Slow ester side-group flips in glassy poly(alkyl methacrylate)s characterized by centerband-only detection of exchange nuclear magnetic resonance †

Slow side-group dynamics in a series of five poly(alkyl methacrylate)s with various side-group sizes [poly(methacrylic acid) (PMAA), poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), poly(isobutyl methacrylate) (PiBMA), and poly(cyclohexyl methacrylate), with H, CH3, CH2CH3, CH2CH(CH3)2, and cyclohexyl alkyl substituents (CODEX), respectively] were studied quantitatively by centerband-only detection of exchange nuclear magnetic resonance (NMR). Flips and small-angle motions of the ester groups associated with the β relaxation were observed distinctly in the CODEX NMR data, and the fraction of slowly flipping groups was measured with a precision of 3%. In PMMA, 34% of the side groups flipped on a 1-s timescale, whereas the fraction was 31% in PEMA at 25 °C. Even the large isobutylether and cyclohexylester side groups flipped in the glassy state, although the flipping fraction was reduced to 22 and about 10%, respectively. In PMAA, no slow side-group flips were detected on the 1-s timescale. A striking difference in the temperature dependence of the flipping fraction in PMMA versus PEMA and PiBMA was observed. In PMMA, the flipping fraction was temperature-independent between 25 and 80 °C, whereas in PEMA, it increased continuously from 31 to 60% between 25 and 60 °C. A similar doubling was also observed in PiBMA. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2444–2453, 2001