Photoinitiators for Polymer Synthesis Scope, Reactivity, and Efficiency
, by Fouassier, Jean-Pierre; Lalevée, Jacques
- ISBN: 9783527332106 | 3527332103
- Cover: Hardcover
- Copyright: 8/7/2012
This handbook covers radical and non-radical photoinitiating systems and describes the basic principles and applications of photopolymerization reactions within the fields of polymer and materials science. It provides a complete survey of the respective photoinitiators and a thorough description of the mechanisms involved. The chemical and photochemical reactivity observed in various experimental conditions is discussed and latest developments are also illustrated.
Jean-Pierre Fouasssier is Professor Emeritus of Physical Chemistry and Photochemistry at the University of Haute Alsace (UHA) in Mulhouse, France. He received his Ph.D at the University of Strasbourg, France, in 1975 and became a full Professor in 1978. From 1980 -1993 he was the Head of the Laboratory of General Photochemistry at CNRS-URA 431, Mulhouse, and then Head of the Molecular Photochemistry and Photopolymerization team at the Department of Photochemistry at UHA (1994-2010). He was the Director of the Ecole Nationale Supérieure de Chimie de Mulhouse (1993-1998), a Member of the National Committee of CNRS (1991-1995), Member of the National Committee of University (1989-2009), French Representative at the Steering Committee of the European Photochemistry Association (EPA, 1992-2000) and Coordinator of the Academic Committee of RadTech Europe (1988-2001). His research interests include time-resolved laser spectroscopy, photopolymerization reactions, as well as photosensitive systems for UV curing and imaging. He has authored 500 research articles, 32 book chapters as well as several books.
Jacques Lalevée received his Ph.D at the University of Mulhouse, France, in 2002. From 2004-2009 he was Associate Professor in Physical Chemistry and became a full Professor of Physical Chemistry at Ecole Nationale Supérieure de Chimie at University of Haute Alsace, Mulhouse, France, in 2009. Jacques Lalevée was a Member of the National Committee of University (2007-2009) and has authored more than 90 research articles. His research is focused on free radical chemistry, photochemistry and photopolymerization reactions, electron spin resonance (ESR), and time-resolved laser spectroscopy.
Jacques Lalevée received his Ph.D at the University of Mulhouse, France, in 2002. From 2004-2009 he was Associate Professor in Physical Chemistry and became a full Professor of Physical Chemistry at Ecole Nationale Supérieure de Chimie at University of Haute Alsace, Mulhouse, France, in 2009. Jacques Lalevée was a Member of the National Committee of University (2007-2009) and has authored more than 90 research articles. His research is focused on free radical chemistry, photochemistry and photopolymerization reactions, electron spin resonance (ESR), and time-resolved laser spectroscopy.
Abbreviations XIX
Introduction XXV
Part I Basic Principles and Applications of Photopolymerization Reactions 1
1 Photopolymerization and Photo-Cross-Linking 3
References 6
2 Light Sources 11
2.1 Electromagnetic Radiation 11
2.2 Characteristics of a Light Source 12
2.3 Conventional and Unconventional Light Sources 13
References 20
3 Experimental Devices and Examples of Applications 21
3.1 UV Curing Area: Coatings, Inks, Varnishes, Paints, and Adhesives 21
3.2 Conventional Printing Plates 25
