Poly(arylether amides) and poly(aryletherketone amides) via aromatic nucleophilic substitution reactions of self-polymerizable AB and AB(2) monomers

Abstract

Two new extended self-polymerizable AB monomers, N-(4-fluorobenzoyl)-4-amino-4′-hydroxybiphenylether and N-(4-fluorobenzoyl)-4-amino-4′-hydroxybiphenyl, were prepared. The monomers were homopolymerized and copolymerized to high-molecular-weight, linear poly(arylether amides) in N-methylpyrrolidone (NMP)/toluene in the presence of potassium carbonate at elevated temperature. The polymers retained NMP up to 200 °C. Samples containing small amounts of the solvent (5-10 wt %) were soluble in polar aprotic solvents. However, after complete removal of the NMP, the polymers were only soluble in strong acids such as sulfuric acid and methanesulfonic acid (MSA). The polymers, which had intrinsic viscosities of 0.57-1.49 dL/g (30.1 ± 0.1 °C in MSA), were semicrystalline with melting temperatures above 400 °C. Two new self-polymerizable AB2 amide monomers, N,N′-bis(4-fluorobenzoyl)-3,4-diamino-4′-hydroxydiphenylether and N,N′-bis(4-fluorobenzoyl)-3,5-diamino-4′-hydroxybenzophenone, were also prepared and polymerized to give a hyperbranched poly(arylether amide) and a hyperbranched poly(aryletherketone) amide. The arylfluoride-terminated, amorphous polymers had intrinsic viscosities of 0.34 and 0.24 dL/g (30.0 ± 0.1 °C in m-cresol), glass-transition temperatures of 210-269 °C, and were soluble in a wide variety of organic solvents. Matrix-assisted laser desorption/ionization time-of-flight analysis indicated that the components of the low-molecular-weight fractions contained cyclic structures.