《NMR spectroscopy of polymersm》核磁电子书

仪器资料 · 发表于 2018-8-10 14:20:22

《NMR spectroscopy of polymersm》核磁电子书
Koichi Hatada - Tatsuki Kitayama

1 INTRODUCTION TO NMR SPECTROSCOPY . . . . . . . . . . . . . . . 1
1.1 Basic Principles of NMR . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Nuclear Magnetic Resonance . . . . . . . . . . . . . . . . . . 1
1.1.2 Relaxation ............................ 3
1.1.3 Chemical Shift . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.4 Spin-Spin Coupling . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2 Spectrometers .............................. 8
1.3 Observable Nuclei . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.4.1 Solvent for NMR Measurement . . . . . . . . . . . . . . . . . 15
1.4.2 Chemical Shift Standards . . . . . . . . . . . . . . . . . . . . 24
1.4.3 NMR Sample Tube and Sample Manipulation . . . . . . . . . 26
1.4.4 NMR Shift Reagent . . . . . . . . . . . . . . . . . . . . . . . . 32
1.5 Outline of NMR Measurement . . . . . . . . . . . . . . . . . . . . . 34
2 MEASUREMENT OF SPECTRUM WITH HIGH QUALITY
INCLUDING QUANTITATIVE ANALYSIS ................. 43
2.1 Effects of Operating Conditions . . . . . . . . . . . . . . . . . . . . 43
2.2 Reliability of Chemical Shift and Signal Intensity . . . . . . . . . . . 57
2.3 Determination of Absolute Signal Intensity . . . . . . . . . . . . . . 58
2.4 Microanalysis by NMR Spectroscopy . . . . . . . . . . . . . . . . . . 62
2.5 Determination of Volume Magnetic Susceptibility by NMR . . . . . 69
3 STEREOCHEMISTRY OF POLYMERS ................... 73
3.1 Definition of Tacticrty . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.2 Methods of Stereochemical Peak Assignments . . . . . . . . . . . . 74
3.3 Quantitative Determination of Tacticity . . . . . . . . . . . . . . . . 83
3.4 Sequence Statistics and Propagation Mechanism . . . . . . . . . . . 86
4 COPOLYMER ................................. 95
4.1 NMR Analysis of Composition and Sequence in Copolymers .... 95
4.2 Chemical Shift Calculation for Peak Assignment
of Hydrocarbon Copolymer . . . . . . . . . . . . . . . . . . . . . . 1 04
4.3 Monomer Reactivity Ratios and Statistical Treatments ........ 107
4.4 Analysis of Diene Polymers ....................... 112
5 NMR FOR THE STUDY OF POLYMERIZATION REACTIONS . . . . . . 123
5.1 Analysis of End Group and Structural Defects in Polymer Chains . . 123
5.2 Analysis of Polymerization Reaction .................. 132
5.3 Chemical Shifts of Vinyl Monomer and Their Reactivities ...... 137
6 TWO-DIMENSIONAL NMR SPECTROSCOPY ............... 143
6.1 Principles of 2D NMR .......................... 143
6.2 'H COSY (2D Correlation Spectroscopy) ................ 148
6.3 13C-'H COSY (13C-'H HETCOR) .................... 152
6.4 Heteronuclear Multiple-Band Correlation Spectroscopy ....... 153
6.5 Two-dimensional Nuclear Overhauser Enhancement Spectroscopy . 156
6.6 Conformation Analysis by 2D NMR .................. 159
6.7 Incredible Natural Abundance Double Quantum
Transfer Experiment .......................... 164
6.8 ]-Resolved Spectroscopy ........................ 166
7 NMRRELAXATION .............................1 69
7.1 Basic Principles of NMR Relaxation .................. 169
7.2 Measurement of T, and NOE ...................... 172
7.3 Sample Preparation - Effect of Oxygen and Type of Sample Tube . . 176
7.4 Reliability of Spin-Lattice Relaxation Time and NOE ......... 178
7.5 Effect of Frequency, Temperature, Solution Concentration
and Solvent on the Measurement of TI and NOE ........... 183
7.6 Tacticity Dependence of 'H TI and 13C Tl Values and NOE ...... 191
7.7 Molecular Weight Dependence of 13C TI ................ 195
8 ON-LINE SECINMR ANALYSIS OF POLYMERS .............. 199
8.1 SECINMR Instrumentation ....................... 199
8.2 Molecular Weight Determination of Polymers by SECINMR ..... 201
8.3 Studies on Molecular Weight Dependence of Copolymer
Composition and Tacticity ....................... 204
8.4 Simple and Accurate Analysis of Oligomers .............. 206
Subject Index ..................................20 9