Maddison I. Segal

Thermally responsive networks have been explored widely for drug delivery applications due to their ability to sequester or release payloads upon thermal triggering. Herein, we report a series of degradable, thermoresponsive polyesters synthesized via ring-opening copolymerization of succinic anhydride, an oligo(ethylene glycol)-derivatized epoxide, and allyl glycidyl ether, and used as resins for additive manufacturing. The oligomers were designed with lower critical solution temperatures such that below 10 °C, they are hydrophilic in aqueous solutions, and are hydrophobic near physiological temperature. Thermoresponsive polyester networks were fabricated via vat photopolymerization, with longer oligomers resulting in more crosslinks and therefore stiffer networks. When placed in water, substrates swelled at 4 °C, experiencing 2-fold volumetric and weight increases and decreased elongational moduli. When solutions were warmed to 37 °C, samples expelled water, recovering their dry properties. This work establishes the development of degradable, 3D printed networks with temperature-induced control over swelling, morphology, and mechanical properties.

Early-career researchers from around the world summarize recent developments and present visions for the future of vat photopolymerization 3D printing.

Poly(ε-caprolactone) (PCL) is a widely utilized polymer within the biomedical field; however, one of its limitations is the multi-year long degradation profile. Herein, we report a semiaromatic polyester-ether (SAEE) PCL copolymer using a salicylic acid-based monomer which can disrupt the semicrystalline nature of the bulk material. The molar percentage of incorporation correlated to a linear decrease in melting and crystallization temperature, until a totally amorphous solid was seen at 37 mol %. Alongside this, mechanical analysis elucidated a softer, more extensible material with E' decreasing from 292 to 222 to 43.8 MPa for PCL to 10 to 22 mol % SAEE, respectively. Accelerated basic degradation studies (2 M NaOH) exhibited total mass loss after 16 weeks for 6 mol % compared to only 38% mass loss for PCL over the same period. Overall, by varying the SAEE mol %, we show the ability to finely tune the thermal, mechanical, and degradation profiles of PCL copolymers while maintaining an advantageous biological profile.

Digital light processing (DLP) printing forms solid constructs from fluidic resins by photochemically crosslinking polymeric resins with reactive functional groups. DLP is used widely due to its efficient, high‐resolution printing, but its use and translational potential has been limited in some applications as state‐of‐the‐art resins experience unpredictable and anisotropic part shrinkage due to the use of solvent needed to reduce resin viscosity and layer dependent crosslinking. Herein, poly(allyl glycidyl ether succinate) (PAGES), a low viscosity, degradable polyester, was synthesized by ring opening copolymerization and used in combination with degradable thiol crosslinkers to afford a solvent free resin that can be utilized in DLP printing. Varying resin formulations of PAGES polymer are shown to decrease part shrinkage from 14 % to 0.3 %. Photochemically printed parts fabricated from PAGES possess tensile moduli between 0.43 and 6.18 MPa and degradation profiles are shown to vary between 12 and 40 days under accelerated conditions based on degree of polymerization and crosslink ratio.

Digital light processing (DLP) printing forms solid constructs from fluidic resins by photochemically crosslinking polymeric resins with reactive functional groups. DLP is used widely due to its efficient, high‐resolution printing, but its use and translational potential has been limited in some applications as state‐of‐the‐art resins experience unpredictable and anisotropic part shrinkage due to the use of solvent needed to reduce resin viscosity and layer dependent crosslinking. Herein, poly(allyl glycidyl ether succinate) (PAGES), a low viscosity, degradable polyester, was synthesized by ring opening copolymerization and used in combination with degradable thiol crosslinkers to afford a solvent free resin that can be utilized in DLP printing. Varying resin formulations of PAGES polymer are shown to decrease part shrinkage from 14 % to 0.3 %. Photochemically printed parts fabricated from PAGES possess tensile moduli between 0.43 and 6.18 MPa and degradation profiles are shown to vary between 12 and 40 days under accelerated conditions based on degree of polymerization and crosslink ratio.

Vat photopolymerization 3D printing has proven very successful for the rapid additive manufacturing (AM) of polymeric parts at high resolution. However, the range of materials that can be printed and their resulting properties remains narrow. Herein, we report the successful AM of a series of poly(carbonate‐b‐ester‐b‐carbonate) elastomers, derived from carbon dioxide and bio‐derived ϵ‐decalactone. By employing a highly active and selective Co(II)Mg(II) polymerization catalyst, an ABA triblock copolymer (M_n=6.3 kg mol⁻¹, Ð_M=1.26) was synthesized, formulated into resins which were 3D printed using digital light processing (DLP) and a thiol‐ene‐based crosslinking system. A series of elastomeric and degradable thermosets were produced, with varying thiol cross‐linker length and poly(ethylene glycol) content, to produce complex triply periodic geometries at high resolution. Thermomechanical characterization of the materials reveals printing‐induced microphase separation and tunable hydrophilicity. These findings highlight how utilizing DLP can produce sustainable materials from low molar mass polyols quickly and at high resolution. The 3D printing of these functional materials may help to expedite the production of sustainable plastics and elastomers with potential to replace conventional petrochemical‐based options.

Vat photopolymerization 3D printing has proven very successful for the rapid additive manufacturing (AM) of polymeric parts at high resolution. However, the range of materials that can be printed and their resulting properties remains narrow. Herein, we report the successful AM of a series of poly(carbonate‐b‐ester‐b‐carbonate) elastomers, derived from carbon dioxide and bio‐derived ϵ‐decalactone. By employing a highly active and selective Co(II)Mg(II) polymerization catalyst, an ABA triblock copolymer (M_n=6.3 kg mol⁻¹, Ð_M=1.26) was synthesized, formulated into resins which were 3D printed using digital light processing (DLP) and a thiol‐ene‐based crosslinking system. A series of elastomeric and degradable thermosets were produced, with varying thiol cross‐linker length and poly(ethylene glycol) content, to produce complex triply periodic geometries at high resolution. Thermomechanical characterization of the materials reveals printing‐induced microphase separation and tunable hydrophilicity. These findings highlight how utilizing DLP can produce sustainable materials from low molar mass polyols quickly and at high resolution. The 3D printing of these functional materials may help to expedite the production of sustainable plastics and elastomers with potential to replace conventional petrochemical‐based options.

Three-dimensional (3D) printing is becoming increasingly prevalent in tissue engineering, driving the demand for low-modulus, high-performance, biodegradable, and biocompatible polymers. Extrusion-based direct-write (EDW) 3D printing enables printing and customization of low-modulus materials, ranging from cell-free printing to cell-laden bioinks that closely resemble natural tissue. While EDW holds promise, the requirement for soft materials with excellent printability and shape fidelity postprinting remains unmet. The development of new synthetic materials for 3D printing applications has been relatively slow, and only a small polymer library is available for tissue engineering applications. Furthermore, most of these polymers require high temperature (FDM) or additives and solvents (DLP/SLA) to enable printability. In this study, we present low-modulus 3D printable polyester inks that enable low-temperature printing without the need for solvents or additives. To maintain shape fidelity, we incorporate physical and chemical cross-linkers. These 3D printable polyester inks contain pendant amide groups as the physical cross-linker and coumarin pendant groups as the photochemical cross-linker. Molecular dynamics simulations further confirm the presence of physical interactions between different pendants, including hydrogen bonding and hydrophobic interactions. The combination of the two types of cross-linkers enhances the zero-shear viscosity and hence provides good printability and shape fidelity.