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EP1866281A1 - Preparation de methylene diphenyldiisocyanate polymere (mmdi) et de methylene diphenyldiisocyanate polymere (pmdi) par phosphogenation en phase gazeuse - Google Patents

Preparation de methylene diphenyldiisocyanate polymere (mmdi) et de methylene diphenyldiisocyanate polymere (pmdi) par phosphogenation en phase gazeuse

Info

Publication number
EP1866281A1
EP1866281A1 EP06725223A EP06725223A EP1866281A1 EP 1866281 A1 EP1866281 A1 EP 1866281A1 EP 06725223 A EP06725223 A EP 06725223A EP 06725223 A EP06725223 A EP 06725223A EP 1866281 A1 EP1866281 A1 EP 1866281A1
Authority
EP
European Patent Office
Prior art keywords
mixture
gas phase
reaction
mmda
pmda
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Withdrawn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
EP06725223A
Other languages
German (de)
English (en)
Inventor
Christian Müller
Eckhard Stroefer
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
Publication of EP1866281A1 publication Critical patent/EP1866281A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • 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
    • 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
    • C07C211/44—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 only one six-membered aromatic ring
    • C07C211/49—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 only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—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 only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton

Definitions

  • the invention relates to a process for the preparation of isocyanates, comprising the steps
  • Aromatic isocyanates are important and versatile raw materials for polyurethane chemistry MDI in particular is one of the most important technical isocyanates.
  • MDI is used in the field and in the context of this application as a generic term for methylene (diphenyldiisocyanate) and polymethylene polyphenylene polyisocyanates.
  • methylene includes the isomers 2,2'-methylene (d ⁇ phenyld ⁇ socyanat) (2,2'-MDI), 2,4'-methylene (d ⁇ phenyldiisocyanat) (2,4'-MDI) and 4,4'- Methylene (diphenyl diisocyanate) (4,4'-MDI)
  • 2,2'-methylene d ⁇ phenyld ⁇ socyanat
  • 2,4'-methylene 2,4'-methylene
  • 4,4'- Methylene diphenyl diisocyanate
  • polymethylene polyphenylene polyisocyanates encompasses the art and within the scope of this invention the so-called “polymer MDI” or “PMDI” containing higher homologues of the monomer MDI and optionally additionally monomeric MDI.
  • MD In usual industrially relevant manufacturing processes, MD! The synthesis takes place in a two-stage process. Aniline is first formaldehyde-treated to form a mixture of monomeric methylenes (diphthenediamines) - known in the art and within the scope of this invention as "MMDA” - and polymethylene polyphenylene polyamines - referred to in the art and within the scope of this invention as "PMDA” - condensed into the so-called crude MDA
  • the crude MDA usually produced by prior art processes contains about 70% MMDA and is preferred for an amine to formaldehyde ratio of about 2.0-2.5
  • This crude MDA is then reacted in a second step with phosgene in a conventional manner to a mixture of the corresponding oligomeric and isomeric methylene (diphenyld ⁇ socyanate) and polymethylene polyphenyle ⁇ -polyisocyanates, the so-called crude MDI
  • the isomer and Oligomerenzu- In general, a part of the 2-core compounds is then used in a further process step (for example by distillation or crystallization). tion), leaving Polymer-MD I (PMDI) with reduced MMDI content as residue.
  • the object of the invention was to provide a process for the preparation of isocyanates which has an advantageous space-time yield compared to the processes known in the prior art. Furthermore, a process should be provided which has a lower phosgene hold-up in In addition, a process should be provided that allows a smaller reactor volume in the phosgenation. Finally, a procedure should be provided that is energetically beneficial
  • the product mix of MMDI and PMDI should be shifted towards MMDI since MMDI is desired on the market Amount of discharged PMDI and MMD! Understood.
  • MDA methylenedianiline
  • the invention thus provides a process for the preparation of isocyanates, in particular of MMDI and PMDI, comprising the steps of (1) preparing a crude MDA mixture containing MMDA and PMDA, by reacting aniline with formaldehyde, the reaction conditions being chosen in that the resulting crude MDA can be converted into the gas phase,
  • step (1) described reaction of aniline with formaldehyde to monomeric methylene (d ⁇ phenyld ⁇ am ⁇ nen) (referred to in the context of this invention as "MMDA") and polymethylene polyphenylene polyamines (referred to in the context of this invention as "PMDA"), said mixture from methylene (d ⁇ phenyld ⁇ am ⁇ nen) and polymethylene polyphenylenepolyamines called "crude MDA", the starting materials are usually mixed in a suitable mixing device, such as in mixing pumps, nozzles or static mixers, and in a suitable reaction apparatus, such as in tubular reactors, Ruhr reactors and reaction columns or combinations thereof, implemented
  • the reaction temperature is generally between 20 and 200 ° C, preferably between 30 and 140 D C.
  • step (1) takes place in the presence of an acid as catalyst, wherein the catalyst is preferably added in admixture with aniline.
  • catalysts are mineral acids, such as, for example, hydrochloric acid, sulfuric acid and phosphoric acid. It is also possible to use mixtures of acids. Hydrochloric acid is particularly preferred. If hydrogen chloride is used as the catalyst, it can also be used in gaseous form.
