EP3080190A1 - Procédé de préparation de polyamide 66 - Google Patents

Procédé de préparation de polyamide 66

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Publication number
EP3080190A1
EP3080190A1 EP14811899.5A EP14811899A EP3080190A1 EP 3080190 A1 EP3080190 A1 EP 3080190A1 EP 14811899 A EP14811899 A EP 14811899A EP 3080190 A1 EP3080190 A1 EP 3080190A1
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EP
European Patent Office
Prior art keywords
hydrogenation
muconic acid
catalyst
muconic
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
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EP14811899.5A
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German (de)
English (en)
Inventor
Christoph Müller
Martin Bock
Marion DA SILVA
Rolf-Hartmuth Fischer
Benoit BLANK
Alois Kindler
Johann-Peter Melder
Bernhard Otto
Mathias SCHELWIES
Andreas Henninger
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14811899.5A priority Critical patent/EP3080190A1/fr
Publication of EP3080190A1 publication Critical patent/EP3080190A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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 producing polyamide 66 from muconic acid and / or one of its esters and / or one of its lactones.
  • the present invention further relates to polyamide 66, which can be produced by means of this process. STATE OF THE ART
  • Polyamides are among the world's most widely produced polymers and serve in addition to the main application areas of films, fibers and materials of a variety of other uses.
  • polyamide 66 nylon, polyhexamethylene adipamide
  • the production of polyamide 66 is carried out predominantly by polycondensation of so-called AH salt solutions, d. H. aqueous solutions containing adipic acid and 1, 6-diaminohexane (hexamethylenediamine) in stoichiometric amounts.
  • Conventional production methods for polyamide 66 are z. B. in Kunststoffhandbuch, 3/4 Engineering thermoplastics: polyamides, Carl Hanser Verlag, 1998, Kunststoff, pp 42-71, described.
  • HMD hexamethylenediamine
  • ADN adiponitrile
  • the US 3,215,742 also describes a process for the preparation of alkylenediamines, such as. For example, hexamethylenediamine, by reaction of the corresponding diols with ammonia. It is taught that hexamethyleneimine formed as an undesirable by-product can be recycled to the amination hydrogenation stage and further converted to hexamethylene diamine. The hexamethyleneimine can simultaneously serve as a solvent for the amination reaction.
  • US 3,520,933 uses cobalt, nickel and / or copper-containing catalysts for the aminating hydrogenation.
  • WO 2012/1 19929 describes inter alia the homogeneously catalyzed hydrogenating 1, 6-hexanediol amination to hexamethylenediamine.
  • WO 2012/141997 describes a process for the preparation of ⁇ -caprolactam in which muconic acid is reacted with ammonia and hydrogen in the presence of a catalyst. It is also described that this reaction can proceed via an adipic acid intermediate and that the resulting caprolactam can be used to produce polyamide 6. The production of polyamide 6.6 from muconic acid is not described in this document.
  • WO 2010/085712 A2 describes a process for the preparation of dodecanedicarboxylic acid in which muconic acid is reduced to hexenedicarboxylic acid and the hexenedicarboxylic acid is reacted with an unsaturated fatty acid in a metathesis reaction.
  • 1, 6-hexanediol can be prepared by hydrogenation of adipic acid or adipic diesters in the presence of Cu, Co or Mn catalysts. The synthesis is carried out at a temperature of 170 to 240 ° C and a pressure of 5 to 30 MPa. 1, 6-hexanediol can also be obtained by catalytic hydrogenation of caprolactone.
  • WO 99/25672 describes a process for preparing 1,6-hexanediol and 6-hydroxycaproic acid or their esters by catalytic hydrogenation of adipic acid.
  • adipic acid monoesters or adipic diesters wherein the obtained in the distillation of the hydrogenation after separation of the hexanediol and hydroxycaproic acid bottom product, which contains substantially oligomeric esters of 6-hydroxy caproic acid, in the hydrogenation.
  • waste product DCL is very inexpensive compared to pure adipic acid.
  • a considerable distillative effort has to be made to produce pure 1,6-hexanediol.
  • the distillative separation of the 1,4-cyclohexanediols which are by-products is particularly difficult.
  • Adipic acid is conventionally synthesized by oxidation of cyclohexanol or cyclohexanone starting from benzene. But it can also be obtained in an environmentally friendly manner from biogenic sources.
  • US 4,968,612 describes a fermentation process for the preparation of muconic acid and the hydrogenation of the resulting muconic acid to adipic acid. Concretely, the muconic acid is reacted as a 40% by weight slurry in acetic acid and in the presence of a palladium catalyst on carbon. The water content of the acetic acid used is not specified. A disadvantage of this reaction is the use of corrosive acetic acid, which requires the use of high-quality corrosion-resistant reactors.
  • WO 2010/141499 describes the oxidation of lignin to vanillic acid, their decarboxylation to 2-methoxyphenol and further conversion to catechol and finally oxidation to muconic acid and the hydrogenation of muconic acid thus obtained with various transition metal catalysts to adipic acid.
  • the solvent used for the hydrogenation is not specified.
  • EP 01 17048 A2 describes a process for the preparation of nylon 6,6-salt, in which toluene is converted to muconic acid by fermentation in the presence of hexamethylenediamine, to obtain a fermentation medium containing hexamethylenediamine. contains conat. From this fermentation medium, the microorganisms are separated and the Hexamethylendiaminmuconat hydrogenated to Hexamethylendiaminadipat. The resulting nylon 6,6 salt can be used to prepare polyamide 6,6.
  • a disadvantage of this process is that the starting material is toluene, which does not come from renewable sources. It is also an essential feature of this process that a salt of the muconic acid with the diamine used for amide formation is used for the hydrogenation.
  • HMDA hexamethylenediamine
  • hexamethylenediamine is prepared by hydrogenation of muconic acid or adipic acid to 1, 6-hexanediol and its catalytic amination.
  • WO 2012/141993 A1 only the hexamethylenediamine, but not the adipic acid, is produced from renewable raw materials.
  • the present invention has for its object to provide an economical process for the production of polyamide 66.
  • this process should not start from petrochemical C6 building blocks but from C6 building blocks that can be produced from renewable raw materials. The aim is to make the polyamide 66 available in high yield and purity.
