Three alka-3,5-diynylmethacrylate and 1,8-Bis(methacryloxy)octa-3-5-dyine were synthesized and their polymerisation in thp molten state was studied. 3,5-Octadiynylene-1,8-dimethacrylate, which was the only one that was solid at room temperature, was not light sensitive in the solid state. All the monomers underwent rapid polymerization at 140 degrees C. The DSC and IR-spectra indicated that the polymerization of the vinyl and diacetylenic groups takes place simultaneously. An optically highly transparent, yellow-orange glass was obtained.