Temperature coefficients for the chain dimensions of polystyrene and polymethylmethacrylate

We have made precise measurements of the unperturbed radius of gyration 〈S2〉1/20 of polystyrene and polymethylmethacrylate molecules in the melt over the temperature range 120 °C–240 °C by small-angle neutron scattering. Contrary to most previous reports, based on dilute solution measurements, we find that neither polymer exhibits a significant change in dimensions with temperature, and we deduce temperature coefficients, κ=d ln〈S2〉0/dT, of (0.0±0.1)×10−3 K−1 for polystyrene and (0.1±0.1)×10−3 K−1 for polymethylmethacrylate. These κ values are close to those given by thermoelastic measurements, but are difficult to reconcile with predictions obtained from the rotational isomeric state model.