Handbook of Maleic Anhydride Based Materials (eBook)

Dr. Osama M. Musa is the Vice President and ASI Technology Chief at Ashland Specialty Ingredients (ASI), Bridgewater, NJ, USA. In this function, he is overseeing, coordinating global research and development for consumer specialties, innovation, biofunctionals, biocides & preservatives and the technology platforms and leading molecular and analytical science, materials science and process research at Ashland.Osama Musa is known as a strategic R&D leader with a broad experience in the specialty chemicals business sector, especially across consumer categories such as personal care, home care, pharma, coatings and adhesives, and many more. He disposes of a wide-ranging network, cooperating with partners both in the industry and in academia. Ashland Inc. is a leading international chemistry company, based in the United States, operating in more than 100 countries worldwide. Ashland Specialty Ingredients is their division offering products, technologies and resources for formulation and product performance in markets ranging from personal care, pharmaceutical, food and beverage, to coatings and energy.

Preface 6
Acknowledgements 8
Contents 10
Biography 12
Part I: Introduction 14
Chapter 1: Progress in Maleic Anhydride Production 15
1.1 Introduction 15
1.2 Historical Overview 18
1.2.1 Early Maleic Anhydride (via C4) Production Examples 19
1.2.1.1 Halcon-Scientific Design (HSD) Fixed-Bed Process [23] 19
1.2.1.2 ALMA Fluid-Bed Process 22
1.2.2 Fixed-Bed and Fluid-Bed Comparisons 23
1.2.3 Industry Response 24
1.3 Catalysis: Progress in Structure and Function 25
1.3.1 Inorganic Catalyst Structure 25
1.3.2 Proposed C4 Catalytic Oxidation Mechanisms 28
1.3.3 Catalyst Improvement and Implementation Strategies in Manufacturing 36
1.3.3.1 Insertion of Enhancement Agents 36
Autoignition Suppression Agents 36
Additions of Process Gases 36
Addition of Phosphates 37
Addition of Peroxides 38
1.3.3.2 Catalytic Co-metal Inclusions 38
1.3.3.3 Multiple Catalytic Zones 38
1.3.3.4 Halide Removal 39
1.3.3.5 Pretreatment and Purity 40
1.3.3.6 Dimensional Stability 41
1.3.3.7 Morphology and Porosity 43
1.3.3.8 Shape Considerations in Production 44
1.3.3.9 Regeneration 47
1.4 Strategic Design Improvements in Existing Plants 49
1.4.1 Reactor Design Modifications 49
1.4.1.1 High-Purity Maleic Anhydride Insertion 49
1.4.1.2 Fixed-Bed Modifications 49
1.4.1.3 Reduction in Fluid-Bed Back-Mixing 50
1.4.1.4 Process Gas Recycling 51
1.4.1.5 Solvent Absorption and Distillation 53
1.5 Improving Product Quality and Safety 57
1.5.1 Distillation in Designed Atmospheres 57
1.5.2 Additives for Distillates 58
1.5.3 Removal of Impurities via Precipitation 59
1.6 Safety 59
1.7 Other Production Routes 61
1.7.1 Circulating Fluidized-Bed (CFB) Reactor 61
1.7.2 Microchannel Reactor 62
1.7.3 Bio-based Reactants 63
References 64
Part II: Reactions and Derivatives 68
Chapter 2: Reactions Involving Maleic Anhydride 69
2.1 Introduction 69
2.1.1 Physical Properties of Maleic Anhydride and Its Derivatives 69
