WO2007088152A1 - Procédé de production d'isocyanates - Google Patents

Procédé de production d'isocyanates Download PDF

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Publication number
WO2007088152A1
WO2007088152A1 PCT/EP2007/050829 EP2007050829W WO2007088152A1 WO 2007088152 A1 WO2007088152 A1 WO 2007088152A1 EP 2007050829 W EP2007050829 W EP 2007050829W WO 2007088152 A1 WO2007088152 A1 WO 2007088152A1
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ions
methyl
pyridinium
ethyl
butyl
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PCT/EP2007/050829
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German (de)
English (en)
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Christian Kuhrs
Wolfgang Staffel
Stefan Maixner
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to a process for the preparation of isocyanates by reacting olefins with isocyanic acid in a solvent.
  • Isocyanates are produced in large quantities and serve mainly as starting materials for the production of polyurethanes. They have hitherto been produced predominantly by reacting the corresponding amines with phosgene.
  • the continuous production of organic isocyanates by reaction of primary organic amines with phosgene is widely described and is carried out on an industrial scale (see, eg, Ullmanns Enzyklopadie der Technischen Chemie, Volume 7 (Polyurethanes), 3rd revised edition, Carl Hanser Verlag, Kunststoff - Vienna, pages 76 ff. (1993)).
  • isocyanates can be carried out without the use of phosgene by addition of isocyanic acid (HNCO) to olefins.
  • HNCO isocyanic acid
  • the reaction was carried out in the liquid phase at about room temperature.
  • HNCO was obtained by the thermal decomposition of cyanuric acid.
  • 1-butoxyethyl isocyanate by addition of butyl vinyl ether to a stirred mixture of benzene, isocyanic acid and catalytic amounts of p-toluenesulfonic acid and subsequent distillation of the resulting product.
  • a mixture of vinyl butyl ether and isocyanic acid is added dropwise to a stirred mixture of diethyl ether and catalytic amounts of p-toluenesulfonic acid.
  • a disadvantage of this method is that only very reactive olefins can be reacted with activated double bond, and that HNCO must be isolated as a pure substance in liquid form.
  • the object of the invention is to provide an advantageous process for the preparation of isocyanates.
  • the object is achieved by a process for the preparation of isocyanates by reacting olefins with isocyanic acid in a solvent, characterized in that the solvent is an ionic liquid.
  • HNCO is soluble in ionic liquids and stabilized.
  • high HNCO concentrations can be provided in the liquid phase without trimerization of HNCO to cyanuric acid. Liquefaction of HNCO can be omitted. This is generally added in gaseous form.
  • stabilization reduces the volatility of HNCO. Higher temperatures and / or HNCO concentrations, however, require higher reaction rates.
  • ionic liquids are understood as meaning compounds which have at least one cationic center and at least one anionic center, in particular at least one cation and at least one anion, one of the ions, in particular the cation, being organic.
  • Ionic liquids are, according to the definition of Wasserscheid and Keim in: Angewandte Chemie 2000, 1 12, 3926-3945 at relatively low temperatures melting salts of non-molecular, ionic character. They are already liquid at relatively low temperatures and relatively low viscous. They have very good solubilities for a large number of organic, inorganic and polymeric substances. In addition, they are generally non-flammable, non-corrosive and have no measurable vapor pressure.
  • Ionic liquids are compounds that are formed from positive and negative ions, but are charge-neutral overall.
  • the positive as well as the negative ions are predominantly monovalent, but it is also possible to use multivalent anions and / or cations, for example one to five, preferably one to four, more preferably with one to three and most preferably with one to two electrical charges per ion.
  • the charges may be located at different localized or delocalized regions within a molecule, ie, betaine-like, or even distributed as a separate anion and cation. Preference is given to those ionic liquids which are composed of at least one cation and at least one anion.
  • the invention is not limited to special ionic liquids; It is possible to use all suitable ionic liquids, including mixtures of different ionic liquids.
  • n 1, 2, 3 or 4
  • [A] + is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y] n 'is a , di-, trivalent or tetravalent anion;
  • the ionic liquids have a melting point of less than 180 ° C.
