Fast and efficient synthesis of polymers driven by solar radiation. New insights on dye/dendrimer photoinitiating systems

• Published in: European polymer journal 2024-10, Vol.219, p.113382, Article 113382
• Main Authors: Grassano, Micaela E., Paula Militello, M., Saavedra, José L., Bertolotti, Sonia G., Previtali, Carlos M., Arbeloa, Ernesto M.
• Format: Article
• Language: English
• Subjects: PAMAM dendrimers; Photopolymerization; Solar energy; Transient spectroscopy; Visible photoinitiating systems; Xanthene dyes
• ISSN: 0014-3057
• DOI: 10.1016/j.eurpolymj.2024.113382

[Display omitted] •New Type II visible photoinitiating systems (Vis-PIs) in solvent-free formulations were tested.•Low toxicity PAMAM dendrimers act as effective co-initiators replacing traditional amines.•Sunlight drives efficient radical polymerization after a few minutes of exposure.•An electron transfer mechanism is elucidated by transient spectroscopy. The performance of a series of visible-light driven photoinitiating systems (Vis-PIs) for radical polymerization was evaluated. The Vis-PIs formulations consisted of aqueous solutions containing xanthene dyes as sensitizers, while polyamido-amine (PAMAM) dendrimers were tested as alternative co-initiators of lower toxicity than the traditional amines. Acrylamide and HEMA were used as probe monomers and the respective polymers were characterized by FTIR, DSC and viscosimmetry. In order to elucidate the mechanism of photopolymerization, the triplet excited-states and semirreduced forms of the dyes were characterized by transient spectroscopy. Photophysical parameters as intersystem crossing and radical quantum yields were also determined for each dye/dendrimer couple. All Vis-PIs operated successfully under solar irradiation, achieving high monomer conversions after short exposure times. Interestingly, formulations with partially halogenated dyes showed the highest efficiency, which correlates inversely with the affinity and the electron transfer capability between the reactants. This study demonstrates the usefulness of dye/dendrimer combinations to operate as efficient aqueous Vis-PIs under an inexpensive, unlimited and natural energy source such as sunlight.