EP2491011A1 - Procédé de production d'uréthannes - Google Patents

Procédé de production d'uréthannes

Info

Publication number
EP2491011A1
EP2491011A1 EP10766287A EP10766287A EP2491011A1 EP 2491011 A1 EP2491011 A1 EP 2491011A1 EP 10766287 A EP10766287 A EP 10766287A EP 10766287 A EP10766287 A EP 10766287A EP 2491011 A1 EP2491011 A1 EP 2491011A1
Authority
EP
European Patent Office
Prior art keywords
carbonate
reaction
mixtures
base
dialkyl
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Withdrawn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
EP10766287A
Other languages
German (de)
English (en)
Inventor
Axel Franzke
Robert Baumann
Michael Bock
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 EP10766287A priority Critical patent/EP2491011A1/fr
Publication of EP2491011A1 publication Critical patent/EP2491011A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides

Definitions

  • the invention relates to a process for the preparation of urethanes by reacting mono-, di- or polyfunctional aromatic amines with a dialkyl carbonate in the presence of a base.
  • the urethanes produced in this way can subsequently be converted into industrially important isocyanates.
  • urethanes also referred to as carbamates
  • Lewis acids such as aluminum shavings with iodine and mercury promoters (US 4550188) and uranium, zinc, iron, titanium, lead, zirconium, antimony, cobalt, scandium or tin salts are used as catalysts, such as for example, in US 3763217, US 4268683 or US 4268684.
  • Disadvantages for the industrial use of these processes are the long reaction times, low conversions, low selectivities or several aspects together.
  • a further general disadvantage in the use of Lewis acids as homogeneous catalysts are the catalyst residues remaining in the product, the separation of which is incomplete and / or complicated.
  • WO 2007/015852 describes the use of Lewis acidic heterogeneous catalysts for the urethanization of aromatic amines. Although this considerably simplifies the separation of the pure product, the sales obtained are suitable for a large However, technical application too low and decrease together with the selectivity with increasing service life of the heterogeneous catalyst.
  • WO 2008/084842 describes the preparation of aromatic carbamates using small excesses of dialkyl carbonates (2.5 to 3 equivalents based on amino groups) and catalytic amounts of sodium methoxide and their further conversion to the corresponding isocyanates.
  • dialkyl carbonates 2.5 to 3 equivalents based on amino groups
  • WO 2009/1 15538 discloses the reaction of aromatic diamines with only slight excesses, namely two equivalents per amino group, of dialkyl carbonates of higher alcohols having at least two carbon atoms in the chain in the presence of stoichiometric amounts of alkali alkoxides, which enables high isolated yields of carbamates.
  • the recycling of such large amounts of base requires a great deal of energy, which reduces the economics of this process on a large scale.
  • WO 2010/020621 also describes a similar presentation of carbamates using only catalytic amounts of base.
  • the carbonates derived from heteroatom-containing alcohols required for this purpose are difficult to synthesize and thus have limited accessibility.
  • the invention was based on the object, an industrially feasible process for the production of urethanes from mono-, di- or polyfunctional aromatic amines to develop, which leads to high space-time yields and selectivities.
  • the process should be possible using commercially available dialkyl carbonates. It should be worked with low molar excesses of dialkyl carbonates based on the amino groups. Furthermore, the amount of base used should be as low as possible.
  • the thus obtained urethanes are to be processed subsequently to technically important aromatic isocyanates.
  • the invention accordingly provides a process for the preparation of urethanes by reaction of aromatic amines with a dialkyl carbonate, characterized in that the alkyl radical of the organic dialkyl carbonate contains 4-18 carbon atoms, preferably 4-10 carbon atoms and is branched in the 2-position and the reaction in the presence of a substoichiometric amount of base relative to the amino groups.
  • the reaction product of the aromatic amine and the dialkyl carbonate is reacted with a protic compound.
