[Show abstract][Hide abstract] ABSTRACT: Dimethacrylate matrix resins and composites are becoming increasingly important in structural and coating components in the development of civil infrastructure. Service lives in excess of 50 years in outdoor environments are desirable for these materials. Aliphatic matrix resins derived from cycloaliphatic epoxies and dicarboxylic acids are under investigation as a means of obtaining coatings and fiber reinforced composites with such extreme durability to sunlight. The cycloaliphatic backbone shows reduced ultraviolet adsorption relative to bisphenol-A/epichlorohydrin resins. A series of new dimethacrylate resins and networks were prepared with 800 and 1200 g/mol oligomers and different concentrations of methyl methacrylate as the reactive diluent. Their thermal and mechanical properties have been compared to the bisphenol-A/epichlorohydrin-based dimethacrylate resins, which have either styrene or methyl methacrylate as the reactive diluent. The molecular weight between crosslinks was controlled by both the oligomer molecular weight as well as the amount of the reactive diluent to tailor network properties. The aliphatic networks exhibit glass transition temperatures ranging from ≈93–115°C with the higher Tgs associated with lower molecular weight oligomers and higher network densities. The aliphatic networks, in general, also have lower fracture toughness and higher hardness values as compared to networks prepared from bisphenol-A/epichlorohydrin oligomers. The fracture toughness, K1C, increases with the percentage of methacrylate diluent due to the increase in the molecular weight between crosslinks. However, networks cured with styrene as the reactive diluent show the reverse trend in fracture toughness.
[Show abstract][Hide abstract] ABSTRACT: One of the major classes of polymer matrix resins under consideration for structural composite applications in the infrastructure and construction industries is theso-called "vinyl esters." These are comprised of low molecular weight poly (hydroxyether) oligomers with methacrylate endgroups diluted with styrene monomer. The methacrylate oligomeric endgroups co-cure with the styrene in free radical copolymerization to yield thermoset networks. Selected properties of such resins and resultant networks where the molecular weights of the poly(hydroxyether) oligomers have been varied from 700 to 1200 g/mole and the concentration of styrene has been systematically changed are presented. In general, both the glass transition temperatures and fracture toughness of the fully cured networks increased as the styrene was decreased in each oligomer series with different molecular weights. As expected, the volume contraction upon cure also decreased significantly as styrene was decreased, and thus residual cure stresses may be reduced in fiber reinforced composites. The resistance to crack propagation was significantly improved for networks prepared with the 1200 Mn dimethacrylate oligomer relative to those from the 700 g/mole material. Crosslink densities were estimated from measurements of the rubbery moduli at Tg + 40°C and relationships between network density, chemical composition and properties are discussed.