ISBN: 3-540-65635-9
TITLE: Size Exclusion Chromatography
AUTHOR: Mori, Sadao; Barth, Howard G.
TOC:

1 Introduction 1
1.1 Molecular Weight Measurements 1
1.2 Brief Description of Size Exclusion Chromatography 4
1.3 Brief Historical Perspective 5
1.4 Applications 6
1.5 General References 7
References 7
2 Fundamental Concepts 11
2.1 Separation Mechanism of SEC 11
2.1.1 Geometric Models 14
2.1.2 Thermodynamic Model 16
2.2 Hydrodynamic Volume Concept 17
2.3 SEC Parameters and Definitions 21
2.3.1 Column and Calibration Curve Characteristics 21
2.3.2 Peak Broadening 23
2.3.3 Column Resolution 25
References 28
3 Instrumentation 31
3.1 SEC Systems Used at Room Temperature 31
3.2 High-Temperature SEC Systems 33
3.3 Pumps and Injectors 34
3.3.1 Pumps 34
3.3.2 Injectors 37
3.4 Detectors 37
3.4.1 Introduction 37
3.4.2 Concentration-Based Detectors 38
3.4.3 Structure-Selective Detectors 43
3.4.4 MW-Sensitive Detectors 44
4 Columns 45
4.1 Introduction 45
4.2 Types of Packing Materials 45
4.3 Non-aqueous SEC Columns 47
4.4 Aqueous SEC Columns 50
4.5 Care and Handling 52
5 SEC Method Development 55
5.1 Sample Preparation 55
5.1.1 Polymer Solubility 55
5.1.2 Sample Solutions 57
5.2 Sample Concentration 58
5.2.1 Effects of Concentration 58
5.2.2 Influence of Concentration Dependence on MW Calculation 60
5.3 Calibration Curves 62
5.3.1 Calibration of Columns 62
5.3.2 Shape of the Calibration Curve 63
5.4 Column Selection 64
5.4.1 Non-aqueous SEC Columns 64
5.4.2 Aqueous SEC Columns 65
5.5 Mobile Phase Selection 66
5.5.1 Non-aqueous SEC 66
5.5.2 Aqueous SEC 68
5.5.3 Preparation of the Mobile Phase 69
5.6 Operating Conditions 69
5.6.1 Injection Volume 69
5.6.2 Flow Rate 71
5.6.3 Column Temperature 73
References 76
6 Molecular Weight Averages and Distributions 77
6.1 Calculation of MW Averages 77
6.1.1 MW Equations 77
6.1.2 Calculation Procedure 78
6.1.3 Reproducibility of Results 82
6.2 Calculation of MW Distribution 85
6.2.1 Equations 85
6.2.2 Calculation Procedure 86
6.3 Automated Data Handling 89
6.4 Band Broadening Corrections 90
6.4.1 Band Broadening Equations 90
6.4.2 Deconvolution Approaches 91
6.4.3 Correction of MW Averages 93
References 94
7 Approaches to Molecular Weight Calibration 95
7.1 Calibration with Monodisperse Standards 95
7.2 Calibration with Polydisperse Standards 97
7.2.1 Assumption of a Calibration Curve or MWD 97
7.2.2 Use of Primary and Secondary Standards 100
7.3 MW vs. Molecular Size 101
7.3.1 Terminology of Molecular Size 101
7.3.2 Parameters for Molecular Size 102
7.3.3 Comparison of Size Parameters 104
7.4 Extended Chain Length 105
7.4.1 Extended Chain Structure 105
7.4.2 Q-Factor 106
7.5 Universal Calibration 107
7.5.1 Intrinsic Viscosity 107
7.5.2 Universal Calibration Curve 109
7.5.3 Transformation of the Universal Calibration Curve 110
7.5.4 Direct Calculation of MW with Universal
Calibration 111
7.5.5 Use of Secondary Standard(s) with Universal Calibration 112
References 113
8 Molecular-Weight-Sensitive Detectors 115
8.1 Light Scattering 115
8.1.1 Theory 115
8.1.2 Instrumentation 117
8.1.3 Methodology 118
8.1.4 Problems of Refractive Index 121
8.2 Viscometry 123
8.2.1 Theory 123
8.2.2 Instrumentation 124
8.2.3 Methodology 125
8.3 Combination with a Concentration Detector 127
8.3.1 Methodology 127
8.3.2 Selected Applications 128
References 129
9 Synthetic Polymers 131
9.1 Separation of Oligomers 131
9.1.1 Refractive Index and MW 131
9.1.2 Retention Volume and MW 134
9.1.3 Epoxy Resins 137
9.1.4 Phenol-Formaldehyde Resins 140
9.1.5 Melamine Resins 141
9.1.6 Miscellaneous 141
9.2 Polymers with Commonly Used Solvents 142
9.2.1 Polymer/Solvent Combinations 142
9.2.2 Poly(vinyl chloride) 142
9.2.3 Polyorganophosphazene 144
9.2.4 Cellulose Derivatives 144
9.3 Polymers Requiring Special Solvents 145
9.3.1 Polyamides 145
9.3.2 Poly(ethylene terephthalate) 146
9.3.3 Other Polymers 147
9.4 Selected Topics 148
9.4.1 Combinations of K and a 148
9.4.2 Calculation of Detector Lag Time 149
9.4.3 Comparison of Chromatograms 150
References 152
10 High-Temperature Size Exclusion Chromatography 155
10.1 General Procedures for Preparation of Sample Solutions 155
10.2 Selected Applications 156
10.2.1 Polyethylene 156
10.2.2 Branched Polyethylene 157
10.2.3 Polypropylene 160
10.2.4 Copolymers of Polyethylene 161
10.2.5 High-Temperature-Resistant Polymers 163
References 165
11 Aqueous Size Exclusion Chromatography 167
11.1 Non-Size Exclusion Effects 167
11.1.1 Thermodynamics 167
11.1.2 Types of Non-Size Exclusion Effects 168
11.1.3 Elution Behavior of Water-Soluble Polymers 169
11.2 Mobile Phase and Packing Selection 174
11.2.1 Nonionic Polymers 174
11.2.2 Anionic Polymers 174
11.2.3 Cationic Polymers 174
11.2.4 Proteins and Peptides 175
11.3 Selected Applications 177
11.3.1 Synthetic Polymers 177
11.3.2 Biopolymers 178
11.3.3 Polysaccharides 180
References 182
12 Special Applications 185
12.1 Copolymer Analysis 185
12.1.1 Introduction 185
12.1.2 Calculation of MW 185
12.1.3 Chemical Heterogeneity 187
12.2 Preparative and Recycle SEC 189
12.2.1 Preparative SEC 189
12.2.2 Recycle SEC 191
12.3 Separation of Small Molecules 194
12.3.1 Selection of Experimental Conditions 194
12.3.2 Additives in Polymers 196
12.3.3 Application as a Cleanup Tool for Residue Analysis 196
References 198
Appendix I 199
Appendix II 209
Appendix III 215
Appendix IV 217
Subject Index 231
END
