Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks
Autor(a) principal: | |
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Data de Publicação: | 2010 |
Outros Autores: | , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10198/2250 |
Resumo: | This work reports experimental and modeling studies concerning the conventional (FRP) and atom transfer radical polymerization (ATRP) of acrylate/diacrylate monomers. In the framework of a recently developed general approach, kinetic models including crosslinking reactions and branching by chain transfer to polymer are discussed for FRP and ATRP polymerization systems. Besides molecular weight distribution (MWD), fairly good predictions of the z-average radius of gyration could be obtained for these non-linear polymers. A set of experiments was performed at 1 L scale in a batch reactor using n-butyl acrylate (BA) or methyl acrylate (MA) as monovinyl monomers and 1,6-Hexanediol diacrylate (HDDA) or bisphenol A ethoxylate diacrylate (BEDA) as crosslinkers. In FRP experiments, AIBN was used as initiator and ATRP polymerizations were initiated by ethyl 2-bromopropionate (EBrP) and mediated by CuBr using PMDETA (N,N,N,N,N-pentamethyldiethylenetriamine) as ligant. Polymerizations were carried out in solution at 60 °C with different dilutions using toluene and DMF as solvents. Products formed at different polymerization times were analyzed by SEC/RI/MALLS yielding average MW, MWD, z-average radius of gyration and monomer conversion. Important differences in the molecular architecture of the synthesized FRP and ATRP highly branched polyacrylates have been identified. Comparisons of experimental results with predictions have put into evidence the important effect of intramolecular cyclizations at all dilutions, even with ATRP polymerizations. |
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Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networksATRPBranchingCrosslinkingModelingRadius of gyrationThis work reports experimental and modeling studies concerning the conventional (FRP) and atom transfer radical polymerization (ATRP) of acrylate/diacrylate monomers. In the framework of a recently developed general approach, kinetic models including crosslinking reactions and branching by chain transfer to polymer are discussed for FRP and ATRP polymerization systems. Besides molecular weight distribution (MWD), fairly good predictions of the z-average radius of gyration could be obtained for these non-linear polymers. A set of experiments was performed at 1 L scale in a batch reactor using n-butyl acrylate (BA) or methyl acrylate (MA) as monovinyl monomers and 1,6-Hexanediol diacrylate (HDDA) or bisphenol A ethoxylate diacrylate (BEDA) as crosslinkers. In FRP experiments, AIBN was used as initiator and ATRP polymerizations were initiated by ethyl 2-bromopropionate (EBrP) and mediated by CuBr using PMDETA (N,N,N,N,N-pentamethyldiethylenetriamine) as ligant. Polymerizations were carried out in solution at 60 °C with different dilutions using toluene and DMF as solvents. Products formed at different polymerization times were analyzed by SEC/RI/MALLS yielding average MW, MWD, z-average radius of gyration and monomer conversion. Important differences in the molecular architecture of the synthesized FRP and ATRP highly branched polyacrylates have been identified. Comparisons of experimental results with predictions have put into evidence the important effect of intramolecular cyclizations at all dilutions, even with ATRP polymerizations.Fundação para a Ciência e a Tecnologia (FCT) Ministry of Science and Technology of Portugal European Community (FEDER); Grant Number: POCI-PPCDT/EQU/60483/2004Financial support by Fundação para a Ciência e a Tecnologia (FCT), Ministry of Science and Technology of Portugal and European Community (FEDER) through project POCI-PPCDT/EQU/60483/2004 is gratefully acknowledged.WileyBiblioteca Digital do IPBGonçalves, Miguel A.D.Dias, RolandoCosta, Mário Rui2010-03-29T11:30:08Z20102010-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10198/2250engGonçalves, Miguel; Dias, Rolando; Costa, Mário (2010). Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks. Macromolecular Symposia. ISSN 1022-1360. 289:1, p.1-171022-1360info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-11-21T10:06:54Zoai:bibliotecadigital.ipb.pt:10198/2250Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T22:55:36.982437Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks |
title |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks |
spellingShingle |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks Gonçalves, Miguel A.D. ATRP Branching Crosslinking Modeling Radius of gyration |
title_short |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks |
title_full |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks |
title_fullStr |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks |
title_full_unstemmed |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks |
title_sort |
Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks |
author |
Gonçalves, Miguel A.D. |
author_facet |
Gonçalves, Miguel A.D. Dias, Rolando Costa, Mário Rui |
author_role |
author |
author2 |
Dias, Rolando Costa, Mário Rui |
author2_role |
author author |
dc.contributor.none.fl_str_mv |
Biblioteca Digital do IPB |
dc.contributor.author.fl_str_mv |
Gonçalves, Miguel A.D. Dias, Rolando Costa, Mário Rui |
dc.subject.por.fl_str_mv |
ATRP Branching Crosslinking Modeling Radius of gyration |
topic |
ATRP Branching Crosslinking Modeling Radius of gyration |
description |
This work reports experimental and modeling studies concerning the conventional (FRP) and atom transfer radical polymerization (ATRP) of acrylate/diacrylate monomers. In the framework of a recently developed general approach, kinetic models including crosslinking reactions and branching by chain transfer to polymer are discussed for FRP and ATRP polymerization systems. Besides molecular weight distribution (MWD), fairly good predictions of the z-average radius of gyration could be obtained for these non-linear polymers. A set of experiments was performed at 1 L scale in a batch reactor using n-butyl acrylate (BA) or methyl acrylate (MA) as monovinyl monomers and 1,6-Hexanediol diacrylate (HDDA) or bisphenol A ethoxylate diacrylate (BEDA) as crosslinkers. In FRP experiments, AIBN was used as initiator and ATRP polymerizations were initiated by ethyl 2-bromopropionate (EBrP) and mediated by CuBr using PMDETA (N,N,N,N,N-pentamethyldiethylenetriamine) as ligant. Polymerizations were carried out in solution at 60 °C with different dilutions using toluene and DMF as solvents. Products formed at different polymerization times were analyzed by SEC/RI/MALLS yielding average MW, MWD, z-average radius of gyration and monomer conversion. Important differences in the molecular architecture of the synthesized FRP and ATRP highly branched polyacrylates have been identified. Comparisons of experimental results with predictions have put into evidence the important effect of intramolecular cyclizations at all dilutions, even with ATRP polymerizations. |
publishDate |
2010 |
dc.date.none.fl_str_mv |
2010-03-29T11:30:08Z 2010 2010-01-01T00:00:00Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10198/2250 |
url |
http://hdl.handle.net/10198/2250 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Gonçalves, Miguel; Dias, Rolando; Costa, Mário (2010). Prediction and experimental characterization of the molecular architecture of FRP and ATRP synthesized polyacrylate networks. Macromolecular Symposia. ISSN 1022-1360. 289:1, p.1-17 1022-1360 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Wiley |
publisher.none.fl_str_mv |
Wiley |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799135160526962688 |