EP3110872A1 - Procédé de fabrication de polyamines - Google Patents

Procédé de fabrication de polyamines

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Publication number
EP3110872A1
EP3110872A1 EP14821096.6A EP14821096A EP3110872A1 EP 3110872 A1 EP3110872 A1 EP 3110872A1 EP 14821096 A EP14821096 A EP 14821096A EP 3110872 A1 EP3110872 A1 EP 3110872A1
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EP
European Patent Office
Prior art keywords
gas
diamine
reactor
hydrogen
molecular weight
Prior art date
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EP14821096.6A
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German (de)
English (en)
Inventor
Christoph Müller
Thomas Reissner
Ansgar Gereon Altenhoff
Andreas Kunst
Christian Müller
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BASF SE
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BASF SE
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Publication of EP3110872A1 publication Critical patent/EP3110872A1/fr
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Classifications

    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines

Definitions

  • the present invention relates to a process for the preparation of polyamines having an average molecular weight of> 203 g / mol, in which the deviation from the average molecular weight per changed ° C of the reaction temperature ⁇ 19% of the average molecular weight, by polycondensation of diamines in the liquid phase in the presence of heterogeneous catalysts based on transition metals of the eighth to eleventh subgroup of the Periodic Table of the Elements and hydrogen at temperatures in the range of 100 to 250 ° C and pressures in the range of 60 to 150 bar Polyamines obtainable by this process, as well as the use of the polyamines.
  • Polymers which have a defined average molecular weight are very much in demand for the preparation of different plastics, since their narrow, defined molecular weight leads to new easily characterizable and / or adjustable material properties for the polymers produced. Methods that can be used to narrow the average molecular weight in a process are therefore of great interest to the end user of the polymers in order to vary specific properties of the polymers.
  • DE 2 540 871 represents a further embodiment of DE 2 439 275.
  • 1,3-propylenediamine is used and reacted under similar conditions as in DE 2,439,275 to dipropylenetriamine and t-propylenetetramine.
  • Work is carried out at 50 to 250 ° C, preferably 120 to 180 ° C, pressures of 1 to 500 bar, preferably 25 to 200 bar.
  • the same catalysts as in DE 2 439 275 are claimed.
  • a catalyst is used which contains 4 wt .-% Cu, 8 wt .-% Co and 9 wt .-% Ni.
  • DE 2 540 871 does not describe a process by means of which it is possible to prepare polyamines with a depleted low boiler fraction which have significantly higher and narrow, defined average molecular weights.
  • WO 2006/082 203 A1 describes the continuous preparation of dipropylenetriamine by reacting 1, 3-propylenediamine with heterogeneous catalysts in a reaction column.
  • WO 2006/082203 does not describe the preparation of polyamines.
  • work is carried out at pressures in the range of 0 to 20 bar.
  • WO 92/17 437 discloses the reaction of 1,6-hexamethylenediamine at 130 to 150 ° C and atmospheric pressure in the presence of Raney nickel. The main products are dimers and trimers. A process for the preparation of polyamines is not described in WO 92/17437.
  • the closest prior art DE 2 605 212 is considered.
  • the comparison of Examples 1 and 2 shows that the conversion of diamines to high boilers (polymers) increases with temperature.
  • Information on how to obtain polyamines having a narrow, defined average molecular weight is not described in DE 2 605 212.
  • DE 2 842 264 describes a process for the preparation of polyhexamethylenepolyamines by reacting hexamethylenediamine in the presence of a palladium catalyst from the group of metallic palladium or palladium compounds. Work is carried out at 50 to 300 ° C, preferably 120 to 250 ° C. Hydrogen is not used in the reaction according to the invention.
  • DE 2 842 264 describes that the degree of polymerization can be controlled by the reaction conditions, such as reaction temperature, residence time or amount of catalyst. Thus, products having a low degree of polymerization are obtained when the amount of catalyst is high, with a high degree of polymerization when the amount of catalyst is low (page 19, second paragraph).
  • a disadvantage of DE 2 842 264 is the long reaction times of up to 98 hours (Example 13) and the high amounts of catalyst (Example 1: 30 hours reaction time and 5.3 g of palladium black, based on 1 16 g of hexamethylenediamine). Although the reaction time can be significantly reduced by high temperatures (Example 5: 0.5 hours at 220 ° C). However, high temperatures lead to increased formation of by-products (page 17, second paragraph).
  • EP 13157314.9 a process for the preparation of polyamines by polycondensation on a cobalt fixed bed catalyst is described in which the pressure is kept constant by 50 bar, for which additional hydrogen or inert gas is pressed and the resulting ammonia together Gas is removed from the process.
  • the object of the present invention is therefore to provide a process for the preparation of polyamines in which even small temperature fluctuations lead to no significant deviations in the set molecular weight, in the preparation of which no large amounts of catalyst have to be used or complicated apparatus measures are required are to achieve a narrow, defined average molecular weight and thus to be able to adjust the material properties of the resulting polyamine targeted and whose low boilers (monomeric diamines and oligomers of diamines) are largely depleted.
  • Low-boiling components are monomeric diamines and oligomers of diamines having a boiling point ⁇ 300 ° C., preferably ⁇ 250 ° C., particularly preferably ⁇ 200 ° C. at 10 mbar.
  • Depleted means concentrations of ⁇ 5 wt .-%, preferably ⁇ 1 wt .-%, particularly preferably ⁇ 0.1 wt .-% in the obtained value product stream of the polyamines.
  • the low boilers are at pressures of 0.5 to 1000 mbar, preferably 0.5-500 mbar, particularly preferably 0.5-50 mbar and temperatures of 150-300 ° C, preferably 165 -265 ° C, particularly preferably 180-230 ° C largely depleted, where largely depleted a low boiler content of ⁇ 5% by weight, preferably ⁇ 1 wt .-%, particularly preferably ⁇ 0.1 wt .-% means.
  • This object is achieved by a process for the preparation of polyamines having an average molecular weight of> 203 g / mol, in which the deviation from the average molecular weight per changed ° C of the reaction temperature ⁇ 19% of the average molecular weight, by polycondensation of diamines in the liquid phase in the presence of hydrogen and catalysts based on metals of the 8th to 1 1.
  • Subgroup of the Periodic Table of the Elements wherein the pressure during the polycondensation by continuously supplied inert gas and / or hydrogen is kept constant and the inert gas and / or the hydrogen and the resulting ammonia is removed from the reactor during the reaction, characterized in that the polycondensation is carried out at 100 to 250 ° C and a pressure of 60 to 150 bar.
  • the process according to the invention is preferably characterized in that the polyamines obtained have a low boiler content of ⁇ 5%.
  • the inventive method is characterized in that the polycondensation at 130 to 180 ° C and 75 to 200 bar is performed.
  • the process according to the invention is preferably characterized in that the gas used is exclusively hydrogen.
  • the diamines used are selected from the group consisting of ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, 1,2-butylenediamine, 1,5 Diaminopentane, 1,2-diaminopentane, 1, 5-diamino-2-methylpentane, 1,6-diaminohexane, 1,2-diaminohexane, 1,7-diaminoheptane, 1,2-diaminoheptane, 1,8-diaminooctane, 1, 2- Diaminooctane, 1, 9-nonamethylenediamine, 1, 10-decamethylenediamine, 1,2-diaminodecane, 1,1,1-undecamethylenediamine, 1,2-diaminound
  • the process according to the invention is preferred when the temperature is in the range from 150 to 180 ° C. and the pressure in the range from 75 to 100 bar and is used as diamine 1, 3-propanediamine
  • the process according to the invention is preferably characterized in that the catalysts used for the polycondensation are those whose catalyst precursors contain one or more oxides of the elements Cu, Co and / or Ni.
  • Another object of the invention are polyamines having an average molecular weight of> 203 g / mol, in which the deviation from the average molecular weight per changed ° C the reaction temperature ⁇ 19% of the average molecular weight, obtainable by the novel process.
  • Another object of the invention is the use of the polyamines according to the invention as or as a component for a) adhesion promoter, for example for printing inks for laminate films;
  • adhesion promoters for adhesives for example in conjunction with polyvinyl alcohol, - butyrate, and acetate and styrene copolymers, or as a cohesion promoter for label adhesives;
  • e) fabric for improving wet adhesion, for example in standard emulsion paints, and for improving the instantaneous rainfastness of paints, for example for road markings;
  • flocculants for example in water treatment / water treatment
  • Penetration aids for example for active metal salt formulations in wood preservation
  • n additive in the cosmetics sector, for example for hair fixatives and rinses
  • n Auxiliaries in the paper industry, for example for dewatering acceleration, impurity elimination, charge neutralization and paper coating as versatile
  • o substance for separation of oil and water, for example in the metalworking industry
  • Gas scrubbing material used as an absorbent for CO2, NOx, SOx, C and aldehydes and for the neutralization of acidic constituents;
  • FIG. 1 shows that the change in the average molecular weight only deviates by 53 g / mol, which corresponds to a 1 1% deviation from the mean target molecular weight of 450 g / mol. If, on the other hand, the reaction is carried out at 100 bar as shown in FIG.
  • FIG. 1 therefore demonstrates that an increase in the pressure leads to a reduction in the change in molecular weight due to temperature fluctuations.
