Modifications in the molecular dynamics of the side-chain relaxation in poly(methyl methacrylate) (PMMA)
have been recorded by monitoring the thermally stimulated depolarization currents (TSDC) β-relaxation band
of PMMA in three systems: bulk PMMA, PMMA polymerized in situ in porous SiO2, and lasing matrixes
with rhodamine 6G/Cl- (R6G) and a perylene derivative (PG). To study the different types of inter- and
intramolecular interactions, a range of dye concentrations and different polymerization initiators have been
tested. In PMMA + SiO2, the low-temperature (LT) shift of the β-band and the increase of the energy barriers
(W) associated with the side-chain (re)orientation are attributed to various counterbalancing effects. A scheme
of extensive hydrogen-bond interactions (surface or chemical
effect) between the ester carbonyls of PMMA
and the silicic acid pore surface is used to explain the overall increase in the distributed energy barriers. In
contrast, the reduction of the polymer's chain entanglements and the increase in the free volume (structural
or
physical effect), due to the pore-directed polymerization, are considered to loosen up several steric hindrances
on the rotational motion. The modification of the relaxation times spectrum prompts the shift of the β-relaxation
in PMMA + SiO2. In R6G + PMMA, the drastic LT shift of the β-band indicates the partial coupling between
the chromophores and the side-group rotations. The TSDC spectrum does not present a rotational relaxation
of the polar rhodamine dye. In R6G + PMMA + SiO2, the presence of the chromophores on the pore surfaces
and the corresponding decrease of the “effective” average pore diameters available for MMA diffusion and
PMMA growth balance the physical and chemical effects, as depicted in the similarity of the energy
distributions. The speedup of the β-relaxation with increasing dye content is ascribed to the reduced exposure
of the side groups to chemical effects. The positive energy shift in PG + PMMA + SiO2 can be explained
by considering the mixing of PG and PMMA, which permits strong hydrogen-bonding interactions and
simultaneously reduces PMMA's free volume. TSDC signals around room temperature (RT) are tentatively
discussed in terms of a Maxwell−Wagner−Sillars (MWS) polarization mode at the PMMA−SiO2 interface.