Synthesis and characterization of novel wholly para-oriented aromatic polyamide-hydrazides containing sulfone-ether linkages

Abstract

Four novel wholly para-oriented aromatic polyamide-hydrazides containing flexibilizing sulfone-ether linkages in their main chains have been synthesized from 4-amino-3-hydroxy benzhydrazide (4A3HBH) with either 4,40-sulfonyldibenzoyl chloride (SDBC), 4,40-[sulfonyl-bis(1,4-phenylene)dioxy]dibenzoyl chloride (SODBC), 4,40-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]dibenzoyl chloride (4MeSODBC), or 4,40-(1,4-phenylenedioxy)diben-zoyl chloride (ODBC) via a low-temperature solution poly-condensation reaction. A polyamide-hydrazide without the flexibilizing linkages is also investigated for comparison. It was synthesized from 4A3HBH and terephthaloyl chloride (TCl) by the same synthetic route. The intrinsic viscosities of the polymer ranged from 2.85 to 4.83 dL g-1 in N,N-di-methyl acetamide (DMAc) at 30°C and decreased with introducing the flexibilizing linkages into the polymer. All the polymers were soluble in DMAc, N,N-dimethyl formamide (DMF), and N-methyl-2-pyrrolidone (NMP), and their solutions could be cast into films with good mechanical strengths. Further, they exhibited a great affinity to water sorption. Their solubility and hydrophilicity increased remarkably by introducing the flexibilizing linkages. The polymers could be thermally cyclodehydrated into the corresponding poly(1,3,4-oxadiazolyl-benzoxa-zoles) approximately in the region of 295-470°C either in nitrogen or in air atmospheres. The flexibilizing linkages improve the solubility of the resulting poly(1,3,4-oxadia-zolyl- benzoxazoles) when compared with poly(1,3,4-oxa-diazolyl-benzoxazoles) free from these linkages. © 2009 Wiley Periodicals, Inc.