3.3 Manufacture of Objects and Composites 25
3.4 Stereolithography 25
3.5 Applications in Microelectronics 26
3.6 Laser Direct Imaging 26
3.7 Computer-to-Plate Technology 27
3.8 Holography 27
3.9 Optics 28
3.10 Medical Applications 28
3.11 Fabrication of Nano-Objects through a Two-Photon Absorption Polymerization 29
3.12 Photopolymerization Using Near-Field Optical Techniques 29
3.13 Search for New Properties and New End Uses 30
3.14 Photopolymerization and Nanotechnology 32
3.15 Search for a Green Chemistry 33
References 34
4 Photopolymerization Reactions 41
4.1 Encountered Reactions, Media, and Experimental Conditions 41
4.2 Typical Characteristics of Selected Photopolymerization Reactions 45
4.3 Two-Photon Absorption-Induced Polymerization 60
4.4 Remote Curing: Photopolymerization without Light 60
4.5 Photoactivated Hydrosilylation Reactions 61
References 61
5 Photosensitive Systems 73
5.1 General Properties 73
5.2 Absorption of Light by a Molecule 74
5.3 Jablonski’s Diagram 78
5.4 Kinetics of the Excited State Processes 78
5.5 Photoinitiator and Photosensitizer 80
5.6 Absorption of a Photosensitive System 81
5.7 Initiation Step of a Photoinduced Polymerization 82
5.8 Reactivity of a Photosensitive System 86
References 87
6 Approach of the Photochemical and Chemical Reactivity 89
6.1 Analysis of the Excited-State Processes 89
6.2 Quantum Mechanical Calculations 93
6.3 Cleavage Process 94
6.4 Hydrogen Transfer Processes 95
6.5 Energy Transfer 96
6.6 Reactivity of Radicals 98
References 99
7 Efficiency of a Photopolymerization Reaction 103
7.1 Kinetic Laws 103
7.2 Monitoring the Photopolymerization Reaction 109
7.3 Efficiency versus Reactivity 111
7.4 Absorption of Light by a Pigment 112
7.5 Oxygen Inhibition 114
7.6 Absorption of Light Stabilizers 115
7.7 Role of the Environment 117
References 118
Part II Radical Photoinitiating Systems 123
8 One-Component Photoinitiating Systems 127
8.1 Benzoyl-Chromophore-Based Photoinitiators 127
8.2 Substituted Benzoyl-Chromophore-Based Photoinitiators 148
8.3 Hydroxy Alkyl Heterocyclic Ketones 157
8.4 Hydroxy Alkyl Conjugated Ketones 158
8.5 Benzophenone- and Thioxanthone-Moiety-Based Cleavable Systems 158
8.6 Benzoyl Phosphine Oxide Derivatives 161
8.7 Phosphine Oxide Derivatives 165
8.8 Trichloromethyl Triazines 165
8.9 Biradical-Generating Ketones 166
8.10 Peroxides 166
8.11 Diketones 167
8.12 Azides and Aromatic Bis-Azides 168
8.13 Azo Derivatives 168
8.14 Disulfide Derivatives 168
8.15 Disilane Derivatives 169
8.16 Diselenide and Diphenylditelluride Derivatives 170
8.17 Digermane and Distannane Derivatives 170
8.18 Carbon–Germanium Cleavable-Bond-Based Derivatives 170
8.19 Carbon–Silicon and Germanium–Silicon Cleavable–Bond-Based Derivatives 172
8.20 Silicon Chemistry and Conventional Cleavable Photoinitiators 172
8.21 Sulfur–Carbon Cleavable-Bond-Based Derivatives 173
8.22 Sulfur–Silicon Cleavable-Bond-Based Derivatives 173
8.23 Peresters 173
8.24 Barton’s Ester Derivatives 174
8.25 Hydroxamic and Thiohydroxamic Acids and Esters 174
8.26 Organoborates 176
8.27 Organometallic Compounds 176
8.28 Metal Salts and Metallic Salt Complexes 178
8.29 Metal-Releasing Compound 178
8.30 Cleavable Photoinitiators in Living Polymerization 179
8.31 Oxyamines 183
8.32 Cleavable Photoinitiators for Two-Photon Absorption 184
8.33 Nanoparticle-Formation-Mediated Cleavable Photoinitiators 185
8.34 Miscellaneous Systems 185
