Summary: The radical polymerization of different substituted methyl 2‐(bicyclo[3.1.0]hex‐1‐yl) acrylates, 1a – f , was initiated by 2,2′‐azoisobutyronitrile (AIBN) at 65 °C in chlorobenzene. The radical homopolymerization of 1a – f occurred through the opening of the cyclopropane ring, and lead to polymers with number‐average molecular weights of 13 000 to 434 400 g · mol?1 and glass transition temperatures between 77 and 121 °C. The monomers 1a – f showed a similar reactivity to MMA (in the copolymerization with MMA). Selected monomers were determined to be diluent monomers for dental filling composites and enable the preparation of composites that show a significantly reduced polymerization shrinkage, compared to composites based on dimethacrylate diluents.
