We emplore metal-organic insertion / light initiated radical (MILRad) polymerization, a technique recently developed by our group, to successfully synthesize diblock copolymers composed of olefins and polar vinyl monomers using light as a critical stimulus. We describe a novel approach that uses visible light (460 nm) to switch the catalytic activity of a cationic palladium catalyst from an insertion route to a radical process when desired. We discovered that in a mixture of polar vinyl monomers and hexene, one monomer can selectively be polymerized using light and dark cycles respectively. As a result, this polymerization process enables the copolymerization of hexene and polar vinyl monomers affording non-polar and polar blocks with great control (PDI&lt;1.3). MILRad polymerization circumvents the need for quantitative conversions during block formation afforded by the orthogonal monomer reactivity dependent upon a light stimulus to acquire distinct polymer architectures with variable block compositions. These polymers find applications as additives, which allow for the blending and compatiblization of non-compatible polymers, affording new recyling approches that afford high-end materials with desired properties.

One-pot synthesis of polar olefinic diblock copolymers via MILRad polymerization

2019 Fall National Meeting

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