  • a protic compound is meant a compound that can transfer a proton.
  • the protic compound is preferably selected from a group containing alcohols, water and mixtures of these two. Particularly preferred is the use of water.
  • the base is preferably used in a molar ratio of 0.3 to less than 0.8 based on the amino groups, particularly preferably from 0.4 to 0.6, based on the amino groups.
  • the dialkyl carbonate is preferably used in a molar ratio of dialkyl carbonate to amino groups of 1: 1 to 6: 1, more preferably from 1: 1 to 3: 1.
  • the reaction of the aromatic amine with the dialkyl carbonate in the presence of the base is preferably carried out at a reaction temperature of 60-180 ° C, more preferably 100-150 ° C. At this temperature, a quantitative conversion of the aromatic amine is obtained within 0.5-10 h.
  • the reaction is usually carried out at normal pressure, or under (autogenous) overpressure or underpressure. In this case, the resulting alcohol can be left in the reaction mixture or distilled off. In one embodiment of the invention, the reaction is carried out in the presence of an inert solvent.
  • Suitable solutions are mono- or polyethers, such as dioxane, diphenyl or benzyl ethers, and dialkylethylene glycols, such as diethylene glycol dimethyl ether, diethylene glycol dibutyl ether or triethylene glycol dimethyl ether, aromatic hydrocarbons with or without alkyl, halogen or alkoxy substituents, such as toluene, the isomeric xylenes , Mesitylene, ethylbenzene, tetralin, the isomeric benzyl and dibenzyl toluenes, chlorobenzene, the isomeric dichloro- and trichlorobenzenes or anisole, or the alcohol contained in the dialkyl carbonate and / or alkoxide. These can be used individually or as a mixture.
  • mono- or polyethers such as dioxane, diphenyl or benzyl ethers
  • dialkylethylene glycols such as diethylene glycol
  • aromatic amines are used.
  • the aromatic amines preferably contain no heteroatoms in the aromatic radical.
  • Representatives from this group are, for example, aniline, o-, m-, p-toluidine and mixtures thereof, o-, m-, p-chloroaniline and mixtures thereof, m-, p-bromoaniline and mixtures thereof, o-, m-, p-trifluoromethylaniline and mixtures thereof, 2,4-, 2,6-, 3,4- and 3,5-dimethyl-, -dichloro-, - dibromo- and -Diethylanilin and isomer mixtures thereof, p-tert-butyl aniline, diaminotoluene (TDA), in particular 2,4- and 2,6-diaminotoluene and mixtures thereof, diaminodiphenylmethane (MDA), in particular 2,4'-di
  • TDA diaminotoluen
  • the alkyl chain of the dialkyl carbonate contains 4-18, preferably 4-10 carbon atoms and is branched in the 2-position. It is derived from the corresponding primary alcohol.
  • the alkyl chain may also contain saturated or unsaturated rings.
  • the alkyl chain of the dialkyl carbonate is modified with an oxygen atom. This is preferably present as ether group.
  • the dialkyl carbonates are selected from the group consisting of di (2-methylpropyl) carbonate, di- (2-methoxypropyl) carbonate, di- (2-ethoxypropyl) carbonate, di- ( 2-methylbutyl) carbonate, di- (2-ethylhexyl) carbonate, di (cyclopentylmethyl) carbonate and di- (cyclohexylmethyl) carbonate, preferably di (2-methylpropyl) carbonate and di- (2-methoxypropyl ) carbonate, more preferably di (2-methylpropyl) carbonate.
  • the dialkyl carbonate is preferably prepared by transesterification of an alkylene carbonate with an alcohol.
  • the base is preferably basic organic metal compounds, in particular compounds of alkali metals. These may be, for example, nitrogen-containing compounds, for example amides, such as sodium amide, or silicon atoms and nitrogen-containing compounds, for example lithium hexamethyldisilazide.
  • the base is particularly preferably an alkoxide of alkali metals or alkaline earth metals.
  • the alkyl chain of the alkoxide is linear, branched or cyclic and contains 1-18, preferably 4-10 carbon atoms.
  • the alcohol may also contain saturated or unsaturated rings.
  • the alkyl chain of the alkoxide is modified with at least one oxygen atom. This is preferably present as ether group.
  • the dialkyl carbonates and the alcoholates are based on the same alcohol. This has the advantage that in the process according to the invention a smaller amount of compounds is present. This reduces the separation effort within the process.
  • the process according to the invention comprises the steps
