Thermomechanical properties of neat phosphine‐catalyzed thiol‐Michael networks fabricated in a controlled manner are reported, and a comparison between thiol‐acrylate and thiol‐vinyl sulfone step‐growth networks is performed. When highly reactive vinyl sulfone monomers are used as Michael acceptors, glassy polymer networks are obtained with glass transition temperatures ranging from 30 to 80 °C. Also, the effect of side‐chain functionality on the mechanical properties of thiol‐vinyl sulfone networks is investigated. It is found that the inclusion of thiourethane functionalities, aryl structures, and most importantly the elimination of interchain ester linkages in the networks significantly elevate the network's glass transition temperature as compared with neat ester‐based thiol‐Michael networks.
