Title

Spectroscopic characterization of PET glycolysis and surface molecular orientation of polymers

Date of Completion

January 2000

Keywords

Chemistry, Polymer|Engineering, Materials Science

Degree

Ph.D.

Abstract

This dissertation seeks to develop novel polymer characterization techniques using UV and fluorescence spectroscopy. The first portion of the dissertation consists of monitoring the glycolytic depolymerization of poly(ethylene terephthalate), PET, using UV and fluorescence spectroscopy. The primary product of the glycolysis of PET is bis(hydroxyethyl) tereplithalate (BHET), along with other low molecular weight oligomers (degree of polymerization = 1–3). The UV absorption of the glycolized products occurs at 287 nm and is associated with the π → π* transition of the tereplithalate moiety. This absorption band shows a linear increase with reaction time that corresponds to an increase in the concentration of glycolized products. BHET was selected as a model compound to represent the glycolized products and was used to calculate the concentration of glycolized products. When using excitation wavelengths of 300 nm and 340 nm, fluorescence emission spectra of the glycolized products were observed at 350 nm and 380 nm respectively. These emission bands also showed an increase in intensity corresponding to the concentration increase. Again, BHET was used as a model compound to simulate and calculate the concentration of the glycolized products. We determined the overall reaction to be second order and that the reaction rate is strongly dependent on the glycol concentration; an increase in the glycol concentration results in an increase in the reaction rate. ^ The second portion of this dissertation consists of the characterization of surface molecular orientation of poly(ethylene terephthalate) (PET) and Kaptono films by UV reflection dichroism using a specular reflection accessory and a bifurcated fiber optic. The UV reflection peaks for PET and Kapton ® occur at 257 nm and 310 nm respectively. The orientation function and dichroic ratio calculated using both specular reflection and the fiber optic agreed well with each other. Additionally, correct placement of the polarizer is essential in producing good results. When placed at either the source or detector side of the fiber, there was no evidence of orientation seen. However, placement at the common end shows good agreement with the results from the specular reflection accessory. These different results are a manifestation of the polarization/depolarization characteristics of the fiber optic. ^