Supercritical Carbon Dioxide – in Polymer Reaction Engineering

Maartje Kemmere (1971) received her MSc in chemical engineering at Eindhoven University of Technology in 1995, followed by a PhD in emulsion polymerisation process development in 1999. Subsequently, she joined the Process Development Group of Eindhoven University of Technology as an assistant professor. Current research areas are polymer reaction engineering with emphasis on supercritical fluids and ultrasound technology, and polymer materials for biomedical purposes. In 2003 she was a visiting scientist at the Flemish Institute for Technological Research. Thierry Meyer, born 1961 in Geneva, obtained his MSc in 1985 at the Swiss Federal Institute of Technology in Lausanne (EPFL), followed in 1989 by a PhD in chemical engineering. He joined Ciba-Geigy in 1994 as development chemist in the pigment division, then as head of development a.i. to become production manager in 1998. In 1999 he switched to the Institute of Chemical Sciences and Engineering at EPFL to head the polymer reaction engineering unit. Since 2002, he also functions as the chairman of the working party on polymer reaction engineering of the European Federation of Chemical Engineering.

Foreword. Preface. List of Contributors. 1 Supercritical Carbon Dioxide for Sustainable Polymer Processes (Maartje Kemmere). 1.1 Introduction. 1.2 Strategic Organic Solvent Replacement. 1.3 Physical and Chemical Properties of Supercritical CO2. 1.4 Interactions of Carbon Dioxide with Polymers and Monomers. 1.5 Concluding Remarks and Outlook. 2 Phase Behavior of Polymer Systems in High--Pressure Carbon Dioxide (Gabriele Sadowski). 2.1 Introduction. 2.2 General Phase Behavior in Polymer/Solvent Systems. 2.3 Polymer Solubility in CO2. 2.4 Thermodynamic Modeling. 2.5 Conclusions. 3 Transport Properties of Supercritical Carbon Dioxide (Frederic Lavanchy, Eric Fourcade, Evert de Koeijer, Johan Wijers, Thierry Meyer, and Jos Keurentjes). 3.1 Introduction. 3.2 Hydrodynamics and Mixing. 3.3 Heat Transfer. 3.4 Conclusions. 4 Kinetics of Free--Radical Polymerization in Homogeneous Phase of Supercritical Carbon Dioxide (Sabine Beuermann and Michael Buback). 4.1 Introduction. 4.2 Experimental. 4.3 Initiation. 4.4 Propagation. 4.5 Termination. 4.6 Chain Transfer. 4.7 Conclusions. 5 Monitoring Reactions in Supercritical Media (Thierry Meyer, Sophie Fortini, and Charalampos Mantelis). 5.1 Introduction. 5.2 On--line Analytical Methods Used in SCF. 5.3 Calorimetric Methods. 5.4 MMA Polymerization as an Example. 5.5 Conclusions. 6 Heterogeneous Polymerization in Supercritical Carbon Dioxide (Philipp A. Mueller, Barbara Bonavoglia, Giuseppe Storti, and Massimo Morbidelli). 6.1 Introduction. 6.2 Literature Review. 6.3 Modeling of the Process. 6.4 Case Study I: MMA Dispersion Polymerization. 6.5 Case Study II: VDF Precipitation Polymerization. 6.6 Concluding Remarks and Outlook. 7 Inverse Emulsion Polymerization in Carbon Dioxide (Eric J. Beckman). 7.1 Introduction. 7.2 Inverse Emulsion Polymerization in CO2: Design Constraints. 7.3 Surfactant Design for Inverse Emulsion Polymerization. 7.4 Inverse Emulsion Polymerization in CO2: Results. 7.5 Future Challenges. 8 Catalytic Polymerization of Olefins in Supercritical Carbon Dioxide (Maartje Kemmere, Tjerk J. de Vries, and Jos Keurentjes). 8.1 Introduction. 8.2 Phase Behavior of Polyolefin--Monomer--CO2 Systems. 8.3 Catalyst System. 8.4 Polymerization of Olefins in Supercritical CO2 Using Brookhart Catalyst. 8.5 Concluding Remarks and Outlook. 9 Production of Fluoropolymers in Supercritical Carbon Dioxide (Colin D. Wood, Jason C. Yarbrough, George Roberts, and Joseph M. DeSimone). 9.1 Introduction. 9.2 Fluoroolefin Polymerization in CO2. 9.3 Fluoroalkyl Acrylate Polymerizations in CO2. 9.4 Amphiphilic Poly(alkylacrylates). 9.5 Photooxidation of Fluoroolefins in Liquid CO2. 9.6 CO2/Aqueous Hybrid Systems. 9.7 Conclusions. 10 Polymer Processing with Supercritical Fluids (Oliver S. Fleming and Sergei G. Kazarian). 10.1 Introduction. 10.2 Phase Behavior of CO2/Polymer Systems and the Effect of CO2 on Polymers. 10.3 Rheology of Polymers Under High--Pressure CO2. 10.4 Polymer Blends and CO2. 10.5 Supercritical Impregnation of Polymeric Materials. 10.6 Conclusions and Outlook. 11 Synthesis of Advanced Materials Using Supercritical Fluids (Andrew I. Cooper). 11.1 Introduction. 11.2 Polymer Synthesis. 11.3 Porous Materials. 11.4 Nanoscale Materials and Nanocomposites. 11.5 Lithography and Microelectronics. 11.6 Conclusion and Future Outlook. 12 Polymer Extrusion with Supercritical Carbon Dioxide (Leon P. B.M. Janssen and Sameer P. Nalawade). 12.1 Introduction. 12.2 Practical Background on Extrusion. 12.3 Supercritical CO2--Assisted Extrusion. 12.4 Mixing and Homogenization. 12.5 Applications. 12.6 Concluding Remarks. 13 Chemical Modification of Polymers in Supercritical Carbon Dioxide (Jesse M. de Gooijer and Cor E. Koning). 13.1 Introduction. 13.2 Brief Review of the State of the Art. 13.3 End--group Modification of Polyamide 6 in Supercritical CO2. 13.4 Carboxylic Acid End--group Modification of Poly(Butylene Terephthalate) with 1,2--Epoxybutane in Supercritical CO2. 13.5 Concluding Remarks and Outlook. 14 Reduction of Residual Monomer in Latex Products Using High--Pressure Carbon Dioxide (Maartje F. Kemmere, Marcus van Schilt, Marc Jacobs, and Jos Keurentjes). 14.1 Introduction. 14.2 Overview of Techniques for Reduction of Residual Monomer. 14.3 Enhanced Polymerization in High--Pressure Carbon Dioxide. 14.4 Extraction Capacity of Carbon Dioxide. 14.5 Process Design for the Removal of MMA from a PMMA Latex Using CO2. 14.6 Conclusion and Future Outlook. Subject Index.