Isosorbide is an inexpensive sugar derived from glucose that has shown great potential as a sustainable substitute in polymeric materials. However, polymerization methods that allow for complete tunability of isosorbide-based polymers are limited. Therefore, the objective of this work is to create a foundation for these materials via ring-opening polymerization (ROP). To this end, we provide mechanistic insights into the ROP of a trianhydrohexitol derived from isosorbide (1,4:2,5:3,6-trianhydro-D-mannitol, 5). An enzyme-catalyzed, regioselective synthetic approach was used to afford 5 with minimal purification. High-throughput screening was then employed to quickly evaluate ROP catalysts and conditions. Density functional theory calculations provided insights into the interplay of ring-strain enthalpy and free energy of activation for ring opening. Ultimately, ring-opening selectivity was achieved by initiating a Sc(OTf)3-catalyzed polymerization with an epoxide. Moreover, the resultant macromolecular architecture (i.e. generation of linear vs. cyclic polymers) can be tuned by careful selection of the polymerization conditions. Finally, unreacted monomer can be easily recycled.

Synthesis and architectural control of isosorbide-based polyethers via ring-opening polymerization

2019 Spring National Meeting

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