Reactive Extrusion

Dr. rer. nat Gunter Beyer is Manager of the physical and chemical laboratories at Kabelwerk EUPEN AG (Belgium). He received his PhD in organic chemistry and photochemistry in 1984 from RWTH Aachen University (Germany) and started to work at Kabelwerk Eupen in the same year. Since 1996 he is responsible for the R&D activities for material development and heads the chemical-physical laboratory. With more than 30 years of experience in polymer science and applications, Dr. Beyer is regularly acting as chairman and speaker at many international conferences, especially in the field of flame retardancy, nanocomposites and polymer science. In 2003 and also in 2004 he received the Jack Spergel Memorial Award for his fundamental work on nanocomposites by organoclays and carbon nanotubes as new classes of flame retardants for polymers. Professor Dr.-Ing. Christian Hopmann is Head of the Institute of Plastics Processing in Industry and the Skilled Crafts (Aachen, Germany) since 2011 and holds the Chair of Plastics Processing at the Faculty of Mechanical Engineering at RWTH Aachen University (Germany). Hopmann studied Mechanical Engineering at RWTH Aachen (Germany) and received his doctoral degree in 2000. From 2001 to 2004 he was Chief Engineer and Senior Vice Director of the Institute of Plastics Processing. In 2005, Hopmann started his industrial career at RKW AG Rheinische Kunststoffwerke (today: RKW SE), Europe's leading manufacturer of high quality polyethylene and polypropylene films, nonwovens and nets, being head of the Quality Management at RKW's site in Petersaurach (Germany). From 2006 to end of 2009 he was Head of Extrusion and thus responsible for the production of polyolefin films for hygiene, consumer packaging and industrial applications. From January 2010 to April 2011 he was Managing Director of RKW Sweden AB in Helsingborg (Sweden).

• Preface xiiiList of Contributors xvPart I Introduction 11 Introduction to Reactive Extrusion 3Christian Hopmann, Maximilian Adamy, and Andreas CohnenReferences 9Part II Introduction to Twin-Screw Extruder for Reactive Extrusion 112 The Co-rotating Twin-Screw Extruder for Reactive Extrusion 13Frank Lechner2.1 Introduction 132.2 Development and Key Figures of the Co-rotating Twin-Screw Extruder 142.3 Screw Elements 162.4 Co-rotating Twin-Screw Extruder – Unit Operations 222.4.1 Feeding 232.4.2 Upstream Feeding 232.4.3 Downstream Feeding 242.4.4 Melting Mechanisms 242.4.5 Thermal Energy Transfer 242.4.6 Mechanical Energy Transfer 252.4.7 Mixing Mechanisms 252.4.8 Devolatilization/Degassing 252.4.9 Discharge 262.5 Suitability of Twin-Screw Extruders for Chemical Reactions 262.6 Processing of TPE-V 272.7 Polymerization of Thermoplastic Polyurethane (TPU) 292.8 Grafting of Maleic Anhydride on Polyolefines 312.9 Partial Glycolysis of PET 322.10 Peroxide Break-Down of Polypropylene 332.11 Summary 35References 35Part III Simulation and Modeling 373 Modeling of Twin Screw Reactive Extrusion: Challenges and Applications 39Françoise Berzin and Bruno Vergnes3.1 Introduction 393.1.1 Presentation of the Reactive Extrusion Process 393.1.2 Examples of Industrial Applications 403.1.3 Interest of Reactive Extrusion Process Modeling 413.2 Principles and Challenges of the Modeling 413.2.1 Twin Screw Flow Module 423.2.2 Kinetic Equations 443.2.3 Rheokinetic Model 443.2.4 Coupling 453.2.5 Open Problems and Remaining Challenges 453.3 Examples of Modeling 463.3.1 Esterification of EVA Copolymer 463.3.2 Controlled Degradation of Polypropylene 503.3.3 Polymerization of ε-Caprolactone 553.3.4 Starch Cationization 593.3.5 Optimization and Scale-up 613.4 Conclusion 65References 664 Measurement and Modeling of Local Residence Time Distributions in a Twin-Screw Extruder 71Xian-Ming Zhang, Lian-Fang Feng, and Guo-Hua Hu4.1 Introduction 714.2 Measurement of the Global and Local RTD 724.2.1 Theory of RTD 724.2.2 In-line RTD Measuring System 734.2.3 Extruder and Screw Configurations 754.2.4 Performance of the In-line RTD Measuring System 764.2.5 Effects of Screw Speed and Feed Rate on RTD 774.2.6 Assessment of the Local RTD in the Kneading