Chemistry and Technology of Polyols for Polyurethanes: 2nd Edition - Two Volume Set

  • ID: 3676749
  • Book
  • Region: Global
  • 796 Pages
  • Smithers Information Ltd
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Polyurethanes are one of the most dynamic groups of polymers, 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, adhesives, sealants, binders and as coatings.

In 2004 10.6 million tons of polyurethanes were produced, in 2014 the world production was close to 20 million tons. In the last decade (2005-2015) important, worldwide developments in the area of polyols for polyurethanes were carried out, especially for polyols from renewable resources, described in detail in this second edition of the book.

The main raw materials used for the production of PU are polyols and isocyanates. The first of these is the subject of this two volume handbook.

Volume 1 is dedicated to polyols for elastic PU (flexible foams, elastomers and so on).

Volume 2 is dedicated to polyols for rigid PU (rigid foams, wood substitute, packaging, flotation materials and so on).

The book considers the raw materials used to build the PU 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 PU. It presents the details of oligo-polyol synthesis, and explains the chemical and physico-chemical subtleties of oligo-polyol fabrication.

This book links data and information concerning the chemistry and technology of oligo-polyols for PU, providing a comprehensive overview of:

- Basic PU chemistry
- Key oligo-polyol characteristics
- Synthesis of the main oligo-polyol families, including: polyether polyols, filled polyether polyols, polyester polyols, polybutadiene polyols, acrylic polyols, polysiloxane polyols, aminic polyols
- Polyols from renewable resources
- Flame retardant polyols
- Chemical recovery of polyols
- Relationships between polyol structure and PU properties

This book will be of interest to all specialists working with polyols for the manufacture of PU and to all researchers that would like to know more about polyol chemistry.
Note: Product cover images may vary from those shown
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Volume I:

1. Polyols
1.1 Introduction

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

3 General Characteristics of Oligo-Polyols
3.1 Hydroxyl Number
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
3.12 Renewable Content

4 Polyether Polyols for Elastic Polyurethanes
4.1 Polyalkylene Oxide Polyether Polyols
4.1.1 Synthesis of Polyether Triols Based on Glycerol Homopolymers of Propylene Oxide Anionic Propylene Oxide Polymerisation Reaction Initiated by Glycerol Transfer Reactions in Anionic Polymerisation of Alkyleneoxides
4.1.2 Kinetics of Propylene Oxide Addition to Glycerol General Considerations Kinetics of Propylene Oxide and Ethylene Oxide Anionic Polymerisation (Propagation Reaction)
4.1.3 Random Copolyethers Propylene Oxide–Ethylene Oxide(Heteropolyether Polyols) Other Random Copolyethers Obtained by Anionic Polymerisation
4.1.4 Polyether Polyols Block Copolymers Propylene Oxide–Ethylene Oxide Synthesis of Polyether Polyols, Block Copolymers Propylene Oxide–Ethylene Oxide with Terminal Poly[EO] Block The Effect of the Catalyst Concentration on the Primary Hydroxyl Content The Effect of Ethylene Oxide Addition Rate on the Primary Hydroxyl Content The Effect of Ethoxylation Temperature on the Primary Hydroxyl Content The Effect of the Catalyst Nature on the Primary Hydroxyl Content Removing Propylene Oxide before the Ethoxylation Reaction
4.1.5 Technology for Polyether Polyol Fabrication Preparation of Starter-Catalyst Solution Anionic Polymerisation of Alkylene Oxides Initiated by Polyolic Starters Digestion Degassing Polyether Polyols Purification Neutralisation with Acids of Poptassium Hydroxide, Followed by the Crystallisation of the Resulting Potassium Salts and Filtration Treatment with Adsorbents Treatment with Solid Inorganic Compounds Treatment with Ion Exchange Resins Polyether Polyol Purification by Extraction Processes Other Methods of Polyether Purification Polyether Polyols Stabilisation The Problem of the Presence of High-Molecular Weight Polypropylene Oxide in Propylene Oxide Monomer The Problem of Colour in Polyether Polyol Fabrication The Oxygen Content in the Inert Gas The Propionaldehyde Content of Propylene Oxide Monomer (or Acetaldehyde in Ethylene Oxide) and the Aldehyde Content of Starter Effect of the Purification Step on the Polyether Polyol Colour The Problem of Odour of Polyether Polyols Considerations of the ‘Scorching’ Phenomenon
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

5 Synthesis of High-Molecular Weight Polyether Polyols with Double Metal Cyanide Catalysts
5.1 Continuous Process for Synthesis of Polyether Polyols with a Double Metal Cyanide Catalyst (IMPACT Catalyst Technology, a Greener Polyether Polyols Process)

