Urethane Science and Technology

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<p>Advances in Urethane Science and TechnologyEditors: D. Klempner K.C. Frisch</p> <p>Advances in Urethane Science and Technology</p> <p>Daniel Klempner and Kurt Frisch</p> <p>Rapra Technology LimitedShawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net</p> <p>First Published in 2001 by</p> <p>Rapra Technology LimitedShawbury, Shrewsbury, Shropshire, SY4 4NR, UK</p> <p>2001, Rapra Technology Limited</p> <p>All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder. A catalogue record for this book is available from the British Library.</p> <p>ISBN: 1-85957-275-8</p> <p>Typeset by Rapra Technology Limited Printed and bound by Lightning Source UK</p> <p>Dedication</p> <p>In memory of Kurt C Frisch One of the founding Fathers of polyurethanes</p> <p>January 15th 1919 to October 21st 2000</p> <p>Contents</p> <p>1 Dimensional Stabilising Additives for Flexible Polyurethane Foams ................ 3 1.1 Introduction ............................................................................................. 3 1.2 Experimental Procedures .......................................................................... 6 1.2.1 Materials ....................................................................................... 6 1.2.2 Handmix Evaluations .................................................................... 8 1.2.3 Machine Evaluation ...................................................................... 9 1.3 TDI - Flexible Moulded Additives .......................................................... 15 1.3.1 Dimensional Stability Additives for TDI ...................................... 16 1.3.2 Low Emission Dimensional Stability Additives ............................ 42 1.4 MDI Flexible Moulded Foam Additives ................................................. 63 1.4.1 Dimensional Stability Additives for MDI .................................... 64 1.4.2 Low Emissions Dimensional Stability Additives in MDI.............. 67 1.5 TDI Flexible Slabstock Low Emission Additives ..................................... 73 1.5.1 Reactivity .................................................................................... 74 1.5.2 Standard Physical Properties ........................................................ 74 1.5.3 TDI Flexible Slabstock Foam Review .......................................... 74 1.6 Foam Model Tool Discussions ................................................................ 75 1.6.1 TDI and MDI Moulded Foam Model .......................................... 75 1.6.2 TDI Flexible Slabstock Foam Model ........................................... 78 1.7 Conclusions ............................................................................................ 81 2 Demands on Surfactants in Polyurethane Foam Production with Liquid Carbon Dioxide Blowing .................................................................... 85 2.1 History of Polyurethane Foams .............................................................. 85 2.1.1 Environmental Concerns in Relation to Flexible Foam Density ... 86</p> <p>i</p> <p>Advances in Urethane Science and Technology</p> <p>2.2 Current Liquid Carbon Dioxide Technologies for Flexible Slabstock ......... Polyether Foam Production .................................................................... 88 2.2.1 Machinery ................................................................................... 88 2.2.2 The Foaming Process ................................................................... 90 2.2.3 Additional Tasks of Silicone Surfactants in Flexible Slabstock Foam Production ......................................................................... 95 2.2.4 Chemistry of a Silicone Surfactant in Flexible Slabstock Foam Production ......................................................................... 99 2.2.5 A Surfactant Development Example .......................................... 101 3 Polyurethane Processing: Recent Developments ........................................... 113 3.1 Industrial Solutions for the Production of Automotive Seats Using Polyurethane Multi-Component Formulations ........................... 113 3.1.1 Market Requirements ................................................................ 113 3.1.2 Dedicated Solutions: Metering Equipment ................................ 114 3.1.3 Dedicated Solutions: Mixing Heads........................................... 116 3.1.4 Dedicated Solutions ................................................................... 121 3.2 Foam &amp; Film Technology - An Innovative Solution to Fully Automate the Manufacture of Automotive Sound Deadening Parts ..... 130 3.2.1 The Problem .............................................................................. 131 3.2.2 The Approach to a Solution ...................................................... 131 3.2.3 The Film .................................................................................... 133 3.2.4 Industrial Applications .............................................................. 135 3.2.5 Applications .............................................................................. 137 3.2.6 Advantages ................................................................................ 138 3.3 InterWet - Polyurethane Co-injection ................................................... 138 3.3.1 Glass-Reinforced Polyurethanes, a Well-Known Technology ..... 139 4 Recent Developments in Open Cell Polyurethane-Filled Vacuum Insulated Panels for Super Insulation Applications ...................................................... 157 4.1 Introduction ......................................................................................... 157 4.2 Some General Properties of Open Cell PU Foams for Vacuum</p> <p>ii</p> <p>Contents</p> <p>Insulated Panels .................................................................................... 158 4.3 Vacuum Issues in the Selection of VIP Components .............................. 163 4.3.1 Vacuum Properties of the Open Cell Foams .............................. 163 4.3.2 Vacuum Properties of the Barrier Film ....................................... 167 4.3.3 The Getter Device ...................................................................... 179 4.4 Vacuum Panel Manufacturing Process and Characterisation ................ 188 4.4.1 Some Manufacturing Issues ....................................................... 188 4.4.2 Characterisation of Vacuum Panels ........................................... 191 4.5 Insulation Performances of Open Cell PU-Filled Vacuum Panels .......... 196 4.6 Examples of VIP Applications and Related Issues................................. 199 4.6.1 Household Appliances ............................................................... 199 4.6.2 Laboratory and Biomedical Refrigerators .................................. 203 4.6.3 Vending Machines ..................................................................... 204 4.6.4 Refrigerated/Insulated Transportation ....................................... 205 4.6.5 Other Applications .................................................................... 206 4.7 Near Term Perspectives and Conclusions.............................................. 206 5 Modelling the Stabilising Behaviour of Silicone Surfactants During the Processing of Polyurethane Foam: The Use of Thin Liquid Films ................. 