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Ионжоогүй гадаргуугын идэвхит бодис: Физик хими
Гадаргуугын шинжлэх ухаан ба технологи
Гадаргуугын идэвхит бодис
Гадаргуугийн үзэгдлийн физик хими
Contents
Preface to the Third Edition xv
1 An Overview of Surfactant Science and Technology 1
1.1 A Brief History of Surfactant Science and Technology 3
1.2 The Economic Importance of Surfactants 5
1.3 Some Traditional and Nontraditional Applications of Surfactants 7
1.3.1 Detergents and Cleaners 7
1.3.2 Cosmetics and Personal Care Products 8
1.3.3 Textiles and fibers 9
1.3.4 Leather and furs 10
1.3.5 Paints, Lacquers, and Other Coating Products 10
1.3.6 Paper and Cellulose Products 11
1.3.7 Mining and Ore Flotation 12
1.3.8 Metal-Processing Industries 12
1.3.9 Plant Protection and Pest Control 13
1.3.10 Foods and Food Packaging 13
1.3.11 The Chemical Industry 14
1.3.12 Oilfield Chemicals and Petroleum Production 14
1.3.13 Plastics and Composite Materials 15
1.3.14 Pharmaceuticals 15
1.3.15 Medicine and Biochemical Research 16
1.3.16 Other ‘‘Hi-Tech’’ Areas 16
1.4 Surfactant Consumption 17
1.5 The Economic and Technological Future 20
1.6 Surfactants in the Environment 21
1.7 Petrochemical versus ‘‘Renewable’’
Oleochemical-Based Surfactants 23
1.8 A Surfactant Glossary 25
2 The Organic Chemistry of Surfactants 29
2.1 Basic Surfactant Building Blocks 30
2.1.1 Basic Surfactant Classifications 31
2.1.2 Making a Choice 32
vii
2.2 The Generic Anatomy of Surfactants 33
2.2.1 The Many Faces of Dodecane 34
2.2.2 Surfactant-Solubilizing Groups 38
2.2.3 Common Surfactant Hydrophobic Groups 39
2.2.3.1 The Natural Fatty Acids 40
2.2.3.2 Saturated Hydrocarbons or Paraffins 41
2.2.3.3 Olefins 41
2.2.3.4 Alkyl Benzenes 42
2.2.3.5 Alcohols 43
2.2.3.6 Alkyl Phenols 44
2.2.3.7 Polyoxypropylenes 44
2.2.3.8 Fluorocarbons 45
2.2.3.9 Silicone Surfactants 46
2.2.3.10 Miscellaneous Biological Structures 47
2.3 The Systematic Classification of Surfactants 47
2.4 Anionic Surfactants 48
2.4.1 Sulfate Esters 50
2.4.1.1 Fatty Alcohol Sulfates 51
2.4.1.2 Sulfated Fatty Acid Condensation Products 51
2.4.1.3 Sulfated Ethers 52
2.4.1.4 Sulfated Fats and Oils 54
2.4.2 Sulfonic Acid Salts 54
2.4.2.1 Aliphatic Sulfonates 55
2.4.2.2 Alkylaryl Sulfonates 56
2.4.2.3 a-Sulfocarboxylic Acids and
Their Derivatives 58
2.4.2.4 Miscellaneous Sulfoester and
Amide Surfactants 60
2.4.2.5 Alkyl Glyceryl Ether Sulfonates 63
2.4.2.6 Lignin Sulfonates 63
2.4.3 Carboxylate Soaps and Detergents 64
2.4.4 Phosphoric Acid Esters and Related Surfactants 65
2.5 Cationic Surfactants 66
2.6 Nonionic Surfactants 69
2.6.1 Polyoxyethylene-Based Surfactants 69
2.6.2 Derivatives of Polyglycerols and Other Polyols 70
2.6.3 Block Copolymer Nonionic Surfactants 73
2.6.4 Miscellaneous Nonionic Surfactants 73
2.7 Amphoteric Surfactants 74
2.7.1 Imidazoline Derivatives 74
2.7.2 Surface-Active Betaines and Sulfobetaines 76
2.7.3 Phosphatides and Related Amphoteric Surfactants 77
Problems 78
viii CONTENTS
3 Fluid Surfaces and Interfaces 80
3.1 Molecules at Interfaces 83
3.2 Interfaces and Adsorption Phenomena 84
3.2.1 A Thermodynamic Picture of Adsorption 85
3.2.2 Surface and Interfacial Tensions 88
3.2.3 The Effect of Surface Curvature 90
3.3 The Surface Tension of Solutions 91
3.3.1 Surfactants and the Reduction of Surface Tension 94
3.3.2 Efficiency, Effectiveness, and Surfactant Structure 95
Problems 105
4 Surfactants in Solution: Monolayers and Micelles 107
