Mechanical Properties of Homogeneous Polymer Networks Prepared by Star Polymer Synthesis Methods

To investigate the effect of the network structure on the mechanical properties of a polymer network formed from a certain polymer, we should prepare polymer networks with clearly different network structures made of the same polymer and compare the mechanical properties of these polymer networks. If a living radical polymerization method is applied to the same monomer constituting the polymer network with a nonuniform network structure obtained by conventional free-radical polymerization, it is possible to obtain a polymer network with a uniform network structure in which the molecular weights of the polymer chains bonded to the cross-linking points are uniform and the number of chains bonded to the cross-linking points is constant. In this study, we worked on the synthesis of a polymer network with a uniform network structure by combining two different types of star-shaped polymer synthesis methods using living radical polymerization, i.e., the core-first method and the linking method. In the core-first method, it was possible to synthesize a star-shaped polymer with a narrow molecular weight distribution in a state with a molecular weight corresponding to the charging ratio of the initiator with four initial groups and the monomer. We confirmed that the polymer network obtained by binding the star-shaped polymers by the linking method had a uniform structure, even when swollen with a good solvent or dried, from small-angle X-ray scattering. Depending on the molecular weight of the star-shaped polymer obtained by the core-first method and the amount of the cross-linking agent added for the linking method, the mesh size of the network could be changed while having a uniform network structure. The dried polymer network with uniform network structures exhibited significantly higher values of fracture extensibility and energy than those with nonuniform network structures via conventional free-radical polymerization, when compared at the same monomer and cross-linker concentration.