  • both the pressure and the temperature must be optimally matched to one another.
  • Diamines (hereinafter also referred to as “monomers”) are preferably used as starting compounds.
  • Aliphatic alkylenediamines having 2 or more carbon atoms in the alkylene chain are particularly preferably used.
  • R 1 and R 2 are simultaneously or independently hydrogen, linear or branched C 1 to C 12 -alkyl, C 7 to C 12 aralkyl, C 6 to C 10 aryl, C 3 to C 8 cycloalkyl or C3 to Cs cycloalkyl in which a Ch group is replaced by O, NH or NR10;
  • R 3 X and R 4 X are simultaneously or independently hydrogen, linear or branched C 1 -C 12 -alkyl, C 7 -C 12 -aralkyl, C 6 -C 10 -aryl, C 3 -C -cycloalkyl or C 3 -C -cycloalkyl in which a Ch group is replaced by O, NH or NR10;
  • R 10 is linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl or C 3 - to C 8 -cycloalkyl; z is a value of 2 to 20, preferably 3 to 20; and x is an index that can take all values from 1 to z.
  • R1, R2, R3 X and R4 X are preferably hydrogen and z is a value of 3 to 8.
  • ethylenediamine is used only in mixtures with the above aliphatic alkylenediamines.
  • the process according to the invention is particularly particularly preferred when ethylenediamine is excluded as the sole diamine to be used.
  • oligomeric polyalkyleneamines consisting of 2 to 5 amine units, or mixtures thereof.
  • Particularly preferred oligomeric polyalkyleneamines can be described by formula II
  • R1, R2, R3 y R4 Y and R 5 are simultaneously or independently of one another are hydrogen, linear or branched d- to Ci2-alkyl, C7-Ci2-aralkyl, C6- to Cio-aryl, C3-Cs-cycloalkyl or C3 - to Cs-cycloalkyl, in which a Ch group is replaced by O, NH or NR10;
  • R10 has the meaning given above; a) is a value of 2 to 5;
  • b) is a value from 2 to 12; and y is an index that can take all values between 1 and b.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • di-1,3-propylenetriamine tri-1,3-propylenetetramine and tetra-1,3-propylenepentamine
  • Di-1, 2-propylenetriamine tri-1,2-propylenetetramine and tetra-1,2-prop
  • diamines are cyclic diamines in which the amino groups are attached either directly or indirectly to one or more unsubstituted or substituted cycloaliphatic, heteroaliphatic, aromatic or heteroaromatic rings bonded together.
  • Particularly preferred cyclic diamines are alicyclic diamines.
  • Preferred alicyclic diamines include diaminodicyclohexylmethane 3,3'-dimethyl-4,4 ', 4,4' -
  • aromatic cyclic diamines aromatic diamines, in which the amino group is not substituted directly on the aromatic nucleus.
  • Preferred aromatic diamines are the isomeric bis (aminomethyl) benzenes, in particular meta-xylenediamine (MXDA), or the isomeric bis (aminomethyl) benzenes, isomers of aminobenzylamine (2-aminobenzylamine, 4-aminobenzylamine), 4- (2-aminoethyl ) aniline, m-xylylenediamine, o-xylylenediamine, or 2,2'-Biphenyldiamine or Oxydianiline, such as 4,4 '-Oxydianilin, isomers of diaminofluorene, isomers of Diaminophenanthren and 4,4' - ethylenedianiline.
  • MXDA meta-xylenediamine
  • isomeric bis (aminomethyl) benzenes isomers of aminobenzylamine (2-aminobenzylamine, 4-aminobenzylamine), 4- (2-amin
  • polyetheramines of the formula III are polyetheramines of the formula III
  • R 1 and R 2 are simultaneously or independently hydrogen, linear or branched C 1 to C 12 alkyl, C 7 to C 12 aralkyl, C 6 to C 10 aryl, C 3 to C 8 cycloalkyl or C 3 to C 8 cycloalkyl, in which a Ch Group is replaced by O, NH or NR10;
  • R 3, R 4 and R 5 are simultaneously or independently hydrogen, linear or branched C 1 to C 12 alkyl, C 7 to C 12 aralkyl, C 6 to C 10 aryl, C 3 to C 8 cycloalkyl or C 3 to C 8 cycloalkyl, by a Ch group is replaced by O, NH or NR10;
  • R 10 is linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl or C 3 - to C 8 -cycloalkyl; u, v and w are independently a value from 0 to 100.
  • u and w take a value of 0 and v a value> 0 and the substituents R 1 to R 5 are preferably hydrogen (polyether amines based on ethylene glycol).
  • v preferably assumes a value of 0 and (u + w) a value of> 0 and the substituents R 1 and R 2 are preferably hydrogen and the substituents R 3 to R 5 are preferably methyl (polyether amines based on propylene glycol).
  • v assumes a value of> 0 and (u + w) a value of> 0 and the substituents R1 to R2 are preferably hydrogen and the substituents 3 to R5 are preferably methyl (block polyetheramines having a middle block based on Polyethylene glycol and outer blocks based on propylene glycol).
  • Polyether diamines are 4,7,10-Trioxatridekan-1, 13-diamine, 4,9-dioxadodecane-1, 12-diamine and so-called Jeffamine® the Fa. Huntsman, especially Jeffamin D230, Jeffamin D400, Jeffamin D2000, Jeffamine D4000, Jeffamin ED600, Jeffamin ED900, Jeffamine ED2003, Jeffamin EDR148 and Jeffamin EDR176
  • Catalysts which may be used as catalysts for the reaction of diamines into polyamines are, in particular, catalysts which contain one or more elements of subgroup 8 of the Periodic Table (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), preferably Co, Ni, Ru, Cu or Pd, more preferably Co, Ni and / or Cu (hereinafter also referred to as catalytically active metals).
  • catalysts which contain one or more elements of subgroup 8 of the Periodic Table (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), preferably Co, Ni, Ru, Cu or Pd, more preferably Co, Ni and / or Cu (hereinafter also referred to as catalytically active metals).
  • the abovementioned catalysts can be doped in the customary manner with promoters, for example with chromium, iron, cobalt, manganese, molybdenum, titanium, tin, metals of the alkali metal group, metals of the alkaline earth metal group and / or phosphorus.
  • promoters for example with chromium, iron, cobalt, manganese, molybdenum, titanium, tin, metals of the alkali metal group, metals of the alkaline earth metal group and / or phosphorus.
  • so-called skeletal catalysts also referred to as Raney® type, hereinafter also referred to as: Raney catalyst
  • Raney catalyst which are obtained by leaching (activation) of an alloy of catalyst, reactive metal and a further component (preferably Al) may preferably be used .
  • Preference is given to using Raney nickel catalysts or Raney cobalt catalysts.
  • catalysts preference is furthermore given to using Pd or Pt supported catalysts.
  • Preferred support materials are activated carbon, Al2O3, T1O2, ZrC "2 and S1O2.
  • catalysts which are prepared by reduction of so-called catalyst precursors in the process according to the invention.
  • the catalyst precursor contains an active material which contains one or more catalytically active components, optionally promoters and optionally a carrier material.
  • the catalytically active components are oxygen-containing compounds of the abovementioned catalytically active metals, for example, and their metal oxides or hydroxides, such as CoO, NiO, CuO and / or their mixed oxides.
  • catalytically active components is used for the abovementioned oxygen-containing metal compounds, but is not intended to imply that these oxygen-containing compounds are in themselves already catalytically active.
  • the catalytically active components have a catalytic activity in the reaction according to the invention only after the reduction has taken place.
  • % oxygen e compounds of molybdenum calculated as M0O3, and 0 to 10 wt .-% oxygen-containing compounds of aluminum and / or manganese, calculated as Al2O3 or MnÜ2 contains, for example, the in loc. cit.
  • Page 8 disclosed catalyst having the composition 31, 5 wt% ZrO 2, 50 wt% NiO, 17 wt% CuO and 1, 5 wt% M0O 3, or disclosed in EP-A-963975 Oxide mixtures containing, prior to reduction with hydrogen, 22 to 45% by weight ZrO2, 1 to 30% by weight oxygenated compounds of copper, calculated as CuO, 15 to 50% by weight oxygenated compounds of nickel, calculated as NiO, wherein the molar Ni: Cu ratio is greater than 1, 15 to 50 wt .-% oxygen-containing compounds of cobalt, calculated as CoO, 0 to 10 wt .-% oxygen-containing compounds of aluminum and / or manganese, calculated as Al2O3 or Mn02 , and contains no oxygen-containing compounds of molybdenum, for example, the in loc. cit. , Page 17, discloses catalyst A having the composition 33% by weight Zr, calculated as ZrC "2, 28% by weight Ni, calculated as NiO, 11% by weight Cu, calculated as CuO and
  • the catalytically active material contained in the catalytically active composition one or more metals selected from the group consisting from Cu, Co and Ni.
  • the molar ratio of the atoms of the components of the active composition to one another can be determined by known methods of elemental analysis, for example atomic absorption spectrometry (AAS), atomic emission spectrometry (AES), X-ray fluorescence analysis (RFA) or ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry ) are measured.
