Application of Solid State NMR on Polymers and Rubbers-柴仕淦.ppt

Application of Solid State NMR on Polymers and Rubbers Shigan Chai 2006-9-8 Contents Broadening of Solid State NMR Why Does the Spectrum Broaden? Dipolar-dipolar Chemical shift anisotropy There is no broadening in the solution because of rapid molecular movement. High-resolution spectra can be obtained with three techniques : Cross-Polarization (CP) Magic-Angle (Sample) Spinning (MAS) Dipolar Dephasing (DD) Cross-Polarization (CP) This is the sequence of solid state NMR which can transfer the signal of proton to carbon to enhance the carbon’s signal. Magic-Angle Sample Spinning (MAS) Only when the orientation of the pairs is such that cos2θ=1/3 (θ=54.7o), the lines coincide to produce a single line We call this θ as magic angle. Chemical shifts Line shapes Relaxation times Applications For Polymer Studies Amorphous Polymers: monitoring the reaction in polymer system 29Si CP/MAS NMR Spectra Of MSP Cured At Various Temperatures Solid-Solid-Phase Transitions Form-I is reported to have an conformation for the bonds between the double bonds, where represents the skew (109°) conformation. Form-II is observed above 75 °C, where the chains are packed in a hexagonal array but with a lower density and the equitorial reflections are blurred. Elastomers NMR imaging (MRI) is a promising method that has been extensively used in the medical community, and is now being used to study the structure of polymers. The NMR imaging of elastomers has been used to investigate the morphology, composition, and defects . It is estimated that a 20% variation in the composition of the cis-polybutadiene/styrene–butadiene rubber can be identified in the T2-weighted image. Inclusion Compounds The mobilities intermediate between solutions and rigid solids. It has been observed that some small molecules, such as perhydrotriphenylene or urea, form stable crystal structures in which long-chain polymers are included into narrow channels. Semicrystalline Polymers