Convenient pd-catalyzed synthesis of large unimolecular star polyethylene nanoparticles

A simplistic convenient "arm-first" catalytic synthesis method is demonstrated to render soft unimolecular star polyethylene nanoparticles. Low-dispersity polyethylene arms of controllable length and topology are first synthesized via Pd-catalyzed "living" ethylene poly-merization. The subsequent addition of norbornadiene as a unique cross-linker renders the block polymer containing a short polynorbornadiene (PNBD) sequence. Efficient and rapid catalytic cross-linking of the PNBD sequences occurs in the polymer precipitation and drying steps to give rise to star polyethylene nanoparticles. The star polymers are featured with tunable arm length and topology, high molecular weight (as high as 1770 kg mol⁻¹), high arm numbers (as high as 88), and desirable average nano-particle size (29-72 nm).