Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar

Detalhes bibliográficos
Ano de defesa: 2024
Autor(a) principal: Rasch, Matheus Barbosa
Orientador(a): Silva Filho, Eloi Alves da lattes
Banca de defesa: Souza, Jefferson Rodrigues lattes, Dalmaschio, Cleocir José lattes
Tipo de documento: Dissertação
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal do Espírito Santo
Mestrado em Química
Programa de Pós-Graduação: Programa de Pós-Graduação em Química
Departamento: Centro de Ciências Exatas
País: BR
Palavras-chave em Português:
Área do conhecimento CNPq:
Link de acesso: http://repositorio.ufes.br/handle/10/18241
Resumo: The search for greener methodologies has challenged analytical chemists, leading to the development of methods that minimize environmental impact and risks to analysts. Green Analytical Chemistry, composed of 12 principles, has been a guide for these innovations, with recent emphasis on deep eutectic solvents (DES). These mixtures formed by intermolecular interactions provide unique physicochemical properties, such as melting point, viscosity, density and solubility, making them attractive for extractions and solubilizations. Among DES, natural deep eutectic solvents (NADES), composed of substances of primary metabolic origin, are even more sustainable, being formed by compounds with low toxic potential. Despite their advantages, DES are still rarely applied to certain samples, such as polymers, which have been the focus of growing concern due to the presence of microplastics and contamination by trace elements. Given this scenario, this study aims to determine trace elements (Al, Ba, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Sb, Ti and Zn) in chemically recycled polymeric resin, developed in partnership between UFES and Vale, using DES as a greener alternative to conventional methods. Four DES were prepared based on choline chloride and water, combined with malic acid, oxalic acid, phenol and urea, of which three are NADES. The polymeric samples were subjected to ultrasound-assisted extraction (UAE-DES) and analyzed by ICP-MS. The characterization of the DES by FTIR and NMR confirmed their adequate formation, and the Hansen solubility parameters (HSP) were used to understand the solvent-sample interactions - wich allowed the unprecedented determination of the sample’s Hansen solubility parameters itself. The results showed that DES were effective in recovering elements such as antimony (Sb), barium (Ba), and manganese (Mn), although the recovery efficiency varied: Sb was determined in all DES, Ba in NADES, and Mn only in solvents formed with acids. The AGREEprep metric demonstrated the environmental advantage of DES over the traditional microwave-assisted acid decomposition (MW-AD) method, with the highest score of 0.61 for NADES. However, elements such as aluminum (Al) and iron (Fe) showed unsatisfactory recoveries, suggesting the need for method optimization. The use of DES is a viable alternative for the preparation of recycled polymeric samples, with promising results for multielement determination and considerable environmental advantages. Additional adjustments may improve the recoveries of some elements and expand the use of the methodology to other matrices
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spelling Lima, Maria Tereza Weitzel Dias Carneiro https://orcid.org/0000-0002-8731-5093http://lattes.cnpq.br/9989703911201351Silva Filho, Eloi Alves da https://orcid.org/0000-0002-9306-7882http://lattes.cnpq.br/8259708288584235Rasch, Matheus Barbosahttps://orcid.org/0009-0002-4069-6180http://lattes.cnpq.br/6640287892395252Souza, Jefferson Rodrigueshttps://orcid.org/0000-0002-3347-8735http://lattes.cnpq.br/2386398242050923Dalmaschio, Cleocir Joséhttps://orcid.org/0000-0002-3773-5786http://lattes.cnpq.br/52099781204307902024-12-23T13:29:15Z2024-12-23T13:29:15Z2024-10-09The search for greener methodologies has challenged analytical chemists, leading to the development of methods that minimize environmental impact and risks to analysts. Green Analytical Chemistry, composed of 12 principles, has been a guide for these innovations, with recent emphasis on deep eutectic solvents (DES). These mixtures formed by intermolecular interactions provide unique physicochemical properties, such as melting point, viscosity, density and solubility, making them attractive for extractions and solubilizations. Among DES, natural deep eutectic solvents (NADES), composed of substances of primary metabolic origin, are even more