Disk Zone 794.3 Residence Time, Residence Revolution, and Residence Volume Distributions 814.3.1 Partial RTD, RRD, and RVD 824.3.2 Local RTD, RRD, and RVD 864.4 Modeling of Local Residence Time Distributions 884.4.1 Kinematic Modeling of Distributive Mixing 884.4.2 Numerical Simulation 894.4.3 Experimental Validation 924.4.4 Distributive Mixing Performance and Efficiency 934.5 Summary 97References 985 In-process Measurements for Reactive Extrusion Monitoring and Control 101José A. Covas5.1 Introduction 1015.2 Requirements of In-process Monitoring of Reactive Extrusion 1035.3 In-process Optical Spectroscopy 1115.4 In-process Rheometry 1165.5 Conclusions 125Acknowledgment 126References 126Part IV Synthesis Concepts 1336 Exchange Reaction Mechanisms in the Reactive Extrusion of Condensation Polymers 135Concetto Puglisi and Filippo Samperi6.1 Introduction 1356.2 Interchange Reaction in Polyester/Polyester Blends 1386.3 Interchange Reaction in Polycarbonate/Polyester Blends 1436.4 Interchange Reaction in Polyester/Polyamide Blends 1486.5 Interchange Reaction in Polycarbonate/Polyamide Blends 1556.6 Interchange Reaction in Polyamide/Polyamide Blends 1596.7 Conclusions 166References 1677 In situ Synthesis of Inorganic and/or Organic Phases in Thermoplastic Polymers by Reactive Extrusion 179Véronique Bounor-Legaré, Françoise Fenouillot, and Philippe Cassagnau7.1 Introduction 1797.2 Nanocomposites 1797.2.1 Synthesis of in situ Nanocomposites 1817.2.2 Some Specific Applications 1837.2.2.1 Antibacterial Properties of PP/TiO 2 Nanocomposites 1837.2.2.2 Flame-Retardant Properties 1847.2.2.3 Protonic Conductivity 1867.3 Polymerization of a Thermoplastic Minor Phase: Toward Blend Nanostructuration 1887.4 Polymerization of a Thermoset Minor Phase Under Shear 1967.4.1 Thermoplastic Polymer/Epoxy-Amine Miscible Blends 1977.4.2 Examples of Stabilization of Thermoplastic Polymer/Epoxy-Amine Blends 2027.4.3 Blends of Thermoplastic Polymer with Monomers Crosslinking via Radical Polymerization 2027.5 Conclusion 203References 2048 Concept of (Reactive) Compatibilizer-Tracer for Emulsification Curve Build-up, Compatibilizer Selection, and Process Optimization of Immiscible Polymer Blends 209Cai-Liang Zhang, Wei-Yun Ji, Lian-Fang Feng, and Guo-Hua Hu8.1 Introduction 2098.2 Emulsification Curves of Immiscible Polymer Blends in a Batch Mixer 2108.3 Emulsification Curves of Immiscible Polymer Blends in a Twin-Screw Extruder Using the Concept of (Reactive) Compatibilizer 2138.3.1 Synthesis of (Reactive) Compatibilizer-Tracers 2138.3.2 Development of an In-line Fluorescence Measuring Device 2148.3.3 Experimental Procedure for Emulsification Curve Build-up 2168.3.4 Compatibilizer Selection Using the Concept of Compatibilizer-Tracer 2198.3.5 Process Optimization Using the Concept of Compatibilizer-Tracer 2208.3.5.1 Effect of Screw Speed 2208.3.5.2 Effects of the Type of Mixer 2218.3.6 Section Summary 2218.4 Emulsification Curves of Reactive Immiscible Polymer Blends in a Twin-Screw Exturder 2228.4.1 Reaction Kinetics between Reactive Functional Groups 2228.4.2 (Non-reactive) Compatibilizers Versus Reactive Compatibilizers 2238.4.3 An Example of Reactive Compatibilizer-Tracer 2248.4.4 Assessment of the Morphology Development of Reactive Immiscible Polymer Blends Using the Concept of Reactive Compatibilizer 2258.4.5 Emulsification Curve Build-up in a Twin-Screw Extruder Using the Concept of Reactive Compatibilizer-Tracer 2298.4.6 Assessment of the Effects of Processing Parameters Using the Concept of Reactive Compatibilizer-Tracer 2338.4.6.1 Effect of the Reactive Compatibilizer-Tracer Injection Location 2338.4.6.2 Effect of the Blend Composition 2358.4.6.3 Effect of the Geometry of Screw Elements 2388.5 Conclusion 241References 241Part V Selected Examples of Synthesis 2459 Nano-structuring of Polymer Blends by in situ Polymerization and in situ Compatibilization Processes 247Cai-Liang Zhang, Lian-Fang Feng, and Guo-Hua Hu9.1 Introduction 2479.2 Morphology Development of Classical Immiscible Polymer Blending Processes 2489.2.1 Solid–Liquid Transition Stage 2499.2.2 Melt Flow Stage 2519.2.3 Effect