Dieses Buch folgt einem modularen Ansatz bei der Modellierung von Polymerisationsreaktionen und versetzt Praktiker in die Lage, ihre eigenen Modelle für Simulationswerkzeuge wie Predici®, C++, MatLab usw. zu entwickeln. Ein überaus nützliches Referenzwerk für Polymeringenieure und Forscher.
Autorentext
Klaus-Dieter Hungenberg has been Vice President Polymer Reaction Engineering at BASF SE until his retirement in 2013. In 2012 he received an Honorary Professorship at the University of Paderborn. He is (co-)author of more than 100 scientific articles and patents.
Michael Wulkow founded the company Computing in Technology (CiT) in 1992 and since then has been involved in projects, research and numerous publications on the modeling and numerical treatment of processes in technical chemistry, biology, particle technology and pharmacokinetics.
Zusammenfassung
Introducing a unique, modular approach to modeling polymerization reactions, this useful book will enable practitioners - chemists and engineers alike - to set up and structure their own models for simulation software like Predici®, C++, MatLab® or others. The generic modules are exemplified for concrete situations for various reactor types and reaction mechanisms and allow readers to quickly find their own point of interest - a highly useful information source for polymer engineers and researchers in industry and academia.
Inhalt
Preface ix
1 Introduction 1
1.1 Special Features of Polymers 1
1.2 Structures in Polymers and Their Influence on Processing and Application Properties 3
1.2.1 Chain Length, Molecular Mass, Moments, and Mean Values 3
1.2.2 Rheological Properties 6
1.2.3 Constitutional Isomers 7
1.2.4 Architectural Isomers 9
1.2.5 Copolymers 11
1.3 Some Analytical Methods for Model Validation 13
1.4 Description of Polymer Properties 15
1.4.1 Chemical Master Equations 17
1.4.2 Approaches to Polymer Properties 21
1.4.3 Stochastic and Deterministic Simulation 22
2 Polymer Reactions 25
2.1 Module Concept 25
2.2 Rate Coefficients in Polymerization Reactions 26
2.3 Building Macromolecules 28
2.4 Only Chain-Forming Reactions Take Place, Step-Growth Polymerization 30
2.4.1 Only One Type of End Group: The A A Case, A Reacting with A 31
2.4.2 Two Types of Functional Groups A and B at One Molecule; A Reacts with B 40
2.4.3 Introducing Monofunctional Molecules to Control Degree of Polymerization 41
2.4.4 Addition of a Second Bifunctional Monomer, Two Functional Groups on Two Different Molecular Species 43
2.4.5 Reversible Reactions 49
2.5 Chain-Growth Polymerization Initiation Required 58
2.5.1 Living Polymerization Only Initiation and Propagation (Chain Growth) Take Place 59
2.5.1.1 Moment Equations 65
2.5.2 Living Polymerization Together with Chain Depropagation 68
2.5.3 Initiation and Chain Growth with Transfer Reactions 75
2.5.4 Initiation and Chain Growth with Deactivation 76
2.5.5 Initiation and Chain Growth with Chain Termination 77
2.5.5.1 Termination by Disproportionation 84
2.5.5.2 Termination by Combination 84
2.5.5.3 Transfer to Monomer or Transfer Agent 86
2.5.5.4 Transfer to Polymer 87
2.5.5.5 Propagation with Change of Characteristics 89
2.5.5.6 𝛽-Scission 90
2.6 Copolymerization 91
2.6.1 Conventional Description of Copolymer Composition 91
2.6.2 Characteristic Values for the Characterization of Copolymers 94
2.6.3 Modules for the Description of Copolymerization 97
2.6.4 Extended Description of a Copolymer 101
2.6.5 Distributed Counters 104
2.7 Nonlinear Polymerization 106
2.7.1 Branching; Graft Polymers via Copolymerization, (Grafting through) 106
2.7.2 Cross-Linking via Copolymerization 107
2.7.3 Nonlinear Structures by Polymerization from an Existing Chain, Grafting from 109
2.7.4 Cross-Linking of Preformed Linear Macromolecules by Low-Molecular-Mass Compounds 111
2.7.5 Nonlinear Step Growth 111
2.7.6 Higher Dimensional Models 113
2.8 List of Modules 114
2.8.1 Elemental Kinetic 115
2.8.2 Combination (P, Q, T, A) 116
2.8.3 Statistical Degradation (P, Q, T, A, B) 119
2.8.4 Change of Characteristics (P, Q, A, B) 120
2.8.5 Intermolecular Transfer (P, Q, T, R, A) 121
2.8.6 Cross Transfer (P, Q, T, R, A) 123
2.8.7 Initiation (P, A, B, C, m) 124
2.8.8 Propagation (P, Q, M, A, m) 125
2.8.9 Depropagation (P, Q, M, A, B, m) 127
2.8.10 Transfer (P, Q, T, M) 128
2.8.11 Disproportionation (P, Q, R, T, A) 129
2.8.12 Transfer to Polymer (P, Q, T, R, A) 131
2.8.13 Scission (P, Q, T, A, B) 132
2.8.14 Cross-Linking (P, Q, T, A) 133
2.8.15 Flow (A1,A2) 134
2.8.16 Phase Transfer (A1,A2) 135
2.8.17 Example System 135
3 Reactors for Polymerization Processes 139
3.1 Introduction 140
3.2 Well-Mixed (Ideal) Batch Reactor (BR) 141
3.2.1 Aspects of the Overall Mass Balance 143
3.2.2 Heat Balance in a Batch Reactor 144
3.2.3 Polymer Properties in Batch Reactors 148
3.3 Semi-Batch Reactor (Semi-BR) 149
3.4 The Continuous Stirred Tank Reactor (CSTR) 151