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Polymerization Processes

Abstract The article contains sections titled: 1. Introduction‐Trends in Polymer Reaction Engineering 2. Polymerization Mechanisms and Kinetics 2.1. Step‐Growth Polymerization 2.1.1. Linear Polymerization 2.1.2. Interfacial Polymerization 2.1.3. Nonlinear Polymerization 2.2. Chain‐Growth Polymerization 2.2.1. Free‐Radical Polymerization 2.2.1.1. Initiation 2.2.1.2. Propagation 2.2.1.3. Termination 2.2.1.4. Chain Transfer to Small Molecules 2.2.1.5. Kinetics of Linear Polymerization 2.2.1.6. Effect of Temperature 2.2.1.7. Branching Reactions 2.2.2. Ionic Polymerization 2.2.2.1. Cationic Polymerization 2.2.2.2. Anionic Polymerization 2.2.2.3. Ziegler ‐ Natta Polymerization 2.3. Copolymerization 2.3.1. Copolymer Composition 2.3.2. Kinetics of Copolymerization 2.3.3. Copolymerization of Vinyl and Divinyl Monomers 3. Polymerization Processes and Reactor Modeling 3.1. Introduction 3.2. Processes and Reactor Modeling for Step‐Growth Polymerization 3.2.1. Types of Reactors and Reactor Modeling 3.2.2. Specific Processes 3.3. Processes and Reactor Modeling for Chain‐Growth Polymerization 3.3.1. Material Balance Equations for Batch, Semi‐Batch, and Continuous Reactors 3.3.1.1. Rates of Reaction and Copolymer Composition 3.3.1.2. Molecular Masses, Long‐Chain Branching, and Cross‐Linking 3.3.2. Examples of Free‐Radical Polymerization 3.3.2.1. Homopolymerization ‐ Linear Chains 3.3.2.2. Copolymerization ‐ Linear Chains 3.3.2.3. Copolymerization ‐ Long‐Chain Branching 3.3.3. Polymerization Processes 3.3.3.1. Solution Polymerization 3.3.3.1.1. Polymer Soluble in Monomer 3.3.3.1.2. Addition of a Solvent in which both Monomer and Polymer are Miscible 3.3.3.1.3. Polymer ‐ Polymer Demixing during Polymerization 3.3.3.2. Precipitation Polymerization 3.3.3.2.1. Polymer Insoluble in its Monomer 3.3.3.2.2. Monomer Functioning as Solvent for the Polymer 3.3.3.3. Suspension Polymerization 3.3.3.3.1. Qualitative Description 3.3.3.3.2. Dispersants 3.3.3.3.3. Mechanism of Particle Formation 3.3.3.3.4. Industrial Applications 3.3.3.4. Emulsion Polymerization 3.3.3.4.1. Theories of Emulsion Polymerization 3.3.3.4.2. Physicochemical Parameters of Dispersions 3.3.3.4.3. Inverse Emulsion Polymerization 3.3.3.4.4. Semi‐Batch Emulsion Polymerization 3.3.3.4.5. Continuous Emulsion Polymerization 3.3.4. Miscellaneous Processes 3.3.5. Ionic Polymerization Modeling 3.3.5.1. Introduction 3.3.5.2. Heterogeneous Coordination Polymerization 3.3.6. Process Variables, Reactor Dynamics/ Stability, On‐Line Monitoring and Control 3.3.6.1. Influence of Reactor Type and Configuration on Molecular Mass and Copolymer Composition Distributions, and on Long‐Chain Branching and Cross‐Linking 3.3.6.1.1. Monomer Coupling with Bimolecular Termination Plug Flow and Batch Reactors (CPFR/BR) 3.3.6.1.2. Monomer Coupling Without Termination Plug Flow and Batch Reactors (CPFR/BR) 3.3.6.1.3. Polymer Coupling 3.3.6.1.4. Copolymerization 3.3.6.1.5. Long‐Chain Branching and Cross‐Linking 3.3.6.2. Reactor Dynamics and Stability 3.3.6.3. On‐Line Monitoring and Control 4. Acknowledgement

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