Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos

Detalhes bibliográficos
Autor(a) principal: Freitas, Augusto Gonzaga Oliveira de
Data de Publicação: 2016
Tipo de documento: Tese
Idioma: por
Título da fonte: Manancial - Repositório Digital da UFSM
dARK ID: ark:/26339/001300000x1zz
Texto Completo: 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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spelling Síntese 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 processRAFT e ROP simultâneasOne-potCopolímeros em blocoPolicaprolactonaSimultaneous RAFT and ROPOne-potBlock copolymersPolycaprolactoneCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe 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.Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorEste 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.Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaGiacomelli, 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/3168039205334003Freitas, Augusto Gonzaga Oliveira de2017-05-112017-05-112016-02-04info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfapplication/pdfFREITAS, 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/1/4278ark:/26339/001300000x1zzporinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2017-07-25T14:05:00Zoai:repositorio.ufsm.br:1/4278Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-25T14:05Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.none.fl_str_mv Síntese de copolímeros em bloco por reações one-pot com processos RAFT e ROP simultâneos
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.none.fl_str_mv Giacomelli, Cristiano
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762951A6
Bellettini, Ismael Casagrande
http://lattes.cnpq.br/3051183459850022
Kessler, Felipe
http://lattes.cnpq.br/1017044993612885
Mazutti, Marcio Antonio
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4770663T7
Lopes, Poliana Pollizello
http://lattes.cnpq.br/3168039205334003
dc.contributor.author.fl_str_mv Freitas, Augusto Gonzaga Oliveira de
dc.subject.por.fl_str_mv 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
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
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.none.fl_str_mv 2016-02-04
2017-05-11
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.uri.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.
http://repositorio.ufsm.br/handle/1/4278
dc.identifier.dark.fl_str_mv ark:/26339/001300000x1zz
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.
ark:/26339/001300000x1zz
url http://repositorio.ufsm.br/handle/1/4278
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Santa Maria
BR
Química
UFSM
Programa de Pós-Graduação em Química
publisher.none.fl_str_mv Universidade Federal de Santa Maria
BR
Química
UFSM
Programa de Pós-Graduação em Química
dc.source.none.fl_str_mv reponame:Manancial - Repositório Digital da UFSM
instname:Universidade Federal de Santa Maria (UFSM)
instacron:UFSM
instname_str Universidade Federal de Santa Maria (UFSM)
instacron_str UFSM
institution UFSM
reponame_str Manancial - Repositório Digital da UFSM
collection Manancial - Repositório Digital da UFSM
repository.name.fl_str_mv Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)
repository.mail.fl_str_mv atendimento.sib@ufsm.br||tedebc@gmail.com
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