2.1.2 Spectroscopic Properties of Maleic Anhydride 76
2.2 Reactions of the Anhydride Functionality 78
2.2.1 Hydrolysis and Acidity 78
2.2.2 Isomerization and Stability 83
2.2.3 Peroxidation 86
2.2.4 Friedel-Crafts Acylation 87
2.2.5 Acid Halide Formation 89
2.2.6 Alkali Metal Salt Formation, Organic Neutralizer, and Metal Chelation 90
2.2.7 Esterification 93
2.2.8 Stabilization of Maleate Monoesters 97
2.2.9 Thioester Formation 98
2.2.10 Amidation Reactions 99
2.2.11 Maleimides and Imidation Reactions 100
2.3 Hydrogenation of the Electron-Deficient Double-Bond Functionality 103
2.3.1 Catalytic Hydrogenation of Maleic into Succinic Derivatives 103
2.3.2 Electrolytic Hydrogenation of Maleic into Succinic Derivatives 106
2.3.3 Transfer Hydrogenation of Maleic into Succinic Derivatives 108
2.4 Oxidation Reactions of the Electron-Deficient Double Bond 109
2.4.1 Epoxidation 109
2.4.2 Ozonolysis 114
2.5 Addition Reactions to the Electron-Deficient Double Bond 115
2.5.1 Hydroformylation Reaction 115
2.5.2 Addition of Water for Conversion of Maleic into Malic Compounds 116
2.5.3 Addition of Halo Acids for Conversion of Maleic into Halosuccinate Compounds 116
2.5.4 Addition of Halogens for Conversion of Maleic into Dihalosuccinate Compounds 119
2.5.5 Michael Additions to the Electron-Deficient Double Bond 122
2.5.6 Sulfonation and Thiol Additions 126
2.5.7 Alkoxylation Reactions to the Double Bond 127
2.5.8 Amination, Amino-Acid Formation, and Biopolymer Synthesis 129
2.6 Cycloaddition (Diels-Alder) Reactions of Maleic Anhydride 130
2.6.1 Ring-Opening Metathesis Monomers from Maleic Anhydride 137
2.6.2 Maleated Fatty Acids and Vegetable Oils 138
2.7 ``Ene´´ Reactions of Maleic Anhydride: ``Ene´´ Reaction 141
2.7.1 Ene Reactions of Fatty Acids and Oils with Maleic Anhydride 145
2.7.2 Grafted Polyethylene or Polypropylene with Maleic Anhydride 146
2.8 Photochemistry of Maleic Anhydride 149
2.8.1 Photodimerization of Maleic Anhydride 151
2.8.2 Photochemistry of Maleimide 152
2.8.3 Photoinitiation and Photopolymerization of Maleimide 153
References 154
Chapter 3: Vegetable Oil-Maleic Anhydride and Maleimide Derivatives: Syntheses and Properties 160
3.1 Syntheses and Properties of Maleic Anhydride Derivatives with Vegetable Oil 160
3.1.1 Introduction on Vegetable Oil 160
3.1.2 Esterification of Maleic Anhydride with Hydroxyls in the Fatty Acid Chain of Vegetable Oil 161
3.1.3 Esterification Reaction of Maleic Anhydride with the Glycerides of Vegetable Oil 165
3.1.4 Polyesterification of Maleic Anhydride with the Glycerides of Vegetable Oil 171
3.1.5 ``Ene´´-Grafting of Maleic Anhydride onto the Allylic Position in the Fatty Chain of the Vegetable Oil 174
3.1.6 Syntheses of Vegetable Oil-Based Resins Using Maleic Anhydride as Cross-Linking Agent 178
3.1.7 Diels-Alder Reaction of Maleic Anhydride with Conjugated Diene in Vegetable Oil 180
3.2 Maleimide Derivatives and Their Properties 183
3.2.1 Recent Advances in the Synthesis of Maleimide Derivatives 183
3.2.2 Syntheses of Novel Maleimide Derivatives and Their Uses 189
