PHOSGENE SYNTHESIS BY CONVERSION OF A GAS MIXTURE CONTAINING CHLORINE AND CARBON MONOXIDE ON AN ORGANIC CATALYST CONTAINING CHLORIDE ANIONS

Abstract

The invention relates to a method for producing phosgene, comprising at least the steps of: a) bringing a gas mixture containing carbon monoxide and chlorine into contact with a catalyst, the catalyst containing at least one ionic organic compound which contains monochloride anions and, on contact with chlorine, forms an ionic organic compound containing polychloride anions; b) converting the gas mixture into phosgene on the catalyst. With the invention, phosgene can be produced using less activation energy and in high yields without the use of conventional activated carbon catalysts.

Claims

1. A method for producing phosgene, comprising: a) bringing a gas mixture containing carbon monoxide and chlorine into contact with a catalyst, wherein the catalyst comprises at least one ionic, monochloride anion-containing organic compound, which forms an ionic, polychloride anion-containing organic compound on contact with the chlorine, and b) converting the gas mixture to phosgene over the catalyst.

2. The method as claimed in claim 1, wherein the at least one ionic, monochloride anion-containing organic compound comprises a cation selected from ammonium, phosphonium, sulfonium, pyrrolidinium, piperidinium, imidazolium, pyridinium, or guanidinium or a mixture thereof and the monochloride anion (Cl.sup.) thereof.

3. The method as claimed in claim 1, wherein at least one ionic organic compound of the general formula (I) and/or (II) is present as the ionic, monochloride anion-containing organic compound of the catalyst,
[NR1.sub.mR2.sub.nR3.sub.o].sup.+Cl.sup.(I)
[PR4.sub.pR5.sub.q].sup.+Cl.sup.,(II) where, in formulae (I) and (II), the radicals R1, R2, R3, R4, and R5 are each independently identical or different alkyl radicals selected from the group of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and 2-methylpropyl, and the characters m, n, o, p, and q are each independently an integer in the series from 0 to 4 and where the sum of m+n+o and the sum of p+q in each case results in the value 4.

4. The method as claimed in claim 3, wherein at least one radical R1, R2 or R3 is different from the other radicals R1, R2 and R3 and the radicals R4 and R5 are different from each other.

5. The method as claimed in claim 4, wherein according to general formula (I), m is 1, 2 or 3, n is 1, 2 or 3 and o is zero, and where m+n+o=4.

6. The method as claimed in claim 1, wherein at least one ionic organic compound selected from NMe.sub.4Cl, NEtMe.sub.3Cl, NEt.sub.2Me.sub.2Cl, NEt.sub.3MeCl, Et.sub.4NCl, or a mixture thereof is present as the ionic, monochloride anion-containing organic compound of the catalyst.

7. The method as claimed in claim 1, wherein the catalyst comprises a cation of which is selected from the group of one or more each differently alkyl- and/or aryl-substituted cations selected from ammonium, phosphonium, sulfonium, pyrrolidinium, piperidinium, imidazolium, pyridinium or guanidinium cations or a mixture thereof and the polychloride anion of which is Cl.sub.(r+2).sup., in which r is an odd integer from 1 to 7.

8. The method as claimed in claim 1, wherein the catalyst comprises at least one polychloride anion-containing compound of the formula (III) or the formula (IV) or a mixture thereof by the contact with the chlorine,
[NR.sup.1.sub.mR.sup.2.sub.nR.sup.3.sub.o].sup.+[Cl.sub.(r+2)].sup.(III)
[PR.sup.4.sub.pR.sup.5.sub.q].sup.+[Cl.sub.(s+2)].sup.(IV) in which the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each independently identical or different alkyl radicals selected from the group of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and 2-methylpropyl, m, n, o, p, and q are each independently an integer in the series from 0 to 4 and where the sum of m+n+o and the sum of p+q results in the value 4, and where r and s are each independently an odd integer from 1 to 7.

9. The method as claimed in claim 8, wherein according to formulas (III) and (IV) at least one radical R1, R2 or R3 is different from the other radicals R1, R2 and R3 and the radicals R4 and R5 are different from each other.

