Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju

Detalhes bibliográficos
Ano de defesa: 2023
Autor(a) principal: Pereira, Rita de Cassia Sousa
Orientador(a): Mazzetto, Selma Elaine
Banca de defesa: Não Informado pela instituição
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Não Informado pela instituição
Programa de Pós-Graduação: Não Informado pela instituição
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Área do conhecimento CNPq:
Link de acesso: http://repositorio.ufc.br/handle/riufc/74997
Resumo: Polyurethanes (PUs) are ranked 6th in polymer global production due to their wide range of applications. These polymers are traditionally obtained from the polyaddition reaction between polyols and di-isocyanates. Currently, most commercially available PUs is still manufactured from petrochemical resources. In this sense, the first part of this work proposes the preparation of PUs from the direct valorization of Cashew Nut Shell Liquid (CNSL) through a synthetic route developed in three stages: (1) epoxidation of CNSL with peracetic acid formed in situ; (2) synthesis of novel polyols by oxirane ring-opening reaction, using ethanol and ethylene glycol; (3) preparation of PUs by combining polyols with toluene diisocyanate (TDI) at different NCO:OH ratios (1.0, 1.5 and 2.0). All formulations were analyzed by Fourier Transform Infrared Spectroscopy (FT-IR), gel content, and Thermogravimetric Analysis (TGA). Also, PUs were applied onto wood surfaces and their adhesive properties were investigated through lap shear strength tests, using a Universal Testing Machine. Gel content results (90%-100%) indicated that PUs showed a high density of crosslinking. According to the TGA curves, PUs undergo thermal degradation around 270 ºC. Mechanical tests showed that PUs obtained with a lower NCO:OH ratio and from polyols containing primary hydroxyls resulted in adhesives with adhesive efficiency 2.5 times higher than PUs obtained with polyols containing only secondary hydroxyls. In the second part of this work, CNSL and ethylene glycol-based polyol was combined with TDI in three different NCO:OH ratios (0.75; 1.0 and 1.5). The resulting PUs were reinforced with coconut husk fibers in a proportion of 30:70 matrix/reinforcement. The manufactured composites showed high values of gel content (94% to 100%), indicating a strong matrix/reinforcement interaction. Scanning electron microscopy (SEM) did not reveal any interphase separation. TGA results revealed that the bio-composites presented flame retardant properties, with LOI values > 28. Dynamic mechanical analyzes (DMA) showed values of glass transitions of 85 ºC, 95 ºC and 121 ºC for the composites with NCO:OH molar ratios at 0.75, 1.00 and 1.50, respectively. In addition, equibiaxial flexural strength results showed values ranging from 71.2 MPa to 88 MPa. Therefore, the results obtained in the present work suggest that the direct valorization of cashew biomass could be explored as a eco-friendly alternative towards the development of bio-based polyurethanes with suitable thermal and mechanical properties for high performance applications.
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spelling Pereira, Rita de Cassia SousaOliveira, Diego Lomonaco Vasconcelos deMazzetto, Selma Elaine2023-11-17T22:31:29Z2023-11-17T22:31:29Z2023PEREIRA, Rita de Cassia Sousa. Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju. 2023. 90 f. Tese (Doutorado em Química) - Universidade Federal do Ceará, Fortaleza, 2023.http://repositorio.ufc.br/handle/riufc/74997Polyurethanes (PUs) are ranked 6th in polymer global production due to their wide range of applications. These polymers are traditionally obtained from the polyaddition reaction between polyols and di-isocyanates. Currently, most commercially available PUs is still manufactured from petrochemical resources. In this sense, the first part of this work proposes the preparation of PUs from the direct valorization of Cashew Nut Shell Liquid (CNSL) through a synthetic route developed in three stages: (1) epoxidation of CNSL with peracetic acid formed in situ; (2) synthesis of novel polyols by oxirane ring-opening reaction, using ethanol and ethylene glycol; (3) preparation of PUs by combining polyols with toluene diisocyanate (TDI) at different NCO:OH ratios (1.0, 1.5 and 2.0). All formulations were analyzed by Fourier Transform Infrared Spectroscopy (FT-IR), gel content, and Thermogravimetric Analysis (TGA). Also, PUs were applied onto wood surfaces and their adhesive properties were investigated through lap shear strength tests, using a Universal Testing Machine. Gel content results (90%-100%) indicated that PUs showed a high density of crosslinking. According to the TGA curves, PUs undergo thermal degradation around 270 ºC. Mechanical tests showed that PUs obtained with a lower NCO:OH ratio and from polyols containing primary hydroxyls resulted in adhesives with adhesive efficiency 2.5 times higher than PUs obtained with polyols containing only secondary hydroxyls. In the second part of this work, CNSL and ethylene glycol-based polyol was combined with TDI in three