Abstract
3D printing of linear and three‐arm star supramolecular polymers with attached hydrogen bonds and their nanocomposites is reported. The concept is based on hydrogen‐bonded supramolecular polymers, known to form nano‐sized micellar clusters. Printability is based on reversible thermal‐ and shear‐induced dissociation of a supramolecular polymer network, which generates stable and self‐supported structures after printing, as checked via melt‐rheology and X‐ray scattering. The linear and three‐arm star poly(isobutylene)s PIB‐B2 (Mn = 8500 g mol −1), PIB‐B3 (Mn = 16 000 g mol −1), and linear poly(ethylene glycol)s PEG‐B2 (Mn = 900 g mol−1, 8500 g mol −1) are prepared and then probed by melt‐rheology to adjust the viscosity to address the proper printing window. The supramolecular PIB polymers show a rubber‐like behavior and are able to form self‐supported 3D printed objects at room temperature and below, reaching polymer strand diameters down to 200–300 µm. Nanocomposites of PIB‐B2 with silica nanoparticles (12 nm, 5–15 wt%) are generated, in turn leading to an improvement of their shape persistence. A blend of the linear polymer PIB‐B2 and the three‐arm star polymer PIB‐B3 (ratio ≈ 3/1 mol) reaches an even higher structural stability, able to build free‐standing structures.
3D printing of linear and three‐arm star supramolecular polymers with attached hydrogen bonds is reported. Printability is based on reversible thermal‐ and shear‐induced dissociation of a nanostructured, supramolecular polymer network, which generates stable and self‐supported structures after printing. Blending of star‐ and linear polymers or including silica nanoparticles into the supramolecular architectures allows building of free‐standing structures.