{"id":{"repo_id":"buffalo","oai_identifier":"oai:ubir.buffalo.edu:10477/80528"},"canonical_url":"https://search.dev.ndltd.org/etd/buffalo/oai:ubir.buffalo.edu:10477/80528","repository":{"repo_id":"buffalo","name":"Buffalo","base_url":"https://ubir.buffalo.edu/oai/request"},"display":{"title":"Polyimide-Containing Molecular Bottlebrushes: Synthesis and Self-Assembly","abstract":"Ph.D.","abstract_html":"Ph.D.","abstract_has_math":false,"creators":["Swanson, Benjamin; 0000-0003-0487-1252"],"institution":"State University of New York at Buffalo","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Rzayev, Javid","Chemistry"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-10-25T15:53:21Z","date_published":"2019-10-25T15:53:21Z","updated_at":"2026-07-27T19:05:23Z","subjects":["polymer chemistry"],"languages":["eng"],"rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10477/80528","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rzayev, Javid","Chemistry"]},{"key":"dc:creator","label":"Author","values":["Swanson, Benjamin; 0000-0003-0487-1252"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2019-10-25T15:53:21Z","2019","2019-08-08 10:26:38"]},{"key":"dc:publisher","label":"Institution","values":["State University of New York at Buffalo"]},{"key":"dc:type","label":"Dc Type","values":["Text","Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["polymer chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/10477/80528"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Ph.D.","A novel poly(amic ester) (PAE) was synthesized via the step-growth polycondensation of an AB-type monomer using a system triphenyl phosphine (PPh3), hexachloroethane, and pyridine as a condensing agent. The AB-type monomer provided good stoichiometric and the end group control necessary for the synthesis of higher order polymeric structures that cannot be achieved through traditional AA-BB step-growth polymerizations. The PAE could be readily converted to a polyimide (PI) structure by thermal treatment and the conversion was monitored by thermogravimetric analysis (TGA) as well as Fourier-transformed infrared (FTIR) spectroscopy. To synthesize the PAE macromonomer, a norbornene carboxylic acid was installed immediately after the polycondensation to provide an end group amenable to ring-opening metathesis polymerization (ROMP). PAE molecular brushes were produced via a ‘grafting through’ strategy at low concentrations ([macromonomer] = 5 mM) and a catalyst to macromonomer ratio of 1:25. Full conversion of macromonomer to brush polymer was confirmed using 1H NMR and DMF-Size Exclusion Chromatography (SEC) analysis.Statistical PAE bottlebrush copolymers were synthesized with polystyrene (PS), poly(ethylene oxide) (PEO), and polylactide (PLA) macromonomers, and analyzed using 1H NMR, DMF-SEC, TGA, and small-angle x-ray scattering (SAXS) techniques. While each copolymer was successfully incorporated into a statistical brush containing PAE, SAXS results indicated that only PAE-PS and PAE-PEO statistical copolymers demonstrated phase separation. PAE-PS samples were thermally treated to degrade PS, but this failed to produce a porous structure. Porous structures were produced from a PAE-PS diblock molecular brush wherein the PS block was removed by the thermal degradation of the triazole linker between the PS side chains and backbone and subsequent immersion into dichloromethane (DCM) to allow for diffusion of polymer chains. PAE-PEO diblock bottlebrush structures also produced porous structures after thermal degradation of PEO. Porosity and surface area of both materials were confirmed by scanning electron microscopy (SEM) and nitrogen adsorption measurements. Core-shell molecular brushes featuring a PAE core and solubilizing PEO shell were synthesized to investigate reported end-to-end aggregation of bottlebrushes driven by intermolecular forces between the polymer cores. Initial attempts to generate the core-shell structure via ROMP of a PAE-PEO diblock macromonomer synthesized through copper-catalyzed azide alkyne cycloaddition (CuAAC) ‘click’ chemistry were unsuccessful due to unreacted alkyne preventing full conversion of macromonomer. The similar application of ‘click’ chemistry of an azide-functionalized PEO to an alkyne-functionalized PAE brush precursor yielded poorly defined structures that were difficult to characterize. The core-shell structure was successfully synthesized by the direct EDC coupling of amine-functionalized PEO to a PAE brush precursor. Imidization of the PAE core was carried out in DMF at 110 ºC and confirmed using 1H NMR and FTIR. SEC analysis could only be conducted following imidization due to an inability to prepare samples with an unimidized PAE core. Dynamic light scattering (DLS) confirmed that the particle size was reduced post imidization. Transmission electron microscopy (TEM) revealed discreet micellular structures in the sub-10 nm range. Finally, a unique chain-growth polymerization of AB-type monomers for the synthesis of aromatic polyamides (APAs) was explored as a method of producing APA macromonomers for molecular brush synthesis. APA macromonomers were synthesized from a norbornene-functionalized methyl ester initiator, but failed to produce well-defined bottlebrush structures. Studies conducted using a PEO-based macroinitiator indicated that the self-condensation of the AB-type monomer prevented controlled polymerization. A survey of polymerization conditions and model initiator molecules revealed that phenyl ester compounds would be required for successful initiation of a chain-growth polycondensation.","**To request an accessible version of the file(s) associated with this item, contact library@buffalo.edu. Please include the item's persistent URL [http://hdl.handle.net/. . .] in your request.