Nylon 6 polymerization in the solid state

Abstract The postcondensation of nylon 6 in the solid state was studied. The reactions were carried out on fine powder in a fluidized bed reactor in a stream of dry nitrogen in the temperature range 110–205°C and during 1–24 h. The solid‐state polymerization (SSP) did not follow melt kinetics, but was found to be limited by the diffusion of the autocatalyzing acid chain end group. Factors thought to influence SSP were studied, e.g., heat treatment, starting molecular weight, and remelting. Surprisningly, heat treatment had little effect, but the starting molecular weight had a strong effect on the reaction rate. The higher the starting molecular weight, the faster the reaction. This could be explained as a changing concentration distribution of the reactive groups in the solid state on SSP. The kinetics of the SSP had more than one region, and the rate of reaction for conversions of over 30% could be expressed as − dc/dt = k(c/t), where k is a dimensionless constant independent of temperature with a value of 0.28. The integrated form has the form − In(c/co) = k In(t/τ), where co is the acid end‐group concentration at the start, t is the reaction time, and τ is the induction time. The value of τ is both dependent on the starting concentration co and the reaction temperature and has an activation energy of 105 kJ/mol.