Solid-Phase Radical Polymerization of Halogen-Bond-Based Crystals and Applications to Pre-Shaped Polymer Materials.

Liquid vinyl monomers were converted into solid crystals via halogen bonding. They underwent solid-phase radical polymerizations through heating at 40 °C or ultraviolet photo-irradiation (365 nm). The X-ray crystallography analysis showed the high degree of monomer alignment in the crystals. The polymerizations of the solid monomer crystals yielded polymers with high molecular weights and relatively low dispersities because of the high degree of the monomer alignment in the crystal. As a unique application of this system, the crystalized monomers were assembled to pre-determined structures, followed by solid-phase polymerization, to obtain a two-layer polymer sheet and a three-dimensional house-shaped polymer material. The two-layer sheet contained a unique asymmetric pore structure and exhibited a solvent-responsive shape memory property and may find applications to asymmetric membranes and polymer actuators.