Department of Chemical Engineering, National Taiwan University of Science and Technology, No.43, Sec. 4, Keelung Rd., Da'an Dist., Taipei City, 10607, Taiwan.
Advanced Research Center for Green Materials Science and Technology, National Taiwan University, Taipei, 10617, Taiwan.
Macromol Rapid Commun. 2021 Oct;42(19):e2100327. doi: 10.1002/marc.202100327. Epub 2021 Aug 6.
Conjugated polymer sorting is currently the best method to select large-diameter single-walled carbon nanotubes (SWCNTs) with tunable narrow chirality in the adaption of highly desired electronics applications. The acceleration on conjugated polymers-SWCNTs interaction with long-term stability through different molecular designs; for example, longer alkyl side-chains or conjugation moieties have been extensively developed in recent years. However, the importance of the macromolecules with abundant van der Waals (VDW) interaction in the conjugated-based block copolymer system acting during SWCNTs sorting is not clearly demonstrated. In this work, a conjugated diblock copolymer involving polyisoprene (PI) and highly dense π-interaction of poly (9,9-dioctylfluorene) (PFO) is utilized to investigate the impact of natural rubber PI physical interaction on sorting effectiveness and stability. Through the rational design of diblock copolymer, PFO with ≈1200 isoprene units can remarkably enhance SWCNTs sorting ability and selected few chiralities with a diameter of ≈0.83-1.1 nm and highly stable solution for more than 1 year. The introduction of long-chain PI system is attributed not only to form weak VDW force with SWCNTs and strengthen the wrapping of PFO around the semiconducting SWCNTs but also to act as a barrier among nanotubes to prevent reaggregation of sorted SWCNTs.
共轭聚合物分类是目前选择具有可调宽窄手性的大直径单壁碳纳米管(SWCNTs)的最佳方法,适用于高度期望的电子应用。通过不同的分子设计,加速共轭聚合物与 SWCNTs 的相互作用并实现长期稳定性,例如,近年来已经广泛开发了具有更长的烷基侧链或共轭部分的共轭聚合物。然而,在 SWCNTs 分类过程中,具有丰富范德华(VDW)相互作用的大分子在基于共轭的嵌段共聚物系统中的重要性尚未得到明确证明。在这项工作中,利用包含聚异戊二烯(PI)和聚(9,9-二辛基芴)(PFO)的高π相互作用的共轭二嵌段共聚物来研究天然橡胶 PI 物理相互作用对分类效果和稳定性的影响。通过二嵌段共聚物的合理设计,具有 ≈1200 个异戊二烯单元的 PFO 可以显著提高 SWCNTs 的分类能力,并选择具有 ≈0.83-1.1nm 直径和高度稳定的溶液的少数手性,超过 1 年。长链 PI 体系的引入不仅归因于与 SWCNTs 形成较弱的 VDW 力,并增强 PFO 对半导体 SWCNTs 的包裹,而且还作为分类 SWCNTs 之间的屏障,以防止其再聚集。