Multi-methacrylated star-shaped, photocurable poly(methyl methacrylate) macromonomers via quasiliving ATRP with suppressed curing shrinkage

Novel, star-shaped multifunctional poly(methyl methacrylate) (PMMA) macromonomers with well-defined average number of pendant methacrylate groups were synthesized by copolymerizing MMA with 2-hydroxyethyl methacrylate (HEMA) via quasiliving ATRP with a tetrafunctional initiator in methanol at 10 °C, followed by methacrylation of the hydroxyl groups of the HEMA units. The resulting tailor-made poly(methyl methacrylate-co-2-methacryloylethyl methacrylate), P(MMA-co-MEMA), multifunctional macromonomers were used as cross-linking agents in photocuring of MMA, a solvent for its own polymer, and thus chemically homogeneous PMMA networks were formed in which the tetrafunctional initiator moiety provides inherent, additional branching points in the resulting cross-linked materials. This approach, even in the presence of relatively low amounts of macromonomers of ∼35-45%, provides sol-free products and up to ∼40% less polymerization shrinkage than that by curing of MMA with a conventional low molecular weight bifunctional methacrylate. These new, unique star-shaped PMMA macromonomers are potential cross-linkers in a variety of solvent-free applications where low curing shrinkage and high conversions are critical requirements, such as in several engineering materials, coatings, dental fillings and restorations, bone cements etc.