Segmental Dynamics of Solid-State Poly(methylphenylsilane) by 1D and 2D Deuterium NMR

The segmental dynamics of solid-state poly(methylphenylsilane) were probed with deuterium solid-echo and two-dimensional exchange (2D-X) NMR via a methyl-d3 label. Between 25 and 50 degreesC, the spectra indicated that the polymer consisted of two fractions-a fast fraction with correlation times (tauc) below 10(-5) s and one with tauc's above 10 s. Above 50 degreesC, motion with tauc's around 10(-3) s was also detected. A minimization routine was developed to fit the 2D-X spectra to a model of isotropic rotational diffusion with a distribution of tauc's. The best fits were obtained with trimodal stretched-exponential distributions. The trimodal distributions consisted of a fast mode with tauc's around 10(-5) s, an intermediate mode with tauc's between 10(-4) and 0.3 s, and a slow mode with tauc's generally above 10 s. As the temperature increased from 56 to 90 degreesC, the fast fraction steadily increased from 21% to 50% while its average tauc remained around 10(-5) s; the intermediate fraction remained relatively constant at 23% while its average tauc decreased from 125 to 8 ms, and the rigid fraction decreased from 55% to 32% with an average tauc around 40 s. The fast fraction was attributed to amorphous segments, the rigid fraction to crystalline segments, and the intermediate fraction to segments that formed an interphase between the two.