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…
Combining recycling of paper wastes (WPs) with extrusion‐based additive manufacturing represents a sustainable route to cellular cellulose composites tailored for lightweight construction. Particularly, shear mixing of shredded WPs with an aqueous solution of a polymer binder like polyvinyl alcohol (PVA) yields aqueous pastes suitable for 3D printing. As a shear thinning additive, both WP and microfibrillated cellulose account for enhanced shear thinning and dimensional stability. Opposite to the formation of dense WP/PVA composites by melt extrusion, 3D printing of aqueous pastes produces cellular cellulose/PVA composites exhibiting hierarchical pore architectures. In spite of low densities around 0.8 g cm−3, high Young’s…