S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila
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| Data de Publicação: | 2018 |
| Tipo de documento: | Dissertação |
| Idioma: | por |
| Título da fonte: | Biblioteca Digital de Teses e Dissertações da UFRRJ |
| Texto Completo: | https://tede.ufrrj.br/jspui/handle/jspui/4511 |
Resumo: | The largest applications of molecular sieves are related to acid catalysis due to the innumerable reactions for petrochemical industries. However, basic catalysis is huge importance for other industries, mainly pharmaceutical. Thus, it is essential to study basic catalysts for the application in heterogeneous catalysis. In this way, the Knoevenagel reaction was chosen as a model, since it is possible to observe the functionalization basic site besides being an important reaction for the industry, generating products such as polymers, bioactive, substituted olefins and synthetic intermediates from various compounds of biological importance. In this work, the anchoring of amino groups in mesoporous materials of type MCM-41 and SBA-15 was studied, aiming at their functionalization to make them catalytically active for reactions between organic molecules promoted by basic centers. For this, samples of MCM-41 and SBA-15 with different pore diameters were synthesized by varying time and temperature conditions of synthesis. Samples of MCM-41 with pore diameter between 31-39 ? and samples of SBA-15 with pore diameter between 63-72 ? were obtained. The anchoring of amino groups on the samples were made through the reaction with DAPTS (3-ethylene diaminopropyltrimethoxysilane) which had the concentration determined by the availability of silanols groups. Thus, In Si-MCM-41 samples, the DAPTS concentration decreased with the temperature and time of synthesis increase, due to the condensation of Si-OH groups. The inverse occurred in Si-SBA-15: with the increase of the synthesis time, the availability of the silanols groups increased, increasing the concentration of the grafted amino groups. The samples were characterized by several techniques: X-ray diffraction, nitrogen adsorption, thermogravimetric analysis and backtitration. The activity was analyzed in a Knoevenagel reaction of benzaldehyde with diethylmalonate by batch, generating products such as cinnamic acid, ethyl cinnamate and diethyl benzylidene malonate for 180 minutes. Both the concentration of the amine groups and the pore diameter influenced in selectivity and reaction activity. |
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Fernandes, Lindoval Domiciano837359257-15http://lattes.cnpq.br/7921814684730923Castro, Rosane NoraMiranda, Jussara Lopes129045157-55http://lattes.cnpq.br/5224402774219733Araujo, Aline Dantas2021-04-07T22:49:43Z2018-06-06Araujo, Aline Dantas. S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila. 2018. [72 f.]. Disserta??o( Programa de P?s-Gradua??o em Engenharia Qu?mica) - Universidade Federal Rural do Rio de Janeiro, [Serop?dica -RJ] .https://tede.ufrrj.br/jspui/handle/jspui/4511The largest applications of molecular sieves are related to acid catalysis due to the innumerable reactions for petrochemical industries. However, basic catalysis is huge importance for other industries, mainly pharmaceutical. Thus, it is essential to study basic catalysts for the application in heterogeneous catalysis. In this way, the Knoevenagel reaction was chosen as a model, since it is possible to observe the functionalization basic site besides being an important reaction for the industry, generating products such as polymers, bioactive, substituted olefins and