## Doctoral Dissertations

Spring 1994

Dissertation

Engineering

#### Degree Name

Doctor of Philosophy

Graft site initiation occurs by primary radical and/or polymeric radical attack on the backbone polymer. Graft site can be generated by either chain transfer reaction or double bond addition mechanism. The controlling mechanism is determined by the structure of the backbone and the activity of the free radicals. The efficiency of incorporation of monomer into the graft chains depends upon the graft site initiation mechanism, the mode of polymer chain termination (recombination or disproportionation) and chain transfer reactions. A series of kinetic studies of different grafting systems results in a series of uniquely different expressions describing the graft efficiency, $\phi$. The dependency of $\phi$ upon monomer, initiator and backbone concentrations is different from case to case. A complete kinetic model is also established, which is capable of predicting reaction rate, graft efficiency, graft frequency, graft ratio, and molecular weight averages and distributions. Simulations are provided to compare predicted results with experimental data for each system.