Estimation of the Degree of Crystallinity of Partially Crystalline Polypropylenes Using 13C\text{}^{13}C NMR

The paper deals with a method for the estimation of the degree of crystallinity for partially-crystalline isotactic-polypropylenes (i-PP) using high-resolution solid-state $\text{}^{13}C$ NMR. For this purpose direct polarization $\text{}^{13}C$ MAS NMR spectra were measured for i-PP samples with different degrees of crystallinity at 98°C. The areas beneath the resonance lines in these spectra correspond to the number of carbons in particular functional groups, while the widths and shapes of the lines reflect the degree of crystallinity, crystalline modifications, distribution of chain conformations and the chain mobility. The $\text{}^{13}C$ MAS NMR spectra, measured using appropriate combination of delay time and high proton decoupling field, made it possible to detect only amorphous domains in the sample. This enabled identification of the lines associated with the amorphous domains in the complete $\text{}^{13}C$ MAS NMR spectra and provided sufficient information for reliable estimation of the degree of crystallinity. The heteronuclear Overhauser enhancement of the $\text{}^{13}C$ NMR signals due to short delay time was taken into account in our calculations

Dynamics of ¹H-¹³C Cross Polarization in Nuclear Magnetic Resonance of Poly(3-hydroxybutyrate)

Poly(3-hydroxybutyrate) (PHB) is a semicrystalline biodegradable polymer with chains consisting of methyl (CH₃), methylene (CH₂), methine (CH) and carbonyl (CO) groups. The ¹H-¹³C cross polarization NMR measurements were performed on an as-supplied powder PHB sample at a magic-angle spinning rate of 10 kHz. The measured cross polarization build-up curves and their analysis provided information on the dynamics of ¹H-¹³C NMR cross polarization in functional groups with directly bonded hydrogens. The measurements required setting up the Hartmann-Hahn condition, which was inferred from the Hartmann-Hahn matching profiles measured for each functional group. The cross polarization build-up curves displayed an oscillatory course, which indicates the presence of rigid ¹H-¹³C spin pairs isolated from the lattice. The frequency of the observed oscillations is directly proportional to the ¹H-¹³C dipolar coupling constant, which is related to the C-H distance and its value also reflects the mobility of particular functional groups. The values of dipolar coupling constants were derived from splittings in the Fourier transforms of cross polarization build-up curves. The mobility of particular groups was assessed with the order parameter ⟨S⟩ calculated using experimental and rigid lattice values of dipolar coupling constants

Solid State 13C\text{}^{13}C NMR Study of Modified Polyhydroxybutyrate

Structural changes in polyhydroxybutyrate (PHB) brought about by addition of chain extender and/or plasticizer were studied using $\text{}^{13}C$ MAS NMR spectra, which were measured using the direct polarization technique at 30 and 98°C. Four resonances associated with the CO, CH, $CH_{2}$ and $CH_{3}$ groups of PHB were observed in the spectra. The $CH_{3}$ resonance appearing at 98°C shows splitting into two lines related to the crystalline and amorphous regions. Analysis of the $CH_{3}$ resonances made it possible to estimate the influence of applied modifications on crystallinity and distribution of conformations in amorphous and crystalline domains of PHB samples

Cross-polarization with magic-angle spinning kinetics and impedance spectroscopy study of proton mobility, local disorder, and thermal equilibration in hydrogen-bonded poly(methacrylic acid)

The 1H–13C cross-polarization with magic-angle spinning (CP MAS) kinetics was studied in poly(methacrylic acid) (PMAA) having the purpose to track the links between the local order in the main chain and the proton dynamics in peripheral hydrogen bond networks. The experimental CP MAS kinetic curves were analyzed applying the models of isotropic and anisotropic spin-diffusion with thermal equilibration. The fractal dimension Dp ≈ 3 was deduced that indicates that PMAA behaves as an isotropic 3D-system. No proton conductivity in the neat PMAA was deduced from the impedance spectroscopy data analyzing the frequency dependences of the complex dielectric permittivity. The value of local order parameter S = 0.70 for CH2 in PMAA occupies an intermediate position between 0.63 and 0.85 deduced for CH2 sites in the main chains of poly(vinyl phosphonic acid) and poly(2-hydroxyethyl methacrylate), that is, the true proton conductor and the polymer that contains the H-bond network, however, no proton conductivity, respectively.</p