure in the reactor is regulated and is 21 bar overpressure.
  • the sump temperature is regulated and is 275 ° C.
  • the temperature profile in the reactor develops adiabatically, with the outlet temperature from the fifth chamber being 243.5 ° C.
  • the total residence time in the reactor is 1.7 h, including a residence time in the bottom region of less than 10 minutes.
  • the mixture of precondensate leaving the reactor (1) is flashed into the separator.
  • the melt remains in the separator, which serves as a polycondensation zone, for a further 20 minutes, is then discharged by means of a discharge trough with evaporation zone in the form of strands, solidified in a water bath and subsequently granulated.
  • the above-mentioned two products were compounded in a twin-screw extruder (ZSK40) with 30 wt .-% glass fiber (diameter 10 .mu.m) at 280 0 C. 179/2 specimens were ten from the production according to ISO injected and stored at 140 0 C in an oven in an air atmosphere for different time. The impact strength of the two products was measured according to ISO 179/2.
  • Example B1 b The granules thus obtained were annealed under N 2 atmosphere at 185 ° C. The samples were taken regularly and the viscosity number (VZ) was measured. (VZ measured in 0.5 wt .-% solution in 96% sulfuric acid, at 25 0 C according to EN ISO 1628-1).
  • VZ measured in 0.5 wt .-% solution in 96% sulfuric acid, at 25 0 C according to EN ISO 1628-1).
  • the results of Example B1 b) and VB 1 b) are summarized in the following table.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne un procédé pour préparer des polyamides, leurs oligomères ou mélanges, éventuellement avec d'autres produits de conversion, par conversion d'aminonitriles ou de dinitriles et de diamines ou leur mélange, contenant de l'aminonitrile, du dinitrile et de la diamine, et éventuellement d'autres monomères et/ou oligomères formant des polyamides, avec de l'eau dans un réacteur (1) ayant un axe longitudinal vertical. Selon l'invention, le produit de conversion qui se trouve dans le réacteur (1), est extrait par le fond, et l'ammoniac qui se forme et éventuellement d'autres composés à bas poids moléculaire qui se forment, et l'eau, sont extraits par le dessus (2). Le réacteur (1) comprend au moins deux chambres (4) disposées l'une au dessus de l'autre dans la direction longitudinale. Selon l'invention, les chambres (4) sont séparées entre elles par des fonds (5) étanches aux liquides; chaque chambre (4) est reliée respectivement par un déversoir (6) à la chambre (4) qui se trouve directement au-dessus d'elle; un flux de produit liquide est extrait au-dessus du déversoir (6) de la chambre (4) la plus inférieure; la chambre à gaz (7) située au-dessus du niveau de liquide dans chaque chambre (4), est reliée à la chambre (4) qui se trouve respectivement directement au-dessus, par un ou plusieurs tubes directeurs (8) qui débouchent en-dessous du niveau de liquide, respectivement dans un répartiteur de gaz (9) qui présente des ouvertures (11) permettant au gaz de sortir, et au moins respectivement une tôle directrice (12) disposée verticalement autour de chaque répartiteur de gaz (9), et dont l'extrémité supérieure se termine en-dessous du niveau de liquide, dont l'extrémité inférieure se termine au-dessus du fond (5) étanche aux liquides de la chambre (4), et qui subdivise chaque chambre (4) en une ou plusieurs chambres alimentées en gaz (13) et une ou plusieurs chambres non alimentées en gaz (14); le temps de séjour dans le réacteur (1) est de 3 à 8 heures.
PCT/EP2006/065321 2005-08-26 2006-08-15 Procede pour preparer des polyamides Ceased WO2007023108A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510040656 DE102005040656A1 (de) 2005-08-26 2005-08-26 Verfahren zur Herstellung von Polyamiden
DE102005040656.4 2005-08-26

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046682A1 (de) 2008-09-10 2010-03-11 Basf Se Amorphe Polyamide
DE102009035974A1 (de) 2009-08-04 2011-02-17 Basf Se Amorphe Polyamide
WO2011069984A1 (fr) 2009-12-09 2011-06-16 Basf Se Copolyamide semi-aromatique, semi-cristallin
WO2011069942A1 (fr) 2009-12-08 2011-06-16 Basf Se Matières à mouler constituées de copolyamide partiellement aromatique à base d'octaméthylène diamine
DE102010051726A1 (de) 2010-11-19 2012-05-24 Basf Se Amorphe Polyamide mit bicyclischen aliphatischen Diaminen
DE102010051708A1 (de) 2010-11-19 2012-05-24 Basf Se Amorphe Polyamide mit dialkylsubstituierten Diaminen
DE102015215118A1 (de) 2014-08-26 2016-03-03 Basf Se Polyamide mit 2,6-BAMP-Derivaten

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114053744B (zh) * 2021-12-13 2023-01-24 鞍山七彩化学股份有限公司 一种反应器和精馏连续化反应方法和系统

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004085512A1 (fr) * 2003-03-26 2004-10-07 Basf Aktiengesellschaft Procede de production de polyamides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004085512A1 (fr) * 2003-03-26 2004-10-07 Basf Aktiengesellschaft Procede de production de polyamides

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046682A1 (de) 2008-09-10 2010-03-11 Basf Se Amorphe Polyamide
DE102009035974A1 (de) 2009-08-04 2011-02-17 Basf Se Amorphe Polyamide
WO2011069942A1 (fr) 2009-12-08 2011-06-16 Basf Se Matières à mouler constituées de copolyamide partiellement aromatique à base d'octaméthylène diamine
WO2011069984A1 (fr) 2009-12-09 2011-06-16 Basf Se Copolyamide semi-aromatique, semi-cristallin
US9109085B2 (en) 2009-12-09 2015-08-18 Basf Se Semi-aromatic, semi-crystalline copolyamides
DE102010051726A1 (de) 2010-11-19 2012-05-24 Basf Se Amorphe Polyamide mit bicyclischen aliphatischen Diaminen
DE102010051708A1 (de) 2010-11-19 2012-05-24 Basf Se Amorphe Polyamide mit dialkylsubstituierten Diaminen
DE102015215118A1 (de) 2014-08-26 2016-03-03 Basf Se Polyamide mit 2,6-BAMP-Derivaten

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