Preparation of poly amides via the phosphorylation reaction. I. Wholly aromatic polyamides and polyamide‐hydrazides

Aromatic polyamides of the AB, AA–BB, and ordered copolyamide types plus aromatic hydrazide and amide–hydrazides were prepared via the phosphorylation reaction. The relationship of the molecular weight, as evidenced by the inherent viscosity values obtained, of the several polymers to the structural features and properties of the monomers used and the polymers obtained is discussed in detail. Some salient observations are that poor solubility of the rodlike polymers definitely appears to set limits to obtaining high molecular weight and strongly basic groups, e.g., —CO—NH—NH2, in monomers, prevent the attainment of high molecular weight because such groups coordinate more strongly with the phosphite complex than does the pyridine catalyst in the phosphorylation reaction. Fibers were spun from two aromatic polyamides prepared via the phosphorylation reaction. Excellent tensile properties were achieved for fiber from poly–p–benzamide (PPB) and the polyisophthalamide of 4, 4′‐methylenedianiline despite the relatively low molecular weight of these polymers (?7inh 1.6 and 1.1, respectively). The PPB fiber was spun from both isotropic and anisotropic spinning solutions. Fiber obtained from the anisotropic dope had moderately high tensile strengths (8–12 gpd) and remarkably high initial modulus values (435–745 gpd). These results indicate that polymers made by the phosphorylation route would give fibers with as high tensile properties as polymer made by the diacid chloride‐diamine polycondensation route providing that the inherent viscosities of polymer prepared by the former process could be increased to equal those by the latter process.