Doctoral Dissertations

Date of Award

12-2014

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Jimmy W. Mays

Committee Members

Sheng Dai, Alexei P. Sokolov, Gajanan S. Bhat

Abstract

Ureidopyrimidone (UPy) is a well-known self-complementary quadruple hydrogen bonding unit, extensively applied in the preparation of supramolecular polymers with enhanced physical properties. The property enhancement is assigned partly to linear chain extension and fibrillar nanophase separation due to secondary hydrogen bonding by urethane and urea linker, though a clear distinctive structure property relationship has not be reported. In this work, two distinct sets of UPy functional polymers, a series of monochelic polybutadienes (PBd) and telechelic polybutadienes, were synthesized and analyzed by solution and bulk characterization techniques to probe the role of polymer chain mobility and polarity on the UPy chain-end association.

ω [omega]-UPy terminated polybutadiene was semi-solid waxy material, indicating association beyond dimers. Solution studies indicate the presence of star-like micelles that are in equilibrium with dimers. These aggregated micellar clusters have distinct endothermic transitions in differential scanning calorimetry (DSC). Atomic force microscopy (AFM) studies show an evidence of micellar-clusters forming associated parallel line-like structures on a mica surface with the well-defined order.

A series of α [alpha], ω [omega]-di-UPy terminated polybutadienes and hydrogenated polybutadienes were synthesized, and their properties was evaluated as a function of 1,2-vinyl content. Telechelic UPy-PBd differs strongly in their physical properties, PBd with low Tg [glass transition temperature] (-90 °C) forms semi-solid and brittle material, whereas PBd with moderate Tg (-45 °C) gave strong thermoplastic elastomer. AFM images give parallel association of micellar clusters. Dynamics of micellar-cluster associated UPy domains with unassociated chain extended dimers lead to gelation at specific temperature depending on the characteristics of the linker precursor oligomers. Supramolecular gel transition temperature (Tsg) was identified in rheological studies on various UPy telechelics. In addition, polystyrene and poly(n-butylacrylate) UPy telechelics were also prepared by copper (I) catalyzed alkyne azide coupling (CuAAC) “click” reaction. The triazole linker in these polymers interferes with the UPy association and reduces the size of the hydrogen bonded UPy aggregates, which was found to improve the physical property of the supramolecular polymers. An attempt was made to examine the role of polymer chain mobility and its polarity was used to correlate structure and property with reference to room temperature.

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