Precision Ethylene/Vinyl Bromide Polymers

Here we report the synthesis of precision ethylene/vinyl bromide (EV/B) polymers via metathesis chemistry followed by exhaustive hydrogenation. The polymer primary structures are supported by 1H NMR, 13C NMR, elemental analysis, TGA, and IR. Thermal analysis by DSC shows that a linear trend exists between increasing bromine content and decreasing melting temperature as bromine is incorporated (as a defect) in the crystalline lattice. In reference to the defect‐free chain, a change in phase structure causes a dramatic decrease in the observed heat of fusion and a smooth decrease within the Br series. This study describes the first family of precise EV/B polymers reported in the literature.