Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

PP-III-19NEW HOMOGENEOUS CATALYTIC SYSTEMS FOR ARYL- ORARYLALKYL ACIDS PRODUCTION AND UTILIZATION OFPERSISTENT ORGANIC POLLUTANTS - POLYCHLOROBIPHENYLSVIA CARBONYLATIONT.E. Zhesko, V.P. Boyarskiy, G.F. Tereshchenko«VNIINephtechim», Russian Academy of Sciences, St. Petersburg Scientific CenterSynthesis of mono- and poly-alkylaromatic and aromatic acids represents the big practicalinterest. Besides the traditional areas of application: drugs, dyes, lubricants, herbicides, atpresent, the use of these compounds in high-tech applications, such as liquid crystal materialsand thermoplastics, polyester fibers, and electroluminescent and nanomaterials, intensivelyexpands.We have suggested universal method and developed flexible economical technology ofaryl- and arylalkyl acids (ethers, salts, amides) production via the halides carbonylation withuse of catalysts on the base of cobalt carbonyl [1-3]:ArHal + CO Co 2 (CO) 8 +AROH + BArCOORThe carbonylation reactions are carried out under very mild conditions, at a CO pressurenot higher then 3 atm and a temperature up to 65 °C in a methanol medium in the presence ofalkali metal hydroxides or carbonates as bases (B):New highly active catalytic systems based on modified carbonyl cobalt were developedfor low-activity aryl halides activation and involvement into the carbonylations reaction. Weproposed and investigated a number of modifiers (cocatalysts) (A) (alkyl halides andepoxides) formed «in situ» active «true» carbonylation catalyst:ClOO> >OOH>Cl PhCl>Epoxides are the most active cocatalysts and benzyl chloride was the most active amongalkyhalides. The best as industrially available is propylen oxide.With the purpose of perfection of the production technology of the key products aromaticand alkylaromatic acids we designed and constructed an original pilot installation forcarbonylation of halides with installed capacity of 10 tons a year. (The volume ofcarbonylation reactor is 100 l). This setup was used for production of experimental batches ofthe products in amount from 10 to 50 kg.339