Towards next-generation degradable polymers via double amplification

Wright, Justin David

Permalink

https://hdl.handle.net/2142/100423 Copy

Description

Title

Towards next-generation degradable polymers via double amplification

Author(s)

Wright, Justin David

Issue Date

2015-04-29

Director of Research (if dissertation) or Advisor (if thesis)

Zimmerman, Steven C.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

M.S.

Degree Level

Thesis

Keyword(s)

Chemical Amplification Photoacid Generators Acid Amplifiers Dual Amplification

Abstract

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.

Graduation Semester

2015-05

Type of Resource

text

Permalink

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

Copyright and License Information

Copyright 2015 Justin D. Wright

Owning Collections