sustainable, being formed by compounds with low toxic potential. Despite their advantages, DES are still rarely applied to certain samples, such as polymers, which have been the focus of growing concern due to the presence of microplastics and contamination by trace elements. Given this scenario, this study aims to determine trace elements (Al, Ba, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Sb, Ti and Zn) in chemically recycled polymeric resin, developed in partnership between UFES and Vale, using DES as a greener alternative to conventional methods. Four DES were prepared based on choline chloride and water, combined with malic acid, oxalic acid, phenol and urea, of which three are NADES. The polymeric samples were subjected to ultrasound-assisted extraction (UAE-DES) and analyzed by ICP-MS. The characterization of the DES by FTIR and NMR confirmed their adequate formation, and the Hansen solubility parameters (HSP) were used to understand the solvent-sample interactions - wich allowed the unprecedented determination of the sample’s Hansen solubility parameters itself. The results showed that DES were effective in recovering elements such as antimony (Sb), barium (Ba), and manganese (Mn), although the recovery efficiency varied: Sb was determined in all DES, Ba in NADES, and Mn only in solvents formed with acids. The AGREEprep metric demonstrated the environmental advantage of DES over the traditional microwave-assisted acid decomposition (MW-AD) method, with the highest score of 0.61 for NADES. However, elements such as aluminum (Al) and iron (Fe) showed unsatisfactory recoveries, suggesting the need for method optimization. The use of DES is a viable alternative for the preparation of recycled polymeric samples, with promising results for multielement determination and considerable environmental advantages. Additional adjustments may improve the recoveries of some elements and expand the use of the methodology to other matricesA busca por metodologias mais verdes tem desafiado os químicos analíticos, levando ao desenvolvimento de métodos que minimizam o impacto ambiental e os riscos aos analistas. A Química Analítica Verde, composta por 12 princípios, tem sido um norte para essas inovações, com destaque recente para os solventes eutéticos profundos (DES). Essas misturas formadas por interações intermoleculares proporcionam propriedades físico-químicas únicas, como ponto de fusão, viscosidade, densidade e solubilidade, tornando-se atraentes para extrações e solubilizações. Entre os DES, os solventes eutéticos profundos naturais (NADES), compostos por substâncias de origem metabólica primária, são ainda mais sustentáveis, sendo formados por compostos de baixo potencial tóxico. Apesar de suas vantagens, os DES ainda são pouco aplicados a determinadas amostras, como os polímeros, que têm sido foco de crescente preocupação devido à presença de microplásticos e à contaminação por elementos-traço. Diante desse cenário, este estudo visa determinar elementos-traço (Al, Ba, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Sb, Ti e Zn) em resina polimérica quimicamente reciclada, desenvolvida em parceria UFES-Vale, utilizando DES como uma alternativa mais verde aos métodos convencionais. Quatro DES foram preparados à base de cloreto de colina e água, combinados com ácido málico, ácido oxálico, fenol e ureia, dos quais três são NADES. As amostras poliméricas foram submetidas à extração assistida por ultrassom (UAE-DES) e analisadas por ICP-MS. A caracterização dos DES por FTIR e RMN confirmou sua formação adequada, e os parâmetros de solubilidade de Hansen (HSP) foram utilizados para entender as interações solvente-amostra – o que permitiu a determinação inédita dos parâmetros de solubilidade de Hansen da própria amostra. Os resultados mostraram que os DES foram eficazes na recuperação de elementos como antimônio (Sb), bário (Ba) e manganês (Mn), embora a eficiência de recuperação tenha variado: Sb foi determinado em todos os DES, Ba nos NADES, e Mn apenas nos solventes formados com ácidos. A métrica AGREEprep demonstrou a vantagem ambiental dos DES em relação ao método tradicional de decomposição ácida assistida por radiação micro ondas (MW-AD), com a pontuação mais alta de 0,61 para os NADES. No entanto, elementos como alumínio (Al) e ferro (Fe) apresentaram recuperações insatisfatórias, sugerindo a necessidade de otimização dos métodos. O uso de DES é uma alternativa viável para o preparo de amostras poliméricas recicladas, com resultados promissores para