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Book Details
Abstract
Photoinitiating systems play a key role in the starting point of a polymerization reaction under exposure to a UV or a visible light. The number of publications discussing photoinitiating systems for polymerization has seen a significant growth in recent years and this book provides an update on their latest research developments.
The book covers different types of photoinitiating systems including UV radical photoinitiators, long wavelength sensitive radical photoinitiators, cationic photoinitiators and water soluble photoinitiators as well as a chapter on how to design novel photoinitiators. The book then focusses on the applications of the photoinitiators from nanoparticles and materials to ionic liquids and solar cells.
Edited by leading names in the field, the book is suitable for postgraduate students and researchers in academia and industry interested in polymer chemistry, organic chemistry, materials science and the applications of the materials.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Preface | vii | ||
| References | x | ||
| Contents | xi | ||
| Chapter 1 Thioxanthone Photoinitiators with Heterocyclic Extended Chromophores | 1 | ||
| 1.1 Introduction | 1 | ||
| 1.2 Photophysical Properties of Heterocyclic Extended Thioxanthones | 4 | ||
| 1.3 Reactivity of Heterocyclic Extended Thioxanthones | 6 | ||
| 1.4 Photopolymerization of Acrylates UsingHeterocyclic Extended Thioxanthones as Photoinitiators for Free Radical Polymerization | 9 | ||
| 1.5 Conclusions | 11 | ||
| References | 12 | ||
| Chapter 2 Long-wavelength-sensitive Radical Photoinitiators | 14 | ||
| 2.1 Introduction | 14 | ||
| 2.2 Long-wavelength Chromophores Acting via Photoreducible Mechanism | 16 | ||
| 2.2.1 Photosensitization of Borate Salts | 16 | ||
| 2.2.2 Photosensitization of Amines | 27 | ||
| 2.3 Long-wavelength Chromophores Acting via Photooxidizable Mechanism | 33 | ||
| 2.3.1 Photosensitization of Borate Salts | 33 | ||
| 2.3.2 Photosensitization of Iodonium Salts | 33 | ||
| 2.3.3 Photosensitization of N-Alkoxypyridinium Salts | 44 | ||
| 2.3.4 Photosensitization of 1,3,5-Triazine Derivatives | 46 | ||
| 2.3.5 Photosensitization of Silane Compounds | 48 | ||
| 2.3.6 Long-wavelength Chromophore–UV Photoinitiator Dyads | 49 | ||
| 2.3.7 Panchromatic Chromophores | 58 | ||
| 2.3.8 Electron-transfer Photosensitization | 61 | ||
| 2.4 Conclusions | 61 | ||
| Abbreviations | 62 | ||
| References | 63 | ||
| Chapter 3 Cationic Photoinitiators | 74 | ||
| 3.1 Introduction | 74 | ||
| 3.2 Application of Photopolymerization Processes | 75 | ||
| 3.3 Comparison of Cationic Photopolymerization withDifferent Types of Photochemically Initiated Processes | 76 | ||
| 3.4 Monomers Used in the Process of Cationic Polymerization | 79 | ||
| 3.5 Cationic Photoinitiators | 83 | ||
| 3.5.1 Onium Salts as Cationic Photoinitiators | 84 | ||
| 3.5.2 Other Initiators of Cationic Polymerization | 117 | ||
| 3.5.3 Indirect Photoinitiation of Cationic Photopolymerization Processes | 121 | ||
| 3.6 Conclusion | 124 | ||
| Acknowledgements | 125 | ||
| References | 125 | ||
| Chapter 4 Monomeric and Polymeric Photoinitiators | 131 | ||
| 4.1 Motivation and Overview | 131 | ||
| 4.1.1 Why Monomeric and Polymeric Photoinitiators? | 131 | ||
| 4.1.2 Overview: Photoinitiating and Polymerizable Groups | 132 | ||
| 4.2 Photoinitiators Derived from (Meth)acrylates | 134 | ||
