Highly Efficient Synthesis of Poly(silylether)s: Access to Degradable Polymers from Renewable Resources

The design of new materials with tunable properties and intrinsic recyclability, derived from biomass under mild conditions, stands as a gold standard in polymer chemistry. Reported herein are platinum complexes which catalyze the formation of poly(silylether)s (PSEs) at low catalyst loadings. These polymers are directly obtained from dual‐functional biobased building blocks such as 5‐hydroxymethylfurfural (HMF) or vanillin, coupled with various dihydrosilanes. Access to different types of copolymer architectures (statistical or alternating) is highlighted by several synthetic strategies. The materials obtained were then characterized as low Tg materials (ranging from −60 to 29 °C), stable upon heating (T−5% up to 301 °C) and resistant towards uncatalyzed methanolysis. Additionally, quantitative chemical recycling of several PSEs could be triggered by acid‐catalyzed hydrolysis or methanolysis. These results emphasize the interest of biobased poly(silylether)s as sustainable materials with high recycling potential. A variety of renewable polymers has been synthesized from easily accessible biobased hydroxyaldehydes and dihydrosilanes. Using low catalyst loadings of platinum complexes, different polymer architectures were obtained, from random to alternated copolymers. The intrinsic chemical recyclability of these poly(silylether)s is also highlighted.