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Benzil ( BZ ) can be converted almost quantitatively to benzoyl peroxide ( BP ) in aerated polymer films upon irradiation at &gt;400 nm (i.e., the long-wavelength edge of the n → π* absorption band of BZ , where BP does not absorb). Here, we summarize results for the photoperoxidation of BZ structures with molecular oxygen, principally in glassy polymer matrices. Some of the polymers are doped directly with BZ or its derivatives, and others, contain covalently attached BZ pendant groups from which BP groups are derived. While the decomposition of low-molecular-weight BP doped into polymer films (such as those of polystyrene (PS)) results in a net decrease in polymer molecular weight, thermal decomposition of pendant BP groups is an efficient method for chain crosslinking. Crosslinking of PS films doped with a molecule containing two covalently linked BZ or BP groups proceeds in a similar fashion. Free radicals from the covalently attached BP allow grafting of new monomers, as well. Additionally, the use of radiation filtered through masks has been used to create patterns of polymers on solid surfaces. Crosslinking of photodegradable poly(phenyl vinyl ketone) with BP structures obtained by photoperoxidation of BZ structures for the preparation of photodegradable polymer networks is described as well. In sum, the use of BZ and BP and their derivatives offers simple and convenient routes for modifying polymer chains and, especially, for crosslinking them. Specific applications of each use and process are provided. Although applications with PS are featured here, the methodologies described are amenable to a wide variety of other polymers.

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers