Influence of tacticity on Tβ, Tg,and TLL in poly(methyl methacrylate)s by the method of thermally stimulated current (TSC)

The thermally stimulated-current method (TSC) has been employed to determine the temperatures and intensities of T_β, T_g, and T > T_g for pure isotactic, pure syndiotactic, and five atactic specimens with syndiotactic triad content from 49.5 to 75%; T_g was found to increase linearly with syndiotactic triad content as T_g (°C) = 48.0 + 0.856 (% syn), with R² = 0.970 standard error 5.6°C; T_g for the syndiotactic specimen is 136.6°C measured, 133.6°C calculated. Several atactic specimens exhibit a second glass temperature 15 to 35 K above the regression line ascribed to some pure syndio content, and/or some isotactic–syndiotactic stereocomplexes. All specimens exhibited the liquid–liquid or T_LL transition (relaxation) which increases linearly with 100-% isotactic triad content. Isotactic PMMA shows a T′_LL relaxation 50 K above T_LL. The T_g and T_LL values obtained correlate extremely well with values from differential scanning calorimetry (DSC) determined in a separate study, as well as with most literature data. Intensities of T_g and T_LL by TSC are greatest for isotactic, next for syndiotactic, with a broad, low minimum for atactic materials. The intensity of a β relaxation increases slowly from isotactic to syndiotactic. The T_LL found by TSC compares well with literature values for isotactic PMMA obtained by several methods, and T_LL in the atactic region compares well with literature values for atactic material. The ratio T_LL/T_g ranges from 1.09 to 1.20 with no dependence on tacticity. T_g follows simple Arrhenius behavior with enthalpies of activation about one-half of the values normally calculated from dielectric and mechanical loss. The frequency dependences of T_LL and T′_LL follow a Vogel–WLF relationship with temperature. The origin of T_LL is discussed in terms of the Frenkel hypothesis of segment–segment interaction. Evidence for T_LL and T_LL from a variety of methods indicates that these two temperatures are not artifacts of the TSC method.