Abstract
Conditions for the synthesis of star-shaped polymers via controlled radical polymerization (CRP) with minimized star–star coupling are presented. By systematically grafting a variety of polyacrylates (methyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate) from cores carrying 4–8 initiating sites, it was found that traditional factors increasing star–star coupling, (i) the number of arms, (ii) the length of the arms, and (iii) the steric bulk of the monomer side-chain, could be controlled. This allows high monomer conversion (>95%) and low-dispersity polymers (Đ < 1.08) to be obtained for molecular weights up to ∼300 000 g mol–1. In addition to the suppression of coupling events, these improved reaction conditions maximize chain-end fidelity and permit the synthesis of well-defined (multi)block copolymer stars through in situ chain extension reactions. These advantages significantly broaden the synthetic scope and structural integrity for CRP-derived star polymers.
Published Version
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