Syntheses and crosslinking reactions of polymers containing spiroorthoester moieties

The radical copolymerization of unsaturated spiroorthoesters such as 2‐methylene‐1,4,6‐trioxaspiro[4.6]undecane (SOE I) and 2‐methylene‐9‐methyl‐1,4,6‐trioxaspiro[4,5]decane (SOE II) with vinyl monomers was carried out to find that SOE I and SOE II were copolymerized with electron‐poor olefins such as methyl acrylate, acrylonitrile, and methyl methacrylate to obtain the corresponding copolymers containing spiroorthoester moieties, respectively. The obtained copolymers were treated with BF3.OEt2 or BzS+SbF to afford crosslinked polymers undergoing expansion in volume on crosslinking in those cases of copolymers of SOE I.