US 5,334,742 AGranted

Process for the continuous preparation of diaryl carbonates from dialkyl carbonates

AssigneeBayer Aktiengesellschaft

InventorsNorbert Schon, Reinhard Langer, Hans-Josef Buysch, Paul Wagner

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Abstract

Diaryl carbonates are prepared by reaction from dialkyl carbonates and phenols using conventional transesterification catalysts in a specific mass-coupled and energy-coupled combination of columns, for example according to FIG. 1, in which the reference numerals have the meaning specified in the description.

Claims20

Dependent claims

A process for the preparation of a diaryl carbonate of the formula

Ar.sup.1 --O--CO--O--Ar.sup.1,
in which
Ar.sup.1 denotes unsubstituted phenyl, phenyl substituted by 1 to 3 C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or halogen radicals, or naphthyl
by transesterification of an aromatic hydroxyl compound of the formula
Ar.sup.1 --OH,
Ar.sup.1 has the meanings given,
with 0.1 to 10 mol of a dialkyl carbonate of the formula
R.sup.1 --O--CO--O--R.sup.1,
in which
R.sup.1 denotes straight-chain or branched C.sub.1 -C.sub.6 -alkyl or C.sub.5 -C.sub.6 -cycloalkyl,
in the presence of a transesterification catalyst in a column apparatus, wherein the reaction is carried out in a mass-coupled and energy-coupled combination of a counter-current column A and a reaction column B, reactions and separations running in parallel in the aforementioned columns, in such a way that, in the counter-current column A, the aromatic hydroxyl compound which was withdrawn at least in part in the liquid state from the reaction column B is reacted in the liquid phase in the presence of a transesterification catalyst with a mixture, conducted in counter-current thereto in the gaseous state, of 100 to 95 parts by weight of dialkyl carbonate and 0 to 5 parts by weight of the underlying alcohol of the formula
R.sup.1 OH,
in which
R.sup.1 has the given meaning,
where the mixture was withdrawn in the gaseous state from the reaction column B and can contain aromatic hydroxyl compounds Ar.sup.1 OH, at temperatures from 100.degree. C. to 300.degree. C. and pressures from 0.05 to 20 bar and the mixture, produced in A as a bottom product, of an alkyl aryl carbonate of the formula
Ar.sup.1 --O--CO--O--R.sup.1,
in which
Ar.sup.1 and R.sup.1 have the meaning given above,
of unreacted aromatic hydroxyl compound, with or without a small amount of the dialkyl carbonate and with or without homogeneously dissolved catalyst in the liquid form, is fed into the bottom part of the reaction column B and the gaseous mixture, produced in A as head product, of the alcohol, as yet unreacted dialkyl carbonate and aromatic hydroxyl compound is fed into the upper part of the reaction column B and is reacted at temperatures of 100.degree. to 300.degree. C. and pressures of 0.05 to 5 bar in the reaction part of B to the extent of 60 to >95%, where, furthermore, diaryl carbonate is withdrawn as a bottom product in the lower part of the column B, the liquid stream, which is to be returned to A, of the aromatic hydroxyl compounds is withdrawn in the central section of B and above the feed of the bottom product of A;
the gaseous mixture, which is to be returned to A, of 95 to 100 parts by weight of dialkyl carbonate and 0 to 5 parts by weight of the alcohols derived therefrom and aromatic hydroxyl compounds is withdrawn int he central section of B between the draw-off of the liquid aromatic hydroxyl compound and the infeed of the head product from A;
and a mixture of 80 to 20% by weight of the derived alcohol and 20 to 80% by weight of dialkyl carbonate is withdrawn as a head stream from B, reacted or withdrawn dialkyl carbonate and reacted aromatic hydroxyl compound being supplemented by feed into A or B.

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Dependencies are inferred from the claim text.

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Abstract

A process for the preparation of a diaryl carbonate of the formula

Ar.sup.1 --O--CO--O--Ar.sup.1,
in which
Ar.sup.1 denotes unsubstituted phenyl, phenyl substituted by 1 to 3 C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or halogen radicals, or naphthyl
by transesterification of an aromatic hydroxyl compound of the formula
Ar.sup.1 --OH,
Ar.sup.1 has the meanings given,
with 0.1 to 10 mol of a dialkyl carbonate of the formula
R.sup.1 --O--CO--O--R.sup.1,
in which
R.sup.1 denotes straight-chain or branched C.sub.1 -C.sub.6 -alkyl or C.sub.5 -C.sub.6 -cycloalkyl,
in the presence of a transesterification catalyst in a column apparatus, wherein the reaction is carried out in a mass-coupled and energy-coupled combination of a counter-current column A and a reaction column B, reactions and separations running in parallel in the aforementioned columns, in such a way that, in the counter-current column A, the aromatic hydroxyl compound which was withdrawn at least in part in the liquid state from the reaction column B is reacted in the liquid phase in the presence of a transesterification catalyst with a mixture, conducted in counter-current thereto in the gaseous state, of 100 to 95 parts by weight of dialkyl carbonate and 0 to 5 parts by weight of the underlying alcohol of the formula
R.sup.1 OH,
in which
R.sup.1 has the given meaning,
where the mixture was withdrawn in the gaseous state from the reaction column B and can contain aromatic hydroxyl compounds Ar.sup.1 OH, at temperatures from 100.degree. C. to 300.degree. C. and pressures from 0.05 to 20 bar and the mixture, produced in A as a bottom product, of an alkyl aryl carbonate of the formula
Ar.sup.1 --O--CO--O--R.sup.1,
in which
Ar.sup.1 and R.sup.1 have the meaning given above,
of unreacted aromatic hydroxyl compound, with or without a small amount of the dialkyl carbonate and with or without homogeneously dissolved catalyst in the liquid form, is fed into the bottom part of the reaction column B and the gaseous mixture, produced in A as head product, of the alcohol, as yet unreacted dialkyl carbonate and aromatic hydroxyl compound is fed into the upper part of the reaction column B and is reacted at temperatures of 100.degree. to 300.degree. C. and pressures of 0.05 to 5 bar in the reaction part of B to the extent of 60 to >95%, where, furthermore, diaryl carbonate is withdrawn as a bottom product in the lower part of the column B, the liquid stream, which is to be returned to A, of the aromatic hydroxyl compounds is withdrawn in the central section of B and above the feed of the bottom product of A;
the gaseous mixture, which is to be returned to A, of 95 to 100 parts by weight of dialkyl carbonate and 0 to 5 parts by weight of the alcohols derived therefrom and aromatic hydroxyl compounds is withdrawn int he central section of B between the draw-off of the liquid aromatic hydroxyl compound and the infeed of the head product from A;
and a mixture of 80 to 20% by weight of the derived alcohol and 20 to 80% by weight of dialkyl carbonate is withdrawn as a head stream from B, reacted or withdrawn dialkyl carbonate and reacted aromatic hydroxyl compound being supplemented by feed into A or B.

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