  • muconic acid starting material which is selected from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof, a reaction to adipic acid on the one hand and to hexamethylenediamine on the other hand.
  • the lactones of muconic acid are especially suitable for the preparation of 1,6-hexanediol which, according to the invention, can serve as an important intermediate for the preparation of the hexamethylenediamine.
  • the muconic acid used is derived from renewable (biogenic) sources.
  • a first aspect of the invention is a process for preparing polyamide 66 comprising: a) providing a muconic acid starting material selected from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof; b) at least the muconic acid starting material provided in step a) partially reacting with hydrogen in the presence of at least one hydrogenation catalyst Hb) to adipic acid, c1) the muconic acid starting material provided in step a) partially reacting with hydrogen in the presence of at least one hydrogenation catalyst
  • Another object of the invention is a polyamide 66 having a C 14 / C 12 isotope ratio in the range of 0.5 x 10 "12 to 5 x 10 " 12 .
  • a further subject of the invention is polyamide 66, which can be prepared starting from muconic acid synthesized from at least one renewable raw material. Specifically, the muconic acid starting material provided in step a) contains no salts of the muconic acid.
  • the hydrogenation takes place in at least one of the steps b) and / or c1) and / or c2) in the liquid phase in the presence of water as solvent. In a more specific embodiment, the hydrogenation is carried out in at least one of steps b) and / or c1) and / or c2) in the liquid phase in the presence of water as the sole solvent.
  • the muconic acid can be hydrogenated in aqueous solvents and especially in water as the sole solvent in high yields to adipic acid and to 1, 6-hexanediol.
  • high adipic acid yields are surprising, since in the light of the prior art was expected to significantly lower yields.
  • Muconic acid (2,4-hexadiene dicarboxylic acid) exists in three stereoisomeric forms, the ice, cis, cis, trans and trans, trans forms, which may be present as a mixture. All three forms are crystalline compounds with high melting points (decomposition), see, for. B. Römpp Chemie Lexikon, 9th edition, Volume 4, page 2867). It has been found that hydrogenation of Muconklareschmelzen technically is hardly possible, since the most preferred hydrogenation temperatures are well below the melting points. Therefore, an inert solvent with the highest possible solubility for muconic acid would be desirable for the hydrogenation.
  • FIG. A process for preparing polyamide 66 comprising: a) providing a muconic acid starting material selected from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof; b) the muconic acid starting material provided in step a) at least partially reacting with hydrogen in the presence at least one hydrogenation catalyst Hb) is subjected to adipic acid, d) the muconic acid starting material provided in step a) partially undergoes a reaction with hydrogen in the presence of at least one hydrogenation catalyst Hc1) to give 1,6-hexanediol, or c2) the adipic acid obtained in step b) is partially replaced by one Reacting with hydrogen in the presence of at least one hydrogenation catalyst Hc2) to give 1,6-hexanediol, the 1,6-hexanediol obtained in step c1) or c2) undergoes an amination in the presence of an amination catalyst
  • step a) a muconic acid starting material is provided in which the muconic acid originates from a renewable source, the preparation of which is preferably carried out by biocatalytic synthesis from at least one renewable raw material.
  • a muconic acid starting material which is selected from muconic acid, Muconklaremonoestern, Mucon Liste- rediester, poly (muconic acid esters) and mixtures thereof.
  • a muconic acid starting material which is selected from lactones (III), (IV) and (V) and mixtures thereof:
  • Step c1) takes place in the liquid phase in the presence of a solvent which is selected from water, aliphatic C 1 to C 8 alcohols, aliphatic C 2 to C 6 diols, ethers and mixtures thereof.
  • a solvent which is selected from water, aliphatic C 1 to C 8 alcohols, aliphatic C 2 to C 6 diols, ethers and mixtures thereof.
  • a homogeneous or heterogeneous transition metal catalyst is used, preferably a heterogeneous transition metal catalyst.
  • a muconic acid starting material is used, which is selected from muconic acid, Muconklaremonoestern, lactones of the muconic acid and mixtures thereof and the hydrogenation catalyst Hc1) at least 50 wt .-% cobalt , Ruthenium or rhenium based on the total weight of the reduced catalyst.
  • a muconic acid starting material is used which is selected from muconic acid diesters, poly (muconic acid esters) and mixtures thereof and the hydrogenation catalyst Hc1) at least 50 wt .-% of copper on the total weight of the reduced catalyst.
  • the hydrogenation catalyst Hc2) used in step c2) contains at least 50% by weight, based on the total weight of the reduced catalyst, of elements which are selected from rhenium, iron, ruthenium, cobalt, rhodium, iridium, nickel and copper.
  • Reactor has a guided in an external circuit current from the reaction zone.
  • Process according to one of the preceding embodiments wherein the 1,6-hexanediol obtained in step c1) or in step c2) is reacted with ammonia in step d) to form hexamethylenediamine in the presence of the amination catalyst.
  • reaction effluent of the amination in step d) is subjected to a separation to give a hexamethyleneimine-enriched fraction and a hexamethylenediamine-depleted fraction.
  • Polyamide 66 characterized in that it comprises a C 14 / C 12 -lsotopeneat range of 0.5 x 10 "12 to 5 ⁇ 10.” 12
  • polyamide 66 characterized in that it can be prepared from biocatalytically at least one renewable raw material synthesized Muconsaure.
  • esters of the muconic acid are the esters with a separate (external) alcohol component.
  • lactones of muconic acid the compounds (III) and (IV) obtainable by intramolecular Michael addition and the product (V) of the hydrogenation of the compound (III) are understood as meaning:
  • the lactone (V) can also be formed by intramolecular Michael addition of dihydromuconic acid.
  • Step a) The muconic acid provided in step a) of the process according to the invention preferably originates from renewable sources.
  • this includes natural (biogenic) sources and non-fossil sources, such as crude oil, natural gas or coal.
  • the compound obtained in step a) of the invention driving provided muconic acid from carbohydrates, eg. As starch, cellulose and sugars, or lignin.
  • Renewable compounds, such as muconic acid have a different 14 C to 12 C isotope ratio than compounds derived from fossil sources such as petroleum.
