Abstract: | This article describes the use of hyperbranched polyester oligomers (HBPs) as modifiers for epoxy thermosets. The effect of HBP molar mass, end group, and loading on prepolymer viscosity, thermoset fracture toughness, Tg, and high‐temperature dynamic storage modulus (E′) were measured. The HBP molar mass was systematically increased from nominal values of ∼ 1750 g mol (Generation 2, or G2) up to ∼ 14,000 g mol (Generation 5, or G5), which corresponds from a low of two layers of monomer up to a maximum of five layers of monomer around the central core. Toughness increased only modestly with the molar mass of the HBP. At 7% loading in the epoxy thermoset, the G5 HBP increased toughness by ∼ 60% over the untoughened control. Toughness increased to 82% above the untoughened control at a loading of 19% G5 HBP, but the toughness decreased at 28% HBP loading. The Tg and E′ were influenced by the HBP modifier, but the effect was not systematic and may have been due to competing effects of HBP molar mass and end group. The effect of the architecture of the thermoplastic modifier was investigated by introducing a linear aliphatic polyester (∼ 5400 g mol) with a repeat unit structure, which was similar to that of the HBP. At the molecular weight range investigated, neither the prepolymer viscosity nor the thermoset toughness of the HBP–epoxy was significantly different from that of the linear polyester in epoxy. Preliminary results are presented showing the effect of thermoplastic molecular weight and architecture on morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 151–163, 1999 |