Method for making aromatic organic carbonates

A method for making an aromatic organic carbonate by carbonylating an aromatic organic hydroxy compound in the presence of a transition metal catalyst, where at the termination of the carbonylation reaction, an aromatic organic carbonate precursor is produced in the form of a 1:1 adduct of aromatic organic hydroxy compound and aromatic organic carbonate, and the transition metal catalyst is sufficiently stable under ambient conditions to allow its reuse as part of the reaction mixture mother liquor after recovery of the aromatic organic carbonate precursor from the resulting reaction mixture, which method comprises,

• (1) charging a reactor with aromatic organic hydroxy compound and an amount of a transition metal catalyst which is sufficient to catalyze the carbonylation of the aromatic organic hydroxy compound,
• (2) introducing a mixture of oxygen and carbon monoxide into the reactor and thereafter agitating and heating the resulting mixture to a temperature of about 60.degree. C. to about 150.degree. C., while maintaining the total reaction pressure and the partial pressures of carbon monoxide and oxygen in the mixture substantially constant until the aromatic organic hydroxy compound is substantially converted to aromatic organic carbonate,
• (3) allowing the resulting mixture of (2) to cool to a temperature of from about 50.degree. C. to about 25.degree. C., to form a 1:1 molar adduct of aromatic organic carbonate and aromatic organic hydroxy compound
• (4) recovering the 1:1 molar aromatic adduct from the reaction mixture of (3), and/or,
• (5) adding make-up aromatic organic hydroxy compound directly to the resulting reaction mixture mother liquor of (4), and,
• (6) recovering the aromatic organic carbonate from the 1:1 molar aromatic adduct of (4), where the transition metal catalyst is a member selected from the group consisting of,
• (a) a mixture consisting essentially of
• (i) 1 gram atom, per 800-10,000 moles of aromatic organic hydroxy compound, of a palladium material selected from catalytically active palladium or chemically combined palladium,
• (ii) 0.5-5.0 gram atom, per gram atom of palladium, of metal in the form of a cocatalyst selected from divalent or trivalent cobalt or manganese or copper compounds selected from the class consisting of salts, complexes with diketones, and complexes with carbon monoxide,
• (iii) 0.1 to 2 moles, per gram atom of palladium, of an aromatic organic amine selected from terpyridines, phenanthrolines and quinolines, and
• (iv) 10 to 100 moles, per gram atom of palladium, of a quaternary ammonium halide, and
• (b) a mixture consisting essentially of
• (v) 1 gram atom, per 800-10,000 moles of aromatic organic hydroxy compound of the palladium material of (a) (i),
• (vi) 0.5 to 5 gram atoms of cobalt, per gram atom of palladium, of a cobalt cocatalyst comprising a cobalt complex containing a pentadentate organic ligand, and a mixture of 0 to 0.5 moles of an aromatic amine of (a) (iii), per gram atom of cobalt of such cobalt complex containing a pentadentate ligand, and
• (vii) 10 to 100 moles, per gram atom of palladium, of a quaternary ammonium or phosphonium halide of (a) (iv).