Springer Laboratory Size Exclusion Chromatography Bearbeitet von Sadao Mori, Howard G Barth 1. Auflage 1999. Buch. xiv, 234 S. Hardcover ISBN 978 3 540 65635 7 Format (B x L): 15,5 x 23,5 cm Gewicht: 1170 g Weitere Fachgebiete > Chemie, Biowissenschaften, Agrarwissenschaften > Analytische Chemie > Instrumentelle Chemische Analytik, Chromatographie schnell und portofrei erhältlich bei Die Online-Fachbuchhandlung beck-shop.de ist spezialisiert auf Fachbücher, insbesondere Recht, Steuern und Wirtschaft. Im Sortiment finden Sie alle Medien (Bücher, Zeitschriften, CDs, ebooks, etc.) aller Verlage. Ergänzt wird das Programm durch Services wie Neuerscheinungsdienst oder Zusammenstellungen von Büchern zu Sonderpreisen. Der Shop führt mehr als 8 Millionen Produkte.
Table of Contents 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
VIII Table of Contents 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 ofmw Averages................... 77 6.1.1 MW Equations....................... 77 6.1.2 Calculation Procedure................... 78 6.1.3 Reproducibility of Results................. 82 6.2 Calculation ofmw 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
Table of Contents IX 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
X Table of Contents 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
Table of Contents XI 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