| Stable Free Radical Polymerization (SFRP) is one of the living radical polymerization (LRP) processes developed to synthesize structurally well-defined polymers with predetermined molecular weights and narrow polydispersities. Knowledge of the fundamental kinetic processes of the polymerization enables a preassessment of the potential success of a given SFRP process.; This dissertation is composed of two main categories: first, the synthesis, purification and characterization of three series of styrene based low-molecular-weight alkoxyamine model compounds, ST series, BST series and BSST series. Second, the kinetic studies of the alkoxyamine model compounds: (1) the diastereoisomeric interconversion kinetics of the dimer alkoxyamines, (2) C-ON bond dissociation kinetics, (3) alkoxyamine decomposition kinetics. To explore the C-ON bond dissociation kinetics and determine the rate constants k d of the alkoxyamine model compounds, we designed a high resolution 1H NMR process using one atmosphere pure oxygen as a transient alkyl radical scavenger. The efficiency and completeness of oxygen irreversible trapping was tested by taking advantage of the equilibrium that exists between the diastereoisomers of the dimer alkoxyamines. The effects of alkoxyamine stereochemistry and chain-length on the C-ON bond dissociation kinetics were also demonstrated. In contrast to existing FSR methods, the 1H NMR procedure allows for the simultaneous determination of multiple kd values in a single experiment. |
