Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos
Ano de defesa: | 2016 |
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Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4278 |
Resumo: | The present work describes a methodology of controlled synthesis of block copolymers by one-pot reactions involving simultaneous RAFT and ROP processes mediated by a bifunctional compound which acts as a chain transfer agent (CTA) for the RAFT process and co-initiator of the ROP process. Reactions involving the RAFT of Styrene (St) and the ROP of ε-Caprolactone (ε-CL) were performed to obtain PS-b-PCL diblock copolymers. The catalysts Sn(Oct)2 and diphenyl phosphate (DPP) were evaluated in the ROP process. Diphenyl phosphate is the most appropriate for this kind of reaction, since Sn(Oct)2 proved to be avid when interacted with CTA, interfering antagonistically in the radical equilibrium of the RAFT process. The reactions were always controlled when DPP was used as a ROP catalyst, wherein copolymers with narrow molar mass distribution were obtained in the end. This methodology was employed in the synthesis of other linear and graft amphiphilic block copolymers, proving to be an excellent alternative for this purpose. Thermoresponsive copolymers based on Poly(oligo(ethylene glycol)methyl ether methacrylate) (POEGMA) and pH responsive based on Poly(acrylic acid) (PAA) were obtained. The physicochemical properties of the copolymers were investigated in solid state as well as in solution, and the results are in total agreement with values reported in the literature. |
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2017-05-112017-05-112016-02-04FREITAS, Augusto Gonzaga Oliveira de. Synthesis of block copolymers by one-pot reactions with simultaneous raft and rop process. 2016. 170 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016.http://repositorio.ufsm.br/handle/1/4278The present work describes a methodology of controlled synthesis of block copolymers by one-pot reactions involving simultaneous RAFT and ROP processes mediated by a bifunctional compound which acts as a chain transfer agent (CTA) for the RAFT process and co-initiator of the ROP process. Reactions involving the RAFT of Styrene (St) and the ROP of ε-Caprolactone (ε-CL) were performed to obtain PS-b-PCL diblock copolymers. The catalysts Sn(Oct)2 and diphenyl phosphate (DPP) were evaluated in the ROP process. Diphenyl phosphate is the most appropriate for this kind of reaction, since Sn(Oct)2 proved to be avid when interacted with CTA, interfering antagonistically in the radical equilibrium of the RAFT process. The reactions were always controlled when DPP was used as a ROP catalyst, wherein copolymers with narrow molar mass distribution were obtained in the end. This methodology was employed in the synthesis of other linear and graft amphiphilic block copolymers, proving to be an excellent alternative for this purpose. Thermoresponsive copolymers based on Poly(oligo(ethylene glycol)methyl ether methacrylate) (POEGMA) and pH responsive based on Poly(acrylic acid) (PAA) were obtained. The physicochemical properties of the copolymers were investigated in solid state as well as in solution, and the results are in total agreement with values reported in the literature.Este trabalho descreve uma metodologia de síntese controlada de copolímeros em bloco por reações one-pot envolvendo processos RAFT e ROP simultâneos, mediados por um composto bifuncional que atua como agente de transferência de cadeia (CTA) para o processo RAFT e co-iniciador do processo ROP. Reações envolvendo a RAFT do estireno (St) e a ROP da ε-Caprolactona (ε-CL) foram realizadas para obter copolímeros dibloco PS-b-PCL. Os catalisadores Sn(Oct)2 e difenil fosfato (DPP) foram avaliados, sendo o último o mais apropriado para este tipo de reação, uma vez que Sn(Oct)2 mostrou-se ávido por interações com o CTA, interferindo antagonicamente no equilíbrio de radicais do processo RAFT. As reações mantiveram o caráter controlado quando DPP foi usado como catalisador ROP, sendo que ao final, copolímeros com estreita distribuição de massa molar foram obtidos. Esta metodologia foi empregada na síntese de outros copolímeros em bloco anfifílicos lineares e enxertados, se mostrando uma excelente alternativa para este propósito. Copolímeros termoresponsivos à base de Poli(metacrilato de poli(etilenoglicol)metil éter) (POEGMA) e pH responsivos à base de Poli(ácido acrílico) (PAA) foram obtidos. As propriedades físico-químicas dos copolímeros foram investigadas em estado sólido e em solução, e os resultados estão em plena concordância com valores relatados na literatura.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaRAFT e ROP simultâneasOne-potCopolímeros em blocoPolicaprolactonaSimultaneous RAFT and ROPOne-potBlock copolymersPolycaprolactoneCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneosSynthesis of block copolymers by one-pot reactions with simultaneous raft and rop processinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisGiacomelli, Cristianohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762951A6Bellettini, Ismael Casagrandehttp://lattes.cnpq.br/3051183459850022Kessler, Felipehttp://lattes.cnpq.br/1017044993612885Mazutti, Marcio Antoniohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4770663T7Lopes, Poliana Pollizellohttp://lattes.cnpq.br/3168039205334003http://lattes.cnpq.br/2698783509266261Freitas, Augusto Gonzaga Oliveira de10060000000040030030030030050030041f37587-ea61-4b16-a6ef-406dce2bea7077cc29d3-75ce-495f-869a-83c9b0bbfdb7294cc04b-2db0-4be5-b655-5a42fe00d581631f44c1-c42b-4fa6-b608-31304e5d3ead937bb80c-a15e-45bd-bf48-db8134f762598ecfe940-0275-44b8-9aff-9d4cfd621c13info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALFREITAS, AUGUSTO