Self-Polymerization Promoting Monomers: In Situ Transformation of Disulfide-Linked Benzoxazines into the Thiazolidine Structure

-N containing a five-membered thiazolidine ring and a phenolic-OH. The structure of the monomer with the oxazine ring and its congener with the thiazolidine ring was characterized by spectroscopic methods and X-ray analysis. Kinetics of structural transformation at a molecular level is studied in detail, and it was found that the reaction proceeded via a transient 2-aminoethanethiol-linked benzoxazine intermediate, as supported by nuclear magnetic resonance spectroscopy and density functional theory studies. The thiazolidine-ring-containing monomer promotes ROP at a substantially low temperature than the reported mono-/bisoxazine monomers due to the dual mode of facilitation of the ROP reaction, both by phenolic-OH and by ring strain. Surprisingly, both the monomer structures led to the formation of a similar polymer structure, as supported by thermogravimetric analysis and Fourier transform infrared study. The current work highlights the benefits of inherent functionalities in naturally sourced feedstocks as biosynthons for the new latest generation of benzoxazine monomers.