Additives in Polymers

Jan C.J. Bart (PhD Structural Chemistry, University of Amsterdam) is a senior scientist with broad interest in materials characterisation, heterogeneous catalysis and product development who spent an industrial carrier in R&D with Monsanto, Montedison and DSM Research in various countries. The author has held several teaching assignments and researched extensively in both academic and industrial areas; he authored over 250 scientific papers, including chapters in books. Dr Bart has acted as a Ramsay Memorial Fellow at the Universities of Leeds (Colour Chemistry) and Oxford (Material Science), a visiting scientist at Institut de Recherches sur la Catalyse (CNRS, Villeurbanne), and a Meyerhoff Visiting Professor at WIS (Rehovoth), and held an Invited Professorship at USTC (Hefei). He is currently a Full Professor of Industrial Chemistry at the University of Messina.He is also a member of the Royal Society of Chemistry, Royal Dutch Chemical Society, Society of Plastic Engineers and The Institute of Materials.

• Foreword ixPreface xiAbout the Author xiiiAcknowledgements xvChapter 1 Introduction 11.1 Additives 21.1.1 Additive functionality 31.2 Plastics formulations 51.2.1 Supply forms 71.2.2 Additive delivery 91.3 Economic impact of polymer additives 91.4 Analysis of plastics 111.4.1 Regulations and standardisation 151.4.2 Prior art 171.4.3 Databases 191.4.4 Scope 201.4.5 Chapter overview 221.5 Bibliography 231.5.1 Plastics additives 231.5.2 Processing technologies 231.5.3 Instrumental analysis 231.5.4 Polymer analysis 241.5.5 Polymer/additive analysis 241.6 References 24Chapter 2 Deformulation Principles 292.1 Polymer identification 302.2 Additive analysis of rubbers: ‘Best Practice’ 322.3 Polymer extract analysis 422.4 In situ polymer/additive analysis 462.5 Class-specific polymer/additive analysis 472.6 Bibliography 482.6.1 Polymer identification 482.6.2 Deformulation of rubbers 482.6.3 Deformulation of polymers 482.7 References 48Chapter 3 Sample Preparation Perspectives 513.1 Solvents 543.1.1 Polymer solubility criteria 553.1.2 Solubility parameters 553.1.3 Polymer solutions 563.2 Extraction strategy 573.3 Conventional extraction technologies 593.3.1 Liquid–liquid extraction 603.3.2 Liquid–solid extraction 603.3.3 Classical solvent extractions of additives from polymers 613.3.4 Sonication 753.4 High-pressure solvent extraction methods 813.4.1 Supercritical fluid technology 813.4.2 Analytical SFE 853.4.3 Subcritical water extraction 1003.4.4 Microwave technology 1013.4.5 Microwave-assisted extractions 1043.4.6 Pressurised fluid extraction 1173.5 Sorbent extraction 1233.5.1 Solid-phase extraction 1243.5.2 Solid-phase microextraction 1293.5.3 Stir bar sorptive extraction 1333.6 Methodological comparison of extraction methods 1343.6.1 Experimental comparisons 1363.6.2 Extraction selectivity 1383.6.3 ‘Nonextractable’ additive analysis 1403.7 Polymer/additive dissolution methods 1463.8 Hydrolysis 1523.9 Bibliography 1553.9.1 Sampling and sample preparation 1553.9.2 Solvents/solubility 1553.9.3 Extraction methods 1563.10 References 156Chapter 4 Separation Techniques 1714.1 Analytical detectors 1774.2 Gas chromatography 1814.2.1 High-temperature gas chromatography 2004.2.2 Headspace gas chromatography 2024.3 Supercritical fluid chromatography 2054.4 Liquid chromatography techniques 2174.4.1 Planar chromatographies 2184.4.2 Column chromatographies 2304.5 Capillary electrophoretic techniques 2734.6 Bibliography 2784.6.1 General texts 2784.6.2 Detectors 2794.6.3 Gas chromatography 2794.6.4 Supercritical fluid chromatography 2794.6.5 Thin-layer chromatography 2794.6.6 Liquid chromatography 2804.6.7 Size-exclusion chromatography 2804.6.8 Ion chromatography 2804.6.9 Capillary electrophoretic techniques 2804.7 References 281Chapter 5 Polymer/Additive Analysis: The Spectroscopic Alternative 2995.1 Ultraviolet/visible spectrophotometry 3025.2 Infrared spectroscopy 3115.3 Luminescence spectroscopy 3185.4 High-resolution nuclear magnetic resonance spectroscopy 3235.4.1 Multidimensional NMR spectroscopy 3365.5 Bibliography 3425.5.1 General spectroscopy 3425.5.2 Ultraviolet/visible spectrophotometry 3425.5.3 Infrared spectroscopy 3425.5.4 Luminescence spectroscopy 3425.5.5 Nuclear magnetic resonance spectroscopy 3425.6 References 342Chapter 6 Organic Mass-Spectrometric Methods 3496.1 Basic instrumentation 3516.1.1 Inlet systems 3526.1.2 Modes of detection 3536.1.3 Mass resolution 3546.1.4 Isotope distributions 3546.1.5 Accurate mass measurements 3556.2 Ion sources 3576.2.1 Electron impact ionisation 3606.2.2 Chemical ionisation 3626.2.3 Metastable atom bombardment 3676.2.4 Fast atom bombardment 3676.2.5 Field ionisation 3726.2.6 Field desorption 3746.2.7 Thermospray ionisation 3766.2.8 Atmospheric pressure ionization techniques 3786.2.9 Desorption/ionisation