Free download Supercritical Carbon Dioxide in Polymer Reaction Engineering by Maartje F. Kemmere

Authors of: Supercritical Carbon Dioxide in Polymer Reaction Engineering by Maartje F. Kemmere

Maartje F. Kemmere

Thierry Meyer

Table of Contents in Supercritical Carbon Dioxide in Polymer Reaction Engineering by Maartje F. Kemmere

Foreword V

Preface VII

List of Contributors XVII

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

Notation

References

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

Notation

References

Supercritical Carbon Dioxide: in Polymer Reaction Engineering

Edited by Maartje F. Kemmere and Thierry Meyer

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

3.2.1 Laser-Doppler Velocimetry and Computational Fluid Dynamics

3.2.2 Flow Characteristics

3.3 Heat Transfer

3.3.1 Specific for Near-Critical Fluids: the Piston Effect

3.3.2 Reaction Calorimetry

3.3.3 Heat Transfer in Stirred Vessel with SCFs

3.4 Conclusions

Notation

References

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

4.4.1 Propagation Rate Coefficients

4.4.2 Reactivity Ratios

4.5 Termination

4.6 Chain Transfer

4.7 Conclusions

Notation

References

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

5.2.1 Spectroscopic Methods

5.2.1.1 FTIR

5.2.1.2 Raman Spectroscopy

5.2.1.3 UV/Vis

5.2.1.4 NMR

5.2.2 Reflectometry

5.2.3 Acoustic Methods

5.3 Calorimetric Methods

5.3.1 Power Compensation Calorimetry

5.3.2 Heat Flow Calorimetry

5.3.2.1 Heat Balance Equations

5.3.2.2 Determination of Physico-Chemical Parameters

5.3.2.3 Calorimeter Validation by Heat Generation Simulation

5.4 MMA Polymerization as an Example

5.4.1 Calorimetric Results

5.4.2 The Coupling of Calorimetry and On-Line Analysis

5.5 Conclusions

Notation

References

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

Notation

References

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

7.3.1 Designing CO2-philic Compounds: What Can We Learn

from Fluoropolymer Behavior?

7.3.2 Non-Fluorous CO2-Philes: the Role of Oxygen

7.4 Inverse Emulsion Polymerization in CO2: Results

7.5 Future Challenges

References

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

8.2.1 Cloud-Point Measurements on the PEP-Ethylene-CO2 System

8.2.2 SAFT Modeling of the PEP-Ethylene-CO2 System

8.3 Catalyst System

8.3.1 Solubility of the Brookhart Catalyst in scCO2

8.3.2 Copolymerization of Ethylene and Norbornene Using a Neutral

Pd-Catalyst

8.3.3 Ring-Opening Metathesis Polymerization of Norbornene

Using an MTO Catalyst

8.4 Polymerization of Olefins in Supercritical CO2 Using Brookhart

Catalyst

8.4.1 Catalytic Polymerization of 1-Hexene in Supercritical CO2

8.4.2 Catalytic Polymerization of Ethylene in Supercritical CO2

8.4.2.1 Experimental Procedure for Polymerization Experiments

8.4.2.2 Determination of Reaction Rate

8.4.2.3 Results of the Ethylene Polymerizations

8.4.2.4 Monitoring Reaction Rate Using SAFT-LKP and SAFT-PR

8.4.2.5 Topology of Synthesized Polyethylenes

8.4.3 Copolymerization of Ethylene and Methyl Acrylate

in Supercritical CO2

8.5 Concluding Remarks and Outlook

Notation

References

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

9.2.1 Overview

9.2.2 TFE-based Materials

9.2.3 Ionomer Resins and Nafion®

9.2.4 VF2-based Materials

9.2.5 VF2 and TFE Telomerization

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

References

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

10.2.1 Solubility of CO2 in Polymers

10.2.2 CO2-Induced Plasticization of Polymers

10.2.3 CO2-Induced Crystallization of Polymers

10.2.4 Interfacial Tension in CO2/Polymer Systems

10.2.5 Diffusion of CO2 in Polymers and Solutes in Polymers

Subjected to CO2

10.2.6 Foaming

10.3 Rheology of Polymers Under High-Pressure CO2

10.3.1 Methods for the Measurements of Polymer Viscosity

Under High-Pressure CO2

10.3.2 Viscosity of Polymer Melts Subjected to CO2

10.3.3 Implications for Processing: Extrusion

10.4 Polymer Blends and CO2

10.4.1 CO2-Assisted Blending of Polymers

10.4.2 CO2-Induced Phase Separation in Polymer Blends

10.4.3 Imaging of Polymeric Materials Subjected to High-Pressure CO2

10.5 Supercritical Impregnation of Polymeric Materials

10.5.1 Dyeing of Polymeric Materials

10.5.2 Preparation of Materials for Optical Application

10.5.3 Preparation of Biomaterials and Pharmaceutical Formulations

10.6 Conclusions and Outlook

Notation

References 234

11 Synthesis of Advanced Materials Using Supercritical Fluids

13 Chemical Modification of Polymers in Supercritical Carbon

Dioxide  

14 Reduction of Residual Monomer in Latex Products

Using High-Pressure Carbon Dioxide

Subject Index

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