| 4.2.1 RHMA-based MPIs and PPIs | 134 | ||
| 4.2.2 More (Meth)acrylate-based MPIs and PPIs | 140 | ||
| 4.3 Photoinitiators Derived from Maleimides | 141 | ||
| 4.4 Photoinitiators Derived from Polysiloxanes | 143 | ||
| 4.5 Photoinitiators Derived from Polyalkylethers | 145 | ||
| 4.6 Photoinitiators Derived from Biodegradable Polymers | 147 | ||
| 4.7 Potoinitiators Derived from Dendrimers/Hyperbranched Polymers | 148 | ||
| 4.8 Others | 148 | ||
| 4.9 Conclusion | 150 | ||
| References | 150 | ||
| Chapter 5 Photoinitiators for Blue to Red LED Exposures | 156 | ||
| 5.1 Introduction | 156 | ||
| 5.2 Photoinitiators for Blue LED Exposure | 157 | ||
| 5.2.1 Camphorquinone | 157 | ||
| 5.2.2 Naphthalimide Derivatives | 158 | ||
| 5.2.3 Metal-based Complexes | 165 | ||
| 5.3 Photoinitiators for Green to Red LED Exposures | 171 | ||
| 5.4 Conclusions and Perspectives | 176 | ||
| Acknowledgements | 176 | ||
| References | 176 | ||
| Chapter 6 How to Design Novel Photoinitiators for Blue Light | 179 | ||
| 6.1 Introduction | 179 | ||
| 6.2 Molecular Orbital Calculations and Light Absorption Properties | 183 | ||
| 6.3 Free Radical Polymerization of Methacrylates Under Blue Light | 185 | ||
| 6.4 Stability of the Studied PISs in the Formulations | 189 | ||
| 6.5 Photobleaching of the Studied Formulations Under Blue Light | 190 | ||
| 6.6 Conclusion | 196 | ||
| Abbreviations | 196 | ||
| References | 196 | ||
| Chapter 7 Photocatalysts as Photoinitiators | 200 | ||
| 7.1 Introduction | 200 | ||
| 7.2 Generalities Concerning the Photoinitiating Systems | 201 | ||
| 7.2.1 The Absorption Properties | 201 | ||
| 7.2.2 Electrochemical Considerations | 202 | ||
| 7.2.3 Photophysical Considerations | 203 | ||
| 7.3 Photocatalysts in Photopolymerization Reactions | 206 | ||
| 7.3.1 The Different Photocatalytic Systems | 206 | ||
| 7.3.2 Metal-based Photocatalysts | 210 | ||
| 7.3.3 Organophotocatalysts | 224 | ||
| 7.4 Conclusion | 238 | ||
| References | 238 | ||
| Chapter 8 Controlled Reversible Deactivation Radical Photopolymerization | 244 | ||
| 8.1 Introduction | 244 | ||
| 8.2 PhotoNMP | 245 | ||
| 8.2.1 Iniferter Polymerization | 245 | ||
| 8.2.2 Development of PhotoNMP | 245 | ||
| 8.3 PhotoRAFT | 246 | ||
| 8.3.1 Initiator-free PhotoRAFT | 246 | ||
| 8.3.2 Photoinduced Electron Transfer-RAFT | 247 | ||
| 8.4 PhotoATRP | 248 | ||
| 8.4.1 Photoinduced Copper-mediated Radical Polymerization | 249 | ||
| 8.4.2 Other Metals | 251 | ||
| 8.4.3 Metal-free ATRP | 253 | ||
| 8.5 Summary and Conclusion | 254 | ||
| 8.6 Multiblock Copolymerization | 254 | ||
| 8.7 PhotoRDRP in Continuous Photoflow | 257 | ||
| 8.8 Surface Functionalization via PhotoRDRP | 259 | ||
| References | 268 | ||
| Chapter 9 Photosynthesis of Polymeric Particles | 274 | ||
| 9.1 Introduction | 274 | ||
| 9.2 Emulsion Polymerization | 276 | ||
| 9.2.1 Radical Photoinduced Emulsion Polymerization | 276 | ||
| 9.2.2 Cationic Photoinduced Emulsion Polymerization | 279 | ||
| 9.3 Aerosol Photopolymerization | 281 | ||
| 9.4 Synthesis of Polymeric Particles by Means of Microfluidic Devices | 283 | ||
| 9.5 Conclusions | 284 | ||
| References | 284 | ||
| Chapter 10 Photoinitiators in Ionic Liquids | 287 | ||
| 10.1 Introduction | 287 | ||
| 10.2 Ionic Liquids | 288 | ||
| 10.3 Photoinitiated Polymerization in Ionic Liquids | 289 | ||
| 10.4 Photochemical Properties of Ionic Liquids and Photochemical Reactions in Ionic Liquids | 290 | ||
| 10.5 Photoinitiators in Ils | 291 | ||
