Eric W. Cochran

Gel Point Suppression in RAFT Polymerization of Pure Acrylic Cross-Linker Derived from Soybean Oil

Here we report the reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylated epoxidized soybean oil (AESO), a cross-linker molecule, to high conversion (>50%) and molecular weight (>100 kDa) without macrogelation. Surprisingly, gelation is suppressed in this system far beyond the expectations predicated both on Flory-Stockmeyer theory and multiple other studies of RAFT polymerization featuring cross-linking moieties. By varying AESO and initiator concentrations, we show how intra- versus intermolecular cross-linking compete, yielding a trade-off between the degree of intramolecular linkages and conversion at gel point. We measured polymer chain characteristics, including molecular weight, chain dimensions, polydispersity, and intrinsic viscosity, using multidetector gel permeation chromatography and NMR to track polymerization kinetics. We show that not only the time and conversion at macrogelation, but also the chain architecture, is largely affected by these reaction conditions. At maximal AESO concentration, the gel point approaches that predicted by the Flory-Stockmeyer theory, and increases in an exponential fashion as the AESO concentration decreases. In the most dilute solutions, macrogelation cannot be detected throughout the entire reaction. Instead, cyclization/intramolecular cross-linking reactions dominate, leading to microgelation. This work is important, especially in that it demonstrates that thermoplastic rubbers could be produced based on multifunctional renewable feedstocks.

Low Temperature Performance of Bio-Derived/Chemical Additives in Warm Mix Asphalt

Corn and soy based bio-derived warm mix asphalt (WMA) additives are currently being developed. In the past, additives with similar properties have been shown to successfully reduce the mixing and compaction temperatures of asphalt by as much as 30°C. Isosorbide distillation bottoms (IDB), a WMA additive, is a co-product from the conversion of sorbitol to isosorbide, where sorbitol is derived by hydrogenating glucose from corn biomass. Past research utilizing IDB at several dosage rates showed there was improvement in low temperature binder performance using the bending beam rheometer (BBR) between dosage rates of 0.5% and 1.0% by weight of the binder. This research investigates whether low temperature improvement occurs with several new bio-derived material additives that have similar properties to materials used in past research, as well as compares their performance to two commercially available/bio-derived WMA additives from the forest products industry. In cold regions of the United States, the main observed distress in asphalt pavements is low temperature cracking. Characterization of binder performance at low temperature is possible with the use of the BBR. For asphalt mixtures, characterization is more challenging at low temperatures due to the response from the aggregate phase of a mixture. To examine low temperature performance of hot mix asphalt (HMA) and WMA, the semi-circular bend (SCB) test was used to characterize the fracture properties. SCB tests showed that additive choice was a statistically significant factor in fracture energy properties but not for stiffness and fracture toughness. All of the new additives were successfully used at reduced mixing and compaction temperatures and did not adversely impact low temperature mix fracture properties of WMA when compared against the control HMA. However, improvement of fracture energy was observed when comparing the epoxidized esterified fatty acid additive to the other five additives used in this work.