Hierarchical Self-Assembly of ABC-Type Bottlebrush Copolymers
Hierarchical Self-Assembly of ABC-Type Bottlebrush Copolymers
复制标题
DOI：
10.1021/acs.macromol.3c00440
复制
发表时间：
2023-07
期刊：
影响因子：
5.5
通讯作者：
Qingliang Song;Qingshu Dong;Ruiqi Liang;Ya-Xin Xue;Mingjiang Zhong;Weihua Li
中科院分区：
文献类型：
--
作者：
Qingliang Song;Qingshu Dong;Ruiqi Liang;Ya-Xin Xue;Mingjiang Zhong;Weihua Li
我们进行了耗散粒子动力学模拟，研究了ABC型洗瓶刷共聚物（BBCP）的自组装，其主链的一部分由成对的A嵌段接枝，另一部分由成对的B/C嵌段接枝，重点研究A侧链的数量、B侧链相对于C侧链的长度以及主链的刚性对分级结构形成的影响。观察到许多分层结构，其中上层结构由A和B/C嵌段之间的相分离形成，而下层结构由B和C嵌段之间的相分离形成。一些分级结构类似于ABC星形共聚物自组装的结构，而ABC型BBCP的稳定参数区域要大得多。另一方面，ABC型BBCP还可以形成一些在ABC星形共聚物中难以形成的新颖的分级结构。虽然许多层次结构中A上层结构和B子结构的形成可以独立控制，但也有一些层次结构的上层结构和子结构的转换是耦合的。换句话说，对于固定fA，A-上层结构随着B-子结构的变换而变化。此外，我们的结果表明，主链的刚性对 ABC 型 BBCP 中分层结构的形成有显着影响，即刚性主链有利于 B 子结构到 A 上层结构的正常排列。我们的工作不仅加深了对 ABC 型 BBCP 自组装机制的理解，而且为构建有趣的层次结构的实验提供了有益的指导。
We have performed dissipative particle dynamics simulations to study the self-assembly of ABC-type bottlebrush copolymers (BBCPs), one portion of whose backbone is grafted by pairs of A-blocks and the other portion is grafted by B/C-blocks in pairs, focusing on the effects of the number of A side chains, the length of B side chains relative to that of C side chains, and the rigidity of the backbone on the formation of hierarchical structures. A number of hierarchical structures with the superstructures formed by the phase separation between A and B/C-blocks and the substructures formed by the phase separation between B and C-blocks are observed. Some hierarchical structures are similar to those self-assembled by ABC star copolymers, whereas their stable parameter regions of ABC-type BBCPs are much larger. On the other hand, the ABC-type BBCPs can also form some novel hierarchical structures that are hard to form in ABC star copolymers. Though the formation of the A-superstructure and the B-substructure in many hierarchical structures can be independently controlled, there are also some hierarchical structures in which the transitions of the superstructure and substructures are coupled. In other words, the A-superstructure changes along with the transformation of the B-substructure for fixedfA. In addition, our results demonstrate that the rigidity of the backbone has a significant effect on the formation of the hierarchical structure in ABC-type BBCPs, i.e., a rigid backbone favors the normal arrangement of B-substructures to A-superstructures. Our work not only deepens the understanding of the self-assembly mechanism of ABC-type BBCPs but also provides helpful guidance for experiments to fabricate interesting hierarchical structures.