1H multiple-quantum nuclear magnetic resonance investigations of molecular order in polymer networks. II. Intensity decay and restricted slow dynamics

We present an approach towards the analysis of the intensity decay in proton multiple-quantum experiments on polymeric networks in terms of slow fluctuations of the residual dipole-dipole coupling tensor. Solutions for individual spin pairs as well as the three-spin system of methyl groups are derived, and the influence of the cycle time of the multiple-quantum pulse sequence is evaluated. The multiple-quantum strategy discussed herein features the advantage that the magnitude of the fluctuating part of the residual dipole-dipole coupling constant and the correlation time of the slow process can be determined independently of the integral residual coupling constant as well as its distribution. The theory is applied to experiments on end-linked poly(dimethylsiloxane) model networks with mono- and bimodal chain length distributions, where it is found that, for all samples, correlation times of the slow processes average to about 1 ms, and that the magnitude of the fluctuating part of the dipole-dipole coupling is significantly smaller than the average dipole-dipole coupling constant. This observation is interpreted in terms of considerably restricted reorientations of topological constraints.