{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/100423"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/100423","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Towards next-generation degradable polymers via double 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.","abstract_html":"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.","abstract_has_math":false,"creators":["Wright, Justin David"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Zimmerman, Steven C."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018-08-14T21:37:15Z","date_published":"2018-08-14T21:37:15Z","updated_at":"2026-07-22T22:24:38Z","subjects":["Chemical Amplification Photoacid Generators Acid Amplifiers Dual Amplification"],"languages":["en"],"rights":["Copyright 2015 Justin D. Wright"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/100423","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Zimmerman, Steven C."]},{"key":"dc:creator","label":"Author","values":["Wright, Justin David"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2018-08-14T21:37:15Z","2020-08-15T09:15:27Z","2015-04-29","2015-05"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemical Amplification Photoacid Generators Acid Amplifiers Dual Amplification"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2015 Justin D. Wright"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/100423"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["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.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2017-05-01","The student, Justin Wright, accepted the attached license on 2015-04-28 at 12:38.","The student, Justin Wright, submitted this Thesis for approval on 2015-04-28 at 12:44.","This Thesis was approved for publication on 2015-04-29 at 13:52.","DSpace SAF Submission Ingestion Package generated from Vireo submission #8157 on 2018-08-14 at 15:59:42","Made available in DSpace on 2018-08-14T21:37:15Z (GMT). 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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.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2017-05-01","The student, Justin Wright, accepted the attached license on 2015-04-28 at 12:38.","The student, Justin Wright, submitted this Thesis for approval on 2015-04-28 at 12:44.","This Thesis was approved for publication on 2015-04-29 at 13:52.","DSpace SAF Submission Ingestion Package generated from Vireo submission #8157 on 2018-08-14 at 15:59:42","Made available in DSpace on 2018-08-14T21:37:15Z (GMT). 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