  • the amount of catalyst can preferably be chosen such that a molar ratio of acid / aniline (S / A) of 0.05 to 0.5, more preferably from 0.08 to 0.3
  • the reaction of step (1) is carried out in aqueous medium with HCl as catalyst. Further, the reaction can be carried out in the presence of a solvent. Particularly suitable are ethers, water and mixtures thereof. Examples thereof are dimethylformamide (DMF), tetrahydrofuran (THF) and diethylsophthalate (DEIP).
  • a solvent particularly suitable are ethers, water and mixtures thereof. Examples thereof are dimethylformamide (DMF), tetrahydrofuran (THF) and diethylsophthalate (DEIP).
  • Formaldehyde can be added to the process according to the invention in the form of monomeric formaldehyde and / or in the form of higher homologs, so-called poly (oxymethylene) glycols
  • composition of the prepared polyamine mixture (crude MDA) is influenced in addition to the acid concentration and the temperature significantly by the molar ver- stop ⁇ i of aniline molecules to formaldehyde molecules (A / F-Behhaltn ⁇ s) within the continuous as well as discontinuous operable MDA process ,
  • a / F ratio is chosen, the greater the MMDA content in the resulting crude MDA solution.
  • a larger A / F ratio not only results in a larger 2-core fraction ( MMDA), but the entire oligomeric spectrum of polyamines is shifted towards smaller molecules.
  • the 4-core MDA content decreases by -80% when the A / F ratio is increased from 2.4 to 5.9.
  • the reaction conditions in step (1) are chosen so that the resulting crude MDA is convertible to the gas phase, ie the reaction conditions are chosen so that the resulting crude MDA has such levels of MMDA and PMDA that it can be converted into the gas phase, preferably completely convertible into the gas phase.
  • the aniline to formaldehyde ratio is chosen such that the resulting crude MDA is convertible to the gas phase.
  • the crude MDA resulting in step (1) is completely convertible into the gas phase.
  • complete is meant that a maximum of a residue of 2 wt .-%, preferably of at most 1 wt .-%, in particular of max. 0.1 wt .-% remains, which is not convertible into the gas phase.
  • the molar ratio of aniline to formaldehyde in the context of this invention in process step (1) is generally from 3 to 10 to 1, preferably 4 to 8 to 1, more preferably from 5 to 7.5 to 1, in particular from 5.5 to 7 1.
  • step (1) of the process according to the invention are selected such that the crude MDA mixture resulting in step (1) has a content of
  • the crude MDA mixture resulting in step (1) has a
  • step (1) of the process according to the invention are selected such that the crude MDA mixture resulting in step (1) has an average functionality of from 2.01 to 2.4, preferably from 2.02 to 2.3, in particular from 2.03 to 2.2.
  • average functionality is meant the average number of amine groups per amine molecule.
  • reaction of aniline with formaldehyde can be carried out either continuously or discontinuously, in a baten or semibatch process.
  • the crude MDA obtained is converted into the gas phase in step (2) of the process according to the invention and phosgenated in step (3) of the process according to the invention, i. implemented with phosgene.
  • Feedstream containing MMDA and PMDA, under the conditions described below in step 3 is converted into a gaseous state.
  • the steps (2) and (3) can take place here in succession or take place simultaneously, i. the amine stream becomes gaseous only by injection into the reactor.
  • the preparation of MMDI and PMDI is usually carried out by reacting the corresponding primary amines of step (2) (i.e., of MMDA and PMDA) with phosgene, preferably an excess of phosgene.
  • This process takes place in the context of this invention in the gas phase.
  • gas phase reaction is meant that the reactant streams (i.e., the amine stream and the phosgene stream) react with each other in the gaseous state.
  • reaction space which is generally arranged in a reactor, ie the reaction space is understood to mean the space where the reaction of the starting materials takes place, the reactor being understood to be the technical apparatus which contains the reaction space.
  • reaction space is understood to mean the space where the reaction of the starting materials takes place, the reactor being understood to be the technical apparatus which contains the reaction space.
  • Suitable materials for contact with the reaction mixture are, for example, metals, such as steel, tantalum, silver or copper, glass, ceramics, enamels or homogeneous or heterogeneous mixtures thereof. Preference is given to using steel reactors.
  • the walls of the reactor can be smooth or profiled. As profiles are, for example, scratches or waves.
  • the reactor types known from the prior art can be used. Pipe reactors are preferably used.
  • the mixing of the reactants takes place in a mixing device, which is characterized by a high shear of the reaction current conducted through the mixing direction.
  • the mixing device used is preferably a static mixing device or a mixing nozzle which precedes the reactor. Particularly preferred is a Mischduse used
  • the reaction of phosgene with amine mixture in the reaction space is usually carried out at absolute pressures of more than 1 bar to less than 50 bar, preferably at more than 2 bar to less than 20 bar, more preferably between 3 bar and 15 bar, particularly preferably between 3.5 bar and 12 bar, in particular from 4 to 10 bar.
  • the pressure in the feed lines to the mixing device is higher than the above-mentioned pressure in the reactor. Depending on the choice of mixing device drops at this pressure.
  • the pressure in the supply lines is preferably 20 to 1000 mbar, more preferably 30 to 200 mbar, higher than in the reaction space