  • step c) separation of the products formed in step b) and the aqueous base d) conversion of the aqueous base from step c) into the corresponding not
  • step b) This process is carried out continuously or batchwise, preferably continuously.
  • the urethane is formed in step b).
  • This embodiment is shown in Figure 1 when using water as the protic compound.
  • the urethane can be isolated as a solution in an organic solvent or as a pure substance in the form of a melt or a solid.
  • the products formed in step b) are the urethane and, in the case of the use of a sodium alkoxide as base, sodium hydroxide solution.
  • Process step a) is carried out in stage 1 of FIG. 1, process step b) in stage 2.
  • stages 1 and 2 can be carried out in the same reaction vessel, in a continuous procedure preferably in different reaction vessels.
  • the product from stage 1 can be converted to stage 2 without further work-up.
  • stage 3 the reaction of the aqueous obtained in stage 2 in the non-aqueous base, in the case of the use of alcoholates, the conversion of the hydroxide into the alkoxide. This is returned to level 1.
  • Excess alcohol obtained in stage 2 is removed there or placed elsewhere in the system. drive back.
  • the water formed in the formation of the base or of the alcoholate can be recycled back to step b).
  • the liquor formed in step b) can be converted with alcohol to the corresponding alkoxide and this can be recycled back to step a).
  • the product from Stage 2 is separated into a non-aqueous and an aqueous phase. From the organic phase containing the urethane, this is separated and isolated as a solid or melt or used directly in this form in further reaction stages, for example a thermal cleavage to the corresponding isocyanate. If necessary, the separated urethanes can be purified by methods known to those skilled in the art, for example by washing with water or organic solvents or recrystallization from a suitable solvent.
  • step f) The thermal cleavage of the urethane to the corresponding isocyanate can be followed immediately as step f) to step e).
  • the dialkyl carbonate used in step a) can preferably be prepared by transesterification of an alkylene carbonate with an alcohol.
  • this invention it has been demonstrated that the reaction of aromatic amines with a slight excess of dialkyl carbonates derived from branched alcohols in the presence of substoichiometric amounts of base to the corresponding carbamates is possible in high selectivities and space-time yields.
  • the urethanes are formed in high purities, so that typically no time-consuming post-purification is required.
  • non-inventive, linear carbonates such as di-n-propyl carbonate or bis (2-methoxyethyl) carbonate only significantly reduced yields of not more than 84% for 2 , 4-diaminotoluene, that is, high conversions at low selectivities achieved.
  • Example 4 In a 500 mL four-necked flask equipped with stirrer, reflux condenser, internal thermometer and protective gas transfer were successively 12.0 g (98.0 mmol) of 2,4- and 2,6-diaminotoluene in the ratio 80:20, 14.1 g (147 mmol) of sodium isobutoxide and 68.1 g (391 mmol) of diisobutyl carbonate were weighed under argon and immersed in an oil bath preheated to 125 ° C. The content of bisurethanes in the reaction mixture was determined at periodic intervals by means of sampling and subsequent HPLC analysis. This was 32.6% by weight (97%) after 3 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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 d'uréthannes, par réaction d'amines aromatiques avec un dialkylcarbonate, caractérisé en ce que le reste alkyle du dialkylcarbonate organique renferme 4-18 atomes de carbone, et est ramifié en position 2, et en ce que la réaction est effectuée en présence d'une quantité de base sous-stoechiométrique par rapport aux groupes amino.
EP10766287A 2009-10-21 2010-10-20 Procédé de production d'uréthannes Withdrawn EP2491011A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10766287A EP2491011A1 (fr) 2009-10-21 2010-10-20 Procédé de production d'uréthannes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09173667 2009-10-21
EP10766287A EP2491011A1 (fr) 2009-10-21 2010-10-20 Procédé de production d'uréthannes
PCT/EP2010/065765 WO2011048124A1 (fr) 2009-10-21 2010-10-20 Procédé de production d'uréthannes