  • AAS atomic absorption spectrometry
  • AES atomic emission spectrometry
  • RMA X-ray fluorescence analysis
  • ICP-OES Inductively Coupled Plasma Optical Emission Spectrometry
  • the molar ratio of the atoms of the components of the active mass to one another can also be determined mathematically, for example by determining the initial weights of the compounds used, which contain the components of the active composition, and determining the proportions of the atoms of the components of the active composition.
  • the stoichiometric formula of the compounds used can also be determined experimentally, for example by one or more of the above-mentioned methods.
  • the catalysts are used as powder, grit or shaped body (preferably extrudates or tablets).
  • the catalysts or catalyst precursors are preferably used in the form of shaped bodies in the process according to the invention.
  • moldings are those with any geometry or shape.
  • Preferred shapes are tablets, rings, cylinders, star strands, cartwheels or balls.
  • Particularly preferred are tablets, rings, cylinders, balls or star strands.
  • Especially suitable is the strand shape. impregnation
  • the catalysts are used in the form of shaped bodies in the process according to the invention, which are produced by impregnation of carrier materials which have the abovementioned geometry or which after impregnation deforms into shaped bodies having the abovementioned geometry become.
  • carrier materials are carbon, such as graphite, carbon black, graphene, carbon nanotubes and / or activated carbon, aluminum oxide (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), silicon dioxide, zirconium dioxide, zeolites, aluminosilicates or their Mixtures are considered.
  • the impregnation of the abovementioned support materials can be carried out by the customary processes (A.B. Stiles, Catalyst Manufacture-Laboratory and Commercial Preparations, Marcel Dekker, New York, 1983), for example by applying a metal salt solution in one or more impregnation stages.
  • Suitable metal salts are, as a rule, water-soluble metal salts, such as the nitrates, acetates or chlorides of the corresponding catalytically active components or doping elements, such as co-nitrate or co-chloride.
  • the impregnated support material is usually dried and optionally calcined.
  • the calcination is generally carried out at temperatures between 300 and 800 ° C, preferably 350 to 600 ° C, especially at 450 to 550 ° C.
  • the impregnation can also be carried out by the so-called "incipient wetness method", in which the support material is moistened to the maximum saturation with the impregnation solution in accordance with its water absorption capacity.
  • the impregnation can also be done in supernatant solution.
  • the multi-step impregnation is advantageous to apply when the carrier material is to be applied in a larger amount with metal salts.
  • the impregnation can take place simultaneously with all metal salts or in any order of the individual metal salts in succession.
  • carrier materials are used which already have the preferred geometry of the shaped bodies described above.
  • carrier materials which are present as powder or grit, and to subject impregnated carrier materials to a shaping.
  • the impregnated and dried or calcined carrier material can be conditioned.
  • the conditioning can be carried out, for example, by adjusting the impregnated carrier material by grinding to a specific grain size.
  • the conditioned, impregnated carrier material can be mixed with molding aids, such as graphite, or stearic acid, and further processed into shaped bodies.
  • After conditioning or shaping is usually a tempering.
  • the temperatures during the heat treatment usually correspond to the temperatures during the calcination.
  • molded articles are used in the process according to the invention, which are prepared by a co-precipitation (mixed precipitation) of all their components and the shaped catalyst precursors are subjected to shaping.
  • the liquid used is usually water.
  • a soluble compound of the active components are usually the corresponding metal salts, such as the nitrates, sulfates, acetates or chlorides, the above-mentioned metals into consideration.
  • Water-soluble compounds of Ti, Al, Zr, Si, etc., for example the water-soluble nitrates, sulfates, acetates or chlorides of these elements, are generally used as the soluble compounds of a carrier material.
  • Water-soluble compounds of the doping elements for example the water-soluble nitrates, sulfates, acetates or chlorides of these elements, are generally used as soluble compounds of the doping elements.
  • the soluble compounds are precipitated by addition of a precipitant as sparingly or insoluble, basic salts.
  • the precipitants used are preferably bases, in particular mineral bases, such as alkali metal bases.
  • bases in particular mineral bases, such as alkali metal bases.
  • precipitants are sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.
  • ammonium salts for example ammonium halides, ammonium carbonate, ammonium hydroxide or ammonium carboxylates.
  • the precipitation reactions may e.g. at temperatures of 20 to 100 ° C, especially 30 to 90 ° C, in particular at 50 to 70 ° C, are performed.
  • the precipitates obtained in the precipitation reactions are generally chemically nonuniform and generally contain mixtures of the oxides, oxide hydrates, hydroxides, carbonates and / or bicarbonates of the metals used. It may prove beneficial to the filterability of the precipitates when they are aged, i. if left for some time after precipitation, possibly in heat or by passing air through it.
  • the precipitates obtained by these precipitation processes are usually processed by washing, drying, calcining and conditioning. After washing, the precipitates are generally dried at 80 to 200 ° C, preferably 100 to 150 ° C, and then calcined.
  • the calcination is generally carried out at temperatures between 300 and 800 ° C, preferably 350 to 600 ° C, especially at 450 to 550 ° C.
  • the powdery catalyst precursors obtained by precipitation reactions are usually conditioned.
  • the conditioning can be carried out, for example, by adjusting the precipitation catalyst by grinding to a specific particle size.
  • the catalyst precursor obtained by precipitation reactions can be mixed with molding assistants such as graphite or stearic acid and further processed into shaped bodies.
  • Common methods of molding include extrusion, tableting, i. mechanical pressing or pelleting, i. Compacting by circular and / or rotating movements.
  • tempering After conditioning or shaping is usually a tempering.
  • the temperatures during tempering usually correspond to the temperatures during the calcination.
  • the shaped bodies can be produced by precipitation.
  • Precipitation is understood as meaning a preparation method in which a sparingly soluble or insoluble carrier material is suspended in a liquid and subsequently soluble compounds, such as soluble metal salts, are added to the corresponding metal oxides, which are then precipitated onto the suspended carrier by addition of a precipitant (eg described in EP-A2-1 106 600, page 4, and AB Stiles, Catalyst Manufacure, Marcel Dekker, Inc., 1983, page 15).
  • a precipitant eg described in EP-A2-1 106 600, page 4, and AB Stiles, Catalyst Manufacure, Marcel Dekker, Inc., 1983, page 15).
  • heavy or insoluble support materials are for example carbon compounds such as graphite, carbon black and / or activated carbon, alumina (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), silica, zirconia, zeolites, aluminosilicates or mixtures thereof into consideration ,
  • the carrier material is usually present as a powder or grit.
  • Suitable soluble compounds are the abovementioned soluble compounds of the active components or of the doping elements.
  • the precipitation reactions may e.g. at temperatures of 20 to 100 ° C, especially 30 to 90 ° C, in particular at 50 to 70 ° C, are performed.
  • the precipitates obtained in the precipitation reactions are generally chemically nonuniform and generally contain mixtures of the oxides, oxide hydrates, hydroxides, carbonates and / or bicarbonates of the metals used. It may prove beneficial to the filterability of the precipitates when they are aged, i. if left for some time after precipitation, possibly in heat or by passing air through it.
  • the precipitates obtained by these precipitation processes are usually processed by washing, drying, calcining and conditioning.
  • the precipitates are generally dried at 80 to 200 ° C, preferably 100 to 150 ° C, and then calcined.
  • the calcination is generally carried out at temperatures between 300 and 800 ° C, preferably 350 to 600 ° C, in particular at 450 to 550 ° C.
  • the powdery catalyst precursors obtained by precipitation reactions are usually conditioned.
  • the conditioning can be carried out, for example, by adjusting the precipitation catalyst by grinding to a specific particle size.
  • the catalyst precursor obtained by precipitation reactions can be mixed with molding aids, such as graphite, or stearic acid, and further processed to give moldings.
  • Formed bodies which have been produced by impregnation or precipitation generally contain the catalytically active components after calcination, generally in the form of their oxygen-containing compounds, for example their metal oxides or hydroxides, such as CoO. NiO, CuO and / or their mixed oxides (catalyst precursor).
  • their oxygen-containing compounds for example their metal oxides or hydroxides, such as CoO. NiO, CuO and / or their mixed oxides (catalyst precursor).
  • the catalyst precursors prepared by impregnation or precipitation as described above are generally reduced after calcination.
  • the reduction usually converts the catalyst precursor into its catalytically active form.
  • the reduction of the catalyst precursor can be carried out at elevated temperature in a moving or stationary reduction furnace.
  • the reducing agent used is usually hydrogen or a gas containing hydrogen.
  • the hydrogen is generally used technically pure.
  • the hydrogen may also be in the form of a hydrogen-containing gas, i. in admixtures with other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide are used.
  • the hydrogen stream can also be recycled as recycle gas into the reduction, possibly mixed with fresh hydrogen and, if appropriate, after removal of water by condensation.
  • the reduction of the catalyst precursor is preferably carried out in a reactor in which the shaped bodies are arranged as a fixed bed. Particularly preferably, the reduction of the catalyst precursor takes place in the same reactor in which the subsequent reaction takes place. Furthermore, the reduction of the catalyst precursor can take place in a fluidized bed reactor in the fluidized bed.
  • the reduction of the catalyst precursor is generally carried out at reduction temperatures of 50 to 600 ° C, in particular from 100 to 500 ° C, particularly preferably from 150 to 450 ° C.