**"]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Polyimide-Containing Molecular Bottlebrushes: Synthesis and Self-Assembly"]}]}],"canonical_facts":{"dc:contributor":["Rzayev, Javid","Chemistry"],"dc:creator":["Swanson, Benjamin; 0000-0003-0487-1252"],"dc:date":["2019-10-25T15:53:21Z","2019","2019-08-08 10:26:38"],"dc:description":["Ph.D.","A novel poly(amic ester) (PAE) was synthesized via the step-growth polycondensation of an AB-type monomer using a system triphenyl phosphine (PPh3), hexachloroethane, and pyridine as a condensing agent. The AB-type monomer provided good stoichiometric and the end group control necessary for the synthesis of higher order polymeric structures that cannot be achieved through traditional AA-BB step-growth polymerizations. The PAE could be readily converted to a polyimide (PI) structure by thermal treatment and the conversion was monitored by thermogravimetric analysis (TGA) as well as Fourier-transformed infrared (FTIR) spectroscopy. To synthesize the PAE macromonomer, a norbornene carboxylic acid was installed immediately after the polycondensation to provide an end group amenable to ring-opening metathesis polymerization (ROMP). PAE molecular brushes were produced via a ‘grafting through’ strategy at low concentrations ([macromonomer] = 5 mM) and a catalyst to macromonomer ratio of 1:25. Full conversion of macromonomer to brush polymer was confirmed using 1H NMR and DMF-Size Exclusion Chromatography (SEC) analysis.Statistical PAE bottlebrush copolymers were synthesized with polystyrene (PS), poly(ethylene oxide) (PEO), and polylactide (PLA) macromonomers, and analyzed using 1H NMR, DMF-SEC, TGA, and small-angle x-ray scattering (SAXS) techniques. While each copolymer was successfully incorporated into a statistical brush containing PAE, SAXS results indicated that only PAE-PS and PAE-PEO statistical copolymers demonstrated phase separation. PAE-PS samples were thermally treated to degrade PS, but this failed to produce a porous structure. Porous structures were produced from a PAE-PS diblock molecular brush wherein the PS block was removed by the thermal degradation of the triazole linker between the PS side chains and backbone and subsequent immersion into dichloromethane (DCM) to allow for diffusion of polymer chains. PAE-PEO diblock bottlebrush structures also produced porous structures after thermal degradation of PEO. Porosity and surface area of both materials were confirmed by scanning electron microscopy (SEM) and nitrogen adsorption measurements. Core-shell molecular brushes featuring a PAE core and solubilizing PEO shell were synthesized to investigate reported end-to-end aggregation of bottlebrushes driven by intermolecular forces between the polymer cores. Initial attempts to generate the core-shell structure via ROMP of a PAE-PEO diblock macromonomer synthesized through copper-catalyzed azide alkyne cycloaddition (CuAAC) ‘click’ chemistry were unsuccessful due to unreacted alkyne preventing full conversion of macromonomer. The similar application of ‘click’ chemistry of an azide-functionalized PEO to an alkyne-functionalized PAE brush precursor yielded poorly defined structures that were difficult to characterize. The core-shell structure was successfully synthesized by the direct EDC coupling of amine-functionalized PEO to a PAE brush precursor. Imidization of the PAE core was carried out in DMF at 110 ºC and confirmed using 1H NMR and FTIR. SEC analysis could only be conducted following imidization due to an inability to prepare samples with an unimidized PAE core. Dynamic light scattering (DLS) confirmed that the particle size was reduced post imidization. Transmission electron microscopy (TEM) revealed discreet micellular structures in the sub-10 nm range. Finally, a unique chain-growth polymerization of AB-type monomers for the synthesis of aromatic polyamides (APAs) was explored as a method of producing APA macromonomers for molecular brush synthesis. APA macromonomers were synthesized from a norbornene-functionalized methyl ester initiator, but failed to produce well-defined bottlebrush structures. Studies conducted using a PEO-based macroinitiator indicated that the self-condensation of the AB-type monomer prevented controlled polymerization. A survey of polymerization conditions and model initiator molecules revealed that phenyl ester compounds would be required for successful initiation of a chain-growth polycondensation.","**To request an accessible version of the file(s) associated with this item, contact library@buffalo.edu. Please include the item's persistent URL [http://hdl.handle.net/. . .] in your request.**"],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/10477/80528"],"dc:language":["eng"],"dc:publisher":["State University of New York at Buffalo"],"dc:rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"dc:subject":["polymer chemistry"],"dc:title":["Polyimide-Containing Molecular Bottlebrushes: Synthesis and Self-Assembly"],"dc:type":["Text","Dissertation"]},"updated_at":"2026-07-27T19:05:23Z"}