MARK F. SONNENSCHEIN, PHD, is research fellow with The Dow Chemical Company. He is inventor of Dow's LESATM (Low Surface Energy Adhesive), Voranol VorativTM polyurethane polyol, HermesTM thermoplastic polyurethane elastomer, RenuvaTM seed oil derived polyol, Voranol 223-060LMTM polyol, and numerous other technologies.

Preface

Acknowledgments

Chapter 1 Introduction

Chapter 2 Polyurethane Building Blocks

2.1 Polyols

2.11 Polyether polyols

2.111 Building blocks

2.112 Polymerization of alkoxides to polyethers

2.12 Polyester polyols

2.121 Polyester polyol building blocks

2.122 Preparation of polyester polyols

2.123 Aliphatic polyester polyols

2.124 Aromatic Polyester Polyols

2. 13 Other Polyols

2.131 Polycarbonate Polyols

2.1311. Preparation of polycarbonate polyols

2. 132 Polyacrylate polyols

2.1321 Preparation of acrylic polyols

2.14. Filled polyols

2.141 Copolymer polyols

2.142 PHD Polyols

2.143 PIPA polyols

2.15 Seed-oil derived polyols

2.151 Preparation of seed oil derived polyols

2.1511 Epoxidation and ring opening

2.1512 Ozonolysis

2.1513 Hydroformylation and reduction

2.1514 Metathesis

2.16 Prepolymers

2.2 Isocyanates

2.21 TDI

2.211 Conventional Production of TDI

2.212 Non-phosgene routes to TDI

2.2121 Thermolysis of Carbamic acid, N,N'-(4-methyl-1,3-phenylene)bis-, C,C'-dimethyl ester made from the reaction of toluene diamine with methyl carbonate

2.2122 Thermolysis of Carbamic acid, N,N'-(4-methyl-1,3-phenylene)bis-, C,C'-dimethyl ester made from the reductive carbonylation of dinitrotoluene.

2.2123 Isocyanates by thermal decomposition of acyl azides - The Curtius rearrangement

2.22 Diphenylmethane diisocyanates (MDI)

2.221 Production of MDI

2.23 Aliphatic Isocyanates

2.231. Production of Aliphatic isocyanates

2.2311 hexamethylene diisocyanate (HDI)

2.2312 Isophorone diisocyanate(IPDI)

2.2313 4,4'- diisocyanatodicyclohexylmethane (H12MDI)

