Abstract：
Conjugated polymers have received significant attention as potentially lightweight and highly tailorable alternatives to inorganic semiconductors, but their synthesis is often complex, produces toxic byproducts, and they are not typically designed to be degradable or recyclable. These drawbacks necessitate dedicated efforts to discover materials with design motifs that enable targeted and efficient degradation of conjugated polymers. In this vein, the synthetic simplicity of 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) is exploited to access azomethine-containing copolymers via a benign acid-catalyzed polycondensation protocol. Polymerizations involve reacting a dialdehyde-functionalized dihydropyrrolopyrrole with p-phenylenediamine as the comonomer using p-toluenesulfonic acid as a catalyst. The inherent dynamic equilibrium of the azomethine bonds subsequently enabled the degradation of the polymers in solution in the presence of acid. Degradation of the polymers is monitored via NMR, UV-vis absorbance, and fluorescence spectroscopies, and the polymers are shown to be fully degradable. Notably, while absorbance measurements reveal a continued shift to higher energies with extended exposure to acid, fluorescence measurements show a substantial increase in the fluorescence response upon degradation. Results from this study encourage the continued development of environmentally-conscious polymerizations to attain polymeric materials with useful properties while simultaneously creating polymers with structural handles for end-of-life management or/and recyclability.
摘要：
共轭聚合物作为无机半导体的潜在轻质和高度可定制的替代品受到了极大的关注，但是它们的合成通常很复杂，产生有毒的副产品，它们通常不是可降解或可回收的。这些缺点需要致力于发现具有设计基序的材料,所述设计基序能够实现共轭聚合物的靶向和有效降解。在这种情况下，1,4-二氢吡咯并[3,2-b]吡咯的合成简单性被利用来通过良性酸催化的缩聚方案获得含有甲亚胺的共聚物。聚合涉及使用对甲苯磺酸作为催化剂使二醛官能化二氢吡咯并吡咯与作为共聚单体的对苯二胺反应。甲亚胺键的固有动态平衡随后使聚合物在酸存在下在溶液中降解。通过NMR监测聚合物的降解，UV-vis吸光度,和荧光光谱法，聚合物被证明是完全可降解的。值得注意的是,虽然吸光度测量显示，随着长时间暴露于酸，继续向更高的能量转移，荧光测量显示在降解时荧光响应的显著增加。这项研究的结果鼓励环保聚合的持续发展，以获得具有有用性能的聚合物材料，同时创造具有结构处理的聚合物，用于报废管理或/和可回收性。本文受版权保护。保留所有权利。
