Structure and Dynamics of Bulk Polymers by NMR-Methods

1 Theoretical Aspects.- 1.1 Line Shape and Transverse Relaxation in Solids.- 1.1.1 Dipole Interaction.- 1.1.2 Chemical Shift.- 1.1.3 Quadrupolar Interaction.- 1.1.4 Line Narrowing in Solids.- 1.2 Spin-Dynamics and Longitudinal Relaxation.- 1.2.1 Spin Temperature.- 1.2.2 Spin Diffusion.- 1.2.3 Spin-Flip Effects.- 1.2.4 Spin-Locking Experiment.- 1.2.5 Multipulse Spin-Locking.- 1.2.6 Cross-Polarization and Nuclear-Overhauser Effect.- 1.3 Effect of Molecular Motion.- 1.3.1 General Remarks on the Form of the Correlation Function.- 1.3.2 Two Approaches to the Analysis of Motional Effects.- 1.3.3 Model-free Approach.- 1.3.4 Correlation Functions for Some Motional Models.- 1.3.5 Quadrupolar Line Shape under the Influence of Molecular Motion.- 2 Experiment.- 2.1 Pulse Methods.- 2.1.1 Nonselective Methods.- 2.1.2 Selective Methods in Solids.- 2.2 Methods of Heterogeneous Analysis.- 2.2.1 Signal Decomposition.- 2.2.2 Two-Dimensional Analysis in Time Domain.- 2.2.3 Two-Dimensional Spectroscopy.- 3 NMR Signal Shape and Polymer Structure.- 3.1 Transverse Magnetization of Protons.- 3.1.1 Experiments.- 3.1.2 Analysis of the Experiments in Semicrystalline Polymers.- 3.1.3 Nature of the Approximating Functions in the Solid State.- 3.1.4 Approximating Functions and Semiquantitative Description of Experiments in Polymer Liquids.- 3.1.5 Connection Between the Signal Parameters and the Polymer Network Structure.- 3.2 Longitudinal Magnetization of Protons.- 3.2.1 Signal Decomposition in Amorphous Polymers and Spin-Dynamics Effects.- 3.2.2 Analysis of Signals in Amorphous Polymers with Molecular Heterogeneities.- 3.2.3 Signal Analysis in Semicrystalline Polymers.- 3.2.4 Comparative Analysis of the Experiments on Pulse and Continuous Spin-Locking.- 3.3 Line Shape Analysis for 13C- and 2H-Spectra.- 3.3.1 Shielding Tensor Distribution in Isotropic Polymers.- 3.3.2 Oriented Polymers.- 3.3.3 Further Methods for the Determination of the Polymer Structure.- 3.3.4 Methods for the Reestablishment of Anisotropy Parameters in Polymers.- 3.4 Improvement of the Structural Information by Different Techniques.- 3.4.1 Suppression of Parts of the Spectrum by the Use of the Differences in the Relaxation Times.- 3.4.2 Consequences for 13C Cross-Polarization Measurements.- 3.4.3 Selective Deuteration.- 3.5 Highly Resolved 13C-Spectra in Solid Polymers.- 3.5.1 General Considerations.- 3.5.2 Connections between the Molecular Structure and the Spectra.- 3.5.3 Typical Applications.- 4 Molecular Motion in Bulk Polymers.- 4.1 Amorphous Polymers.- 4.1.1 Local Motion of the Backbone.- 4.1.2 Motion of Side- and End Groups.- 4.1.3 Segmental Motion.- 4.1.4 Special Applications of 2H NMR.- 4.2 Molecular Motion and Relaxation Transitions in Solid Polyethylene.- 4.2.1 Qualitative Analysis of the Experiments and Attribution of the Relaxation Transitions.- 4.2.2 Determination of the Microdynamic Parameters.- 4.2.3 Discussion from the Viewpoint of the Models of Molecular Motion.- 4.2.4 Connection between Molecular Motion and Structure in PE.- 5 Special Polymer Systems and Phenomena.- 5.1 Relaxation Times and Mechanical Properties.- 5.2 Translational Motion of Macromolecules.- 5.3 Multicomponent Polymer Systems.- 5.3.1 General Considerations.- 5.3.2 Some Methodical Aspects.- 5.3.3 Other Applications.- 5.4 Molecular Motion in Globular Proteins.- 5.4.1 Selective NMR Experiments in Solutions.- 5.4.2 Non-Selective NMR Experiments.- References.