Stable copper acetylacetonate-based oxidizing agents in redox (NIR photoactivated) polymerization: an opportunity for the one pot grafting from approach and an example on a 3D printed object

Abstract

The use of new stable copper acetylacetonates in combination with specific bidentate ligands (e.g. 2dppba) is proposed for redox free radical polymerization (FRP) under mild reaction conditions (under air and at room temperature). These systems show high performances so that they can compete with the well-established reference redox initiating systems based on the amine/benzoylperoxide combination. Remarkably, some of our systems are also highly efficient when excited in the near infrared region (NIR), demonstrating that our redox systems can also be activated by light. Using this strategy, the initial redox free radical polymerization could be converted into a redox photoactivated one. More interestingly, a stable copper methacryloyloxy-ethylacetoacetate (Cu(AAEMA)₂) bearing a reactive methacrylate function and a copper acetylacetonate moiety could be used to polymerize a first polymer layer onto which a second polymerization could be carried out. Precisely, the second polymerization was initiated by a redox process using mild reaction conditions (at room temperature and under air), different from the process used to form the underlayer. To the best of our knowledge, this re-initiation of polymerization from a pre-polymerized layer by a second polymerization technique is highly original and is of crucial industrial/academic interest as no high energy consumption/harmful wavelengths are required to reinitiate the polymerization. The efficiency of this strategy is illustrated by grafting from a 3D printed object.