Ma Warrick, Wright Nathaniel, Wang Yadong
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1801, United States.
Meinig School of Biomedical Engineering, College of Engineering, Cornell University, Ithaca, New York 14853-1801, United States.
ACS Macro Lett. 2024 Aug 20;13(8):915-920. doi: 10.1021/acsmacrolett.4c00334. Epub 2024 Jul 11.
Carbic anhydride is an underappreciated starting material for 3D-printable, non-hydrogel photopolymers. Compared with other norbornene precursors, carbic anhydride is cheaper and reactive via aminolysis. As a result, the generalized and efficient functionalization with carbic anhydride can increase the utilization of thiol-norbornene photopolymers. Here, we report carbic anhydride's catalyst-free condensation with two commodity polymers: amine-functionalized polypropylene glycol and polydimethylsiloxane. The reaction completes in 1 h, produces water as the only byproduct, and does not require purification. It is therefore affordable, facile, and green. Mixing the product with thiol cross-linkers and the appropriate photoadditives produces photopolymers that are printable via Digital Light Processing. The photopolymers exhibit tunable tensile properties and a functional surface by varying the polymer backbone and thiol stoichiometry. Moreover, the photopolymers are 3D-printed into true-to-scale human aorta models and porous scaffolds with high resolution. The simple yet versatile platform will benefit additive manufacturing of soft materials and beyond.
碳酸酐是一种未得到充分重视的3D可打印非水凝胶光聚合物的起始原料。与其他降冰片烯前体相比，碳酸酐更便宜且可通过氨解反应。因此，用碳酸酐进行的通用且高效的功能化可以提高硫醇-降冰片烯光聚合物的利用率。在此，我们报道了碳酸酐与两种商用聚合物：胺官能化聚丙二醇和聚二甲基硅氧烷的无催化剂缩合反应。该反应在1小时内完成，仅产生水作为唯一副产物，且无需纯化。因此，它价格低廉、操作简便且环保。将产物与硫醇交联剂和合适的光添加剂混合可制得可通过数字光处理进行打印的光聚合物。通过改变聚合物主链和硫醇化学计量比，这些光聚合物展现出可调节的拉伸性能和功能性表面。此外，这些光聚合物被3D打印成与真实尺寸相符的人体主动脉模型和高分辨率的多孔支架。这个简单却通用的平台将有益于软材料及其他材料的增材制造。