  • the muconic acid used in step a) accordingly has preferably a C 14-to-12 C lsotopenfound in the range of 0.5 * 10 12 to 5x10 "12.
  • the production of muconic acid from renewable sources can be carried out by all methods known to those skilled in the art, preferably biocatalytically.
  • the biocatalytic production of muconic acid from at least one renewable raw material is described, for example, in the following documents: US Pat. No. 4,968,612, US Pat.
  • WO 2010/148063 A2 WO 2010/148080 A2 and K. M. Draths and J. W. Frost, J. Am. Chem. Soc. 1994, 16, 339-400 and W. Niu et al., Biotechnol. Prog. 2002, 18, 201 - 21 1.
  • muconic acid (2,4-hexadiene dicarboxylic acid) exists in three isomeric forms, the cis, cis, cis, trans and trans, trans forms, which may be present as a mixture.
  • the term "muconic acid” encompasses the different conformers of the muconic acid in any desired composition.
  • a muconic acid starting material which is enriched in cis, trans-muconic acid and / or its esters or which consists of cis, trans-muconic acid and / or their esters.
  • cis, trans-muconic acid and their esters have a higher solubility in water and in organic media than cis, cis-muconic acid and trans, trans-muconic acid.
  • a muconic acid starting material which comprises at least one component selected from cis, cis-muconic acid, trans, trans-muconic acid and / or their esters
  • this muconic acid starting material can be present before or during the hydrogenation in step b) or step c1) an isomerization to cis, trans-muconic acid or their esters are subjected.
  • the isomerization of cis, cis-muconic acid to cis, trans-muconic acid is shown in the following scheme:
  • Suitable catalysts are, in particular, inorganic or organic acids, hydrogenation catalysts, iodine or UV radiation.
  • Suitable hydrogenation catalysts are those described below.
  • the isomerization can be carried out, for example, according to the method described in WO 201 1/08531 1 A1.
  • the starting material for the reaction with hydrogen in step b) and / or in step c1) to at least 80 wt .-%, particularly preferably at least 90 wt .-% of cis, trans-muconic acid and / or their esters, based on the total weight of all muconic acid and Muconklareester- conformers contained in the feedstock.
  • muconic acid starting material which is selected from muconic acid, muconic acid monoesters, muconic diesters, poly (muconic acid esters) and mixtures thereof.
  • muconic acid polyester also denotes oligomeric muconic acid esters which have at least one repeating unit derived from the muconic acid or the diol used for ester formation and at least two repeating units which are complementary thereto via carboxylic acid ester groups.
  • the muconic acid monoester used is at least one compound of the general formula (I)
  • R 1 independently of one another represent straight-chain or branched Ci-Cs-alkyl.
  • muconic acid diester preference is given to at least one compound of the general formula (II)
  • Preferred as poly (muconic acid ester) is at least one compound of the general formula (VI)
  • R 3 is H, straight-chain or branched C 1 -C 5 -alkyl or a group HO- (CH 2) x -
  • the degree of polymerization of the poly denotes the sum of repeating units which formally derive from muconic acid and repeating units which formally derive from diols HO- (CH 2) x -OH.
  • a muconic acid starting material is used which is selected from muconic acid, muconic acid monoesters, muconic diesters, poly (muconic acid esters) and mixtures thereof.
  • the hydrogenation in step b) uses a muconic acid starting material selected from lactones (III), (IV and (V) and mixtures thereof:
  • a muconic acid starting material is used which is selected from muconic acid, muconic acid monoesters, muconic diesters, poly (muconic acid esters) and mixtures thereof and the hydrogenation is carried out in the liquid phase.
  • the hydrogenation takes place in step b) and / or in step c1) and / or in step c2) in the liquid phase in the presence of a solvent which is selected from water, aliphatic Ci- to Cs- Alcohols, C2 to C6 aliphatic diols, ethers and mixtures thereof.
  • a solvent which is selected from water, aliphatic Ci- to Cs- Alcohols, C2 to C6 aliphatic diols, ethers and mixtures thereof.
  • the solvent is preferably selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol, ethylene glycol, 1, 3-propanediol, 1, 4- Butanediol, 1, 5-pentanediol, 1, 6-hexanediol, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether and mixtures thereof. Aliphatic C to Cs alcohols, water and mixtures of these solvents are preferred.
  • methanol n-butanol
  • isobutanol water and mixtures of these solvents.
  • 1, 6-hexanediol can be used alone or in admixture with alcohols and / or water.
  • a solution which comprises 10 to 60% by weight of muconic acid or one of its esters, more preferably 20 to 50% by weight .-%, most preferably 30 to 50 wt .-%, contains.
  • step b) and / or c1) at least one muconic acid diester of the general formula (II)
  • Suitable hydrogenation catalysts for the reaction in steps b), c1) and c2) are in principle the transition metal catalysts known to those skilled in the art for hydrogenating carbon-carbon double bonds.
  • the catalyst comprises at least one transition metal of groups 7, 8, 9, 10 and 1 1 of the period Systems according to IUPAC.
  • the catalyst comprises at least one transition metal selected from the group consisting of Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu and Au.
  • the catalyst has at least one transition metal from the group Co, Ni, Cu, Re, Fe, Ru, Rh, Ir.
  • the hydrogenation catalysts consist of the mentioned transition metals as such or comprise the said transition metals supported, as precipitation catalysts, as Raney catalysts or as mixtures thereof.
  • supported catalysts for example carbon, S1O2 (quartz), porcelain, magnesium oxide, tin dioxide, silicon carbide, T1O2 (rutile, anatase), Al2O3 (alumina), aluminum silicate, steatite (magnesium silicate), zirconium silicate , Cersilikat or mixtures of these carrier materials, are used.
  • Preferred support materials are carbon, alumina and silica.
  • a particularly preferred carrier material is carbon.
  • the silica support material can silica materials of different origin and production, for. B.
  • pyrogenic silicas or wet-chemically prepared silicas such as silica gels, aerogels or precipitated silicas, are used for catalyst preparation (for the preparation of various S1O2 starting materials see: W. Büchner, R. Sch Kunststoffs, G. Winter, KH Büchel: Industrial Inorganic Chemistry, 2nd ed., P. 532-533, VCH Verlagsgesellschaft, Weinheim 1986).
