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This chapter discusses the recent advances with monomeric and polymeric/hyperbranched photoinitiators for UV/visible curing applications, in particular their structures and structure–reactivity relationships in some of these photoinitiators. The basic motivation for these materials is to minimize undesired migration of small molecules in the photocured matrix. The effect of monomeric and polymeric/hyperbranched structures on the photoinitiating activity is discussed in connection with the different polymerizable groups (monomeric) or backbones (polymeric) and the incorporation of hydrogen-donating groups together with the chromophoric groups. Both the photoinitiating activities and migration stabilities of the photoinitiators are compared with low-molecular-weight non-monomeric analogues.

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