213 5.1 Introduction ......................................................................................... 213 5.2 Film Drainage Rate: Reynolds Model and Further Modifications ........ 216 5.2.1 Rigid Film Surfaces .................................................................... 216 5.2.2 Mobile Film Surfaces ................................................................. 217 5.2.3 Surface Viscosity ........................................................................ 217 5.2.4 Surface Tension Gradients ......................................................... 218 5.3 Experimental Investigation of Model, Thin Liquid Polyurethane Films and the Development of Qualitative and Semi-Quantitative Models of Film Drainage ...................................................................... 219 5.3.1 Experimental Details ................................................................. 221 5.3.2 Qualitative Description of Polyurethane Films .......................... 223</p> <p>iii</p> <p>Advances in Urethane Science and Technology</p> <p>5.3.3 Quantitative Measurement of Film Drainage Rates: Bulk and Surface Effects ............................................................ 226 5.4 The Development of Theoretical Models of Vertical, Draining Thin Liquid Model PU Films ................................................................ 236 5.4.1 Rigid-Surfaced Collapsing Wedge Model ................................... 236 5.4.2 Deforming Film Models ............................................................ 239 5.4.3 Tangentially-Immobile Films ..................................................... 242 5.4.4 Finite Surface Viscosity .............................................................. 245 5.4.5 Adding Surfactant Transport ..................................................... 249 5.5 Summary .............................................................................................. 254 6 Synthesis and Characterisation of Aqueous Hybrid Polyurethane-UreaAcrylic/Styrene Polymer Dispersions ............................................................ 261 6.1 Preface .................................................................................................. 261 6.2 Introduction ......................................................................................... 261 6.2.1 General Considerations ............................................................. 261 6.2.2 Acrylic Dispersions and Polyurethane Dispersions (DPUR) ....... 264 6.2.3 Hybrid Acrylic-Urethane Dispersions ........................................ 266 6.3 Concept of the Study ............................................................................ 268 6.3.1 Selection of Starting Materials ................................................... 268 6.3.2 Assumptions for Synthesis of Hybrid Dispersions ..................... 269 6.4 Methods of Testing ............................................................................... 276 6.4.1 Dispersions ................................................................................ 276 6.4.2 Coatings .................................................................................... 277 6.4.3 Films .......................................................................................... 278 6.5 Experimental results ............................................................................. 279 6.5.1 Characterisation of Starting Dispersions Used for Synthesis of MDPUR ................................................................................ 279 6.5.2 Synthesis of MDPUR and MDPUR-ASD ................................... 288 6.5.3 Investigation of the Effect of Various Factors on the Properties of Hybrid Dispersions ............................................... 290</p> <p>iv</p> <p>Contents</p> <p>6.5.4 Additional Experiments ............................................................. 312 6.6 Discussion of results ............................................................................. 320 6.6.1 Estimation of the Effect of Various Factors on the Properties of Hybrid Dispersions and Films and Coatings Made from Them ................................................................................ 320 6.6.2 Mechanism of Hybrid Particle Formation ................................. 326 6.7 Summary ................................................................................................ 330 7 Adhesion Behaviour of Urethanes ................................................................ 335 7.1 Introduction ......................................................................................... 335 7.2 Surface Characteristics of PU Adhesive Formulations ........................... 335 7.2.1 Experimental ............................................................................. 336 7.2.2 Results and Discussion .............................................................. 338 7.2.3 Conclusions ............................................................................... 347 7.3 Acid/Base Interactions and the Adhesion of PUs to Polymer Substrates 347 7.3.1 Experimental ............................................................................. 348 7.3.2 Results and Discussion .............................................................. 351 7.4 The Effectiveness of Silane Adhesion Promoters in the Performance of PU Adhesives .................................................................................... 355 7.4.1 Experimental ............................................................................. 356 7.4.2 Results and Discussion .............................................................. 358 7.4.3 Conclusions ............................................................................... 364 8 HER Materials for Polyurethane Applications ............................................. 369 8.1 Introduction ......................................................................................... 369 8.2 Experimental Conditions ...................................................................... 370 8.2.1 Chain Extenders ........................................................................ 370 8.2.2 Prepolymers ............................................................................... 370 8.2.3 Preparation of Cast Elastomers ................................................. 372 8.2.4 Physical and Mechanical Properties Determination ................... 372 8.3 HER Materials Synthesis and Characterisation .................................... 373v</p> <p>Advances in Urethane Science and Technology</p> <p>8.4 Cast Poly(Ether Urethanes) ................................................................... 375 8.4.1 Pot Life Determination .............................................................. 375 8.4.2 Polyurethane Castings ............................................................... 376 8.4.3 Calculation of Hard and Soft Segment Contents ....................... 376 8.4.4 Hard Segment Versus Hardness ................................................. 378 8.4.5 Tensile Properties ....................................................................... 378 8.4.6 Tear, Compression Set and Rebound Properties......................... 380 8.4.7 Differential Scanning Calorimetry ............................................. 381 8.4.8 Dynamic Mechanical Analysis ................................................... 383 8.5 Cast Poly(Ester Ur...</p>

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