synthetic intermediates from various compounds of biological importance. In this work, the anchoring of amino groups in mesoporous materials of type MCM-41 and SBA-15 was studied, aiming at their functionalization to make them catalytically active for reactions between organic molecules promoted by basic centers. For this, samples of MCM-41 and SBA-15 with different pore diameters were synthesized by varying time and temperature conditions of synthesis. Samples of MCM-41 with pore diameter between 31-39 ? and samples of SBA-15 with pore diameter between 63-72 ? were obtained. The anchoring of amino groups on the samples were made through the reaction with DAPTS (3-ethylene diaminopropyltrimethoxysilane) which had the concentration determined by the availability of silanols groups. Thus, In Si-MCM-41 samples, the DAPTS concentration decreased with the temperature and time of synthesis increase, due to the condensation of Si-OH groups. The inverse occurred in Si-SBA-15: with the increase of the synthesis time, the availability of the silanols groups increased, increasing the concentration of the grafted amino groups. The samples were characterized by several techniques: X-ray diffraction, nitrogen adsorption, thermogravimetric analysis and backtitration. The activity was analyzed in a Knoevenagel reaction of benzaldehyde with diethylmalonate by batch, generating products such as cinnamic acid, ethyl cinnamate and diethyl benzylidene malonate for 180 minutes. Both the concentration of the amine groups and the pore diameter influenced in selectivity and reaction activity.As maiores aplica??es de peneiras moleculares est?o relacionadas ? cat?lise ?cida devido ? in?meras rea??es do meio petroqu?mico. Por?m, a cat?lise b?sica ? de suma import?ncia nas demais ind?strias, principalmente farmac?utica. Assim, torna-se imprescind?vel o estudo de catalisadores b?sico para a aplica??o em cat?lise heterog?nea. Dessa forma, foi escolhida a rea??o de Knoevenagel como modelo, pois assim ? poss?vel observar a funcionaliza??o de um s?tio b?sico al?m de ser uma rea??o importante para a ind?stria, gerando produtos como pol?meros, bioativos, olefinas substitu?das e intermedi?rios sint?ticos de variados compostos de import?ncia biol?gica. Neste trabalho foi estudado o ancoramento de grupamentos amino em materiais mesoporosos do tipo MCM-41 e SBA-15, visando a sua funcionaliza??o de forma a torn?-los cataliticamente ativos para rea??es entre mol?culas org?nicas promovidas por centros b?sicos. Para tal, amostras de MCM-41 e SBA-15 apresentando diferentes di?metros de poros foram sintetizadas variando as condi??es de tempo e temperatura de s?ntese. Foram obtidas amostras de MCM-41 com di?metro de poros entre 31-39 ? e amostras de SBA-15 com di?metro de poros entre 63-72 ?. Estas amostras tiveram grupamentos amino ancorados sobre sua superf?cie atrav?s da rea??o com DAPTS (3-etilenodiaminopropiltrimetoxi- silano) que tiveram a concentra??o determinada pela disponibilidade de grupos silan?is. Assim, nas Si-MCM-41, a concentra??o de DAPTS diminuiu com aumento de temperatura e tempo de s?ntese devido a condensa??o dos grupos Si-OH. O inverso aconteceu a Si-SBA-15: com o aumento do tempo de s?ntese, maior foi a disponibilidade dos grupos silan?is, aumentando a concentra??o dos grupos aminos enxertados. As amostras foram caracterizadas por diversas t?cnicas: difra??o de raios X, adsor??o de nitrog?nio, an?lise termogravim?trica e titula??o indireta. A atividade foi analisada em uma rea??o de Knoevenagel do benzalde?do com malonato de dietila por batelada, gerando produtos como o ?cido cin?mico, etilcinamato e benzilideno-malonato de dietila em um per?odo de 180 minutos. Tanto a concentra??o dos grupos aminos e o di?metro dos poros influenciaram na seletividade e atividade da rea??o.Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2021-04-07T22:49:43Z No. of bitstreams: 1 2018 - Aline Dantas Araujo.pdf: 3502480 bytes, checksum: 94cf5bc480adfcaa3ca50f442f6ea7d5 (MD5)Made available in DSpace on 2021-04-07T22:49:43Z (GMT). No. of bitstreams: 1 2018 - Aline Dantas Araujo.pdf: 3502480 bytes, checksum: 94cf5bc480adfcaa3ca50f442f6ea7d5 (MD5) Previous issue date: 2018-06-06application/pdfhttps://tede.ufrrj.br/retrieve/64551/2018%20-%20%20Aline%20Dantas%20Araujo.pdf.jpgporUniversidade Federal Rural do Rio de JaneiroPrograma de P?s-Gradua??o em Engenharia Qu?micaUFRRJBrasilInstituto de TecnologiaALBUQUERQUE, M. S?ntese, caracteriza??o e aplica??o de catalisadores heterog?neos para produ??o de biocombust?veis. Universidade Federal do Cear?. Fortaleza. 2008. ANGELESCU, E. et al. Solid base catalysts obtained from hydrotalcite precursors, for Knoevenagel synthesis of cinamic acid and coumarin derivatives. Applied Catalysis, v. 308, p. 13-18, maio 2006. ATKINS, P.; JONES, L. Princ?pios de Qu?mica - Questionando a Vida Moderna e o Meio Ambiente. [S.l.]: Bookman, 2006. BANDYOPADHYAY, M.; TSUNOJI, N.; SANO, T. Mesoporous MCM-48 immobilized with aminoporpyltriethoxysilane: a potential catalyst for trasesterification of triacetin. Catalysis Letters, v. 147, p. 1040-1050, Abril 2017. BAO, Y. et al. Application of amine-functionalized MCM-41 modified ultrafiltration membrane to remove chromium (VI) and copper (II). Chemical Engineering Journal, 281, 1 dezembro 2015. 460-467. BASTOS, D. S. et al. S?ntese de Peneiras Moleculares Mesoporosas MCM-41 Apresentando Diferentes Di?metros de Poros. XII Congresso Brasileiro de Cat?lise. [S.l.]: Sociedade Brasileira de Cat?lise. 2003. p. 28-32. BECK, J. S. et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates. American Chemical Society, Junho 1992. 10834-10843. BRANDON, D.; KAPLAN, W. D. Microstructural Characterization of Materials. 2?. ed. [S.l.]: John Wiley & Sons, 2008. BROEKHOFF, J.; DEBOER, J. Studies on pore system in catalysts IX. Calculation of pore distribution from the adsorption branch of nitrogen sorption isotherm in the case of open cylindrical pores a fundamental equations. Journal of Catalysis, 9, 1967. 8-14. BROEKHOFF, J.; DEBOER, J. Studies on pore system in catalysts X. Calculation of pore distribution from the adsorption branch of nitrogen adorption isotherm in the case of open cylindrical pores. b. applications. Journal of Catalysis, 9, 1967. 15-27. BROEKHOFF, J.; DEBOER, J. Studies on pore system in catalysts. XI. Calculation of pore distribution from the adsorption branch of a nitrogen sorption isotherm in the case of "inkbottle" pores. Journal of Catalysis, 10, 1968. 153-165. CAKIRYILMAZ, N. et al. Effect of W incorporation on the product distribution in steam reforming of bio-oil derived acetic acid over Ni based Zr-SBA-15 catalyst. International Journal os Hydrogen Energy, 43, 2018. 3629-3642. CHEN, H.; WANG, Y. Preparation os MCM-41 with high thermal stability and complementary textural porosity. Ceramics International, 2002. 541-547. CHOUDARY, B. M. et al. Knoevenagel and aldol condensations catalysed by a new diaminofunctionalised mesoporous material. Journal of Molecular Catalysis, p. 361-365, 1999. CLIMENT, M. J. et al. Base catalysis for fine chemicals production: Claisen-Schmidt condensation on Zeolites and Hydrotalcites for the production of Chalcones and Flavonones of pharmaceutical interest. Journal of Catalysis, 1995. 