EP2421816A2 - Procédé de production de mda en passant par l'étape de l'aminal - Google Patents

Procédé de production de mda en passant par l'étape de l'aminal

Info

Publication number
EP2421816A2
EP2421816A2 EP10715797A EP10715797A EP2421816A2 EP 2421816 A2 EP2421816 A2 EP 2421816A2 EP 10715797 A EP10715797 A EP 10715797A EP 10715797 A EP10715797 A EP 10715797A EP 2421816 A2 EP2421816 A2 EP 2421816A2
Authority
EP
European Patent Office
Prior art keywords
formaldehyde
content
highly concentrated
aminal
mda
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Withdrawn
Application number
EP10715797A
Other languages
German (de)
English (en)
Inventor
Eckhard Stroefer
Kai Thiele
Michael Zoellinger
Johnny Moors
Jon S. Speier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10715797A priority Critical patent/EP2421816A2/fr
Publication of EP2421816A2 publication Critical patent/EP2421816A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines

Definitions

  • the invention relates to a process for the preparation of methylenediphenyldiamine (MDA), wherein formaldehyde and aniline are first converted to aminal. After at least partial removal of water, an acid catalyst is added to the aminal to give MDA.
  • MDA methylenediphenyldiamine
  • Formaldehyde is used in highly concentrated form with a CH 2 O content> 50 wt .-%, wherein the formaldehyde is prepared by oxidative dehydrogenation from methanol.
  • MDA is a representative of the polyamines of the diphenylmethane series. MDA is used in particular as an intermediate from which the corresponding polyisocyanate (MDI) is synthesized by phosgenation. Methods for producing MDA have been known for some time.
  • EP-A 1 616 890 provides an overview of MDA production processes. Usually, the preparation is carried out by reacting aniline and formaldehyde in the presence of acidic catalysts (acid condensation). The condensation of aniline and formaldehyde can proceed in different reaction steps, depending on the time of catalyst addition.
  • aniline and formaldehyde give rise directly to the aminobenzylanilines, which subsequently react further to form the binuclear MDA isomers and the higher-nuclear MDA homologs.
  • aniline and formaldehyde are first reacted such that a water content of ⁇ 20% by weight and a degree of protonation of ⁇ 15% are set in the acidic reaction mixture. If the ratio of the weight fractions of p-aminobenzylaniline to 4,4'-MDA in the acidic reaction mixture falls below a value of 1, the reaction temperature is increased.
  • the method is used to form aminal as an intermediate and subsequent Addition of the acid catalyst carried out, wherein after the conversion to the aminal initially the water can be at least partially removed from the aminal.
  • EP-B 1 063 221 relates to a process for the reaction of a solution with at least one further chemical compound.
  • the solution contains a mixture of at least two chemically balanced chemical compounds and may be an aqueous solution of formaldehyde.
  • the reaction of a formaldehyde solution containing polyoxymethylene glycols and optionally monomeric formaldehyde and / or methylene glycol with aniline in the presence of an acidic catalyst is excluded.
  • WO 2004/078678 relates to a process for the preparation of highly concentrated formaldehyde solution having a CH 2 O content> 50 wt .-%.
  • the educt used is an aqueous formaldehyde solution with a low CH 2 O content, part of this solution being evaporated (partial evaporation).
  • the aqueous formaldehyde solution is heated to an evaporation temperature at which water accumulates in the gas phase relative to the liquid phase, and the gas phase formed is withdrawn continuously or discontinuously.
  • a further process for the preparation of highly concentrated formaldehyde solutions is described in WO 2005/077877, according to which water is separated off from a lower-concentration formaldehyde solution having a formaldehyde content of between 5 and 50% by weight.
  • the low concentrated formaldehyde solution is fed to a preheater and heated therein, then expanded by means of a pressure-holding device and concentrated in a coiled-tube evaporator.
  • WO 2004/078691 relates to a process for the thermal stabilization of highly concentrated formaldehyde solutions having a formaldehyde content ⁇ 70% by weight against solid precipitation.
  • the highly concentrated formaldehyde solution is heated immediately after its preparation with a special heating rate to temperatures of 80 to 200 0 C and then stored in this temperature range.
  • WO 2004/078690 relates to a process for the provision of highly concentrated gaseous formaldehyde with a molar formaldehyde to water ratio of> 0.6.
  • this process at least part of this solution is first evaporated from an aqueous formaldehyde solution by heating the aqueous formaldehyde solution to an evaporation temperature and removing the gas phase formed.
  • the object underlying the present invention is to provide an economical process for the production of MDA, wherein aminal is formed as an intermediate.
  • MDA methylenediphenyldimine
  • step b) removing water from the aminal obtained in step a), wherein a water content of 0 to 5 wt .-% based on the aminal is set, and
  • step a) formaldehyde is used as highly concentrated formaldehyde having a CH 2 O content> 50 wt .-% and the formaldehyde is prepared by oxidative dehydrogenation from methanol.
