Well-defined poly(methyl methacrylate) grafted to polyethylene with reverse atom transfer radical polymerization initiated by peroxides

Abstract A reverse atom transfer radical polymerization (ATRP) with FeCl 3 /PPh 3 /peroxides was applied to grafting of methyl methacrylate (MMA) to polyethylene (PE). Peroxides on PE were generated by γ-ray irradiation in air. A reverse ATRP of methyl methacrylate with benzoyl peroxide, cumene hydroperoxide, and di- t -butyl peroxide as models of the PE peroxides was confirmed to proceed successfully in living fashion. In an inhomogeneous (bulk) grafting system, the grafting ratio (GR) of PMMA to PE weights, molecular weight ( M n ) and its distribution of grafted PMMA were not controlled with time, i.e. the grafting of MMA with a reverse ATRP to the oxidized PE failed in well-defined grafting. On the other hand, a homogeneous (in o -xylene solution) grafting system provided a well-controlled M n , narrow polydispersity of grafted PMMA and a linear relation between M n and GR, indicating a controlled grafting. The controlled grafting with a reverse ATRP combined to a radiation-induced grafting was achieved successfully. The grafting of MMA to polypropylene in this way also seemed to be controlled well.