Jean-Pierre Fouassier & Jacques Lalevée 
Photoinitiators for Polymer Synthesis [PDF ebook] 
Scope, Reactivity, and Efficiency

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 Systems
Photosensitive Systems for Living Cationic Polymerization
Photosensitive Systems for Hybrid Cure
ANIONIC PHOTOINITIATORS
Inorganic Complexes
Organometallic Complexes
Cyano Derivative/Amine System
Photosensitive Systems for Living Anionic Polymerization
PHOTOACID GENERATORS (PAG) SYSTEMS
Iminosulfonates and Oximesulfonates
Naphthalimides
Photoacids and Chemical Amplification
PHOTOBASE GENERATORS (PBG) SYSTEMS
Oxime Esters
Carbamates
Ammonium Tetraorganyl Borate Salts
N-Benzylated-Structure-Based Photobases
Other Miscellaneous Systems
Photobases and Base Proliferation Processes
PART IV: Reactivity of the Photoinitiating System
ROLE OF THE EXPERIMENTAL CONDITIONS IN THE PERFORMANCE OF A RADICAL PHOTOINITIATOR
Role of Viscosity
Role of the Surrounding Atmosphere
Role of the Light Intensity
REACTIVITY AND EFFICIENCY OF RADICAL PHOTOINITIATORS
Relative Efficiency of Photoinitiators
Role of the Excited-State Reactivity
Role of the Medium on the Photoinitiator Reactivity
Structure/Property Relationships in Photoinitiating Systems
REACTIVITY OF RADICALS TOWARD OXYGEN, HYDROGEN DONORS, MONOMERS, AND ADDITIVES: UNDERSTANDING AND DISCUSSION
Alkyl and Related Carbon-Centered Radicals
Aryl Radicals
Benzoyl Radicals
Acrylate and Methacrylate Radicals
Aminoalkyl Radicals
Phosphorus-Centered Radicals
Thiyl Radicals
Sulfonyl and Sulfonyloxy Radicals
Silyl Radicals
Oxyl Radicals
Peroxyl Radicals
Aminyl Radicals
Germyl and Stannyl Radicals
Boryl Radicals
Lophyl Radicals
Iminyl Radicals
Metal-Centered Radicals
Propagating Radicals
Radicals in Controlled Photopolymerization Reactions
Radicals in Hydrosilylation Reactions
REACTIVITY OF RADICALS: TOWARDS THE OXIDATION PROCESS
Reactivity of Radicals toward Metal Salts
Radical/Onium Salt Reactivity in Free-Radical-Promoted Cationic Photopolymerization
INDEX

Jean-Pierre Fouassier was a Professor of Physical Chemistry at the University of Haute Alsace, Mulhouse until October 2011. He was Head of a University/CNRS Laboratory, a Member of the Organizing Committees of many International Conferences, a Director of the Ecole Nationale
Superieure de Chimie de Mulhouse and a Member of the French National University Council. His research interests focused both on the excited-state processes in photoinitiatiors and photosensitizers and their application to photopolymerization reactions in various areas. He has
published a total of around 600 research articles, book chapters, review papers, technical papers, proceedings, and patents, as well as authoring one book, one technical report and editing 6 books (14 volumes).
Jacques Lalevee is a Professor of Physical Chemistry at the University of Haute Alsace, Mulhouse. His research interests are focused on free-radical chemistry and the design of efficient systems for photopolymerization processes. He has published a total of around 160 research
articles, technical papers, proceedings, patents, review papers, and book chapters. He is also a Member of the Institut Universitaire de France (Paris).