Publications (1)

Publication Number Publication Date
EP2491011A1 true EP2491011A1 (fr) 2012-08-29

Family

ID=43530311

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10766287A Withdrawn EP2491011A1 (fr) 2009-10-21 2010-10-20 Procédé de production d'uréthannes

Country Status (7)

Country Link
US (1) US8871965B2 (fr)
EP (1) EP2491011A1 (fr)
JP (1) JP5882216B2 (fr)
KR (1) KR20120087949A (fr)
CN (1) CN102596900B (fr)
BR (1) BR112012009485A2 (fr)
WO (1) WO2011048124A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8946459B2 (en) 2011-08-31 2015-02-03 Basf Se Process for preparing EDDN and/or EDMN by reacting EDFA and/or EDMFA with HCN
US9012638B2 (en) 2011-08-31 2015-04-21 Basf Se Process for preparing EDDN and/or EDMN by conversion of FACH and EDA
US8952156B2 (en) 2011-08-31 2015-02-10 Basf Se Process for working up reaction outputs from the hydrogenation of EDDN or EDMN
US9096497B2 (en) 2011-08-31 2015-08-04 Basf Se Process for preparing EDDN and EDMN
JP2015137255A (ja) * 2014-01-22 2015-07-30 宇部興産株式会社 カルバメート化合物の製造方法
TWI613184B (zh) * 2016-05-24 2018-02-01 中國石油化學工業開發股份有限公司 一種胺基甲酸酯的製造方法
EP3450424A1 (fr) 2017-09-04 2019-03-06 Covestro Deutschland AG Procédé de fabrication d'isocyanates

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US3763217A (en) 1970-12-03 1973-10-02 Halcon International Inc Preparation of carbamates
US4268683A (en) 1980-02-21 1981-05-19 The Dow Chemical Company Preparation of carbamates from aromatic amines and organic carbonates
US4268684A (en) 1980-02-25 1981-05-19 The Dow Chemical Company Preparation of carbamates from aromatic amines and organic carbonates
DE3035354A1 (de) * 1980-09-19 1982-04-29 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von n,o-disubstituierten urethanen und ihre verwendung als ausgangsmaterial zur herstellung von organischen isocyanaten
IT1141960B (it) 1981-01-28 1986-10-08 Anic Spa Procedimento per la preparazione di uretani aromatici
US4550188A (en) 1984-06-27 1985-10-29 The Dow Chemical Company Preparation of carbamates
US5773643A (en) * 1987-01-13 1998-06-30 Daicel Chemical Industries, Ltd. Process for preparation of isocyanate compounds
IT1229144B (it) 1989-04-07 1991-07-22 Enichem Sintesi Procedimento per la produzione di carbammati.
HUP0003114A3 (en) * 1997-06-05 2001-03-28 Huntsman Ici Chemicals Llc The Method for the preparation of carbamates
AU7766098A (en) 1997-06-05 1998-12-21 Huntsman Ici Chemicals Llc Method for the preparation of carbamates
WO1999047493A1 (fr) * 1998-03-17 1999-09-23 Huntsman Ici Chemicals Llc Procede de preparation de carbamates organiques
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CN100540587C (zh) * 2004-12-23 2009-09-16 华东理工大学 一种环境友好的合成聚氨酯的方法
EP1943214A2 (fr) 2005-07-20 2008-07-16 Dow Gloval Technologies Inc. Preparation de carbamates avec un catalyseur heterogene supporte
WO2008084842A1 (fr) 2007-01-12 2008-07-17 Nec Corporation Procédé et dispositif de génération de fonction de noyau et dispositif de classification de données
WO2009115538A1 (fr) * 2008-03-18 2009-09-24 Basf Se Procédé de fabrication d'uréthanes à partir d'amines aromatiques monofonctionnelles et difonctionnelles
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US9233918B2 (en) * 2008-05-15 2016-01-12 Asahi Kasei Chemicals Corporation Isocyanate production process
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Also Published As

Publication number Publication date
CN102596900B (zh) 2015-09-09
JP2013508336A (ja) 2013-03-07
CN102596900A (zh) 2012-07-18
BR112012009485A2 (pt) 2016-05-03
US8871965B2 (en) 2014-10-28
US20120203022A1 (en) 2012-08-09
JP5882216B2 (ja) 2016-03-09
WO2011048124A1 (fr) 2011-04-28
KR20120087949A (ko) 2012-08-07

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