  • the hydrogenation catalysts can be used as shaped bodies, for. B. in the form of spheres, rings, cylinders, cubes, cuboids or other geometric bodies.
  • Unsupported catalysts can be formed by conventional methods, e.g. By extruding, tableting, etc.
  • the shape of supported catalysts is determined by the shape of the support.
  • the support may be subjected to a molding process before or after application of the catalytically active component (s).
  • the transition metal catalysts K can, for. B. in the form of pressed cylinders, tablets, pastilles, carriage wheels, rings, stars or extrudates, such as solid strands, polylobd strands, hollow strands and honeycomb bodies or other geometric bodies are used.
  • the catalyst particles generally have an average of the (largest) diameter of 0.5 to 20 mm, preferably 1 to 10 mm.
  • These include z. B. transition metal catalysts K in the form of tablets, for. B. with a diameter of 1 to 7 mm, preferably 2 to 6 mm, and a height of 3 to 5 mm, rings with z. B. 4 to 7 mm, preferably 5 to 7 mm, outer diameter, 2 to 5 mm in height and 2 to 3 mm hole diameter, or strands of different lengths of a diameter of z. B. 1, 0 to 5 mm.
  • Such forms can be obtained in a manner known per se by tableting, extrusion or extrusion.
  • the catalyst can mass customary tools, z.
  • lubricants such as graphite, polyethylene oxide, celluloses or fatty acids (such as stearic acid) and / or molding aids and reinforcing agents, such as glass fibers, asbestos or silicon carbide, are added.
  • the catalyst can be present under the hydrogenation conditions both as a homogeneous and as a heterogeneous catalyst.
  • the catalyst is present under the hydrogenation conditions as a heterogeneous catalyst.
  • the catalyst is present under the hydrogenation conditions in at least one of steps b) and / or c1) and / or c2) as a heterogeneous catalyst. More specifically, the catalyst is present under the hydrogenation conditions in each of steps b) and / or c1) and / or c2) as a heterogeneous catalyst.
  • a heterogeneous catalyst is used, this can be applied, for example, to a reticulated carrier.
  • the heterogeneous catalyst can be applied to the inner wall of a tubular support, wherein the tubular support is flowed through by the reaction mixture.
  • the catalyst can be used as a particulate solid.
  • the hydrogenation takes place in at least one of steps b), c1) and c2) in the liquid phase and the catalyst is in the form of a suspension.
  • the hydrogenation in each of steps b), c1) and c2) takes place in the liquid phase and the catalyst is in the form of a suspension.
  • the suspended catalyst can be kept in the reaction zone by retention methods known to those skilled in the art. These retention methods preferably comprise cross-flow filtration, gravity filtration and / or filtration by means of at least one filter candle.
  • the hydrogenation takes place in at least one of steps b), c1) and c2) in n hydrogenation reactors connected in series (in series), where n is an integer of at least 2. Suitable values for n are 2, 3, 4, 5, 6, 7, 8, 9 and 10. Preferably, n is 3 to 6 and in particular 2 or 3. In this embodiment, the hydrogenation is preferably carried out continuously.
  • the reactors used for the hydrogenation may independently have one or more reaction zones within the reactor.
  • the reactors may be the same or different reactors. These can be z. B. each have the same or different mixing characteristics and / or be subdivided by internals one or more times.
  • Suitable pressure-resistant reactors for the hydrogenation are known to the person skilled in the art. These include the commonly used reactors for gas-liquid reactions, such as. B. tubular reactors, tube bundle reactors, gas circulation reactors, bubble columns, loop apparatuses, stirred tank (which can also be configured as Rrockkesselkaskaden), air-lift reactors, etc.
  • the process according to the invention using heterogeneous hydrogenation catalysts can be carried out in fixed bed or suspension mode.
  • the fixed bed mode can be z. B. in sump or in trickle run.
  • the hydrogenation catalysts are preferably used as shaped bodies, as described above, for. In the form of pressed cylinders, tablets, pastilles, carriage wheels, rings, stars or extrudates, such as solid strands, poly-polar strands, hollow strands, honeycomb bodies, etc.
  • heterogeneous catalysts are also used.
  • the heterogeneous catalysts are usually used in a finely divided state and are finely suspended in the reaction medium before. Suitable heterogeneous catalysts and processes for their preparation are those described above.
  • a reactor In the hydrogenation on a fixed bed, a reactor is used, in the interior of which the fixed bed is arranged, through which the reaction medium flows.
  • the fixed bed can be formed from a single or multiple beds.
  • Each bed may have one or more zones, wherein at least one of the zones contains a material active as a hydrogenation catalyst.
  • Each zone can have one or more different catalytically active materials and / or one or more different inert materials. Different zones may each have the same or different compositions. It is also possible to provide a plurality of catalytically active zones, which are separated from each other, for example, by inert beds. The individual zones may also have different catalytic activity.
  • various catalytically active materials can be used and / or at least one of the zones can contain an inert material. be mixed.
  • the reaction medium flowing through the fixed bed contains at least one liquid phase.
  • the reaction medium may also contain a gaseous phase in addition.
  • reactors in the hydrogenation in suspension are in particular loop apparatuses, such as jet loops or propeller loops, stirred tank, which can also be configured as R Industrialkesselkaskaden, bubble columns or air-lift reactors are used.
  • the continuous hydrogenation is carried out in at least one of the steps b), c1) and / or c2) in at least two fixed bed reactors connected in series (in series).
  • the reactors are preferably operated in direct current.
  • the feeding of the feed streams can be done both from above and from below.
  • at least two of the reactors may have a different temperature from each other.
  • each downstream reactor is operated at a higher temperature than the previous reactor.
  • each of the reactors may have two or more different temperature reaction zones.
  • another, preferably a higher, temperature than in the first reaction zone or in each subsequent reaction zone can be set to a higher temperature than in a preceding reaction zone, for. B. to achieve the fullest possible conversion in the hydrogenation.
  • At least two of the reactors may have a different pressure from each other.
