Poly solid-state photolysis

Solid-State Photolysis of Poly(p-Formyloxystyrene) A 10% solution of poly(p-formyloxystyrene) (IV) (Mn 18,000) in diglyme was prepared under... 

A considerable amount of attention has also been paid to the photo-Fries rearrangement of polymer pendant groups. For example, the rearrangement of poly (phenyl acrylate) (10,11) in solution or in the solid-state, is usually incomplete and results in the formation of both the ortho and the para-hydroxyphenone rearranged products in amounts which vary with the conditions of the photolysis. A concurrent side-reaction, which we term the Fries degradation, also results in the liberation of small amounts of phenol (Scheme 2). Similar results have been obtained with poly (phenyl methacrylate) and other substituted aryl acrylates (4,9,12). 

It is important to point out that the quantum yield for the Norrish II chain scission reaction ( Cs) is highly affected by the mobility of polymer chains. For example, the photolysis CS for a film of the copolymer poly(styrene-co-phenyl vinyl ketone) irradiated at 313 nm in the solid state was shown to be low (0.04—0.09) at temperatures below the copolymer Tg (glass transition temperature) but increased dramatically at,... 

David et al. [9] have studied the photolysis of poly(phenyl vinyl ketone) in detail. Irradiation in solution or in the solid state reduces the molecular weight and was compared with the photolysis of butyrophenone. The principal mechanism was... 

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