| 10.5.1 Photoinitiation in Ils | 291 | ||
| 10.5.2 IL-containing Photoinitiators | 293 | ||
| 10.6 Applications | 293 | ||
| 10.7 Conclusions | 294 | ||
| Acknowledgements | 294 | ||
| References | 294 | ||
| Chapter 11 Photoinitiators in Dentistry: Challenges and Advances | 297 | ||
| 11.1 Introduction | 297 | ||
| 11.2 Type I Photoinitiators in Dentistry | 298 | ||
| 11.2.1 Photoinitiation Mechanisms of Type I Photoinitiators | 298 | ||
| 11.2.2 Challenges to Use Type I Photoinitiators in Dental Materials | 300 | ||
| 11.2.3 Advances with Type I Photoinitiators in Dentistry | 302 | ||
| 11.2.4 Opportunities and Directions for Future Research | 303 | ||
| 11.2.5 Summary | 304 | ||
| 11.3 Type II Photoinitiator Mechanisms | 305 | ||
| 11.3.1 Free Radical Inhibition and Thioxanthone Derivatives | 309 | ||
| 11.3.2 Benzophenone Derivative | 309 | ||
| 11.3.3 Dyes and Dye Derivative Photoinitiators | 310 | ||
| 11.3.4 Mechanisms Involving Iodonium Salt | 312 | ||
| 11.3.5 Co-initiators for Type II Photoinitiator System | 314 | ||
| 11.3.6 Challenges of Type II Photoinitiator System for Dental Application | 316 | ||
| 11.3.7 Advances in the Type II Photoinitiator System | 321 | ||
| 11.3.8 Opportunities | 322 | ||
| 11.4 Directions for Future Research | 323 | ||
| 11.4.1 Modeling Free RadicalPhotopolymerization for a Dental Adhesive | 323 | ||
| Acknowledgements | 331 | ||
| References | 331 | ||
| Chapter 12 ZnO Nanoparticle-based Photoinitiators | 337 | ||
| 12.1 Introduction | 337 | ||
| 12.2 Problems and Developments: History | 338 | ||
| 12.3 Summary of Possible, Assumed, and Proven Reaction Pathways | 340 | ||
| 12.4 ZnO, TiO2, and Other Players | 341 | ||
| 12.5 Brief Description of Nanoinitiator Synthesis | 342 | ||
| 12.6 Proof of Concept for Norrish Type I Initiators: Photo-Kolbe-based Photoinitiation | 344 | ||
| 12.6.1 Modification: A Whole New World | 344 | ||
| 12.6.2 Midchain Radicals and Particle-based Curing | 346 | ||
| 12.6.3 Curing Induced by 365 nm LED, Simulated LED, and Xenon Flash Light | 347 | ||
| 12.7 Proof of Concept for Norrish Type II Initiators | 347 | ||
| 12.8 Surface-attached Photosemiconductor | 349 | ||
| 12.9 Alternative Initiation Pathway in Water and Organic Liquids | 350 | ||
| 12.10 Additional Results, Open Questions, Challenges and Research Opportunities | 350 | ||
| 12.10.1 Addressed or Introduced Topics | 351 | ||
| 12.10.2 Important Open Questions | 352 | ||
| 12.11 Conclusions | 354 | ||
| Acknowledgements | 355 | ||
| References | 355 | ||
| Chapter 13 Water-soluble Photoinitiators: Present and Future | 358 | ||
| 13.1 Water-Soluble Photoinitiators: Present and Future | 358 | ||
| 13.1.1 Introduction | 358 | ||
| 13.1.2 Water-soluble Type I Photoinitiators | 364 | ||
| 13.1.3 Water-soluble Benzophenone and Thioxanthone Photoinitiators | 389 | ||
| 13.1.4 Supramolecular-structured Photoinitiators | 399 | ||
| 13.1.5 Dual Water-and Oil-soluble Photoinitiator Packages | 401 | ||
| 13.1.6 Semiconductor Nanoparticles as Photoinitiators in Aqueous Solutions | 401 | ||
| 13.1.7 Colloidal Graphene Oxide asPhotoinitiator for Aqueous Solutions of Acrylamide | 406 | ||
| 13.1.8 Photoinitiators for Aqueous RAFT Polymerization | 406 | ||
| 13.1.9 Water-soluble Photoinitiators for Two-photon Photopolymerization | 407 | ||
| 13.1.10 Conclusions and Outlook | 423 | ||
| References | 424 | ||
| Chapter 14 NIR Light for Initiation of Photopolymerization | 431 | ||
| 14.1 Introduction | 431 | ||
| 14.2 Light Sources for NIR Exposure | 433 | ||