3.2.3 Syntheses of Fluorescent Maleimide Derivatives and Their Properties 190
3.2.4 Syntheses and Properties of Maleimide Derivatives Based on the Diels-Alder Reaction 194
3.2.5 Syntheses of Multifunctional Maleimide Derivatives and Their Uses 195
3.2.6 Syntheses of Liquid Maleimide Compounds and Their Properties 199
3.2.7 Syntheses of Maleimide Derivatives with Reworkable Acetal Linkage and Their Properties 204
3.2.8 Syntheses of Maleimide Derivatives Based on Reversible Diels-Alder Reaction 209
3.2.9 Bioconjugates Containing Maleimides and Their Uses 210
References 212
Part III: Maleic Anydride-Derived Polymers 218
Chapter 4: The Quintessential Alternating Copolymer Family: Alkyl Vinyl Ether co-Maleic Anhydride Copolymers 219
4.1 Maleic Anhydride-co-Alkyl Vinyl Ether Copolymer 219
4.1.1 Composition of Maleic Anhydride-co-Alkyl Vinyl Ether Copolymers 219
4.1.1.1 Maleic Anhydride-co-Methyl Vinyl Ether Copolymer 219
4.1.1.2 Maleic Anhydride-Methyl Vinyl Ether-Isobutylene Terpolymer 220
4.1.1.3 Cross-Linked Copolymer of Maleic Anhydride-Methyl Vinyl Ether 222
4.1.1.4 Branched Copolymer of Maleic Anhydride-Methyl Vinyl Ether 222
4.1.1.5 Maleic Anhydride-Mixed Alkyl Vinyl Ether Copolymers 223
4.1.1.6 Maleic Anhydride-Divinyl Ether Copolymer 224
4.1.2 Mechanism of Copolymerization of Maleic Anhydride and Alkyl Vinyl Ethers 225
4.1.2.1 Radical Copolymerization of Non-homopolymerizable Monomers 225
4.1.2.2 Charge-Transfer Complex 227
4.1.2.3 Copolymerization with Monomer Complex Participation 232
4.1.2.4 Spontaneous Copolymerizations Involving Maleic Anhydride and Alkyl Vinyl Ethers 239
4.1.3 Physical Properties of Maleic Anhydride-Alkyl Vinyl Ether Copolymers 243
4.1.3.1 Molecular Weight 243
4.1.3.2 Glass Transition Temperature of Maleic Anhydride-Alkyl Vinyl Ether Copolymers 243
4.1.3.3 Solubility of Maleic Anhydride-Alkyl Vinyl Ether Copolymers 244
4.1.3.4 Stability of Maleic Anhydride-Alkyl Vinyl Ether Copolymers in the Solid State 245
4.1.3.5 Stability in Aqueous Solution 245
4.1.4 Derivatives of Maleic Anhydride/Alkyl Vinyl Ether Copolymers 249
4.1.4.1 Polyacids and Their Salts from Maleic Anhydride-Alkyl Vinyl Ether Copolymers 250
4.1.4.2 Half Esters from Maleic Anhydride-Alkyl Vinyl Ether Copolymers 252
4.1.4.3 Polyamides and Imides from Maleic Anhydride-Alkyl Vinyl Ether Copolymers 255
References 256
Chapter 5: Industrially Significant Copolymers Containing Maleic Anhydride 259
5.1 Introduction to Unsaturated Polyester Resins Based on Maleic Anhydride 259
5.2 Production of Unsaturated Polyester Resins 259
5.2.1 Composition of Unsaturated and Saturated Dicarboxylic Anhydride/Acid 262
5.2.2 Composition of Dihydric Alcohols 264
5.2.3 Addition Sequence of Dibasic Acids and Dihydric Alcohols 267
5.3 Unsaturated Polyester Resins from Polyethylene Terephthalate Waste 268
5.4 Condensation Kinetics of Dibasic Acid and Diol 269
5.4.1 Condensation Kinetics of Maleic Anhydride and Phthalic Anhydride with Propylene Glycol 270
