WO2002050020A1 - Procede pour la production d'isocyanates - Google Patents

Procede pour la production d'isocyanates Download PDF

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Publication number
WO2002050020A1
WO2002050020A1 PCT/EP2001/014563 EP0114563W WO0250020A1 WO 2002050020 A1 WO2002050020 A1 WO 2002050020A1 EP 0114563 W EP0114563 W EP 0114563W WO 0250020 A1 WO0250020 A1 WO 0250020A1
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Prior art keywords
compound
carbamate
reaction
compounds
isocyanate
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PCT/EP2001/014563
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German (de)
English (en)
Inventor
Wilfried Hübner
Wolfgang Klauck
Johann Klein
Thomas Bachon
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU2002233243A priority Critical patent/AU2002233243A1/en
Publication of WO2002050020A1 publication Critical patent/WO2002050020A1/fr

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    • 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 present invention relates to a ner process for the preparation of isocyanates, in which at least one compound containing carbamate groups is converted to an isocyanate at a reaction temperature above the boiling point of an isocyanate formed.
  • Isocyanates represent a valuable raw material for the production of a number of monomeric and polymeric products.
  • the wide range of variation options with regard to the monomer composition in the production of polymers with the participation of polyisocyanates generally permit specific influencing of certain polymer properties.
  • the monoisocyanates also represent an increasingly frequently used building block for the functionalization of monomeric or polymeric compounds.
  • functional groups can also be introduced into molecules due to their Sensitivity to drastic reaction conditions cannot be attached to a molecule by means of reactions requiring such reaction conditions.
  • Organic compounds in particular polymers, which carry both a silyl group and a urethane or urea group are used in many branches of industry, for example in coating or adhesive technology.
  • the advantages of such compounds, in particular of such polymers lie in particular in their ability to develop a binding effect both to hydrophobic and to hydrophilic substrates and to crosslink them with one another in the event of moisture.
  • Adhesives that contain such polymers are able, for example, to permanently bond both hydrophilic and hydrophobic substrates, as well as substrates of different polarities.
  • an isocyanate carrying silyl groups is often used due to the sensitivity of the silyl groups to drastic reaction conditions, in particular due to their sensitivity to compounds bearing OH groups. Because of the high reactivity of isocyanate groups with respect to OH groups, such isocyanates permit simple and gentle introduction of silyl groups into molecules which carry a functional group which is reactive toward isocyanate groups.
  • US Pat. No. 6,008,396 describes a process for producing an isocyanato-organosilane in which a carbamato-organosilane is converted into an isocyanato-organosilane in an inert liquid medium.
  • a silyl carbamate is introduced into an inert reaction medium at a temperature of 200 to 400 ° C. and a pressure of 10 to 200 mbar, the carbamate being decomposed into the isocyanate.
  • the isocyanate distills into a receiver.
  • the fact that the introduction of the carbamate into the reaction medium often leads to a strong, difficult to control foam development has a disadvantage in the process described. This results in a low space-time yield due to the associated careful operation or a correspondingly voluminous reaction apparatus.
  • fractions of inert reaction medium are often found in the distilled product due to the passage of fine droplets.
  • US Pat. No. 5,886,205 describes a process for the preparation of an isocyanate containing silyl groups, in which a carbamic acid ester containing silyl groups is decomposed at a pH of at most 8 in the presence of a catalyst and is collected via a distillation column.
  • the backward reaction between isocyanate and alcohol in the bottom of the distillation and in the lower region of the distillation column require a high level of equipment to obtain the isocyanate.
  • the space-time yields in the process described are also low.
  • the present invention is therefore based on the object of making such a method available.
  • the task is solved by a method as described in the following text.
  • the present invention therefore relates to a process for the preparation of isocyanates, in which at least one compound having at least one carbamate group is converted to at least one isocyanate and at least one compound A which has functional groups X which are reactive toward isocyanate groups, the reaction being carried out at a reaction temperature above the boiling point of the isocyanate formed in the presence of at least one compound B which has a higher boiling point than the isocyanate formed and the compound A formed during the reaction or a mixture of two or more such compounds A, with regard to the reactivity of the compound A or the mixture two or more compounds A deactivated towards isocyanate groups.
