1,1,3,3-Tetramethylguanidine-Mediated Zwitterionic Ring-Opening Polymerization of Sarcosine-Derived N‑Thiocarboxyanhydride toward Well-Defined Polysarcosine

• Published in: Macromolecules 2022-04, Vol.55 (7), p.2509-2516
• Main Authors: Siefker, David, Chan, Brandon A, Zhang, Meng, Nho, Ju-Woo, Zhang, Donghui
• Format: Article
• Language: English
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/acs.macromol.1c02472

Zwitterionic ring-opening polymerization (ZROP) of sarcosine-derived N-thiocarboxy­anhydrides (Me-NNTAs) can be induced by using 1,1,3,3-tetramethylguanidine (TMG) initiators in CH2Cl2 at 25 °C, rapidly producing well-defined polysarcosine polymers with controlled molecular weights (M n = 1.9–37 kg/mol) and narrow molecular weight distributions (Đ = 1.01–1.12). The reaction exhibits characteristics of a living polymerization, evidenced by pseudo-first-order polymerization kinetics, the linear increase of polymer molecular weight (M n) with conversion, and the successful chain extension experiments. The polymerization is proposed to proceed via propagating macro-zwitterions bearing a cationic 1,1,3,3-tetramethyl­guanidinium and an anionic thiocarbamate chain end. The TMG not only initiates the polymerization but also serves to stabilize the thiocarbamate chain end where the monomer addition occurs. Because of the enhanced hydrolytic stability of Me-NNTA, the polymerization can be conducted without the rigorous exclusion of moisture, further enhancing the appeal of the method to access well-defined polysarcosine.