Photoinitiators for Polymer Synthesis -- Contents -- Abbreviations -- Introduction -- Part I Basic Principles and Applications of Photopolymerization Reactions -- 1 Photopolymerization and Photo-Cross-Linking -- References -- 2 Light Sources -- 2.1 Electromagnetic Radiation -- 2.2 Characteristics of a Light Source -- 2.3 Conventional and Unconventional Light Sources -- 2.3.1 Xenon Lamp -- 2.3.2 Mercury Arc Lamp -- 2.3.3 Doped Lamps -- 2.3.4 Microwave Lamps -- 2.3.5 Excimer Lamps -- 2.3.6 Light-Emitting Diodes (LEDs) -- 2.3.7 Pulsed Light Sources -- 2.3.8 Laser Sources -- 2.3.9 Sun -- 2.3.10 Household Lamps -- 2.3.11 UV Plasma Source -- References -- 3 Experimental Devices and Examples of Applications -- 3.1 UV Curing Area: Coatings, Inks, Varnishes, Paints, and Adhesives -- 3.1.1 Equipment -- 3.1.2 End Uses -- 3.1.3 Coating Properties -- 3.2 Conventional Printing Plates -- 3.3 Manufacture of Objects and Composites -- 3.4 Stereolithography -- 3.5 Applications in Microelectronics -- 3.6 Laser Direct Imaging -- 3.7 Computer-to-Plate Technology -- 3.8 Holography -- 3.9 Optics -- 3.10 Medical Applications -- 3.11 Fabrication of Nano-Objects through a Two-Photon Absorption Polymerization -- 3.12 Photopolymerization Using Near-Field Optical Techniques -- 3.13 Search for New Properties and New End Uses -- 3.14 Photopolymerization and Nanotechnology -- 3.15 Search for a Green Chemistry -- References -- 4 Photopolymerization Reactions -- 4.1 Encountered Reactions, Media, and Experimental Conditions -- 4.2 Typical Characteristics of Selected Photopolymerization Reactions -- 4.2.1 Film Radical Photopolymerization of Acrylates -- 4.2.2 Film Cationic Photopolymerization -- 4.2.3 Thiol-ene Photopolymerization -- 4.2.4 Photopolymerization of Water-Borne Light Curable Systems -- 4.2.5 Photopolymerization of Powder Formulations.

4.2.6 Charge-Transfer Photopolymerization -- 4.2.7 Dual Cure Photopolymerization -- 4.2.8 Hybrid Cure Photopolymerization -- 4.2.9 Anionic Photopolymerization -- 4.2.10 Metathesis Photopolymerization -- 4.2.11 Controlled Photopolymerization Reactions -- 4.2.11.1 Radical Photopolymerization Reactions -- 4.2.11.2 Cationic Photopolymerization Reactions -- 4.2.11.3 Anionic Photopolymerization Reactions -- 4.2.12 Hybrid Sol-Gel Photopolymerization -- 4.2.13 Photo-Cross-Linking Reactions in the Presence of Photobases or Photoacids -- 4.3 Two-Photon Absorption-Induced Polymerization -- 4.4 Remote Curing: Photopolymerization without Light -- 4.5 Photoactivated Hydrosilylation Reactions -- References -- 5 Photosensitive Systems -- 5.1 General Properties -- 5.2 Absorption of Light by a Molecule -- 5.2.1 Absorption -- 5.2.2 Molecular Orbitals and Energy Levels -- 5.2.3 Absorption of Light and Optical Transitions -- 5.2.4 Reciprocity Law -- 5.2.5 Multiphotonic Absorption -- 5.3 Jablonski's Diagram -- 5.4 Kinetics of the Excited State Processes -- 5.5 Photoinitiator and Photosensitizer -- 5.6 Absorption of a Photosensitive System -- 5.7 Initiation Step of a Photoinduced Polymerization -- 5.7.1 Production of Initiating Species -- 5.7.2 Competitive Reactions in the Excited States -- 5.7.3 Reactivity in Bulk versus Solution: Role of the Diffusion -- 5.7.4 Cage Effects -- 5.8 Reactivity of a Photosensitive System -- References -- 6 Approach of the Photochemical and Chemical Reactivity -- 6.1 Analysis of the Excited-State Processes -- 6.1.1 Nanosecond Laser Flash Photolysis -- 6.1.2 Picosecond Pump-Probe Spectroscopy -- 6.1.3 Photothermal Techniques -- 6.1.4 Time-Resolved FTIR Spectroscopy -- 6.1.5 Direct Detection of Radicals -- 6.1.6 CIDNP, CIDEP, and ESR Spectroscopy -- 6.2 Quantum Mechanical Calculations -- 6.3 Cleavage Process -- 6.4 Hydrogen Transfer Processes.