GONZAGA OLIVEIRA DE.pdfapplication/pdf7798696http://repositorio.ufsm.br/bitstream/1/4278/1/FREITAS%2c%20AUGUSTO%20GONZAGA%20OLIVEIRA%20DE.pdf61ebabb2f7d8b6fec31a0ff35a6db7f9MD51TEXTFREITAS, AUGUSTO GONZAGA OLIVEIRA DE.pdf.txtFREITAS, AUGUSTO GONZAGA OLIVEIRA DE.pdf.txtExtracted texttext/plain270162http://repositorio.ufsm.br/bitstream/1/4278/2/FREITAS%2c%20AUGUSTO%20GONZAGA%20OLIVEIRA%20DE.pdf.txta1941df9b8eef38595c6cf2cacff0b87MD52THUMBNAILFREITAS, AUGUSTO GONZAGA OLIVEIRA DE.pdf.jpgFREITAS, AUGUSTO GONZAGA OLIVEIRA DE.pdf.jpgIM Thumbnailimage/jpeg4570http://repositorio.ufsm.br/bitstream/1/4278/3/FREITAS%2c%20AUGUSTO%20GONZAGA%20OLIVEIRA%20DE.pdf.jpgcd8ae4221347952efc75291d700de224MD531/42782017-07-25 11:05:00.565oai:repositorio.ufsm.br:1/4278Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T14:05Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos |
dc.title.alternative.eng.fl_str_mv |
Synthesis of block copolymers by one-pot reactions with simultaneous raft and rop process |
title |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos |
spellingShingle |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos Freitas, Augusto Gonzaga Oliveira de RAFT e ROP simultâneas One-pot Copolímeros em bloco Policaprolactona Simultaneous RAFT and ROP One-pot Block copolymers Polycaprolactone CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos |
title_full |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos |
title_fullStr |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos |
title_full_unstemmed |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos |
title_sort |
Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos |
author |
Freitas, Augusto Gonzaga Oliveira de |
author_facet |
Freitas, Augusto Gonzaga Oliveira de |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Giacomelli, Cristiano |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762951A6 |
dc.contributor.referee1.fl_str_mv |
Bellettini, Ismael Casagrande |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/3051183459850022 |
dc.contributor.referee2.fl_str_mv |
Kessler, Felipe |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/1017044993612885 |
dc.contributor.referee3.fl_str_mv |
Mazutti, Marcio Antonio |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4770663T7 |
dc.contributor.referee4.fl_str_mv |
Lopes, Poliana Pollizello |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/3168039205334003 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/2698783509266261 |
dc.contributor.author.fl_str_mv |
Freitas, Augusto Gonzaga Oliveira de |
contributor_str_mv |
Giacomelli, Cristiano Bellettini, Ismael Casagrande Kessler, Felipe Mazutti, Marcio Antonio Lopes, Poliana Pollizello |
dc.subject.por.fl_str_mv |
RAFT e ROP simultâneas One-pot Copolímeros em bloco Policaprolactona |
topic |
RAFT e ROP simultâneas One-pot Copolímeros em bloco Policaprolactona Simultaneous RAFT and ROP One-pot Block copolymers Polycaprolactone CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Simultaneous RAFT and ROP One-pot Block copolymers Polycaprolactone |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present work describes a methodology of controlled synthesis of block copolymers by one-pot reactions involving simultaneous RAFT and ROP processes mediated by a bifunctional compound which acts as a chain transfer agent (CTA) for the RAFT process and co-initiator of the ROP process. Reactions involving the RAFT of Styrene (St) and the ROP of ε-Caprolactone (ε-CL) were performed to obtain PS-b-PCL diblock copolymers. The catalysts Sn(Oct)2 and diphenyl phosphate (DPP) were evaluated in the ROP process. Diphenyl phosphate is the most appropriate for this kind of reaction, since Sn(Oct)2 proved to be avid when interacted with CTA, interfering antagonistically in the radical equilibrium of the RAFT process. The reactions were always controlled when DPP was used as a ROP catalyst, wherein copolymers with narrow molar mass distribution were obtained in the end. This methodology was employed in the synthesis of other linear and graft amphiphilic block copolymers, proving to be an excellent alternative for this purpose. Thermoresponsive copolymers based on Poly(oligo(ethylene glycol)methyl ether methacrylate) (POEGMA) and pH responsive based on Poly(acrylic acid) (PAA) were obtained. The physicochemical properties of the copolymers were investigated in solid state as well as in solution, and the results are in total agreement with values reported in the literature. |
publishDate |
2016 |
dc.date.issued.fl_str_mv |
2016-02-04 |
dc.date.accessioned.fl_str_mv |
2017-05-11 |
dc.date.available.fl_str_mv |
2017-05-11 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
FREITAS, Augusto Gonzaga Oliveira de. Synthesis of block copolymers by one-pot reactions with simultaneous raft and rop process. 2016. 170 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4278 |
identifier_str_mv |
FREITAS, Augusto Gonzaga Oliveira de. Synthesis of block copolymers by one-pot reactions with simultaneous raft and rop process. 2016. 170 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. |
url |
http://repositorio.ufsm.br/handle/1/4278 |
dc.language.iso.fl_str_mv |
por |
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por |
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100600000000 |
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400 300 300 300 300 500 300 |
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openAccess |
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Universidade Federal de Santa Maria |
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