  • a “carbamate group” is understood to mean a structural element of the general formula I.
  • radical R 8 is a linear or branched, saturated or unsaturated alkyl radical with 1 to about 10 C atoms, a saturated or unsaturated cycloalkyl radical with about 6 to about 24 C atoms, or an aryl radical with 6 to about 24 C atoms and X represents O or S.
  • carbamate group therefore also includes thiocarbamate groups in the context of the present invention.
  • a compound which can be used in the context of the present invention and has at least one carbamate group can have, for example, only one carbamate group. However, it is also possible according to the invention that such a compound has two or more carbamate groups.
  • isocyanates are understood to mean compounds with at least one NCO group. However, the term also includes compounds with two or more NCO groups. For the purposes of such compounds, the terms “isocyanates” and, Polyisocyanates "used synonymously.
  • Carbamates which can be used in the process according to the invention have at least one carbamate group.
  • Suitable carbamates can have, for example, two or more carbamate groups, provided that the isocyanates formed from such carbamates are still removed by distillation from the reaction mixture present during the reaction.
  • the carbamates which can be used according to the invention can in principle be of any nature, that is to say that the carbamate group or the two or more carbamate groups can be covalent with an optionally substituted linear or branched, saturated or unsaturated aliphatic or a saturated or unsaturated cycloaliphatic radical having 2 to about 44 C atoms be connected.
  • Carbamates which are linked to an optionally substituted aromatic or araliphatic radical having 6 to about 44 C atoms can likewise be used in the context of the present invention. In principle, therefore, all customary aliphatic or aromatic mono- or polyisocyanates can be prepared by the process according to the invention, provided the corresponding mono- or polycarbamates are accessible.
  • carbamates are used in the process according to the invention which, in addition to the carbamate group, have at least one further functional group.
  • Carbamates which are preferred in the context of the present invention for carrying out the process according to the invention have, for example, at least one ether group, thioether group or a silyl group as the functional group.
  • a “silyl group” is understood to mean a functional group of the general formula U
  • a compound which carries a silyl group according to the general formula ⁇ is used as at least one compound bearing carbamate groups.
  • Suitable compounds with at least one carbamate group are in particular compounds of the general formula HI
  • R 7 for an optionally substituted alkylene radical having 1 to about 44 C atoms, an optionally substituted cycloalkenyl radical with 6 to about 24 C. -Atoms or an optionally substituted arylene radical having 6 to about 24 carbon atoms and Z represents a carbamate group.
  • Suitable substituents for R 7 are, for example, functional groups such as thioether, mercapto, amino, ester, amido, nitro or ether groups or mixtures of two or more thereof.
  • R 7 has none of the above-mentioned substituents.
  • Carbamates such as can be used in the process according to the invention in the context of the present invention can be, for example, by reacting an amine, for example an aminosilane, with a dialkyl or diaryl carbonate or a dialkyl or diaryl pyrocarbonate, or a mixture of two or more thereof, receive. Such a reaction is usually carried out in the presence of a basic catalyst. In principle, however, all other processes known to those skilled in the art are also suitable for the production of carbamates. Suitable is e.g. the implementation of amino compounds, for example aminososilanes, with chloroformic acid esters.
  • Suitable carbonates for the preparation of the carbamates which can be used in the process according to the invention are, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, di-tert-butyl carbonate, diisopentyl carbonate, diisopropyl carbonate, ethyl methyl carbonate, ethyl 2- butoxyethyl carbonate, bis (2-chloroethyl) carbonate, diphenyl carbonate, bis (o, m-chlorophenyl) carbonate, bis (o, p-chlorophenyl) carbonate, bis (dichlorophenyl) carbonate, bis (trichl ⁇ henyl) carbonate or bis (o-, m -, p-Tolyl) carbonate or mixtures of two or more thereof.
  • Suitable dialkyl pyrocarbonates are, for example, dimethyl pyrocarbonate, diethyl pyrocarbonate or di-tert-butyl pyrocarbonate.
  • carbamates for example carbamatosilanes, are preferably used which have been prepared using dimethyl carbonate, diethyl carbonate or dipropyl carbonate or pyrocarbonate or mixtures of two or more thereof.