  • the inventive method has the advantage that by the use of highly concentrated formaldehyde a lower water content in the system, in particular in step a) is present.
  • Commercially available formaldehyde is normally present as an aqueous formaldehyde solution with a total concentration of about 20 to 30 wt .-% formaldehyde (CH 2 O content). The remaining percentages by weight of such a commercially available aqueous formaldehyde solution originate mainly from water.
  • a large amount of water is introduced into the MDA synthesis along with the formaldehyde.
  • this water is generally not needed in the synthesis; rather, water is liberated during the reaction of formaldehyde and aniline, so that the addition of a large amount of water has a fundamentally negative effect on MDA formation.
  • step a) less water is introduced into the system due to the use of highly concentrated formaldehyde. Consequently, in step b) only a smaller amount of water needs to be removed, which has a positive effect on the size of the reactor and the associated costs on an industrial scale.
  • a further advantage of the process according to the invention is the fact that less formic acid (by-product) is introduced into the process by the use of formaldehyde, which is prepared by oxidative dehydrogenation, in particular by fat oxidative dehydrogenation from methanol.
  • formaldehyde which is prepared by oxidative dehydrogenation, in particular by fat oxidative dehydrogenation from methanol.
  • the MDA produced by the process according to the invention also has a higher degree of purity.
  • step a) the reaction of formaldehyde and aniline to aminal takes place.
  • Aminal is an intermediate in the production of MDA.
  • step a) is carried out in complete or almost complete absence of an acidic catalyst.
  • the molar ratio of aniline to formaldehyde is normally 1: 5: 1 to 6: 1, preferably 1: 8: 1 to 5: 1.
  • the temperature is normally 20 to 100 0 C, preferably 30 to 95 ° C, aeration Sonders preferably 40 to 90 0 C.
  • formaldehyde is used as highly concentrated formaldehyde having a CH 2 O content of> 50% by weight, preferably> 70% by weight, in particular> 80% by weight.
  • Methods for the preparation of highly concentrated formaldehyde with a CH 2 O content> 50 wt .-% are known in the art.
  • formaldehyde is used which has been prepared by oxidative dehydrogenation from methanol.
  • formaldehyde is used which has been prepared by fatty oxidative dehydrogenation.
  • fat means that the molar ratio of methanol to acid substance in the feed to the synthesis of formaldehyde is equal to or exceeds 2: 1.
  • Formaldehyde synthesis methods by oxidative dehydrogenation of methanol are known in the art.
  • the formaldehyde incurred directly as highly concentrated formaldehyde, but normally formaldehyde is first prepared with a lower CH 2 O content, from which as above described by methods known in the art of highly concentrated formaldehyde having a CH 2 O content> 50 wt .-% is obtained.
  • the highly concentrated formaldehyde can be used as an aqueous solution or in gaseous form.
  • step a) highly concentrated formaldehyde solution having a CH 2 O content> 50% by weight, which is prepared from an aqueous formaldehyde solution having a lower CH 2 O content by evaporating a part of this solution, is used the aqueous formaldehyde solution is heated to an evaporation temperature at which water accumulates in the gas phase relative to the liquid phase and the gas phase formed is withdrawn continuously or discontinuously.
  • the aqueous formaldehyde solution is heated to an evaporation temperature T for the following applies:
  • c is the actual CH 2 O content of the aqueous formaldehyde solution during the evaporation in wt .-% and is from 20 to 99 wt .-%.
  • the evaporation of the aqueous formaldehyde solutions of this embodiment takes place in a stirred tank, a helical tube, a film evaporator or another apparatus with a heat exchanger characteristic.
  • the pressure during the evaporation is 0.1 to 50 bar.
  • the aqueous formaldehyde solution having a lower CH 2 O content in the pressure holding device is expanded to a biphasic mixture, which is then fed to the helical tube evaporator.
  • a stripping gas and / or a stabilizer can be added to the two-phase mixture before it is fed into the spiral tube evaporator.
  • the stripping gas is preferably nitrogen
  • the stabilizer is preferably methanol, ethanol, a propanol, a butanol, urea or melamine.
  • a wavy film flow is set in the helical tube evaporator by the appropriate choice of the geometry thereof as well as the operating conditions, in particular the total amount flow and the gas content in the two-phase mixture, which is passed through the helical tube evaporator.
  • the condensed fraction of the vapor stream and / or the bottom stream from the helical tube evaporator can be completely or partially recycled into the preheater.
  • step a) a highly concentrated formaldehyde solution having a CH 2 O content> 50 wt .-% is used, which is stabilized against solid precipitation by immediately after its preparation at a heating rate of at least 5 ° C. / min is heated to a temperature of at least 80 to a maximum of 200 0 C and stored at a temperature in this range.
  • the heating rate is at least 10 ° C / min and / or it is heated to a temperature of at least 100 to a maximum of 150 0 C.
  • the high concentration formaldehyde solution is obtained from a low concentration formaldehyde solution in a film evaporator.