  • the hydrogen partial pressure is generally from 1 to 300 bar, in particular from 1 to 200 bar, more preferably from 1 to 100 bar, wherein the pressure data here and below relate to the absolute measured pressure.
  • the duration of the reduction is preferably 1 to 20 hours, and more preferably 5 to 15 hours.
  • a solvent may be supplied to remove any water of reaction formed and / or, for example, to heat the reactor faster and / or to be able to dissipate the heat better during the reduction can.
  • the solvent can also be supplied supercritical
  • Suitable solvents can be used the solvents described above.
  • Preferred solvents are water; Ethers, such as methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran. Particularly preferred are water or tetrahydrofuran.
  • Suitable suitable solvents are also suitable mixtures.
  • the resulting shaped article can be handled after reduction under inert conditions.
  • the molded article may be handled and stored under an inert gas such as nitrogen or under an inert liquid, for example, an alcohol, water or the product of the respective reaction, for which the catalyst is used. If necessary, the catalyst must then be freed from the inert liquid before the start of the actual reaction.
  • the storage of the catalyst under inert substances allows uncomplicated and safe handling and storage of the molding.
  • the shaped body can also be brought into contact with an oxygen-containing gas stream such as air or a mixture of air with nitrogen.
  • an oxygen-containing gas stream such as air or a mixture of air with nitrogen.
  • the passivated molded body generally has a protective oxide layer. Through this protective oxide layer, the handling and storage of the catalyst is simplified, so that, for example, the incorporation of the passivated molded body is simplified in the reactor.
  • a passivated molding is preferably reduced prior to contacting with the reactants as described above by treatment of the passivated catalyst with hydrogen or a hydrogen-containing gas.
  • the reduction conditions generally correspond to the reduction conditions used in the reduction of the catalyst precursors. Activation typically removes the protective passivation layer.
  • hydrogen is fed in as gas.
  • the hydrogen is generally used technically pure.
  • the hydrogen can also be used in the form of a gas containing hydrogen, ie with admixtures of other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide.
  • Hydrogen-containing gases can be used, for example, reformer gases, refinery gases, etc., if and insofar as these gases do not contain any contact poisons for the catalysts used, for example CO.
  • preference is given to using pure hydrogen or essentially pure hydrogen in the process for example hydrogen having a content of more than 99% by weight of hydrogen, preferably more than 99.9% by weight of hydrogen, particularly preferably more than 99.99 Wt .-% hydrogen, in particular more than 99.999 wt .-% hydrogen.
  • the reaction is carried out in the presence of hydrogen, then high conversions and reaction rates and / or degrees of polymerization can be achieved without the need to change anything at an adjusted pressure or temperature profile. Furthermore, the polyamines obtained have a lower degree of discoloration.
  • the gas supplied contains at least 50 mol% of hydrogen, more preferably at least 75 mol% of hydrogen and most preferably at least 99 mol% of hydrogen.
  • the supplied gas consists of hydrogen.
  • Hydrogen is fed to the polymerization reactor below or above the feed point for diamine, preferably below continuously.
  • the hydrogen leaves the reactor together with the ammonia formed.
  • the ammonia is condensed out, for example by cooling and separated from the process.
  • the hydrogen can also be discharged from the process or recycled to the reactor.
  • the pressure in the reactor is optionally kept constant by repressing hydrogen.
  • the reaction according to the invention can be carried out in bulk or in a liquid as a solvent.
  • Suitable liquids are, for example, liquids which behave as far as possible inert under reaction conditions.
  • Preferred liquids are C4 to C12 dialkyl ethers, such as diethyl ether, diisopropyl ether, dibutyl ether or tert-butyl methyl ether, or cyclic C4 to C12 ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran or dioxane, dimethoxyethane, diethylene glycol dimethyl ether or hydrocarbons such as pentane, hexane, heptane, 2,2,4-trimethylpentane, octane, cyclohexane, cyclooctane, methylcyclohexane, xylene, toluene or ethylbenzene, or amides such as formamide, dimethylformamide or N-methylpyrrolidon
  • Suitable liquids may also be mixtures of the abovementioned liquids.
  • the reaction according to the invention is preferably carried out in the absence of solvent in the substance.
  • the concentration of monomers used at the beginning of the reaction is generally in the range of 0.1 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 30% by weight, and most preferably 5 to 25% by weight.
  • the reaction according to the invention can be carried out continuously, semicontinuously or batchwise. Can be worked in suspension and fixed bed reactors. suspension
  • the catalyst is suspended in the reaction mixture to be polymerized.
  • the polymerization in suspension mode can preferably be carried out in a stirred reactor, jet loop reactor, jet nozzle reactor, bubble column reactor, or in a cascade of such identical or different reactors.
  • the polymerization is particularly preferably carried out in suspension operation in a stirred reactor.
  • the settling rate of the catalyst in the liquid diamines or the chosen solvent should be low in order to keep the catalyst well in suspension.
  • the particle size of the catalysts used in the suspension procedure is therefore preferably between 0.1 and 500 ⁇ m, in particular 1 and 100 ⁇ m.
  • the polymerization is carried out in a reactor in which the catalyst is arranged as a fixed bed.
  • Suitable fixed bed reactors are described, for example, in the article "Catalytic Fixed Bed Reactors”(Ullmann's Encyclopedia of Industrial Chemistry, Published Online: 15 JUN 2000, DIO: 10.1002 / 14356007.b04_199).
  • the process is preferably carried out in a shaft reactor, shell-and-tube reactor or tubular reactor.
  • the process is particularly preferably carried out in a tubular reactor.
  • the reactors can each be used as a single reactor, as a series of individual reactors and / or in the form of two or more parallel reactors.
  • the fixed bed arrangement comprises a catalyst feed in the true sense, d. H. loose, supported or unsupported moldings, which are preferably in the geometry or shape described above.
  • the moldings are introduced into the reactor.
  • a grid base or a gas- and liquid-permeable sheet is usually used, on which the shaped bodies rest.
  • the shaped bodies can be surrounded by an inert material both at the inlet and at the outlet of the reactor.
  • the inert material used is as a rule moldings which have a similar geometry to the catalyst moldings described above, but are inert in the reaction, e.g. Pall rings, balls of an inert material (e.g., ceramic, steatite, aluminum).
  • the shaped bodies can also be mixed with inert material and introduced as a mixture into the reactor.
  • the catalyst bed (molding + optionally inert material) preferably has a bulk density (according to EN ISO 6) in the range of 0.1 to 3 kg / l, preferably from 1, 5 to 2.5 kg / l and particularly preferably 1, 7 to 2.3 kg / l on. process parameters
  • the polycondensation is carried out at temperatures of 100 to 250 ° C, preferably 120 to 200 ° C, more preferably 130 to 180 ° C, particularly preferably 150 to 180 ° C.
  • the polycondensation is carried out at a pressure at which monomers and oligomers are largely in the liquid state at the reaction temperature.
  • the polycondensation takes place at a hydrogen partial pressure in the range of 60 to 150 bar, preferably 70 to 150 bar, more preferably 75 to 100 bar.
  • the catalyst loading in a continuous procedure is 0.1 to 1.5, preferably 0.3 to 1.4, more preferably 0.5 to 1.3 kg of starting material per liter of catalyst per hour.
  • the residence time in the case of discontinuous or semi-continuous operation is typically 0.5 to 3, preferably 0.5 to 2.5, more preferably 0.5 to 1.5 hours.
  • the diamines are preferably initially charged in the reactor.
  • the diamines can be treated with suitable conveying devices, e.g. Liquid pumps, vacuum conveyors or pneumatic conveyors are conveyed into the reactor.
  • suitable conveying devices e.g. Liquid pumps, vacuum conveyors or pneumatic conveyors are conveyed into the reactor.
  • suitable devices for filling a reactor, depending on the state of matter of the substance to be delivered are known in the art.
  • the diamines are preferably conveyed in the liquid state into the reactor. For this purpose it may be necessary to heat the diamines to a temperature above their melting or solidification point and / or to operate under a pressure at which the diamines are in the liquid state. Furthermore, it may be preferable to dissolve the diamines in one of the aforementioned solvents.
  • the diamines are preferably pumped in the liquid state into the reactor.
  • the stream of feedstocks in the reactor can be from top to bottom (trickle) or from bottom to top (sumping).
  • the amount of gas supplied is preferably in the range of 1 to 1000 liters of gas per hour per liter of free reactor volume, more preferably 5 to 500, most preferably 10 to 300 and particularly preferably 50 to 200 liters of gas per hour per liter of free reactor volume, the free reactor volume is to be understood as the difference between the reactor void volume and the volume of the catalyst charge (including the internals).
  • the free reactor volume corresponds to the volume of a liquid which is required to fill the catalyst-filled reactor (including all internals).
  • the supply of the gas is preferably carried out continuously, ie substantially without interruption.
  • the supply can also be periodic or aperiodic with periodic or aperiodic interruptions, in which case it is advantageous for the average interruptions to be shorter than the average phases of the supply.
  • the average interruptions are preferably shorter than 15 minutes, preferably shorter than 2 minutes, and particularly preferably shorter than 1 minute.
  • the supply of the gas is uniform over the duration of the reaction, i. without major fluctuations over time.
