Rheological study on lower critical solution temperature behavior of organo-soluble cyano-substituted p-aramid in isotropic phase

Poly(2-cyano-p-phenylene terephthalamide) (CY-PPTA) has garnered significant interest as a promising precursor for super p-aramid fibers because of its organosolubility in N,N-dimethyl acetamide/lithium chloride (DMAc/LiCl) while conserving the superior properties of the resultant fibers. However, CY-PPTA has been reported to exhibit abnormal phase behavior owing to the strong dipole–dipole interactions induced by the cyano groups. Herein, we rheologically study the isotropic phases of CY-PPTA/DMAc solutions with respect to the concentration and temperature and compare them with those of CY-PPTA/sulfuric acid (H₂SO₄) solutions. In the isotropic region, the CY-PPTA solutions yield a higher power-law exponent of the dynamic viscosity (η') versus concentration of 6.0 (ηʹ ~ c^6.0) in the DMAc system than that in H₂SO₄ (ηʹ ~ c^3.2). Moreover, the CY-PPTA/DMAc solutions exhibit a lower critical solution temperature (LCST) behavior with increasing temperature, in contrast with the upper critical solution temperature in H₂SO₄. Consequently, the viscosity and exponent of the CY-PPTA/DMAc solutions increase at elevated temperatures. As shown by the Cole–Cole plot, the heterogeneity in the DMAc system becomes worse. The LCST of the CY-PPTA solution is ascribed to the intermolecular interactions between the highly polar cyano groups, which are negligible in H₂SO₄.