Polymerization-Induced Self-Assembly with Assistance of Aromatic Interactions Facilitates the Formation of Polymeric Nanotubes,Macromolecules

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Polymerization-Induced Self-Assembly with Assistance of Aromatic Interactions Facilitates the Formation of Polymeric Nanotubes
Macromolecules ( IF 5.1 ) Pub Date : 2023-04-25 , DOI: 10.1021/acs.macromol.3c00302
Ren-Man Zhu ₁ , Zi-Xuan Chang ₁ , Wen-Jian Zhang ₂ , Chun-Yan Hong ₁

Affiliation

Polymerization-induced self-assembly (PISA) has been demonstrated to be a powerful strategy for producing polymeric nano-objects. Polymeric nanotubes with hollow and anisotropic structures have attracted great interest in materials science. However, according to the theoretical prediction of the packing parameter, polymeric nanotubes are hard to be produced by the self-assembly of block copolymers, which may be due to the lack of directionality of solvophobic interactions. Herein, we demonstrate that aromatic interactions between the solvophobic blocks facilitate the formation of polymeric nanotubes. Polymeric nanotubes with a remarkable length (>11 μm) are generated in the reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of the aromatic monomer 2-(methacryloyloxy) ethyl anthracene-9-carboxylate (MAEAC) using poly(ethylene glycol) as the macro RAFT agent (PEG₄₅-CPADB). When the aromatic interactions of the membrane-forming blocks are weakened by high temperature or copolymerization of MAEAC with a weakly aromatic monomer 2-(methacryloyloxy)ethyl benzoate (MAEB), spherical nano-objects instead of nanotubes tend to be produced. The concentration of polymer chains also plays a vital role in the formation of polymeric nanotubes. The aspect ratio of the polymeric nanotubes can be adjusted by controlling the polymer concentration without varying the polymer composition, and polymeric nanotubes with a larger aspect ratio tend to be generated at higher concentrations of block copolymers. The formation of polymersomes with different aspect ratios for a given polymer provides significant opportunities to investigate the shape-determined performances of the polymersomes while eliminating the influence of polymer composition.

中文翻译：

芳香族相互作用辅助下的聚合诱导自组装促进了聚合物纳米管的形成

聚合诱导自组装 (PISA) 已被证明是生产聚合物纳米物体的强大策略。具有中空和各向异性结构的聚合物纳米管引起了材料科学的极大兴趣。然而，根据堆积参数的理论预测，聚合物纳米管很难通过嵌段共聚物的自组装产生，这可能是由于疏溶剂相互作用缺乏方向性。在此，我们证明了疏溶剂块之间的芳香族相互作用促进了聚合物纳米管的形成。具有非凡长度的聚合物纳米管 (>₄₅-CPADB）。当成膜嵌段的芳族相互作用因高温或 MAEAC 与弱芳族单体苯甲酸 2-(甲基丙烯酰氧基)乙酯 (MAEB) 的共聚而减弱时，往往会产生球形纳米物体而不是纳米管。聚合物链的浓度在聚合物纳米管的形成中也起着至关重要的作用。聚合物纳米管的纵横比可以通过控制聚合物浓度而不改变聚合物组成来调节，并且具有较大纵横比的聚合物纳米管往往在较高的嵌段共聚物浓度下产生。

更新日期：2023-04-25

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