Volume 1 Introduction xv Part I Photopolymerization Reactions and Photoinitiators: Backgrounds 1 1 Backgrounds in Photopolymerization Reactions: A Short Overview 3 1.1 Photopolymerization and Photo-cross-linking 3 1.1.1 Reactions 3 1.1.2 Photoinitiation Step 4 1.1.3 Different Kinds of Photopolymerization Reactions 4 1.
1.4 Monomers and Oligomers 4 1.1.5 Photopolymerizable Formulations 6 1.1.6 UV Curing 6 1.1.7 Imaging 6 1.
1.8 Controlled Photopolymerization 7 1.2 Photopolymerization Reactions 7 1.2.1 Monomers and Oligomers in Photopolymerization Reactions 7 1.2.1.1 Monomers/Oligomers in Radical Photopolymerization 8 1.
2.1.2 Monomers/Oligomers in Cationic Photopolymerization 10 1.2.1.3 Monomers in Thiol-ene Photopolymerization 11 1.2.1.
4 Monomers in Charge Transfer Photopolymerization 12 1.2.1.5 Monomers in Anionic Photopolymerization 12 1.2.1.6 Monomers in Photoinduced Copper-Catalyzed Azide-Alkyne Cycloaddition 12 1.2.
1.7 Monomers in Photoactivated Hydrosilylation Reactions 12 1.2.2 Monitoring the Photopolymerization Reaction 13 1.2.3 Kinetic Laws in Photopolymerization Reactions 13 1.2.3.
1 Radical Photopolymerization 13 1.2.3.2 Cationic Photopolymerization 15 1.2.3.3 Dependence of Photopolymerization Rate 15 1.2.
3.4 Laser-Induced Photopolymerization 16 1.2.3.5 Kinetics of the Photopolymerization in Bulk 17 1.2.4 Oxygen Inhibition 18 1.2.
5 Role of Light Stabilizers 18 1.2.6 Competitive Absorption of Light by a Pigment 20 1.2.7 Role of Environment in the Polymerization Reaction 21 1.3 Implementation of Photopolymerization Reactions and Brief Overview of the Applications 22 1.3.1 Light Sources for Photopolymerization Reactions 22 1.
3.1.1 Electromagnetic Radiation 22 1.3.1.2 Characteristics of a Light Source 23 1.3.1.
3 Available Light Sources 23 1.3.2 Brief Overview of the Application Areas 27 References 29 2 Photoinitiating System 35 2.1 Characteristics of a Photoinitiating System 35 2.1.1 General Properties 35 2.1.2 Absorption of Light by a Molecule 35 2.
1.2.1 Absorption Spectrum 35 2.1.2.2 Molecular Orbitals and Energy Levels 36 2.1.2.
3 Absorption of Light and Optical Transitions 36 2.1.2.4 Absorption Intensity 37 2.1.2.5 Reciprocity Law 38 2.1.
2.6 Multiphotonic Absorption 38 2.1.3 Jablonski''s Diagram 39 2.1.4 Kinetics of the Excited State Processes 40 2.1.5 Photoinitiator and Photosensitizer 40 2.
1.6 Absorption of a Photosensitive System 42 2.1.7 Initiation Step of a Photoinduced Polymerization 42 2.1.7.1 Production of Initiating Species 43 2.1.
7.2 Competitive Reactions in the Excited States 43 2.1.7.3 Reactivity in Bulk vs. Solution: Role of Diffusion 43 2.1.7.
4 Cage Effects 44 2.2 Approach of Photochemical and Chemical Reactivity 45 2.3 Reactivity of a Photosensitive System 46 2.4 Efficiency vs. Reactivity 48 References 49 Part II Photoinitiators: Structures, Excited States, Reactivity, and Efficiency 55 3 Cleavable Radical Photoinitiators 59 3.1 Benzoyl Chromophore-Based Photoinitiators 59 3.1.1 Benzoin Derivatives 61 3.