| 14.3 NIR Absorbers | 435 | ||
| 14.3.1 Photophysics of NIR Absorbers | 435 | ||
| 14.3.2 Photochemistry of NIR Absorbers | 438 | ||
| 14.4 Upconverting Nanoparticles and Phosphors | 450 | ||
| 14.4.1 Mechanism of Upconversion with UCNPs | 452 | ||
| 14.4.2 Summary of Light Generated Converted by UCNPs | 453 | ||
| 14.4.3 Photochemistry with UCNPs | 454 | ||
| 14.5 NIR-sensitized Photopolymerization with NIR Absorbers | 455 | ||
| 14.5.1 NIR Polymerization in Polymeric Binders | 455 | ||
| 14.5.2 NIR Polymerization of Liquid Coatings | 458 | ||
| 14.5.3 NIR Polymerization of Powder Coatings | 462 | ||
| 14.6 Applications and Further Prospective Uses | 463 | ||
| 14.6.1 Computer-to-Plate | 463 | ||
| 14.6.2 Dental Composites | 465 | ||
| 14.6.3 NIR Photopolymers for Micro-optics and Waveguides | 465 | ||
| 14.6.4 Controlled Polymer Synthesis | 467 | ||
| 14.7 Outlook | 470 | ||
| Acknowledgements | 471 | ||
| References | 472 | ||
| Chapter 15 D–π–A-type Sulfonium Salt Photoinitiators for Photopolymerizations Under Near-UV and Visible Light-emitting Diodes | 479 | ||
| 15.1 Introduction | 479 | ||
| 15.2 Experimental | 481 | ||
| 15.3 Results and Discussion | 484 | ||
| 15.3.1 Effects of Different Electron-pushing Groups (D) on the Photochemical and Photophysical Properties of PAGs | 484 | ||
| 15.3.2 Effects of Different Conjugated Structures (π) on the Photochemical and Photophysical Properties of PAGs | 489 | ||
| 15.3.3 Effects of Different Electron-withdrawing Groups (A) on the Photochemical and Photophysical Properties of PAGs | 495 | ||
| 15.3.4 Effects of Different Numbers of Brancheson the Photochemical and Photophysical Properties of PAGs | 497 | ||
| 15.4 Conclusion | 500 | ||
| Acknowledgements | 500 | ||
| References | 500 | ||
| Chapter 16 Photopolymers for Third-generation Solar Cells | 504 | ||
| 16.1 Introduction | 504 | ||
| 16.2 Photopolymers as Multifunctional Coating Systems for Third-generation PVs | 506 | ||
| 16.2.1 Photopolymer Coatings for DSSCs | 509 | ||
| 16.2.2 Photopolymer Coatings for PSCs | 511 | ||
| 16.2.3 Photopolymer Coatings for OPVs | 513 | ||
| 16.3 Photopolymers for DSSCs | 516 | ||
| References | 520 | ||
| Chapter 17 Photopolymerization of Amphiphilic Molecule Self-assemblies | 524 | ||
| 17.1 Introduction | 524 | ||
| 17.2 Surfactant Micelles | 525 | ||
| 17.3 Surfactant Vesicles | 529 | ||
| 17.4 Other Surfactant Structures | 538 | ||
| 17.5 Block Copolymer Self-assemblies | 539 | ||
| 17.6 Topochemical Polymerization: Photopolymerization Rate vs. Exchange Rate | 543 | ||
| 17.6.1 Case of Surfactants | 543 | ||
| 17.6.2 Case of Block Copolymers | 545 | ||
| 17.7 Conclusion | 547 | ||
| Abbreviations | 548 | ||
| References | 548 | ||
| Chapter 18 Emulsion Photopolymerization | 552 | ||
| 18.1 Introduction | 552 | ||
| 18.2 Emulsion Polymerization | 554 | ||
| 18.3 Thermal vs. Photochemical Initiation | 555 | ||
| 18.4 Chemical Nature and Location of the Photoinitiator | 557 | ||
| 18.5 Effects of the Photoinitiator Concentration, Monomer Concentration and Light Intensity | 560 | ||
| 18.5.1 Influence of Photoinitiator Concentration and Light Intensity | 560 | ||
| 18.5.2 Influence of Monomer Concentration | 561 | ||
| 18.6 Photoactive Surfactants (PHINISURF) | 562 | ||
| 18.7 Photoinitiated Controlled Radical Polymerization in Emulsion | 565 | ||
| 18.8 Conclusion | 568 | ||
| Abbreviations | 569 | ||
| References | 569 | ||
| Conclusion | 573 | ||
| Subject Index | 575 |