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Kinetics and Modeling of the Radical Polymerization of Acrylic Acid and of Methacrylic Acid in Aqueous Solution

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Kinetics and Modeling of the Radical Polymerization of Acrylic Acid and of Methacrylic Acid in Aqueous Solution Kinetics and Modeling of the Radical Polymerization of Acrylic Acid and of Methacrylic Acid in Aqueous Solution Dissertation zur Erlangung des mathematisch-naturwissenschaftlichen Doktorgrades „Doctor rerum naturalium“ der Georg-August-Universität Göttingen im Promotionsprogramm Chemie der Georg-August University School of Science (GAUSS) vorgelegt von Nils Friedrich Gunter Wittenberg aus Hamburg Göttingen, 2013 Betreuungsausschuss Prof. Dr. M. Buback, Technische und Makromolekulare Chemie, Institut für Physikalische Chemie, Georg-August-Universität Göttingen Prof. Dr. P. Vana, MBA, Makromolekulare Chemie, Institut für Physikalische Chemie, Georg-August-Universität Göttingen Mitglieder der Prüfungskommission Referent: Prof. Dr. M. Buback, Technische und Makromolekulare Chemie, Institut für Physikalische Chemie, Georg-August-Universität Göttingen Korreferent: Prof. Dr. P. Vana, MBA, Makromolekulare Chemie, Institut für Physikalische Chemie, Georg-August-Universität Göttingen Weitere Mitglieder der Prüfungskommission: Prof. Dr. G. Echold, Physikalische Chemie fester Körper, Institut für Physikalische Chemie, Georg-August-Universität Göttingen Prof. Dr. B. Geil, Biophysikalische Chemie, Institut für Physikalische Chemie, Georg-August- Universität Göttingen Jun.-Prof. Dr. R. Mata, Computerchemie und Biochemie,Institut für Physikalische Chemie, Georg-August-Universität Göttingen Prof. Dr. A. Wodtke, Physikalische Chemie I / Humboldt-Professur, Institut für Physikalische Chemie, Georg-August-Universität Göttingen Tag der mündlichen Prüfung: 24.10.2013 Meiner Familie Table of Contents Table of Contents Abstract .......................................................................................................................... 1 1 Introduction ............................................................................................................ 3 2 Theoretical Background ......................................................................................... 7 2.1 General Aspects of Radical Stability and Reactivity ...................................... 7 2.2 Ideal Polymerization Kinetics of Radical Polymerization .............................. 9 2.2.1 Formation of Radicals and Initiation ..................................................... 10 2.2.2 Propagation ............................................................................................. 13 2.2.3 Termination ............................................................................................ 13 2.2.4 Steady State Kinetics ............................................................................. 14 2.3 Additional Reactions...................................................................................... 15 2.3.1 Transfer Reactions to Small Molecules .................................................. 15 2.3.2 Intermolecular Transfer to Polymer ...................................................... 19 2.3.3 Intramolecular Transfer to Polymer – Backbiting ................................ 20 2.3.1 β-Scission Reaction ................................................................................. 24 2.3.2 Retardation and Inhibition .................................................................... 26 2.4 Influences on Rate Coefficients ..................................................................... 27 2.4.1 Temperature and Pressure ..................................................................... 29 2.4.2 Concentration ......................................................................................... 30 2.4.3 Ionization ................................................................................................ 33 2.4.4 Chain Length .......................................................................................... 38 2.4.5 Conversion .............................................................................................. 45 2.5 Computer Modeling of Polymerizations ........................................................ 51 3 Materials, Experimental Procedures and Data Evaluation ................................ 55 3.1 Chemicals ....................................................................................................... 55 V Table of Contents 3.1.1 Monomers ............................................................................................... 55 3.1.2 Solvents .................................................................................................. 57 3.1.3 Initiators ................................................................................................. 58 3.1.4 Inhibitors ................................................................................................ 60 3.1.5 Substances used to prepare Buffer Solutions ........................................ 60 3.1.6 Others ..................................................................................................... 61 3.2 Purification Procedures ................................................................................. 63 3.3 NIR ................................................................................................................ 63 3.3.1 Setup ....................................................................................................... 63 3.3.2 Thermally initiated Polymerization in a Cuvette.................................. 64 3.3.3 Photoinitiated Polymerization in a Cuvette .......................................... 65 3.3.4 Degree of Monomer Conversion ............................................................. 65 3.4 EPR ................................................................................................................ 69 3.4.1 Setup ....................................................................................................... 69 3.4.2 Organic Samples .................................................................................... 69 3.4.3 Aqueous Samples ................................................................................... 70 3.4.1 Deconvolution of Spectra ........................................................................ 70 3.4.2 Calibration .............................................................................................. 70 3.5 NMR ............................................................................................................... 71 3.5.1 Quantitative 1H-NMR ............................................................................ 71 3.5.2 Quantitative 13C-NMR ........................................................................... 72 3.5.3 Polymerization in NMR Sample Tube ................................................... 77 3.6 Density Measurement ................................................................................... 78 3.7 Viscosity Measurement ................................................................................. 78 3.7.1 Important Features of Polymer Solutions ............................................. 79 3.7.2 Polymerization in Viscosity Measurement Capillary ............................ 80 3.8 Preparation of Buffer Solutions .................................................................... 80 3.9 SEC ................................................................................................................ 81 VI Table of Contents 3.10 ESI-MS ........................................................................................................... 81 3.11 HPLC ............................................................................................................. 81 3.12 pH-Meter ........................................................................................................ 82 3.13 High-Temperature Polymerizations.............................................................. 83 3.13.1 Stopped-Flow experiments in High-Pressure Cell ................................. 84 3.13.2 Polymerization in a Tubular Reactor ..................................................... 84 3.14 Other Setups for Polymerization ................................................................... 88 3.14.1 1 L Automated Reactor ........................................................................... 88 3.14.2 Polymerization in a Heating Block ........................................................ 89 3.14.3 Polymerization in a Flask ...................................................................... 89 3.14.4 Polymerization in a Lined Flask ............................................................ 90 3.15 Computer Programs ...................................................................................... 90 3.15.1 Curve Fitting .......................................................................................... 90 3.15.2 Determination of Joint Confidence Regions .......................................... 90 3.15.3 Simulation .............................................................................................. 91 3.16 Error Estimate ............................................................................................... 91 4 Methacrylic Acid ................................................................................................... 95 4.1 Chain-Transfer to 2-Mercaptoethanol .......................................................... 96 4.1.1 Chain Transfer Constants deduced by the Mayo Method ..................... 97 4.1.2 Chain Transfer Constants deduced by the CLD Method .................... 101 4.1.3 Comparison of Mayo and CLD methods .............................................. 103 4.2 Model development for Non-ionized
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