4.1 Surfactant Solubility 108
4.2 The Phase Spectrum of Surfactants in Solution 112
4.3 The History and Development of Micellar Theory 116
4.3.1 Manifestations of Micelle Formations 117
4.3.2 Thermodynamics of Dilute Surfactant Solutions 121
4.3.3 Classical Theories of Micelle Formation 122
4.3.4 Free Energy of Micellization 124
4.4 Molecular Geometry and the Formation of Association Colloids 125
4.5 Experimental Observations of Micellar Systems 129
4.5.1 Micellar Aggregation Numbers 129
4.5.2 The Critical Micelle Concentration 130
4.5.3 The Hydrophobic Group 131
4.5.4 The Hydrophilic Group 140
4.5.5 Counterion Effects on Micellization 142
4.5.6 The Effects of Additives on the Micellization Process 143
4.5.6.1 Electrolyte Effects on Micelle Formation 144
4.5.6.2 The Effect of pH 146
4.5.6.3 The Effects of Added Organic Materials 147
4.5.7 The Effect of Temperature on Micellization 149
4.6 Micelle Formation in Mixed Surfactant Systems 150
4.7 Micelle Formation in Nonaqueous Media 153
4.7.1 Aggregation in Polar Organic Solvents 153
4.7.2 Micelles in Nonpolar Solvents 154
Problems 157
5 Higher-Level Surfactant Aggregate Structures: Liquid Crystals,
Continuous Biphases, and Microemulsions 160
5.1 The Importance of Surfactant Phase Information 161
5.2 Amphiphilic Fluids 162
CONTENTS ix
5.2.1 Liquid Crystalline, Bicontinuous, and Microemulsion
Structures 163
5.2.2 ‘‘Classical’’ Liquid Crystals 166
5.2.3 Liquid Crystalline Phases in Simple Binary Systems 167
5.3 Temperature and Additive Effects on Phase Behavior 170
5.4 Some Current Theoretical Analyses of Novel Mesophases 171
5.5 Vesicles and Bilayer Membranes 172
5.5.1 Vesicles 174
5.5.2 Polymerized Vesicles 176
5.6 Biological Membranes 177
5.6.1 Some Biological Implications of Mesophases 178
5.6.2 Membrane Surfactants and Lipids 180
5.7 Microemulsions 182
5.7.1 Surfactants, Cosurfactants, and Microemulsion
Formation 186
5.7.1.1 Ionic Surfactant Systems 187
5.7.1.2 Nonionic Surfactant Systems 188
5.7.2 Applications 188
Problems 189
6 Solubilization and Micellar and Phase Transfer Catalysis 191
6.1 Solubilization in Surfactant Micelles 192
6.1.1 The ‘‘Geography’’ of Solubilization in Micelles 194
6.1.2 Surfactant Structure and the Solubilization Process 196
6.1.3 Solubilization and the Nature of the Additive 199
6.1.4 The Effect of Temperature on Solubilization
Phenomena 201
6.1.5 The Effects of Nonelectrolyte Solutes 203
6.1.6 The Effects of Added Electrolyte 204
6.1.7 Miscellaneous Factors Affecting Solubilization 205
6.2 Micellar Catalysis 206
6.2.1 Micellar Catalysis in Aqueous Solution 206
6.2.2 Micellar Catalysis in Nonaqueous Solvents 208
6.3 Phase Transfer Catalysis 209
6.3.1 Cross-phase Reactions 210
6.3.2 Some Examples of PTC Applications 213
6.3.2.1 Alkylnitrile Synthesis 213
6.3.2.2 Dihalocyclopropanes 215
6.3.3 Some Notes on the Use of PTC 216
6.3.4 Some Requirements for a Successful PTC Reaction 216
Problems 218
x CONTENTS
7 Polymeric Surfactants and Surfactant–Polymer Interactions 220
7.1 Polymeric Surfactants and Amphiphiles 220
7.2 Some Basic Chemistry of Polymeric Surfactant Synthesis 223
7.2.1 Modification of Natural Cellulosics, Gums,
and Proteins 223
7.2.2 Synthetic Polymeric Surfactants 223
7.3 Polymeric Surfactants at Interfaces: Structure
and Methodology 229
7.4 Interactions of ‘‘Normal’’ Surfactants with Polymers 230
7.4.1 Surfactant–Polymer Complex Formation 232
7.4.2 Nonionic Polymers 235
7.4.3 Ionic Polymers and Proteins 237