  • the melting point is particularly preferably in the range from -50 ° C. to 150 ° C., more preferably in the range from -20 ° C. to 120 ° C., and especially preferably below 100 ° C.
  • Such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1 to 10 nitrogen atoms, especially preferably 1 to 5, very particularly preferably 1 to 3 and in particular 1 to 2 nitrogen atoms.
  • nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion to produce an electrically neutral molecule.
  • a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle.
  • the quaternization can be carried out by alkylation of the nitrogen atom.
  • salts with different anions are obtained.
  • this can be done in a further synthesis step.
  • the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid.
  • replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the metal halide formed, via a ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 112, p. 3926-3945 and the literature cited therein.
  • Suitable alkyl radicals with which the nitrogen atom in the amines or nitrogen heterocycles can be quaternized are C 1 -C 8 -alkyl, preferably C 1 -C 10 -alkyl, particularly preferably C 1 -C 6 -alkyl and very particularly preferably methyl.
  • the alkyl group may be unsubstituted or have one or more identical or different substituents.
  • radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms;
  • radicals R 1 to R 9 independently of one another are hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical having 1 to 20 carbon atoms, where the radicals R 1 to R 9 , which in the abovementioned formulas (III) are bonded to a carbon atom (and not to a heteroatom), can additionally also stand for halogen or a functional group ; or
  • the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
  • the radicals R 1 to R 9 can in the cases in which these in the above formulas (IM) to a carbon atom (and not bound to a heteroatom) may also be bound directly via the heteroatom.
  • Functional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR'- (tertiary amide), are included, for example, di- (Ci-C 4 alkyl) amino, CrC 4 - alkyloxycarbonyl or dC 4 alkyloxy.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R preferably stands for
  • Fluoromethyl pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;
  • R A O- (CH 2 CH 2 CH 2 CH 2 O) m -CH 2 CH 2 CH 2 CH 2 O- with R A and R B preferably hydrogen, methyl or ethyl and m preferably 0 to 3, in particular 3-oxabutyl .
  • N, N-di-d-Ce-alkyl-amino such as N, N-dimethylamino and N 1 N-diethylamino.
  • the radical R is unbranched and unsubstituted C 1 -C 1 represents 1 8 alkyl, such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, -Decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, in particular methyl, ethyl, 1-butyl and 1-octyl, and also CH 3 O- (CH 2 CH 2 O) n -CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2 - with m equal to 0 to 3.
  • C 1 -C 1 represents 1 8 alkyl, such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl
  • radicals R 1 to R 9 are preferably each independently
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups Ci 8 alkyl;
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C 2 -Ci ⁇ alkenyl;
  • aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C 6 -C 2 -aryl;
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted d-C-i ⁇ -alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl , 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3 pentyl,
  • C 1 -C 2 -aryl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, toIyI, xylyl, .alpha.-naphthyl, .beta.-naphthyl, 4 -Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, / so-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropyl
  • C 5 -C 2 -cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthio cyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C m F 2 ( m -a) - (ib) H 2 3 -b with m ⁇ 30, 0 ⁇ a ⁇
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, Oxygen-, nitrogen- and / or sulfur-containing heterocycle are preferably furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-Ci-C 4 -Alkyl-1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1, 4-buta-1,3-dienylene or 2-aza-1,4-buta -1, 3-
  • radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
  • radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.
  • radicals R 1 to R 9 are each independently
  • R 1 is - (CH 2 CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 CH 2 O- with R A and R B is preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9, 12-tetraoxatetradecyl;
  • N 1 N-di-Cr to C ⁇ -alkyl-amino, such as N, N-dimethylamino and N 1 N-diethylamino.
