This presentation will report the synthesis, printing, and post-printing covalent modification of CO2-based triblock copolymers. Triblock copolymers consisting of soft and hard blocks were prepared by co-polymerization of CO2 and epoxides using a salenCo(III)TFA/PPNTFA binary catalyst system, and the chemical composition and thermal properties of the copolymers studied. Thixotropic inks were then formulated by dissolving polymer in organic solvent and adding particles of NaCl. Direct ink write (DIW) 3D printing was used to produce objects that could be washed with water to remove the NaCl, producing porous polycarbonate materials. The mechanical properties were found to correlate to the ratio of hard and soft blocks, and the ability to chemically degrade the structures via hydrolysis was demonstrated. Judicious choice of triblock copolymer composition allowed for post-polymerization modification with small molecules or chemical cross-linking of selective blocks. The convenient and atom economical synthetic strategy, combined with the impressive surface modification capability, give access to high value-added CO2-based polycarbonates suitable for additive manufacturing, thereby expanding the scope of applications of this materials class.

3D printing and post-printing modification of CO2-based triblock copolymers

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ACS Fall 2022

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