COMPETING PROCESSES FOR POLY(ARYL ETHER-KETONE) SYNTHESIS .3. POLYMERIZATION REACTIONS OF 1,3-BIS(4-CHLOROBENZOYL)BENZENE AND 1,3-BIS(4-FLUOROBENZOYL)BENZENE IN N-METHYL-2-PYRROLIDINONE

The effects of N-methyl-2-pyrrolidinone (NMP) as solvent on the polyme rizaton reactions of 1,3-bis(4-chlorobenzoyl)benzene (1,3-CBB) and 1,3 -bis(4-fluorobenzoyl)benzene (1,3-FBB) with 4,4'-isopropylidenedipheno l (bisphenol-A) were examined. The failure of these reactions to produ ce high molecular weight polymers in the presence of anhydrous potassi um carbonate is due to dehalogenation of 1,3-CBB via substitution radi cal-nucleophilic unimolecular (S(RN)1) processes. On the other hand, 1 ,3-FBB undergoes nucleophilic aromatic substitution reactions (S(N)AR) with the carbonate anion at elevated temperatures. However, it is pos sible to synthesize high molecular weight polymers from 1,3-FBB and bi sphenol-A in NMP either by first forming the bisphenoxide with stoichi ometric amounts of aqueous sodium hydroxide or in the presence of anhy drous potassium carbonate at a lower reaction temperature.