Facile synthesis of thiol-functionalized long-chain highly branched romp polymers and surface-decorated with gold nanoparticles

Abstract

The synthesis of thiol-functionalized long-chain highly branched polymers (LCHBPs) has been accomplished in combination of ring-opening metathesis polymerization (ROMP) and thiol-Michael addition click reaction. A monotelechelic polymer with a terminal acrylate and many pendent thiol groups is first prepared through adding an internal cis-olefin terminating agent to the reaction mixture immediately after the completion of the living ROMP, and then utilized as an ABn-type macromonomer in subsequent thiol-ene reaction between acrylate and thiol, yielding LCHBPs as the reaction time prolonged. Au nanoparticles are then covalently conjugated onto the surface of thiol-functionalized LCHBP to fabricate novel hybrid nanostructures, which is shown as one interesting application of such functionalized metathesis polymers. This facile approach can be extended toward the fabrication of novel nanomaterials with sophisticated structures and tunable multifunctionalities. Branched ring-opening metathesis polymerization (ROMP)-polymer architecture is successfully constructed employing ABn-type macromonomer that carries several thiol groups along the polymer chain and one acrylate group at the chain end. A thiol-Michael addition click reaction between these functional groups yields long-chain highly branched polymer. The coating of gold nanoparticles is shown as one interesting application of such functionalized metathesis polymers. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.