Charland-Martin Ariane, Collier Graham S
Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw, Georgia 30144, United States.
School of Polymer Science and Engineering, University of Southern Mississippi, Hattiesburg, Mississippi 39406, United States.
Macromolecules. 2024 Jun 18;57(13):6146-6155. doi: 10.1021/acs.macromol.4c01168. eCollection 2024 Jul 9.
Understanding the influence of chemical environments on the degradation properties of conjugated polymers is an important task for the continued development of sustainable materials with potential utility in biomedical and optoelectronic applications. Azomethine-containing polymers were synthesized via palladium-catalyzed direct arylation polymerization (DArP) and used to study fundamental degradation trends upon exposure to acid. Shifts in the UV-vis absorbance spectra and the appearance/disappearance of aldehyde and imine diagnostic peaks within the H NMR spectra indicate that the polymers will degrade in the presence of acid. After degradation, the aldehyde starting material was recovered in high yields and was shown to maintain structural integrity when compared with commercial starting materials. Solution-degradation studies found that rates of degradation vary from 5 h to 90 s depending on the choice of solvent or acid used for hydrolysis. Additionally, the polymer was shown to degrade in the presence of perfluoroalkyl substances (PFASs), which makes them potentially useful as PFAS-sensitive sensors. Ultimately, this research provides strategies to control the degradation kinetics of azomethine-containing polymers through the manipulation of environmental factors and guides the continued development of azomethine-based materials.
了解化学环境对共轭聚合物降解性能的影响，对于持续开发在生物医学和光电应用中具有潜在用途的可持续材料而言是一项重要任务。含甲亚胺的聚合物通过钯催化直接芳基化聚合反应（DArP）合成，并用于研究暴露于酸时的基本降解趋势。紫外可见吸收光谱的变化以及核磁共振氢谱中醛和亚胺诊断峰的出现/消失表明，聚合物在酸存在下会降解。降解后，醛起始原料以高产率回收，并且与市售起始原料相比显示出保持结构完整性。溶液降解研究发现，降解速率从5小时到90秒不等，这取决于用于水解的溶剂或酸的选择。此外，该聚合物在全氟烷基物质（PFASs）存在下会降解，这使其有可能用作PFAS敏感传感器。最终，本研究提供了通过操纵环境因素来控制含甲亚胺聚合物降解动力学的策略，并指导了基于甲亚胺材料的持续开发。