6 Polymer Polyols (Filled Polyols)
6.1 Graft Polyether Polyols
6.2 The Chemistry of the Graft Polyether Polyol Synthesis
6.2.1 Generation In Situ of Non-Aqueous Dispersant by Grafting Reactions
6.2.2 Stabilisation of Polymer Dispersions in Polymer Polyols with Macromers (Reactive Non-Aqueous Dispersant)
6.2.3 Non-reactive Non-Aqueous 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 Graft Polyether Polyols with High Solid Content Synthesis of a Macromer Synthesis of a Preformed Stabiliser Synthesis of Graft Polyether Polyols
6.3.2 Synthesis of Polymer Polyols by using Preformed Aqueous Polymeric Lattices
6.4 Poly Harnststoff Dispersion Polymer Polyols (Polyurea Dispersions)
6.5 Polyisocyanate Polyaddition Polymer Polyols
6.6 Other Polymer Polyols
6.7 Epoxy Dispersions
6.7.1 Polyamide Dispersions
6.7.2 Aminoplast Dispersions

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 Tetrahydrofuran- alkylene Oxides

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

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

10 Crylic Polyols

11 Polysiloxane Polyols


Volume II:

1. Polyols for Rigid Polyurethanes - General Considerations

2. Polyether Polyols for Rigid Polyurethane Foams
2.1 The Polyaddition of Alkylene Oxides to Hydroxyl Groups
2.1.1 The Mechanism of Alkylene Oxide Polyaddition to Hydroxyl Groups Catalysed by the Tertiary Amines
2.2 Polyether Polyol Technologies for Rigid Foam Fabrication
2.2.1 Anionic Polymerisation of Propylene Oxide (or/and Ethylene Oxide) Initiated by Polyols which are Liquid at the Reaction Temperature
2.3 Kinetic Considerations Concerning the Alkoxylation of Polyols to Rigid Polyether Polyols
2.3.1 Anionic Polymerisation of Propylene Oxide (or/and Ethylene Oxide) Initiated by High Melting Point Polyols which are Solid at the Reaction Temperature

3 Aminic Polyols

4 Rigid Polyols Based on the Alkoxylation of Aromatic Compound Condensates with Aldehydes
4.1 Mannich Polyols
4.1.1 Synthesis of Mannich Base
4.1.2 Alkoxylation of Mannich Base
4.1.3 Synthesis of Mannich Polyols using Oxazolidine Chemistry Synthesis of 1,3-N-hydroxyethyl oxazolidine Synthesis of the Mannich Base The Alkoxylation of the Synthesised Mannich Base
4.2 Novolak-based Polyether Polyols
4.3 Bisphenol A-based Polyols
4.4 Resorcinol-based Diols
4.5 Melamine-based Polyols for Rigid Polyurethanes

5 Polyester Polyols for Rigid Polyurethane Foams
5.1 Aromatic Polyester Polyols from Bottom Residues Resulting in Dimethyl Terephthalate Fabrication
5.2 Aromatic Polyester Polyols from Polyethylene Terephthalate Wastes (Bottles, Films, Fibres)
5.3 Aromatic Polyester Polyols Based on Phthalic Anhydride
5.4 Other Methods for the Synthesis of Polyester Polyols for Rigid Foams

6 Polyols by Thiol-ene ‘Click’ Chemistry
6.1 Synthesis of Polyols for Rigid Polyurethanes by Thiol-ene Reactions
6.2 Polyols for Elastic Polyurethanes by Thiol-ene Click Chemistry