of Compatibilizer 2539.3 In situ Polymerization and in situ Compatibilization of Polymer Blends 2559.3.1 Principles 2559.3.2 Classical Polymer Blending Versus in situ Polymerization and in situ Compatibilization 2559.3.3 Examples of Nano-structured Polymer Blends by in situ Polymerization and in situ Compatibilization 2579.3.3.1 PP/PA6 Nano-blends 2579.3.3.2 PPO/PA6 Nano-blends 2649.3.3.3 PA6/Core–Shell Blends 2649.4 Summary 267References 26810 Reactive Comb Compatibilizers for Immiscible Polymer Blends 271Yongjin Li, Wenyong Dong, and Hengti Wang10.1 Introduction 27110.2 Synthesis of Reactive Comb Polymers 27210.3 Reactive Compatibilization of Immiscible Polymer Blends by Reactive Comb Polymers 27410.3.1 PLLA/PVDF Blends Compatibilized by Reactive Comb Polymers 27410.3.1.1 Comparison of the Compatibilization Efficiency of Reactive Linear and Reactive Comb Polymers 27410.3.1.2 Effects of the Molecular Structures on the Compatibilization Efficiency of Reactive Comb Polymers 27810.3.2 PLLA/ABS Blends Compatibilized by Reactive Comb Polymers 28210.4 Immiscible Polymer Blends Compatiblized by Janus Nanomicelles 28910.5 Conclusions and Further Remarks 293References 29311 Reactive Compounding of Highly Filled Flame Retardant Wire and Cable Compounds 299Mario Neuenhaus and Andreas Niklaus11.1 Introduction 29911.2 Formulations and Ingredients 30011.2.1 Typical Formulation and Variations for the Evaluation 30011.2.2 Principle of Silane Crosslinking by Reactive Extrusion 30111.2.3 Production of Aluminum Trihydroxide (ATH) 30111.2.4 Mode of Action of Aluminum Trihydroxide 30211.2.5 Selection of Suitable ATH Grades 30311.3 Processing 30611.3.1 Compounding Line 30611.3.2 Compounding Process for Cross Linkable HFFR Products 30811.3.2.1 Two-Step Compounding Process 30811.3.2.2 One-Step Compounding Process 30911.3.2.3 Advantages and Disadvantages of the Two Process Concepts (Two-Step vs One-Step) 31311.4 Evaluation and Results on the Compound 31411.4.1 Crosslinking Density 31411.4.2 Mechanical Properties 31511.4.3 Aging Performance 31511.4.4 Fire Performance on Laboratory Scale 31711.4.5 Results of the Non-Polar Compounds 31811.5 Cable Trials 32211.5.1 Fire Performance of Electrical Cables According to EN 50399 32211.5.2 Burning Test on Experimental Cables According to EN 50399 32311.6 Conclusions 328References 32912 Thermoplastic Vulcanizates (TPVs) by the Dynamic Vulcanization of Miscible or Highly Compatible Plastic/Rubber Blends 331Yongjin Li and Yanchun Tang12.1 Introduction 33112.2 Morphological Development of TPVs from Immiscible Polymer Blends 33312.3 TPVs from Miscible PVDF/ACM Blends 33412.4 TPVs from Highly Compatible EVA/EVM Blends 33812.5 Conclusions and Future Remarks 342References 342Part VI Selected Examples of Processing 34513 Reactive Extrusion of Polyamide 6 with Integrated Multiple Melt Degassing 347Christian Hopmann, Eike Klünker, Andreas Cohnen, and Maximilian Adamy13.1 Introduction 34713.2 Synthesis of Polyamide 6 34713.2.1 Hydrolytic Polymerization of Polyamide 6 34713.2.2 Anionic Polymerization of Polyamide 6 34813.3 Review of Reactive Extrusion of Polyamide 6 in Twin-Screw Extruders 35213.4 Recent Developments in Reactive Extrusion of Polyamide 6 in Twin-Screw Extruders 35413.4.1 Reaction System and Experimental Setup 35413.4.2 Influence of Number of Degassing Steps and Activator Content on Residual Monomer Content and Molecular Weight 35613.4.3 Influence of Amount and Type of Entrainer on Residual Monomer Content and Molecular Weight 36513.4.4 Influence of Polymer Throughput on Residual Monomer Content 36713.5 Conclusion 368References 36914 Industrial Production and Use of Grafted Polyolefins 375Inno Rapthel, Jochen Wilms, and Frederik Piestert14.1 Grafted Polymers 37514.2 Industrial Synthesis of Grafted Polymers 37614.2.1 Melt Grafting Technology 37714.2.2 Solid State Grafting Technology 37814.3 Main Applications 38014.3.1 Use as Coupling Agents 38014.3.2 Grafted Polyolefins for Polymer Blending 39214.3.2.1 Reactive Blending of Polyamides 39214.3.3 Grafted TPE’s for Overmolding Applications 40014.4 Conclusion and Outlook 403References 404Index 407