Tacticity effects on the barriers to rotation of the ester methyl group in poly (methyl methacrylate): a deuteron magnetic resonance study.

In isotactic poly(methyl methacrylate) (PMMA), we investigate the dynamics of the ester methyl groups by means of deuteron magnetic resonance (DMR) in a deuterated sample. We find that the motion of the CD(3)-group affects the deuteron spin-lattice relaxation as well as the DMR line shape in a characteristic way. Quadrupolar order spin lattice relaxation measurements between T=291 K and T=70 K reveal a broad temperature dependent probability distribution of autocorrelation times tau(c) for the 2pi/3 reorientation. This broad distribution corresponds to a temperature independent Gaussian distribution of activation energies rho(E(a)) with variance sigma(E(a) )=13.8+/-0.5 meV (1.33 kJ/mol). The line shape transition between T=70 K and T=23 K is explained with the freezing in of the methyl group reorientation. By comparing our results in an 88% isotactic sample with results obtained from a 50% syndiotactic, 30% atactic, and 20% isotactic sample of a previous investigation, we demonstrate the higher local order of the 88% isotactic sample, which corresponds to a ratio of 1.6 in the relative width sigma(E(a) )/E(a) of the E(a) distribution. We show that different stereospecific forms of PMMA can be easily distinguished by the characteristics of their line shape transition between T=70 K and T=23 K.