6.5 Energy Transfer -- 6.6 Reactivity of Radicals -- References -- 7 Efficiency of a Photopolymerization Reaction -- 7.1 Kinetic Laws -- 7.1.1 Radical Photopolymerization -- 7.1.2 Cationic Photopolymerization -- 7.1.3 Dependence of the Photopolymerization Rate -- 7.1.4 Laser-Induced Photopolymerization -- 7.1.5 Kinetics of the Photopolymerization in Bulk -- 7.2 Monitoring the Photopolymerization Reaction -- 7.2.1 FTIR Analysis -- 7.2.2 Photocalorimetry -- 7.2.3 Optical Pyrometry -- 7.2.4 Other Methods -- 7.3 Efficiency versus Reactivity -- 7.4 Absorption of Light by a Pigment -- 7.5 Oxygen Inhibition -- 7.6 Absorption of Light Stabilizers -- 7.7 Role of the Environment -- References -- Part II Radical Photoinitiating Systems -- 8 One-Component Photoinitiating Systems -- 8.1 Benzoyl-Chromophore-Based Photoinitiators -- 8.1.1 Benzoin Derivatives -- 8.1.2 Benzoin Ether Derivatives -- 8.1.3 Halogenated Ketones -- 8.1.4 Dialkoxyacetophenones and Diphenylacetophenones -- 8.1.5 Morpholino and Amino Ketones -- 8.1.6 Hydroxy Alkyl Acetophenones -- 8.1.7 Ketone Sulfonic Esters -- 8.1.8 Thiobenzoate Derivatives -- 8.1.9 Sulfonyl Ketones -- 8.1.10 Oxysulfonyl Ketones -- 8.1.11 Oxime Esters -- 8.2 Substituted Benzoyl-Chromophore-Based Photoinitiators -- 8.2.1 Benzoin Ether Series -- 8.2.2 Morpholino Ketone and Amino Ketone Series -- 8.2.3 Hydroxy Alkyl Acetophenone Series -- 8.2.3.1 Oil- or Water-Soluble Compounds -- 8.2.3.2 Difunctional Compounds -- 8.2.4 Modified Sulfonyl Ketones -- 8.2.5 Limit of the Substituent Effect -- 8.2.6 Macrophotoinitiators -- 8.2.7 Supported Cleavable Photoinitiators -- 8.3 Hydroxy Alkyl Heterocyclic Ketones -- 8.4 Hydroxy Alkyl Conjugated Ketones -- 8.5 Benzophenone- and Thioxanthone-Moiety-Based Cleavable Systems -- 8.5.1 Benzophenone Phenyl Sulfides -- 8.5.2 Ketosulfoxides -- 8.5.3 Benzophenone Thiobenzoates.

