Photocrosslinking of a maleimide functionalized polymethacrylate

A polymethacrylate bearing pendent maleimide (MI) groups has been crosslinked by UV irradiation of the photoinitiator‐free functionalized polymer. The reaction was followed in situ by real‐time IR spectroscopy and shown to proceed with an initial quantum yield of two maleimide double bonds polymerized per photon absorbed, the value expected for a photocycloaddition mechanism. A twofold increase of the reaction rate was achieved by performing the UV irradiation in the presence of a thioxanthone photosensitizer (1 wt%). Insolubilization of the photoresist requires the reaction of at least 18 MI double bonds per polymer chain, thus implying the occurrence of an intramolecular coupling process between neighbouring MI groups located on the same polymer chain. In the presence of an electron donor monomer, like the divinylether of triethyleneglycol used, the cycloaddition reaction gives way to a radical‐induced copolymerization of maleimide and vinyl ether double bonds, which becomes the only crosslinking process in a stoichiometric mixture of the two components.