EP2585433A1 - Dissociation de carbamate en présence d'un catalyse hétérogène pour la synthèse d'isocyanates sur des acides de lewis solides - Google Patents

Dissociation de carbamate en présence d'un catalyse hétérogène pour la synthèse d'isocyanates sur des acides de lewis solides

Info

Publication number
EP2585433A1
EP2585433A1 EP11725938.2A EP11725938A EP2585433A1 EP 2585433 A1 EP2585433 A1 EP 2585433A1 EP 11725938 A EP11725938 A EP 11725938A EP 2585433 A1 EP2585433 A1 EP 2585433A1
Authority
EP
European Patent Office
Prior art keywords
cleavage
zeolite
carbamate
catalyst
isocyanates
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Withdrawn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
EP11725938.2A
Other languages
German (de)
English (en)
Inventor
Tobias Rosendahl
Torsten Mäurer
Eckhard Stroefer
Axel Franzke
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 EP11725938.2A priority Critical patent/EP2585433A1/fr
Publication of EP2585433A1 publication Critical patent/EP2585433A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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 by cleavage of the corresponding carbamates.
  • the carbamate cleavage is becoming increasingly important as a phosgene-free process for the preparation of isocyanates.
  • Various apparatuses have been proposed for carrying out the carbamate cleavage industrially, in particular columns (in EP 0 795 543), fluidized bed reactors (in EP 555 628 and in DE 199 07 648), falling film or thin film evaporators (in EP 0 092 738).
  • the carbamate cleavage can be operated in the liquid or gas phase.
  • a problem in the thermal cleavage of carbamates is the formation of high molecular weight secondary components, which are formed by further reaction of the cleavage products with itself or with starting materials. These can form deposits in the equipment, thus restricting continuous operation and resulting in yield losses.
  • the residues contain in particular allophanates and isocyanurates.
  • the by-products are also formed by the reaction of hemi-urethanes (semicarbamates, ie a difunctional compound containing urethane and an isocyanate function, intermediates of cleavage of bisurethanes) with themselves. They are also formed by the reaction of the desired end product with the feedstock.
  • the object is achieved by a process for the preparation of isocyanates by cleavage of the corresponding carbamates, which is characterized in that the cleavage of the carbamates is carried out in the presence of a heterogeneous Lewis acidic catalyst.
  • Lewis acidic heterogeneous catalysts increase the rate of carbamate cleavage by up to 80-fold over pure thermal cleavage, with high selectivity, above 90%, of cleavage to the corresponding isocyanates. It has surprisingly been found that these high rate increases and selectivities are achieved only with catalysts that are Lewis acid, but not with Brönsted acids, which lead to undesirable side reactions in the cleavage.
  • carbamates also called carbamic acid esters or urethanes
  • urethanes preferably biscarbamates and polycarbamates
  • amines preferably diioder polyamines, preferably diamines, with urea and at least one alcohol.
  • Suitable alcohols for the preparation of the carbamates are in principle all aliphatic alcohols. Preferably, those are selected whose boiling points differ sufficiently from the boiling point of the isocyanates to ensure optimum separation. Particularly preferred for the preparation of the carbamate aliphatic monohydroxy alcohols having 1 to 4 carbon atoms per molecule, i. Methanol, ethanol, propanol, isopropanol, n-butanol and / or isobutanol used. Also preferred are alcohols having at least one oxygen heteroatom, in particular 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2-methoxy-1-propanol and / or 1-methoxy-2-propanol.
  • the amines used are preferably 2,4- and / or 2,6-toluenediamine (TDA), 2,2 ', 2,4'- and / or 4,4'-diaminodiphenylmethane (MDA) and / or higher homologs (poly).
  • TDA 2,4- and / or 2,6-toluenediamine
  • MDA 4,4'-diaminodiphenylmethane
  • poly homologs
  • phenylenepolymethylenepolyamine pMDA
  • 1,6-hexamethylenediamine HDA
  • 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane hereinafter also referred to as isophoronediamine, IPDA
  • 1, 5 and / or 1, 8 Diaminonaphthalene, 4,4'-diaminodiphenyl, 1, 3 and / or 1, 4-diaminobenzene, 2,4- and / or 2,6-hexahydrotoluylenediamine and / or 4,4'-, 2,4'- and or 2,2'-dicyclohexylmethanediamine used.
  • the structures of the amines used determine the structures of the isocyanates obtainable after the thermal cleavage.
  • the urethanes used are based on 2,4- and / or 2,6-toluenediamine (TDA), 2,2'-, 2,4'- and / or 4,4'-diaminodiphenylmethane (MDA) and / or higher homologues (polyphenylenepolymethylenepolyamines, pMDA), 1,6-hexamethylenediamine (HDA), isophoronediamine (IPDA) and / or 1,5-diaminonaphthalene as the amine component and methanol, n-propanol, isopropanol, n-butanol, or in particular isobutanol or 2-methoxyethanol as alcohol.