  • each downstream reactor is operated at a higher pressure than the previous reactor.
  • the feeding of the hydrogen required for the hydrogenation can be carried out in the first and optionally additionally in at least one further reactor.
  • the feed of hydrogen takes place only in the first reactor.
  • the amount of hydrogen fed to the reactors results from the amount of hydrogen consumed in the hydrogenation reaction and the amount of hydrogen optionally discharged with the exhaust gas.
  • the setting of the reacted in the respective reactor portion of compound to be hydrogenated can, for. B. on the reactor volume and / or the residence time in the reactor.
  • one or more of the reactors may be provided with at least one cooling device.
  • at least the first reactor is provided with a cooling device.
  • the heat of reaction can be removed by cooling an external recycle stream or by internal cooling in at least one of the reactors.
  • the customary devices generally hollow body modules, such as field pipes, pipe coils, heat exchanger plates, etc. can be used.
  • the reaction can also be carried out in a cooled tube bundle reactor.
  • the hydrogenation is carried out in n series-connected hydrogenation reactors, where n is an integer of at least two, and wherein at least one reactor has a guided in an external circuit stream from the reaction zone (external recycle stream, liquid circulation, loop mode).
  • n stands for two or three.
  • the hydrogenation is preferably carried out in n hydrogenation reactors connected in series, where n is preferably two or three, and the first to (n-1).
  • Reactor has a guided in an external circuit current from the reaction zone.
  • the hydrogenation is preferably carried out in n hydrogenation reactors connected in series, n preferably being two or three, and the reaction being carried out adiabatically in the nth reactor (the last reactor through which the reaction mixture to be hydrogenated is passed).
  • the hydrogenation is carried out in n series-connected hydrogenation reactors, where n is preferably two or three, and wherein the n. Reactor is operated in a straight pass.
  • a reactor is operated "in straight pass", it should be understood here and below that a reactor is operated without recycling the reaction product in the sense of the loop procedure.
  • the straight-through operation basically excludes backmixing internals and / or stirring devices in the reactor. If the hydrogenated reaction mixture in one of the reactors downstream of the first reactor (ie the 2nd to nth reactor) has only small amounts of hydrogenatable muconic acid, then the heat of reaction occurring during the reaction is insufficient to maintain the desired temperature in the reactor. it may also be necessary to heat the reactor (or individual reaction zones of the second reactor). This can be done analogously to the previously described removal of the heat of reaction by heating an external circulation stream or by internal heating. In a suitable embodiment, the heat of reaction from at least one of the previous reactors can be used to control the temperature of a reactor.
  • the heat of reaction removed from the reaction mixture can be used to heat the feed streams of the reactors.
  • This can z. B. the feed stream of the compound to be hydrogenated in the first reactor at least partially mixed with an external recycle stream of this reactor and the combined streams are then fed into the first reactor.
  • the feed stream from the (m-1) th reactor in the mth reactor can be mixed with a recycle stream of the mth reactor and the combined streams then fed to the mth reactor
  • the feed stream of the compound to be hydrogenated and / or another feed stream can be heated by means of a heat exchanger which is operated with withdrawn hydrogenation heat.
  • a reactor cascade of n reactors connected in series is used, the reaction being carried out adiabatically in the nth (nth) reactor.
  • This term is understood in the context of the present invention in the technical and not in the physico-chemical sense.
  • Adiabatic reaction is understood to mean a procedure in which the amount of heat liberated during the hydrogenation is taken up by the reaction mixture in the reactor and no cooling by cooling devices is used.
  • the heat of reaction with the reaction mixture is discharged from the second reactor, except for a residual portion, which is discharged by natural heat conduction and heat radiation from the reactor to the environment.
  • the nth reactor is operated in a straight pass.
  • a two-stage reactor cascade is used for the hydrogenation, wherein the first hydrogenation reactor has a current conducted in an external circuit from the reaction zone.
  • the Process is a reactor cascade of two reactors connected in series, wherein the reaction is carried out adiabatically in the second reactor.
  • a three-stage reactor cascade is used for the hydrogenation, wherein the first and the second hydrogenation reactor have a current conducted in an external circuit from the reaction zone.
  • a reactor cascade of three reactors connected in series is used, the reaction being carried out adiabatically in the third reactor.
  • additional mixing can take place in at least one of the reactors used.
  • An additional mixing is particularly advantageous if the hydrogenation takes place at high residence times of the reaction mixture.
  • the streams introduced into the reactors can be used by introducing them into the respective reactors via suitable mixing devices, such as nozzles.
  • suitable mixing devices such as nozzles.
  • the first (n-1) th reactor is each discharged from an outlet which still contains hydrogenatable components and is fed into the respective downstream hydrogenation reactor.
  • the discharge is separated into a first and a second partial stream, wherein the first partial stream is recycled as a circular stream to the reactor to which it was taken and the second partial stream is fed to the subsequent reactor.
  • the discharge may contain dissolved or gaseous portions of hydrogen.
  • the discharge from the first to (n-1) th reactor is fed to a phase separation vessel, separated into a liquid and into a gaseous phase, the liquid phase separated into the first and the second partial stream and the gas phase at least partially the subsequent Reactor fed separately.
  • the discharge from the first to (n-1) th reactor is fed to a phase separation vessel and separated into a first liquid hydrogen-depleted substream and a second hydrogen-enriched substream.
  • the first partial flow is then recycled as a circulating stream to the reactor, to which it has been removed and the second partial flow fed to the subsequent reactor.
  • the feed of the second to nth reactor with hydrogen is not carried out via a hydrogen-containing feed taken from the upstream reactor, but with fresh hydrogen via a separate feed line.
  • the inlet temperature may be set higher to achieve a higher reaction rate and thus to compensate for the decreasing catalyst activity.
  • the service life of the hydrogenation catalyst used can thus be extended as a rule.
  • step b) of the process according to the invention the muconic acid starting material provided in step a) is at least partially subjected to a reaction with hydrogen in the presence of at least one hydrogenation catalyst Hb) to give adipic acid.
  • the hydrogenation catalyst Hb) is selected from Raney cobalt, Raney nickel and Raney copper.
