A new technique for functionalization of polyolefin surfaces using C-H bond activation catalysts has been developed. The Gif system which was developed by the Barton group as a model of methane monooxygenase has been employed to functionalize polyolefins' surfaces. Surface techniques including contact angle goniometry, ATR-IR spectroscopy, fluorescence spectroscopy, and X-ray photoelectron spectroscopy were used to analyze the product polymers. The results suggested that the Gif reagent is capable of functionalizing a polyolefin's surfaces without altering the bulk properties of polymer itself. In the second part of this research, a new synthetic grafting technique using thiohydroxamic acid esters as radical precursors has been studied for the surface modification of polyethylene films. This new technique has been proven to be an effective method to incorporate various vinyl monomers onto the functionalized polyethylene's surfaces. Results from XPS spectroscopy and ATR-IR spectroscopy indicate that the extent of surface grafting can be controlled by the monomer concentrations, the reaction conditions, and the choice of solvent. The new synthetic grafting technique also provides high levels of control of graft densities and of the degree of polymerization of graft. It generates the grafted polyethylene film without homopolymer formation and alteration of the bulk polymer.
