Li Mingzhao, Jing Xiaoyi, Xia Jiehui, Tian Qi, Zhang Qiang, Wang Bingnan, Qin Anjun, Zhong Tang Ben
State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, Center for Aggregation-Induced Emission, South China University of Technology, 510640, Guangzhou, China.
Center for Aggregation-Induced Emission, AIE Institute, South China University of Technology, 510640, Guangzhou, China.
Angew Chem Int Ed Engl. 2024 Oct 24;63(44):e202410846. doi: 10.1002/anie.202410846. Epub 2024 Sep 24.
Polyamide plays a pivotal role in engineering thermoplastics. Constrained by the harsh conditions and arduous procedures for its industrial synthesis, developing facile synthesis of polyamides is still challengeable and holds profound significance. Herein, we successfully utilized water as one of the monomers to synthesize functional polyamides under ambient conditions. A powerful multicomponent polymerization of water, isocyanides, and chlorooximes was established in phosphate-buffered saline. Soluble and thermally stable polyamides with high weight-average molecular weights (up to 53 900) were obtained in excellent yields (up to 95 %). The polymerization exhibits unique polymerization-induced emission characteristics, successfully converting non-emissive monomers into unconventional emissive polymers. Notably, the resultant polyamides could undergo effective post-modification via the hydroxyl-yne click reaction. By incorporating various functional groups into the polyamide, its emission color could be fine-tuned from blue to green and to red. Remarkably, the refractive index (n) of the polyamide at 589 nm could be increased from 1.6173 to 1.7227 and the Δn could be unprecedentedly as high as 0.1054 for non-heavy atom-containing polymers after post-modification, and its micron-thick films exhibited excellent transparency in the visible region. Thus, this work not only establishes a powerful polymerization toward novel polyamides but also opens up an avenue for their versatile functionalization.
聚酰胺在工程热塑性塑料中起着关键作用。由于其工业合成条件苛刻、过程繁琐，开发简便的聚酰胺合成方法仍然具有挑战性且意义重大。在此，我们成功地利用水作为单体之一，在环境条件下合成了功能性聚酰胺。在磷酸盐缓冲盐溶液中建立了水、异腈和氯肟的高效多组分聚合反应。以优异的产率（高达95%）获得了具有高重均分子量（高达53900）的可溶性且热稳定的聚酰胺。该聚合反应表现出独特的聚合诱导发光特性，成功地将非发光单体转化为非常规发光聚合物。值得注意的是，所得聚酰胺可通过羟基-炔点击反应进行有效的后修饰。通过将各种官能团引入聚酰胺中，其发射颜色可从蓝色微调至绿色再到红色。显著的是，对于经过后修饰的不含重原子的聚合物，聚酰胺在589 nm处的折射率（n）可从1.6173提高到1.7227，Δn可高达0.1054，并且其微米厚的薄膜在可见光区域表现出优异的透明度。因此，这项工作不仅建立了一种强大的新型聚酰胺聚合方法，还为其多功能化开辟了一条途径。
