CHEMISTRY AND

TECHNOLOGY OF
ISOCYANATES

HENRI ULRICH
Chemical Consultant
Guilford, CT, USA

JOHN WILEY & SONS

Chichester • New York • Brisbane • Toronto • Singapore
 CONTENTS

Preface xi

Acknowledgments xüi

1 Monoisocyanates 1
1.1 Alkyl and Aryl Isocyanates 1
1.1.1 Introduction 1
1.1.2 Synthesis of Alkyl and Aryl Isocyanates 3
1.1.2.1 Synthesis by Phosgenation Reactions 3
1.1.2.2 Formation of Alkyl and Aryl Isocyanates via
Nitrene Intermediates 11
1.1.2.3 Formation of Alkyl and Aryl Isocyanates by
Thermal Processes 19
1.1.2.4 Rearrangements of Nitrile Oxides and Cyanates 26
1.1.2.5 Reactions of Organic Halides with Salts of
Cyanic Acid 27
1.1.2.6 Reaction of Olefins and Aldehydes with
Isocyanic Acid 28
1.1.2.7 Isocyanates from Other Heterocumulenes 29
1.1.2.8 From Imines and Phosphineimines 30
1.1.2.9 Miscellaneous Synthetic Methods 31
1.1.3 References 36
1.1.4 Reactions of Alkyl and Aryl Isocyanates 42
1.1.4.1 Introduction 42
1.1.4.2 rOligomerization and Polymerization 45
1.1.4.3 Cycloaddition Reactions 54
1.1.4.4 Nucleophilic Reactions 98
1.1.4.5 Insertion Reactions 106
1.1.4.6 Miscellaneous Reactions 124
1.1.5 References 133
vi CONTENTS

1.2 Unsaturated Isocyanates 149

1.2.1 Introduction 149
1.2.2 Synthesis of Unsaturated Isocyanates 149
1.2.2.1 Elimination of Hydrogen Halide from
Halogenated Isocyanates 149
1.2.2.2 Synthesis via Nitrene Intermediates 150
1.2.2.3 From Amines, Imines or Nitriles and Phosgene 152
1.2.2.4 Miscellaneous Synthetic Methods 154
1.2.3 Reactions of Unsaturated Isocyanates 157
1.2.3.1 Homopolymerization 157
1.2.3.2 Copolymerization 157
1.2.3.3 Nucleophilic Reactions 157
1.2.3.4 Cycloaddition Reactions 157
1.2.3.5 Miscellaneous Reactions 160
1.2.4 References 161
1.3 Halogenated Alkyl and Aryl Isocyanates 163
1.3.1 Introduction 163
1.3.2 Synthesis of Halogenated Alkyl and Aryl Isocyanates 163
1.3.2.1 Halogenation of Alkyl and Aryl Isocyanates 163
1.3.2.2 Halogenation of Acyl and Thioacyl Isocyanates 167
1.3.2.3 Addition of Halogen to Unsaturated
Isocyanates 168
1.3.2.4 Reaction of Amines, Imines and Nitriles with
Phosgene and Analogues 168
1.3.2.5 Synthesis of Halogenated Isocyanates via
Nitrene Intermediates 172
1.3.2.6 Miscellaneous Synthetic Methods 174
1.3.3 Reactions of Halogenated Isocyanates 179
1.3.3.1 Nucleophilic Reactions 179
1.3.3.2 Elimination of Hydrogen Halides and Acids 188
1.3.3.3 Exchange Reactions with Silylated
Heterocumulenes 188
1.3.3.4 Reactions with Oxiranes and Aziridines 188
1.3.3.5 Reactions with Multiple Bond Systems 189
1.3.3.6 Cycloaddition Reactions 190
1.3.3.7 Insertion Reactions 190
1.3.3.8 Miscellaneous Reactions 190
1.3.4 References 192
1.4 Carbonyl, Thiocarbonyl and Imidoyl Isocyanates 197
1.4.1 Introduction 197
1.4.2 Synthesis 197
1.4.2.1 Synthesis of Carbonyl Isocyanates 197
1.4.2.2 Synthesis of Thiocarbonyl Isocyanates 212
1.4.2.3 Synthesis of Imidoyl Isocyanates 213
 CONTENTS vii

1.4.3 Reactions 216

1.4.3.1 Reactions of Carbonyl Isocyanates 216
1.4.3.2 Reactions of Thiocarbonyl Isocyanates 231
1.4.3.3 Reactions of Imidoyl Isocyanates 235
1.4.4 References 235
1.5 Sulfur Isocyanates 241
1.5.1 Introduction 241
1.5.2 Synthesis 241
1.5.2.1 Synthesis of Divalent Sulfur Isocyanates 241
1.5.2.2 Synthesis of Tetravalent Sulfur Isocyanates 242
1.5.2.3 Synthesis of Hexavalent Sulfur Isocyanates 242
1.5.3 Reactions of Sulfur Isocyanates 248
1.5.3.1 Nucleophilic Reactions 248
1.5.3.2 Cycloaddition Reactions 252
1.5.3.3 Miscellaneous Reactions 269
1.5.4 References 274
1.6 Phosphorus Isocyanates 279
1.6.1 Introduction 279
1.6.2 Synthesis of Phosphorus Isocyanates 280
1.6.2.1 From Phosphorus Halides and Cyanic Acid
and Its Salts 280
1.6.2.2 From Carbamates 281
1.6.2.3 From Phosphoryl Amides and Oxalyl Chloride 282
1.6.2.4 Miscellaneous Synthetic Methods 282
1.6.3 Reactions of Phosphorus Isocyanates 284
1.6.3.1 Reaction with —OH Compounds 284
1.6.3.2 Reaction with Amines and Hydrazines 284
1.6.3.3 Cycloaddition Reactions 284
1.6.3.4 Miscellaneous Reactions 286
1.6.4 References 287
1.7 Inorganic Isocyanates 290
1.7.1 Introduction 290
1.7.2 Synthesis of Inorganic Isocyanates 290
1.7.2.1 Main Group lila Isocyanates 290
1.7.2.2 Main Group IVa Isocyanates 291
1.7.2.3 Main Group Va Isocyanates 293
1.7.2.4 Main Group Via Isocyanates 296
1.7.2.5 Main Group Vlla Isocyanates 297
1.7.2.6 Liganded Transition Metal Isocyanates 297
1.7.3 Reactions of Inorganic Isocyanates 299
1.7.4 References 300
1.8 Applications of Monoisocyanates 303
1.8.1 Agricultural and Pharmaceutical Products 303
1.8.2 Monoisocyanates in Polymer Modification 305
viii CONTENTS

