Biobased Polyols for Industrial Polymers

Deny Kyriacos is the President & CEO of GEM-Chem which is based in Brussels, Belgium. He holds a B.Sc. (Distinction, Honours, University award in Chemistry) from Alexandria, Egypt, and Ph.D. from Loughborough University in the UK. Before starting his own company, Dr. Kyriacos has worked at Upjohn, GE and ICI International.

• Preface xi1 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 11.1 Introduction 11.2 Sustainability 31.3 Polyols from Vegetable Oils 51.3.1 Polyols from Triglycerides 51.3.2 Polyols from Glycerol 101.4 Polyols from Carbohydrates 121.4.1 Ligno-Cellulosics 121.4.2 Cellulose 121.4.2.1 Hydrolysis 131.4.2.2 Oxidative Degradation 131.4.2.3 Thermal Degradation 141.4.3 Hemicellulose 141.4.4 Lignin 151.4.5 Sucrose 161.4.6 Starch 191.4.6.1 Glucose 191.4.6.2 Sorbitol 20References 222 Polyurethanes, Polyesters and Epoxies 252.1 Introduction 252.2 Polyurethanes 252.2.1 Rigid Foams 252.2.1.1 Isocyanates 262.2.1.2 Polyols 262.2.2 Flexible Foams 272.2.2.1 Isocyanates 282.2.2.2 Polyols 282.2.3 Microcellular Elastomers 282.2.3.1 Footwear 292.2.3.2 Integral Skin 312.2.4 Thermoplastic Polyurethane (TPU) Elastomers 322.2.4.1 Isocyanates 332.2.4.2 Polyols/Diols (Chain Extenders) 342.2.5 Casting Systems 342.2.5.1 Isocyanates 362.2.5.2 Polyols 362.2.5.3 Crosslinkers 362.2.5.4 Examples 362.2.6 Coatings 372.2.6.1 Urethane Oils/Uralkyds 372.2.6.2 Moisture Curable Coatings 382.2.6.3 Blocked Isocyanates 392.2.6.4 Two-Component Coatings 392.3 Polyesters 402.3.1 Unsaturated Polyesters 402.3.1.1 Alkyds 402.3.1.2 Drying Oils 422.3.2 Thermoplastic Polyesters 432.3.3 Polyester Polyols 452.4 Epoxies 46References 483 Vegetable Oils and Fats 513.1 Introduction 513.2 Sources, Components and Extraction of Vegetable Oils 523.2.1 Soybean Oil 523.2.1.1 Source 523.2.1.2 Components of Soya Bean 543.2.1.3 Triglyceride (Oil) Extraction 673.2.2 Palm Oil 733.2.2.1 Source 743.2.2.2 Components 763.2.2.3 Extraction 793.2.3 Corn Oil 853.2.3.1 Source 853.2.3.2 Corn Kernel Components 873.2.3.3 Processing of Corn Kernels 883.2.3.4 Corn Oil Extraction and Refining 923.2.4 Linseed Oil 933.2.4.1 Source 933.2.4.2 Components of Flaxseed 943.2.5 Castor Oil 943.2.5.1 Source 943.2.5.2 Oil Extraction 943.2.5.3 Castor Oil Components 1003.2.6 Rapeseed Oil 1003.2.6.1 Source 1003.2.6.2 Oil Extraction 1013.2.6.3 Components of Canola Seeds, Rapeseeds and Canola Oil 1053.2.7 Sunflower Oil 1073.2.7.1 Source 1073.2.7.2 Processing 1093.2.7.3 Components of Sunflower Oil 1103.2.7.4 Producers of Sunflower Oil 1103.2.8 Vernonia Oil 1103.2.9 Cashew Nut and Nutshell Oil 1133.3 Comparative Data 1173.3.1 Typical Oil Extraction from 100 kg of Oil Seeds 1173.3.2 Fatty Acid Components of Vegetable Oil Triglycerides 1183.3.3 Global Production 1183.4 Fats 1203.4.1 Fish Oil 1203.4.2 Animal Fat 1233.4.2.1 Lard 1233.4.2.2 Beef Tallow 1243.4.3 Comparative Data 124References 1264 Chemistry of Triglycerides and Fatty Acids 1334.1 Introduction 1334.2 Reactions of Double Bonds 1334.2.1 Epoxidation 1334.2.1.1 Chemical Epoxidation 1344.2.1.2 Enzymatic Epoxidation 1394.2.2 C=C Bond Cleavage 1404.2.2.1 Ozonolysis 1404.2.2.2 Metal Catalysis 1424.2.2.3 Microbial Oxidation 1444.2.2.4 Acid-Catalyzed Oxidation 1444.2.3 C=C Bond Metathesis 1454.2.4 Polymerization Reactions of