  • the pressure in the workup device is lower than in the reaction space.
  • the pressure is preferably 50 to 500 mbar, particularly preferably 80 to 150 mbar, lower than in the reaction space.
  • step (3) of the process according to the invention can be carried out in the presence of an additional inert medium.
  • the inert medium is a medium which is gaseous in the reaction space at the reaction temperature and does not react with the educts.
  • the inert medium is generally mixed with amine and / or phosgene before the reaction.
  • nitrogen, noble gases such as helium or argon or aromatics such as chlorobenzene, dichlorobenzene or xylene may be used.
  • Nitrogen is preferably used as the inert medium. Particularly preferred is monochlorobenzene or a mixture of monochlorobenzene and nitrogen.
  • the inert medium is used in an amount such that the molar ratio of inert medium to amine is more than 2 to 30, preferably 2.5 to 15.
  • the inert medium is introduced into the reaction space together with the amine
  • the temperature in the reaction space is chosen so that it is below the boiling point of the most heavily used amine, based on the pressure conditions prevailing in the reaction chamber. Depending on the amine used (mixture) and the pressure set, this usually results an advantageous temperature in the reaction space of more than 200 0 C to less than 600 0 C, preferably from 280 0 C to 400 0 C.
  • step (3) it may be advantageous to preheat the streams of the reactants prior to mixing, usually at temperatures of 100 to 600 0 C, preferably from 200 to 400 ° C.
  • the average contact time of the reaction mixture in step (3) of the process according to the invention is generally between 0.1 seconds and less than 5 seconds, preferably from more than 0.5 seconds to less than 3 seconds, particularly preferably more than 0.6 seconds to less than 1, 5 seconds.
  • the term "average contact time” is understood to mean the period of time from the beginning of the mixing of the educts until it leaves the reaction space.
  • the dimensions of the reaction space and the flow rates are such that a turbulent flow, i. a flow having a Reynolds number of at least 2300, preferably at least 2700, is present, wherein the Reynolds number is formed with the hydraulic diameter of the Reaktio ⁇ sraumes.
  • the gaseous reaction partners preferably pass through the reaction space at a flow rate of from 3 to 180 meters / second, preferably from 10 to 100 meters / second.
  • the molar ratio of phosgene to amine groups used is usually 1: 1 to 15: 1, preferably 1: 2: 1 to 10: 1, more preferably 1: 5: 1 to 6: 1.
  • the reaction conditions are selected such that the reaction gas at the exit from the reaction space has a phosgene concentration of more than 25 mol / m 3 , preferably from 30 to 50 mol / m 3 .
  • an inert medium concentration of more than 25 mol / m 3 preferably from 30 to 100 mol / m 3, is generally present at the outlet from the reaction space.
  • the reaction conditions are selected such that the reaction gas at the exit from the reaction space has a phosgene concentration of more than 25 mol / m 3 , in particular from 30 to 50 mol / m 3 , and at the same time an inert medium concentration of more than 25 mol / m 3 , in particular from 30 to 100 mol / m 3 , has.
  • the reaction volume is usually tempered via its outer surface.
  • several reactor tubes can be connected in parallel.
  • the inventive method is preferably carried out in one stage. This is to be understood as meaning that the mixing and reaction of the starting materials takes place in one step and in one temperature range, preferably in the abovementioned temperature range. Furthermore, the process according to the invention is preferably carried out continuously.
  • the gaseous reaction mixture is generally washed preferably at temperatures greater than 150 0 C with a solvent.
  • Preferred solvents are hydrocarbons which are optionally substituted by halogen atoms, for example chlorobenzene, dichlorobenzene and toluene.
  • halogen atoms for example chlorobenzene, dichlorobenzene and toluene.
  • monochlorobenzene is particularly preferably used.
  • the isocyanate is selectively transferred to the wash solution.
  • the remaining gas and the resulting wash solution are preferably separated by rectification in isocyanate (s), solvent, phosgene and hydrogen chloride. Small amounts of by-products which remain in the isocyanate (mixture) can be separated from the desired isocyanate (mixture) by means of additional rectification or else crystallization.
  • FIG. 1 A preferred embodiment of the method according to the invention is illustrated in FIG. 1
  • 25 wass ⁇ ge salt solution (for example NaCl, when using HCl and NaOH as base)
  • the mixture according to the invention has a content of
  • the inventive mixture has a content of 90 to 99.5 wt .-% of MMDA, especially 95 to 99 weight percent of monomeric methylene (d ⁇ phenyld ⁇ am ⁇ nen) and 0.5 to 10 wt .-% of PMDA, in particular 1 to 5 weight percent on polymethylene polyphenylene polyamine ⁇ .
  • the invention further provides a gaseous mixture comprising (a) an amine mixture according to the invention comprising MMDA and PMDA, and (b) an inert medium
  • the inert medium the above-described inert media are suitable.
  • the components (a) and (b) are used in an amount in the gaseous mixture, so that the molar ratio of inert medium to amine is more than 2 to 30, preferably 2.5 to 15.
  • the invention relates to the use of a mixture according to any one of claims 5 to 7 for the production of isocyanates by means of gas phase phosgenation.
  • inventive use also find the preferred embodiments explained for the method according to the invention.