different NCO:OH ratios (0.75; 1.0 and 1.5). The resulting PUs were reinforced with coconut husk fibers in a proportion of 30:70 matrix/reinforcement. The manufactured composites showed high values of gel content (94% to 100%), indicating a strong matrix/reinforcement interaction. Scanning electron microscopy (SEM) did not reveal any interphase separation. TGA results revealed that the bio-composites presented flame retardant properties, with LOI values > 28. Dynamic mechanical analyzes (DMA) showed values of glass transitions of 85 ºC, 95 ºC and 121 ºC for the composites with NCO:OH molar ratios at 0.75, 1.00 and 1.50, respectively. In addition, equibiaxial flexural strength results showed values ranging from 71.2 MPa to 88 MPa. Therefore, the results obtained in the present work suggest that the direct valorization of cashew biomass could be explored as a eco-friendly alternative towards the development of bio-based polyurethanes with suitable thermal and mechanical properties for high performance applications.Poliuretanos (PUs) são classificados como o sexto tipo de polímero mais produzido no mundo em virtude de sua ampla variedade de aplicações. Esses polímeros são tradicionalmente obtidos a partir da reação de poliadição entre polióis e diisocianatos. Atualmente, os principais PUs disponíveis comercialmente ainda são preparados a partir de fontes petroquímicas. Diante desse contexto, a primeira parte deste trabalho propõe a preparação de PUs a partir da valorização direta do Líquido da Casca da Castanha-de-Caju (LCC), através de uma rota sintética desenvolvida em três etapas: (1) epoxidação do LCC com ácido peracético formado in situ; (2) síntese de novos polióis a partir da abertura do anel oxirânico utilizando etanol e etilenoglicol; (3) preparação de PUs a partir da combinação dos polióis com diisocianato de tolueno (TDI) em diferentes proporções NCO:OH (1,0; 1,5 e 2,0). Todos os PUs foram analisados através de espectroscopia de Infravermelho com Transformada de Fourier (FT-IR), teor de gel e Análise Termogravimétrica (TGA). Os PUs foram aplicados em superfícies de madeira e suas propriedades adesivas foram investigadas através de testes de resistência ao cisalhamento em uma Máquina Universal de Ensaios. Os resultados de teor de gel (90%-100%) indicaram que os PUs apresentaram alta densidade de reticulação. As curvas de TGA mostraram que os PUs sofreram degradação térmica por volta de 270 ºC. Os ensaios mecânicos revelaram que os PUs obtidos com menor razão NCO:OH e a partir de polióis contendo hidroxilas primárias resultaram em adesivos com eficiência adesiva 2,5 vezes superior aos PUs obtidos com polióis contendo apenas hidroxilas secundárias. Na segunda parte deste trabalho, o poliol obtido a partir de LCC e etilenoglicol foi combinado com TDI em três diferentes proporções NCO:OH (0,75; 1,0 e 1,5). Os PUs resultantes foram reforçados com fibras da casca do coco seco na proporção 30:70 matriz/reforço. Os compósitos fabricados apresentaram valores elevados de teor de gel (94% a 100%), indicando forte interação matriz/reforço. A microscopia eletrônica de varredura (MEV) não revelou nenhuma separação de interface. Os resultados de TGA demonstraram que os biocompósitos apresentaram propriedades retardantes de chamas, com valores de LOI > 28. As análises mecânico-dinâmica (DMA) mostraram valores de transições vítreas de 85 ºC, 95 ºC e 121 ºC para os compósitos com NCO:OH de 0,75, 1,00 e 1,50, respectivamente. Além disso, os resultados de resistência à flexão equibiaxial apresentaram valores variando de 71,2 MPa a 88,0 MPa. Portanto, os resultados obtidos no presente trabalho sugerem que a valorização direta do LCC pode ser explorada como uma alternativa ambientalmente correta para o desenvolvimento de PUs com propriedades térmicas e mecânicas apropriadas para aplicações de alto desempenho.Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-cajuDevelopment of novel polyurethanes from the direct valorization of cashew nutshell liquidinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisBiomassaLCCPoliuretanos biobaseadosAdesivos de madeiraBiomassCNSLBio-based PUsWood adhesivesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAinfo:eu-repo/semantics/openAccessporreponame:Repositório Institucional da Universidade Federal do Ceará (UFC)instname:Universidade Federal do Ceará (UFC)instacron:UFChttps://orcid.org/0000-0003-3741-7224http://lattes.cnpq.br/1803868925028419https://orcid.org/0000-0002-6879-3209http://lattes.cnpq.br/5542552498627352https://orcid.org/0000-0001-5763-4336http://lattes.cnpq.br/79336903278106112023-11-17LICENSElicense.txtlicense.txttext/plain; charset=utf-81748http://repositorio.ufc.br/bitstream/riufc/74997/4/license.txt8a4605be74aa9ea9d79846c1fba20a33MD54ORIGINAL2023_tese_rcspereira.pdf2023_tese_rcspereira.pdfapplication/pdf3271984http://repositorio.ufc.br/bitstream/riufc/74997/3/2023_tese_rcspereira.pdfeb5f3e7b9d62017f42923c97bdd07d92MD53riufc/749972023-11-17 19:31:31.115oai:repositorio.ufc.br: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Repositório InstitucionalPUBhttp://www.repositorio.ufc.br/ri-oai/requestbu@ufc.br || repositorio@ufc.bropendoar:2023-11-17T22:31:31Repositório Institucional da Universidade Federal do Ceará (UFC) - Universidade Federal do Ceará (UFC)false