5.4.2 Condensation Kinetics of 2-Methyl-1,3-Propanediol with Maleic Anhydride and Phthalic Anhydride 271
5.5 Mechanical Properties of Cured Unsaturated Polyester Resins 272
5.6 Introduction to Alkyd Resins 273
5.6.1 Alkyd Resins Containing Maleic Anhydride 274
5.7 Olefin/Maleic Anhydride Copolymers 279
5.8 Acrylic/Maleic Anhydride Copolymers 284
5.9 N-Vinyl Amide/Maleic Anhydride Copolymers 288
5.10 Introduction to Styrene-Maleic Anhydride Copolymers and Their Physical Properties 292
5.11 Graft Copolymers of Styrene-Maleic Anhydride via Chemical Acylation Reactions 299
5.12 Recent Advances in the Synthesis of Styrene-Maleic Anhydride Copolymers by Controlled Free Radical Polymerization 302
5.12.1 Nitroxide-Mediated Polymerizations 303
5.12.2 Atom Transfer Radical Polymerization 307
5.12.3 Reversible Addition-Fragmentation Chain Transfer 308
5.12.4 Production of Styrene-Maleic Anhydride/N-Vinyl Pyrrolidone Gradient Terpolymers by RAFT 311
References 315
Chapter 6: Ring-Opening Metathesis Polymerization (ROMP) Using Maleic Anhydride-Based Monomers 319
6.1 Introduction to Ring-Opening Metathesis Polymerization (ROMP) Using Maleic Anhydride-Based Monomers 319
6.1.1 ROMP Mechanism 320
6.1.2 Initial Monomers Used in ROMP 322
6.1.3 Catalyst Choice 323
6.1.4 ROMP Polymerization Stages 328
6.1.5 Synthesis of Random Versus Block Copolymers by ROMP 330
6.1.6 ROMP Monomers Based on Maleic Anhydride or Its Derivatives 332
6.1.7 Microstructure of ROMP Polymers 336
6.1.8 Aqueous ROMP as Green Chemistry 340
6.2 Solid-Phase Supports for ROMP Synthesis 349
6.3 Ring-Opening Metathesis Polymerization of Monomers Containing Amino Acids, Peptide, and Protein Mimetics 356
6.4 Antimicrobial ROMP Polymers 367
6.5 Self-Assembly ROMP Polymers 373
6.6 Thermosetting ROMP Polymers 379
6.7 Microstructural Analysis of Maleic Anhydride-Based ROMP Polymers 387
References 401
Chapter 7: Colloidal and Physicochemical Properties of Maleic Anhydride Polymers 407
7.1 Introduction 407
7.2 Conformational Behavior of Dilute Solutions of Maleic Anhydride Copolymers 408
7.3 Potentiometric Titration Studies of Polyacids 409
7.3.1 Treatment of Titration Data 409
7.3.2 Potentiometric Titration Studies of Hydrophobically Modified Poly(Maleic Acid) 410
7.4 Thermodynamics of the Ionization Process for Copolymers of Maleic Anhydride 412
7.5 Rheological Properties of Polyacids 415
7.6 Spectrofluorescence Studies of Polymer Conformation 417
7.7 Conformation Behavior of Copolymers of Maleic Anhydride and Styrene in Water 422
7.8 Interactions Between Maleic Anhydride-Based Polymers and Surfactants 424
7.8.1 Nonionic Surfactants 425
7.8.2 Anionic Surfactants 428
7.8.3 Cationic Surfactants 430
7.9 Thin Films of Copolymers of Maleic Anhydride 433
7.10 Polyelectrolyte Complexes of Maleic Anhydride-Based Polymers 436
7.11 Concluding Remarks 441
References 443
Part IV: Applications 446
Chapter 8: Maleic Anhydride Applications in Personal Care 447
8.1 Introduction 447
8.2 Applications of Maleic Anhydride Copolymers in Hair Care 448
8.2.1 Structure and Function of Hair 448
8.2.2 Hair Sprays 451