  • the feed stream of gas may increase with increasing reaction time, but preferably should not exceed the upper limit of the preferred range. As a result, the amount of monomers, which is possibly entrained with the gas from the reactor, is reduced.
  • the gas supply is continuous, i. essentially without interruption.
  • the supply of the gas is preferably carried out separately from the supply of the diamines.
  • the gas may be simultaneously fed together with the diamines via one or more separate feeders.
  • the supplied gas is dispersed in the liquid phase.
  • Dispersion is understood to be the fine and as homogeneous as possible distribution of the gas in the liquid phase.
  • a dispersion of the gas in the liquid phase can be achieved, in which the gas is passed into the reactor via suitable access openings.
  • a dispersion of the gas in the liquid phase can be achieved in which a shear stresses generated by flow acts on the supplied gas and causes a sufficient deformation against the stabilizing effect of the interfacial tension on the supplied gas, so that a Zer- division of the gas flow is done in bubbles.
  • the energy input for generating a shear stress which acts on the gas or the gas bubbles for example, by the introduction of energy in the dispersion medium, for example by generating a flow in the dispersion medium, ie, the liquid phase, take place.
  • a turbulent flow is generated.
  • a flow as described below, for example, by stirring or circulation of the liquid phase take place.
  • the largest contiguous volume of gas in the liquid phase should preferably not exceed 1%, better 0.1% of the stirred tank volume (above the liquid phase, in the upper part of the reactor, a larger volume of gas may be present). It is preferred that the diameter of the gas bubbles, and thus the largest contiguous gas space in the liquid phase in the range of 0.1 mm to 100 mm diameter, more preferably in the range of 0.5 to 50 mm and most preferably in the range of 1 to 10 mm.
  • the dispersion of the gas in the liquid phase has the advantage that the ammonia formed during the reaction of the diamines to polyamine can be converted into the gas phase and removed from the reactor. By removing the resulting ammonia along with the gas supplied, polyamines of high molecular weight and low degree of branching can be achieved. access openings
  • the introduction of the gas takes place through one or more access openings.
  • Preferred access openings are a gas inlet tube, a distributor ring or a nozzle.
  • the term nozzle designates in the usual way a tube which tapers in the direction of flow.
  • distribution devices such as sintered or perforated plates in the region of the feed openings.
  • the perforated plates or sintering trays may be distributed over the entire cross-section or part of the cross-sectional area of the reactor.
  • the distribution of the gas in the liquid is improved by distributing the access openings uniformly over the cross-section of the reactor, such as a distributor ring.
  • the supplied gas is removed from the reactor together with ammonia formed in the reaction of the diamines into polyamine.
  • the removal of ammonia from the reactor has the advantage that high degrees of polymerization and a good space-time yield can be achieved.
  • the supplied gas and the ammonia formed in the reaction can be substantially separated or removed from the reactor together with the liquid phase.
  • the gas added to and removed from the reactor is measured in NL (standard liters) according to DIN 1343 and is in the range of 1 to 1000 NL per free reactor volume, the free reactor volume being the difference between the reactor void volume and the volume of catalyst charge (inclusive the internals) is to be understood.
  • the free reactor volume corresponds to the volume of a liquid which is required to fill the catalyst-filled reactor (including all internals).
  • the gas and ammonia are removed from the reactor substantially separately from the liquid phase.
  • the supplied gas is preferably discharged together with the resulting ammonia at a gas outlet from the reactor.
  • the gas outlet is preferably a valve, since the reaction of the diamines is preferably carried out at higher pressures.
  • the gas outlet can also be a simple opening, for example a pipeline. If the supplied gas is discharged separately from the liquid phase together with the ammonia formed, measures can be taken so that the liquid phase is not discharged together with the gas from the reactor.
  • the gas outlet in the upper region of the reactor in the gas space above the level of the liquid phase can be attached.
  • a membrane, a sinter plate, or a frit that is only permeable to the gaseous phase may also be placed in front of the gas outlet to retain the liquid phase in the reactor.
  • the gas stream removed from the reactor may be appropriately disposed of or worked up.
  • the gas stream removed from the reactor is returned to the reactor.
  • ammonia is separated from the gas stream prior to its recycling. This is preferably done in the ammonia is condensed from the gas stream, so that a gas stream is obtained, which is substantially free of ammonia, and a liquid stream is obtained which contains ammonia.
  • entrained or entrained diamine or oligomers of the diamine are first separated off from the gas stream and subsequently the separation of ammonia from the gas stream takes place.
  • the discharged gas is introduced into a phase separator or liquid separator. In the phase separator, the entrained liquid phase is separated from the gas phase containing ammonia and supplied gas.
  • the liquid phase separated in the phase separator which consists essentially of unreacted monomers or lower oligomers, can preferably be returned to the reactor or used in a subsequent reaction.
  • This has the advantage that yield losses, based on the diamine used, can be reduced.
  • the recycled stream of diamine, oligomers of the diamine and optionally solvent is substantially free of ammonia. This is generally achieved after the liquid separator. If the recirculated stream still contain ammonia, ammonia can be removed from the liquid phase separated in the phase separator, for example by distillation or degassing (stripping).
  • the separation of ammonia from the discharged gas stream can preferably take place in that the gas stream is cooled by a cooling device to a temperature at which ammonia passes into the liquid state, and the supplied gas remains in the gas phase.
  • the cooling device is preferably a condenser.
  • ammonia is condensed out of the gas stream, so that a gas stream is obtained, which is substantially free of ammonia, and a liquid stream is obtained which contains ammonia, and if necessary, the gas separated from ammonia can lead back into the reactor ,
  • the capacitor can be made up of almost all capacitors known to those skilled in the art, e.g. Plate capacitor, tube bundle condenser or snake cooler.
  • the capacitor is designed as a tube bundle capacitor.
  • the condenser can be operated standing or lying, the condensation can take place in the shell space or in the pipes.
  • the gas stream usually contains only the gas supplied, since the ammonia contained in the gas stream was condensed out.
  • the uncondensed gas stream is preferably recycled to the reactor. It is preferred that the recycle stream contains substantially no ammonia. This will be in Generally already reached after the cooling device. Should the ammonia levels be higher, the gas stream can be cooled again, for example at lower temperatures.
  • ammonia is first separated from the gas stream together with the entrained or entrained liquid phase in which the gas stream is cooled, so that liquefied ammonia, and the liquid phase is separated from the gas phase.
  • the separation of ammonia from the discharged gas stream can then preferably take place in that the gas stream is cooled by a cooling device to a temperature at which ammonia passes into the liquid state, and the gas supplied remains in the gas phase.
  • the cooling device is preferably a condenser.
  • the cooling device is preferably a condenser.
  • the capacitor can be made up of almost all capacitors known to those skilled in the art, e.g. Plate capacitor, tube bundle condenser or snake cooler.
  • the capacitor is designed as a tube bundle capacitor.
  • the condenser can be operated standing or lying, the condensation can take place in the shell space or in the pipes.
  • the separated liquid phase contains in addition to ammonia possibly entrained or entrained amounts of diamine, oligomers of diamine and optionally solvent.
  • ammonia is separated from the liquid phase diamine or oligomers of the diamine, for example by distillation, degassing (stripping) or evaporation of the ammonia.
  • the remaining after the separation of the ammonia liquid phase can be recycled to the reactor or used in a subsequent reaction.
  • the liquid phase of diamine, oligomers of diamine and optionally solvent which is recycled or reused is preferably substantially free of ammonia.
  • the uncondensed gas phase containing inert gas and / or hydrogen, can be discharged from the reactor or preferably recycled to the reactor. Extraction together with reaction discharge
  • the supplied gas and the resulting ammonia are discharged together with a portion of the liquid phase from the reactor.
  • the liquid phase is discharged together with the gas dispersed in the liquid phase and the resulting ammonia through a liquid outlet from the reactor.
  • the liquid outlet is usually a pipe at the end of which is a valve.
  • the catalyst is not used as a fixed bed but as a suspension, then it is preferable to separate the catalyst from the reactor effluent before further workup.
  • the reactor discharge can be filtered, for example.
  • the catalyst may be by cross-flow filtration.
  • the catalyst can also be separated from the reactor by centrifugation or sedimentation.
  • the reactor discharge is expanded at the reactor outlet, so that still in the liquid phase ammonia present, which is still in the liquid state, is largely completely transferred to the gas phase.
  • the reactor discharge is usually transferred through a valve in a space with less than in the reactor prevailing pressure, in which, however, unreacted diamine monomer still remains in the liquid phase
  • the gaseous phase containing ammonia and the gas fed in is separated from the liquid phase containing polyamine, oligomers of diamine and diamine and optionally solvent.
  • the liquid phase is preferably recycled to the reactor as described below. It is preferred that the recycled liquid phase containing diamine, oligomers of the diamine and optionally solvent is substantially free of ammonia. This is generally achieved already after the flash evaporation. If the ammonia contents are nevertheless higher, then ammonia can be removed from the liquid phase deposited in the phase separator, for example by distillation or degassing (stripping).
  • the proportion of the components which are present in gaseous form after the flash evaporation is preferably partially condensed in a cooler, the condensation preferably being operated so that ammonia is essentially completely condensed.
  • the supplied gas such as inert gas and or hydrogen, are preferably not condensed.
  • Ammonia is preferably discharged from the process.