  • the reaction between the aminosilane and the organic carbonate can take place, for example, using stoichiometric amounts of the reactants. However, it is also possible and often preferred to use an excess of organic carbonate from about 0.05 to about 1 mole per mole of aminosilane. Good results can be achieved, for example, with an excess of carbonate of about 0.1 to about 0.4 moles per mole of aminosilane. With higher molecular weight aminosilanes, for example a molecular weight of more than about 200 or more than about 500 or with aminosilanes with a sterically hindered amino group, it may be necessary to use a higher excess of carbonate.
  • the reaction between amino compound and carbonate is usually catalyzed by a basic catalyst.
  • a strongly basic catalyst is preferably used here.
  • Suitable basic catalysts are, for example, alkali metal alkoxides, as can be obtained by reacting monohydric alcohols with alkali metals.
  • Suitable alkali metals are for example lithium, sodium or potassium
  • suitable monohydric alcohols are for example methanol, ethanol, propanol or butanol.
  • Suitable strongly basic catalysts are in particular sodium methoxide, sodium ethanolate, sodium propanolate, sodium tert-butoxide, potassium methoxide, potassium ethanolate, potassium propanolate or potassium tert-butoxide and the like.
  • the amount of catalyst during the reaction is about 0.01 to about 2% by weight, based on the carbonate and amine used.
  • the reaction between amine and organic carbonate is slightly exothermic.
  • amine and organic carbonate are reacted with one another in the presence of the basic catalyst such that the reaction temperature remains within a range of about 10 to about 120 ° C, for example about 20 to about 80 ° C or about 25 to about 60 ° C.
  • the constancy of the temperature within this range can be achieved, for example, by conventional cooling methods such as cold water, ice bath, dry ice bath or by controlling the rate of addition of the reactants.
  • the reaction is usually carried out at ambient pressure under a protective gas atmosphere.
  • Suitable neutralizing agents are, for example, inorganic acids such as anhydrous hydrochloric acid, anhydrous phosphoric acid or organic acids such as glacial acetic acid, propionic acid, butyric acid, hexanoic acid, oleic acid, maleic acid, fumaric acid, succinic acid and the like.
  • Weak organic acids such as glacial acetic acid or inorganic acids such as anhydrous phosphoric acids, for example superphosphoric acid or polyphosphoric acid or, if present, their anhydrides are preferably used for the neutralization.
  • reaction product can be separated off using customary methods known to the person skilled in the art.
  • separation of precipitated salts by filtration for example over silica gel or a suitable filter paper, and subsequent removal of volatile components by reduced pressure or temperature increase or both, is particularly suitable.
  • all compounds which have at least one amino group are suitable for the preparation of carbamates suitable in the context of the present invention. Such compounds are referred to in the context of the present text as synonymous as amines or amino compounds.
  • Amines suitable for the preparation of carbamates suitable for use in the context of the present invention are, for example, monoalkylamines such as ethylamine, propylamine, butylamine, pentylamine, hexylamine and their linear or branched higher homologues with up to about 100 C atoms, the position of the amino group being terminal or can be located anywhere within the alkyl group.
  • the alkyl group of the monoalkylamines can optionally be substituted.
  • Suitable substituents are, for example, hydroxyl groups, ester groups, carboxylic acid groups, sulfonic acid groups, phosphonic acid groups and the corresponding esters of the acid groups mentioned.
  • amino compounds which have two or more amino groups are also suitable for producing carbamates which are suitable in the context of the present invention.
  • These compounds include, for example, butylene diamine, hexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, diethylene triamine, 1,12-diaminododecane, diamines derived from dimer fatty acids or triamines derived from trimer fatty acids, or mixtures of two or more of the compounds mentioned.
  • amino compounds which have a saturated or unsaturated, optionally substituted cycloalkyl radical having 6 to about 24 C atoms are used for the production of carbamates which can be treated in the process according to the invention.
  • a corresponding cycloalkyl group can have one or more amino groups.
  • Suitable cycloalkyl compounds are, for example, cyclohexylamine, dicyclohexylamine, 1,4-cyclohexyldiamine, 4,4'-dicyclohexylmethane diamine,
  • Isophoronediamine 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and hydrogenated toluenediamines such as l-methyl-2,4, -diaminocyclohexane, l-methyl-2,6, -diaminocyclohexane and the like.
