Albunia / Prades / Jeremic Multimodal Polymers with Supported Catalysts

Design and Production
1. Auflage 2019
ISBN: 978-3-030-03476-4
Verlag: Springer Nature Switzerland
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 280 Seiten

This book provides an overview of polyolefine production, including several recent breakthrough innovations in the fields of catalysis, process technology, and materials design. The industrial development of polymers is an extraordinary example of multidisciplinary cooperation, involving experts from different fields.  An understanding of structure-property and processing relationships leads to the design of materials with innovative performance profiles. A comprehensive description of the connection between innovative material performance and multimodal polymer design, which incorporates both flexibility and constraints of multimodal processes and catalyst needs, is provided. This book provides a summary of the polymerization process, from the atomistic level to the macroscale, process components, including catalysts, and their influence on final polymer performance. This reference merges academic research and industrial knowledge to fill the gaps between academic research and industrial processes.  ·         Connects innovative material performance to the flexibility of multimodal polymer design processes; ·         Provides a comprehensive description of the polymerization process from the atomic level to the macroscale; ·         Presents a polyhedric view of multimodal polymer production, including structure, property, and processing relationships, and the development of new materials.

Dusan Jeremic is a Senior Group Expert  and Alexandra Albunia and Floran Prades are Senior Scientists at Borealis Polyolefine GmbH.

Autoren/Hrsg.