  • the hydrogenation in step b) is preferably carried out at a temperature in the range from 50 to 160.degree. C., more preferably from 60 to 150.degree. C., very particularly preferably from 70 to 140.degree.
  • Step b) can be carried out, for example, using at least one loop reactor.
  • a combination of at least one loop reactor and at least one subsequent tubular reactor is used for the reaction in step b).
  • a run in a straight passage tubular reactor can connect.
  • the hydrogenation in step b) is preferably carried out in bottom or trickle mode.
  • a muconic acid starting material is used for the hydrogenation in step c1), which is selected from muconic acid, muconic monoesters, lactones of muconic acid and mixtures thereof.
  • the hydrogenation in step c1) is preferably carried out using a hydrogenation catalyst which contains at least 50% by weight of cobalt, ruthenium or rhenium, based on the total weight of the reduced catalyst.
  • catalysts which contain at least 50% by weight of cobalt are used for the hydrogenation, they may furthermore contain, in particular, phosphoric acid and / or further transition metals, preferably copper, manganese and / or molybdenum.
  • the preparation of a suitable catalyst precursor is known from DE 2321 101. This contains in the unreduced, calcined state 40 to 60 wt .-% cobalt (calculated as Co), 13 to 17 wt .-% copper (calculated as Cu), 3 to 8 wt .-% manganese (calculated as Mn ), 0.1 to 5 wt .-% of phosphates (calculated as H3PO4) and 0.5 to 5 wt .-% molybdenum (calculated as M0O3).
  • EP 636 409 B1 describes the preparation of further suitable cobalt catalyst precursors containing from 55 to 98% by weight of cobalt, from 0.2 to 15% by weight of phosphorus, to from 0.2 to 15% by weight. % of manganese and 0.2 to 15 wt .-% of alkali metals (calculated as oxide) exist.
  • Such catalyst precursors can be reduced to the active, metallic cobalt-containing catalysts by treatment with hydrogen or mixtures of hydrogen and inert gases such as nitrogen. These catalysts are full contacts, which are predominantly made of metal and contain no catalyst support.
  • a muconic acid starting material is used for the hydrogenation in step c1), which is selected from muconic diesters, poly (muconic acid esters) and mixtures thereof.
  • the hydrogenation in step c1) is preferably carried out using a hydrogenation catalyst which contains at least 50% by weight of copper, based on the total weight of the reduced catalyst.
  • a hydrogenation catalyst which contains at least 50% by weight of copper, based on the total weight of the reduced catalyst.
  • Such catalysts are preferably used for the hydrogenation of Muconklareestern.
  • Suitable catalysts are in principle all suitable for the hydrogenation of carbonyl homogeneous and heterogeneous catalysts such as metals, metal oxides, metal compounds or mixtures thereof into consideration.
  • homogeneous catalysts are for example in Houben-Weyl, Methods of Organic Chemistry, Volume IV / 1 c, Georg Thieme Verlag Stuttgart, 1980, pp 45-67 and examples of heterogeneous catalysts are, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume IV / 1 c, pp. 16 to 26 described.
  • catalysts which contain one or more of the elements from subgroups I and VI. to VIII. of the Periodic Table of the Elements, preferably copper, chromium, molybdenum, manganese, rhenium, ruthenium, cobalt, nickel or palladium, particularly preferably copper, cobalt or rhenium.
  • cobalt, ruthenium or rhenium-containing catalysts mentioned above can also be used in the hydrogenation of the muconic acid diesters, oligoesters and polyesters. However, it is preferred to use at least 50% by weight of copper (based on the total weight of the reduced catalyst) containing catalysts instead of these catalysts.
  • the catalysts may consist solely of active components or their active components may be supported.
  • Suitable support materials are, in particular, Cr 2 O 3, Al 2 O 3, SiO 2, ZrO 2, ZnO, BaO and MgO or mixtures thereof.
  • catalysts as described in EP 0 552 463 A1. These are catalysts which in the oxidic form the composition
  • CUaAlbZrcMn d Ox where a> 0, b> 0, c a 0, d> 0, a> b / 2, b> a / 4, a> c and a> d and x are to preserve the electron neutrality per Formula unit called required number of oxygen ions.
  • the preparation of these catalysts can be carried out, for example, according to the specifications of EP 552 463 A1 by precipitation of sparingly soluble compounds from solutions containing the corresponding metal ions in the form of their salts.
  • Suitable salts are, for example, halides, sulfates and nitrates.
  • Suitable precipitants are all agents which lead to the formation of such insoluble intermediates, which can be converted by thermal treatment in the oxides.
  • Particularly suitable intermediates are the hydroxides and carbonates or bicarbonates, so that alkali metal carbonates or ammonium carbonate are used as particularly preferred precipitants.
  • the BET surface area of such catalysts is between 10 and 150 m 2 / g. Further suitable as catalysts having a BET surface area of 50 to
  • WO 2004/085 356 A1 also describes copper catalysts suitable for the process according to the invention, the copper oxide, aluminum oxide and at least one of the oxides of lanthanum, tungsten, molybdenum, titanium or zirconium and additionally pulverulent metallic copper, copper flakes, pulverulent cement, Containing graphite or a mixture thereof. These catalysts are particularly suitable for all the ester hydrogenations mentioned.
  • the hydrogenation in step c1) can be carried out batchwise or continuously, with continuous hydrogenation being preferred.
  • the hydrogenation in step c1) can be carried out in the gas phase or in the liquid phase.
  • the hydrogenation in step c1) uses a hydrogenation device comprising at least 2 reactors or at least one reactor having at least two reaction zones. Then, the hydrogenation is carried out initially in a temperature range of 50 to 160 ° C and then in a temperature range of 160 to 240 ° C.
  • the catalyst loading in continuous operation is preferably 0.1 to 2 kg, more preferably 0.5 to 1 kg of starting material to be hydrogenated per kg of hydrogenation catalyst and hour.
  • the molar ratio of hydrogen to muconic acid starting material is preferably from 50: 1 to 10: 1, more preferably from 30: 1 to 20: 1.
  • the muconic acid starting material is selected from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof.
  • a muconic acid starting material which is selected from at least two of the abovementioned compounds, the amount of hydrogen used, depending on the proportion of the compounds to be hydrogenated, is selected according to the abovementioned design rule.
