Photopolymerization of Acrylated Epoxidized Soybean Oil: A Photocalorimetry-Based Kinetic Study

Photocure kinetics of acrylated epoxidized soybean oil (AESO) was studied via photocalorimetry without adding any diluent/comonomer, in the presence of two different photoinitiators, namely, 2,2-dimethoxy phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone. The effect of varying photoinitiator concentration, light intensity, and temperature on the extent of crosslinking was calculated from the ratio of experimentally measured reaction enthalpy to the theoretical enthalpy of reaction (Delta H-theoretical). Photocuring of AESO was observed to be a second-order reaction exhibiting autocatalytic behavior. Nevertheless, due to the occurrence of vitrification, incomplete crosslinking (a not equal 1) was observed in most curing conditions. Rate constants and activation energies were determined using both nonlinear model-fitting and model-free isoconversional methods. Activation energy, as determined from the model-free isoconversional method, was observed to increase as the reaction proceeded, indicating the shift in cure mechanism from kinetic-controlled to diffusion-controlled. Finally, the reaction termination mechanism was observed to be a combination of second-order and primary radical termination mechanisms.