  • the uncondensed gas which consists essentially of inert gas and / or hydrogen, is preferably recycled to the process.
  • the recirculated gas preferably contains substantially no ammonia.
  • the reaction product is discharged into a distillation device.
  • the distillation device is generally operated in such a way that ammonia and supplied gas are withdrawn at the top of the distillation device and the remaining liquid phase (monomer, oligomers and polymers) is withdrawn at the bottom of the distillation device (variant 1).
  • the distillation device K1 can also be operated in such a way that ammonia and the supplied gas are withdrawn from the top, monomeric and oligomeric diamine is withdrawn from a withdrawal in the middle region of the distillation device and higher molecular weight polyamine is withdrawn at the bottom of the distillation device (variant 2).
  • the exact operating conditions of the distillation device can be routinely determined according to the separation efficiency of the distillation device used by a person skilled in the art on the basis of the known vapor pressures and evaporation equilibria of the introduced into the distillation device components according to conventional calculation methods.
  • the reactor discharge is preferably expanded into the middle region, a distillation device K1.
  • the distillation device K1 is particularly preferably a tray column.
  • a tray column there are intermediate trays in the interior of the column on which the mass transfer takes place. Examples of different soil types are sieve trays, tunnel trays, dual-flow trays, bubble trays or valve trays.
  • the distillative internals can also be in the form of an ordered packing, for example as a sheet-metal pack, such as Mellapak 250 Y or Montz Pak, type B1 -250, or as a structured ceramic pack or as disordered packing, for example from pall rings, IMTP rings (US Pat. Co. Koch-Glitsch), Raschig-Superringen, etc.
  • a sheet-metal pack such as Mellapak 250 Y or Montz Pak, type B1 -250
  • a structured ceramic pack or as disordered packing, for example from pall rings, IMTP rings (US Pat. Co. Koch-Glitsch), Raschig-Superringen, etc.
  • IMTP rings US Pat. Co. Koch-Glitsch
  • Raschig-Superringen etc.
  • ammonia is separated from the overhead stream of gas.
  • the separation of ammonia from the discharged gas stream can preferably take place in that the gas stream is cooled by a cooling device to a temperature at which ammonia passes into the liquid state, and the gas supplied remains in the gas phase.
  • the cooling device is preferably a condenser.
  • the condenser of the distillation device K1 is generally operated at a temperature at which the ammonia is largely completely condensed at the corresponding top pressure.
  • the condensed ammonia is preferably discharged from the process.
  • the uncondensed gas which consists essentially of inert gas and / or hydrogen, is preferably recycled to the process.
  • the recirculated gas preferably contains less than 5% by weight of ammonia.
  • the distillation device K1 usually requires no additional evaporator at the bottom of the distillation device, since the difference between the boiling points of ammonia and monomeric diamine is usually so high that a good separation of ammonia and monomeric diamine succeeds without additional bottom heating.
  • the temperature in the bottom of the distillation device should then be adjusted so that at the top pressure prevailing in the distillation device ammonia largely completely evaporated, while monomeric diamine remains in the liquid phase.
  • the bottoms discharge of the distillation unit K1 essentially contains diamine, oligomers of the diamine, polyamine and possibly solvent.
  • Part of the bottom product can be recycled to a) the reactor, or
  • low-boiling oligomer is separated from higher-boiling polyamine, or c) are removed from the reactor as a reaction product.
  • the distillation device K1 can also be operated in such a way that ammonia and the supplied gas are produced at the top of the distillation device, a fraction is taken off in the middle region as a side draw which contains monomeric diamine and low-boiling oligomers and polyamine is obtained at the bottom of the distillation device K1.
  • the reactor discharge is, as in the variant 1 described above, preferably in the central region, a previously described distillation device K1 relaxed. At the top of the distillation device K1 is usually obtained a gaseous stream of the supplied gas and ammonia.
  • ammonia is separated from the overhead stream of gas.
  • the separation of ammonia from the discharged gas stream can preferably take place in that the gas stream is cooled by a cooling device to a temperature at which ammonia passes into the liquid state, and the supplied gas remains in the gas phase.
  • the cooling device is preferably a condenser.
  • the condenser of the distillation device K1 is generally operated at a temperature at which the ammonia is largely completely condensed at the corresponding top pressure.
  • the condensed ammonia is preferably discharged from the process.
  • the uncondensed gas which consists essentially of inert gas and / or hydrogen, is preferably recycled to the process.
  • the distillation device K1 usually requires no additional evaporator at the bottom of the distillation apparatus, since the difference between the boiling points of ammonia and monomeric diamine is usually so high that a good separation of ammonia and monomeric diamine succeeds without additional bottom heating.
  • the temperature in the bottom of the distillation device should be adjusted so that at the prevailing in the distillation overhead pressure ammonia largely completely evaporated, while monomeric diamine remains in the liquid phase.
  • a fraction is preferably withdrawn, which contains substantially oligomers of the diamine and diamine.
  • the side take-off can a) be removed from the process, or
  • the side draw When the side draw is recycled to the process, it is preferred that the side draw contain substantially no ammonia. This is generally achieved already after the flash evaporation (distillation). If the ammonia levels are nevertheless higher, the ammonia content can be reduced, for example by distillation or degassing (stripping).
  • the bottoms discharge of the distillation unit K1 essentially contains diamine, oligomers of the diamine, polyamine and possibly solvent.
  • a portion of the bottom product can, as described under variant 1 a) be returned to the reactor, or
  • the sump discharge from distillation device K1 can be introduced into a further distillation device K2, which is operated such that monomeric diamine and low-boiling oligomers are obtained at the top of the distillation device and polymeric polyamine is formed at the bottom of the distillation device.
  • the distillation device K2 can also be operated so that predominantly monomeric diamine can be withdrawn at the top, predominantly oligomeric diamine at a side draw and polymeric diamine at the bottom.
  • the bottoms discharge from the distillation device K1 is preferably fed into the middle region, a distillation device K2.
  • the distillation device K2 preferably has internals for increasing the separation efficiency.
  • the distillative internals may, for example, be in the form of an ordered packing, for example as a sheet-metal package such as Mellapak 250 Y or Montz Pak, type B1 -250. There may also be a package of lesser or increased specific surface area, or a fabric packing or other geometry package such as Mellapak 252Y may be used.
  • the advantage of using these distillative internals is the low pressure loss and the low specific liquid hold-up in comparison to, for example, valve trays.
  • the installations can be in one or more beds.
  • the bottom of the distillation device K2 is preferably equipped with a bottom evaporator.
  • the temperature in the bottom of the distillation device should be adjusted so that at the top pressure prevailing in the distillation device ammonia monomer diamine evaporates almost completely and a portion of the oligomers, while polymeric polyamine remains in the liquid phase.
  • a gaseous stream is usually withdrawn, which consists essentially of monomeric diamine and other low boilers.
  • the gas stream produced at the top is fed to a condenser, which is connected to the distillation device K2.
  • the condenser of the distillation device K2 is generally operated at a temperature at which the diamine is largely completely condensed at the corresponding top pressure.
  • the condensate of the distillation device K2 which consists essentially of monomeric diamine and other low boilers, can be discharged or recycled to the process.
  • the recycled diamine preferably contains substantially no ammonia.
  • a portion of the bottoms discharge can be recycled to the reactor or removed from the reactor as a reaction product.
  • the bottom product of the distillation device K2 is discharged as a reaction product.
  • a side draw can be taken, which contains a fraction of low-boiling oligomers. These oligomers may be discharged or recycled to the reactor along with the diamine exhausted at the top.
  • Preferred process variants K2 can also be reduced to an evaporator and / or a combination of a plurality of evaporators.
  • the distillation unit K2 can also be operated as a stripping column, so that low-boiling components (monomeric diamine and oligomers) are taken off at the top of the column with the aid of a stripping agent and polymer polyamines are obtained at the bottom.
  • Suitable stripping agents are substances whose boiling point is less than the boiling point of the low boilers to be separated (for example preferably nitrogen, methanol, monomeric diamine, ammonia, hydrogen) and which do not react with diamines, oligomeric diamines and polyamines.
  • FIG. 2 shows a batch process in which monomer is introduced into a stirred tank reactor R 1 which contains the catalyst in suspended or fixed form, for example in a metal net. Then inert gas and / or hydrogen is continuously fed.
  • the introduction preferably takes place through a gas inlet tube, a gas distributor ring or a nozzle, which is preferably arranged below a stirrer.
  • the introduced gas stream is smashed by the energy input of the stirrer into small gas bubbles and homogeneously distributed in the reactor.
  • a mixture of formed ammonia and inert gas and / or hydrogen is continuously discharged from the reactor through an outlet opening in the upper region of the reactor.
  • the suspension catalyst is first removed as part of the workup of the desired product when the product is discharged, eg. B. by filtration or centrifugation.
  • the reaction product obtained in the batchwise polycondensation can be passed into a distillation apparatus K1, in which a stream of diamine and oligomers of the diamine is separated at the top. In the bottom of the distillation unit, polyamine is obtained.
  • the reaction product obtained in the batchwise polycondensation can alternatively be passed into a distillation apparatus K1 in which a stream of diamine is removed at the top and a fraction which consists essentially of oligomers of the diamine is removed as side draw. In the bottom of the distillation unit polyamine is withdrawn.
