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

Abstract

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-<i>b</i>-γ-methyl-ε-caprolactone-<i>b</i>-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 <i>in vitro</i> with minimal loss of mechanical performance during degradation.