Vegetable Oils 1484.2.4.1 Homopolymerization 1494.2.4.2 Copolymerization 1494.2.4.3 Oxypolymerization 1534.2.5 Hydrogenation 1554.2.6 Dihydroxylation 1584.2.6.1 Anti-Dihydroxylation 1584.2.6.2 Syn Dihydroxylation 1594.2.7 Addition 1604.2.7.1 Hydroxybromination 1604.2.7.2 Addition of Acetone/Malonic Acid 1614.3 Reactions of Ester Groups 1624.3.1 Hydrolysis of Ester Groups 1624.3.1.1 Chemical Hydrolysis 1624.3.1.2 Enzymatic Hydrolysis 1634.3.2 Alcoholysis/Glycerolysis 1644.3.3 Transesterification 1674.3.4 Aminolysis 1684.4 Reactions of Hydroxyl Groups 1704.4.1 Dehydration 1704.4.2 Esterification 170References 1715 Polyols from Triglycerides 1775.1 Introduction 1775.2 Reactions of Epoxides 1785.2.1 Hydrolysis of Oxirane Rings 1795.2.1.1 With Inorganic Acids 1795.2.1.2 With Organic Acids 1805.2.2 Alcoholysis of Oxirane Rings 1825.2.2.1 Clay Catalyzed 1825.2.2.2 HBF4 Catalyzed 1845.2.3 Esterification of Oxirane Rings 1855.2.3.1 With Carboxylic Acids 1855.2.3.2 Acid Anhydrides 1885.2.3.3 Hydroxy Carboxylic Acids 1885.2.4 Aminolysis 1895.3 Reactions of Ozonides 1915.3.1 Ozonolysis Followed by Hydrogenation 1915.3.2 Polyols from the Transesterification of Ozonolysis Intermediates 1935.3.2.1 Amidification of Esters 1945.3.2.2 Interesterification with Glycerol 1945.4 Hydroformylation 1965.5 Examples of Synthetic Methods 1995.5.1 Glycerol Propoxylates 1995.5.2 Castor Oil Alkoxylates 1995.5.3 Mixed Alkoxylates 2005.5.4 Oxidation in the Presence of Organometallic Complexes 2005.5.5 Use of Double-Metal Cyanide (DMC) Complex Catalysts 2015.5.6 Polyols from Palm Oil 2035.5.7 Polyols from Oleic Acid (or Canola Oil) 2065.5.8 Polyols from Soybean Oil and Chicken Fat 2075.5.9 Autocatalytic Polyols 2085.5.9.1 From Diethanolamine and Epoxidized Soybean Oil 2085.5.9.2 Mannich Polyols from Cardanol 210References 2136 Carbohydrate-Based Polyols 2196.1 Introduction 2196.2 Bio Ethylene Oxide 2196.3 Bio Propylene Glycol 2236.3.1 1,3-Propanediol 2236.3.1.1 Fermentation 2246.3.1.2 Hydrogenation 2256.3.2 1,2-Propanediol 2256.3.2.1 Hydrocracking 2256.3.2.2 Fermentation 2266.4 Bio-Butanediol 2266.5 Sucrose 2286.5.1 Introduction 2286.5.1.1 Sucrose from Cane Sugar 2296.5.1.2 Sucrose from Beets 2306.5.2 Propoxylated Sucrose Initiated Polyols 2316.5.3 Propoxylated/Ethoxylated Polyols with Mixed Initiators 2326.5.3.1 Sucrose/Ethylene Diamine Initiators 2336.5.3.2 Sucrose/Glycerol Initiators 2336.5.4 Propoxylation of Glucose Obtained from Starch 2346.6 Sorbitol 2356.6.1 Synthesis 2356.6.2 Synthesis of Polyols from the Alkoxylation of Sorbitol 2366.6.3 Sorbitol Derivatives 2376.7 Carbohydrates from Corn Fibers 2396.7.1 Chemical Treatment 2396.7.2 Biochemical Treatment 240References 2427 Biobased Polyols and Their Applications 2477.1 Commercial Vegetable Oil Polyols 2477.1.1 Producers 2477.1.2 PU Applications 2477.1.2.1 Rigid Foams 2477.1.2.2 Flexible Foams 2697.1.2.3 Viscoelastic Foams 2757.1.2.4 Castings/Sealants 2847.1.2.5 Carpet Backing 2897.1.2.6 Elastomers and Coatings 2957.1.3 Epoxies 3027.1.4 Polyesters 3067.1.4.1 Alkyd Resins 3067.1.4.2 Thermoplastic Polyesters 3097.1.5 Acrylate Coatings 3117.1.5.1 Introduction 3117.1.5.2 Examples 3117.2 Commercial Carbohydrate-Derived Polyols 3137.2.1 Producers 3137.2.2 General Technical Considerations 314References 315Appendix 319Index 327