  • TDA 2,4- and / or 2,6-toluenediamine
  • MDA 2,2'-, 2,4'- and / or 4,4'-di
  • diurethanes or polyurethanes are used for cleavage: 2,4- and / or 2,6-toluylenediisobutylurethane, 2,4- and / or 2,6-toluene.
  • isocyanates are particularly preferably prepared by thermal cleavage of the corresponding diurethanes: 2,4- and / or 2,6-toluene diisocyanate (TDI), 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI, polyphenylene, polymethylene, polyisocyanates, p-MDl), 1,6-hexamethylene diisocyanate (HDI), 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophorone diisocyanate, IPDI) and / or 1, 5 Diisocyanato naphthalene (NDI).
  • TDI 2,4- and / or 2,6-toluene diisocyanate
  • MDI polyphenylene, polymethylene, polyisocyanates, p-MDl
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone di
  • the heterogeneous Lewis acidic catalyst used according to the invention is preferably a supported catalyst comprising a ceramic support to which a metal is applied.
  • Zeolites, spinels and perovskites, in particular zeolites have proven useful as ceramic supports for the use according to the invention.
  • Particularly suitable are zeolites, in particular Na-Y zeolites.
  • metal which is applied to the carrier, are particularly suitable zinc, aluminum and iron.
  • zinc is applied to the ceramic carrier as the metal.
  • the heterogeneous Lewis acidic catalyst may preferably be prepared by solid-state reaction of ZnCl 2 and Na-Y zeolite by heat treatment or under microwave irradiation. Such methods are described, for example, in Journal of Molecular Catalysis A: Chemical 209 (2004) pages 171 to 177.
  • the Lewis acidic heterogeneous catalyst can be used in a preferred embodiment as a suspension catalyst.
  • the Lewis acid heterogeneous catalyst is used as a coating on the inner wall of a reactor in which the carbamate cleavage is carried out.
  • the reactor in which the carbamate cleavage is carried out and whose inner wall is coated with the Lewis acid catalyst is preferably a falling film evaporator.
  • the growth of zeolite-based catalysts on different materials, in particular glass or metal is known from the literature.
  • Carrying out the carbamate cleavage in the falling-film evaporator has the further advantage over carbamate cleavage in the presence of a suspension catalyst that the reaction products of cleavage, ie alcohol and isocyanate, can be taken at different points in the reactor so that the formation of undesirable by-products is prevented by further reaction thereof can.
  • TDU 2,4-di-n-propyl toluenedimethyl urethane
  • TDI corresponding tolylene diisocyanate
  • the catalyst was tested in a system designed for thermal cleavage of carbamates, comprising a 250 ml four-necked flask, a 600 mm glass column filled with 5 x 5 mm glass rings, with heating and stirrer. As a reference, the results of the thermal cleavage served. The analysis of the test results was carried out by liquid chromatography (HPLC).
  • the reaction courses that is, the weight loss of the carbamate used in percent over time in minutes
  • curve I the course of the reaction for the thermal cleavage
  • curve II the course of the reaction for the cleavage in the presence of 1 mol% of heterogeneous Lewis acidic catalyst
  • curve III represents the course of the reaction in the presence of 10 mol% of the heterogeneous Lewis acidic catalyst.
  • the figures show that in the presence
  • the rate constants of the carbamate cleavage of the embodiments are shown. The rate constants show an increase up to 80 times for the catalytic cleavage compared to the thermal cleavage.
  • Figure 1 is a graphical representation of the reaction courses of the thermal cleavage compared to the novel catalytic cleavage in the presence of a heterogeneous Lewis acidic zeolites and
  • FIG. 2 shows the graphic representation of the reaction constants for the same cleavage reactions as in FIG. 1.
  • FIG. 1 shows on the ordinate the decrease in the concentration of the educt TDU in percent by weight over time, t [min], on the abscissa.
  • the upper curve I shows the course of the reaction for the thermal cleavage for comparison
  • curve II the course of the reaction for the catalytic cleavage in the presence of 1 mol% with zinc-treated Na-Y zeolite
  • the lower curve III the course of the reaction for the catalytic cleavage in the presence of 10 mol% Na-Y zeolite.
  • Curves II and III illustrating the examples according to the invention show a marked increase in the reaction rate over the comparative example, curve I, for purely thermal cleavage.
  • the representation in FIG. 2 shows the rate constants In (c 0 / c) on the ordinate with respect to time, tt 0 [min] on the abscissa, for the thermal cleavage, for comparison (curve I), for the inventive catalytic cleavage in the presence of 1 mol% zinc-treated Na-Y zeolite (curve II) or for the inventive catalytic cleavage in the presence of 10 mol% zinc-treated Na-Y zeolite (curve III).

