Dyes and Chromophores in Polymer Science

The design and development of dyes and chromophores have recently attracted much attention in various research fields such as materials, radiation curing, (laser) imaging, optics, medicine, microelectronics, nanotechnology, etc.. In this book, the recent research for the use of dyes and chromophores in polymer science is presented. The interaction of the visible light with the dyes or the selected chromophores is particularly important in different fields (e.g. for photovoltaic, display applications (LED ...), laser imaging or laser direct writing, green chemistry with sunlight induced photopolymerization etc ...).  This book gives an overview of the dyes and chromophores for all the important fields. 

PREFACE xi

CHAPTER 1. TRENDS IN DYE PHOTOSENSITIZED RADICAL POLYMERIZATION REACTIONS  1
Jacques LALEVÉE and Jean-Pierre FOUASSIER

1.1. Introduction 1

1.2. A brief overview of dye-based PISs 6

1.2.1. Dye one-component systems 6

1.2.2. Dye two-component systems 7

1.2.3. Dye three-component systems 10

1.3. A discussion on specific or recent developments in dye-based photoinitiating systems 12

1.3.1. Dyes for use with polychromatic visible lights 14

1.3.2. Dyes for blue, green and red laser light-induced polymerizations 16

1.3.3. Dyes as part of PISs in the medical area 18

1.3.4. Dyes in controlled radical photopolymerization reactions 19

1.3.5. Photoinitiation under soft irradiation conditions: novel three-component systems 19

1.3.6. Dyes with red-shifted absorptions and high molar extinction coefficients 22

1.3.7. Performances of novel three-component PISs in low-viscosity matrices under LEDs/laser diodes and low-intensity household devices 23

1.3.8. Recoverable dyes: the concept of photoinitiator catalysts 25

1.3.9. Metal-based dyes: recent perspectives 26

1.3.10. Dyes under sunlight exposure 27

1.3.11. Dye-based PISs as a source of mediator radicals: application to FRPCP 27

1.3.12. Dyes exhibiting a dual radical/cationic behavior: application to concomitant radical/cationic photopolymerizations 28

1.3.13. Dyes in thiol-ene photopolymerizations 29

1.3.14. Dyes for the manufacture of photopolymerizable panchromatic films 29

1.3.15. Dyes for polymerization of in situ nanoparticle containing films 30

1.4. Dye-based photoinitiating systems: properties, efficiency and reactivity 31

1.5. Trends and perspectives 32

1.6. Bibliography 34

CHAPTER 2. SENSITIZATION OF CATIONIC PHOTOPOLYMERIZATIONS 45
James CRIVELLO

2.1. Introduction 45

2.2. Photosensitization of onium salts 48

2.3. Synthesis of long wavelength absorbing photoinitiators 50

2.4. Photosensitization of onium salt cationic photoinitiators 51

2.5. Early dye sensitization studies 55

2.6. Polynuclear aromatic hydrocarbons and their derivatives 56

2.7. Phenothiazine photosensitizers 60

2.8. Carbazole photosensitizers 62

2.9. Thioxanthone photosensitizers 63

2.10. Curcumin as a photosensitizer 64

2.11. Quinoxaline photosensitizers 65

2.12. Miscellaneous electron-transfer photosensitizers 66

2.13. Free-radical-promoted photosensitization 66

2.14. Conclusions 70

2.15. Bibliography 71

CHAPTER 3. CONTROLLED PHOTOPOLYMERIZATION AND NOVEL ARCHITECTURES  81
Sean DORAN, Omer Suat TASKIN, Mehmet Atilla TASDELEN and Yusuf YACI

3.1. Introduction 81

3.2. Photoinitiated controlled radical polymerizations 84

3.2.1. Photoiniferter 84

3.2.2. Photoinitiated nitroxide-mediated radical polymerization 87

3.2.3. Photoinitiated atom transfer radical polymerization 89

3.2.4. Photoinitiated RAFT polymerization 97

3.3. Photoinitiated living ionic polymerization 102

3.3.1. Living cationic photopolymerization 102

3.3.2. Living anionic photopolymerization 106

3.4. Acknowledgments 108

3.5. Bibliography 109

CHAPTER 4. APPLIED PHOTOCHEMISTRY IN DENTAL MATERIALS: FROM BEGINNINGS TO STATE OF THE ART 123
Joachim E. KLEE, Maximilian MAIER and Christoph P. FIK

4.1. Photoinitiated free radical polymerization 123

4.1.1. Introduction: from ultraviolet to visible light curing 123

4.1.2. The camphorquinone/amine system 124

4.1.3. Acyl phosphine oxides 127

4.1.4. Various other photoinitiator systems 129

4.2. Cationic photopolymerization 133

4.3. Conclusion 134

4.4. Bibliography 134

CHAPTER 5. PHOTOINITIATED CROSS-LINKING IN OLEDS: AN EFFICIENT TOOL FOR ADDRESSING THE SOLUTION-PROCESSED DEVICES ELABORATION AND STABILITY ISSUES 139
Frédéric DUMUR and Didier GIGMES

