3D Printed CO2‐Based Triblock Copolymers and Post‐Printing Modification. Issue 37 (8th August 2022)

• Record Type: Journal Article
• Authors: Wei, Peiran; Bhat, Gulzar A.; Cipriani, Ciera E.; Mohammad, Hamza; Schoonover, Krista; Pentzer, Emily B.; Darensbourg, Donald J.
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 37(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-08
• Subjects: 3D Printing -- Block Copolymers -- Click Reaction -- Polycarbonates -- Surface Modification; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202208355
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We report the facile synthesis and 3D printing of a series of triblock copolymers consisting of soft and hard blocks and demonstrate that alkene pendant groups of the hard block can be covalently modified. The polymers are prepared using a salenCo(III)TFA/PPNTFA binary catalyst system and 1, 2‐propanediol as a chain transfer agent, providing an efficient one‐pot, two‐step strategy to tailor polymer thermal and mechanical properties. Thixotropic inks suitable for direct ink write printing were formulated by dissolving the block copolymers in organic solvent and dispersing NaCl particles. After printing, porous structures were produced by removing solvent and NaCl with water to give printed structures with surfaces that could be modified via UV‐initiated thiol‐ene click reactions. Alternatively, a tetra‐thiol could be incorporated into the ink and used for cross‐linking to give objects with high solvent resistance and selective degradability. Abstract : Degradable CO2 ‐based triblock polycarbonates with tailored thermal and mechanical properties were synthesized via a one‐pot, two‐step strategy. By dispersing NaCl particles in polymer solutions, thixotropic inks can be formulated and 3D printed. Subsequent removal of the filler yields porous structures. The alkene pendant groups on the polymer backbone can be further modified via UV‐ induced thiol‐ene surface functionalization and crosslinking.