  • the optionally substituted aryl groups with 6 to about 24 C- Have atoms are, for example, aniline, 1,4-diaminobenzene, aminotoluene, m- or p-phenylenediamine, diaminobiphenyl, p-methoxyaniline, p-chloroaniline, o-, m- or p-toluidine, 2,4-xylidine, 2 , 4-, and 2,6-toluenediamine and corresponding mixtures, 4,4'-diphenylenediamine, methylene bis (aniline), including 4.4, methylenebis (aniline), 2,4'-methylenebis (aniline), 4,4 ' -Oxybis (aniline), 4,4'-carbonylbis (aniline), 4,4'-sulfonylbis (aniline) or
  • aminosilanes are used in the process according to the invention for the production of the carbamates which can be treated according to the invention.
  • Suitable aminosilanes are, for example, N- ( ⁇ -memyldimethoxysilylmeyl) amine, N- ( ⁇ -trimemoxysilylmeyl) amine, N- ( ⁇ -dimethylmethoxysilylmyl) amine, N- ( ⁇ -)
  • Triethoxysilyknethyl N- ( ⁇ -Emyldiemoxysilylme yl) amine, N- (ß-
  • Memyldimethoxysilylethyl) amine N- (ß-trimethoxysilylethyl) amine, N- (ß-)
  • Triethoxysilylethyl) amine N- (ß-ethyldiethoxysilylethyl) amine, N- ( ⁇ -methyldimethoxysilylpropyl) amine, N- ( ⁇ -trimethoxysilylpropyl) amine, N- ( ⁇ -ethyldimethoxysilylpropyl) amine, N- (di- ) amine, N- ( ⁇ -triethoxysilylpropyl) amine, N- ( ⁇ -ethyldiethoxysilylpropyl) amine, N- (4-memyldimethoxysilylbutyl) amine, N- (4-trimethoxysilylbutyl) amine, N- (4-triethylsilinbutyl) silylbutyl) (4-
  • Methyldiethoxysilylbutyl) amine N- (4-triethoxysilylbutyl) amine, N- (4-
  • Methyldimethoxysilylpentyl) amine N- (5-trimethoxysilylpentyl) amine, N- (5-triethylsilylpentyl) amine, N- (5-ethyldimethoxysilylpentyl) amine, N- (5-methyldiethoxysilylpentyl) amine, N- (5-triethyl) amine, N- (5-triethyl) , N- (5-dimethyl oxysilylpentyl) amine, N- (5- (5-(5)-
  • Methyldiethoxysilylhexyl) amine N- (6-triethoxysilylhexyl) amine, N- (6-ethyl- diethoxysilylhexyl) amine, N- [ ⁇ -tris (trimethoxysiloxy) silylpropyl] amine, N- [ ⁇ -tris (trimethoxysiloxy) silylpropyl] amine, N- ( ⁇ -trimethoxysiloxydimethylsilylpropyl) amine, N- ( ⁇ -trimemylsilyl) ammylsilylpimylsilylpropyl) - ( ⁇ -triethoxysiloxydiemylpropyl) arnine, N- ( ⁇ -triethoxysiloxychethoxysilylpropyl) amine, N, N-butyl- ( ⁇ -trimemoxysilylpropyl) amine, N, N-butyl ( ⁇ -triethoxys
  • Trimethoxysilylpropyl) amine N, NE yl- ( ⁇ -trimemoxysilylpropyl) arnine, diethyl-N- (trimethoxysilylpropyl) aspartate, diethyl-N- (triethoxysilylpropyl) aspartate N, N-ethyl- ( ⁇ -dimemoxymethylnilnylpropyl) Ethyl ( ⁇ -trimethoxysilylisobutyl) amine, N, N-bis (trimethoxypropyl) amine, N, N-ethyl- ( ⁇ -trimethoxysilylisobutyl) amine, N, N-ethyl ( ⁇ -trimethoxysilynethyl) amine, dibutyl -N- (trimethoxysilylpropyl) aspartate, dibutyl-N- (triethoxysilylpropyl) aspartate, N, N-
  • Carbamatosilanes according to the general formula LTJ can be prepared from the aminosilanes mentioned in accordance with the process described above.
