Microgel-like network polymer precursor formation in free-radical cross-linking multiallyl polymerization

The present study is an extension of our preceding work on gelation behavior. We observed no substantial difference in the actual gel points among three isomeric diallyl phthalates: diallyl phthalate, diallyl isophthalate and diallyl terephthalate. The resulting network polymer precursors (NPPs) were characterized by size-exclusion chromatography with both multiangle laser light scattering and viscometry. It is of note that the structure of NPP, consisting of oligomeric primary polymer chains, becomes core-shell type dendritic or nanogel-like with the progress of polymerization. The nanogel-like NPPs can then collide with one another to form cross-links, eventually leading to gelation. Although the concentration of NPP should be high at the conversion close to the gel point, the dilution of NPP by adding monomer could prevent the cross-link formation among NPPs, and consequently lead to the successive growth of high-molecular-weight NPP from a nanogel to a microgel. The further growth of the microgel as an inhomogeneous NPP with high cross-link density could eventually reach an extremely inhomogeneous network polymer. These processes were pursued as typical examples using the bulk polymerization of DAT.