Molecular Simulation Strategies for Understanding the Degradation Mechanisms of Acrylic Polymers

[Image: see text] Acrylic polymers, commonly used in paints, can degrade over time by several different chemical and physical mechanisms, depending on structure and exposure conditions. While exposure to UV light and temperature results in irreversible chemical damage, acrylic paint surfaces in museums can also accumulate pollutants, such as volatile organic compounds (VOCs) and moisture, that affect their material properties and stability. In this work, we studied the effects of different degradation mechanisms and agents on properties of acrylic polymers found in artists’ acrylic paints for the first time using atomistic molecular dynamics simulations. Through the use of enhanced sampling methods, we investigated how pollutants are absorbed into thin acrylic polymer films from the environment around the glass transition temperature. Our simulations suggest that the absorption of VOCs is favorable (−4 to −7 kJ/mol depending on VOCs), and the pollutants can easily diffuse and be emitted back into the environment slightly above glass transition temperature when the polymer is soft. However, typical environmental fluctuations in temperature (<16 °C) can lead for these acrylic polymers to transition to glassy state, in which case the trapped pollutants act as plasticizers and cause a loss of mechanical stability in the material. This type of degradation results in disruption of polymer morphology, which we investigate through calculation of structural and mechanical properties. In addition, we also investigate the effects of chemical damage, such as backbone bond scission and side-chain cross-linking reactions on polymer properties.