Poly(thioctic acid): From Bottom‐Up Self‐Assembly to 3D‐Fused Deposition Modeling Printing

Inspired by the bottom-up assembly in nature, an artificial self-assembly pattern is introduced into 3D-fused deposition modeling (FDM) printing to achieve additive manufacturing on the macroscopic scale. Thermally activated polymerization of thioctic acid (TA) enabled the bulk construction of poly(TA), and yielded unique time-dependent self-assembly. Freshly prepared poly(TA) can spontaneously and continuously transfer into higher-molecular-weight species and low-molecular-weight TA monomers. Poly(TA) and the newly formed TA further assembled into self-reinforcing materials via microscopic-phase separation. Bottom-up self-assembly patterns on different scales are fully realized by 3D FDM printing of poly(TA): thermally induced polymerization of TA (microscopic-scale assembly) to poly(TA) and 3D printing (macroscopic-scale assembly) of poly(TA) are simultaneously achieved in the 3D-printing process; after 3D printing, the poly(TA) modes show mechanically enhanced features over time, arising from the microscopic self-assembly of poly(TA) and TA. This study clearly demonstrates that micro- and macroscopic bottom-up self-assembly can be applied in 3D additive manufacturing.