  • Carbamatosilanes of the general formula UI which are particularly suitable for use in the process according to the invention are, for example, methyl N- ( ⁇ -methyldimethoxysilylknethyl) carbamate, methyl N- ( ⁇ -trimethoxysilylknethyl) carbamate, methyl-N- ( ⁇ -ethyldimethoxysilylmethyl) carbamate, methyl -N- ( ⁇ -methyldiethoxysilylmethyl) carbamate, methyl-N- ( ⁇ -triethoxysilylmethyl) carbamate, methyl-N- (ß-methyldimethoxysilylethyl) carbamate, methyl-N- (ß-trimethoxysilylethyl) carbamate, methyl-N - (ß-Diethynethoxysilylethyl) carbamate, methyl-N- (ß-ethyldimethoxysilylethyl) carbamate, methyl-N
  • Ethyldimethoxysilylpropyl) carbamate methyl N- ( ⁇ -methyldiethoxysilylpropyl) carbamate, methyl N- ( ⁇ -triethoxysilylpropyl) carbamate, methyl N- ( ⁇ - Ethyl diethoxysilylpropyl) carbamate, methyl N- (4-trimethoxysilylbutyl) carbamate, methyl N- (4-ethyldimethoxysilylbutyl) carbamate, methyl N- (4-methyldiethoxysilylbutyl) carbamate, methyl N- (4-triethutylsilyl), carbamate Methyl-N- (4-ethyldiethoxysilyl-butyl) carbamate, methyl-N- (5-methyldimethoxysilylpentyl) carbamate, methyl-N- (5-trimethoxysilylpentyl) carbamate, methyl-N- (5
  • Triethoxy silylpentyl) carbamate methyl N- (5-ethyldiethoxysilylpentyl) carbamate, methyl N- (6-trimethoxysilylhexyl) carbamate, methyl N- (6-ethyldimethoxysilylhexyl) carbamate, methyl-N- (6-triethoxysilylhexyl carbamate, methyl-N- (6-ethyl-diethoxysilylhexyl) carbamate, methyl-N- [ ⁇ -tris (trimethoxysiloxy) silylpropyl] carbamate, ethyl-N- ( ⁇ -methyldimethoxysilylmethyl) carbamate, ethyl-N- ( ⁇ -tri - methoxysilylmethyl) carbamate, ethyl-N- ( ⁇ -methyldiethoxysilyknethyl) carbamate, ethyl-N- (
  • Dimethylethoxysilylethyl) carbamate ethyl-N- (ß-methyldiethoxysilylethyl) carbamate, ethyl-N- (ß-triethoxysilylethyl) carbamate, ethyl-N- ( ⁇ -trimethoxysilylpropyl) carbamate, ethyl-N- ( ⁇ -ethyldimethoxyl) carbamate N- ( ⁇ -methyldiethoxysilylpropyl) carbamate, ethyl N- ( ⁇ -triethoxysilylpropyl) carbamate, ethyl N- ( ⁇ -ethyldiethoxysilylpropyl) carbamate, ethyl N- (4-methyldimethoxysilylbutyl) carbamate,
  • reaction according to the process of the invention can be carried out without a catalyst.
  • reaction according to the method according to the invention takes place in the presence of a catalyst.
  • Suitable catalysts are, for example, compounds of the general formula IV
  • M is a metal selected from the group consisting of aluminum, titanium, magnesium or z conium and R 9 is identical or different linear or branched hydrocarbon radicals having 1 to 8 carbon atoms and x is 2, 3 or 4.
  • Suitable catalysts are, for example, aluminum alkoxides, titanium alkoxides, magnesium alkoxides and zconium alkoxides.
  • aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum trisec-butoxide, aluminum tri-tert-butoxide, titanium ( ⁇ N) methoxide, titanium (rV) ethoxide, titanium (TN) isopropoxide, titanium (IN) butoxide, titanium (IV) are particularly suitable.
  • Tin compounds in particular organotin carboxylates such as dibutyltin dilaurate, are also suitable as catalysts in the process according to the invention, Dibutyltin diacetate, dibutyltin bis (2-ethylhexanoate) or others
  • Organotin compounds such as dibutyltin oxide, dibutyltin dimethoxide,
  • Dimethyltin dibromide, dimethyltin dichloride, diphenyltin dichloride or tin octoate are preferred.