60-66. 67 CORMA, A. et al. Synthesis of MCM-41 with Different Pore Diameters without Addition of Auxiliary Organics. Chemistry of Materials, 9 (10), 1997. 2123-2126. CORMA, A.; KAN, Q.; REY, F. Synthesis of Si and Ti-Si-MCM-48 mesoporous materials with controlled pore sizes in the absence of polar organic additives and alkali metal ions. Chem. Commun., 1998. 579-580. EL-NAHHAL, I. M. et al. Synthesis and structural characterization of ZnO and CuO nanoparticles supported mesoporous silica SBA-15. Chemical Physics Letters, 2017. 165- 171. FERREIRA, J. M. G. D. O. Otimiza??o da rea??o de Knoevenagel em sistema bin?rio etanol:?gua. UFPB. Jo?o Pessoa, p. 135. 2016. FIGUEIREDO, J. L.; RIBEIRO, F. R. Cat?ise Heterog?nea. Lisboa: Funda??o Calouste Gulbenkian, 1989. GALV?O, L. P. et al. Iodeto de Pot?ssio suportado em peneiras moleculares mesoporosas (SBA-15 e MCM-41) como catalisador b?sico para a s?ntese do biodiesel. Qu?mica Nova, 35, 2012. 41-44. GRECCO, D. T.; RANGEL, M. D. C.; URQUETA-GONZ?LEZ, E. A. Ze?litas hierarquicamente estruturadas. Qu?mica Nova, v. 36, 2013. GR?N, M. et al. Novel pathways for the preparationn of mesoporous MCM-41 materials: control of porosity and morphology. Microporous and Mesoporous Materials, 1999. 207- 216. HATTORI, H. Solid base catalysts: generation of basic sites and application to organic synthesis. Applied Catalysis A, 222, 2001. 247-259. KAUFMANN, E. N. Characterization of Materials. [S.l.]: John Wiley & Sons, v. 1, 2003. KOH, M. H. et al. Surface morphology and physicochemical properties of ordered mesoporous silica SBA-15 synthesized at low temperature. 29th Symposium of Malaysian Chemical Engineers. [S.l.]: [s.n.]. 2016. KUBOTA, Y. et al. Organic?silicate hybrid catalysts based on various defined structures for Knoevenagel condensation. Microporous and Mesoporous Materials, p. 135-149, 2004. LEOFANTI, G. et al. Surface area and pore texture of catalysts. Catalysis Today, p. 207-219, 1998. LIN, X.; CHUAH, G. K.; JAENICKE, S. Base-functionalized MCM-41 as catalysts for the synthesis of monoglycerides. Journal of Molecular Catalysis A: Chemical, Singapore, 150, 6 maio 1999. 287-294. MAGALH?ES, J. B. T. S?ntese de Peneiras Moleculares MCM-41 Ativas em Cat?lise B?sica para a Produ??o de Chalconas. UFRRJ. Serop?dica, p. 67. 2006. MAIA, D. S?ntese e caracteriza??o de complexos de Base de Schiff com n?quel (II) ancorados no material mesoporoso SBA-15. Universidade Federal do Rio Grande do Norte. Natal, Rio Grande do Norte. 2015. 68 MARTINS, L.; CARDOSO, D. Aplica??o catal?tica de peneiras moleculares b?sicas micro e mesoporosas. Qu?mica Nova, S?o Paulo, 29, 2006. Disponivel em: <www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422006000200028>. Acesso em: 30 abr. 2018. MOUSSAOUI, Y.; SALEM, R. B. Catalyzed Knoevenagel reactions on inorganic solids supports: Application to the synthesis of coumarine compounds. Compters Rendus Chimie, 2007. 1162-1169. ONO, Y. Solid base catalysts for the synthesis of fine chemicals. Journal of Catalysis, 216, 2003. 406-415. PARIDA, K. M. et al. A facile method for synthesis of amine-functionalized mesoporous zirconia and its catalytic evaluation in Knoevenagel condensation. Applied Catalysis A: General, 2010. 226-232. PARIDA, K. M.; RATH, D. Amine functionalized MCM-41: An active and reusable catalyst for Knoevenagel condensation reaction. Journal of Molecular Catalysis A: Chemical, Junho 2009. 93-100. PEREIRA, M. G. A. et al. Aplica??o do catalisador KI-MCM-41 na rea??o de esterifica??o do ?leo de oiticica (licania rigida benth). 5? Encontro Regional de Qu?mica & 4? Encontro Nacional de Qu?mica. [S.l.]: Blucher Chemistry Proceedings. 