1.8.3 As Reagents in Organic Synthesis 308

1.8.4 Miscellaneous Applications 311
1.8.5 References 312

Diisocyanates 315
2.1 Aliphatic Diisocyanates 315
2.1.1 Introduction 315
2.1.2 Synthesis of Aliphatic Diisocyanates 328
2.1.2.1 Phosgenation of Amines 328
2.1.2.2 Nonphosgene Processes 333
2.1.2.3 Formation via Nitrene Intermediates 334
2.1.2.4 From Olefins and Isocyanic Acid or Ethyl
Carbamate 337
2.1.2.5 From Organic Dihalides and Salts of Isocyanic
Acid 338
2.1.2.6 Miscellaneous Synthetic Methods 338
2.1.3 Manufacture of Major Aliphatic Diisocyanates 342
2.1.3.1 Hexamethylene Diisocyanate (HDI) 342
2.1.3.2 Isophorone (IPDI) and Tnmethylhexamethylene
Diisocyanates (TMHDI) 343
2.1.3.3 HMDI 344
2.1.3.4 trans-Cyclohexane Diisocyanate (CHDI) 345
2.1.3.5 Tetramethylxylylene Diisocyanate (TMXDI) 346
2.1.4 Reactions of Aliphatic Diisocyanates 347
2.1.4.1 Homopolymerization 347
2.1.4.2 Copolymerization 348
2.1.4.3 Addition Polymerization 349
2.1.4.4 Condensation Polymerization 350
2.1.4.5 Other Reactions of Aliphatic Diisocyanates 351
2.1.5 Applications of Aliphatic Diisocyanates 356
2.1.5.1 Polyurethanes 356
2.1.6 References 361
2.2 Aromatic Diisocyanates 368
2.2.1 Introduction 368
2.2.2 Synthesis 372
2.2.2.1 Phosgenation of Amines 372
2.2.2.2 Nonphosgene Processes 375
2.2.2.3 Aromatic Diisocyanates via Nitrene
Intermediates 379
2.2.2.4 Aromatic Diisocyanates by Coupling of
Monoisocyanates or Isocyanate Precursors 380
2.2.2.5 Miscellaneous Syntheses of Aromatic
Diisocyanates 384
2.2.3 Manufacture of Aromatic Diisocyanates 385
 CONTENTS ix

2.2.3.1 MDI and Polymerie Isocyanates (PMDI) 385

2.2.3.2 Tolylene Diisocyanate (TDI) 392
2.2.3.3 p-Phenylene Diisocyanate (PPDI) 394
2.2.3.4 Naphthalene Diisocyanate (NDI) 394
2.2.4 Reactions of Aromatic Diisocyanates 395
2.2.4.1 Homopolymerization Reactions 395
2.2.4.2 Copolymerization Reactions 395
2.2.4.3 Cyclopolymerization Reactions 395
2.2.4.4 Addition Polymerization Reactions 396
2.2.4.5 Condensation Polymerization Reactions 410
2.2.4.6 Other Reactions of Aromatic Diisocyanates 416
2.2.5 Applications of Aromatic Diisocyanates 426
2.2.5.1 Polyurethanes 426
2.2.5.2 Poly(urethane ureas) and Polyureas 446
2.2.5.3 Poly(urethane isoeyanurates) 450
2.2.5.4 Binder Resins 452
2.2.5.5 Polyamides 455
2.2.5.6 Poly(amide imides) and Polyimides 456
2.2.6 References 456

3 Environmental Considerations 469

3.1 Toxicity 469
3.1.1 Toxicity of Isocyanates 469
3.1.2 Toxicity of Chemicals Used in Isocyanate Manufacture 472
3.1.3 Toxicity of Isocyanate Derived Products 472
3.2 Safety Aspects 473
3.2.1 Storage and Handling of Isocyanates 473
3.2.2 Safety of Isocyanate Production 474
3.2.3 Fire Safety of Isocyanate Derived Products 475
3.3 Environmental Impact 475
3.3.1 Disposal of By-products in Isocyanate Manufacture 475
3.3.2 Disposal of Isocyanate Derived Products 476
3.3.3 Replacement of CFCs in Cellular Products 477
3.4 Isocyanates and Polyurethane Chemicals based on Renewable
Resources 478
3.4.1 Isocyanates based on Renewable Resources 478
3.4.2 Polyols based on Renewable Resources 479
3.5 A World without Isocyanates 479
3.6 References 481

Index 483