  • dibutyltin dilaurate, dibutyltin oxide and dibutyltin diacetate are preferred.
  • Neritatien which have at least one of the metals selected from the group consisting of antimony, iron, cobalt, nickel, copper, chromium, manganese, molybdenum, tungsten or lead.
  • the oxides, halides, carboxylates, phosphates or organometallic compounds of the metals mentioned are particularly suitable.
  • iron acetate, iron benzoate, iron naphthenates are particularly suitable; Iron acetylacetonates, manganese acetate, manganese naphthenate and manganese acetylacetonate.
  • the amount of catalyst used in the process according to the invention is in a range from 0 to about 0.8% by weight, for example about 0.01 to about 0.5% by weight, in particular about 0.05 up to about 0.2% by weight, based on the total amount of carbamate.
  • reaction according to the invention is carried out at a reaction temperature above the boiling point of the isocyanate formed or the mixture of two or more isocyanates in the presence of at least one compound B which has a higher boiling point than the isocyanate formed and the Compound A formed during the reaction or a mixture of two or more such compounds A is deactivated with regard to the reactivity of compound A or the mixture of two or more compounds A with isocyanate groups.
  • the at least one compound B is used in such an amount that at least 1.1 times the amount of compounds A which are formed at most during the reaction can be deactivated.
  • the maximum amount of compounds A formed during the reaction can be determined in a simple manner within the scope of the present invention by making the assumption that each mole of carbamate groups present in the reaction mixture releases a maximum of one mole of compound A.
  • the compound B is used in such an amount that at least twice the amount of compounds A which are formed at most during the reaction can be deactivated.
  • the carbamates to be treated according to the invention are preferably selected such that a preferably monofunctional alcohol having 1 to about 8 carbon atoms, in particular 1 to 3 carbon atoms, is formed as compound A.
  • Deactivation of a compound A or a mixture of two or more compounds A by a compound B or a mixture of two or more such compounds can be carried out physically or chemically in the context of the present invention.
  • a suitable method for physical deactivation consists, for example, in adding a compound to the reaction mixture which, owing to adsorption of molecules of compound A, deactivates it for a further reaction with an isocyanate formed in the process according to the invention.
  • a suitable class of compounds of compounds B are, for example, the zeolites.
  • Zeolites have cavities different polarity, in which polar molecules of compound A can be reversibly incorporated and thus removed from the reaction mixture.
  • the deactivation of the zeolites can be supported, for example, by carrying out the implementation according to the invention in an environment which is essentially non-polar.
  • the adsorption of a polar compound A in a polar zeolite can be supported, for example, by a non-polar environment.
  • the amount of compound B is preferably selected such that at room temperature at least twice, for example at least 3, 4 or 5 times the amount of compounds A which are formed at most during the reaction can be deactivated.
  • the method according to the invention can be carried out with a compound B or a mixture of two or more such compounds B which cause chemical deactivation.
  • the functional group HX is bound in a covalent bond in such a way that the compound A is at least temporarily no longer available for a reaction with an isocyanate group formed in the course of the process according to the invention.
  • Compounds B which are suitable for the chemical deactivation of a compound A in the process according to the invention are therefore compounds which have one or more functional groups Y which form a covalent bond with a functional group HX of a compound A.
  • Suitable functional groups Y in the context of the present invention are in principle all functional groups which can form a covalent bond with the functional groups HX of the compound A under the reaction conditions.
  • a compound is therefore used as compound B which, as functional group Y, has an NCO group, an epoxy group, a carboxylic acid group, an anhydride group or a carboxylic acid chloride group or a mixture of two or more thereof.
  • at least one compound selected from the group consisting of isocyanates, epoxides, carboxylic acids or carboxylic acid anhydrides and carboxylic acid chlorides is therefore used as compound B.
  • Suitable compounds B have, for example, one or more NCO groups. Such compounds react with a functional group HX of a compound A to form a covalent bond and thus at least temporarily remove the compound A from the reaction mixture. Since in the process according to the invention this covalent bond can also be cleaved with renewed release of a compound A, the amount of compounds B which has one or more NCO groups is preferably such that the molar ratio of functional groups Y to the maximum The amount of functional groups HX formed during the reaction is at least 1.1 to 1.
