“…A large variety of nitroxide precursors has been considered, which includes nitrones, nitroso compounds, hydroxylamines, amines, sodium nitrite, and nitric oxide (Scheme ). Most of these precursors are known as inhibitors of radical polymerization. − 2 …”
Introduction 1104 2. Common Radical Synthesis of Alkoxyamines Active in NMP 1106 3. Nitrones: Precursors of Nitroxides for the Synthesis of Alkoxyamines and in-Situ NMP 1107 3.1. Nitrones as Precursors of Nitroxides 1107 3.2. Contributions of Nitrones to the in-Situ NMP 1107 3.3. Cyclic Oxazolidine as Initiator and Regulator for the Radical Polymerization of Vinyl Monomers 1111 3.4. Advantages and Drawbacks of the Nitrone Systems 1112 4. Nitroso Compounds 1112 4.1. Reaction of C-Nitroso Compounds with Free Radicals 1112 4.2. Use of C-Nitroso Compounds in Controlled Radical Polymerization 1113 4.3. Limitations of C-Nitroso Compounds 1116 5. Sodium Nitrite and NO/NO 2 Mixtures for the in-Situ NMP 1116 5.1. Preliminary Results and Mechanistic Considerations 1116 5.2. Controlled Radical Polymerization of Alkyl Methacrylates in the Presence of the in-Situ-Formed R-Nitro-ω-nitroso Adducts 1117 5.3. NO/NO 2 Mixtures: An Alternative Way to the Nitroso Compounds as Precursors of Nitroxides 1118 5.4. Advantages and Limitations of the Sodium Nitrite and NO/NO 2 Systems 1118 6. Hindered Secondary Amines and the in-Situ NMP 1118 6.1. Oxidation of Secondary Amines into Nitroxides 1118 6.2. One-Pot Processes for the Preparation of Alkoxyamines Active in NMP 1118 6.3. In-Situ NMP Using Hindered Secondary Amines and Oligomeric Secondary Amines 1120 6.4. Advantages and Limitations 1120 7. Hydroxylamines and the in-Situ NMP 1120 7.1. Oxidation of Hydroxylamines into Nitroxides 1120 7.2. Hydroxylamines and the in-Situ NMP 1120 7.3. High Molecular Weight Hydroxylamines for the Polymerization of Vinyl Monomers and Synthesis of Block Copolymers 1122 7.4. Advantages and Limitations 1122 8. Conclusions 1122 9. Acknowledgments 1123 10. References 1123
“…A large variety of nitroxide precursors has been considered, which includes nitrones, nitroso compounds, hydroxylamines, amines, sodium nitrite, and nitric oxide (Scheme ). Most of these precursors are known as inhibitors of radical polymerization. − 2 …”
Introduction 1104 2. Common Radical Synthesis of Alkoxyamines Active in NMP 1106 3. Nitrones: Precursors of Nitroxides for the Synthesis of Alkoxyamines and in-Situ NMP 1107 3.1. Nitrones as Precursors of Nitroxides 1107 3.2. Contributions of Nitrones to the in-Situ NMP 1107 3.3. Cyclic Oxazolidine as Initiator and Regulator for the Radical Polymerization of Vinyl Monomers 1111 3.4. Advantages and Drawbacks of the Nitrone Systems 1112 4. Nitroso Compounds 1112 4.1. Reaction of C-Nitroso Compounds with Free Radicals 1112 4.2. Use of C-Nitroso Compounds in Controlled Radical Polymerization 1113 4.3. Limitations of C-Nitroso Compounds 1116 5. Sodium Nitrite and NO/NO 2 Mixtures for the in-Situ NMP 1116 5.1. Preliminary Results and Mechanistic Considerations 1116 5.2. Controlled Radical Polymerization of Alkyl Methacrylates in the Presence of the in-Situ-Formed R-Nitro-ω-nitroso Adducts 1117 5.3. NO/NO 2 Mixtures: An Alternative Way to the Nitroso Compounds as Precursors of Nitroxides 1118 5.4. Advantages and Limitations of the Sodium Nitrite and NO/NO 2 Systems 1118 6. Hindered Secondary Amines and the in-Situ NMP 1118 6.1. Oxidation of Secondary Amines into Nitroxides 1118 6.2. One-Pot Processes for the Preparation of Alkoxyamines Active in NMP 1118 6.3. In-Situ NMP Using Hindered Secondary Amines and Oligomeric Secondary Amines 1120 6.4. Advantages and Limitations 1120 7. Hydroxylamines and the in-Situ NMP 1120 7.1. Oxidation of Hydroxylamines into Nitroxides 1120 7.2. Hydroxylamines and the in-Situ NMP 1120 7.3. High Molecular Weight Hydroxylamines for the Polymerization of Vinyl Monomers and Synthesis of Block Copolymers 1122 7.4. Advantages and Limitations 1122 8. Conclusions 1122 9. Acknowledgments 1123 10. References 1123
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