Albunia, Alexandra Romina

Prades, Floran

Jeremic, Dusan

Inhaltsverzeichnis

1;Overview of Polyolefins - Role of Polyolefins in Our Daily Lives;5
2;Contents;9
3;Chapter 1: Recent Developments in Supported Polyolefin Catalysts: A Review;10
3.1;1.1 Overview;10
3.1.1;1.1.1 Scope of the Chapter;11
3.2;1.2 Ziegler Catalysts;12
3.2.1;1.2.1 Ziegler/Natta Polypropylene Catalysis;12
3.2.1.1;TiCl3 Catalysts (First and Second Generation);12
3.2.1.2;Third Generation: ``Activated´´ MgCl2;13
3.2.1.3;Fourth Generation: Phthalate ID/Alkoxysilane ED;13
3.2.1.4;Fifth-Generation Catalysts: Diethers, Succinates, and Polyol Esters;14
3.2.1.5;Sixth-Generation Ziegler: Phthalate Replacement;16
3.2.1.6;Catalyst Morphology Control;17
3.2.1.7;External Donors;23
3.2.2;1.2.2 Ziegler Catalysts: Polyethylene;27
3.2.2.1;MgCl2-Titanium Catalysts on Silica;27
3.2.2.2;Spray-Dried MgCl2-Titanium Catalysts;28
3.2.2.3;MgCl2-Titanium Catalysts Based on Mg(OR)2;30
3.2.2.4;MgCl2-Titanium Catalysts Based on MgCl2 alcohol adducts;32
3.2.2.5;MgCl2-Titanium Catalysts Based on MgRCl;34
3.3;1.3 Supported Molecular Catalysts;35
3.3.1;1.3.1 Polypropylene Complex Development;35
3.3.2;1.3.2 Polyethylene Complex Development;36
3.3.3;1.3.3 Supported Activator Development;40
3.3.3.1;Silica-Supported Methylaluminoxane or Boron-Based Cocatalysts;40
3.3.3.2;Supported Methylaluminoxane System Free of a Support;41
3.3.3.3;Supported System Free of Methylaluminoxane;42
3.3.4;1.3.4 Supported Hybrid Catalyst for Multimodal Polyethylene;44
3.3.4.1;Challenges of Single Supported Systems;46
3.3.4.2;Challenges of Hybrid Supported Systems;46
3.3.4.3;Hybrid Systems;47
3.4;1.4 Conclusion;51
3.5;References;51
4;Chapter 2: Support Designed for Polymerization Processes;63
4.1;2.1 General Considerations;63
4.2;2.2 MgCl2-Based Support;64
4.2.1;2.2.1 MgCl2 Methods of Preparation;65
4.2.1.1;Emulsion;66
4.2.1.2;Spray Drying;66
4.2.1.3;Reactive Precipitation;67
4.3;2.3 SiO2-Based Support;68
4.3.1;2.3.1 Synthesis;68
4.3.1.1;Granular Silica Particles;68
4.3.1.1.1;Acidification-Polymerization;68
4.3.1.1.2;Gelation;69
4.3.1.1.3;Aging;69
4.3.1.1.4;Washing and Solvent Exchange;69
4.3.1.1.5;Drying;69
4.3.1.2;Spheroidal Silica Particles;70
4.3.2;2.3.2 Thermal Modification of the Silica Particle;70
4.4;2.4 Influence of Support Design on the Fragmentation Process;71
4.4.1;2.4.1 Polymer Particle Growth;73
4.4.2;2.4.2 Physical Properties of the Support Particles;74
4.4.3;2.4.3 Impact of Catalyst-Support System on the Polymerization Technology;75
4.4.4;2.4.4 Kinetics;76
4.5;2.5 Influence of Catalyst Support on Tailoring Polyolefin Grades;78
4.5.1;2.5.1 Ziegler-Natta Catalyst;78
4.5.1.1;High Impact Polypropylene;79
4.5.1.2;Differences in Support Design for HDPE and LLDPE;80
4.5.2;2.5.2 Chromium Catalyst;81
4.5.2.1;Influence of Catalyst Porosity and Surface Area;82
4.5.3;2.5.3 Metallocenes;83
4.6;2.6 Conclusion;84
4.7;References;84
5;Chapter 3: Fragmentation, Particle Growth and Single Particle Modelling;89
5.1;3.1 Introduction;89
5.2;3.2 Particle Fragmentation and Growth;92
5.2.1;3.2.1 The Fragmentation Step;93
5.2.2;3.2.2 Particle Growth;101
5.3;3.3 Single Particle Modeling;103
5.3.1;3.3.1 The Multigrain and Polymer Flow Models;103
5.3.2;3.3.2 Solving the PFM;108
5.3.2.1;Choice of Key Model Parameters and Boundary Conditions;108
5.3.2.2;Brief Overview of the Solution Methods;116
5.4;3.4 Conclusions;118
5.5;References;119
6;Chapter 4: Polymerization Kinetics and the Effect of Reactor Residence Time on Polymer Microstructure;123
6.1;4.1 Polyolefin Microstructure;123
6.1.1;4.1.1 Molecular Weight Distribution;124
6.1.2;4.1.2 Chemical Composition Distribution;127
6.1.3;4.1.3 Chain Sequence Length Distribution;129
6.2;4.2 Reaction Kinetics;129
6.2.1;4.2.1 Multi-Scale Approach;129
6.2.2;4.2.2 Polymerization Kinetic Scheme;130
6.2.3;4.2.3 Polymer Design;135
6.2.3.1;Single-Stage Processes;135
6.2.3.2;Effect of Hydrogen;136
6.2.3.3;Effect of Comonomer;136
6.2.3.4;Multi-Stage Processes;137
6.2.4;4.2.4 Microstructural Deconvolution Techniques;138
6.2.5;4.2.5 Deconvolution and Estimation of Kinetic Constants;142
6.3;4.3 Reactor Residence Time Distribution Effects;143
6.3.1;4.3.1 Bench-Scale Versus Industrial Reactors;143
6.3.2;4.3.2 Residence Time Distribution Fundamentals;145
6.3.3;4.3.3 Case Study: Effect of RTD on MWD and Chemical Composition;150
6.4;References;158
7;Chapter 5: Industrial Multimodal Processes;162
7.1;5.1 Introduction;162
7.2;5.2 Properties and Applications;163
7.3;5.3 Polyolefin Reactor Technologies;164
7.3.1;5.3.1 The Evolution of Industrial Polyolefin Manufacturing Technologies;164
7.3.2;5.3.2 Gas-Phase Reactor Technology;166
7.3.3;5.3.3 Slurry-Phase Ethylene Polymerization Reactors;169
7.3.4;5.3.4 Comparing Slurry and Gas-Phase Reactors: A Fundamental Approach;173
7.4;5.4 Polyolefin Multimodal Processes;177
7.4.1;5.4.1 Introduction;177
7.4.2;5.4.2 Multimodal PE Processes;180
7.4.2.1;The Split Loop Borstar Process;180
7.4.2.2;Advanced Cascade Process by Hostalen;187
7.4.2.3;The Spherilene C Process;189
7.4.3;5.4.3 Multimodal PP Processes;192
7.4.3.1;The Spheripol PP Process;192
7.4.3.2;Multi-zone Circulating Reactor (MZCR) Process Technology: Spherizone Process;197
7.4.3.3;The Borstar PP Process;199
7.4.3.4;The Hypol PP Process by Mitsui Chemicals;202
7.4.3.5;The Unipol II PP Process;205
7.5;5.5 Overview;208
7.6;References;209
8;Chapter 6: Multimodal Polypropylenes: The Close Interplay Between Catalysts, Processes and Polymer Design;211
8.1;6.1 Introduction;211
8.2;6.2 An Overview of the Main PP Processes and Catalyst Requirements;213
8.3;6.3 Tailoring the Continuous Phase: A Complex Undertake;220
8.3.1;6.3.1 Processes and Operating Conditions;220
8.3.2;6.3.2 Bulk Polymerisation and Design of Continuous Phase;221
8.3.3;6.3.3 Gas-Phase and Design of Continuous Phase;222
8.3.4;6.3.4 Hybrid Systems and Design of Continuous Phase;223
8.3.5;6.3.5 Some Process Tricks to Create and Enhance Multimodality;224
8.3.6;6.3.6 Unique Product Features Via Matrix Multimodality;225
8.4;6.4 Tailoring the Dispersed Phase: A Polymer Design Challenge;230
8.4.1;6.4.1 Which Processes for Multimodal Rubbers?;230
8.4.2;6.4.2 Additional Catalyst Requirements;232
8.4.3;6.4.3 Why Multimodal Rubbers?;236
8.5;6.5 Conclusions;240
8.6;References;241
9;Chapter 7: Bimodal Polyethylene: Controlling Polymer Properties by Molecular Design;248
9.1;7.1 Introduction;248
9.2;7.2 Molecular Structure and Properties of PE;250
9.3;7.3 Catalysts for the Synthesis of PE;253
9.3.1;7.3.1 Ziegler-Natta Catalysts;253
9.3.2;7.3.2 Phillips Catalysts;255
9.3.3;7.3.3 Single Site Catalysts/Metallocenes;256
9.4;7.4 Processes for the Production of PE;256
9.4.1;7.4.1 Suspension (Slurry) Process;257
9.4.1.1;Autoclave Process;257
9.4.1.2;Loop Process;257
9.4.2;7.4.2 Gas-Phase Process;257
9.4.3;7.4.3 Solution Process;258
9.4.4;7.4.4 Multistage Process;258
9.5;7.5 Multimodality: Tailoring the Polymer Properties;258
9.5.1;7.5.1 Benefits of Multimodality for PE;260
9.5.2;7.5.2 Multi-Reactor Design;262
9.5.3;7.5.3 One-Reactor Process;264
9.5.4;7.5.4 Properties of Bimodal PE Resins;266
9.5.5;7.5.5 Homogeneity;266
9.6;7.6 Summary and Conclusions;267
9.7;References;268
10;Summary and Perspectives;271
11;Index;275