高分子材料研究方法核磁共振与电子顺磁共振波谱法解析.ppt

3.4.2 Instrumentation Sampling Widely used spin traps Nitroxides Forming free radicals of nitroxides 3.4.3 Elucidation of EPR Spectra EPR Spectra Horizontal axis: the field intensity Vertical axis: The relative absorbance: The differential of the relative absorbance: 3.4.3 Elucidation of EPR Spectra Hyperfine Structure (HFS): interactions between unpaired electrons and nuclei Dipole-dipole interaction: anisotropic 3.4.3 Elucidation of EPR Spectra Hyperfine Structure (HFS): Interaction of Fermi contact: Electrons in s orbitals: isotropic interaction Free radicals in solutions Hyperfine splitting constant (a): 2nI+1 rule 3.4.4 Comparison between EPR Spectroscopy and NMR Spectroscopy 3.5 Applications on Polymers Applications of NMR on Polymers Applications of EPR on Polymers 3.5.1 Applications of NMR on Polymers Identification: Polyethyl acrylate Ha=4.12 ppm, Hb=1.21ppm Polyethyl pentanoate Ha=2.25 ppm, Hb=1.11ppm 3.5.1 Applications of NMR on Polymers Quantitative Analysis Polybutadiene styrene (PBS) δC=CH=5 ppm, δC6H=7ppm the number of styrene unit: A/5a the number of butadiene unit: 3.5.1 Applications of NMR on Polymers Tacticity 3.5.1 Applications of NMR on Polymers Structures in Copolymers 3.5.1 Applications of NMR on Polymers Molecular Movement: spin-spin relaxation time Solid NMR 3.5.2 Applications of EPR on Polymers Free Radicals in Initiating Systems ROOH-para-N,N-dimethylbenzylamine system MNP heptacoset 3.5.2 Applications of EPR on Polymers Free Radicals in Initiating Systems Ammonium persulfate (APS)-cycloamine system MNP heptacoset 3.5.2 Applications of EPR on Polymers Dynamics of Polymerization Decomposition of initiators Chain initiation Chain termination Chain propagation 3.5.2 Applications of EPR on Polymers Chain Structure Head-head structure in PVC MNP nonet 3.5.2 Applications of EPR on Polymers Chain Structure Head-tail structure in PVC MNP hexet δ similarly δ 3.2.1 Chemical Shifts C