New sustainable polymers and oligomers for Cultural Heritage conservation.

The development of "green" chemistry materials with enhanced properties is a central topic in numerous applicative fields, including the design of polymeric systems for the conservation of works of art. Traditional approaches in art restoration comprise polymer thickeners and viscous dispersions to partially control solvents in the removal of soil or aged varnishes/coatings from artifacts. Alternatively, polymeric gel networks can be specifically designed to grant full control of the cleaning action, yielding safe, time- and cost-effective restorations. The selection of polymers and oligomers in gel design is crucial to tune solvent upload, retention, and controlled release over the sensitive artistic surfaces. Starting from an overview of traditional polymer formulations and state-of-the-art gel systems for cleaning works of art, we provide here the design of a new class of gels, focusing on the selection of oligomers to achieve gels with tailored hydrophilicity/hydrophobicity. We evaluated the oligomers Hydrophilic-Lipophilic Balance (HLB) by developing, for the first time, a novel methodology combining SEC and DOSY NMR analysis, which was tested on a library of "green" oligoesters synthesized by polycondensation and poorly explored in the literature. Oligomers with moderate polydispersity were chosen to validate the new protocol as a robust tool for designing polymeric gels even on industrial scale. The methodology is more time-effective than traditional methods, and gives additional insights on the oligomers physico-chemical nature, evaluating their compatibility with different solvents. Then, we used the selected oligoesters with castor oil to obtain a new class of organogels able to upload solvents with varying polarity, which effectively removed different types of unwanted layers typically found in painting restoration. These results validate the oligomers screening approach and the new class of gels as promising chemical processes/materials in art preservation. The methodology can potentially allow evaluation of HLB also for small molecules (