  • the radicals R 1 to R 9 independently of one another are hydrogen or C 1 -C 8 -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl Phenyl, for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N- Diethylamino, for chlorine and for CH 3 O- (CH 2 CH 2 O) m - CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2 - with m is 0 to third
  • pyridinium ions which are those in which • one of the radicals R 1 to R 5 is methyl, ethyl or chlorine and the remaining radicals R 1 to R 5 are hydrogen;
  • R 3 is dimethylamino and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 1 and R 2 or R 2 and R 3 are 1, 4-buta-1, 3-dienylene and the remaining R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 1 to R 5 are hydrogen
  • pyridinium ions (IIIa) which may be mentioned are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) -pyridinium, 1 (1-Hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium, 1, 2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl)
  • R 1 to R 4 are hydrogen
  • radicals R 1 to R 4 are methyl or ethyl and the remaining radicals R 1 to R 4 are hydrogen
  • MIc very particularly preferred pyrimidinium ions
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl; or R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl;
  • R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen;
  • R 1 to R 4 are methyl
  • R 1 to R 4 are methyl hydrogen.
  • Imidazoliumionen are those in which
  • R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 are independently hydrogen, methyl or ethyl ,
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • R 1 to R 4 are independently hydrogen or methyl.
  • R 1 to R 6 are hydrogen or methyl.
  • MIj 2-pyrazolinium
  • MIj ' 2-pyrazolinium
  • R 1 is hydrogen, methyl, ethyl or phenyl
  • R 2 to R 6 are independently hydrogen or methyl.
  • MIk 3-pyrazolinium ions
  • MIk ' 3-pyrazolinium ions
  • R 1 and R 2 are independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R 3 and R 4 are independently hydrogen, methyl or ethyl, and R 5 and R 6 are independently hydrogen or methyl.
  • Imidazoliniumionen (Ulm) or (MIm ') are those in which
  • R 1 and R 2 are independently hydrogen, methyl or ethyl and R 3 to R 6 are independently hydrogen or methyl.
  • MIn imidazolinium ions
  • R 1 to R 3 are independently hydrogen, methyl or ethyl and R 4 to R 6 are independently hydrogen or methyl.
  • MIo thiazolium ions
  • MIp oxazolium ions
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • R 1 is hydrogen, methyl or ethyl and R 2 and R 3 are independently hydrogen or methyl, or R 2 and R 3 together are 1, 4-buta-1, 3-dienylene.
  • MIs very particularly preferred pyrrolidinium ions
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are independently hydrogen or methyl.
  • imidazolidinium ions mit
  • R 1 and R 4 are independently hydrogen, methyl, ethyl or phenyl and R 2 and R 3 and R 5 to R 8 are independently hydrogen or methyl.
  • MIu ammonium ions
  • R 1 to R 3 are independently of each other Ci-Ci 8 alkyl
  • R 1 and R 2 together are 1, 5-pentylene or 3-oxa-1, 5-pentylene, and R 3 is C 1 -C 1 8 alkyl, 2-hydroxyethyl or 2-cyanoethyl.
  • ammonium ions may be mentioned methyl tri (1-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
  • tertiary amines from which the quaternary ammonium ions of the general formula (IMu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, Diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethyl - hexyl) amine, di-isopropylethylamine, di-iso-propyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine
  • Preferred tertiary amines are di-iso-propylethylamine, diethyl-tert-butylamine, diisopropyl-propylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
  • tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers.
  • Another preferred tertiary amine having three identical residues is triallylamine.
  • MIv guanidinium ions
  • R 1 to R 5 are methyl.
  • guanidinium ion N, N, N ', N', N ", N" - hexamethylguanidinium.
  • MIw cholinium ions
  • R 1 and R 2 are independently methyl, ethyl, 1-butyl or 1-octyl and R 3 is hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ;
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is a -CH 2 -CH 2 -OR 4 group and R 3 and R 4 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ; or
  • R 1 is a -CH 2 -CH 2 -OR 4 group
  • R 2 is a -CH 2 -CH 2 -OR 5 group
  • R 3 to R 5 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or
  • Particularly preferred cholinium ions are those in which R 3 is selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 1 1-methoxy 3,6,9-trioxa undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy 5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9 trioxa undecyl, 7-ethoxy-4-oxa-heptyl,
  • MIx phosphonium ions
  • R 1 to R 3 are, independently of one another, C 1 -C 8 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.
  • the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazolium ions are preferable. Furthermore, ammonium ions are preferred.
