Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
  • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds

Definitions

• the present invention relates to a process for the preparation of a dicarboxylic acid of the formula (I)
• R 1 , R 2 independently of one another are Ci-, C 2 -, C 3 -, C 4 -alkyl, aryl, heteroaryl and can be the same or different
• step b) the dicarboxylic acid of the formula (I) obtained in step a) is separated from the reaction mixture obtained in step a),
• step a) the C 2 H 3 -COOR 1 , C 2 H 3 -COOR 2 or mixtures thereof obtained in step a) are dimerized to give n-butenedicarboxylic acid diester and
• step c) the dicarboxylic acid diesters obtained in step c) are cleaved into the corresponding dicarboxylic acid of the formula (I).
• Example XX No. 3,013,066 in Examples XX and XXI describes the dimerization of methyl acrylate in the presence of ruthenium chloride as a catalyst.
• Example XX n-butene-dicarboxylic acid dimethyl ester is separated from the product mixture as fraction II in a yield of only 24% and in Example XXI as fraction III in a yield of only 37%, based in each case on methyl acrylate used , receive.
• Example I the dimerization of methyl acrylate in the presence of chlorobis (ethylene) rhodium (I) dimer and silver tetrafluoroborate as a catalyst. With a conversion of 100%, dimethyl n-butenedicarboxylate was obtained in a yield of only 60%, based on the methyl acrylate used, determined by means of NMR.
• EP-A-475 386 describes the dimerization of methyl acrylate in the presence of specific rhodium complexes as a catalyst. According to Example 4, a conversion of 97% to n-butene-dicarboxylic acid dimethyl ester is achieved, determined by means of NMR.
• Adipic acid is an important intermediate in the production of polymer plasticizers, polyesterols, for example for polyurethanes, and a starting monomer for the production of technically important polymers, such as nylon6.6.
• the n-butene-dicarboxylic acid dimethyl ester obtained in the dimerization can then be hydrogenated to the dimethyl adipate after separation from the product mixture and the adipic acid can be obtained by saponification of the adipic acid diester.
• the process for the production of adipic acid starting from methyl acrylate described in US Pat. No. 3,013,066 thus disadvantageously comprises a large number of process steps for the production of four intermediate products, namely acrylic acid, methyl acrylate, dimethyl n-butene-dicarboxylate, dimethyl adipate, taking into account that in addition to the acrylic acid esterification and the hydrogenation of the n-butenedicarboxylic acid dimethyl ester to adipic acid dimethyl ester, a separation step is also required, as after the saponification of the Dimethyl adipate the separation of the adipic acid obtained from the product mixture.
• the methyl acrylate used in the described dimerization processes must first be prepared from acrylic acid by esterification, at least one separation step also being necessary to obtain the ester in pure form.
• the object of the present invention was to provide a process which enables the production of a dicarboxylic acid (I), in particular adipic acid, from acrylic acid in a technically simple and economical manner.
• step a) uses acrylic acid with a dicarboxylic acid diester of the formula (II)
• R 1 , R 2 are independently C 1 ⁇ , C 2 -, C 3 -, C 4 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, preferably methyl, aryl, such as phenyl, or heteroaryl, preferably R 1 , R 2 are independently C 1 ⁇ , C 2 -, C 3 -, C 4 -alkyl, such as methyl, ethyl, n Propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, especially methyl.
• R 1 , R 2 can be different. In a preferred embodiment, R 1 , R 2 are the same. In a particularly preferred embodiment, R 1 and R 2 are the same and both represent methyl.
• the dicarboxylic acid on which the dicarboxylic acid ester of the formula (II) is based represents adipic acid.
• adipic diesters of the formula (II) and their preparation are known per se.
• the adipic diesters can be obtained by double carbonylation of butadiene in the presence of alcohols, such as methanol.
• the butenedicarboxylic acid ester obtained in step c) of the process according to the invention can be hydrogenated to adipic diester. This hydrogenation can be carried out in a manner known per se, for example homogeneously or heterogeneously, preferably heterogeneously catalyzed.
• Suitable heterogeneous catalysts are preferably those which contain a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• metals can be used in unsupported form, for example as suspension catalysts, preferably in the case of nickel or cobalt.
• metals can be used in supported form, for example on activated carbon, metal oxides, transition metal oxides, in particular aluminum oxide, silicon dioxide, preferably as fixed bed catalysts.
• the adipic diester obtained in this hydrogenation can advantageously be used in step a).
• the dicarboxylic acid on which the dicarboxylic acid ester of formula (II) is based represents n-butenedicarboxylic acid or a mixture of isomeric n-butenedicarboxylic acid esters.
• n-butenedicarboxylic acid diesters of the formula (II) and their preparation are known per se.
• the n-butenecarboxylic acid diesters can be dimerized, for example, by acrylic acid esters, as described in US Pat. Nos. 3,013,066, 4,638,084, EP-A-475 386 or in J. Am. Chem. Soc. 87 (1965) 5638-5645 or J. Molecular Catalysis 29 (1985) 65-76 or step c) according to the invention described below.