8.5.4 Benzophenone-Sulfonyl Ketones -- 8.5.5 Halogenated Derivatives -- 8.5.6 Cleavable Benzophenone, Xanthone, and Thioxanthone Derivatives -- 8.6 Benzoyl Phosphine Oxide Derivatives -- 8.6.1 Compounds -- 8.6.2 Excited State Processes -- 8.6.3 Absorption Properties and Photolysis -- 8.6.4 Bis-acyl phosphine oxide/Phenolic Compound Interaction -- 8.7 Phosphine Oxide Derivatives -- 8.8 Trichloromethyl Triazines -- 8.9 Biradical-Generating Ketones -- 8.10 Peroxides -- 8.11 Diketones -- 8.12 Azides and Aromatic Bis-Azides -- 8.13 Azo Derivatives -- 8.14 Disulfide Derivatives -- 8.15 Disilane Derivatives -- 8.16 Diselenide and Diphenylditelluride Derivatives -- 8.17 Digermane and Distannane Derivatives -- 8.18 Carbon-Germanium Cleavable-Bond-Based Derivatives -- 8.19 Carbon-Silicon and Germanium-Silicon Cleavable-Bond-Based Derivatives -- 8.20 Silicon Chemistry and Conventional Cleavable Photoinitiators -- 8.21 Sulfur-Carbon Cleavable-Bond-Based Derivatives -- 8.22 Sulfur-Silicon Cleavable-Bond-Based Derivatives -- 8.23 Peresters -- 8.24 Barton's Ester Derivatives -- 8.25 Hydroxamic and Thiohydroxamic Acids and Esters -- 8.26 Organoborates -- 8.27 Organometallic Compounds -- 8.27.1 Titanocenes -- 8.27.2 Chromium Complexes -- 8.27.3 Aluminate Complexes -- 8.28 Metal Salts and Metallic Salt Complexes -- 8.29 Metal-Releasing Compound -- 8.30 Cleavable Photoinitiators in Living Polymerization -- 8.30.1 Cleavable C-S- or S-S-Bond-Based Photoiniferters -- 8.30.2 TEMPO-Based Alkoxyamines -- 8.31 Oxyamines -- 8.31.1 Alkoxyamines -- 8.31.2 Silyloxyamines -- 8.32 Cleavable Photoinitiators for Two-Photon Absorption -- 8.33 Nanoparticle-Formation-Mediated Cleavable Photoinitiators -- 8.34 Miscellaneous Systems -- 8.35 Tentatively Explored UV-Light-Cleavable Bonds -- References -- 9 Two-Component Photoinitiating Systems -- 9.1 Ketone-/Hydrogen-Donor-Based Systems.

9.1.1 Basic Mechanisms -- 9.1.2 Hydrogen Donors -- 9.1.2.1 Amines -- 9.1.2.2 Thio Derivatives -- 9.1.2.3 Benzoxazines -- 9.1.2.4 Aldehydes -- 9.1.2.5 Acetals -- 9.1.2.6 Hydroperoxides -- 9.1.2.7 Silanes -- 9.1.2.8 Silylamines -- 9.1.2.9 Metal-(IV) and Amine-Containing Structures -- 9.1.2.10 Silyloxyamines -- 9.1.2.11 Germanes and Stannanes -- 9.1.2.12 Phosphorus-Containing Compounds -- 9.1.2.13 Borane Complexes -- 9.1.2.14 Alkoxyamines -- 9.1.2.15 Monomers -- 9.1.2.16 Photoinitiator Itself -- 9.1.2.17 Alcohols and THF -- 9.1.2.18 Polymer Substrate -- 9.1.2.19 Silicon-Hydride-Terminated Surface -- 9.1.3 Benzophenone Derivatives -- 9.1.3.1 Benzophenone -- 9.1.3.2 Aminobenzophenones -- 9.1.3.3 Other Benzophenones -- 9.1.3.4 Photopolymerization Activity -- 9.1.4 Thioxanthone Derivatives -- 9.1.4.1 Thioxanthone -- 9.1.4.2 Substituted Thioxanthones -- 9.1.5 Diketones -- 9.1.5.1 Aromatic Diketones -- 9.1.5.2 Camphorquinone -- 9.1.6 Ketocoumarins -- 9.1.7 Coumarins -- 9.1.8 Alkylphenylglyoxylates -- 9.1.9 Other Type II Ketone Skeletons -- 9.1.9.1 Anthraquinones -- 9.1.9.2 Fluorenones -- 9.1.10 Aldehydes -- 9.1.11 Aliphatic Ketones -- 9.1.12 Cleavable Ketones as Type II Photoinitiators -- 9.1.13 Tailor-Made Type II Ketones -- 9.1.13.1 Low- and High-Molecular-Weight Compounds and Macrophotoinitiators -- 9.1.13.2 Water-Soluble Compounds -- 9.1.13.3 Two-Photon Absorption Photoinitiators -- 9.1.13.4 Photomasked Photoinitiator -- 9.1.13.5 Oxygen Self-Consuming Thioxanthone Derivatives -- 9.1.13.6 Low-Molecular-Weight One-Component Systems -- 9.2 Dye-Based Systems -- 9.2.1 Dye/Amine Systems -- 9.2.2 Dye/Coinitiator Systems -- 9.2.3 Improvement of Dye/Amine Systems -- 9.2.4 Dye/Amine Water-Soluble Systems -- 9.2.5 Kinetic Data -- 9.3 Other Type II Photoinitiating Systems -- 9.3.1 Maleimide/Amine and Photoinitiator/Maleimide -- 9.3.2 Donor/Acceptor Systems.

9.3.3 Bisarylimidazole Derivative/Additive.