  • the solvent used is an ionic liquid mixed with hydrogen halide, in particular hydrogen chloride.
  • the ratio of hydrogen chloride to ionic liquid in this embodiment is greater than 0 to 400 mol%, preferably 5 to 300 mol%, very particularly preferably 10 to 150 mol%, based on the ionic liquid.
  • acids protic, aprotic, Lewis acids and also solid acids, for example zeolites, preferably in the amounts indicated above.
  • Preferred anions [Y] n " are selected from the group of the halides and halogen-containing compounds, the sulfates, sulfites and sulfonates, the phosphates, phosphonates, phosphinates, phosphites, phosphonites and phosphinites, the carboxylates, the borates and boronates, the Silicates, the carboxylic acid imides, bis (sulfonyl) imides and sulfonylimides and the methides.
  • HNCO is presumably stabilized as carbamoyl chloride in the presence of hydrogen chloride chemically bound in the ionic liquid and / or additionally added. Accordingly, other anions, such as the halides listed below and halogen-containing anions act.
  • the anion [Yf " is selected from
  • silicates and silicic acid esters of the general formula: SiO 4 4 " , HSiO 4 3" , H 2 SiO 4 2 “ , H 3 SiO 4 “ , R 3 SiO 4 3 “ , R 3 R b Si0 4 2" , R 3 R b R c Si0 4 " , HR 3 SiO 4 2” , H 2 R 3 SiO 4 " , HR 3 R b Si0 4 "
  • R a , R b , R c and R d are each independently hydrogen, C 1 -C 30 -alkyl, optionally substituted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imines.
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted CrCi ⁇ -alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3, 3-tetramethylbutyl, benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butyl),
  • C 2 -C 8 -alkyl which is interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups are, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3, 6-dioxaoctyl, 1 1-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9- Hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxo-octyl, 1-methoxy-3,6,9-trioxaundecyl , 7-methoxy-4-oxahepty
  • radicals can be taken together, for example, as fused building block 1, 3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa 1, 3-propenylene, 1-aza-1, 3-propenylene, 1-dC 4 -alkyl-1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza 1, 4-buta-1, 3-dienylene or 2-aza-1,4-buta-1,3-dienylene.
  • the number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • the term "functional groups” is to be understood as meaning, for example, the following: carboxy, carboxamide, hydroxy, di- (C 1 -C 4 -alkyl) -amino, C 1 -C 4 -alkyloxycarbonyl, cyano or C 1 -C 4 -alkoxy, where C 1 to C 4 - Alkyl is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • Heteroatoms and / or heterocycles substituted C 6 -C 4 -aryl are, for example
  • Me optionally substituted by functional groups, aryl, alkyl, aryloxy, halogen, Heteroato- and / or heterocycles substituted C5-Ci2 cycloalkyl, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
  • functional groups aryl, alkyl, ary
  • a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl , Dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Preferred anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates.
  • Particularly preferred anions are fluoride, chloride, bromide, iodide, SCN “ , OCN “ , CN “ , acetate, C r C 4 -alkyl sulfates, R a -COO " , R 3 SO 3 " , R a R b PO 4 " , Methanesulfonate (CH 3 SO 3 " ), tosylate, C r C 4 dialkyl phosphates, (C 2 H 5 O) 2 PO “ , hydrogen sulfate, triflate (CF 3 SO 3 “ ), AICI 4 " , Al 2 Cl 7 “ .
  • an ionic liquid of the formula I is used or a mixture of ionic liquids of the formula I, preferably an ionic liquid of the formula I is used.
  • an ionic liquid of the formula II it is possible to use an ionic liquid of the formula II or a mixture of ionic liquids of the formula II.
  • ionic liquids of the formulas I and II it is possible to use a mixture of ionic liquids of the formulas I and II.
  • an ionic liquid of the formula I is used.
  • suitable ionic liquids are ethylmethylimidazolium chloride, preferably with hydrogen chloride, in particular with one mole of HCl, methylimidazolium butanesulfonic acid triflate and pyridinium-3-S-triflate hydrogen sulfate.
