Achieving Closed-Loop Recycling of a Semi-Conjugated Polymer Through the Incorporation of Ester Linkers Along the Backbone.

Abstract

Design strategies to achieve degradation and ideally closed-loop recycling of organic semiconductors have attracted great interest in order to minimize the electronic waste (E-waste). In this work, three ester-incorporated monomers were synthesized by the names of Thiophene-Ester-Ethylene-Thiophene (TEET), Thiophene-Ester-Methylene-Thiophene (TEMT), and Thiophene-Ester-Thiophene (TET), which were co-polymerized via Stille polycondensation with a benzodithiophene (BnDT) π-conjugated unit to yield a series of ester-incorporated polymers: PBnDT-TEET, PBnDT-TEMT, and PBnDT-TET. While the ester-only linker can maintain some extended conjugation in PBnDT-TET, the other two ester linkers having conjugation breaking units result in isolated conjugated segments in PBnDT-TEET and PBnDT-TEMT, evidenced by UV-Vis and CV results. This yields an improved photovoltaic performance of PBnDT-TET compared to PBnDT-TEET. While all three polymers can depolymerize under methanolysis, the alternating co-polymer PBnDT-TEET demonstrates the highest recyclability potential with a single dimethyl ester-functionalized product with an excellent 92 % isolated yield, which can then be repolymerized to reobtain PBnDT-TEET with a 36 % yield. This work provides a framework towards achieving recyclable organic semiconductors to reduce E-waste. Although the incorporation of ester linkers allowed for closed-loop recycling, the low solar cell efficiency of PBnDT-TEET highlights the significant challenge in achieving both recycling and high device performance.