  • gaseous highly concentrated formaldehyde having a CH 2 O content> 50% by weight and a molar CH 2 O to H 2 O ratio> 0.6 is used in step a), the gaseous highly concentrated formaldehyde being used
  • Formaldehyde is prepared by evaporation of at least a portion of an aqueous formaldehyde solution.
  • the aqueous formaldehyde solution is heated to an evaporation temperature T and the gas phase formed is withdrawn, wherein for the evaporation temperature T:
  • T ' min (c) A + B x (c / 100) + C x (c / 100) 2 + D x (c / 100) 3 and
  • c is the actual CH 2 O content of the aqueous formaldehyde solution during the evaporation in wt .-% and is from 20 to 99 wt .-%.
  • the pressure during the evaporation is 0.1 to 50 bar.
  • the molar CH 2 O to H 2 O ratio is> 1.4.
  • step b) of the process according to the invention the removal of water takes place from the aminal obtained in step a).
  • a water content of 0 to 5 wt .-% is adjusted based on the aminal.
  • the water falls on the one hand as the second main product in the aminal synthesis according to step a), on the other hand it is present at least in traces in the educt used in step a) (highly concentrated formaldehyde with a CH 2 O content> 50 wt .-%) ,
  • a water content of 0.5 to 5 wt .-%, particularly preferably 1 to 4 wt .-% based on the aminal adjusted is determined, for example, by the Karl Fischer method described, for example, in Jander, Jahr, duplicate analyses, 15th edition, de Gruyter, Berlin (1989), p. 289 to p. 292.
  • step c) of the process according to the invention the addition of an acidic catalyst to the aminal with a water content of 0 to 5 wt .-% takes place.
  • acidic catalysts strong organic or strong inorganic acids can be used. Suitable acids are, for example, hydrochloric acid (HCl), sulfuric acid, phosphoric acid and methanesulfonic acid. Preference is given to using aqueous hydrochloric acid in the process according to the invention.
  • the aqueous hydrochloric acid is usually present in concentrations of 25 to 36 wt .-% before.
  • gaseous HCl is preferably used.
  • the addition of the acidic catalyst is carried out in catalytic amounts. This means that based on the aminal a significantly lower amount of catalyst is used.
  • step c) a much smaller amount of water is introduced into the reaction system compared to step a), provided that the acidic catalyst is used as an aqueous solution.
  • the acidic catalyst By adding the acidic catalyst, the rearrangements of the aminals described above can be via the aminobenzylaniline intermediates to MDA.
  • HCl is predominantly bound to aniline and MDA, the specific amount of HCl used is calculated from the stated degrees of protonation.
  • the process according to the invention produces 4,4'-MDA as the main product and also 2,4'-MDA and 2,2'-MDA as by-products and optionally further higher homologs.
  • MDA in the weight ratio of the isomers 2,4'-MDA to 4,4'-MDA of between 0.05 and 0.15 can be obtained.
  • the addition of the acidic catalyst to the aminal with a water content of 0 to 5 wt .-% in step c) is preferably carried out by mixing, in particular at temperatures of 20 to 60 0 C.
  • the mixing of aminal with a water content of 0 to 5 wt. -% with the acidic catalyst is preferably carried out with a specific power input of> 10 kW / m 3 mixing space, more preferably of> 20 kW / m 3 mixing space.
  • the aminal at temperatures of 20 to 100 0 C and / or at water contents of 0 to 20 wt .-% rearranged to MDA (implemented).
  • the amount of acidic catalyst is chosen so that a degree of protonation of ⁇ 15%, preferably from 5 to 14%, particularly preferably from 6 to 13% is set.
  • the temperature of the reaction can be increased to values of from 10 to 250 ° C., if the ratio of the proportions by weight of p-aminobenzylaniline to 4,4'-MDA in the acidic reaction mixture is 1, 00 falls below.
  • the temperature increase of the reaction mixture can be carried out in stages or continuously and optionally under overpressure.
  • the temperature 1 10 to 180 0 C, in particular from 1 10 to 160 ° C.
  • the abovementioned value with regard to falling below the weight proportions is preferably 0.50, particularly preferably 0.25 and in particular 0.2.
  • reaction product (MDA) obtained in the process according to the invention be worked up further, for example by adding a base. Such work-up steps are known to the person skilled in the art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de diamine de diphénylméthylène (MDA) comprenant les étapes suivantes a) à c) : a) réaction de formaldéhyde et d'aniline pour obtenir un aminal; b) élimination d'eau dans l'aminal obtenu à l'étape a), la teneur en eau étant ajustée entre 0 et 15 % en poids rapporté à l'aminal; et c) addition d'un catalyseur acide à l'aminal présentant une teneur en eau comprise entre 0 et 5 % en poids. Le procédé selon l'invention est caractérisé en ce qu'à l'étape a), on utilise du formaldéhyde sous la forme de formaldéhyde de concentration élevée présentant une teneur en CH2O supérieure à 50 % en poids, et en ce que le formaldéhyde est produit par déshydrogénation oxydante à partir de méthanol.
EP10715797A 2009-04-20 2010-04-19 Procédé de production de mda en passant par l'étape de l'aminal Withdrawn EP2421816A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10715797A EP2421816A2 (fr) 2009-04-20 2010-04-19 Procédé de production de mda en passant par l'étape de l'aminal