methods 3836.2.10 Photoionisation techniques 3856.3 Mass analysers 3866.3.1 Sector analysers 3876.3.2 Quadrupole mass spectrometers 3896.3.3 Time-of-flight mass spectrometry 3906.3.4 Quadrupole ion trap 3936.3.5 Fourier-transform ion-cyclotron resonance mass spectrometry 3956.3.6 Tandem mass spectrometry 3986.4 Direct mass-spectrometric polymer compound analysis 4076.5 Ion mobility spectrometry 4156.6 Bibliography 4176.6.1 Mass spectrometry (General) 4176.6.2 Mass spectrometers 4176.6.3 Ionisation modes 4176.7 References 418Chapter 7 Multihyphenation and Multidimensionality in Polymer/Additive Analysis 4257.1 Precolumn hyphenation 4287.1.1 Chromatographic sampling methods 4327.2 Coupled sample preparation – spectroscopy/spectrometry 4497.3 Postcolumn hyphenation 4527.3.1 (Multi) hyphenated GC techniques 4567.3.2 (Multi) hyphenated SFC techniques 4757.3.3 (Multi) hyphenated HPLC techniques 4897.3.4 Hyphenated SEC techniques 5277.3.5 Hyphenated TLC techniques 5307.3.6 Hyphenated CE techniques 5437.4 Multidimensional chromatography 5457.4.1 Multidimensional gas chromatography 5487.4.2 Multidimensional supercritical fluid chromatography 5507.4.3 Multidimensional liquid chromatography 5507.4.4 Multidimensional thin-layer chromatography 5587.5 Multidimensional spectroscopy 5607.6 Bibliography 5627.6.1 General 5627.6.2 Multihyphenation and multidimensionality 5637.6.3 Precolumn hyphenation 5637.6.4 Postcolumn hyphenation 5637.6.5 Multidimensional chromatography 5637.6.6 Multidimensional spectroscopy 5637.7 References 564Chapter 8 Inorganic and Element Analytical Methods 5858.1 Element analytical protocols 5878.1.1 Element analytical pretreatment protocols 5888.1.2 Elemental analysis methods 5898.2 Sample destruction for classical elemental analysis 5918.2.1 Combustion analysis 5938.2.2 Wet matrix digestion 5978.2.3 Fusion methods 6048.3 Analytical atomic spectrometry 6058.3.1 Atomic absorption spectrometry 6088.3.2 Atomic emission spectrometry 6138.3.3 Atomic fluorescence spectrometry 6248.3.4 Direct spectrometric analysis of solid samples 6258.4 X-ray spectrometry 6278.4.1 X-ray fluorescence spectrometry 6288.4.2 Particle-induced X-ray emission spectrometry 6398.4.3 X-ray absorption spectrometry 6428.4.4 X-ray diffraction 6448.5 Inorganic mass spectrometry 6488.5.1 Spark-source mass spectrometry 6508.5.2 Glow-discharge mass spectrometry 6518.5.3 Inductively coupled plasma–mass spectrometry 6528.5.4 Isotope dilution mass spectrometry 6598.6 Radioanalytical and nuclear analytical methods 6628.6.1 Activation analysis 6638.7 Electroanalytical techniques 6668.7.1 Potentiometric methods 6688.7.2 Voltammetric methods 6698.7.3 Coulometric methods 6738.8 Solid-state speciation analysis 6748.9 Bibliography 6778.9.1 Sampling and sample preparation 6778.9.2 Atomic spectrometry 6778.9.3 X-ray spectrometry 6788.9.4 Inorganic mass spectrometry 6788.9.5 Nuclear analytical methods 6798.9.6 Trace-element analysis 6798.9.7 Electroanalysis 6798.9.8 Speciation analysis 6798.10 References 679Chapter 9 Direct Methods of Deformulation of Polymer/Additive Dissolutions 6919.1 Chromatographic methods 6929.1.1 Size-exclusion chromatography 6939.2 Spectroscopic techniques 6969.2.1 Nuclear magnetic resonance spectroscopy 6969.3 Mass-spectrometric methods 7019.3.1 MALDI-MS analysis of polymer/additive dissolutions 7029.4 References 709Chapter 10 A Vision for the Future 71110.1 Trends in polymer technology 71210.2 Trends in additive technology 71510.2.1 Advances in additives 71710.3 Environmental, legislative and regulatory constraints 72310.3.1 Trends in manufacturing, processing and formulation 72410.4 Analytical consequences 72510.4.1 General analytical tool development 72810.4.2 Future trends in polymer/additive analysis 72910.4.3 Analytical challenges 73910.4.4 Polymer/additive analysis at the extremes 74010.4.5 Advanced polymer/additive deformulation schemes 74310.5 Epilogue 74610.6 Bibliography 74710.7 References 747Appendix I List of Symbols 751Appendix II Functionality of Common Additives Used in Commercial Thermoplastics, Rubbers and Thermosetting Resin 773Appendix III Specimen Polymer Additives Product Sheets 793Index 803

"This book tries to cover the whole subject, and I acknowledge that this difficult goal has been…fully achieved." (Polymer News, September 2005) "...provides comprehensive coverage of the current status of the (qualitative and quantitative) analysis techniques for additive determination in commercial polymers..." (Apollit, 2005)"...the author has done a marvellous job in bringing together such a wealth of information in one volume..." (Polymer International, Vol 54 (10), October 2005)"Coupled with its readability and extensive bibliography, this book will be a valuable reference work for those working in many areas" (Society of Chemical Industry (SCI) 2006)