Kinetic aspects of the formation of the ordered phase in stiff‐chain helical polyamino acids

Abstract

AbstractThe helical polyamino acids exhibit a two‐component temperature‐composition phase diagram that corresponds well in overall appearance to the Flory prediction for rigid, impenetrable rods. The phase diagram may be characterized as a narrow, typically 1–2%, biphasic region separating the disordered (isotropic) state from the ordered (liquid–crystalline) state, connected to a wide biphasic region in which nearly pure polymer is in equilibrium with nearly pure solvent. Initial studies have been undertaken to deduce the kinetics of formation of the ordered phase, both when the thermodynamically stable state is the ordered state, as well as when it is in an ordered‐disordered biphasic state. The time course of the formation of the ordered phase at different temperatures is reminiscent of analogous studies on polymer crystallization, describable by a nucleation and growth mechanism. Formation of the ordered phase when the final state is the narow biphasic state appears also to follow a nucleation‐growth mechanism. However, when the final state is the wide biphasic region, the morphology of the final state is that of an optically clear, self‐supporting gel, even at very low concentrations (as low as 0.03 wt %). The reasons for and nature of the gel state are believed to be a kinetic phenomenon. The shape of the phase diagram is such that the temperature range of thermodynamic metastability is small and phase separation occurs in the thermodynamically unstable region. In the unstable region the zero activation‐energy spinodal decomposition mechanism dominates the kinetics of phase separation, leading to bicontinuous interconnected phases that have little possibility or driving force to rearrange further. The polymer network structure is proposed to be a bulk thermodynamic phase, characterized by bundles or sheets of polymer between branch points, rather than individual chains as in the usual polymer network. Rheological, electron microscope, and light‐scattering data are presented that support this view. The possibility of other stiff‐chain polymers forming a network structure for similar reasons is discussed.