Novel functional materials obtained by catalytic polymerization

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We propose to prepare a platform of innovating polymeric materials by catalytic polymerization of olefins. The polymerization of ethylene and higher olefins is widely used for preparing commodity plastics such as polyethylene but it is rarely exploited to prepare functional materials, mostly because the catalysts have little to no tolerance to functional groups. We envision that the preparation of functional materials based on polyolefins would offer considerable benefits such as an excellent chemical and environmental resistance, the possibility to take advantage of the facile crystallization of the main repeat unit, the ability to tailor the architecture of the material, the possibility to take advantage of the unique range of mechanical properties and of the relative low cost of these polymers. Our research program will be based on Pd phosphine sulfonates, a family of catalysts which exhibits an unprecedented versatility, allowing the insertion of functional monomers never catalytically polymerized so far. A first facet of our program consists in improving the performance of these catalysts. Then, we propose to develop a novel strategy to synthesize end-functionalized oligomers based either on the decomposition of palladium formates into hydrides or on the oxidative addition of hydrosilanes. The resulting oligomers and polymers containing main-chain functional units will be then used for the formation of nanoparticles with tunable crystallinity upon self-assembly into a selective solvent.