AbstractThe crosslinking and degradation of seven polyacrylates by 1000 kvp. electrons has been investigated. Gel content‐radiation dose analysis reveals the energy dissipation per main‐chain fracture,Ed, to be the same (530 ± 100 electron volts) for methyl,n‐butyl,sec‐butyl, isobutyl, andtert‐butyl acrylate polymers. The energy dissipation per crosslinked unit formation,Ec, is 80–90 e.v. for methyl,n‐butyl, isobutyl and neopentyl acrylate polymers.Ecmay be slightly higher for poly‐sec‐butyl acrylate. Poly‐tert‐butyl acrylate possesses a uniquely highEcof 300 e.v. The presence of hydrogen atoms alpha to the alcoholic oxygen of the ester group is believed to contribute strongly to the crosslinking reactions of polyacrylates under ionizing radiations. Poly‐1,1‐dihydroperfluorobutyl acrylate exhibits an initialEcof ∼45 e.v. and anEdof ∼450 e.v. Beyond 15 megareps the ration of main‐chain fracture