Industrial Photoinitiators: A Technical Guide
by Green; W. Arthur-
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Summary
Author Biography
Table of Contents
| Acknowledgments | p. xiii |
| Introduction | p. xv |
| Let there be light | p. 1 |
| The electromagnetic spectrum | p. 1 |
| The generation of UV energy | p. 2 |
| The medium-pressure mercury lamp | p. 3 |
| The standard mercury arc lamp | p. 3 |
| The electrodeless microwave-powered UV lamp | p. 5 |
| Wavelength output of the medium-pressure mercury lamp | p. 7 |
| Doped lamps | p. 8 |
| The low-pressure mercury lamp | p. 10 |
| The high-pressure mercury lamp or capillary lamp | p. 10 |
| Flash lamps | p. 10 |
| Fluorescent lamps | p. 11 |
| Excimer lamps | p. 11 |
| Light emitting diodes | p. 11 |
| Lasers | p. 12 |
| The light absorption process | p. 13 |
| UV safety and ozone | p. 15 |
| References | p. 15 |
| A little chemistry | p. 17 |
| Free radical chemistry | p. 17 |
| The chromophore and absorption of UV energy | p. 18 |
| The generation of radicals | p. 18 |
| The polymerization process | p. 20 |
| Type I photoinitiators: Mechanism of the scission process | p. 22 |
| Alpha-scission | p. 22 |
| Beta-scission | p. 23 |
| Type II photoinitiators: Mechanism of the abstraction process | p. 24 |
| Hydrogen abstraction from a donor molecule | p. 24 |
| Intramolecular ¿-hydrogen abstraction: The Norrish Type II reaction | p. 25 |
| The influence of molecular substitution on absorption and photoactivity | p. 26 |
| Type I photoinitiators: Substitution effects | p. 27 |
| Type II photoinitiators: Substitution effects | p. 28 |
| Commercial photoinitiators | p. 30 |
| Photobleaching | p. 31 |
| Diverse mechanisms: Variations on the Type I and Type II process | p. 33 |
| Acyloximino esters | p. 33 |
| Anthraquinones | p. 34 |
| BCIM and the lophyl radical | p. 35 |
| Benzoylformate esters | p. 36 |
| Substituted maleimides as photoinitiators | p. 37 |
| Phosphine oxides and secondary scission | p. 38 |
| Photo-acid generation | p. 39 |
| Photo-base generation | p. 41 |
| Anthracene peroxy radicals | p. 42 |
| The thiol-ene photopolymerization | p. 43 |
| References | p. 45 |
| Academics unlimited | p. 47 |
| Triplet lifetimes and monomer quenching reactions | p. 48 |
| Modification of hydroxyacetophenones | p. 49 |
| Alkylaminoacetophenones and wavelength selection | p. 50 |
| Phosphine oxides: Reactivity and solvolytic stability | p. 53 |
| Benzophenone and thioxanthone triplet reactions | p. 54 |
| Substituted benzophenones | p. 58 |
| Substituted thioxanthones | p. 60 |
| Novel photoinitiators | p. 64 |
| Radical reactions | p. 66 |
| Primary radical reactions | p. 67 |
| Recombination reactions | p. 67 |
| Rearrangement reactions | p. 68 |
| Disproportionation reactions | p. 69 |
| Oxygen effects and chain transfer | p. 70 |
| Termination reactions | p. 71 |
| Identification of radicals and excited states | p. 71 |
| References | p. 72 |
| Commercial photoinitiators | p. 75 |
| Type I photoinitiators (see Tables A.1 and A.2) | p. 75 |
| Hydroxyacetophenones | p. 75 |
| Alkylaminoacetophenones | p. 77 |
| Benzil ketals and dialkoxyacetophenones | p. 78 |
| Benzoin ethers | p. 79 |
| Phosphine oxides | p. 80 |
| Specialties | p. 82 |
| Acyloximino esters | p. 82 |
| BCIM and HABIs | p. 82 |
| Photoacid generators | p. 83 |
| Alphahaloacetophenones | p. 84 |
| Trichloromethyl-S-triazines | p. 84 |
| Photobase generators | p. 85 |
| Type II photoinitiators | p. 86 |
| Benzophenones | p. 86 |
| Substituted benzophenones | p. 87 |
| Thioxanthones | p. 88 |
| Anthraquinones | p. 89 |
| Benzoylformate esters | p. 90 |
| Camphorquinone | p. 91 |