  • the solvent used is an ionic liquid mixed with hydrogen halide, in particular hydrogen chloride.
  • the ratio of hydrogen chloride to ionic liquid in this embodiment is greater than 0 to 400 mol%, preferably 5 to 300 mol%, very particularly preferably 10 to 150 mol%, based on the ionic liquid.
  • the process according to the invention can be used to prepare the customary industrially produced isocyanates.
  • these are - optionally substituted - straight-chain or branched aliphatic, cycloaliphatic or araliphatic mono-, di- or polyolefins having 2 to 100 carbon atoms.
  • Another example of preferred alpha, omega-diolefins is 1,1-dodecene.
  • Cyclic olefins and diolefins having 5 to 30 carbon atoms to the corresponding cycloalkyl isocyanates or cycloalkylene diisocyanates are examples. Examples are the reaction of cyclohexene to give 1-cyclohexyl isocyanate, 1,3- or 1,4-cyclohexadiene to give 1,3- or 1,4-bisisocyanatocyclohexane, bis (methylidene) cyclohexane to bisisocyanatomethylcyclohexane, bis (cyclohexenyl) methane to methylenedicyclohexyl diisocyanate, from tricyclodecadiene to tricyclodecanediisocyanate and from bis (methylidene) tricyclodecane
  • Alkenylbenzenes having 8 to 100 carbon atoms to the corresponding araliphatic isocyanates for example of di (prop-1-enyl) benzene to (prop-1-enyl) phenylpropyl isocyanate (with one equivalent of HNCO) or to Bis (1- isocyanato-1-methylethyl) benzene (with 2 equivalents of HNCO).
  • Another example of preferred alkenylbenzenes is alpha-methylstyrene.
  • the isocyanic acid is dissolved in the ionic liquid used as solvent and olefin is reacted with this solution.
  • the olefin is dispersed in the ionic liquid, the two-phase mixture of olefin and ionic liquid introduced and gaseous isocyanic acid, preferably in an inert gas stream such as a stream of nitrogen or argon, introduced into the mixture.
  • the reaction can be carried out here preferably at low pressure.
  • reactors for example, gassed stirred tanks or bubble column reactors can be used.
  • a 2-phase mixture of olefin and ionic liquid on the one hand and a solution of isocyanic acid in the ionic liquid on the other hand can be prepared and then mixed mixture and solution.
  • the ionic liquid can be preloaded with HNCO and the pure olefin added.
  • the olefin may also be dissolved in a solvent dissolved in the ionic liquid.
  • the present invention also relates to the ionic liquids used according to the invention, which contain HNCO dissolved.
  • the stabilized HNCO contained therein can also be provided in this way for other types of reactions, for example for substitution reactions.
  • HNCO may be present at least partially in the form of carbamoyl chloride in the ionic liquid.
  • the temperature in the reactor is between 10 ° C and
  • the absolute pressure is generally between 0.2 bar and
  • 50 bar preferably between 0.8 bar and 25 bar, more preferably between 1 and 17 bar.
  • the mixture of substances preferably by means of simple phase separation, optionally by adding a further solvent, in isocyanate, optionally with further solvent on the one hand and ionic liquid on the other hand, separated.
  • isocyanate remaining in the ionic liquid may, if necessary, be separated by means of additional extraction or crystallization of the ionic liquid.
  • the isocyanate can be freed from by-products by the common purification methods.
  • the separated ionic liquid can then be recycled again as a solvent.
  • the isocyanic acid is preferably obtained by oxidation of HCN with oxygen in accordance with U.S. Pat. 4,364,913 and U.S. Pat. 4,389,386 on a catalyst, for example an Ag-Pd catalyst.
  • HNCO can be generated by urea pyrolysis, with ammonia as a by-product. The latter can be separated from HNCO, for example as described in EP-A 0416236, if this proves to be necessary.
  • the invention is further illustrated by the following example.
  • HNCO was generated by thermal decomposition of cyanuric acid at about 400 ° C. Nitrogen was used as transport gas. Thus, a HNCO / N 2 stream was provided containing approximately 40 g / h of HNCO in approximately 200 Nl / h of nitrogen.
