Novel Sulfur-Containing Polyurethanes using 5-(Chloromethyl)Furfural as a Renewable Building Block

The development of novel polymeric materials with unique properties and applications across various industries, driven by biomass-based molecular platforms, has experienced remarkable growth. Among these, 5-(chloromethyl)furfural (CMF) has emerged as a promising precursor to produce biomass-derived monomers and innovative chemical products. Herein, an efficient method is presented for synthesizing novel biomass-derived diols, achieved in very good yields by reacting CMF with various dithiols, followed by reduction of the resulting dialdehydes. Subsequently, 12 new polyurethanes are synthesized via polyaddition of these diols with commercially available diisocyanates, using an organic base as a catalyst. The resulting polymers exhibit molecular weights ranging from 1.7 to 57.7 kDa, glass transition temperatures between 22 and 120 °C, and degradation temperatures (Td5%) exceeding 170 °C. Additionally, a nearly fully biomass-derived polymer is synthesized through the reaction of furandiazylazide (FDAz) with one of the obtained diols, via Curtius rearrangement. Recognizing the importance of developing innovative polymers alongside efficient chemical degradation and recycling methods, a synthesized polyurethane is also subjected to chemical degradation studies.