a determinação multielementar e consideráveis vantagens ambientais. Ajustes adicionais podem melhorar as recuperações de alguns elementos e expandir o uso da metodologia para outras matrizesFundação de Amparo à Pesquisa e Inovação do Espírito Santo (Fapes)Fundação Espírito-santense de Tecnologia (FEST)Texthttp://repositorio.ufes.br/handle/10/18241porptUniversidade Federal do Espírito SantoMestrado em QuímicaPrograma de Pós-Graduação em QuímicaUFESBRCentro de Ciências Exatashttps://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessQuímicaSolvente eutético profundo Deep Eutectic Solvents (DES)Inductively Coupled Plasma Mass Spectrometry (ICP-MS)Extração assistida por ultrassomQuímica Analítica VerdeSolubilidade de HansenResina poliméricaQuímica analíticaElementos traçoSolventesUltrasound-assisted extractionGreen analytical chemistryHansen solubilityPolymeric resinUtilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementarUtilization of deep eutectic solvents in chemically recycled polymeric resins for multielement determinationinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisreponame:Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)instname:Universidade Federal do Espírito Santo (UFES)instacron:UFESmatheusbrasch@gmail.comORIGINALMatheusBarbosaRasch-2024-dissertacao.pdfMatheusBarbosaRasch-2024-dissertacao.pdfapplication/pdf4568208http://repositorio.ufes.br/bitstreams/1494a0ac-8e5d-4994-9498-5bc3f1ecb4ae/download1bcca417ebe26422d6d9e2b4ee696133MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81748http://repositorio.ufes.br/bitstreams/e0447443-0868-4928-a5ef-29aa73d1b0b5/download8a4605be74aa9ea9d79846c1fba20a33MD5210/182412025-06-27 20:15:49.323https://creativecommons.org/licenses/by/4.0/open accessoai:repositorio.ufes.br:10/18241http://repositorio.ufes.brRepositório InstitucionalPUBhttp://repositorio.ufes.br/oai/requestriufes@ufes.bropendoar:21082025-06-27T20:15:49Repositório Institucional da Universidade Federal do Espírito Santo (riUfes) - Universidade Federal do Espírito Santo (UFES)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
dc.title.none.fl_str_mv Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
dc.title.alternative.none.fl_str_mv Utilization of deep eutectic solvents in chemically recycled polymeric resins for multielement determination
title Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
spellingShingle Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
Rasch, Matheus Barbosa
Química
Solvente eutético profundo
Deep Eutectic Solvents (DES)
Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Extração assistida por ultrassom
Química Analítica Verde
Solubilidade de Hansen
Resina polimérica
Química analítica
Elementos traço
Solventes
Ultrasound-assisted extraction
Green analytical chemistry
Hansen solubility
Polymeric resin
title_short Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
title_full Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
title_fullStr Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
title_full_unstemmed Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
title_sort Utilização de solventes eutéticos profundos em resinas poliméricas quimicamente recicladas para determinação multielementar
author Rasch, Matheus Barbosa
author_facet Rasch, Matheus Barbosa
author_role author
dc.contributor.authorID.none.fl_str_mv https://orcid.org/0009-0002-4069-6180
dc.contributor.authorLattes.none.fl_str_mv http://lattes.cnpq.br/6640287892395252
dc.contributor.advisor-co1.fl_str_mv Lima, Maria Tereza Weitzel Dias Carneiro
dc.contributor.advisor-co1ID.fl_str_mv https://orcid.org/0000-0002-8731-5093
dc.contributor.advisor-co1Lattes.fl_str_mv http://lattes.cnpq.br/9989703911201351
dc.contributor.advisor1.fl_str_mv Silva Filho, Eloi Alves da
dc.contributor.advisor1ID.fl_str_mv https://orcid.org/0000-0002-9306-7882
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/8259708288584235
dc.contributor.author.fl_str_mv Rasch, Matheus Barbosa
dc.contributor.referee1.fl_str_mv Souza, Jefferson Rodrigues
dc.contributor.referee1ID.fl_str_mv https://orcid.org/0000-0002-3347-8735
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/2386398242050923
dc.contributor.referee2.fl_str_mv Dalmaschio, Cleocir José
dc.contributor.referee2ID.fl_str_mv https://orcid.org/0000-0002-3773-5786
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/5209978120430790
contributor_str_mv Lima, Maria Tereza Weitzel Dias Carneiro
Silva Filho, Eloi Alves da
Souza, Jefferson Rodrigues
Dalmaschio, Cleocir José
dc.subject.cnpq.fl_str_mv Química
