Photolytic crosslinking of poly(p-hydroxystyrene)

Light-induced crosslinking of poly(p-hydroxystyrene) (PPHS) is significantly enhanced by O₂. This was evidenced by molar mass (light scattering measurements) and by gel content determinations which were performed on various polymer samples before and after continuous irradiation at λ_inc = 254 nm. The following mechanism was elucidated with the aid of flash photolysis studies: Crosslinking in the absence or presence of O₂ is mainly due to the combination of phenoxyl type radicals. In the absence of O₂ the latter are exclusively formed by O? H bond cleavage of singlet excited phenolic groups. Triplet excited phenolic groups which are also formed do not deactivate via O? H bond cleavage but react very effectively with O₂. This reaction leads to the formation of HO and additional phenoxyl type radicals. All Commercial and most laboratory-prepared PPHS samples contain chemically bound impurities of quinoid nature. On the basis of results performed with model compounds of low molar mass, it is concluded that triplet excited quinoid groups react effectively with phenolic groups forming phenoxyl type radicals and that they are quite unreactive with respect to the abstraction of alphatic hydrogen atoms. Irradiation of PPHS at λ_inc = 254 nm causes the formation of quinoid groups which absorb strongly at this wavelength. Light absorption by these groups becomes a determining factor with respect to photochemical alteration in the course of further irradiation.