Reversible Diels-Alder (DA) type networks were prepared from furan and maleimide monomers of different structure and functionality. The factors controlling the dynamic network formation and their properties were discussed. Evolution of structure during both dynamic nonequilibrium and isothermal equilibrium network formation/breaking was followed by monitoring the modulus and conversion of the monomer. The gelation, postgel growth, and properties of the thermoreversible networks from tetrafunctional furan (F4) and different bismaleimides (M2) were controlled by the structure of the maleimide monomer. The substitution of maleimides with alkyl (hexamethylene bismaleimide), aromatic (diphenyl bismaleimide), and polyether substituents affects differently the kinetics and thermodynamics of the thermoreversible DA reaction, and thereby the formation of dynamic networks. The gel-point temperature was tuned in the range Tgel = 97-122 °C in the networks of the same functionality (F4-M2) with different maleimide structure. Theory of branching processes was used to predict the structure development during formation of the dynamic networks and the reasonable agreement with the experiment was achieved. The experimentally inaccessible information on the sol fraction in the reversible network was received by applying the theory. Based on the acquired results, the proper structure of a self-healing network was designed.
Keywords: Diels–Alder reaction; Network formation; Reversible covalent network; Self-healing of networks.