7 Polyols from Renewable Resources
7.1 Bio-based Monomers for Synthesis of Polyols
7.1.1 Bio-based Monomers that Generate New Chains by Ring-opening Polymerisation Reactions Tetrahydrofuran Glycidol Glycerine Carbonate (4-Hydroxymethyl-1,3-Dioxolan-2-One) Lactides
7.1.2 Bio-based Monomers that Generate New Chains by Polycondensation Reactions Bio-based Diacids Bio-based Diols Bio-based Hydroxyacids
7.2 Natural Compounds used as Starters for Polyol Synthesis
7.2.1 Glycerol, Sucrose, Sorbitol, and Xylitol
7.2.2 Starch, Glucose, and Glucosides
7.2.3 Lignin
7.2.4 Betulinol and Isosorbide
7.2.5 Catechins and Tannins
7.2.6 Castor Oil
7.3 Vegetable Oil Polyols (Oleochemical Polyols)
7.3.1 Castor Oil: a Natural Polyol Bio-based Polyols by Chemical Reactions of Castor Oil
7.3.2 Synthesis of Vegetable Oil Polyols using Reactions Involving Ester Bonds
7.3.3 Synthesis of Vegetable oil Polyols by using Reactions Involving Double-Bonds Epoxidation Reactions followed by Ring-opening of Epoxy Groups with Hydrogene-active Compounds Reaction with Acids (Organic or Inorganic) Hydrolysis Alcoholysis Bio-based Polyols from Palm Oil Hydrogenolysis Aminolysis Hydroformylation Reactions Bio-based Polyols for Flexible Polyurethane Foams by Hydroformylation Reactions Metathesis Reactions Polyols by Ozonolysis ‘Honey Bee’ Polyols Bio-based Polyols by Thiol-ene Reactions High-Molecular-Weight Bio-based Telechelics by Thiol-ene Coupling Bio-based Polyols by Nucleophilic Michael Thiol-ene Reaction ‘One-Pot/One-Step’ Synthesis of Polyols from Vegetable Oils Dimerisation of Unsaturated Fatty Acid Polyols Based on Dimer Acids Bio-based Polyols from Polymerised Vegetable Oils Thermal Polymerisation of Vegetable Oils (Bodied Oils) Air-Blown Polymerisation of Vegetable Oils Cationic Polymerisation of Vegetable Oils Polyols from Fatty Acids with Triple-Bonds Polyols from Polymerised Epoxidised Fatty Acids Esters
7.3.4 High-Molecular-Weight Bio-based Polyols from Low-Molecular-Weight Bio-based Polyols Self-condensed Polyols Bio-based Polyols by Chain Extension Bio-based Hyperbranched Polyols for Flexible Polyurethane Foams Polyols by Alkoxylation of Low-Molecular Weight Bio-based Polyols High-Molecular-Weight Polyesters from Low-Molecular-Weight Bio-based Polyols
7.4 Bio-based Polyols Based on Other Natural Compounds
7.4.1 Bio-based Polyols from D-Isosorbide
7.4.2 Polytrimethylene Ether Polyols
7.4.3 Bio-based Polyols with Lactic Acid Units (Lactate Polyols)
7.4.4 Carbon Dioxide-based Polyols Copolymerisation of Carbon Dioxide with Alkylene Oxides in the Presence of Double Metal Cyanide Catalysts Copolymerisation of Carbon Dioxide with Epoxides using Dinuclear Complex Catalysts Cobalt Chelates as Catalysts for Copolymerisation of Carbon Dioxide with Alkylene Oxides
7.4.5 Polyester Polyols from Bio-succinic Acid
7.4.6 Polyglycerol-based Polyols Propoxylation of Polyglycerol Reaction of Polyglycerol with e-Caprolactone Formation of Partial Esters of Polyglycerol with Fatty Acids
7.4.7 Polyols from Proteins
7.4.8 Polyols from the Liquid of Cashew Nut Shells Hydoxyl Functionalisation of Cashew Nut Shell Liquid by Mannich Reactions Synthesis of Polyols from Novolac Resins Derived from Cardanol Polyols from Cardanol by using Reactions Associated with the Double-bonds of C15 Chains
7.4.9 Polyols for Polyurethanes Based on D-Limonene
7.4.10 Polyols Derived from Fish Oil
7.4.11 Polyols by Phenolation of Unsaturated Natural Compounds
7.4.12 High Functionality Bio-based Polyols from Sucrose Soyate
7.5 Looking to the Future of Polyols from Renewable Resources

8 Flame Retardant Polyols
8.1 Chlorine and Bromine Containing Polyols
8.2 Phosphorus Polyols
8.2.1 Esters of Ortho-Phosphoric Acid
8.2.2 Esters of Phosphorus Acid
8.2.3 Phosphonate Polyols
8.2.4 Phosphine Oxide Polyols
8.2.5 Phosphoramidic Polyols

9 Special Polyol Structures for Rigid Polyurethane Foams
9.1 Amidic Polyols
9.2 Hyperbranched Polyols and Dendritic Polyols

10 Oligo-Polyols by Chemical Recovery of Polyurethane Wastes
10.1 Hydrolysis of Polyurethane Polymers
10.2 Glycolysis of Polyurethane Polymers
10.3 Aminolysis of Polyurethane Polymer
10.4 Alkoxylation of Polyurethane Polymer
10.5 Chemical Recovery of Flexible Polyurethane Foam Wastes by Hydrolysis
10.6 Rigid Polyols by Glycolysis of Rigid Polyurethane Foam Wastes
10.7 Rigid Polyols by Aminolysis of Rigid Polyurethane Foam Wastes
10.8 Technology for Chemical Recovery of Rigid Polyurethane Foams (and Isocyanuric Foams) by the Glycolysis Processes

11 Relationships between the Oligo-Polyol Structure and Polyurethane Properties
11.1 Molecular Weight
11.1.1 The Effect of the Molecular Weight of Oligo-Polyols
11.2 Intermolecular Forces
11.2.1 The Effect of the Chemical Nature of Oligo-Polyol Chains
11.3 Stiffness of the Chain
11.4 Crystallinity
11.5 Crosslinking
11.5.1 The Effect of Oligo-Polyol Functionality
11.5.2 The Effect of Oligo-Polyol Structure on the Polyurethane Behaviour in Contact with Organic Solvents and Water
11.6 Thermal Stability and Flame Retardancy
11.6.1 Flame Retardancy

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