High molecular weight polyhydroxymethylene (PHM) has a repeat unit identical to that of low molecular weight sugar alcohols and exhibits carbohydrate‐like properties. Herein, cryogenic extrusion‐based 3D printing is combined with a phase separation in water to fabricate hierarchically porous PHM scaffolds containing interconnected macro‐, micro‐, and nanopores. As PHM is infusible and insoluble in common solvents, its precursor polyvinylene carbonate (PVCA) dissolved in dimethylsulfoxide (DMSO) is used to 3D print hierarchically porous PVCA scaffolds that are converted into PHM by hydrolysis without impairing the pore architectures. Similar to low‐temperature deposition manufacturing, the PVCA/DMSO freezes on a build platform at −78…
Common sugar alcohols used as artificial sweeteners and components of polymer networks represent low molecular weight polyhydroxymethylenes (PHMs) with the general formula [CH(OH)]n H2 but very low degree of polymerization (n = 2–6). Herein high molecular weight PHM (n >> 100) unparalleled in nature is tailored for 3D printing and medical applications by free radical polymerization of 1,3‐dioxol‐2‐one vinylene carbonate to produce polyvinylene carbonate (PVCA) which yields PHM by hydrolysis. Furthermore, PVCA is solution processable and enables PHM functionalization, membrane formation, and extrusion‐based 3D printing. Opposite to cellulose, amorphous PHM is plasticized by water and is readily functionalized via PVCA…
In a versatile modular scaffold system, gradient nonwovens of in situ crosslinked gelatin nanofibers (CGN), fabricated by reactive electrospinning, are laminated with perforated layers and nonwovens of thermoplastic non-crosslinked biodegradable polyesters. The addition of glyoxal to a gelatin solution in a non-toxic solvent mixture consisting of acetic acid, ethyl acetate, and water (5:3:2 w/w/w) enables the in situ crosslinking of gelatin nanofibers during electrospinning. The use of this fluorine-free crosslinking system eliminates the need of post-treatment crosslinking and purification steps typical for conventional CGN scaffolds. The slowly progressing crosslinking of the dissolved gelatin in the presence of glyoxal increases the…