2.232 Use of aliphatic isocyanates

2.3 Chain extenders

Chapter 3 Introduction to Polyurethane Chemistry

3.1 Introduction

3.2 Mechanism and Catalysis of Urethane Formation

3.3 Reactions of Isocyanates with Active Hydrogen Compounds

3.31 Urea Formation

3.32 Allophanate Formation

3.33 Formation of Biurets

3.34 Formation of Uretdione (isocyanate dimer)

3.35 Formation of Carbodiimide

3.36 Formation of uretonimine

3.37 Formation of amides

Chapter 4 Theoretical Concepts and Techniques in Polyurethane Science

4.1 Formation of Polyurethane Structure

4.2 Properties of Polyurethanes

4.21 Models and Calculations for Polymer Modulus

4.22 Models for Elastomer Stress Strain Properties

4.221 Factors that affect Polyurethane Stress-Strain Behavior

4.222 Calculating Foam Properties

4.23 The Polyurethane Glass Transition Temperature

Chapter 5 Analytical Characterization of Polyurethanes

5.1 Analysis of reagents for making polyurethanes

5.11 Analysis of Polyols

5.111 Hydroxyl number

5.112 CPR

5.12 Analysis of Isocyanates

5.121 Analysis of pMDI composition

5.2 Instrumental Analysis of Polyurethanes

5.21 Microscopy

5.211 Optical microscopy

5.212 Scanning electron microscopy

5.213 Transmission electron microscopy (TEM)

5.214 Atomic Force Microscopy (AFM)

5.22 Infra-red Spectrometry

5.23 X-ray Analyses

5.231 Wide Angle X-ray Scattering (WAXS)

5.232 Small Angle X-ray scattering (SAXS)

5.3 Mechanical Analysis

5.31 Tensile, tear and elongation testing

5.32 Dynamic mechanical analysis

5.4 Nuclear Magnetic Spectroscopy (NMR)

5.5 Foam Screening: FoamatR

Chapter 6 Polyurethane Flexible Foams: Chemistry and Fabrication

6.1 Making Polyurethane Foams

6.11 Slabstock Foams

6.12 Molded Foams

6.2 Foam Processes

6.21 Surfactancy and Catalysis

6.211 Catalysis

6.212 Surfactancy

6.3 Flexible Foam Formulation and Structure Property Relationships

6.31 Screening tests

6.32 Foam Formulation and Structure Property Relationships

Chapter 7 Polyurethane Flexible Foams: Markets, Applications, Markets and Trends

7.1 Applications

7.11 Furniture

7.12 Mattresses and Bedding

7.13 Transportation

7.14 The Molded Foam Market

7.2 Trends in Molded Foam Technology and Markets

Chapter 8 Polyurethane Rigid Foams: Markets, Applications, Markets and Trends

8.1 Regional Market Dynamics

8.2 Applications

8.21 Construction Foams

8.211 Polyisocyanurate Foams

8.212 Spray, Poured and Froth Foams

8.2121 Spray foam

8.2122. Froth Foams

8.2123 Pour-in-place foams

8. 22 Rigid Construction Foam Market Segments

8.23 Appliance Foams

8.3 Blowing Agents and Insulation Fundamentals

8.31 Blowing Agents

8.32 Blowing Agent Phase-out Schedule

8.4 Insulation Fundamentals

8.5 Trends in Rigid Foams Technology

Chapter 9 Polyurethane Elastomers: Markets, Applications, Markets and Trends

9.1 Regional Market Dynamics

9.2 Applications

9.21 Footwear

9.211 Trends in Footwear Applications

9.22 Non-footwear Elastomer Applications and Methods of Manufacture

9.221 Cast Elastomers

9.222 Thermoplastic polyurethanes

9.223 RIM Elastomers

9.224 Polyurethane Elastomer Fibers

9.3 Trends in Polyurethane Elastomers

Chapter 10 Polyurethane Adhesives and Coatings: Manufacture, Applications, Markets and Trends

10.1 Adhesives and Coatings Industries: Similarities and Differences

10.2 Adhesives

10.2.1 Adhesive Formulations

10.2.1.1 1-Part Adhesives

10.2.1.2 Hot-melt adhesives

10.2.1.2.1 Non-reactive hot-melt adhesive

10.2.1.2.2 Reactive hot-melt adhesive

10.2.1.3 Water borne polyurethane adhesives

10.3 Trends in Polyurethane Adhesives

10.3 Coatings

10.3.1 Polyurethane coating formulations

10.3.1.1 2-part solvent borne coating

10.3.1.2 Water-borne coatings

10.3.1.3 Water-borne hybrids

10.3.1.4 UV cured water-borne dispersions for coatings

10.3.1.5 Polyurethane Powder Coatings

10.3.2 Trends in Polyurethane Coatings

Chapter 11 Special Topics: Medical Uses of Polyurethane

11.1 Markets and Participants

11.2 Technology

11.2.1 Catheters

11.2.2 Wound dressings

11.2.3 Bioabsorbable polyurethanes.

11.2.4 Hydrogels

11.2.5 Gloves and Condoms

11.3 Future Trends

Chapter 12 Special Topic: Non-isocyanate Routes to Polyurethanes

12.1 Governmental Regulation of Isocyanates

12.2 Non-isocyanate routes to polyurethanes

12.2.1 Reactions of polycyclic carbonates with polyamines

12.2.2 Direct transformations of amines to urethanes

12.2.3 Reactions of polycarbamates

12.2.4 Conversion of hydroxamic acids to polyurethane

12.2.5 Conversion of hydroxylamines to polyurethanes

Chapter 13 Polyurethane hybrid polymers

13.1 Introduction

13.2 Polyurethane-acrylate hybrids

13.3 Polyurethane-epoxy hybrids

13.4 Polyurethane-silicone hybrids

13.4.1 Silicone modified prepolymers

13.4.2 Urethane/silicone hybrids produced using diblock compatabilizers

13.4.3 Hybrids employing covalent and hydrogen bonded crosslinks

13.4.4 Polyurethane hybridization with polyhedral oligomeric silsesquixanes (POSS)

13.5 Polyurethane- polyolefin hybrids

13.6 Hybridization via transurethanification

Chapter 14. Recycling of polyurethanes

14.1 Introduction

14.2 Glycolysis/Hydrolysis/Aminolysis/Acidolysis

14.3 Pyrolysis

14.4 Recycle for fuel value

14.5 Regrinding and incorporation

Index