  • FIG. 3 shows a variant of the method in which the discharged gas stream is expanded after the discharge.
  • the withdrawn gas stream is introduced into a liquid separator.
  • the liquid deposited in the liquid separator is discharged from the process.
  • the mixture of ammonia and inert gas and / or hydrogen discharged from the reactor is preferably cooled, wherein the ammonia is liquefied and can be separated off from the inert gas and / or hydrogen.
  • the inert gas and / or hydrogen can be compressed again, if necessary mixed with fresh inert gas and / or hydrogen and recycled to the polymerization stage.
  • FIG. 4 shows a further variant in which the liquid deposited in the liquid separator, which consists essentially of diamine, oligomers of the diamine and optionally solvent, is recycled to the process. If the mixture of diamines and / or oligomers of the diamines contain by-products, they may be separated off, for example by distillation, from the diamines and their oligomers prior to their recycling. Thus, in the polycondensation of 1,3-propanediamine according to the invention, for example, N-propyl-1,3-propanediamine can be formed as a by-product which can be separated off by distillation.
  • Variant K-1 consists essentially of diamine, oligomers of the diamine and optionally solvent
  • FIG. 5 shows a continuous process for the preparation of polyamines. Diamine is passed together with inert gas and / or hydrogen over a catalyst which is fixedly arranged in an inertized pressure reactor R1.
  • the reaction effluent is passed to a distillation device K1.
  • a distillation device K1 About the top of the distillation device K1 is a mixture of ammonia and hydrogen, which is discharged from the process.
  • the bottom product of the distillation device K1 is fed to a distillation device K2. Unreacted diamine is separated off at the top of the distillation device K2 and recycled to the reactor R1. If necessary, oligomers are withdrawn from a side draw of the distillation device K2, which are discharged and / or returned to the reactor R1.
  • the bottom product of the distillation device K2 contains polyamine.
  • FIG. 6 shows a continuous process for the preparation of polyamines. Diamine is passed together with inert gas and / or hydrogen over a catalyst which is fixedly arranged in an inertized pressure reactor R1.
  • the reaction effluent is passed to a distillation device K1.
  • a distillation device K1 About the top of the distillation device K1 is a mixture of ammonia and hydrogen, from which the ammonia is condensed out. Inert gas and / or hydrogen can be recycled to the reactor R1.
  • the bottom product of the distillation device K1 is fed to a distillation device K2. Unreacted diamine and low-boiling oligomer are separated off at the top of the distillation device K2 and recycled to the reactor R1. If necessary, oligomers are withdrawn from a side outlet of the distillation device K2, which are discharged and / or returned to the reactor R1.
  • the bottom product of the distillation device K2 contains polyamine.
  • FIG. 7 shows a variant of the continuous process.
  • Diamine is passed together with inert gas and / or hydrogen over a catalyst which is fixedly arranged in an inertized pressure reactor R1. Under the reaction conditions, a reaction effluent is formed, which is passed to a distillation device K1.
  • the distillation device K1 is operated so that the top product obtained is a mixture of ammonia and inert gas and / or hydrogen mixture from a side draw a mixture of diamine and oligomers of the diamine and taken as the bottom product polyamine.
  • the distillation device K2 in Figure 5 or 6 is omitted.
  • the polymerization is preferably worked up so that unreacted diamine and oligomeric Diame having a boiling point less ⁇ 300 ° C, Favor ⁇ 250 ° C, particularly preferably of ⁇ 200 ° C at 10 mbar are depleted by distillation of the polymers.
  • the mixture of unreacted diamines and oligomers can be recycled to the reactor without further workup.
  • a stripping agent-assisted distillation apparatus is preferably used in order to obtain concentrations of low-boiling components of ⁇ 5% by weight, preferably ⁇ 1% by weight, particularly preferably ⁇ 0.1% by weight, in the bottom product of the polyamines.
  • the low-boiling components are at pressures of 0.5 to 1000 mbar, preferably 0.5-500 mbar, more preferably 0.5-50 mbar and temperatures of 150-300 ° C, preferably 165-265 ° C, particularly preferably 180 -230 ° C largely depleted,
  • Suitable stripping agents are substances whose boiling point is less than the boiling point of the low boilers to be separated (for example preferably nitrogen, methanol, monomeric diamine, ammonia, hydrogen) and which do not react with the diamines, oligomeric diamines and polyamines. Nitrogen is preferably used as the stripping agent.
  • the amount of stripping agent in relation to the mass of the bottoms product of K1 can vary ⁇ 1000 NL stripping agent / kg sump product K1, preferably ⁇ 600 NL / kg and very particularly preferably ⁇ 300 NL / kg.
  • distillations or evaporations according to the invention can be carried out in any suitable apparatus known to the person skilled in the art.
  • apparatuses are suitable, as described for example in Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Edition, Volume 8, John Wiley and Sons, New York 1996, pages 334 to 348, such as sieve tray columns, bubble tray columns, packed columns and packed columns.
  • Suitable single-stage evaporators are falling film evaporators, thin film evaporators, flash evaporators, multiphase spiral tube evaporators, natural circulation evaporators or forced circulation expansion evaporators.
  • polyamines By means of the process described above, polyamines (hereinafter also “polymers”) can be prepared with particular properties.
  • the present invention therefore also relates to homopolymers and copolymers which are obtainable by reacting the abovementioned diamine monomers according to the invention.
  • the polymers may be prepared from repeat units of only one kind of diamine monomer (hereinafter referred to as homopolymers). However, the polymers may also be prepared from mixtures of two or more different types of diamine monomer (hereinafter referred to as copolymers).
  • Preferred polymers are polymers of at least one diamine selected from the group consisting of 1, 3-propylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 2-butylenediamine, 1, 5-diaminopentane, 1, 2-diaminopentane , 6-diaminohexane, 1, 2-
  • Further preferred polymers are polymers of at least one diamine selected from the group consisting of N, N-bis (3-aminopropyl) methylamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), di-1,3-propylenetriamine, Tri-1,3-propylenetetramine, tetra-1,3-propylenepentamine, di-1,2-propylenetriamine, tri-1,2-propylenetetramine, tetra-1,2-propylenepentamine, dihexamethylenetriamine, trihexamethylenetetramine and tetrahexamethylenepentamine.
  • diamine selected from the group consisting of N, N-bis (3-aminopropyl) methylamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), di-1,3-propylenetriamine, Tri-1,3-propylenetetra
  • polymers of at least one diamine selected from the group consisting of 3,3 '-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4' - diaminodicyclohexylmethane, isophoronediamine, [bis- (4-amino-cyclohexyl) -methane ], [Bis (4-amino-3,5-dimethylcyclohexyl) methane], [bis (4-amino-3-methylcyclohexyl) methane], 3- (cyclohexylamino) propylamine, piperazine and bis (aminomethyl) piperazine.
  • diamine selected from the group consisting of 3,3 '-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4' - diaminodicyclohexylmethane, isophoronediamine, [bis- (4-amino-cyclohexyl
  • polymers are polymers of at least one diamine selected from the group consisting of 4,7,10-Trioxatridecane-1, 13-diamine, 4,9-dioxadodecane-1, 12-diamine and so-called Jeffamine® Fa. Huntsman, in particular Jeffamin D230, Jeffamine D400, Jeffamin D2000, Jeffamine D4000, Jeffamine ED600, Jeffamine ED900, Jeffamine ED2003, Jeffamin EDR148, and Jeffamin EDR176
  • the polymers prepared by the process described above contain diamine monomers of the formula
  • the polymers contain repeating units of the formula
  • the repeating units may be linearly linked or branched.
  • Branching (D) denotes a linkage in which three repeat units are linked via a tertiary amine (-N ⁇ ).
  • the polymers may have primary amine end groups (-NH 2) (T).
  • DB is defined as follows:
  • D corresponds to the number of tertiary amino groups in the polymer
  • L (linear) corresponds to the number of secondary amino groups in the polymer
  • T (terminal) corresponds to the number of primary amino groups in the polymer.
  • the degree of branching can be determined by determining the primary, secondary and tertiary amine numbers.
  • the determination of the primary, secondary or tertiary amine number can be carried out in accordance with ASTM D2074-07.
  • the degree of branching can also be determined qualitatively by means of 15 N-NMR.
  • the polyamines according to the invention preferably have no signal or only a weak signal in the range typical for tertiary N atoms. This can be considered as an indicator of a low degree of branching.
  • the linking of the repeat units can thus be carried out to unbranched or branched polymer chains or unbranched or branched polymeric rings. In rings, at least two end groups of the same linear or branched chains are linked, so that a ring structure is formed. The likelihood that two primary amine groups of the same chain will be linked to one ring will decrease with the number of repeat units between the linking primary amine groups.
  • the polymers of the invention may preferably have at least one, or any combination of 2 or more of the following properties a) to i): a) degree of branching
  • the polymers generally have a high proportion of linearly linked repeat units.
  • the degree of branching (DB) is preferably in the range of 0 to 1, more preferably in the range of 0 to 0.5, and most preferably in the range of 0.01 to 0.3
  • Polymers with a low degree of branching have good processing properties. They are particularly suitable for subsequent reactions in which the polymer is chemically modified (alkoxylation with, for example, ethylene oxide and / or propylene oxide, reaction with isocyanates, reaction with acrylonitrile, reaction with epichlorohydrin, reaction with ethylene dichloride, reaction with Esters / acids, quaternization with methyl chloride or dimethyl sulphate), since in the reaction of polyamines according to the invention, as a rule, a slight increase in viscosity takes place, in comparison to branched polyamines.
