Krista G. Schoonover

Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase‐separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat‐unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO ₂ ‐based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non‐crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block‐selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x‐ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three‐orders‐of‐magnitude range in toughness (0.003 to 9.1 MJ m ⁻³ ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.

Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase‐separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat‐unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO ₂ ‐based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non‐crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block‐selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x‐ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three‐orders‐of‐magnitude range in toughness (0.003 to 9.1 MJ m ⁻³ ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.

Charge and mass transfer are key functionalities of redox-active polymers, impacting applications in energy storage. Tacticity affects polymer chain conformation and mobility, free volume, and redox unit spacing, but the consequences on their ability to store charge remain unclear. Here, we control tacticity in poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA) and demonstrate its decisive influence on electrochemical properties. Isotactic, atactic, and syndiotactic PTMA with mm ∼80%, mr or rm ∼44%, and rr ∼77% configurations, respectively, are synthesized by anionic polymerization. Overall, isotactic PTMA possessed the highest specific capacity and energy -37% higher than syndiotactic PTMA at 5C. Electrochemical analysis of the reaction diffusion and kinetics, as well as electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) analysis of the mass transfer process, reveal that specific capacity and energy are influenced by both processes. Of the three polymers studied, isotactic PTMA exhibited moderate charge transfer kinetics but the least mass transferred in the redox reaction. Meanwhile, atactic PTMA exhibited the fastest kinetics but the most mass transferred. All-atom molecular dynamics (MD) simulations explain this effect, showing that atactic PTMA bears the lowest density and the greatest conformational heterogeneity, leaving greater free volume for solvated ion (de)insertion. This work highlights that tacticity is an important consideration in developing next-generation nonconjugated redox-active polymers for electrochemical energy storage.

The composition and architecture of CO₂-based aliphatic polycarbonates is revealed to impact DLP resin printability and bulk properties, offering significant prospects for advancing sustainable materials in 3D printing through polymer design.