Hou Xiaojian, Hu Lingjuan, Yang Huanzhi, Jin Bixin, Luo Yunjun, Li Xiaoyu
School of Materials Science and Engineering, Key Laboratory of High Energy Density Materials (MOE), Beijing Institute of Technology, Beijing 100081, China.
Zhuhai Campus, Beijing Institute of Technology, No. 6 Jinfeng Road, Tangjiawan, Xiangzhou District, Zhuhai 519000, China.
Polymers (Basel). 2024 Nov 28;16(23):3339. doi: 10.3390/polym16233339.
Block copolymers (BCPs) have attracted considerable attention due to their ability to form a variety of complex assemblies with diverse morphologies and functions in solution. By incorporating liquid crystalline (LC) moieties, the LC side chains significantly affect the morphologies and sizes of BCP assemblies. In this study, we synthesized the copolymer with an LC block containing triphenylene (HAT) discotic mesogen and short methylene side chains. By enhancing the π-π interaction between triphenylene discotic mesogens, and doping the discotic mesogens, the LC orderedness was significantly enhanced and able to dictate the self-assembly behaviors of the BCP in solution. Additionally, the lengths of resultant fibrillar micelles were easily tuned by adjusting the dopant content. More interestingly, two growth modes, nucleation growth and coupling, were observed during the formation of fibrils. Consequently, with long-term aging and sufficient concentration, a large portion of these fibrils underwent end-to-end coupling to form long fibrils, allowing the formation of organogel via inter-fibrillar entanglement.
嵌段共聚物(BCP)因其能够在溶液中形成具有多种形态和功能的复杂聚集体而备受关注。通过引入液晶(LC)部分,LC侧链会显著影响BCP聚集体的形态和尺寸。在本研究中,我们合成了一种具有含并五苯(HAT)盘状液晶元以及短亚甲基侧链的LC嵌段的共聚物。通过增强并五苯盘状液晶元之间的π-π相互作用以及对盘状液晶元进行掺杂,LC有序性显著增强,并且能够决定BCP在溶液中的自组装行为。此外,通过调节掺杂剂含量可以轻松调节所得纤维状胶束的长度。更有趣的是,在纤维形成过程中观察到了两种生长模式,即成核生长和偶联。因此,经过长期老化且浓度足够时,这些纤维中的很大一部分会发生端对端偶联以形成长纤维,从而通过纤维间缠结形成有机凝胶。