Abstract: In various embodiments, the present invention is directed to ABA triblock copolymers having crosslinkable poly(propylene fumarate A blocks and a more flexible poly(lactone) B block formed by sequential ring-opening polymerization and ring-opening copolymerization. These ABA triblock polymers made using ring-opening polymerization of one or more lactone monomers using a bifunctional initiator to form a poly(lactone) B block having terminal hydroxyl groups and the ring-opening copolymerization of maleic anhydride and propylene oxide followed by isomerization of the maleate double bond using an organic base to form the poly(propylene fumarate)(PPF) A blocks. When crosslinked photochemically using, for example, a continuous liquid interface production digital light processing (DLP) Carbon M2 printer, these ABA type triblock copolymers form durable elastomers with tunable degradation and elastic properties.

Abstract: In various embodiments, the present invention provides well-defined biodegradable poly(lactone-b-propylene fumarate) diblock and triblock polymers formed using a novel one-pot, scalable ring-opening block-order copolymerization (ROBOCOP) technique that utilizes magnesium 2,6-di-tert-butyl-4-methylphenoxide (Mg(BHT)2(THF)2) to “switch” from the ROP of cyclic esters to the ROCOP of maleic anhydride (MAn) and propylene oxide (PO) to produce PPF based block copolymers for application in additive manufacturing and patient specific regenerative medicine. These block copolymers are fully resorbable and can be photochemically crosslinked in a number of applications, including 3D printing. By adding the lactone block to the PPF polymer, the viscosity of the resulting block copolymer at working temperatures can be precisely controlled and the quantity of the reactive diluent in printable resins can be reduced or eliminated.