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SynopsisThe photodegradation of films (2 x cm thick) of poly(viny1-acetophenone) [poly(4acetylstyrene)] exposed to 254 nm radiation under high vacuum at 25 & 1°C was studied. The principal gaseous product was H,, but CH,, C,H,, and smaller amounts of acetaldehyde and CO were also formed. The photochemistry more closely resembles that of other substituted styrene polymers than that occurring on the long wave ( A > 300 nm) irradiation of the polymer in that the principal initial processes involve fissions of bonds in the /?-position to the phenyl chromophores. Studies of a deuterated analogue (D3 acetyl) indicate that H-abstractions occur from the polymer and also that fission of C-H bonds in the acetyl group does not occur. The polymer undergoes rapid cross linking. Mechanisms of the various primary and secondary processes are discussed.