Photoinitiators for Polymer Synthesis

INTRODUCTION

PART I: Basic Principles and Applications of Photopolymerization Reactions

PHOTOPOLYMERIZATION AND PHOTO-CROSS-LINKING LIGHT SOURCES
Electromagnetic Radiation
Characteristics of a Light Source
Conventional and Unconventional Light Sources

EXPERIMENTAL DEVICES AND EXAMPLES OF APPLICATIONS
UV Curing Area: Coatings, Inks, Varnishes, Paints, and Adhesives
Conventional Printing Plates
Manufacture of Objects and Composites
Stereolithography
Applications in Microelectronics
Laser Direct Imaging
Computer-to-Plate Technology
Holography
Optics
Medical Applications
Fabrication of Nano-Objects through a Two-Photon Absorption Polymerization
Photopolymerization Using Near-Field Optical Techniques
Search for New Properties and New End Uses
Photopolymerization and Nanotechnology
Search for a Green Chemistry

PHOTOPOLYMERIZATION REACTIONS
Encountered Reactions, Media, and Experimental Conditions
Typical Characteristics of Selected Photopolymerization Reactions
Two-Photon Absorption-Induced Polymerization
Remote Curing: Photopolymerization without Light
Photoactivated Hydrosilylation Reactions

PHOTOSENSITIVE SYSTEMS
General Properties
Absorption of Light by a Molecule
Jablonski's Diagram
Kinetics of the Excited State Processes
Photoinitiator and Photosensitizer
Absorption of a Photosensitive System
Initiation Step of a Photoinduced Polymerization
Reactivity of a Photosensitive System

APPROACH OF THE PHOTOCHEMICAL AND CHEMICAL REACTIVITY
Analysis of the Excited-State Processes
Quantum Mechanical Calculations
Cleavage Process
Hydrogen Transfer Processes
Energy Transfer
Reactivity of Radicals

EFFICIENCY OF A PHOTOPOLYMERIZATION REACTION
Kinetic Laws
Monitoring the Photopolymerization Reaction
Efficiency versus Reactivity
Absorption of Light by a Pigment
Oxygen Inhibition
Absorption of Light Stabilizers
Role of the Environment

PART II: Radical Photoinitiating Systems

ONE-COMPONENT PHOTOINITIATING SYSTEMS
Benzoyl-Chromophore-Based Photoinitiators
Substituted Benzoyl-Chromophore-Based Photoinitiators
Hydroxy Alkyl Heterocyclic Ketones
Hydroxy Alkyl Conjugated Ketones
Benzophenone- and Thioxanthone-Moiety-Based Cleavable Systems
Benzoyl Phosphine Oxide Derivatives
Phosphine Oxide Derivatives
Trichloromethyl Triazines
Biradical-Generating Ketones
Peroxides
Diketones
Azides and Aromatic Bis-Azides
Azo Derivatives
Disulfide Derivatives
Disilane Derivatives
Diselenide and Diphenylditelluride Derivatives
Digermane and Distannane Derivatives
Carbon - Germanium Cleavable-Bond-Based Derivatives
Carbon - Silicon and Germanium 'Silicon Cleavable' Bond-Based Derivatives
Silicon Chemistry and Conventional Cleavable Photoinitiators
Sulfur - Carbon Cleavable-Bond-Based Derivatives
Sulfur - Silicon Cleavable-Bond-Based Derivatives
Peresters
Barton's Ester Derivatives
Hydroxamic and Thiohydroxamic Acids and Esters
Organoborates
Organometallic Compounds
Metal Salts and Metallic Salt Complexes
Metal-Releasing Compound
Cleavable Photoinitiators in Living Polymerization
Oxyamines
Cleavable Photoinitiators for Two-Photon Absorption
Nanoparticle-Formation-Mediated Cleavable Photoinitiators
Miscellaneous Systems
Tentatively Explored UV-Light-Cleavable Bonds

TWO-COMPONENT PHOTOINITIATING SYSTEMS
Ketone-/Hydrogen-Donor-Based Systems
Dye-Based Systems
Other Type II Photoinitiating Systems

MULTICOMPONENT PHOTOINITIATING SYSTEMS
Generally Encountered Mechanism
Other Mechanisms
Type II Photoinitiator/Silane: Search for New Properties
Miscellaneous Multicomponent Systems

OTHER PHOTOINITIATING SYSTEMS
Photoinitiator-Free Systems or Self-Initiating Monomers
Semiconductor Nanoparticles
Self-Assembled Photoinitiator Monolayers

PART III: Nonradical Photoinitiating Systems

CATIONIC PHOTOINITIATING SYSTEMS
Diazonium Salts
Onium Salts
Organometallic Derivatives
Onium Salt/Photosensitizer Systems
Free-Radical-Promoted Cationic Photopolymerization
Miscellaneous Sy