Description:
AbstractPoly(4‐thiostyrene), a historically challenging to synthesize polymer, is synthesized herein via a feasible three‐step protocol. Based on the newly developed protection–deprotection strategy, the precursor polymer containing thiomethyl groups is deprotected using Li/naphthalene to yield poly(4‐thiostyrene) after acidification. This newly developed procedure is crucial for preventing crosslinking of the thiol groups and therefore the resulting polymer is soluble in common organic solvents (e.g., chloroform, tetrahydrofuran) and can be stored long‐term, which has been challenging to accomplish over the past 60 years. The successful synthesis is confirmed by various characterization techniques including NMR, Fourier‐transform infrared spectroscopy (FTIR), and Raman analysis, which collectively are new and useful data that have generally been unavailable in previous reports. This work provides a robust approach for synthesizing this promising polymer and offers a new route to investigate thiol‐containing polymers.