Convergent Synthesis of Branched Metathesis Polymers with Enyne Reagents.

Branched polymers have found utility in an array of fields due to the high density of functional groups combined with unique physical properties. Despite the abundant methods reported to synthesize various branched structures, controlling parameters such as the location of branch points and molecular weight distribution still remains a challenge. This report explores the ability of enyne-containing branching agents to synthesize star and miktoarm star polymers through a convergent synthesis pathway using ring-opening metathesis polymerization (ROMP). The branching agents contain an enyne metathesis terminator covalently linked to a norbornene monomer. When these agents are introduced into a living ROMP, macromonomers are generated in situ that continue to propagate via a grafting-through process with the remaining living chains. This strategy permits control over the degree of polymerization of the star arms, control of the number of star arms, and chain-extension with additional monomer to produce functional asymmetric miktoarm star polymers.