The Use Of Amido- And Imido-Functionalized Alpha Hydroxy Acids In The Creation Of Biodegradable Polyesters: An Exploration Of Va

The purpose of this thesis was to synthesize biodegradable polyesters from a wide array of functionalized ¿-hydroxy acids. The initial strategy was to use amido-functionalized ¿-hydroxy acids and 2-bromopropanoyl bromide to form amido-functionalized cyclic diesters. Then, the resulting cyclic diesters would be used in ring opening polymerization to create biodegradable polyesters. However, the spontaneous rapid degradation of the secondary amido-functionalized cyclic diester structure, as seen with 2-benzamido-hydroxyacetic acid, limited ring formation to tertiary amido-functionalized ¿-hydroxy acids. Also, the hydrophilic nature of most ¿-hydroxy acids allowed water into the crystal structure of the ¿-hydroxy acid. Then, when the ¿-hydroxy acid was used in ring forming reactions, the associated water deactivated reactive reagents and limited cyclic diester synthesis. These issues led to the synthesis of hydrophobic and tertiary amido- and imido-functionalized ¿-hydroxy acids, 2-phthalimido-2-hydroxyacetic acid and 2-(1-oxoisoindolin-2-yl) hydroxyacetic acid. The new ¿-hydroxy acids were used in two new polymerization techniques, melt polycondensation and solution polymerization, instead of ring open polymerization. Melt polycondensation and solution polymerization had shown previous success in forming oligomers of amido-functionalized ¿-hydroxy acids. Melt polycondensation was conducted by heating the monomer past its melting temperature under reduced pressure. The uncatalyzed melt polycondensation of 2-(1-oxoisoindolin-2-yl) hydroxyacetic acid created polyesters (¿ 960 g/mol). The scandium(III) trifluoromethanesulfonate enhanced melt polycondensation polymerization created slightly larger oligomers (¿ 1340 g/mol). However, 2-phthalimido-2-hydroxyacetic acid was not compatible with melt polycondensation because thermal degradation occurred. Thus, solution polymerization was conducted via Steglich esterification. Only oligomeric functionalized polyesters were formed (¿ 1060 g/mol). Future work should focus on optimization of the catalyst and the reaction conditions to obtain higher molecular weight polyesters. Also, 2-(1-oxoisoindolin-2-yl) hydroxyacetic acid should be utilized in the cyclic diester synthesis technique.

Transport of Hydraulic Fracturing Water and Wastes in the Susquehanna River Basin, Pennsylvania

The development of the Marcellus Shale gas play in Pennsylvania and the northeastern United States has resulted in significant amounts of water and wastes transported by truck over roadways. This study used geographic information systems (GIS) to quantify truck travel distances via both the preferred routes (minimum distance while also favoring higher-order roads) as well as, where available, the likely actual distances for freshwater and waste transport between pertinent locations (e. g., gas wells, treatment facilities, freshwater sources). Results show that truck travel distances in the Susquehanna River Basin are greater than those used in prior life-cycle assessments of tight shale gas. When compared to likely actual transport distances, if policies were instituted to constrain truck travel to the closest destination and higher-order roads, transport mileage reductions of 40-80% could be realized. Using reasonable assumptions of current practices, greenhouse gas (GHG) emissions associated with water and waste hauling were calculated to be 70-157 MT CO2 eq per gas well. Furthermore, empty so-called backhaul trips, such as to freshwater withdrawal sites or returning from deep well injection sites, were found to increase emissions by an additional 30%, underscoring the importance of including return trips in the analysis. The results should inform future life-cycle assessments of tight shale gases in managed watersheds and help local and regional governments plan for impacts of transportation on local infrastructure. (C) 2013 American Society of Civil Engineers.