Synthesis of telechelics with furanyl end‐groups by radical polymerisation with azo‐initiators and network formation with unsaturated polyesters via Diels‐Alder additions

New azo‐initiators with two and four furanyl groups were prepared: N,N′,N″,N″′‐Tetrafurfuryl 2,2′‐azo‐2,2′‐dimethyldiglutaramide (2), tetrakis[2‐(2‐furoyloxy)ethyl] 2,2′‐azo‐2,2′‐dimethyldiglutarate (4), bis[2‐(2‐furoyloxy)ethyl] 2,2′‐azodiisobutyrate (6), and N,N′‐difurfuryl‐2,2′‐azodiisobutyramide (9). The decay constants and the activation energies of the decomposition of the azo compounds were measured by thermogravimetric analysis. Radical polymerisations of styrene and some (meth)acrylates were performed under “dead‐end” conditions. The telechelic oligomers were characterized by GPC and NMR spectroscopy, proving a furanyl functionality of nearly two or four. The kinetics of Diels‐Alder reactions between the telechelics and the dienophils maleic anhydride and dimethyl maleate were measured under pseudo‐first order conditions. Addition of the telechelics to an unsaturated polyester prepared from maleic anhydride and diols led to a solid material with network structure.