Synthesis of telechelics with furanyl end‐groups, 2 Radical polymerization with cc‐bond splitting initiators and network formation with unsaturated polyesters via diels‐alder additions

New CC‐bond splitting initiators with two furanyl groups were prepared: 1,2‐di‐2‐furanyl‐1,2‐diphenyl‐1,2‐bis(trimethylsiloxy)ethane (4a), 1,2‐di‐2‐furanyl‐1, 2‐di‐p‐tolyl‐1, 2‐bis(trimethylsiloxy)ethane (4b) and 1,2‐di‐2‐furanyl‐1, 2‐dimesityl‐1,2‐bis(trimethylsiloxy)ethane (4c). Radical polymerizations of styrene and (meth)acrylates with the new CC‐bond splitting initiators were performed in solution at temperatures between 80–105°C. The telechelic oligomers were characterized by GPC and NMR spectroscopy, proving a furanyl functionality of two. The kinetics of the Diels‐Alder reactions between the furanyl‐terminated telechelics and dienophiles such as maleic anhydride and dimethyl maleate were measured under pseudo‐first‐order conditions. Addition of the telechelics to unsaturated polyesters prepared from maleic anhydride and diols led to a solid material with network structure.