  • the conversion in the first reactor, based on adipic acid or adipic acid ester formed, is preferably at least 70%, more preferably at least 80%.
  • the total conversion in the hydrogenation, based on hydrogenatable starting material, is preferably at least 97%, particularly preferably at least 98%, in particular at least 99%.
  • the selectivity in the hydrogenation, based on formed 1,6-hexanediol, is preferably at least 97%, particularly preferably at least 98%, in particular at least 99%.
  • step c2) the adipic acid obtained in step b) is partially subjected to a reaction with hydrogen in the presence of at least one hydrogenation catalyst Hc2) to 1, 6-hexanediol.
  • the hydrogenation catalyst used in step c2) Hc2) based on the total weight of the reduced catalyst contains at least 50 wt .-% of elements selected from rhenium, iron, ruthenium, cobalt, rhodium, iridium, nickel and copper.
  • the catalyst Hc2) contains at least 50% by weight of elements selected from the group consisting of rhenium, ruthenium and cobalt.
  • the catalyst c2) contains at least 50% by weight of copper.
  • the hydrogenation in step c2) is preferably carried out at a temperature which is in the range from 160 to 240 ° C., particularly preferably from 170 to 230 ° C., very particularly preferably from 170 to 220 ° C.
  • Step c2) can be carried out, for example, using at least one loop reactor.
  • a combination of at least one loop reactor and at least one subsequent tubular reactor is used for the reaction in step c2).
  • a run in a straight passage tubular reactor can connect.
  • the hydrogenation in step c2) is preferably carried out in bottom or trickle mode. Working up of 1,6-hexanediol from step c1) or c2)
  • the discharge from the hydrogenation in step c1) or c2) is subjected to a distillative separation to obtain a fraction enriched in 1,6-hexanediol and the fraction enriched in 1,6-hexanediol for the amination in step d ) used.
  • muconic acid in water is used as solvent for the hydrogenation.
  • the reaction product obtained in the hydrogenation of muconic acid in step c1) in water as solvent provides an aqueous 1, 6
  • Hexanediol solution After cooling and relaxing the hydrogenation, the water is preferably removed by distillation and 1, 6-hexanediol can be obtained in high purity (> 97%).
  • the muconic acid hydrogenation is carried out in a hydrogenation variant after step c1), for example in methanol as solvent, a part of the muconic acid is converted in situ into the muconic acid monomethyl and muconic acid dimethylester.
  • the hydrogenation is a solution of 1, 6-hexanediol in a mixture of methanol and water. By distillation, methanol and water are separated from 1, 6-hexanediol. Methanol is preferably separated from water and recycled to the hydrogenation. Water is discharged.
  • n-butanol or isobutanol is used as the solvent in the hydrogenation of the mucous acid, a liquid two-phase mixture is obtained after cooling and venting of the hydrogenation effluent.
  • the aqueous phase is separated from the organic phase by phase separation.
  • the organic phase is distilled.
  • Butanol is separated off as the top product and is preferably recycled to the muconic acid hydrogenation.
  • 1, 6-hexanediol can, if necessary, be further purified by distillation. If muconic acid diesters are used for the hydrogenation, largely anhydrous solutions of 1,6-hexanediol are obtained, which can be worked up by distillation to give pure 1,6-hexanediol.
  • the resulting alcohols are preferably recycled to the esterification step.
  • a predominantly composed of 1,6-hexanediol precipitates
  • step d) of the process according to the invention the 1,6-hexanediol obtained in step c1) or c2) is subjected to an amination in the presence of an amination catalyst to obtain hexamethylenediamine.
  • the 1,6-hexanediol is preferably reacted with ammonia in step d) to form hexamethylenediamine in the presence of the amination catalyst.
  • the amination according to the invention can be carried out without the supply of hydrogen, but preferably with the supply of hydrogen.
  • the catalysts used in one embodiment of the invention are preferably predominantly cobalt, silver, nickel, copper or ruthenium or mixtures of these metals. By “predominantly” it is to be understood that one of these metals is more than 50% by weight in the catalyst (calculated without carrier)
  • the catalysts can be used as unsupported catalysts, ie without catalyst carrier or as carrier catalysts.
  • the supports used are preferably S1O2, Al2O3, T1O2, ZrO2, activated carbon, silicates and / or zeolites
  • the catalysts mentioned are preferably used as fixed bed catalysts It is also possible to use cobalt, nickel and / or copper in the form of Raney type suspension catalysts use.
  • the amination of the 1,6-hexanediol is carried out in a homogeneous phase and the catalyst is a complex catalyst containing at least one element selected from groups 8, 9 and 10 of the Periodic Table (IUPAC) and at least one donor ligand.
  • IUPAC Periodic Table
  • Such catalysts are known, for example, from WO 2012/1 19929 A1.
  • the amination is preferably carried out at temperatures of 100 to 250 ° C, more preferably 120 to 230 ° C, most preferably 100 to 210 ° C.
  • the total pressure is preferably in the range of 5 to 30 MPa, more preferably 7 to 27 MPa, most preferably 10 to 25 MPa.
  • the molar ratio of 1,6-hexanediol to ammonia is preferably 1 to 30, more preferably 1 to 25, most preferably 1 to 20.
  • the amination can be carried out solvent-free. However, it is preferably carried out in the presence of at least one solvent.
  • Preferred solvents are water, ethers or mixtures of these solvents, ethers being particularly preferably selected from dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, dibutyl ether and methyl tert-butyl ether.
  • the aqueous 1,6-hexanediol solutions obtained in the hydrogenation of muconic acid are used without work-up in the amination step.
  • step c1) or c2 It may be advantageous to completely or partially dehydrate part of the aqueous 1,6-hexanediol obtained in step c1) or c2).
  • partial dehydration it is possible, for example, to remove 50%, preferably 70%, particularly preferably 90%, of the water present in the crude 1,6-hexanediol. This can be z. B. by evaporation of the water at 50 to 90 ° C at reduced pressure (eg., On a rotary evaporator) or by distillation.
  • the amination is carried out in the presence of hexamethyleneimine as solvent or hexamethyleneimine / water mixtures.