• acrylic acid used in step a) and processes for its preparation are known.
• acrylic acid can be obtained by gas phase oxidation of propene or propane in the presence of heterogeneous catalysts.
• Acrylic acid is usually added during storage or processing to one or more stabilizers which, for example, avoid the polymerization or decomposition of acrylic acid or reduce, such as p-methoxy-phenol or 4-hydroxy-2, 2,4, 4-piperidine-N-oxide ("4-hydroxy-TEMPO").
• stabilizers such as p-methoxy-phenol or 4-hydroxy-2, 2,4, 4-piperidine-N-oxide ("4-hydroxy-TEMPO").
• Such stabilizers can be partially or completely removed before the use of acrylic acid in the process according to the invention.
• the stabilizers can be removed by processes known per se, such as distillation, extraction or crystallization.
• Such stabilizers can remain in the amount previously used in acrylic acid.
• Acrylic acid esters can also be obtained, for example, by esterification of acrylic acid with the corresponding alcohols in the presence of homogeneous catalysts, such as p-toluenesulfonic acid.
• reaction of the dicarboxylic acid ester of formula (II) with acrylic acid can be carried out uncatalytically.
• a homogeneous or heterogeneous catalyst in particular a heterogeneous catalyst, comes into consideration.
• An inorganic or organic, Lewis or Brönstedt acidic compound can preferably be used as the catalyst.
• ion exchangers can advantageously be used.
• oxides with acidic centers, such as zeolites are advantageous.
• a homogeneous catalyst together with a heterogeneous catalyst can be considered.
• An inorganic or organic, Lewis or Brönstedt acidic compound can preferably be used as the catalyst.
• Homogeneous and heretogenic catalysts can be used simultaneously or in succession, such as first the homogeneous and then the heterogeneous catalyst or first the heterogeneous and then the ho ogen catalyst.
• a homogeneous catalyst can be considered.
• An inorganic or organic, Lewis or Brönstedt acidic compound can preferably be used as the catalyst.
• p-toluenesulfonic acid can advantageously be used; in the case of inorganic compounds, sulfuric acid or phosphoric acid are advantageous.
• the reaction in step a) can be carried out in a reactor, such as a stirred tank, a boiler cascade, such as a stirred tank cascade, or in a distillation apparatus, preferably one with a reaction vessel, advantageously in a reactive distillation column, in particular one with a dividing wall.
• a reactor such as a stirred tank, a boiler cascade, such as a stirred tank cascade
• a distillation apparatus preferably one with a reaction vessel, advantageously in a reactive distillation column, in particular one with a dividing wall.
• this catalyst can advantageously be installed in the region between the bottom and the top of the distillation device in the presence of a catalyst.
• Step a) gives a reaction mixture comprising a dicarboxylic acid of the formula (I) and a mixture of acrylic acid esters of the formula C 2 H 3 -COOR 1 and C 2 H 3 -COOR 2 , where R 1 and R 2 have the meanings mentioned ,
• the reaction mixture can also contain dicarboxylic acid diesters of the formula (II), acrylic acid, dicarboxylic acid monoesters of the formula R 1 - OOC - (nC 4 H x ) - COOH or HOOC - (nC 4 H x ) - COO - R 2 , where R 1 , R 2 and x have the meanings already mentioned, R 1 0H, R 2 0H, water or mixtures thereof.
• step b) the dicarboxylic acid of the formula (I) obtained is separated off from the reaction mixture obtained in step a).
• step b) can take place in a step separate from step a). If, for example, one of the said boilers or the aforementioned boiler cascade is used in step a), the product mixture can be removed from the boiler or the last boiler of the boiler cascade and then by known separation operations, such as distillation, extraction or crystallization, the dicarboxylic acid of the formula (I) are separated off from the reaction mixture obtained in step a) in one or more steps.
• ADS adipic acid
• ADS-MME methyl adipate
• ADS-DME methyl adipate
• steps a) and b) can be carried out partially or completely together.
• the reaction according to step a) in a distillation device is preferred.
• the distillation device can be operated in such a way that the dicarboxylic acid is obtained as a component separate from the rest of the reaction mixture.
• This is shown schematically in drawings 2 and 4, again by way of example using the reaction of dimethyl adipate with acrylic acid, the abbreviations having the meanings already mentioned.
• the distillation device can be operated in such a way that the dicarboxylic acid and at least one of its esters, ie dicarboxylic acid monoesters, dicarboxylic acid diesters or mixtures thereof, is obtained as a separate component from the rest of the reaction mixture and the dicarboxylic acid is subsequently separated from this mixture.
• This is shown schematically in drawing 3, again exemplified by the reaction of methyl adipate with acrylic acid, the abbreviations having the meanings already mentioned.
• adipic acid can be obtained from step b).
• n-butenedicarboxylic acid can be obtained from step b).
• the butenedicarboxylic acid obtained in step b) of the process according to the invention can be hydrogenated to adipic acid. This hydrogenation can be carried out in a manner known per se, for example homogeneously or heterogeneously, preferably catalyzed heterogeneously.
