Towards next-generation degradable polymers via double amplification

A refinement of the existing synthetic methods in the literature was developed in order to synthesize tris(aminomethyl)ethanes from pentaerythritol. The result was a scalable, azide free route that produced tris(aminomethyl)ethanol as the trihydochloride salt in high yield. In addition to this approach, a novel route was explored beginning from hexamine to synthesize tris(aminomethyl)methanes. When attempting to produce the trisamine from a (1,3,5)-triazaadamantane or a (1,3,5)-triazabicyclo- [3.3.1]nonane, retro-Mannich reactions were found to occur if a nitro group remained from earlier synthetic steps. Removal of this nitro group via reduction is expected to allow for the synthesis of tris(aminomethyl)methanes to occur as predicted. The concept of double amplification was explored in the context of developing novel triggered release systems with very rapid responses. The system explored in this work was designed to trigger in response to sunlight, using long-wave UV-sensitive photoacid generators as initiators, and acid amplifiers as the bulk phase. Small-molecule and polymeric acid amplifiers were designed, based on the known acid amplifier structures in the literature. It was found that three of the acid amplifiers decomposed rapidly upon initiation by elevated temperature. The decomposition products were characterized and support a decomposition-polymerization mechanism. In addition, a thermally reversible epoxy was designed based on preliminary results showing that electron rich 2,4,6-triaryl-(1,3,5)triazaadamantanes underwent thermal decomposition in water. When a triveratryl-substituted analog was heated in the presence of bisphenol-A-diglycidyl ether, no curing was observed. When the curing was conducted at room temperature, curing was observed, and it was found that it reversed at elevated temperatures.

Name thesis:degree_name

M.S.

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2018

Author dc:creator

• Wright, Justin David

Contributors dc:contributor

• Zimmerman, Steven C.

• Chemical Amplification Photoacid Generators Acid Amplifiers Dual Amplification

Statement dc:rights

• Copyright 2015 Justin D. Wright

Language dc:language

en

Handle dc:identifier

http://hdl.handle.net/2142/100423

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/100423