Chemistry and Technology of Polyols for Polyurethanes

This book considers the raw materials used to build the polyurethane polymeric architecture. It covers the chemistry and technology of oligo-polyol fabrication, the characteristics of the various oligo-polyol families and the effects of the oligo-polyol structure on the properties of the resulting polyurethane. It presents the details of oligo-polyol synthesis, and explains the chemical and physico-chemical subtleties of oligo-polyol fabrication. This book will be of interest to all specialists working with polyols for the manufacture of polyurethanes and to all researchers that would like to know more about polyol chemistry.

Table of Contents:
1 Polyols 1.1 Introduction References 2 Basic Chemistry of Polyurethanes 2.1 Reaction of Isocyanates with Alcohols 2.2 Reaction of Isocyanates with Water 2.3 Reaction of Isocyanates with Urethanes 2.4 Reaction of Isocyanates with Urea Groups 2.5 Reaction of Isocyanates with Carboxylic Acids 2.6 Dimerisation of Isocyanates 2.7 Trimerisation of Isocyanates 2.8 Reaction of Isocyanates with Epoxide Compounds 2.9 Reaction of Isocyanates with Cyclic Anhydrides 2.10 Prepolymer Technique 2.11 Quasiprepolymer Technique 2.12 One Shot Technique 2.13 Several Considerations on the Polyaddition Reaction References 3 The General Characteristics of Oligo-Polyols 3.1 Hydroxyl Number 3.1.1 Hydroxyl Percentage 3.2 Functionality 3.3 Molecular Weight and Molecular Weight Distribution 3.4 Equivalent Weight 3.5 Water Content 3.6 Primary Hydroxyl Content 3.7 Reactivity 3.8 Specific Gravity 3.9 Viscosity 3.10 Colour 3.11 Acid Number References 4 Oligo-Polyols for Elastic Polyurethanes 4.1. Polyalkylene Oxide Polyether Polyols 4.1.1 Synthesis of Polyether Triols Based on Glycerol Homopolymers of PO 4.1.2 Kinetics of PO Addition to Glycerol 4.1.3 Random Copolyethers PO-EO (Heteropolyether Polyols) 4.1.4 Polyether Polyols Block Copolymers PO-EO 4.1.5 Technology for Polyether Polyol Fabrication 4.2 Anionic Polymerisation of Alkylene Oxides Catalysed by Phosphazenium Compounds 4.3 High Molecular Weight Polyether Polyols Based on Polyamine Starters. Autocatalytic Polyether Polyols References 5 Synthesis of High Molecular Weight Polyether Polyols with Double Metal Cyanide Catalysts (DMC Catalysts) References 6 Polymer Polyols (Filled Polyols) 6.1 Graft Polyether Polyols 6.2 The Chemistry of the Graft Polyether Polyols Synthesis 6.2.1 Generation in situ of NAD by Grafting Reactions 6.2.2 Stabilisation of Polymer Dispersions in Polymer Polyols with Macromers (Reactive NAD) 6.2.3 Nonreactive Nonaqueous Dispersants 6.2.4 The Mechanism of Polymer Particle Formation in Polymer Polyols Synthesis by Radical Polymerisation 6.3 The Technology of Polymer Polyols Manufacture by Radical Processes 6.3.1 Synthesis of Polymer Polyols by Using Preformed Aqueous Polymeric Lattices 6.4 PHD Polymer Polyols (Polyurea Dispersions) 6.5 Polyisocyanate Polyaddition (PIPA) Polymer Polyols 6.6 Other Polymer Polyols 6.6.1 Epoxy Dispersions 6.6.2 Polyamide Dispersions 6.6.3 Aminoplast Dispersions References 7 Polyether Polyols by Cationic Polymerisation Processes 7.1 Polytetrahydrofuran (Polytetramethylene Glycols) 7.2 High Molecular Weight Polyalkylene Oxide Polyols by Cationic Polymerisation 7.3 Polyether Diols and Triols, Copolymers THF-alkylene Oxides References 8 Polyester Polyols for Elastic Polyurethanes 8.1 Chemistry of Polyester Polyol Synthesis 8.2 Consideration of the Kinetics of Polyesterification Reactions 8.2.1 Self Catalysed Polyesterification Reactions (Without Catalyst) 8.2.2 Side Reactions in Polyesterification 8.2.3 Hydrolysis Resistant Polyester Polyols 8.3 Technology for Polyester Polyols Fabrication 8.4 Poly (e-caprolactone) Polyols 8.5 Polycarbonate Polyols References 9 Polybutadiene Polyols 9.1 Polybutadiene Polyols by Radical Polymerisation of Butadiene 9.2 Synthesis of Polybutadiene Polyols by Radical Polymerisation of Butadiene 9.3 Synthesis of Polybutadiene Polyols by Anionic Polymerisation of Butadiene References 