topic Química
Solvente eutético profundo
Deep Eutectic Solvents (DES)
Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Extração assistida por ultrassom
Química Analítica Verde
Solubilidade de Hansen
Resina polimérica
Química analítica
Elementos traço
Solventes
Ultrasound-assisted extraction
Green analytical chemistry
Hansen solubility
Polymeric resin
dc.subject.por.fl_str_mv Solvente eutético profundo
Deep Eutectic Solvents (DES)
Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Extração assistida por ultrassom
Química Analítica Verde
Solubilidade de Hansen
Resina polimérica
Química analítica
Elementos traço
Solventes
Ultrasound-assisted extraction
Green analytical chemistry
Hansen solubility
Polymeric resin
description The search for greener methodologies has challenged analytical chemists, leading to the development of methods that minimize environmental impact and risks to analysts. Green Analytical Chemistry, composed of 12 principles, has been a guide for these innovations, with recent emphasis on deep eutectic solvents (DES). These mixtures formed by intermolecular interactions provide unique physicochemical properties, such as melting point, viscosity, density and solubility, making them attractive for extractions and solubilizations. Among DES, natural deep eutectic solvents (NADES), composed of substances of primary metabolic origin, are even more sustainable, being formed by compounds with low toxic potential. Despite their advantages, DES are still rarely applied to certain samples, such as polymers, which have been the focus of growing concern due to the presence of microplastics and contamination by trace elements. Given this scenario, this study aims to determine trace elements (Al, Ba, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Sb, Ti and Zn) in chemically recycled polymeric resin, developed in partnership between UFES and Vale, using DES as a greener alternative to conventional methods. Four DES were prepared based on choline chloride and water, combined with malic acid, oxalic acid, phenol and urea, of which three are NADES. The polymeric samples were subjected to ultrasound-assisted extraction (UAE-DES) and analyzed by ICP-MS. The characterization of the DES by FTIR and NMR confirmed their adequate formation, and the Hansen solubility parameters (HSP) were used to understand the solvent-sample interactions - wich allowed the unprecedented determination of the sample’s Hansen solubility parameters itself. The results showed that DES were effective in recovering elements such as antimony (Sb), barium (Ba), and manganese (Mn), although the recovery efficiency varied: Sb was determined in all DES, Ba in NADES, and Mn only in solvents formed with acids. The AGREEprep metric demonstrated the environmental advantage of DES over the traditional microwave-assisted acid decomposition (MW-AD) method, with the highest score of 0.61 for NADES. However, elements such as aluminum (Al) and iron (Fe) showed unsatisfactory recoveries, suggesting the need for method optimization. The use of DES is a viable alternative for the preparation of recycled polymeric samples, with promising results for multielement determination and considerable environmental advantages. Additional adjustments may improve the recoveries of some elements and expand the use of the methodology to other matrices
publishDate 2024
dc.date.accessioned.fl_str_mv 2024-12-23T13:29:15Z
dc.date.available.fl_str_mv 2024-12-23T13:29:15Z
dc.date.issued.fl_str_mv 2024-10-09
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.uri.fl_str_mv http://repositorio.ufes.br/handle/10/18241
url http://repositorio.ufes.br/handle/10/18241
dc.language.iso.fl_str_mv por
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language por
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dc.rights.driver.fl_str_mv https://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv Text
dc.publisher.none.fl_str_mv Universidade Federal do Espírito Santo
Mestrado em Química
dc.publisher.program.fl_str_mv Programa de Pós-Graduação em Química
dc.publisher.initials.fl_str_mv UFES
dc.publisher.country.fl_str_mv BR
dc.publisher.department.fl_str_mv Centro de Ciências Exatas
publisher.none.fl_str_mv Universidade Federal do Espírito Santo
Mestrado em Química
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institution UFES
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collection Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)
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