The self-assembly of block copolymers into 1D, 2D and 3D nano- and microstructures is of great interest for a wide range of applications. A key challenge in this field is obtaining independent control over molecular structure and hierarchical structure in all dimensions using scalable one-pot chemistry. Here we report on the ring opening polymerization-induced crystallization-driven self-assembly (ROPI-CDSA) of poly-L-lactide-block-polyethylene glycol block copolymers into 1D, 2D and 3D nanostructures. A key feature of ROPI-CDSA is that the polymerization time is much shorter than the self-assembly relaxation time, resulting in a non-equilibrium self-assembly process. The self-assembly mechanism is analyzed by cryo-transmission electron microscopy, wide-angle x-ray scattering, Fourier transform infrared spectroscopy, and turbidity studies. The analysis revealed that the self-assembly mechanism is dependent on both the polymer molecular structure and concentration. Knowledge of the self-assembly mechanism enabled the kinetic trapping of multiple hierarchical structures from a single block copolymer.

嵌段共聚物自组装成 1D、2D 和 3D 纳米和微米结构在广泛的应用中引起了极大的兴趣。该领域的一个关键挑战是使用可扩展的一锅化学来获得对所有维度的分子结构和层次结构的独立控制。在这里，我们报告了聚-L-丙交酯-嵌段-聚乙二醇嵌段共聚物的开环聚合诱导结晶驱动自组装（ROPI-CDSA）成1D、2D和3D纳米结构。 ROPI-CDSA的一个关键特征是聚合时间远短于自组装弛豫时间，从而导致非平衡自组装过程。通过低温透射电子显微镜、广角 X 射线散射、傅里叶变换红外光谱和浊度研究来分析自组装机制。分析表明，自组装机制取决于聚合物分子结构和浓度。自组装机制的知识使得能够从单个嵌段共聚物中动态捕获多个层次结构。