Fe-Catalyzed Structurally Divergent γ-Polyhaloalkylation of Siloxydienes.

Regioselective γ-polyhaloalkylation is achieved using tetrahalomethanes or α,α,α-trihaloalkyl compounds and siloxydienes via Fe(II) catalysis. A range of siloxydienes are functionalized in good yields with high stereoselectivity under mild reaction conditions. Structural divergence is observed as either haloalkylated or haloalkenylated products are formed on the basis of the substitution pattern of the siloxydiene.

Penetrant-induced plasticization in microporous polymer membranes.

Penetrant-induced plasticization has prevented the industrial deployment of many polymers for membrane-based gas separations. With the advent of microporous polymers, new structural design features and unprecedented property sets are now accessible under controlled laboratory conditions, but property sets can often deteriorate due to plasticization. Therefore, a critical understanding of the origins of plasticization in microporous polymers and the development of strategies to mitigate this effect are needed to advance this area of research.

Side-Chain Length and Dispersity in ROMP Polymers with Pore-Generating Side Chains for Gas Separations.

Bottlebrush polymers with flexible backbones and rigid side chains have shown ultrahigh CO permeability and plasticization resistance for membrane-based gas separations. To date, this class of polymers has only been studied with polydisperse side chains. Herein, we report gas transport properties of a methoxy (OMe) functionalized polymer synthesized via ring-opening metathesis polymerization (ROMP) with uniform side-chain lengths ranging from = 2 to 5 repeat units to elucidate the role of both side-chain length and dispersity on gas transport properties and plasticization resistance.