7.5 Polymers, Surfactants, and Solubilization 240
7.6 Surfactant–Polymer Interactions in Emulsion Polymerization 242
Problems 243
8 Foams and Liquid Aerosols 245
8.1 The Physical Basis for Foam Formation 246
8.2 The Role of Surfactant in Foams 250
8.2.1 Foam Formation and Surfactant Structure 253
8.2.2 Amphiphilic Mesophases and Foam Stability 256
8.2.3 Effects of Additives on Surfactant Foaming Properties 257
8.3 Foam Inhibition 259
8.4 Chemical Structures of Antifoaming Agents 261
8.5 A Summary of the Foaming and Antifoaming Activities
of Additives 262
8.6 The Spreading Coefficient 263
8.7 Liquid Aerosols 265
8.7.1 The Formation of Liquid Aerosols 265
8.7.1.1 Spraying and Related Mechanisms of Mist
and Fog Formation 266
8.7.1.2 Nozzle Atomization 267
8.7.1.3 Rotary Atomization 268
8.7.2 Aerosol Formation by Condensation 270
8.7.3 Colloidal Properties of Aerosols 272
8.7.3.1 The Dynamics of Aerosol Movement 273
8.7.3.2 Colloidal Interactions in Aerosols 275
Problems 277
9 Emulsions 280
9.1 The Liquid–Liquid Interface 281
CONTENTS xi
9.2 General Considerations of Emulsion Stability 282
9.2.1 Lifetimes of Typical Emulsions 286
9.2.2 Theories of Emulsion Stability 289
9.3 Emulsion Type and Nature of the Surfactant 290
9.4 Surface Activity and Emulsion Stability 293
9.5 Mixed Surfactant Systems and Interfacial Complexes 298
9.6 Amphiphile Mesophases and Emulsion Stability 302
9.7 Surfactant Structure and Emulsion Stability 305
9.7.1 Hydrophile–Lipophile Balance (HLB) 306
9.7.2 Phase Inversion Temperature (PIT) 311
9.7.3 Application of HLB and PIT in Emulsion Formulation 312
9.7.4 Effects of Additives on the ‘‘Effective’’ HLB
of Surfactants 314
9.8 Multiple Emulsions 315
9.8.1 Nomenclature for Multiple Emulsions 316
9.8.2 Preparation and Stability of Multiple Emulsions 316
9.8.3 Pathways for Primary Emulsion Breakdown 318
9.8.4 Surfactants and Phase Components 319
Problems 321
10 Solid Surfaces and Dispersions 323
10.1 The Nature of Solid Surfaces 323
10.2 Liquid versus Solid Surfaces 327
10.3 Adsorption at the Solid–Liquid Interface 329
10.3.1 Adsorption Isotherms 329
10.3.2 Mechanisms of Surfactant Adsorption 331
10.3.2.1 Dispersion Forces 332
10.3.2.2 Polarization and Dipolar Interactions 333
10.3.2.3 Electrostatic Interactions 334
10.3.3 The Electrical Double Layer 335
10.4 The Mechanics of Surfactant Adsorption 337
10.4.1 Adsorption and the Nature of the Adsorbent Surface 338
10.4.2 Nonpolar, Hydrophobic Surfaces 338
10.4.3 Polar, Uncharged Surfaces 339
10.4.4 Surfaces Having Discrete Electrical Charges 340
10.5 Surfactant Structure and Adsorption from Solution 342
10.5.1 Surfaces Possessing Strong Charge Sites 343
10.5.2 Adsorption by Uncharged, Polar Surfaces 346
10.5.3 Surfactants at Nonpolar, Hydrophobic Surfaces 347
10.6 Surfactant Adsorption and the Character of Solid Surfaces 347
10.7 Wetting and Related Phenomena 349
10.7.1 Surfactant Manipulation of the Wetting Process 352
xii CONTENTS
10.7.2 Some Practical Examples of Wetting Control
by Surfactants 355
10.7.3 Detergency and Soil Removal 355
10.7.4 The Cleaning Process 355
10.7.5 Soil Types 357
10.7.6 Solid Soil Removal 357
10.7.7 Liquid Soil Removal 358
10.7.8 Soil Redeposition 360
10.7.9 Correlations of Surfactant Structure and Detergency 361
10.7.10 Nonaqueous Cleaning Solutions 363
10.8 Enhanced Oil Recovery 364
10.9 Suspensions and Dispersions 366
Problems 367
Bibliography 370
Index 375
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