5.1. Introduction 139

5.2. Cross-linking of light-emitting materials 141

5.2.1. Polymer-based light-emitting materials 141

5.2.2. Small-molecule-based light-emitting materials 154

5.3. Cross-linking of charge-transport materials 157

5.3.1. Polymer-based hole-transport materials 157

5.3.2. Polymer-based electron-transport/injection materials 165

5.3.3. Small-molecule-based hole-transport materials 167

5.4. Conclusion 169

5.5. Bibliography 170

CHAPTER 6. POLYMERS AS LIGHT-HARVESTING DYES IN DYE-SENSITIZED SOLAR CELLS 183
Thanh-Tuân BUI, Xavier SALLENAVE and Fabrice GOUBARD

6.1. Introduction 183

6.2. Characterization of DSSC devices 185

6.3. Poly(3-thiophenylacetic acid)-based polymers 188

6.4. Phenylenevinylene-based polymers 194

6.5. Triphenylamine-based polymer 195

6.6. Fluorene-based polymers 196

6.7. Dye polymers with acceptor–donor structure 197

6.8. Polymer containing metal complexes 199

6.9. Conclusion 205

6.10. Bibliography 206

CHAPTER 7. NIR-DYES FOR PHOTOPOLYMERS AND LASER DRYING IN THE GRAPHIC INDUSTRY 213
Bernd STREHMEL, Thomas BRÖMME, Christian SCHMITZ, Knut REINER, Steffen ERNST and Dietmar KEIL

7.1. Introduction 213

7.2. Computer to plate systems 216

7.2.1. Technical remarks 216

7.2.2. Photochemical aspects of photoinitiation using NIR lasers 218

7.2.3. Importance of thermal deactivation 230

7.2.4. Contrast materials and color on demand 232

7.2.5. Sensitivity 236

7.3. Laser-drying and offset-printing 239

7.3.1. Principle of laser-drying 239

7.3.2. Chemical systems 241

7.4. Conclusions and outlook 243

7.5. Acknowledgments 244

7.6. Bibliography 244

CHAPTER 8. DYES AND PHOTOPOLYMERS  251
Yue QI and John T. SHERIDAN

8.1. Photopolymer 251

8.2. Dye study of the photopolymer materials 260

8.3. Conclusion 271

8.4. Bibliography 272

CHAPTER 9. ADVANCED STRATEGIES FOR SPATIALLY RESOLVED SURFACE DESIGN VIA PHOTOCHEMICAL METHODS 279
Anja S. GOLDMANN, Guillaume DELAITTRE, Jan O. MUELLER and Christopher BARNER-KOWOLLIK

9.1. Introduction 279

9.2. Inorganic surfaces 282

9.3. Bio and bioinspired surfaces 296

9.4. Cross-linking 309

9.5. Conclusion 314

9.6. Bibliography 315

CHAPTER 10. PHOTOSYNTHESIZED HIGH-PERFORMANCE BIOMATERIALS  327
Julien BABINOT, Estelle RENARD, Valérie LANGLOIS and Davy-Louis VERSACE

10.1. Introduction 327

10.2. Surface photografting methodology 329

10.2.1. Photoinduced “grafting-from” method 329

10.2.2. Benzophenone and derivatives 329

10.2.3. Ketones and derivatives 331

10.2.4. Photo-oxidation process 333

10.2.5. Photoiniferters for living/controlled surface photografting 334

10.2.6. Triarylsulfonium salts 335

10.3. Photoinduced “grafting-to” procedure 337

10.3.1. Aryl azides chemistry 337

10.3.2. Anthraquinone-derived monomers 337

10.4. Achievements and biomedical applications of the photosynthesized materials 339

10.4.1. Achievements 339

10.4.2. Stimuli-responsive materials 341

10.4.3. Modification of membranes 343

10.4.4. Biomedical applications 344

10.4.5. Enzymes and proteins immobilization 347

10.4.6. Cell adhesion and compatibility 348

10.5. Conclusion 350

10.6. Bibliography 350

CHAPTER 11. LIGHT-CURED LUMINESCENT COATINGS FOR PHOTOVOLTAIC DEVICES 361
Federico BELLA, Gianmarco GRIFFINI, Roberta BONGIOVANNI and Stefano TURRI

11.1. Photovoltaics: technology, devices and spectral management 361

11.1.1. Energy demand and photovoltaic converters 361

11.1.2. Spectral management for photovoltaics: principles, materials and applications 364

11.2. Photocurable luminescent downshifting layers and dye-sensitized solar cells 371

11.3. Luminescent solar concentrators 378

11.4. Bibliography 385

CHAPTER 12. POLYMERS WITH PHOTOINDUCED SELF-HEALING PROPERTIES 393
Julien POLY

12.1. Introduction 393

12.2. Healing based on photo-reversible cycloadditions 395

12.3. Healing based on photoinduced homolytic dissociations of covalent bonds 399

12.4. Photoinduced healing in supramolecular polymers and related systems 408

12.5. Healing based on photothermally induced phase transitions or photo-isomerizations 413

12.6. Conclusion and perspectives 416

12.7. Bibliography 418

LIST OF AUTHORS 423

INDEX 427

Jean Pierre Fouassier, ENSCMu-UHA, Mulhouse, France.