Gelation in Photoinduced ATRP with Tuned Dispersity of the Primary Chains

[Image: see text] We investigated gelation in photoinduced atom transfer radical polymerization (ATRP) as a function of Cu catalyst loading and thus primary chain dispersity. Using parallel polymerizations of methyl acrylate with and without the addition of a divinyl crosslinker (1,6-hexanediol diacrylate), the approximate values of molecular weights and dispersities of the primary chains at incipient gelation were obtained. In accordance with the Flory–Stockmayer theory, experimental gelation occurred at gradually lower conversions when the dispersity of the primary chains increased while maintaining a constant monomer/initiator/crosslinker ratio. Theoretical gel points were then calculated using the measured experimental values of dispersity and initiation efficiency. An empirical modification to the Flory–Stockmayer equation for ATRP was implemented, resulting in more accurate predictions of the gel point. Increasing the dispersity of the primary chains was found not to affect the distance between the theoretical and experimental gel points and hence the extent of intramolecular cyclization. Furthermore, the mechanical properties of the networks, such as equilibrium swelling ratio and shear storage modulus showed little variation with catalyst loading and depended primarily on the crosslinking density.