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09158207 2009-04-20
EP10715797A EP2421816A2 (fr) 2009-04-20 2010-04-19 Procédé de production de mda en passant par l'étape de l'aminal
PCT/EP2010/055126 WO2010121990A2 (fr) 2009-04-20 2010-04-19 Procédé de production de mda en passant par l'étape de l'aminal

Publications (1)

Publication Number Publication Date
EP2421816A2 true EP2421816A2 (fr) 2012-02-29

Family

ID=42732425

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10715797A Withdrawn EP2421816A2 (fr) 2009-04-20 2010-04-19 Procédé de production de mda en passant par l'étape de l'aminal

Country Status (6)

Country Link
US (1) US8710267B2 (fr)
EP (1) EP2421816A2 (fr)
JP (1) JP2012524046A (fr)
KR (1) KR20110138288A (fr)
CN (1) CN102405208B (fr)
WO (1) WO2010121990A2 (fr)

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
US9815769B2 (en) * 2013-04-24 2017-11-14 Covestro Deutschland Ag Process for the preparation of di- and polyamines from the diphenylmethane series
CN115181027B (zh) * 2022-07-25 2023-09-22 万华化学集团股份有限公司 一种生产dam过程中控制废盐水中难处理苯胺类杂质的方法

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Also Published As

Publication number Publication date
JP2012524046A (ja) 2012-10-11
CN102405208A (zh) 2012-04-04
KR20110138288A (ko) 2011-12-26
US8710267B2 (en) 2014-04-29
WO2010121990A2 (fr) 2010-10-28
CN102405208B (zh) 2015-02-25
WO2010121990A3 (fr) 2010-12-23
US20120035396A1 (en) 2012-02-09

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