Polyurethanes

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.

• PrefaceAcknowledgmentsChapter 1   IntroductionChapter 2 Polyurethane Building Blocks2.1 Polyols2.11 Polyether polyols2.111 Building blocks2.112 Polymerization of alkoxides to polyethers2.12 Polyester polyols2.121 Polyester polyol building blocks2.122 Preparation of polyester polyols2.123 Aliphatic polyester polyols2.124 Aromatic Polyester Polyols2. 13  Other Polyols2.131 Polycarbonate Polyols2.1311. Preparation of polycarbonate polyols2. 132 Polyacrylate polyols2.1321 Preparation of acrylic polyols2.14.  Filled polyols2.141 Copolymer polyols2.142 PHD Polyols2.143 PIPA polyols2.15 Seed-oil derived polyols2.151 Preparation of seed oil derived polyols2.1511 Epoxidation and ring opening2.1512 Ozonolysis2.1513 Hydroformylation and reduction2.1514  Metathesis2.16 Prepolymers2.2 Isocyanates2.21 TDI2.211 Conventional Production of TDI2.212 Non-phosgene routes to TDI2.2121  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 carbonate2.2122  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 rearrangement2.22 Diphenylmethane diisocyanates (MDI)2.221 Production of MDI2.23 Aliphatic Isocyanates2.231. Production of Aliphatic isocyanates2.2311 hexamethylene diisocyanate (HDI)2.2312 Isophorone diisocyanate(IPDI)2.2313  4,4’- diisocyanatodicyclohexylmethane (H12MDI)2.232 Use of aliphatic isocyanates2.3 Chain extendersChapter 3 Introduction to Polyurethane Chemistry3.1 Introduction3.2 Mechanism and Catalysis of Urethane Formation3.3 Reactions of Isocyanates with Active Hydrogen Compounds3.31 Urea Formation3.32 Allophanate Formation3.33 Formation of Biurets3.34 Formation of Uretdione (isocyanate dimer)3.35 Formation of Carbodiimide3.36 Formation of uretonimine3.37 Formation of amidesChapter 4 Theoretical Concepts and Techniques in Polyurethane Science4.1  Formation of Polyurethane Structure4.2 Properties of Polyurethanes4.21 Models and Calculations for Polymer Modulus4.22 Models for Elastomer Stress Strain Properties4.221 Factors that affect Polyurethane Stress-Strain Behavior4.222 Calculating Foam Properties4.23 The Polyurethane Glass Transition TemperatureChapter 5 Analytical Characterization of Polyurethanes5.1 Analysis of reagents for making polyurethanes5.11 Analysis of Polyols5.111 Hydroxyl number5.112 CPR5.12 Analysis of Isocyanates5.121 Analysis of pMDI composition5.2 Instrumental Analysis of Polyurethanes5.21 Microscopy5.211 Optical microscopy5.212 Scanning electron microscopy5.213 Transmission electron microscopy (TEM)5.214 Atomic Force Microscopy (AFM)5.22 Infra-red Spectrometry5.23 X-ray Analyses5.231 Wide Angle X-ray Scattering (WAXS)5.232 Small Angle X-ray scattering (SAXS)5.3 Mechanical Analysis5.31 Tensile, tear and elongation testing5.32 Dynamic mechanical analysis5.4 Nuclear Magnetic Spectroscopy (NMR)5.5 Foam Screening: FoamatRChapter 6 Polyurethane Flexible Foams: Chemistry and Fabrication6.1 Making Polyurethane Foams6.11 Slabstock Foams6.12 Molded Foams6.2 Foam Processes6.21 Surfactancy and Catalysis6.211 Catalysis6.212 Surfactancy6.3 Flexible Foam Formulation and Structure Property Relationships6.31 Screening tests6.32 Foam Formulation and Structure Property RelationshipsChapter 7 Polyurethane Flexible Foams: Markets, Applications, Markets and Trends7.1 Applications7.11 Furniture7.12 Mattresses and Bedding7.13 Transportation7.14 The Molded Foam Market7.2 Trends in Molded Foam Technology and MarketsChapter 8 Polyurethane Rigid Foams: Markets, Applications, Markets and Trends8.1 Regional Market Dynamics8.2 Applications8.21 Construction Foams8.211 Polyisocyanurate Foams8.212 Spray, Poured and Froth Foams8.2121 Spray foam8.2122. Froth Foams8.2123 Pour-in-place foams8. 22 Rigid Construction Foam Market Segments8.23 Appliance Foams8.3 Blowing Agents and Insulation Fundamentals8.31 Blowing Agents8.32 Blowing Agent Phase-out Schedule8.4 Insulation Fundamentals8.5 Trends in Rigid Foams TechnologyChapter  9 Polyurethane Elastomers: Markets, Applications, Markets and Trends9.1 Regional Market Dynamics9.2 Applications9.21 Footwear9.211 Trends in Footwear Applications9.22 Non-footwear Elastomer Applications and Methods of Manufacture9.221 Cast Elastomers9.222 Thermoplastic polyurethanes9.223  RIM Elastomers9.224 Polyurethane Elastomer Fibers9.3 Trends in Polyurethane ElastomersChapter 10 Polyurethane Adhesives and Coatings: Manufacture, Applications, Markets and Trends10.1 Adhesives and Coatings Industries: Similarities and Differences10.2 Adhesives10.2.1 Adhesive Formulations10.2.1.1 1-Part Adhesives10.2.1.2  Hot-melt adhesives10.2.1.2.1  Non-reactive hot-melt adhesive10.2.1.2.2 Reactive hot-melt adhesive10.2.1.3 Water borne polyurethane adhesives10.3  Trends in Polyurethane Adhesives10.3 Coatings10.3.1  Polyurethane coating formulations10.3.1.1   2–part solvent borne coating10.3.1.2  Water-borne coatings10.3.1.3  Water-borne hybrids10.3.1.4  UV cured water-borne dispersions for coatings10.3.1.5  Polyurethane Powder Coatings10.3.2  Trends in Polyurethane CoatingsChapter 11 Special Topics:  Medical Uses of Polyurethane11.1 Markets and Participants11.2 Technology11.2.1 Catheters11.2.2 Wound dressings11.2.3 Bioabsorbable polyurethanes.11.2.4 Hydrogels11.2.5 Gloves and Condoms11.3 Future TrendsChapter 12 Special Topic: Non-isocyanate Routes to Polyurethanes12.1 Governmental Regulation of Isocyanates12.2 Non-isocyanate routes to polyurethanes12.2.1 Reactions of polycyclic carbonates with polyamines12.2.2  Direct transformations of amines to urethanes12.2.3 Reactions of polycarbamates12.2.4 Conversion of hydroxamic acids to polyurethane12.2.5 Conversion of hydroxylamines to polyurethanesChapter 13 Polyurethane hybrid polymers13.1 Introduction13.2 Polyurethane-acrylate hybrids13.3 Polyurethane-epoxy hybrids13.4 Polyurethane-silicone hybrids13.4.1 Silicone modified prepolymers13.4.2 Urethane/silicone hybrids produced using diblock compatabilizers13.4.3 Hybrids employing covalent and hydrogen bonded crosslinks13.4.4 Polyurethane hybridization with polyhedral oligomeric silsesquixanes (POSS)13.5 Polyurethane- polyolefin hybrids13.6 Hybridization via transurethanificationChapter 14. Recycling of polyurethanes14.1 Introduction14.2 Glycolysis/Hydrolysis/Aminolysis/Acidolysis14.3 Pyrolysis14.4 Recycle for fuel value14.5 Regrinding and incorporationIndex