| Blends of photoinitiators | p. 91 |
| Migration and polymeric photoinitiators | p. 93 |
| Migration of low-molecular weight species | p. 93 |
| Polymeric photoinitiators | p. 95 |
| Polymeric Type I photoinitiators | p. 98 |
| Polymeric Type II photoinitiators | p. 98 |
| Polymeric aminobenzoate hydrogen donors | p. 99 |
| The "Nestlé list" | p. 99 |
| Visible light curing | p. 99 |
| Titanocenes | p. 101 |
| Dibenzylidene ketones | p. 101 |
| 1,2-Diketones | p. 101 |
| Ketocoumarins | p. 102 |
| Dye sensitized photoinitiation | p. 102 |
| Dye plus coinitiator | p. 102 |
| Dye plus borate salt | p. 103 |
| Dye plus HABIs | p. 103 |
| Dye plus S-triazine | p. 103 |
| Water-based UV curing | p. 103 |
| Hydrogen donors | p. 105 |
| Tertiary amines | p. 106 |
| Alpha-amino acids | p. 108 |
| Other types of hydrogen donor | p. 108 |
| References and further reading | p. 109 |
| Factors affecting the use of photoinitiators | p. 115 |
| Matching the photoinitiator absorption to the UV source | p. 115 |
| Absorption properties | p. 115 |
| Formulating for LED UV | p. 116 |
| Type I photoinitiator LED systems | p. 117 |
| Type II photoinitiator LED systems | p. 117 |
| The use of ITX as a sensitizer for LEDs | p. 118 |
| Oxygen inhibition | p. 118 |
| Radical-oxygen interaction | p. 118 |
| Nitrogen and carbon dioxide inertion | p. 119 |
| The effect of viscosity on cure | p. 121 |
| Film thickness, surface and depth cure, shrinkage and adhesion | p. 123 |
| Surface and depth cure | p. 123 |
| Shrinkage and adhesion | p. 127 |
| Sensitization and synergy | p. 128 |
| Sensitization | p. 128 |
| Synergy | p. 130 |
| The effect of pigments on the UV curing process | p. 131 |
| Pigment absorption and the pigment window: Choice of photoinitiator | p. 131 |
| Replacing ITX | p. 133 |
| Titanium dioxide whites and carbon blacks | p. 134 |
| References and further reading | p. 136 |
| Photoproducts and the yellowing of coatings | p. 139 |
| Intrinsic color, photoyellowing, and oxidation products | p. 139 |
| The formation of photoproducts | p. 139 |
| Photoproducts from Type I photoinitiators | p. 140 |
| Photoproducts from Type II photoinitiators | p. 145 |
| References | p. 147 |
| Cationic chemistry | p. 149 |
| The light absorption process and the generation of acid | p. 150 |
| Triphenylsulphonium salts | p. 150 |
| Diphenyliodonium salts | p. 151 |
| Epoxy polymerization and the dark reaction | p. 153 |
| The polymerization process | p. 153 |
| The effect of alcohols and chain transfer | p. 154 |
| Hybrid cure | p. 155 |
| Triarylsulphonium salts (see Tables A.7 and A.8) | p. 155 |
| Sulphonium salts that may release benzene | p. 156 |
| Sulphonium salts that are "benzene free" | p. 157 |
| Dialkylphenacylsulphonium salts | p. 160 |
| Diaryliodonium salts | p. 160 |
| Iodonium salts that may produce benzene | p. 162 |
| Iodonium salts that are "benzene free" | p. 162 |
| Ferrocenium salts | p. 164 |
| References and further reading | p. 165 |
| Factors affecting the use of cationic photoinitiators | p. 167 |
| The influence of the anion | p. 167 |
| Photochemical radical decomposition of onium salts | p. 168 |
| Sensitization of the cationic photoinitiator | p. 169 |
| Extension of absorption wavelength by a sensitizer | p. 169 |
| Sensitizers for cationic photoinitiators | p. 170 |
| The influence of temperature on the polymerization | p. 170 |
| The effect of water on polymerization | p. 172 |
| References and further reading | p. 172 |
| Tables and absorbance graphs | p. 175 |
| Further information | p. 279 |
| Index | p. 283 |
| Table of Contents provided by Ingram. All Rights Reserved. |
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