Synthesis and characterization of m-aminophenoxide functionalized poly(tetramethylene oxide)

The primary research objective of this thesis was to functionalize bifunctional cationic living poly(tetramethylene oxide) (PTMO) with m-aminophenoxide to produce aromatic amine telechelic PTMO of controlled molecular weight and narrow molecular weight distribution. TrifHc anhydride was used to initiate a bifunctional cationic living polymerization of tetrahydrofuran (THP). An anhydrous solution of m-aminophenoxide was used to terminate the polymerization, which resulted in aromatic amine telechelic PTMO of controlled molecular weight. The order of addition of the m-aminophenoxide to the living PTMO was found to be crucial. In order to produce linear aromatic amine telechelic PTMO, the living PTMO must be charged to the m-aminophenoxide solution.

The aromatic amine telechelic PTMO was characterized using IR spectroscopy, 1 H NMR spectroscopy, HBr titration and 19p NMR spectroscopy. Trifluoroacetic anhydride was reacted with the m-aminophenoxide terminated PTMO to serve as a fluorine tag, then analyzed using 19p NMR spectroscopy to dquantify the amount of hydroxy end groups present (if any) relative to primary amine end groups. In order to compare 19p NMR spectra, the model compounds m-phenetidine (Model NH2) and 3-dimethylaminophenol (Model OH) were also reacted with trifluoroacetic anhydride and analyzed using 19p NMR spectroscopy.

The 'aromatic amine telechelic PTMO may be further reacted in a step growth polymerization to form segmented block copolymers. PTMO segments show promise serving as flexible low T g blocks between reinforcing high T g blocks such as polyamides, polyurea copolymers and epoxies, and may act to toughen these types of materials.