Macromolecules, Vol.37, No.4, 1576-1582, 2004
High-pressure study of the local dynamics of melt cis-1,4-polybutadiene and cis-1,4-polyisoprene
Time-resolved optical spectroscopy has been employed to study the local melt segmental dynamics of anthracene-labeled cis-1,4-polybutadiene (PB) as a function of pressure (0.1-150 MPa) over a temperature range of 303-323 K. PB activation volumes calculated at fixed temperatures were observed to be independent of pressure but dependent on temperature. PB activation energies calculated at fixed pressures were observed to be independent of temperature but dependent on pressure. These results are qualitatively similar to previously reported findings for cis-1,4-polyisoprene (PI). The high-pressure dynamics of PB and PI are shown to be well described by an empirical function of pressure and temperature. An average dT/dP value of 0.15 K MPa-1 for PB is calculated and is observed to be significantly temperature and pressure dependent. The ratio of the activation energy at constant volume to the activation energy at constant pressure, Q(V)/Q(P), increases from 0.76 to 0.91 as the PB density is increased from 0.88 to 0.94 g cm(-3) via variations in temperature and pressure.