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Ph.D. Thesis. |
Chapter 1. Introduction
1.1 The Ways of Science
1.2 Polymers
1.3 Free - Radical Polymerization
1.4 Objective and Outline of this Thesis
1.5 References
Chapter 2. RAFT Perspectives
2.1 Living Radical Polymerization
2.1.1 Reversible Termination
2.1.2 Reversible Transfer
2.1.2 Reversible Transfer
2.2 The Transfer Rate in RAFT Polymerization
2.2.1 The Influence of the Transfer Constant
2.2.2 Determination of the Transfer Constant
2.2.2 Determination of the Transfer Constant
2.3 Retardation in RAFT Polymerization
2.3.1 Model Development
2.3.2 Investigations of Proposed Explanations
2.3.2 Investigations of Proposed Explanations
2.4 Conclusion
2.5 Experimental
2.6 References
2.5 Experimental
2.6 References
Chapter 3. Experimental Procedures
3.1 Introduction
3.2 Synthetic Approaches to Dithioesters
3.2 Synthetic Approaches to Dithioesters
3.2.1 Substitution Reactions with Dithiocarboxylate Salts.
3.2.2 Addition of Dithio Acids to Olefins
3.2.3 Thioalkylation of Thiols and Thiolates.
3.2.4 via Imidothioate Intermediates
3.2.5 with Sulfur Organo-Phosphorus Reagents
3.2.6 Friedel-Crafts Chemistry
3.2.7 via Bis(thioacyl)disulfides
3.2.2 Addition of Dithio Acids to Olefins
3.2.3 Thioalkylation of Thiols and Thiolates.
3.2.4 via Imidothioate Intermediates
3.2.5 with Sulfur Organo-Phosphorus Reagents
3.2.6 Friedel-Crafts Chemistry
3.2.7 via Bis(thioacyl)disulfides
3.3 Conclusion
3.4 Experimental Section
3.4 Experimental Section
3.4.1 Synthesis of Benzyl Dithiobenzoate
3.4.2 Synthesis of 2-(ethoxycarbonyl)prop-2-yl Dithiobenzoate
3.4.3 Synthesis of 2-phenylprop-2-yl Dithiobenzoate
3.4.4 Synthesis of 2-cyanoprop-2-yl Dithiobenzoate
3.4.5 Synthesis of 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic Acid
3.4.6 Synthesis of a Polyolefin Macromolecular Transfer Agent
3.4.7 Synthesis of a Poly(ethylene oxide)-based RAFT Agent
3.4.2 Synthesis of 2-(ethoxycarbonyl)prop-2-yl Dithiobenzoate
3.4.3 Synthesis of 2-phenylprop-2-yl Dithiobenzoate
3.4.4 Synthesis of 2-cyanoprop-2-yl Dithiobenzoate
3.4.5 Synthesis of 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic Acid
3.4.6 Synthesis of a Polyolefin Macromolecular Transfer Agent
3.4.7 Synthesis of a Poly(ethylene oxide)-based RAFT Agent
3.5 References
Chapter 4. Living Radical Copolymerization of Styrene and Maleic Anhydride and the Synthesis of Novel Polyolefin-based Block Copolymers via RAFT Polymerization
4.1 Polyolefin - based Architectures
4.2 Results and Discussion
4.2 Results and Discussion
4.2.1 The Macromolecular RAFT Agent
4.2.2 Styrene Polymerizations
4.2.3 UV Irradiation
4.2.4 Styrene - Maleic Anhydride Copolymerizations
4.2.2 Styrene Polymerizations
4.2.3 UV Irradiation
4.2.4 Styrene - Maleic Anhydride Copolymerizations
4.3 Conclusions
4.4 Experimental
4.5 References
4.4 Experimental
4.5 References
Chapter 5. Living Radical Polymerization in Emulsion using RAFT.
5.1 Emulsion Polymerization
5.1.1 Introduction
5.1.2 A Qualitative Description
5.1.3 Living Radical Polymerization in Emulsion
5.1.4 Research Target
5.1.2 A Qualitative Description
5.1.3 Living Radical Polymerization in Emulsion
5.1.4 Research Target
5.2 Seeded Emulsion Polymerizations
5.2.1 Background Theory
5.2.2 Experimental Design
5.2.3 Results and Discussion
5.2.2 Experimental Design
5.2.3 Results and Discussion
5.3 Ab Initio Emulsion polymerizations
5.3.1 Variations in Reaction Conditions
5.3.2 Variations in RAFT Concentration and Structure
5.3.2 Variations in RAFT Concentration and Structure
5.4 Emulsion Polymerizations with Nonionic Surfactants.
5.5 Conclusion
5.6 Experimental
5.7 References
5.5 Conclusion
5.6 Experimental
5.7 References
Chapter 6. Living Radical Polymerization in Miniemulsion using Reversible Addition-Fragmentation Chain Transfer
6.1 Miniemulsions
6.1.1 Introduction
6.1.2 Miniemulsion Preparation & Stability
6.1.3 Nucleation Processes
6.1.4 Living Radical Polymerization in Miniemulsions
6.1.2 Miniemulsion Preparation & Stability
6.1.3 Nucleation Processes
6.1.4 Living Radical Polymerization in Miniemulsions
6.2 Anionic Surfactants
6.2.1 Kinetics
6.2.2 Conductivity & pH Considerations
6.2.2 Conductivity & pH Considerations
6.3 Cationic Surfactants
6.4 Nonionic Surfactants
6.5 Controlled Polymerization
6.4 Nonionic Surfactants
6.5 Controlled Polymerization
6.5.1 Homopolymerizations & Kinetics
6.5.2 Block copolymers
6.5.2 Block copolymers
6.6 Conclusions
6.7 Experimental
6.8 References
6.7 Experimental
6.8 References
Appendix: Polymerization Models
A.1 Numerical Integration of Differential Equations
A.2 Models
A.2 Models
A.2.1 Model withouth Chain Lengths
A.2.2 Exact Model
A.2.3 The Method of Moments
A.2.2 Exact Model
A.2.3 The Method of Moments
A.3 Monte Carlo Simulations
A.4 References
A.4 References
