| Autor: |
Hoff EA; Robert Frederick Smith School of Chemical & Biomolecular Engineering, Cornell University, 120 Olin Hall, Ithaca, New York 14835, United States., De Hoe GX; Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States., Mulvaney CM; Robert Frederick Smith School of Chemical & Biomolecular Engineering, Cornell University, 120 Olin Hall, Ithaca, New York 14835, United States., Hillmyer MA; Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States., Alabi CA; Robert Frederick Smith School of Chemical & Biomolecular Engineering, Cornell University, 120 Olin Hall, Ithaca, New York 14835, United States. |
| Abstrakt: |
To date, scalability limitations have hindered the exploration and application of sequence-defined polymers in areas such as synthetic plastics, fibers, rubbers, coatings, and composites. Additionally, the impact of sequence on the properties of cross-linked networks remains largely unknown. To address the need for synthetic methods to generate sequence-defined materials in gram quantities, we developed a strategy involving inexpensive and readily functional vanillin-based monomers to assemble sequence-defined polyurethane oligomers via sequential reductive amination and carbamation. Three oligomers were synthesized with monomer sequence precisely dictated by the placement of reactive side chains during the reductive amination reaction. Avoiding excessive chromatographic purification and solid- or liquid-phase supports enabled synthesis of sequence-defined oligomers on the gram-scale. Remarkably, sequence was shown to influence network topology upon cross-linking, as evidenced by sequence-dependent rubbery moduli values. This work provides one of the first examples of a scalable synthetic route toward sequence-defined thermosets that exhibit sequence-dependent properties. |
