The objective of research presented in this thesis is to elucidate the effect of polymer composition and structure on the photo-Fries rearrangement in polymers bearing aryl ester moieties. Towards this end, a systematic study wherein constraint, proximity, and dielectric constant were varied was carried out. This study was enabled by the synthesis of poly(phenylacrylate), poly(p-acetoxystyrene) and copolymers of phenylacrylate or p-acetoxystyrene with ethylacrylate, butylacrylate and 2- hydroxyethylmethacrylate. In addition, siloxane polymers with pendant aryl ester groups were also synthesized. Varying constraint by tethering aryl esters to the polymer backbone at the ester group, tethering aryl esters to the polymer backbone through the aryl group and varying the Tg of polymers had no effect on the rate of the photo-Fries rearrangement. The hydration state of hydrophilic copolymers had no effect on conversion but did increase formation of cage escape products and changed the ratio of products formed. Decreasing the proximity of aryl ester units relative to one another lead to increased ultimate conversion in the rearrangement. Altering from a carbon to siloxane polymer backbone may have had an effect on the initial rate of rearrangement but the effect could not be isolated from other variables (proximity and Tg). Refractive index changes ( n) which occurred as the polymers underwent rearrangement were also evaluated. Refractive index changes between 0.01 and 0.07 were observed, with the n being controlled in a dose dependent manner. Findings discussed here may be significant in the development of holographic imaging systems, optical data storage devices, waveguides and intra-ocular lens implants where materials capable of significant refractive index modulation are desirable.
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School of Chemistry and Materials Science (COS)
Labenski, Glen David, "The effect of polymer composition and structure on the photo-Fries rearrangement" (2008). Thesis. Rochester Institute of Technology. Accessed from
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