2015. POSTNOVA, I. V.; HA, C.-S.; SHCHIPUNOV, Y. A. Dependence of SBA-15 formation on the block copolymer concentration in the course of synthesis with precursor containing ethylene glycol residues. Colloid Journal, 2017. 378-385. QUEVEDO, G. P. et al. SBA-type mesoporous materials with cylindrical and spherical structures for the controlled loading and release of ibuprofen. Journal Sol-Gel, Hybrids and Solution Chemistries, 85, 2017. 486-494. RANA, S.; JONNALAGADDA, S. B. Synthesis and characterization of amine functionalized graphene oxide and scope as catalyst for Knoevenagel condensation reaction. Catalysis Communications, n. 92, p. 31-34, 2017. REIS, M. et al. Produ??o de biodiesel a partir de ?cidos graxos provenientes do refino de ?leos vegetais via cat?lise ?cida heterog?nea e micro-ondas. Qu?mica Nova, 38, Outubro 2015. 1307-1312. RESENDE FILHO, J. B. Condensa??o de knoevenagel e s?ntese de n-acilidrazonas catalisadas por nanopart?culas magn?ticas funcionalizadas. Universidade Federal da Para?ba. Jo?o Pessoa. 2016. ROCHA, A. S.; NUNES, R. M.; HIRSCH, T. K. Compara??o entre difra??o de raios X e "m?todo do furo cego" para medi??o de tens?es residuais em barras cil?ndricas. Mat?ria, Rio de Janeiro, v. 14, 2009. Disponivel em: <www.materia.coppe.ufrj.br/sarra/artigos/artigo11078/>. Acesso em: 21 dez. 2017. RODRIGUEZ, I. et al. Heterogeneized Br?nsted base catalysts for fine chemicals production: grafted quaternary organic ammonium hydroxides as catalyst for the production of chromenes and coumarins. Applied Catalysis A: General, 2000. 241-252. 69 SCARAMUZZI, et al. Uma hist?ria contada no futuro: complexo imunog?nico constitu?do por ant?genos vacinais adsorvidos/encapsulados em s?lica mesoporosa nanoestruturada. Cadernos de Hist?ria da Ci?ncia, S?o Paulo, 5, 2009. SKOOG, D. A. et al. Fundamentos de Qu?mica Anal?tica. 8?. ed. [S.l.]: THOMSON, 2005. SKOOG, D. A.; HOLLER, F. J.; NIEMAN, T. A. Princ?pios de an?lise instrumental. 5?. ed. Porto Alegre: Bookman, 2002. SOLOMONS, T. W. G.; FRYHLE, C. B. Qu?mica Org?nica. Tradu??o de Robson Mendes Matos. 8?. ed. Rio de Janeiro: LTC Editora, v. 1, 2005. SUGINO, K. et al. A simple modification creates a great difference: new solid-base catalyst using methylated N-substituted SBA-15. Journal of the American Chemical Society, novembro 2011. 20030-20032. TERASAKI, O. Mesoporous crystals and related nano-structured materials. [S.l.]: Elsevier, 2004. TSENG, H.-H. et al. Structure-controlled mesoporous SBA-15-derived mixed matrix membranes for H2 purification and CO2 capture. International Journal of Hydrogen Energy Publications LLC, v. 42, p. 11379 - 11391, 2017. VARADWAJ, G. B. B.; RANA, S.; PARIDA, K. M. Amine functionalized K10 montmorillonite: a solid acid?base catalyst for the Knoevenagel condensation reaction. Dalton Transactions, Fevereiro 2013. 5122-5129. VOEGTLIN, A. C. et al. Room-temperatura synthesis of silicate mesoporous MCM-41-type materials: influence of the synthesis pH on the porosity of the materials obtained. Microporous Materials, p. 137-147, 1997. VRBKOV?, E. et al. Heterogeneous basic catalysts in 2- butylcinnamylaldehyde synthesis, 2015. WANG, J.; GE, H.; BAO, W. Synthesis andcharacteristics ofSBA-15 with thick pore wall and high hydrotermal stability. Materials Latters, p. 4, 2015. ZENDEHDEL, M.; ZAMANI, F. MCM-41-supported NNO type Schiff base complexes: a highly selective heterogeneous nanocatalyst for esterification, Diels?Alder and aldol condensation. Journal J Porous Mater, 16 Fevereiro 2017. ZHANG, X. et al. An investigation of Knoevenagel condensation reaction in microreactors using a new zeolite catalyst. Applied Catalyst A: General, 2004. 