Date of Award

1-1-2013

Document Type

Open Access Dissertation

Department

Chemistry and Biochemistry

Sub-Department

Chemistry

First Advisor

Ken D Shimizu

Abstract

Programmable polymer is a type of stimuli-responsive polymer which can keep their induced properties after removal of the stimulu, as well as programmable polymers maintain the general properties as stimuli-responsive polymers, such as recognize and respond to the stimulus. The previous reported solvent Caryl-Nimide bonds based programmable polymers (SPP-1) can freely rotate and change the carboxylic acid recognition group orientation in response to templates. Solvent templates were used in the SPP-1. One potential application for SPPs is using their recognition and memory properties for the identification and separation of mixture solutions of various analytes. In my first project, I wanted to develop a series of new SPPs with improved recognition and memory properties. There are several ways to optimize SPPs, such as changing the crosslinking degree, crosslinker length, crosslinker percentage, changing the recognition groups or modifying the ring opening metathesis polymerization (ROMP) catalyst to prepare the SPPs. Development of new SPPs through free radical polymerization (FRP) instead of ROMP were meaningful to obtain various programmable polymers with varying applications. To obtain an optimized programmable polymer with higher amount of recognition groups, the second generation SPP (SPP-2) was prepared by the third generation Grubbs catalysts (Grubbs III) instead of the second generation (Grubbs II). In conclusion, the SPP-2 showed similar recognition and memory properties with SPP-1, however, the wet-processed SPP showed higher recognition and lower memory capability than the wet-processed SPP.

The other aspect of optimization on programmable polymers is applying them on recognizing and remembering solute templates instead of solvents. In another word, we want to develop new programmable polymers in the separation of solute templates, especially for the chiral templates. The new amide programmable polymers were designed and the SPP-1 was used as blank groups. The recognition and memory properties of the new programmable polymers were measured and compared with the SPP-1. Also three solute templates (lactic acid, 2-hydroxy-3-pinanone and camphor) were found to make significant induced change on both amide and carboxylic acid programmable polymers.

Rights

© 2013, Yinyan He

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