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  • 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

La présente invention concerne un procédé pour préparer des isocynates, comprenant les étapes suivantes: (1) préparation d'un mélange de méthylène diphényldiamines monomères (MDA) brutes par conversion d'aniline avec du formaldéhyde, les conditions réactionnelles étant sélectionnées de sorte que l'intégralité des MDA brutes obtenues peuvent être mises en phase gazeuse; (2) mise en phase gazeuse du mélange de MDA brutes de l'étape (1); (3) phosphogénation des MDA brutes en phase gazeuse, pour donner MMDI et PMDI.
EP06725223A 2005-03-30 2006-03-22 Preparation de methylene diphenyldiisocyanate polymere (mmdi) et de methylene diphenyldiisocyanate polymere (pmdi) par phosphogenation en phase gazeuse Withdrawn EP1866281A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005014847A DE102005014847A1 (de) 2005-03-30 2005-03-30 MMDI und PMDI Herstellung mittels Gasphasenphosegenierung
PCT/EP2006/060939 WO2006103188A1 (fr) 2005-03-30 2006-03-22 Preparation de methylene diphenyldiisocyanate polymere (mmdi) et de methylene diphenyldiisocyanate polymere (pmdi) par phosphogenation en phase gazeuse

Publications (1)

Publication Number Publication Date
EP1866281A1 true EP1866281A1 (fr) 2007-12-19

Family

ID=36572053

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06725223A Withdrawn EP1866281A1 (fr) 2005-03-30 2006-03-22 Preparation de methylene diphenyldiisocyanate polymere (mmdi) et de methylene diphenyldiisocyanate polymere (pmdi) par phosphogenation en phase gazeuse

Country Status (7)

Country Link
US (1) US20080171894A1 (fr)
EP (1) EP1866281A1 (fr)
JP (1) JP2008534549A (fr)
KR (1) KR20070116951A (fr)
CN (1) CN101151241A (fr)
DE (1) DE102005014847A1 (fr)
WO (1) WO2006103188A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2476248T3 (es) 2006-10-26 2014-07-14 Basf Se Procedimiento para la preparación de isocianatos
PL2200976T3 (pl) * 2007-09-19 2012-04-30 Basf Se Sposób wytwarzania izocyjanianów
KR20170058927A (ko) * 2014-09-19 2017-05-29 코베스트로 도이칠란트 아게 이소시아네이트의 기체 상 제조 방법

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4039581A (en) * 1975-06-27 1977-08-02 The Upjohn Company Process for the preparation of di(amino phenyl)methanes
US5310769A (en) * 1992-05-01 1994-05-10 Bayer Aktiengesellschaft Process for the production of polyamine mixtures of the polyamino-polyaryl-polymethylene series
DE4217019A1 (de) * 1992-05-22 1993-11-25 Bayer Ag Verfahren zur Herstellung von aromatischen Diisocyanaten
DE10145787A1 (de) * 2001-09-17 2003-04-10 Basf Ag Verfahren zur Herstellung von Methylendi(phenylisocyanat)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006103188A1 *

Also Published As

Publication number Publication date
DE102005014847A1 (de) 2006-10-05
WO2006103188A1 (fr) 2006-10-05
KR20070116951A (ko) 2007-12-11
JP2008534549A (ja) 2008-08-28
US20080171894A1 (en) 2008-07-17
CN101151241A (zh) 2008-03-26

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