Synthesis of stable fluorescent ethylene-vinyl acetate copolymers based on in-situ grafted rare-earth organic complexes and antioxidants through transesterification

Abstract

The synthesis and application of rare earth organic complexes (REOCs) are gaining attention due to their advantages including low excitation thresholds and high luminescence efficiencies. However, their integration as functional fillers in polymer matrices is constrained by challenges related to poor dispersion and limited stability. This study introduces a novel method for synthesizing stable fluorescent polymers by co-grafting europium (Eu) complexes and the antioxidant 3,9-bis-{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl-)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5.5]-undecane (AO-80) onto an ethylene-vinyl acetate (EVA) matrix through an in-situ synchronous grafting strategy, aiming to address these dual challenges of poor dispersion and rapid aging. In this study, Eu complexes characterized by low excitation thresholds and high hexahydrate (EuCl₃) and selected ligands - 1,10-phenanthroline (Phen), alpha-thienyl trifluoroacetone (HTTA), and 4-acetoxybenzoic acid (4-ABA). Through transesterifications, the Eu complexes were successfully grafted onto the EVA chain, achieving a uniform dispersion within the EVA matrix to form fluorescent polymers. Furthermore, the incorporation of antioxidant AO-80 as a radical scavenger can significantly mitigate fluorescence attenuation. Through detailed exploration of transesterifications under various conditions, optimal grafting rates of 11.34% for EVA with Eu complexes and 22.87% for EVA with AO-80 were achieved. The synthesized fluorescent polymers of EVA synchronously grafted with Eu complexes and AO-80 have been proven to obtain markedly improved fluorescence stability and aging resistance by outdoor aging tests. Our findings not only validate the in-situ reaction grafting method as an efficient strategy for producing polymer composites with excellent fluorescence stability but also pave the way for future research aimed at overcoming the limitations of REOCs in photovoltaic and agricultural applications.