  • the amount of solvent is preferably such that 5 to 80, preferably 10 to 70, particularly preferably 15 to 60 wt .-% strength 1, 6-hexanediol solutions. Per mole of 1,6-hexanediol, preferably 10 to 150 liters, more preferably 10 to 100 liters of hydrogen are fed.
  • the amination of 1,6-hexanediol with ammonia takes place in a first substep d1) to give a mixture of 1-amino-6-hydroxyhexane and hexamethylenediamine which contains more than 50% by weight of 1-amino Contains 6-hydroxyhexane.
  • This is separated in a partial step d2) together with hexamethylenediamine from unreacted 1, 6-hexanediol and reacted in a partial step d3) with further ammonia to hexamethylenediamine.
  • the amination can be carried out batchwise or continuously, in the liquid or gas phase, preference being given to a continuous process.
  • the workup of the still 1-amino-6-hydroxyhexane-containing target product hexamethylenediamine is preferably carried out by distillation. Since 1-amino-6-hydroxyhexane and He- xamethylenediamine have very similar vapor pressures, pure hexamethylenediamine is discharged. Mixtures of 1-amino-6-hydroxyhexane and hexamethylenediamine are recycled to the distillation stage. In a further, particularly preferred embodiment, the hexamethyleneimine formed in the amination of 1,6-hexanediol is separated by distillation from the amination discharge and recycled to the amination stage.
  • the recycled hexamethyleneimine amount is 34% by weight (based on the total weight of 1,6-hexanediol and hexamethyleneimine), then advantageously no additional hexamethyleneimine is formed.
  • Hexamethyleneimine can be separated by distillation as an azeotrope with water.
  • the resulting hexamethylenediamine may be subjected to further purification. This preferably comprises at least one distillation step.
  • the obtained hexamethylenediamine is brought to "fiber quality" by fractional distillation (i.e., a hexamethylenediamine content of at least 99.9%).
  • fractional distillation i.e., a hexamethylenediamine content of at least 99.9%.
  • AMCPA 2-aminomethylcyclopentylamine
  • DACH 1,2-diaminocyclohexane
  • Step e) In the process of this invention can be synthesized polyamide 66 having a C 14 / C 12 -lsotopeneat in the range of 0.5 x 10 "12 to 5 ⁇ 10.” 12
  • adipic acid prepared in step b) is polycondensed with the hexamethylenediamine prepared in step d) to form polyamide 66.
  • This is preferably carried out in the following substeps: e1) reacting adipic acid and hexamethylenediamine in a molar ratio of essentially 1: 1 to hexamethylenediammonium adipate (AH salt), and e2) reacting the hexamethylenediammonium adipate to polyamide 66 at a temperature of not more than 275 ° C.
  • muconic acid prepared in step a) is polycondensed with the hexamethylenediamine prepared in step d) to give polyamide 66 (see EP 1 17048 A2). This is preferably carried out in the following substeps: e1.1) reacting muconic acid and hexamethylenediamine in a molar ratio of essentially 1: 1 to hexamethylenediammonium muconate,
  • the reaction of the hexamethylenediammonium adipate to give polyamide 66 takes place in particular in the presence of water at a temperature of not more than 280 ° C., more preferably of not more than 275 ° C.
  • the discharges were analyzed by gas chromatography (% by weight, method with internal standard). The yield of 1, 6-hexanediol was 94%, the conversion of adipic acid was 98.5%. Other products that were found were 3% 6-hydroxycaproic acid, 1% 6-hydroxycaproic acid 1,6-hexanediol ester and 1% hexanol.
  • the water content of the crude 1,6-hexanediol prepared according to Example 3 of this application was lowered to 5% by weight by evaporation at 70 ° C. and water-jet vacuum.

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Abstract

La présente invention concerne un procédé de préparation de polyamide 66 dans lequel a) on produit une matière de départ à base d'acide muconique qui est choisie parmi l'acide muconique, des esters de l'acide muconique, des lactones de l'acide muconique, et leurs mélanges, b) on soumet la matière de départ à base d'acide muconique produite à l'étape a) au moins partiellement à une réaction avec de l'hydrogène en présence d'au moins un catalyseur d'hydrogénation Hb) pour obtenir de l'acide adipique, c1) on soumet la matière de départ à base d'acide muconique produite à l'étape a) partiellement à une réaction de transformation avec de l'hydrogène en présence d'au moins un catalyseur d'hydrogénation Hc1) pour obtenir du 1,6-hexanediol, ou c2) on soumet l'acide adipique obtenu à l'étape b) partiellement à une réaction de transformation avec de l'hydrogène en présence d'au moins un catalyseur d'hydrogénation Hc2) pour obtenir du 1,6-hexanediol, d) on soumet le 1,6-hexanediol obtenu à l'étape c1) ou c2) à une amination en présence d'un catalyseur d'amination pour obtenir de l'hexaméthylène diamine, e) on soumet au moins une partie de l'acide adipique obtenu à l'étape b) et de l'hexaméthylène diamine obtenue à l'étape d) à une polycondensation pour obtenir du polyamide 66.
EP14811899.5A 2013-12-13 2014-12-12 Procédé de préparation de polyamide 66 Withdrawn EP3080190A1 (fr)

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WO2017012842A1 (fr) 2015-07-22 2017-01-26 Basf Se Procédé de préparation d'acide furane-2,5-dicarboxylique
US20200040183A1 (en) * 2018-08-01 2020-02-06 Braskem America, Inc. Thermoplastic compositions having improved toughness, articles therefrom, and methods thereof
WO2020150247A1 (fr) * 2019-01-15 2020-07-23 Sabic Global Technologies, B.V. Utilisation d'énergie renouvelable dans la synthèse de méthanol
JP2021014429A (ja) * 2019-07-12 2021-02-12 旭化成株式会社 ヘキサメチレンジアミンの製造方法
JP2021014427A (ja) * 2019-07-12 2021-02-12 旭化成株式会社 ヘキサメチレンジアミンの製造方法
WO2021060335A1 (fr) * 2019-09-26 2021-04-01 東レ株式会社 Procédé de fabrication d'acide adipique
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