  • the amount of compounds B is dimensioned such that at least 1.5 times, but preferably at least 2 times, for example at least 3, 4 or 5 times the amount during the Implementation of the resulting connections A can be deactivated.
  • Suitable compounds with at least one NCO group are, for example, monoisocyanates, such as the linear or branched aliphatic monoisocyanates having 6 to 44 carbon atoms, for example hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tridecyl isocyanate, quaterdecyl isocyanate, pentadecyl isocyanate, pentadecyl isocyanate, pentadecyl isocyanate , Octadecyl isocyanate and the corresponding higher homologues of this series, as they result from a gradual extension of the carbon chain by one carbon atom each.
  • Aromatic monoisocyanates such as phenyl isocyanate, benzyl isocyanate or biphenyl isocyanate and
  • Also suitable as compounds with at least one NCO group are compounds from the group of the diisocyanates, for example tekamethylene diisocyanate, Hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, dimer fatty acid diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDi), 4,4'-diisocyanato-dicyclohexylmethane , 4'-Diisocyanato-dicyclohexylpropane-2,2, 1,3- and 1,4-diisocyanatobenzene, 2,4- or 2,6-diisocyanatotoluene (2,4- or 2,6-TDI) or a mixture thereof , 2,2'-, 2,4 or 4,4'-diisocyanatodip
  • monoisocyanates are used as the compound B carrying NCO groups.
  • epoxides Compounds B which have at least one epoxy group (epoxides) can likewise be used as compounds B in the context of the present invention.
  • Suitable epoxides in the context of the present invention are, for example, epoxidized, unsaturated fatty acids or the reaction products of aromatic hydroxy compounds with epichlorohydrin, for example the diglyzidyl ether of bisphenol A or epoxidized long-chain olefins having at least about 8 carbon atoms.
  • Carboxylic acids, their anhydrides or chlorides can also be used as compounds B in the context of the present invention.
  • Suitable monocarboxylic acids are, for example, the linear or branched, saturated or unsaturated, homologous alkane carboxylic acids with 8 to about 44 carbon atoms, as are known in particular from fat chemistry.
  • Typical examples of such acids are caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, paknitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, pecoselic acid, linoleic acid, linolenic acid, elaeostearic acid, and technical acid, erachic acid, arachene acid, arachene acid Mixtures that occur, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids.
  • Suitable polycarboxylic acids are, for example succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, glutaric anhydride, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, TekahydrophthalTexreanhydrid, hexahydrophthalic anhydride, TekacMorphthal Acidanhydrid, hydrophthalic Endomethylentefra-, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acids or trimer fatty acids or Mixtures of two or more of the polycarboxylic acids mentioned.
  • the anhydrides (if any) or acid chlorides of the carboxylic acids mentioned are also suitable.
  • the process according to the invention is preferably carried out at a pH of about 0 to about 12, in particular about 1 to about 7, for example about 2 to about 5.
  • At least one preferably anhydrous inorganic acid for example HCl, H 2 SO 4 , phosphoric acid or partial phosphoric acid ester, is added to the reaction mixture.
  • the reaction is preferably carried out at a temperature of about 50 to about 300, in particular about 50 to about 250 ° C. Suitable reaction temperatures are in particular in a range from about 80 to about 220 or about 150 to about 190 ° C.
  • the reaction time is about 0.1 to about 10 hours. In a preferred embodiment of the present invention, the reaction conditions are chosen so that the reaction time is about 0.5 to about 3 hours.
  • the process according to the invention can optionally be carried out in an inert solvent or dispersant which does not boil at the reaction temperature. This is particularly recommended when a compound whose melting point is above the reaction temperature is used as compound B.
  • the boiling temperature of such a solvent or dispersant should be higher than the boiling temperature of the isocyanate formed.
  • Aromatic or aliphatic oils with a boiling point of more than about 150 ° C. are suitable for this purpose. Corresponding oils are described, for example, in EP-B 0 870 769, the corresponding oils disclosing disclosure of which are understood as part of the disclosure of the present text.
  • the process according to the invention can also be carried out in such a way that the reaction is carried out in the melt of one of the compounds present in the course of the reaction, in particular in the melt of a compound B or a mixture of two or more compounds B.
