Hurrle Silvana, Goldmann Anja S, Gliemann Hartmut, Mutlu Hatice, Barner-Kowollik Christopher
Macromolecular Architectures, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstraße 18, 76128 Karlsruhe, Germany.
School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT), 2 George Street, QLD 4000, Brisbane, Australia.
ACS Macro Lett. 2018 Feb 20;7(2):201-207. doi: 10.1021/acsmacrolett.7b01001. Epub 2018 Jan 30.
We introduce two AB-type monomers able to undergo a facile catalyst-free photoinduced polycycloaddition of photocaged dienes, enabling rapid Diels-Alder ligations under UV-irradiation (λ = 350 nm) at ambient temperature, closely adhering to Carother's equation established by a careful kinetic study (17800 g mol < < 24700 g mol). The resulting macromolecules were in-depth analyzed via size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Additionally, SEC hyphenated to high resolution-electrospray ionization-mass spectrometry (HR-ESI-MS) enabled the careful mapping of the end group structure of the generated polymers. Furthermore, we demonstrate that both monomer systems can be readily copolymerized. The study thus demonstrates that Diels-Alder ligation resting upon photocaged dienes is a powerful tool for accessing step-growth polymers.
我们引入了两种AB型单体，它们能够在无催化剂的情况下，使光笼蔽二烯发生 facile 光诱导多环加成反应，从而在室温下于紫外线照射（λ = 350 nm）时实现快速的狄尔斯-阿尔德环加成连接反应，紧密符合通过仔细的动力学研究建立的卡罗瑟斯方程（17800 g mol < < 24700 g mol）。通过尺寸排阻色谱法（SEC）和核磁共振（NMR）光谱对所得大分子进行了深入分析。此外，与高分辨率电喷雾电离质谱联用的 SEC（HR-ESI-MS）能够精确绘制所生成聚合物的端基结构。此外，我们证明这两种单体体系都能很容易地进行共聚。因此，该研究表明基于光笼蔽二烯的狄尔斯-阿尔德环加成连接反应是合成逐步增长聚合物的有力工具。 （注：“facile”这个词在中文里较难找到完全对应的词，这里暂保留英文，因为直接翻译可能会影响语义的流畅性，你可以根据实际需求进一步调整对这个词的处理。）