1.2 Benzoin Ether Derivatives 62 3.1.2.1 Absorption of Benzoin Ethers 62 3.1.2.2 Photolysis of Benzoin Ethers 63 3.
1.2.3 Cleavage Process in Benzoin Ethers 64 3.1.2.4 Initiating Radicals in Benzoin Ethers 64 3.1.2.
5 Substitution Effects in Benzoin Ether Derivatives 64 3.1.2.6 Effect of Lewis Acids on Benzoin Ethers 65 3.1.3 Halogenated Ketones 65 3.1.4 Dialkoxyacetophenones and Diphenylacetophenones 65 3.
1.5 Morpholino and Amino Ketones 66 3.1.6 Hydroxy Alkyl Acetophenones 67 3.1.7 Ketone Sulfonic Esters 69 3.1.8 Thiobenzoate Derivatives 70 3.
1.9 Sulfonyl Ketones 70 3.1.10 Oxysulfonyl Ketones 71 3.1.11 Oxime Esters 71 3.2 Hydroxy Alkyl Heterocyclic Ketones 72 3.3 Benzophenone and Thioxanthone Moiety-Based Cleavable Systems 72 3.
3.1 Benzophenone Phenyl Sulfides 72 3.3.2 Ketosulfoxides 72 3.3.3 Benzophenone Thiobenzoates 73 3.3.4 Benzophenone Sulfonyl Ketones 73 3.
3.5 Silyl Moiety Containing Cleavable Benzophenone and Thioxanthone Derivatives 73 3.4 Benzoyl Phosphine Oxide Derivatives: a C--P Bond Breaking 73 3.5 Trichloromethyl Triazines 76 3.6 Biradical Generating Ketones 76 3.7 Diketones 76 3.8 Silyl Glyoxylates 77 3.9 Peroxides 77 3.
10 Peresters 78 3.11 Azides and Aromatic Bis-azides 79 3.12 Carbon-Germanium Cleavable Bond-Based Derivatives 79 3.13 Carbon-Tin Cleavable Bond-Based PIs 81 3.14 Carbon-Silicon Cleavable Bond-Based PIs 81 3.14.1 Bis Silyl Ketones 81 3.14.
2 Tetraacylsilanes 82 3.15 Carbon-Nitrogen Cleavable Bond Containing PIs 82 3.15.1 Azo Derivatives 82 3.15.2 Phenacyl Pyridinium Derivatives 83 3.15.3 Phenacyl Ethyl Carbazolium Derivatives 83 3.
15.4 N-substituted Diazabicyclononanes 83 3.16 Boron-Sulfur Cleavable Bond Containing PIs 84 3.17 Boron-Nitrogen Cleavable Bond Containing PIs 84 3.18 Disilane Derivatives 84 3.19 Diselenide and Diphenylditelluride Derivatives 85 3.20 Sulfur-Carbon Cleavable Bond-Based Derivatives 85 3.21 Disulfide Derivatives 86 3.
22 Oxyamines 86 3.22.1 Alkoxyamines 86 3.22.2 Silyloxyamines 86 3.23 Barton''s Ester Derivatives 87 3.24 Hydroxamic and Thiohydroxamic Acids and Esters 87 3.25 Ion Pair PIs 87 3.
25.1 Organoborates 88 3.25.2 Polyoxometalate-onium Salt Ion Pairs 88 3.25.3 Naphthalimide-Iodonium Salt Ion Pairs 89 3.26 Organometallic Compounds 90 3.26.
1 Titanocenes 90 3.26.2 Miscellaneous Organometallic PIs 90 3.26.2.1 Chromium Complexes 90 3.26.2.
2 Aluminate Complexes 90 3.26.2.3 Zirconocene Dichloride 91 3.26.2.4 Zinc Complexes 91 3.27 Metal Salts and Metallic Salt Complexes 91 3.
28 Miscellaneous Systems 91 3.28.1 Acetone 91 3.28.2 Phosphine Oxide Derivatives 92 3.28.3 Sulfur-Silicon Cleavable Bond-Based Derivatives 92 3.28.
4 Digermane and Distannane Derivatives 92 3.28.5 Halogenated Ketones 92 3.28.6 Hydroxy Alkyl-Conjugated Ketones 92 3.28.7 Dibenzothiophenes 93 3.28.
