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.

中文翻译：

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超分子聚合物的3D打印：纳米颗粒和相分离对可印刷性的影响。

报道了具有连接的氢键及其纳米复合材料的线性和三臂星形超分子聚合物的3D打印。该概念基于氢键超分子聚合物，已知可形成纳米级胶束簇。可印刷性基于超分子聚合物网络的可逆热和剪切诱导解离，该网络在印刷后产生稳定且自支撑的结构，通过熔体流变学和X射线散射检查。线性和三臂星形聚（异丁烯）s PIB-B2（Mn = 8500 g mol -1），PIB-B3（Mn = 16 000 g mol -1）和线性聚（乙二醇）s PEG-B2制备（Mn = 900 g mol-1，8500 g mol -1），然后通过熔体流变学进行探测，以调节粘度以达到合适的印刷窗口。超分子PIB聚合物表现出类似橡胶的性能，并且能够在室温及以下温度下形成自支撑的3D打印物体，达到的聚合物线直径低至200-300 µm。生成了具有二氧化硅纳米颗粒（12 nm，5-15 wt％）的PIB-B2纳米复合材料，进而改善了其形状持久性。线性聚合物PIB-B2和三臂星形聚合物PIB-B3（比率≈3/1 mol）的共混物达到了甚至更高的结构稳定性，能够构建独立式结构。