109-118. ZHAO, D. et al. Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores. SCIENCE, 279, Janeiro 1998. 548-552.Peneira molecular mesoporosaCat?lise heterog?nea b?sicaCondensa??o de KnoevenagelMesoporous molecular sieveBasic heterogeneous catalysisKnoevenagel condensationEngenharia Qu?micaS?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietilaSynthesis of active mesoporous molecular sieves in Knoevenagel reaction with benzaldehyde and diethyl malonateinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UFRRJinstname:Universidade Federal Rural do Rio de Janeiro (UFRRJ)instacron:UFRRJTHUMBNAIL2018 - Aline Dantas Araujo.pdf.jpg2018 - Aline Dantas Araujo.pdf.jpgimage/jpeg3738http://localhost:8080/tede/bitstream/jspui/4511/4/2018+-++Aline+Dantas+Araujo.pdf.jpg9975d2154cf3204822b1a7cbe7284b9cMD54TEXT2018 - Aline Dantas Araujo.pdf.txt2018 - Aline Dantas Araujo.pdf.txttext/plain116002http://localhost:8080/tede/bitstream/jspui/4511/3/2018+-++Aline+Dantas+Araujo.pdf.txt0d07e4143b14927854e980a9ab3531a6MD53ORIGINAL2018 - Aline Dantas Araujo.pdf2018 - Aline Dantas Araujo.pdfapplication/pdf3502480http://localhost:8080/tede/bitstream/jspui/4511/2/2018+-++Aline+Dantas+Araujo.pdf94cf5bc480adfcaa3ca50f442f6ea7d5MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-82089http://localhost:8080/tede/bitstream/jspui/4511/1/license.txt7b5ba3d2445355f386edab96125d42b7MD51jspui/45112021-04-08 01:00:24.485oai:localhost: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Biblioteca Digital de Teses e Dissertaçõeshttps://tede.ufrrj.br/PUBhttps://tede.ufrrj.br/oai/requestbibliot@ufrrj.br||bibliot@ufrrj.bropendoar:2021-04-08T04:00:24Biblioteca Digital de Teses e Dissertações da UFRRJ - Universidade Federal Rural do Rio de Janeiro (UFRRJ)false |
| dc.title.por.fl_str_mv |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila |
| dc.title.alternative.eng.fl_str_mv |
Synthesis of active mesoporous molecular sieves in Knoevenagel reaction with benzaldehyde and diethyl malonate |
| title |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila |
| spellingShingle |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila Araujo, Aline Dantas Peneira molecular mesoporosa Cat?lise heterog?nea b?sica Condensa??o de Knoevenagel Mesoporous molecular sieve Basic heterogeneous catalysis Knoevenagel condensation Engenharia Qu?mica |
| title_short |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila |
| title_full |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila |
| title_fullStr |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila |
| title_full_unstemmed |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila |
| title_sort |
S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila |
| author |
Araujo, Aline Dantas |
| author_facet |
Araujo, Aline Dantas |
| author_role |
author |
| dc.contributor.advisor1.fl_str_mv |
Fernandes, Lindoval Domiciano |
| dc.contributor.advisor1ID.fl_str_mv |
837359257-15 |
| dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/7921814684730923 |
| dc.contributor.referee1.fl_str_mv |
Castro, Rosane Nora |
| dc.contributor.referee2.fl_str_mv |
Miranda, Jussara Lopes |
| dc.contributor.authorID.fl_str_mv |
129045157-55 |
| dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/5224402774219733 |
| dc.contributor.author.fl_str_mv |
Araujo, Aline Dantas |
| contributor_str_mv |
Fernandes, Lindoval Domiciano Castro, Rosane Nora Miranda, Jussara Lopes |
| dc.subject.por.fl_str_mv |
Peneira molecular mesoporosa Cat?lise heterog?nea b?sica Condensa??o de Knoevenagel |
| topic |