10 Acrylic Polyols References 11 Polysiloxane Polyols References 12 Polyols for Rigid Polyurethanes - General Considerations References 13 Polyether Polyols for Rigid Polyurethane Foams 13.1 The Polyaddition of Alkylene Oxides to Hydroxyl Groups 13.1.1 The Mechanism of Alkylene Oxide Polyaddition to Hydroxyl Groups Catalysed by the Tertiary Amines 13.2 Polyether Polyols Technologies for Rigid Foam Fabrication 13.2.1 Anionic Polymerisation of PO (or/and EO) Initiated by Polyols which are Liquid at the Reaction Temperature 13.3 Kinetic Considerations Concerning the Alkoxylation of Polyols to Rigid Polyether Polyols 13.3.1 Anionic Polymerisation of PO (or/and EO) Initiated by High Melting Point Polyols which are Solid at the Reaction Temperature References 14 Aminic Polyols References 15 Rigid Polyols Based on the Alkoxylation of Aromatic Compounds Condensates with Aldehydes 15.1 Mannich Polyols 15.2 Novolak-Based Polyether Polyols 15.3 Bisphenol A Based Polyols 15.4 Resorcinol Based Diols 15.4 Melamine-Based Polyols for Rigid Polyurethanes References 16 Polyester Polyols for Rigid Polyurethane Foams 16.1 Aromatic Polyester Polyols from Bottom Residues Resulting in DMT Fabrication 16.2 Aromatic Polyester Polyols from Polyethylene Terephthalate Wastes (Bottles, Films, Fibres) 16.3 Aromatic Polyester Polyols Based on Phthalic Anhydride (PA) 16.4 Other Methods for the Synthesis of Polyester Polyols for Rigid Foams References 17 Polyols from Renewable Resources - Oleochemical Polyols 17.1 Vegetable Oil Polyols (Oleochemical Polyols) 17.1.1 Synthesis of Vegetable Oil Polyols by using Reactions Involving Ester Groups 17.1.2 Synthesis of Vegetable Oil Polyols by using Reactions Involving the Double Bonds 17.1.3 Other Reactions Involving Reactions of Double Bonds of Vegetable Oils 17.1.4 Other Renewable Materials References 18 Flame Retardant Polyols 18.1 Chlorine and Bromine Containing Polyols 18.2 Phosphorus Polyols 18.2.1 Esters of Ortho-Phosphoric Acid 18.2.2 Esters of Phosphorus Acid 18.2.3 Phosphonate Polyols 18.2.4 Phosphine Oxide Polyols 18.2.5 Phosphoramidic Polyols References 19 New Polyol Structures for Rigid Polyurethane Foams 19.1 Amidic Polyols 19.2 Hyperbranched Polyols and Dendritic Polyols References 20 Oligo-Polyols by Chemical Recovery of PU Wastes 20.1 Hydrolysis of PU Polymers 20.2 Glycolysis of PU Polymers 20.3 Aminolysis of PU Polymer 20.4 Alkoxylation of PU Polymer 20.5 Chemical Recovery of Flexible PU Foam Wastes by Hydrolysis 20.6 Rigid Polyols by Glycolysis of Rigid PU Foam Wastes 20.7 Rigid Polyols by Aminolysis of Rigid PU Foam Wastes 20.8 Technology for Chemical Recovery of Rigid PU Foams (and Isocyanuric Foams) by the Glycolysis Processes References 21 Relationships Between the Oligo-Polyol Structure and Polyurethane Properties 21.1 Molecular Weight 21.1.1 The Effect of the Molecular Weight of Oligo-Polyols 21.2 Intermolecular Forces 21.2.1 The Effect of the Chemical Nature of Oligo-Polyol Chains 21.3 Stiffness of the Chain 21.4 Crystallinity 21.5 Crosslinking 21.5.1 The Effect of Oligo-Polyol Functionality 21.5.2 The Effect of Oligo-Polyol Structure on the Polyurethane Behaviour in Contact with Organic Solvents and Water 21.6 Thermal Stability and Flame Retardancy 21.6.1 Flame Retardancy Postface Abbreviations Index

About the Author :
Mihail Ionescu gained his first degree from the University Polytechnica Bucharest, Faculty of Industrial Chemistry, and gained his PhD from the same institution in 1986. He has had a varied career and is currently a Senior Research Scientist at Pittsburg State University, Kansas, USA. He was President of the Scientific Council of the Institute of Chemical Research (ICECHIM) in Bucharest, Romania from 1993 -2004; the Scientific Director of ICECHIM from 1997-2004; Head of the Polymer Synthesis Department at ICECHIM from 1992-1997; Secretary of the Romanian Polymer Society from 1992; an active member of the New York Academy of Science (1996 ); and is a Member of American Chemical Society and American Oil Chemists Society.