Synthesis of hyperbranched polyacrylates by a chloroinimer approach

(2-Chloro-2-alkoxycarbonyl)ethyl acrylates with methyl, dodecyl, perfluoroalkyl, siloxane, oligooxyethylene, and mesogenic ester substituents were synthesized as inimers for self-condensing vinyl polymerization (SCVP) to produce hyperbranched polyacrylates. The inimers were polymerized by atom transfer radical polymerization under a variety of conditions to produce soluble polymers with broad polydispersities (up to PDI = 5.24) characteristic of hyperbranched polymers, although the isolated polymers had narrower polydispersities. The molecular weight distribution was followed as a function of time and inimer conversion for the polymerization of the mesogenic inimer. The first-order inimer conversion was linear with time. The buildup of a hyperbranched structure during the SCVP was confirmed by comparison of the error in the GPC_PSt-determined molecular weights of the mesogenic polymer with those of the corresponding linear, three-arm star, and comb architectures.