Polyurethanes have become one of the most dynamic groups of polymers and they find use in nearly every aspect of modern life, in applications such as furniture, bedding, seating and instrument panels for cars, shoe soles, thermoinsulation, carpet backings, packaging, and as coatings.

The main raw materials used for the production of polyurethanes are polyols, isocyanates and propylene oxide. The first of these is the subject of the latest Rapra Handbook: 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 attempts to link data and information concerning the chemistry and technology of oligo-polyols for polyurethanes, providing a comprehensive overview of: 

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.

Mihail has completed around 200 research projects - laboratory, pilot plant and industrial scale (unpublished in the open literature, closed circuit); has devised more than 20 technologies for polyether polyols which are applied industrially - the resulting polyethers (for flexible and rigid PU foams), are exported to: Germany, Italy, Turkey, France, The Netherlands, Poland, Hungary, Serbia; has 70 patents in the field of telechelic polyether synthesis and in the field of aromatic polymers; and has authored around 85 scientific papers; he is thus well qualified to write this book.

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