Dendronized exo-7-oxanorbornene monomers were synthesized and polymerized via thiol–Michael coupling and ring-opening metathesis polymerization. The polymerization rate was highly dependent on the steric hindrance of the terminal group. The space linker between the polymerizable group and dendron was a crucial factor. Ru-based kinetics was investigated using nuclear magnetic resonance (NMR), which showed that the monomer was completely converted to a generally narrow polydispersity material. The second generation of functional macromonomer was grafted from the first with a different linker length and consumed completely at 50 ^oC in toluene. Considering the properties of the space linker, we found that a short space linker of dendronized exo-7-oxanorbornene macromonomer leads to narrow molecular weight distributions of obtained dendronized polymers. This work provides a further understanding of the effect of steric hindrance on dendronized polymers, thereby allowing the development of functional materials.

Keywords: thiol–Michael, ring-opening metathesis polymerization, functional polymer, steric hindrance