Polyolefin Reaction Engineering

João B. P. Soares is Professor in the Department of Chemical Engineering at the University of Waterloo, Canada. He has also worked as a research and development engineer at Pronor, COPENE, and Polibrasil in Brazil. He obtained his PhD from McMaster University working with Professor A. E. Hamielec. He has authored more than 160 articles in refereed journals and 11 book chapters. Professor Soares is a Fellow of the Chemical Institute of Canada and is the recipient of the Premier's Research Excellence Award, the Union Carbide/ Dow Innovation Award, and the Syncrude/ CSChE Canada Innovation Award for contributions to Chemical Engineering under the age of 40. He is also Editor-in-Chief for the Canadian Journal of Chemical Engineering and a member of the Executive Advisory Board of Wiley-VCH Macromolecular Journals. He is a consultant for several polyolefin-manufacturing companies in Canada, USA, Europe Asia, and Brazil. Timothy F. L. McKenna is a Directeur de Recherche (DR2) at the Laboratoire de Chimie, Catalyse, Polymères et Procédés (C2P2, a CNRS laboratory), in Villeurbanne, France. He obtained his PhD in Chemical Engineering from the University of Massachusetts at Amherst, then moved to France to work with Elf-Aquitaine an Atochem on modeling polyethylene particle growth. After three years with Elf-Atochem, he joined the academic world in 1993 at the Laboratoire de Chimie et Procédés de Polymérisation (LCPP, CNRS). Since then Dr. McKenna has authored or co-authored more than 180 papers and 8 book chapters, and is a consultant at companies in Europe, the middle East and Asia. He is currently an active participant in the Dutch Polymer Institute (DPI), an associate editor of the Canadian Journal of Chemical Engineering, and serves in the International Advisory Board of 2 Macromolecular Journals, and of Chemical Engineering Technology, all from Wiley-VCH. Prof. Soares and McKenna have given in-house industrial short courses on Polyolefin Reaction Engineering to many polyolefin manufacturing companies worldwide. They also offer an annual short course on the same topic open to industrial and academic participants.

• AcknowledgmentsxiPreface xiiiNomenclature xvii1 Introduction to Polyolefins 11.1 Introduction 11.2 Polyethylene Resins 41.3 Polypropylene Resins 10Further Reading 132 Polyolefin Microstructural Characterization 152.1 Introduction 152.2 Molecular Weight Distribution 172.2.1 Size Exclusion Chromatography 172.2.2 Field Flow Fractionation 272.3 Chemical Composition Distribution 292.3.1 Crystallizability-Based Techniques 292.3.2 High-Performance Liquid Chromatography 402.4 Cross-Fractionation Techniques 432.5 Long-Chain Branching 46Further Reading 513 Polymerization Catalysis and Mechanism 533.1 Introduction 533.2 Catalyst Types 563.2.1 Ziegler–Natta Catalysts 563.2.2 Phillips Catalysts 613.2.3 Metallocenes 623.2.4 Late Transition Metal Catalysts 673.3 Supporting Single-Site Catalysts 703.4 Polymerization Mechanism with Coordination Catalysts 76Further Reading 864 Polyolefin Reactors and Processes 874.1 Introduction 874.2 Reactor Configurations and Design 894.2.1 Gas-Phase Reactors 904.2.1.1 Fluidized Bed Gas-Phase Reactors 914.2.1.2 Vertical Stirred Bed Reactor 974.2.1.3 Horizontal Stirred Gas-Phase Reactor 994.2.1.4 Multizone Circulating Reactor 1024.2.2 Slurry-Phase Reactors 1044.2.2.1 Autoclaves 1054.2.2.2 Slurry Loop Reactors 1064.2.3 Solution Reactors 1074.2.4 Summary of Reactor Types for Olefin Polymerization 1084.3 Olefin Polymerization Processes 1094.3.1 Polyethylene Manufacturing Processes 1124.3.1.1 Slurry (Inert Diluent) Processes 1124.3.1.2 Gas-Phase Processes 1154.3.1.3 Mixed-Phase Processes 1184.3.1.4 Solution Processes 1194.3.2 Polypropylene Manufacturing Processes 1214.3.2.1 Slurry (Inert Diluent) Processes 1224.3.2.2 Gas-Phase Processes 1224.3.2.3 Mixed-Phase Processes 1254.4 Conclusion 128References 128Further Reading 1295 Polymerization Kinetics 1315.1 Introduction 1315.2 Fundamental Model for Polymerization Kinetics 1345.2.1 Single-Site Catalysts 1345.2.1.1 Homopolymerization 1345.2.1.2 Copolymerization 1455.2.2 Multiple-Site Catalysts 1495.2.3 Temperature Dependence of Kinetic Constants 1525.2.4 Number of Moles of Active Sites 1545.3 Nonstandard Polymerization Kinetics Models 1565.3.1 Polymerization Orders Greater than One 1565.3.2 Hydrogen Effect on the Polymerization Rate 1615.3.3 Comonomer Effect on the Polymerization Rate 1735.3.4 Negative Polymerization Orders with Late Transition Metal Catalysts 1795.4 Vapor-Liquid-Solid Equilibrium Considerations 181Further Reading 1846 Polyolefin Microstructural Modeling 1876.1 Introduction 1876.2 Instantaneous Distributions 1886.2.1 Molecular Weight Distribution 1886.2.1.1 Single-Site Catalysts 1886.2.1.2 Multiple-Site Catalysts 1996.2.2 Chemical Composition Distribution 2126.2.2.1 Single-Site Catalysts 2126.2.2.2 Multiple-Site Catalysts 2226.2.3 Comonomer Sequence Length Distribution 2326.2.4 Long-Chain Branching Distribution 2376.2.5 Polypropylene: Regio- and Stereoregularity 2506.3 Monte Carlo Simulation 2516.3.1 Steady-State Monte Carlo Models 2526.3.2 Dynamic Monte Carlo Models 262Further Reading 2687 Particle Growth and Single Particle Modeling 2717.1 Introduction 2717.2 Particle Fragmentation and Growth 2747.2.1 The Fragmentation Step 2757.2.2 Particle Growth 2847.3 Single Particle Models 2867.3.1 Particle Mass and Energy Balances: the Multigrain Model (MGM) 2877.3.2 The Polymer Flow Model (PFM) 2927.3.3 An Analysis of Particle Growth with the MGM/PFM Approach 2957.3.4 Convection in the Particles – High Mass Transfer Rates at Short Times 3017.4 Limitations of the PFM/MGM Approach: Particle Morphology 304References 307Further Reading 3078 Developing Models for Industrial Reactors 3118.1 Introduction 311References 321Further Reading 322Index 325