Abstract: | New polymer networks were prepared by free radical initiated copolymerization of crystallizable α,ω‐bismethacrylate‐terminated poly(octadecyl vinyl ether) (polyODVE) with butyl acrylate (BA). The polyODVE bismacromonomers were obtained by end‐capping the bifunctionally living cationic polymerization of ODVE with 2‐hydroxyethyl methacrylate (HEMA). The segmented networks show a high degree of phase separation over a wide range of compositions. The shape memory properties of a material containing 20 wt.‐% of polyODVE are reported. |