Wu Di, Dev Vaibhav, Bobrin Valentin A, Lee Kenny, Boyer Cyrille
Cluster for Advanced Macromolecular Design, School of Chemical Engineering, University of New South Wales Sydney NSW 2052 Australia.
Australian Centre for Nanomedicine, School of Chemical Engineering, University of New South Wales Sydney NSW 2052 Australia
Chem Sci. 2024 Nov 1;15(46):19345-58. doi: 10.1039/d4sc05597g.
Polymerization-induced microphase separation (PIMS) has been previously combined with 3D printing to develop customized nanostructured materials with a wide range of functional applications. In traditional PIMS, monofunctional, linear macromolecular chain transfer agents (macroCTAs) are used to develop macroCTA--P(monomer--crosslinker) networks that self-assemble into unique disordered nanostructures. In this work, we designed a significantly altered network structure by utilizing linear macroCTAs with pendant CTA groups, which provides a novel network upon polymerization (, branched copolymers, [macroCTA--[P(monomer--crosslinker)] ]--P(monomer--crosslinker)). Intriguingly, this method leads to the development of alternative disordered morphologies where the internal nanostructure can be precisely controlled. By systematically varying the number of pendant CTA groups, we demonstrate controlled transitions in macroCTA domain continuity, nanodomain size, and phase interface sharpness. These tunable properties translate to adjustable mechanical and swelling behaviors in the resulting 3D printed objects, ultimately enabling the fabrication of smart 4D materials (swelling-induced actuators and temperature-responsive shape-morphing objects). This research significantly expands the design toolbox for 3D printed PIMS materials, providing increased flexibility in the development of advanced materials with specific nanostructures and functionalities.
聚合诱导微相分离（PIMS）此前已与3D打印相结合，以开发具有广泛功能应用的定制纳米结构材料。在传统的PIMS中，单官能线性大分子链转移剂（macroCTA）用于构建macroCTA-P（单体-交联剂）网络，该网络会自组装成独特的无序纳米结构。在这项工作中，我们通过使用带有侧链CTA基团的线性macroCTA设计了一种显著改变的网络结构，这种结构在聚合时会形成一种新型网络（支化共聚物，[macroCTA-[P（单体-交联剂）]]-P（单体-交联剂））。有趣的是，这种方法导致了另一种无序形态的产生，其内部纳米结构可以得到精确控制。通过系统地改变侧链CTA基团的数量，我们展示了macroCTA域连续性、纳米域尺寸和相界面清晰度的可控转变。这些可调节的特性转化为所得3D打印物体中可调节的机械性能和溶胀行为，最终实现了智能4D材料（溶胀诱导致动器和温度响应形状变形物体）的制造。这项研究显著扩展了3D打印PIMS材料的设计工具箱，为开发具有特定纳米结构和功能的先进材料提供了更大的灵活性。