10. The method as claimed in claim 8, wherein the compound of the formula (III) or (IV) comprises: NMe.sub.4Cl, NEt.sub.4Cl, Pr.sub.4NCl, NEtMe.sub.3Cl.sub.(r+2), NEt.sub.2Me.sub.2Cl.sub.(r+2), NEt.sub.3MeCl.sub.(r+2), NBuEt.sub.2MeCl.sub.(r+2), NMePr.sub.3Cl.sub.(r+2), NBu.sub.2Me.sub.2Cl.sub.(r+2), PEt.sub.3MeCl.sub.(r+2), or a mixture thereof, where Me represents methyl, Et represents ethyl, Pr represents propyl, and Bu represents n-butyl.

11. The method as claimed in claim 8, wherein the compound of the formula (III) comprises at least one compound of the series: NEtMe.sub.3Cl.sub.(r+2), NEt.sub.2Me.sub.2Cl.sub.(r+2), NEt.sub.3MeCl.sub.(r+2), NMe.sub.4Cl, NEt.sub.4NCl.sub.(r+2), or a mixture thereof, where Me represents methyl and Et represents ethyl.

12. The method as claimed in claim 1, wherein in step a), the molar ratio of carbon monoxide and chlorine is at least 1.

13. The method as claimed in claim 1, wherein steps a) and b) are carried out at temperatures<100 C.

14. The method as claimed in claim 1, the phosgene formed in step b) is collected by condensation or by dissolution in a liquid composition containing organic solvent.

15. The method as claimed in claim 1, wherein the phosgene formed in step b) is dissolved in a liquid composition containing organic solvent and thereby collected, wherein said liquid composition is in contact with the catalyst of step a).

16. The method as claimed in claim 14, wherein the organic solvent present in the liquid composition comprises an organic solvent in which phosgene dissolves at 20 C. and 1013 mbar to an extent of at least 1 g/L.

17. The method as claimed in claim 1, wherein the phosgene from step b) is reacted in a step c) with at least one phosgene-reactive component.

18. A composition having at least two phases, comprising as the first phase a gas mixture containing carbon monoxide and chlorine, and a catalyst-containing phase different therefrom, which comprises at least one ionic, monochloride anion-containing organic compound which forms an ionic, polychloride anion-containing organic compound on contact with the chlorine.

19. (canceled)

Description

EXAMPLES

[0126] The following examples are given to illustrate by way of example the implementation of the teaching according to the invention, without limiting its subject matter thereto:

Example 1: Discontinuous Method in the Reactor with the Addition of o-Dichlorobenzene

[0127] [NEt.sub.3Me]Cl (53 mg, 0.351 mmol, 3.5 mol %) was initially charged in a reactor, and dried to remove residual moisture. Then, 20 mL of o-dichlorobenzene was added and the resulting suspension degassed. The reactor was filled with a mixture of chlorine (700 mg, 10.009 mmol, 1 eq.) and carbon monoxide (16 mmol, 1.6 eq.) and the reaction mixture was mixed, wherein the formation of phosgene was clearly detected by IR spectroscopy (v=3632(vw) cm.sup.1, 1826(s) cm.sup.1, 1626(w) cm.sup.1, 1409(vw) cm.sup.1, 1107(w) cm.sup.1, 851(vs) cm.sup.1 and 571(w) cm.sup.1). Quantitative conversion of the chlorine to phosgene was achieved.

Example 2: Discontinuous Method in a Tubular Reactor

[0128] A tubular reactor was filled with solid, fine-grained [NEt.sub.4]Cl (230 mg, 1.393 mmol). The tubular reactor was connected to a peristaltic pump and an IR spectrometer to form a circuit. The system was filled with a mixture of carbon monoxide (20.20 mmol) and chlorine gas (3.5 mmol). The gas phase was continuously pumped through the system and the gas phase was characterized by IR spectroscopy. In the IR spectra, the formation of phosgene was directly observed, evident from the steady decrease in the characteristic absorption band of carbon monoxide at 2171 cm.sup.1 and the increase in the absorption band characteristic of phosgene at 1682 cm.sup.1.