  • degree of polymerization with, for example, ethylene oxide and / or propylene oxide, reaction with isocyanates, reaction with acrylonitrile, reaction with epichlorohydrin, reaction with ethylene dichloride, reaction with Esters / acids, quaternization with methyl chloride or dimethyl sulphate
  • the average number of repeating units Pn of the monomers in the polymers is generally between 4 and 50,000.
  • the polymers have a high average molecular weight, i. a degree of polymerization Pn of 4 or more, preferably 10 or more, more preferably 15 or more and most preferably 20 or more.
  • the number of repeating units is preferably in the range from 4 to 1000, very particularly preferably in the range from 10 to 500, particularly preferably in the range from 15 to 100 and very particularly preferably in the range from 20 to 50.
  • polydispersity in the range of 100 to 1,000,000 g / mol, more preferably in the range of 200 to 100,000 g / mol, most preferably in the range of 245 to 10,000 g / mol.
  • the polydispersity (Pw / Pn) of the polymers is generally in the range of 1.2 to 20, preferably 1.5 to 7.5, where Pn is the number average degree of polymerization and Pw is the weight average degree of polymerization.
  • the polydispersity (Pw / Pn) of the polymers is preferably in the range from 1.2 to 5, particularly preferably in the range from 1.3 to 4, very particularly preferably in the range from 1.5 to 5. Such polymers have a good property profile and can be processed well. d) metal content
  • the polymers preferably have a low metal content.
  • the metal content is preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 10 ppm, and most preferably less than 1 ppm.
  • Such polymers have a low reactivity. Low reactivity means that the reaction rate of the polymers in subsequent reactions, for example, the reaction with diisocyanates to polyureas, is low.
  • polymers with a low metal content have an increased stability to environmental influences, such as light, ultraviolet radiation, temperature or moisture.
  • Phosphorus Content The polymers preferably have a low phosphorus content.
  • the phosphorus content is preferably less than 500 ppm, more preferably less than 100 ppm, most preferably less than 10 ppm, and most preferably less than 1 ppm. Polymers with a low phosphorus content generally have an increased stability to environmental influences, such as light, ultraviolet radiation, temperature or humidity.
  • color number such as light, ultraviolet radiation, temperature or humidity.
  • the polymers also preferably have a low color number.
  • the color number is preferably less than 200 Hazen, more preferably less than 150 Hazen, most preferably less than 100 Hazen and even more preferably less than 80 Hazen.
  • the Hazen color number preferably ranges from 0 to 200, more preferably from 5 to 150, most preferably from 10 to 100, and most preferably from 20 to 60.
  • the Hazen color number is usually measured in accordance with ASTM D1209 or DIN 53409.
  • a low color number allows the application of the polymers in areas in which the color is regarded as a quality feature. These are most industrial applications, especially applications in paints, inks or adhesives. g) OH number
  • the polymers In contrast to polyamines, which are prepared by homogeneously catalyzed reaction of diamines and diols or by reaction of amino alcohols, the polymers preferably have a low OH number and are less branched. A low OH number has the advantage that the polymers have a higher charge density and a lower water solubility.
  • a higher charge density can be advantageous in the use of the polymers as such or as a building block for a) adhesion promoter, for example for printing inks for laminate films;
  • e) fabric for improving wet adhesion, for example in standard emulsion paints, and for improving the instantaneous rainfastness of paints, for example for road markings;
  • flocculants for example in water treatment / water treatment
  • Penetration aids for example for active metal salt formulations in wood preservation
  • n aids in the paper industry, for example for dewatering acceleration, elimination of contaminants, charge neutralization and paper coating;
  • Gas scrubbing material used as an absorbent for CO2, NOx, SOx, C and aldehydes and for the neutralization of acidic constituents;
  • crosslinker for conformance control and for selective water shut-off in the field of oil and gas production
  • the OH number is preferably less than 5 mg KOH / g, more preferably less than 2 mg KOH / g, most preferably less than 1 mg KOH / g and most preferably less than 0.5 mg KOH / g.
  • the OH number can be determined by means of DIN 53240. h) chloride content
  • the polymers preferably have a low chloride content.
  • the chloride content is less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 10 ppm and most preferably less than 1 ppm.
  • the polymers preferably have a low degree of deamination.
  • the proportion of deaminated polymers is preferably less than 3 wt .-%, more preferably less than 2 wt .-% and particularly preferably less than 1 wt .-%.
  • the polymers after the preparation and before the preparation, have at least one or any combination of at least two of the following properties: a) a degree of branching of 0 to 0.5, preferably 0.01 to 0.3; and / or b) an average degree of polymerization Pn of 5 or more, preferably in the range
  • the abovementioned polymers have all of the abovementioned properties a), b), c) d), e), f), and g).
  • the abovementioned polymers have all of the abovementioned properties a), b), c) d), e), f), g), and h)). In a very particularly preferred embodiment, the abovementioned polymers have all the abovementioned properties a), b), c) d), e), f), g), h) and i).
  • the abovementioned polymers are preferably suitable for the following applications as such or as building blocks for a) adhesion promoters, for example for printing inks for laminate films;
  • adhesion promoters for adhesives for example in conjunction with polyvinyl alcohol, - butyrate, and acetate and styrene copolymers, or as a cohesion promoter for label adhesives;
  • e) fabric for improving wet adhesion, for example in standard emulsion paints, and for improving the instantaneous rainfastness of paints, for example for road markings;
  • flocculants for example in water treatment / water treatment
  • Penetration aids for example for active metal salt formulations in wood preservation
  • corrosion inhibitors for example for iron and non-ferrous metals and in areas of gasoline production, the secondary oil production
  • n additive in the cosmetics sector, for example for hair fixatives and rinses; n) aids in the paper industry, for example for dewatering acceleration, elimination of contaminants, charge neutralization and paper coating;
  • Gas scrubbing material used as an absorbent for CO2, NOx, SOx, C and aldehydes and for the neutralization of acidic constituents;
  • crosslinker for conformance control and for selective water shut-off in oil and gas production
  • the present invention allows the use of a variety of monomers, so that a wide variety of homo- and co-polymers can be achieved (by the choice of monomers, the properties of the polymers produced can be tailored),
  • the method according to the invention can have the following advantages:
  • the catalyst used for the polymerization can be easily from
  • Example 4 (according to the invention)
  • Example 6 (according to the invention)
  • the procedure is as in Comparative Example 1, but the pressure is 100 bar and the temperature is 161 ° C.
  • the catalyst load was 0.7 kg per liter of catalyst per hour.
  • the resulting average molecular weight of the polymer mixture was 310 g / mol.
  • Example 9 (according to the invention) The procedure is as in Comparative Example 1, but the pressure is 100 bar and the temperature is 163 ° C. The catalyst load was 0.7 kg per liter of catalyst per hour. The resulting average molecular weight of the polymer mixture was 320 g / mol.
  • Example 10 (according to the invention)
  • the workup by distillation of the crude material based on 1, 3-diaminopropane was carried out in an apparatus with thin-film evaporator, with the aim of lowering the mass fraction of the trimer below 0.1%.
  • liquid raw material was introduced from above onto the vertical glass evaporator surface (0.016 m 2 ) of the thin-film evaporator, while nitrogen flowed through the apparatus from the bottom to the top in a counterflow principle.
  • a liquid film was formed by means of a stirring system with movable stirring blades on the inner wall of the evaporator surface.
  • the necessary energy input for partial evaporation of the supplied raw stream was introduced into the liquid film from outside through a double jacket space through which hot oil flows.
  • the gaseous phase produced under the prevailing conditions was fed in series coolers with decreasing coolant temperature in order to liquefy condensable constituents.
  • the low-boiler streams obtained in this way consisting predominantly of monomer, dimer, trimer and tetramer, can be recycled as starting material component into the reaction part.
  • the low-boiler stream of the distillation does not represent a loss in yield within the overall process.
  • the non-volatile liquid components are collected as a product of value at the lower end of the thin-film evaporator.

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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de fabrication de polyamines ayant une masse moléculaire moyenne de ≥ 203 g/mole, dans lequel la déviation par rapport à la masse moléculaire moyenne par °C de variation de la température de réaction est de < 19% de la masse moléculaire moyenne; le procédé s'effectue par polycondensation de diamines dans la phase liquide en présence de catalyseurs hétérogènes à base de métaux de transition du huitième au 11ème sous-groupe du système périodique des éléments, et d'hydrogène à des températures dans la plage de 100 à 250 °C et des pressions dans la plage de 60 à 150 bar. L'invention porte aussi sur des polyamines pouvant être obtenues par ce procédé, ainsi que sur l'utilisation des polyamines.
EP14821096.6A 2014-02-26 2014-12-12 Procédé de fabrication de polyamines Withdrawn EP3110872A1 (fr)

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CN108485633B (zh) * 2018-03-31 2021-10-08 青岛大学 一种网状聚季胺油气井页岩防膨剂的制备方法

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