Macromolecules, Vol.40, No.10, 3615-3623, 2007
Identification of oxidation products in selectively labeled polypropylene with solid-state C-13 NMR techniques
Oxidatively degraded polypropylene (PP) samples, with selective C-13 labeling of the three carbon sites on the PP chain (tertiary, secondary, and methyl carbons), have been analyzed with a suite of one-and two-dimensional solid-state C-13 nuclear magnetic resonance (NMR) experiments that have been used to assign several C-13 resonances attributed to oxidation-induced functional groups. These NMR techniques, several of which were recently developed, included dipolar dephasing for MAS speeds >= 10 kHz, chemical shift anisotropy (CSA) filtering, SUPER NMR to separate quasi-static CSA patterns, and H-1-C-13 heteronuclear correlation (HETCOR). In the course of the study, it has been demonstrated that NMR experiments which utilize the C-13 CSA for resonance identification can be sensitive to sample temperature as a result of molecular motion-induced averaging of the CSA. These experiments have allowed hemiketal groups to be identified for the first time to our knowledge in oxidized PP. Possible mechanisms for the formation of hemiketals and other functional groups have been discussed.