Versatile Method to Expand the Morphology Library of Block Copolymer Solution Self-Assemblies with Tubular Structures

Self-assembly
of block copolymers (BCPs) in solution is a powerful
technology to achieve a broad range of structures, such as spheres,
cylinders, vesicles, and other hierarchical structures. However, the
BCP self-assembly library is limited, especially with respect to tubular
structures. Here we show a versatile strategy to expand the morphology
library of block copolymer solution self-assemblies with tubular structures
(including tubular dumbbells and tubules) via self-assembly of the
most common diblock copolymers P4VP-b-PS BCPs in
methanol. No special chemistry is needed in this strategy, which proves
the universality of this method. The novelty of the strategy is to
keep the BCPs both highly asymmetric and with very high molecular
weight. The underlying formation mechanism and kinetics of these tubular
structures were elucidated. The prepared tubular structures expand
the structure library of BCP solution self-assemblies and open up
a new avenue for the further applications of a variety of tubular
materials.

溶液中嵌段共聚物（block copolymers, BCPs）的自组装是一种可精准构建多样化结构的强大制备技术，能够得到球形、圆柱形、囊泡及其他多级有序结构。然而，当前嵌段共聚物自组装结构库仍较为有限，在管状结构领域尤为突出。本研究通过在甲醇中自组装最常用的二嵌段共聚物（diblock copolymers）P4VP-b-PS，开发了一种通用策略，用以拓展嵌段共聚物溶液自组装的管状结构形貌库（涵盖管状哑铃结构与微管结构）。该策略无需特殊化学反应，充分证明了此方法的普适性。本策略的创新之处在于，同时保留了嵌段共聚物的高度不对称性与极高分子量。研究阐明了此类管状结构的潜在形成机制与动力学过程。所制备的管状结构拓展了嵌段共聚物溶液自组装的结构库，为各类管状材料的后续应用开辟了全新路径。