8.2.3 Hair Gel and Mousse Applications 453
8.2.4 Split End Mending with a Polyelectrolyte Complex 456
8.2.5 Thermal Styling and Protection 459
8.3 Maleic Anhydride Chemistry in Applications for Skin Care and Transdermal Delivery 462
8.3.1 Skin Structure and Function 462
8.3.1.1 Epidermis 464
8.3.1.2 Dermal-Epidermal Junction 464
8.3.1.3 Dermis 465
8.3.1.4 Cutaneous Appendages 467
8.3.2 Bioadhesives 467
8.3.3 Biosensors 469
8.3.4 Wound Healing 469
8.3.5 Keratotic Plug Removal 470
8.3.6 Antiperspirant Technology 472
8.3.7 Transdermal Drug Delivery 475
8.3.7.1 Transdermal Patch Applications 475
8.3.7.2 Microneedles 479
8.3.7.3 Nanoparticle Technology 480
8.3.8 Delivery of Active Ingredients 484
8.3.9 Skin Care Formulations 486
8.3.9.1 Applications of Skin Care Emollients 486
8.3.9.2 Skin Cleansing Formulations 489
8.3.9.3 Soap Bar Dimensional Stability 491
8.3.9.4 Stabilization of Vitamin C 492
8.3.9.5 Alpha Hydroxy Acids 492
8.3.10 Incorporation of Maleic Anhydride Derivatives in Sunscreen Formulations 493
8.3.11 Rheology Modifiers for Skin Care Formulations 495
8.3.12 Skin Tightening 497
8.4 Maleic Anhydride Chemistry in Oral Care 498
8.4.1 Bioadhesive Properties of Poly(Methyl Vinyl Ether-Maleic Acid) 498
8.4.2 Tooth Anatomy 499
8.4.3 Plaque, Calculus, Caries, and Gingivitis and Strategies for Protection 501
8.4.4 Denture Adhesives 503
References 505
Applications of Maleic Anhydride Copolymers in Hair Care 505
Maleic Anhydride Chemistry in Applications for Skin Care and Transdermal Delivery 506
Maleic Anhydride Chemistry in Oral Care 512
Chapter 9: Application of Maleic Anhydride in Coatings, Adhesives and Printing 514
9.1 Introduction 514
9.2 Coatings 514
9.2.1 Binders: Alkyd Resins 515
9.2.2 Binders: Styrene-Acrylic-Maleic Anhydride 519
9.2.3 Binders: Corrosion Protection 524
9.2.4 Binders: Prevention of Marine Fouling 531
9.2.5 Reactive Polymeric Surfactants 532
9.2.6 Photostabilizers 535
9.2.7 Antimicrobial Compositions 536
9.3 Composite Resins and Adhesives 537
9.3.1 Unsaturated Polyesters 537
9.3.2 Bismaleimide Resins and Adhesives 548
9.3.3 Epoxy-Based Adhesives 562
9.4 Printing and Imaging 564
9.4.1 Adhesion 564
9.4.2 Nonaqueous Printing 566
9.4.3 Aqueous Printing 571
References 577
Chapter 10: Application of Maleic Anhydride-Based Materials 581
10.1 Introduction 581
10.2 Additives for Automotive Applications 581
10.2.1 Fuel Additives 582
10.2.2 Lubricants and Fuels: Detergents and Dispersants 584
10.2.3 Anti-static Additive for Fuels 587
10.3 Biologically Active Compounds and Pharmaceutical Compositions 588
10.3.1 Introduction 588
10.3.2 Salt Formation 589
10.3.3 Organophosphates 591
10.3.4 Polymer-Enhanced Active Compounds 592
10.4 Microencapsulation 596
10.5 Thermoplastics and Films 599
10.5.1 Molding 599
10.5.2 Tubing 601
10.5.3 Films 606
10.5.3.1 Airbags 606
10.5.3.2 Tamper Evident Products 607
10.5.3.3 Packaging 608
10.6 Water Treatment 611
10.6.1 Desalination of Seawater 611
10.6.2 Oil Spill Dispersants 615
10.6.3 Cleaners and Detergents 620
10.6.4 Membranes 624
References 629
Index 633