Synthesis And Property Of Free-radical Cationic Hybrid Photo-Polymerization Monomer

Hybrid photo-polymerization means that the mechanism and method in which reactive groups having two or more different polymerization mechanisms simultaneously participated in curing reaction in the same system,and both are photo-polymerization processes,and may form a variety of polymer networks.Using hybrid photo-polymerization systems could make up for weakness and give full play to the advantages of free-radical and cationic photo-polymerization systems.In this paper,using common cyclic anhydrides as linking groups,and 3-ethyl-3-((oxiran-2-ylmethoxy)methyl)oxetane(DOX-107),(3-ethyloxetan-3-yl)methanol(TMPO),hydroxyethyl acrylate(HEA)glycidyl methacrylate(GMA),to provide oxetane groups and(meth)acrylate double bonds for hybrid photo-polymerization monomers,respectively.Hydroxyl groups are reacted with acid anhydride groups to produce carboxyl groups.Then,the carboxyl groups are esterified with epoxy groups to finally synthesis a series of free radical-cationic hybrid photo-polymerization monomers which have both(meth)acrylate double bonds and oxetane groups.Through real-time infrared spectroscopy(RT-IR),dynamic thermo-mechanical analysis(DMA),thermogravimetric analysis(TGA)and other methods,the monomers have been characterized in various aspects such as curing properties,mechanical properties,and thermal properties,and compares the characteristic of hybrid photo-polymerization monomers with mixed photo-polymerization systems.The results indicated that hybrid photo-polymerization monomers have excellent curing,thermal and mechanical properties,and hybrid photo-polymerization monomers are superior to mixed photo-polymerization systems in all aspects.Among the monomers synthesized herein,1-(2-(acryloyloxy)ethyl)2-(3-((3-ethyloxetan-3-yl)methoxy)-2-hydroxypropyl)cyclohexane-1,2-dicarboxy late(HHD),which uses hexahydrophthalic anhydride as a linking group,has the best overall performance.