Benzyl triflate (BnOTf) was demonstrated as a new initiator in cationic ring-opening polymerization (ROP) of cyclic dithiocarbonate, yielding poly(dithiocarbonate) with a benzylated chain end. BnOTf was generated in situ from benzyl bromide and silver trifluoromethanesulfonate (AgOTf). Several arylmethyl triflates were prepared from 1,4-bis(bromomethyl)benzene, 1,3,5-tris(bromomethyl)benzene, and 1,2,4,5-tetrakis(bromomethyl)benzene. These triflates were used for the synthesis of polymeric architectures, such as two-armed linear polymers and tri- and tetra-armed polymers. The number of polymer arms was related to the number of arylmethyl triflate groups bound in the initiators through divergent chain propagation. The chain length of each arm was adjusted with initiators at theoretical concentrations considering the number of substituted triflates and confirmed via 1H NMR analysis of the prepared polymers. The lengths agreed with the results determined by the number-average molecular weights retrieved from gel permeation chromatography analysis. A symmetric structure of the aromatic cores and low polydispersities of the prepared polymers were suggested for divergent chain propagation. Fluorescent dye-attached polymers were prepared through ROP, and the presence of cores retrieved from the initiators was verified.
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This work was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (No. NRF-2019R1F1A1060583).
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Kim, C.G., Jeong, H.J. & Do, J.Y. Divergent chain growth of poly(dithiocarbonate)s through arylmethyl triflate-mediated ring-opening polymerization of cyclic dithiocarbonate. Polym J 55, 571–580 (2023). https://doi.org/10.1038/s41428-022-00745-6