Relationship between segmental dynamics and tracer diffusion of low mass compounds in polyacrylates

We studied the relationship between segmental dynamics of matrix polymers and tracer diffusion of low mass compounds by the use of forced Rayleigh scattering and dielectric spectroscopy. Specifically poly(methyl acrylate), poly(ethyl acrylate) and poly(n-butyl acrylate) were used as the polymer matrices and six azobenzene derivatives with various substituents as the diffusant. The temperature dependence of the tracer diffusion coefficient D was measured on methylyellow (MY)/polyacrylate blends at the MY concentration of 1 wt%. The results indicate that the temperature dependence of D is weaker than the dielectric loss maximum frequencies f_m for the α processes of the matrices. The effect of volume of the dye molecules on D was also investigated at 305 K. Comparison of the tracer diffusion coefficients among various dye/polymer systems indicates that log D in the same matrix decreases linearly with the molar volume of the dyes.