Degradable, Photochemically Printable Poly(propylene fumarate)-Based ABA Triblock Elastomers

Additive manufacturing is rapidly advancing tissue engineering, but the scope of its clinical translation is limited by a lack of materials designed to meet specific mechanical properties and resorption timelines. Materials that are printable via photochemical cross-linking, fully degradable, and elastomeric have proven to be particularly challenging to develop. Herein, we report the synthesis of a series of poly(propylene fumarate-b-γ-methyl-ε-caprolactone-b-propylene fumarate) ABA triblock polymers using sequential ring-opening polymerization and ring-opening copolymerization. When cross-linked photochemically using a continuous liquid interface production digital light processing Carbon M2 printer, these ABA-type triblock copolymers are durable elastomers with tunable degradation and elastic properties. The polymers are shown to undergo slow, hydrolytic degradation in vitro with minimal loss of mechanical performance during degradation.