Quinizarin Derivatives as Photoinitiators for Free-Radical and Cationic Photopolymerizations in the Visible Spectral Range

• Published in: Macromolecules Vol. 53; no. 4; pp. 1129 - 1141
• Main Authors: Sautrot-Ba, Pauline, Jockusch, Steffen, Malval, Jean-Pierre, Brezová, Vlasta, Rivard, Michael, Abbad-Andaloussi, Samir, Blacha-Grzechnik, Agata, Versace, Davy-Louis
• Format: Journal Article
• Language: English
• Published: American Chemical Society 10.02.2020
• Subjects: Chemical Sciences
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/acs.macromol.9b02448

We report the use of efficient visible-light sensitive allyl (QA) and epoxidized (QE) quinizarin derivatives as photoinitiating systems when combined with an appropriate electron donor (methyldiethanol amine, MDEA), an electron acceptor (iodonium salt, Iod), or a H donor (thiol derivative), for free-radical photopolymerization (FRP), cationic photopolymerization (CP), and a thiol–ene process. These systems have demonstrated excellent initiating properties under air or in laminated conditions under visible-light irradiation (LEDs@405, 455, and 470 nm or Xe lamp) for FRP, CP, or the thiol–ene process and appear more efficient than the well-known camphorquinone-based photoinitiating systems. As highlighted by electron paramagnetic resonance (EPR) and laser flash photolysis experiments, QA (or QE) acts either as an electron donor via a photoinduced electron transfer pathway with Iod or as a proton/proton-coupled electron transfer promoter with MDEA or a thiol derivative. Two types of interpenetrated polymer networks have been synthesized either by CP and the thiol–ene process with di(ethylene glycol) divinyl ether/trithiol or by a concomitant free-radical and cationic photopolymerization with an epoxide/acrylate blend mixture upon LED@455 or 470 nm exposure. Interestingly, the resulting quinizarin-derived materials showed antiadherence properties under visible-light exposure even after two cycles of antibacterial experiments. Quinizarin derivatives can not only initiate photopolymerization but also generate singlet oxygen on the surface of the materials for preventing the adhesion and proliferation of bacteria under visible-light activation.