Stereochemistry-Controlled Mechanical Properties and Degradation in 3D-Printable Photosets

Stereochemistry provides an appealing handle by which to control the properties of small molecules and polymers. While it is established that stereochemistry in linear polymers affects their bulk mechanical properties, the application of this concept to photocurable networks could allow for resins that can accommodate the increasing demand for mechanically diverse materials without the need to significantly change their formulation. Herein, we exploit cis and trans stereochemistry in pre-resin oligomers to create photoset materials with mechanical properties and degradation rates that are controlled by their stereochemistry and molecular weight. Both the synthesis of stereopure (cis or trans) acrylate-terminated pre-polymers and the subsequent UV-triggered cross-linking occurred with a retention of stereochemistry, close to 100%. The stereochemistry of a 4 kDa oligomer within the resin enabled the tuning of the formulation to either a fast eroding, soft cis elastomer or a stiff trans plastic that is more resistant to degradation. These results demonstrate that stereochemistry is a powerful tool to modify the stiffness, toughness, and degradability of high-resolution, three-dimensional printed scaffolds from the same formulated ratio of components.