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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'isocyanates par dissociation des carbamates correspondants, caractérisé en ce que la dissociation des carbamates se fait en présence d'un catalyseur hétérogène à base d'acide de Lewis.
EP11725938.2A 2010-06-22 2011-06-20 Dissociation de carbamate en présence d'un catalyse hétérogène pour la synthèse d'isocyanates sur des acides de lewis solides Withdrawn EP2585433A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11725938.2A EP2585433A1 (fr) 2010-06-22 2011-06-20 Dissociation de carbamate en présence d'un catalyse hétérogène pour la synthèse d'isocyanates sur des acides de lewis solides

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10166781 2010-06-22
PCT/EP2011/060176 WO2011161029A1 (fr) 2010-06-22 2011-06-20 Dissociation de carbamate en présence d'un catalyse hétérogène pour la synthèse d'isocyanates sur des acides de lewis solides
EP11725938.2A EP2585433A1 (fr) 2010-06-22 2011-06-20 Dissociation de carbamate en présence d'un catalyse hétérogène pour la synthèse d'isocyanates sur des acides de lewis solides

Publications (1)

Publication Number Publication Date
EP2585433A1 true EP2585433A1 (fr) 2013-05-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP11725938.2A Withdrawn EP2585433A1 (fr) 2010-06-22 2011-06-20 Dissociation de carbamate en présence d'un catalyse hétérogène pour la synthèse d'isocyanates sur des acides de lewis solides

Country Status (6)

Country Link
US (1) US20110313192A1 (fr)
EP (1) EP2585433A1 (fr)
JP (1) JP2013540101A (fr)
KR (1) KR20130089233A (fr)
CN (1) CN102947267A (fr)
WO (1) WO2011161029A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2445869B1 (fr) 2009-06-26 2014-12-24 Basf Se Procédé de fabrication d isocyanates, de préférence de diisocyanates et de polyisocyanates, avec recirculation du solvant
JP2012532918A (ja) 2009-07-16 2012-12-20 ビーエーエスエフ ソシエタス・ヨーロピア ジフェニルメタンジイソシアネート類の明色イソシアネートの製造方法
US8859805B2 (en) 2009-09-22 2014-10-14 Basf Se Process for preparing isocyanates
WO2011048124A1 (fr) 2009-10-21 2011-04-28 Basf Se Procédé de production d'uréthannes
WO2011051314A1 (fr) 2009-10-27 2011-05-05 Basf Se Procédé de production couplée de di- et/ou polyisocyanates et glycols
PT2507205E (pt) 2009-12-01 2014-08-22 Basf Se Processo para a produção de isocianatos por dissociação térmica de carbamatos
WO2011067369A1 (fr) 2009-12-04 2011-06-09 Basf Se Procédé de production d'isocyanates
US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
CN115569670A (zh) * 2022-09-29 2023-01-06 四川元理材料科技有限公司 异佛尔酮二氨基甲酸正丁酯工业化热裂解工艺中的催化剂

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US3734941A (en) * 1968-09-06 1973-05-22 American Cyanamid Co Process for converting urethanes to isocyanates
US3919279A (en) * 1974-06-26 1975-11-11 Atlantic Richfield Co Catalytic production of isocyanates from esters of carbamic acids
JPS5219624A (en) * 1975-08-07 1977-02-15 Mitsui Toatsu Chem Inc Process for preparation of isocyanates
DE2942543A1 (de) * 1979-10-20 1981-05-07 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von arylisocyanaten durch thermische spaltung von arylurethanen
JPS57158747A (en) * 1981-03-26 1982-09-30 Asahi Chem Ind Co Ltd Preparation of isocyanate
DE3215591A1 (de) * 1982-04-27 1983-10-27 Bayer Ag, 5090 Leverkusen Verfahren zur kontinuierlichen thermischen spaltung von carbamidsaeureestern
US5194660A (en) * 1990-12-21 1993-03-16 Union Carbide Chemicals & Plastics Technology Corporation Processes for producing carbamates and isocyanates
US5326903A (en) 1992-01-10 1994-07-05 Nippon Shokubai Co., Ltd. Process for preparing isocyanates using sintered oxides
DE59705128D1 (de) 1996-03-15 2001-12-06 Bayer Ag Verfahren zur thermischen Spaltung von Carbamidsäureestern
DE19907648A1 (de) 1999-02-23 2000-08-24 Basf Ag Verfahren zur Herstellung von Isocyanaten durch Spaltung von Urethanen
JP2001031639A (ja) * 1999-07-15 2001-02-06 Mitsubishi Gas Chem Co Inc １，５−ナフチレンジイソシアネートの製造方法
DE102004036499A1 (de) * 2004-07-28 2006-03-23 Degussa Ag Mehrstufiges Verfahren zur kontinuierlichen Herstellung von cycloaliphatischen Diisocyanaten
CN101011657A (zh) * 2007-01-25 2007-08-08 中国科学院成都有机化学有限公司 一种芳(烷)基氨基甲酸酯热分解制备异氰酸酯的催化剂及应用
CN101492397A (zh) * 2008-01-22 2009-07-29 中国科学院成都有机化学有限公司 连续制备1,6-六亚甲基二异氰酸酯的方法
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Also Published As

Publication number Publication date
WO2011161029A1 (fr) 2011-12-29
KR20130089233A (ko) 2013-08-09
JP2013540101A (ja) 2013-10-31
US20110313192A1 (en) 2011-12-22
CN102947267A (zh) 2013-02-27

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