8.35 Tentatively Explored UV-Light-Cleavable Bonds 185
References 187
9 Two-Component Photoinitiating Systems 199
9.1 Ketone-/Hydrogen-Donor-Based Systems 199
9.2 Dye-Based Systems 238
9.3 Other Type II Photoinitiating Systems 241
References 258
10 Multicomponent Photoinitiating Systems 269
10.1 Generally Encountered Mechanism 269
10.2 Other Mechanisms 271
10.3 Type II Photoinitiator/Silane: Search for New Properties 279
10.4 Miscellaneous Multicomponent Systems 281
References 281
11 Other Photoinitiating Systems 283
11.1 Photoinitiator-Free Systems or Self-Initiating Monomers 283
11.2 Semiconductor Nanoparticles 284
11.3 Self-Assembled Photoinitiator Monolayers 284
References 285
Part III Nonradical Photoinitiating Systems 287
12 Cationic Photoinitiating Systems 289
12.1 Diazonium Salts 289
12.2 Onium Salts 289
12.3 Organometallic Derivatives 308
12.4 Onium Salt/Photosensitizer Systems 311
12.5 Free-Radical-Promoted Cationic Photopolymerization 318
12.6 Miscellaneous Systems 332
12.7 Photosensitive Systems for Living Cationic Polymerization 332
12.8 Photosensitive Systems for Hybrid Cure 333
References 333
13 Anionic Photoinitiators 343
13.1 Inorganic Complexes 343
13.2 Organometallic Complexes 343
13.3 Cyano Derivative/Amine System 344
13.4 Photosensitive Systems for Living Anionic Polymerization 344
References 345
14 Photoacid Generators (PAG) Systems 347
14.1 Iminosulfonates and Oximesulfonates 347
14.2 Naphthalimides 348
14.3 Photoacids and Chemical Amplification 349
References 349
15 Photobase Generators (PBG) Systems 351
15.1 Oxime Esters 351
15.2 Carbamates 351
15.3 Ammonium Tetraorganyl Borate Salts 351
15.4 N-Benzylated-Structure-Based Photobases 352
15.5 Other Miscellaneous Systems 353
15.6 Photobases and Base Proliferation Processes 354
References 354
Part IV Reactivity of the Photoinitiating System 357
16 Role of the Experimental Conditions in the Performance of a Radical Photoinitiator 359
16.1 Role of Viscosity 360
16.2 Role of the Surrounding Atmosphere 361
16.3 Role of the Light Intensity 361
References 364
17 Reactivity and Efficiency of Radical Photoinitiators 367
17.1 Relative Efficiency of Photoinitiators 367
17.2 Role of the Excited-State Reactivity 377
17.3 Role of the Medium on the Photoinitiator Reactivity 381
17.4 Structure/Property Relationships in Photoinitiating Systems 388
References 394
18 Reactivity of Radicals toward Oxygen, Hydrogen Donors, Monomers, and Additives: Understanding and Discussion 399
18.1 Alkyl and Related Carbon-Centered Radicals 399
18.2 Aryl Radicals 401
18.3 Benzoyl Radicals 402
18.4 Acrylate and Methacrylate Radicals 403
18.5 Aminoalkyl Radicals 404
18.6 Phosphorus-Centered Radicals 412
18.7 Thiyl Radicals 413
18.8 Sulfonyl and Sulfonyloxy Radicals 417
18.9 Silyl Radicals 418
18.10 Oxyl Radicals 425
18.11 Peroxyl Radicals 426
18.12 Aminyl Radicals 431
18.13 Germyl and Stannyl Radicals 432
18.14 Boryl Radicals 435
18.15 Lophyl Radicals 439
18.16 Iminyl Radicals 439
18.17 Metal-Centered Radicals 440
18.18 Propagating Radicals 442
18.19 Radicals in Controlled Photopolymerization Reactions 443
18.20 Radicals in Hydrosilylation Reactions 446
References 447
19 Reactivity of Radicals: Towards the Oxidation Process 455
19.1 Reactivity of Radicals toward Metal Salts 455
19.2 Radical/Onium Salt Reactivity in Free-Radical-Promoted Cationic Photopolymerization 456
References 459
Conclusion 461
Index 465
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