One-Pot Synthesis of Hyperbranched Polyethylenes Tethered with Pendant Acryloyl Functionalities by Chain Walking Copolymerizations

Chain walking copolymerization of ethylene with 1,4-butanediol diacrylate at elevated concentrations for the synthesis of low-viscosity hyperbranched polyethylenes tethered with a controllable amount of acryloyl functionality is reported. At concentrations much higher than the critical gelation concentrations, the diacrylate comonomer is copolymerized predominantly following the mono-insertion pattern. A range of hyperbranched polyethylenes tethered with acryloyl functionality (1.3-4.8 mol-%) and having low melt viscosity (ca. 25 Pa . s at 25 degrees C) and low glass transition temperature (T-g = -69 degrees C) has been synthesized. This unique method is specific to the Pd-diimine-catalyzed chain-walking copolymerization system.