INTERFACIAL SYNTHESIS OF POLYPHOSPHONATE AND POLYPHOSPHATE ESTERS .7. TEMPERATURE EFFECTS AND REACTION LOCI IN POLYCONDENSATIONS OF HYDROQUINONE WITH PHENYLPHOSPHONIC DICHLORIDE AND 4-METHYLTHIOPHENYL PHOSPHORODICHLORIDATE

In the reported experiments, polyphosphate and polyphosphonate esters of molecular weights greater than 10,000 were synthesized by base-promoted, liquid-vapor and liquid-liquid interfacial polycondensations of hydroquinone (HQ) with 4-methylthiophenyl phosphorodichloridate (MTPP) and phenylphosphonic dichloride (PPD). The barium hydroxide-initiated liquid-vapor polycondensation of PPD and HQ in the temperature range of 15-95 degree C shows that left bracket eta right bracket increases with reaction temperature and unfrationated yields exhibit a maximum at about 45 degree C. The analogous liquid-vapor polycondensation of MTPP and HQ between 25 and 85 degree C also shows a maximum yield at 45 degree C, whereas left bracket eta right bracket decreases with increase in reaction temperature. The results are contrasted with temperature dependencies of base-catalyzed, liquid-liquid polycondensation of HQ with MTPP and PPD.