8 Self-initiating Monomers 93 3.28.9 Self-assembled PI Monolayers 93 3.28.10 Silicon-Hydride Terminated Surface 93 3.28.11 Semiconductor Nanoparticles 93 3.28.
12 Perovskites (Nanocrystals) 94 References 95 4 Two-Component Radical Photoinitiators 117 4.1 Ketone/Hydrogen Donor and Ketone/Electron/Proton Donor Couples 117 4.1.1 Basic Mechanism 117 4.1.2 Hydrogen Donors and Electron/Proton Donors 119 4.1.2.
1 Amines 119 4.1.2.2 Thio Derivatives 121 4.1.2.3 Benzoxazines 121 4.1.
2.4 Aldehydes 122 4.1.2.5 Acetals 122 4.1.2.6 Hydroperoxides 122 4.
1.2.7 Silanes 122 4.1.2.8 Silylamines 123 4.1.2.
9 Metal(IV) and Amine Containing Structures 123 4.1.2.10 Silyloxyamines 123 4.1.2.11 Germanes and Stannanes 124 4.1.
2.12 Borane Complexes 124 4.1.2.13 Phosphorus Containing Compounds 124 4.1.2.14 Monomers 125 4.
1.2.15 Photoinitiator Itself 125 4.1.2.16 Alcohols and THF 125 4.1.2.
17 Polymer Substrates 125 4.2 Ketone/Electron Acceptor Systems 125 4.2.1 Ketone/Iodonium Salt 125 4.2.1.1 Benzophenone (or Thioxanthone)/Iodonium Salt 125 4.2.
1.2 Silyl Ketone/Iodonium Salt 126 4.2.1.3 Silylglyoxylate/Iodonium Salt 126 4.2.1.4 Ketone/Novel Iodonium Salts 126 4.
2.2 Ketone/Triazine 126 4.3 Ketone/Diethoxyacetate Salt 127 4.4 Well-Known and Novel Type II Ketones 127 4.4.1 Benzophenone Derivatives 127 4.4.1.
1 Benzophenone 127 4.4.1.2 Modified Benzophenones 128 4.4.2 Thioxanthone Derivatives 132 4.4.2.
1 Thioxanthone: Absorption and Excited States 132 4.4.2.2 Well-Known Thioxanthones as Models 134 4.4.2.3 Novel Thioxanthones 136 4.4.
3 Diketones 138 4.4.3.1 Aromatic Diketones 138 4.4.3.2 Camphorquinone 139 4.4.
4 Ketocoumarins 140 4.4.5 Coumarins 140 4.4.6 Alkyl Phenylglyoxylates 141 4.4.7 Silyl Ketones 141 4.4.
8 Silyl Glyoxylates 141 4.4.9 Other Type II Ketone Skeletons 142 4.4.9.1 Anthraquinones 142 4.4.9.
2 Fluorenones 142 4.4.9.3 Naphthoquinones 142 4.4.9.4 Aliphatic Ketones 142 4.4.
9.5 Ketoesters 142 4.4.9.6 Cleavable Ketones as Type II Photoinitiators 143 4.4.9.7 Aldehydes 143 4.
4.9.8 Acetals 143 4.5 Dye-Based Systems 143 4.5.1 Usual Dye/Amine Systems 143 4.5.1.
1 Eosin or Rose Bengal as Models 143 4.5.1.2 Dye/Amine Interaction: Some Kinetic Data 144 4.5.2 Dye/Additive Systems: Some Examples 144 4.5.2.
1 Dyes: Overview 144 4.5.2.2 Additives 146 4.5.2.3 Some Typical Examples of Dye/Additive Systems 147 4.5.
3 Dye-Linked Additive Ion Pairs 149 4.5.4 Dye-Linked Photoinitiator or Co-initiator-Based Systems 149 4.5.5 Dye/Onium Salts: A Revival of Interest 150 4.5.5.1 Dyes with D-Ï-A-Ï-D Arrangements 150 4.
5.5.2 NIR Polymethine Dyes 150 4.5.5.3 Squaraine Dye 151 4.5.5.
4 Other Examples of Novel Dyes for Novel Applications 151 4.6 Organometallic Compound-Based Systems 165 4.6.1 Metallocene/Add.