Silicone bottlebrush copolymers and networks derived from cyclic carbosiloxanes are reported and shown to have enhanced properties and recyclability compared with traditional dimethylsiloxane-based materials. The preparation of these materials is enabled by the synthesis of well-defined heterotelechelic macromonomers with Si-H and norbornene chain ends via anionic ring-opening polymerization of the hybrid carbosiloxane monomer 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane. These novel heterotelechelic α-Si-H/ω-norbornene macromonomers undergo efficient ring-opening metathesis copolymerization to yield functional bottlebrush polymers with accurate control over molecular weight and functional-group density.
View Article and Find Full Text PDFThe synthetic utility of heterotelechelic polydimethylsiloxane (PDMS) derivatives is limited due to challenges in preparing materials with high chain-end fidelity. In this study, anionic ring-opening polymerization (AROP) of hexamethylcyclotrisiloxane (D) monomers using a specifically designed silyl hydride (Si-H)-based initiator provides a versatile approach toward a library of heterotelechelic PDMS polymers. A novel initiator, where the Si-H terminal group is connected to a C atom (H-Si-C) and not an O atom (H-Si-O) as in traditional systems, suppresses intermolecular transfer of the Si-H group, leading to heterotelechelic PDMS derivatives with a high degree of control over chain ends.
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