  • the HNCO / N 2 stream was passed for about 20 minutes into a wash bottle containing 20 g of ⁇ -methylstyrene in 50 g of ethylmethylimidazolium chloride / HCl (1 mole of HCl per mole of ethylmethylimidazolium chloride) at 85 ° C.
  • the corresponding isocyanate (2-phenylpropyl isocyanate) was found.
  • 2-phenyl-2-chloropropane was found as a by-product.

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  • Organic Chemistry (AREA)
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Abstract

Procédé de production d'isocyanates par la réaction d'oléfines avec de l'acide isocyanique dans un solvant, ledit solvant étant un liquide ionique. De préférence, le liquide ionique est choisi parmi (A) des sels de formule générale (I), dans laquelle n vaut 1, 2, 3 ou 4, [A]<SUP>+</SUP> représente un cation d'ammonium quaternaire, un cation d'oxonium, un cation de sulfonium ou un cation de phosphonium, et [Y]<SUP>n-</SUP> représente un anion mono-, di-, tri- ou tétravalent ; (B) des sels mixtes des formules générales (II) [A1]<SUP>+</SUP>[A<SUP>2</SUP>]<SUP>+</SUP> [Y]<SUP>n-</SUP> (IIa), où n = 2 ; [A<SUP>1</SUP>]<SUP>+</SUP> [A<SUP>2</SUP>]<SUP>+</SUP>[A<SUP>3</SUP>]<SUP>+</SUP> [Y]<SUP>n-</SUP> (IIb), où n = 3 ; [A<SUP>1</SUP>]<SUP>+</SUP> [A<SUP>2</SUP>]<SUP>+</SUP>[A<SUP>3</SUP>]<SUP>+</SUP>[A<SUP>4</SUP>]<SUP>+</SUP> [Y]<SUP>n-</SUP> (IIc), où n = 4 et où [A<SUP>1</SUP>]<SUP>+</SUP>, [A<SUP>2</SUP>]<SUP>+</SUP>, [A<SUP>3</SUP>]<SUP>+</SUP> et [A<SUP>4</SUP>]<SUP>+</SUP> sont choisis indépendamment les uns des autres parmi les groupes cités pour [A]<SUP>+</SUP>, et [Y]<SUP>n-</SUP> a la signification indiquée en (A).
PCT/EP2007/050829 2006-02-01 2007-01-29 Procédé de production d'isocyanates WO2007088152A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10202838A1 (de) * 2002-01-24 2003-08-07 Basf Ag Verfahren zur Abtrennung von Säuren aus chemischen Reaktionsgemischen mit Hilfe von ionischen Flüssigkeiten
WO2003093246A1 (fr) * 2002-04-30 2003-11-13 Bayer Materialscience Ag Liquides ioniques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10202838A1 (de) * 2002-01-24 2003-08-07 Basf Ag Verfahren zur Abtrennung von Säuren aus chemischen Reaktionsgemischen mit Hilfe von ionischen Flüssigkeiten
WO2003093246A1 (fr) * 2002-04-30 2003-11-13 Bayer Materialscience Ag Liquides ioniques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HOOVER, F. W. ET AL: "Chemistry of isocyanic acid. III. Reaction of isocyanic acid with olefins", JOURNAL OF ORGANIC CHEMISTRY, 29(1), 143 -5 CODEN: JOCEAH; ISSN: 0022-3263, 1964, XP002426570 *
LESIAK T ET AL: "PRO-ECOLOGICAL SYNTHESIS OF INTERMEDIATES FOR THE MANUFACTURE OF POLYURETHANES PART 1. PREPARATION OF ORGANIC DIISOCYANATES BY ADDITION OF ISOCYANIC ACID TO UNSATURATED ETHERS AND DIETHERS", INTERNATIONAL POLYMER SCIENCE AND TECHNOLOGY, RAPRA TECHNOLOGY, SHREWABURY, GB, vol. 22, no. 1, January 1995 (1995-01-01), pages T - 94, XP000512443, ISSN: 0307-174X *

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