• Suitable heterogeneous catalysts are preferably those which contain a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• metals can be used in unsupported form, for example as suspension catalysts, preferably in the case of nickel or cobalt.
• metals can be used in supported form, for example on activated carbon, metal oxides, transition metal oxides, in particular aluminum oxide, silicon dioxide, preferably as fixed bed catalysts.
• step c) the acrylic esters C 2 H 3 -COOR 1 , CH 3 -COOR 2 or their mixtures obtained in step a) are dimerized to give n-butenedicarboxylic acid diester.
• the dimerization can advantageously be carried out in the presence of a catalyst.
• a homogeneous catalyst such as a catalyst containing an element of Group 8 of the Periodic Table of the Elements, in particular rhodium or ruthenium, preferably in the form of a salt, such as a chloride, or a complex compound.
• a homogeneous catalyst such as a catalyst containing an element of Group 8 of the Periodic Table of the Elements, in particular rhodium or ruthenium, preferably in the form of a salt, such as a chloride, or a complex compound.
• the dicarboxylic acid ester obtained in step c) is split into the corresponding dicarboxylic acid of the formula (I).
• Processes for cleaving an ester to obtain the corresponding carboxylic acid are known per se, for example from US Pat. No. 5,710,325 or US Pat. No. 5,840,959.
• the n-butenedicarboxylic acid obtained in step d) can advantageously be hydrogenated to give adipic acid.
• This hydrogenation can be carried out in a manner known per se, for example homogeneously or heterogeneously, preferably catalyzed heterogeneously.
• Suitable heterogeneous catalysts are preferably those which contain a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• metals can be used in unsupported form, for example as suspension catalysts, preferably in the case of nickel or cobalt.
• metals can be used in supported form, for example on activated carbon, metal oxides, transition metal oxides, in particular aluminum oxide, silicon dioxide, preferably as fixed bed catalysts.
• the cleavage of n-butenedicarboxylic acid diester according to step d) can be carried out by recycling the n-butenedicarboxylic acid ester obtained in step c) in step a), according to this n-butenedicarboxylic acid diester Step a) is converted to n-butenedicarboxylic acid and in step b) n-butenedicarboxylic acid is obtained as the dicarboxylic acid of the formula (I).
• This hydrogenation can be carried out in a manner known per se, for example homogeneously or heterogeneously, preferably catalyzed heterogeneously.
• Suitable heterogeneous catalysts are preferably those into consideration, the active as a catalytic component containing a noble metal of Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, "platinum, nickel, cobalt, copper, preferably palladium.
• a noble metal of Group 8 of the Periodic Table of the Elements such as palladium, ruthenium, rhodium, iridium, "platinum, nickel, cobalt, copper, preferably palladium.
• These metals can be used in unsupported form, for example as suspension catalysts, preferably in the case of nickel or cobalt.
• metals can be used in supported form, for example on activated carbon, metal oxides, transition metal oxides, in particular aluminum oxide, silicon dioxide, preferably as fixed bed catalysts.
• the n-butenedicarboxylic acid diester obtained in step c) can be hydrogenated between step c) and d) to give adipic acid diester.
• This hydrogenation can be carried out in a manner known per se, for example homogeneously or heterogeneously, preferably heterogeneously catalyzed.
• Suitable heterogeneous catalysts are preferably those which contain a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• a noble metal from Group 8 of the Periodic Table of the Elements, such as palladium, ruthenium, rhodium, iridium, platinum, nickel, cobalt, copper, preferably palladium, as the catalytically active component.
• metals can be used in unsupported form, for example as suspension catalysts, preferably in the case of nickel or cobalt.
• metals can be in supported form, for example on active carbon, metal oxides, transition metal oxides, in particular
• Aluminum oxide, silicon dioxide, preferably as fixed bed catalysts, are used.
• Adipic acid can be obtained by cleaving the diester of adipic acid according to step d).
• the cleavage of the adipic acid diester in step d) can be carried out by recycling the adipic acid diester obtained in step a), converting this adipic acid diester in step a) to adipic acid and in step b) obtaining adipic acid as the dicarboxylic acid of the formula (I) ,
• azeotropes can occur which can lead to insignificant and only minor changes in the material flows mentioned in the sense of the present invention.
• the separation of such azeotropes while maintaining the in the Substances called steps according to the invention can be carried out by methods known per se.
• Examples 1-3 a three-necked round-bottom flask with a capacity of 500 ml was used as the reaction vessel, which was flushed with nitrogen before the start of the experiment.
• the batch was heated to the respective temperature with stirring.
• a heated line led from an outlet of the flask to a cold trap cooled with dry ice. After the cold trap, a regulated vacuum pump followed, secured by a backstop.
• Table 1 shows the percentages by weight based on the sum of the weights of the five components mentioned in the respective samples.
• ADS-DME adipic acid dimethyl ester ADS-MME adipic acid monomethyl ester ADS adipic acid
• Table 2 shows the percentages by weight based on the sum of the weights of the five components mentioned in the respective samples.
• Table 3 shows the percentages by weight based on the sum of the weights of the five components mentioned in the respective samples.

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