Mechanism and selectivity of 2,3-dimethyl-2,3-diphenylbutane mediated addition of vinyltriethoxysilane to polyethylene

The thermolysis of 2,3-dimethyl-2,3-diphenylbutane (bicumene) at temperatures ranging from 220 to 310 °C is used to initiate the radical-mediated graft addition of vinyltriethoxysilane (VTEOS) to polyethylene. Model hydrocarbon studies indicate that the cumyl radicals generated by the slow decomposition of bicumene are capable of direct hydrogen atom abstraction at levels that are sufficient to sustain a graft propagation sequence of high kinetic chain length. The interaction of O2 with cumyl radicals can lead to oxidation of the initiator and the hydrocarbon substrate, thereby enhancing the macroradical population and improving grafting rates and yields. In addition to providing remarkable kinetic chain lengths for VTEOS additions, high-temperature bicumene-based processes can induce HDPE and LDPE fragmentation such that the effects of radical combination on melt viscosity are counteracted. As a result, alkoxysilane-modified polymers that moisture-cure efficiently can be produced without incurring the undesirable increases in molecular weight that accompany conventional grafting processes.