Date of Award
Doctor of Philosophy
Mark D. Dadmun
Jimmy W. Mays, Charles S. Feigerle, Kevin M. Kit
Copolymers are used to increase the interfacial strength of immiscible components and suppress recombination of the minor phase by steric hindrance. The experiments conducted in these studies are designed to investigate in situ polymer loop formation at soft interfaces and functionalized nanotube surfaces. Block copolymers are the most effective type of copolymer for compatibilization because they extend perpendicular to the interface, allowing good entanglement with the homopolymer chains. Multiblock copolymers are more effective than diblock copolymers for strengthening the interface because they can cross the interface multiple times, forming “loops” in each phase that provide entanglement points for the homopolymer.
The first part of this dissertation focuses on understanding how telechelic variables influence their effectiveness to compatibilize an immiscible polystyrene (PS)/polyisoprene (PI) homopolymer blend. A fast reacting anhydride and amine telechelic pair (Anh-PS-Anh/NH2-PI-NH2) are compared with a slower reacting epoxy and carboxylic acid pair (Epoxy-PS-Epoxy/COOH-PI-COOH). Different molecular weight pairs are used to investigate the influence of end group concentrations and steric effects. We also investigate how the loading level affects the conversion of one telechelic pair. The PI telechelic has a fluorescent tag, which enables gel permeation chromatography (GPC) with fluorescence detection to be used for determining the amount of tagged PI converted and the molecular weight of the copolymer formed in situ as a function of mixing time. The effectiveness of these telechelic pairs as compatibilizers is quantified by annealing the samples and using scanning electron microscopy (SEM) to measure the domain size of the minor phase as a function of annealing time.
The second part of this study investigates the grafting of polymer loops to carboxylated multiwall nanotube (COOH-MWNT) surfaces and determining the reaction rate. These polymer loops will improve the nanotube dispersion by steric hindrance and improve energy transfer by creation of polymer chain entanglements. Fourier transform infrared spectroscopy (FT-IR) is used as a novel technique to measure the quantity of Epoxy-PS-Epoxy grafted to the nanotube surface. In addition, we determined the fraction of telechelics that form loops by further reacting the grafted nanotubes with monocarboxy terminated poly(4-methylstryrene) (COOH-P4MS), which only reacts with unbound Epoxy-PS-Epoxy chain ends.
Ashcraft, Earl, "Polymeric Loop Formation at Hard and Soft Interfaces. " PhD diss., University of Tennessee, 2010.