Dielectric study on dynamics and conformation of poly(d,l-lactic acid) in dilute and semi-dilute solutions

Fractionated samples of d,l-poly(lactic acid) (PLA) were prepared and the dielectric normal mode relaxation was studied for dilute and semi-dilute solutions of the PLA in a good solvent benzene. Results indicate that in the dilute regime the normal mode relaxation time is proportional to [η]Mw in agreement with the Rouse–Zimm theory, where [η] and Mw denote the intrinsic viscosity and weight average molecular weight, respectively. The dielectric relaxation strength which is proportional to the mean square end-to-end distance 〈r2〉 increases with increasing Mw with the power of 2ν, where ν is the excluded volume parameter determined from [η]. The relaxation time in the semi-dilute regime increases with increasing concentration C due to increases of the entanglement density and the friction coefficient. The relaxation time corrected to the iso-friction state agrees approximately with the dynamic scaling theories. The relaxation strength decreases with increasing concentration indicating that 〈r2〉 decreases on account of the screening of the excluded volume effect. The concentration dependence of 〈r2〉 agrees approximately with the scaling theory proposed by Daoud and Jannink.