Journal of Polymer Science Part B: Polymer Physics, Vol.32, No.8, 1399-1406, 1994
Investigation of Molecular Motions of Cross-Linked Polyepichlorohydrin by Nuclear-Magnetic-Resonance Spectroscopy
The molecular motion of crosslinked polyepichlorohydrin (PECH) is studied qualitatively by NMR techniques. The results of temperature dependence of H-1 T2 and T1 indicate that the crosslinking (crosslink density < 3%) restricts molecular motions of the polymer even far above its T(g). The H-1 T1 minimum, corresponding to the large-scale chain-motion of crosslinked PECH, shifts to higher temperatures with increasing crosslink density. H-1 T2 data also show that the crosslinking hinders free chain motions of the polymer above its T(g). The C-13 T1 relaxation time is sensitive to such motional changes as well. C-13 linewidths of crosslinked PECHs vary with the crosslink density in both the swollen state and the solid state. The mechanism of C-13 linewidth broadening of crosslinked polymers is discussed in detail. In the case of PECH, the linewidth broadening is caused by changing molecular environment due to crosslinking (such as presence of various chemical shift structures and freezing effects in conformational environment as chain mobility decreases), rather than increasing correlation times, which shorten the relaxation time (T2) of polymer chains.
Keywords:STATE C-13 NMR;SPIN-LATTICE RELAXATION;SOLID-STATE;VULCANIZED ELASTOMERS;POLY(ETHYLENE OXIDE);SULFUR VULCANIZATION;NATURAL-RUBBER;CROSS-LINKING;NETWORKS;SPECTRA