This work presents a robust method to achieve the synthesis of low molecular weight polyesters 26 via ring-opening polymerization (ROP) initiated by 2-hydroxyethyl-methacrylate (HEMA) 27 when using triazabicyclodecene (TBD) as catalyst. The effect that the HEMA:TBD ratio has 28 upon the final reaction rate and final polymer molecular architecture is discussed. The optimum 29 HEMA:TBD ratio and reaction conditions required to minimize competing transesterification 30 reactions were determined, in order to synthesize successfully the target ROP macromonomer 31 species containing only a single 2-methacryloyloxyethyl end-group. Additionally, to confirm 32 the terminal end-group fidelity of the product macromonomers and confirm TBD utility for 33 block copolymer manufacture, a small series of di-block polyesters were synthesized using 34 TBD and shown to exhibit good control over the final polymer structure whilst negating the 35 side transesterification reactions, irrespective of the monomers used.
Ruiz-Cantu, L. A., Pearce, A. K., Burroughs, L., Bennett, T. M., Vasey, C. E., Wildman, R., …Taresco, V. (2019). Synthesis of methacrylate-terminated block copolymers with reduced transesterification by controlled ring-opening polymerization. Macromolecular Chemistry and Physics, 220(2), https://doi.org/10.1002/macp.201800459