dc.title.pt_BR.fl_str_mv Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
dc.title.en.pt_BR.fl_str_mv Development of novel polyurethanes from the direct valorization of cashew nutshell liquid
title Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
spellingShingle Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
Pereira, Rita de Cassia Sousa
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Biomassa
LCC
Poliuretanos biobaseados
Adesivos de madeira
Biomass
CNSL
Bio-based PUs
Wood adhesives
title_short Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
title_full Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
title_fullStr Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
title_full_unstemmed Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
title_sort Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju
author Pereira, Rita de Cassia Sousa
author_facet Pereira, Rita de Cassia Sousa
author_role author
dc.contributor.co-advisor.none.fl_str_mv Oliveira, Diego Lomonaco Vasconcelos de
dc.contributor.author.fl_str_mv Pereira, Rita de Cassia Sousa
dc.contributor.advisor1.fl_str_mv Mazzetto, Selma Elaine
contributor_str_mv Mazzetto, Selma Elaine
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
topic CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Biomassa
LCC
Poliuretanos biobaseados
Adesivos de madeira
Biomass
CNSL
Bio-based PUs
Wood adhesives
dc.subject.ptbr.pt_BR.fl_str_mv Biomassa
LCC
Poliuretanos biobaseados
Adesivos de madeira
dc.subject.en.pt_BR.fl_str_mv Biomass
CNSL
Bio-based PUs
Wood adhesives
description Polyurethanes (PUs) are ranked 6th in polymer global production due to their wide range of applications. These polymers are traditionally obtained from the polyaddition reaction between polyols and di-isocyanates. Currently, most commercially available PUs is still manufactured from petrochemical resources. In this sense, the first part of this work proposes the preparation of PUs from the direct valorization of Cashew Nut Shell Liquid (CNSL) through a synthetic route developed in three stages: (1) epoxidation of CNSL with peracetic acid formed in situ; (2) synthesis of novel polyols by oxirane ring-opening reaction, using ethanol and ethylene glycol; (3) preparation of PUs by combining polyols with toluene diisocyanate (TDI) at different NCO:OH ratios (1.0, 1.5 and 2.0). All formulations were analyzed by Fourier Transform Infrared Spectroscopy (FT-IR), gel content, and Thermogravimetric Analysis (TGA). Also, PUs were applied onto wood surfaces and their adhesive properties were investigated through lap shear strength tests, using a Universal Testing Machine. Gel content results (90%-100%) indicated that PUs showed a high density of crosslinking. According to the TGA curves, PUs undergo thermal degradation around 270 ºC. Mechanical tests showed that PUs obtained with a lower NCO:OH ratio and from polyols containing primary hydroxyls resulted in adhesives with adhesive efficiency 2.5 times higher than PUs obtained with polyols containing only secondary hydroxyls. In the second part of this work, CNSL and ethylene glycol-based polyol was combined with TDI in three different NCO:OH ratios (0.75; 1.0 and 1.5). The resulting PUs were reinforced with coconut husk fibers in a proportion of 30:70 matrix/reinforcement. The manufactured composites showed high values of gel content (94% to 100%), indicating a strong matrix/reinforcement interaction. Scanning electron microscopy (SEM) did not reveal any interphase separation. TGA results revealed that the bio-composites presented flame retardant properties, with LOI values > 28. Dynamic mechanical analyzes (DMA) showed values of glass transitions of 85 ºC, 95 ºC and 121 ºC for the composites with NCO:OH molar ratios at 0.75, 1.00 and 1.50, respectively. In addition, equibiaxial flexural strength results showed values ranging from 71.2 MPa to 88 MPa. Therefore, the results obtained in the present work suggest that the direct valorization of cashew biomass could be explored as a eco-friendly alternative towards the development of bio-based polyurethanes with suitable thermal and mechanical properties for high performance applications.
publishDate 2023
dc.date.accessioned.fl_str_mv 2023-11-17T22:31:29Z
dc.date.available.fl_str_mv 2023-11-17T22:31:29Z
dc.date.issued.fl_str_mv 2023
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 PEREIRA, Rita de Cassia Sousa. Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju. 2023. 90 f. Tese (Doutorado em Química) - Universidade Federal do Ceará, Fortaleza, 2023.
dc.identifier.uri.fl_str_mv http://repositorio.ufc.br/handle/riufc/74997
identifier_str_mv PEREIRA, Rita de Cassia Sousa. Desenvolvimento de novos poliuretanos a partir da valorização direta do líquido da casca da castanha-de-caju. 2023. 90 f. Tese (Doutorado em Química) - Universidade Federal do Ceará, Fortaleza, 2023.
url http://repositorio.ufc.br/handle/riufc/74997
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