  • a compound or a mixture of two or more compounds is therefore used as compound B, the melting point of which lies within the range specified for the reaction temperature.
  • the solvent or dispersant or the compounds B or a mixture of solvent or dispersant and compounds B is initially introduced, optionally kneaded and optionally mixed with a catalyst or a catalyst system composed of two or more different catalysts. If necessary, a corresponding amount of inorganic acid can be added to regulate the pH at this point.
  • the mixture thus obtained is then brought to the reaction temperature and the carbamate to be reacted or a mixture of two or more carbamates is added.
  • the isocyanate formed is preferably collected in a receiver via a corresponding distillation device, for example a Vigreux or sieve plate column.
  • a corresponding distillation device for example a Vigreux or sieve plate column.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour la production d'isocyanates, selon lequel au moins un composé contenant des groupes carbamate est transformé en un isocyanate à une température de réaction supérieure au point d'ébullition d'un isocyanate se formant. La réaction se produit à une température de réaction supérieure au point d'ébullition de l'isocyanate se formant ou du mélange de deux ou de plusieurs isocyanates, en présence d'au moins un composé B qui désactive un composé A se formant lors de la réaction ou un mélange de deux ou de plusieurs composés A de ce type, la désactivation concernant la réactivité du composé A ou du mélange de deux ou de plusieurs composés A aux groupes isocyanate.
PCT/EP2001/014563 2000-12-21 2001-12-12 Procede pour la production d'isocyanates WO2002050020A1 (fr)

Priority Applications (1)

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AU2002233243A AU2002233243A1 (en) 2000-12-21 2001-12-12 Method for producing isocyanates

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DE10064104.0 2000-12-21
DE10064104 2000-12-21

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WO2002050020A1 true WO2002050020A1 (fr) 2002-06-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1160239A2 (fr) * 2000-06-01 2001-12-05 Repsol Quimica S.A. Procédé de préparation d'isocyanates
EP1484331A1 (fr) * 2003-06-05 2004-12-08 Wacker-Chemie GmbH Procédé de préparation des composés organosiliciques contenant un groupement isocyanate
WO2005055974A2 (fr) * 2003-12-11 2005-06-23 Consortium für elektrochemische Industrie GmbH Procede de production d'isocyanato-organosilanes

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7825243B2 (en) 2005-06-03 2010-11-02 Momentive Performance Materials Inc. Process for the production of isocyanatosilane and silylisocyanurate
US7060849B1 (en) 2005-09-15 2006-06-13 General Electric Company Method for production of isocyanatosilanes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5886205A (en) * 1996-04-15 1999-03-23 Takeda Chemical Industries, Ltd. Process for producing silicon-containing isocyanate compound
US6008396A (en) * 1997-04-11 1999-12-28 Osi Specialties, Inc. Hot oil process for producing isocyanato organosilanes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5886205A (en) * 1996-04-15 1999-03-23 Takeda Chemical Industries, Ltd. Process for producing silicon-containing isocyanate compound
US6008396A (en) * 1997-04-11 1999-12-28 Osi Specialties, Inc. Hot oil process for producing isocyanato organosilanes

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1160239A2 (fr) * 2000-06-01 2001-12-05 Repsol Quimica S.A. Procédé de préparation d'isocyanates
EP1160239A3 (fr) * 2000-06-01 2003-07-30 Repsol Quimica S.A. Procédé de préparation d'isocyanates
EP1484331A1 (fr) * 2003-06-05 2004-12-08 Wacker-Chemie GmbH Procédé de préparation des composés organosiliciques contenant un groupement isocyanate
WO2005055974A2 (fr) * 2003-12-11 2005-06-23 Consortium für elektrochemische Industrie GmbH Procede de production d'isocyanato-organosilanes
WO2005055974A3 (fr) * 2003-12-11 2005-07-28 Consortium Elektrochem Ind Procede de production d'isocyanato-organosilanes
US7385069B2 (en) 2003-12-11 2008-06-10 Wacker Chemie Ag Method for producing isocyanate-organosilanes
CN100415751C (zh) * 2003-12-11 2008-09-03 瓦克化学股份公司 制造异氰酸酯基有机硅烷的方法

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