Abstract
Hyperbranched polyethylenes containing covalently tethered polyhedral oligomeric silsesquioxane (POSS) nanoparticles were synthesized in this work by chain walking ethylene copolymerization with a POSS macromonomer bearing a polar acrylate group, acryloisobutyl-POSS. The unique hyperbranched chain topology of these polymers was achieved owing to the chain walking mechanism of the Pd−diimine catalyst, [(ArNC(Me)−(Me)CNAr)Pd(CH3)(N⋮CMe)]SbF6 (Ar = 2,6−(iPr)2C6H3). Regardless of its bulky structure and polar nature, the acryloisobutyl-POSS macromonomer was successfully copolymerized to give a range of POSS−ethylene copolymers with the POSS macromonomer content up to 35 wt %. A systematic study of the effects of covalent POSS incorporation on the polymer properties was undertaken using techniques including gel permeation chromatography with on-line viscometry (GPC-VIS), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and rheometry. It was found from GPC-VIS ...
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