Peneira molecular mesoporosa Cat?lise heterog?nea b?sica Condensa??o de Knoevenagel Mesoporous molecular sieve Basic heterogeneous catalysis Knoevenagel condensation Engenharia Qu?mica |
| dc.subject.eng.fl_str_mv |
Mesoporous molecular sieve Basic heterogeneous catalysis Knoevenagel condensation |
| dc.subject.cnpq.fl_str_mv |
Engenharia Qu?mica |
| description |
The largest applications of molecular sieves are related to acid catalysis due to the innumerable reactions for petrochemical industries. However, basic catalysis is huge importance for other industries, mainly pharmaceutical. Thus, it is essential to study basic catalysts for the application in heterogeneous catalysis. In this way, the Knoevenagel reaction was chosen as a model, since it is possible to observe the functionalization basic site besides being an important reaction for the industry, generating products such as polymers, bioactive, substituted olefins and synthetic intermediates from various compounds of biological importance. In this work, the anchoring of amino groups in mesoporous materials of type MCM-41 and SBA-15 was studied, aiming at their functionalization to make them catalytically active for reactions between organic molecules promoted by basic centers. For this, samples of MCM-41 and SBA-15 with different pore diameters were synthesized by varying time and temperature conditions of synthesis. Samples of MCM-41 with pore diameter between 31-39 ? and samples of SBA-15 with pore diameter between 63-72 ? were obtained. The anchoring of amino groups on the samples were made through the reaction with DAPTS (3-ethylene diaminopropyltrimethoxysilane) which had the concentration determined by the availability of silanols groups. Thus, In Si-MCM-41 samples, the DAPTS concentration decreased with the temperature and time of synthesis increase, due to the condensation of Si-OH groups. The inverse occurred in Si-SBA-15: with the increase of the synthesis time, the availability of the silanols groups increased, increasing the concentration of the grafted amino groups. The samples were characterized by several techniques: X-ray diffraction, nitrogen adsorption, thermogravimetric analysis and backtitration. The activity was analyzed in a Knoevenagel reaction of benzaldehyde with diethylmalonate by batch, generating products such as cinnamic acid, ethyl cinnamate and diethyl benzylidene malonate for 180 minutes. Both the concentration of the amine groups and the pore diameter influenced in selectivity and reaction activity. |
| publishDate |
2018 |
| dc.date.issued.fl_str_mv |
2018-06-06 |
| dc.date.accessioned.fl_str_mv |
2021-04-07T22:49:43Z |
| dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
| dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
| format |
masterThesis |
| status_str |
publishedVersion |
| dc.identifier.citation.fl_str_mv |
Araujo, Aline Dantas. S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila. 2018. [72 f.]. Disserta??o( Programa de P?s-Gradua??o em Engenharia Qu?mica) - Universidade Federal Rural do Rio de Janeiro, [Serop?dica -RJ] . |
| dc.identifier.uri.fl_str_mv |
https://tede.ufrrj.br/jspui/handle/jspui/4511 |
| identifier_str_mv |
Araujo, Aline Dantas. S?ntese de peneiras moleculares mesoporosas ativas na rea??o de Knoevenagel entre benzalde?do e malonato de dietila. 2018. [72 f.]. Disserta??o( Programa de P?s-Gradua??o em Engenharia Qu?mica) - Universidade Federal Rural do Rio de Janeiro, [Serop?dica -RJ] . |
| url |
https://tede.ufrrj.br/jspui/handle/jspui/4511 |
| dc.language.iso.fl_str_mv |
por |
| language |
por |
| dc.relation.references.por.fl_str_mv |
ALBUQUERQUE, M. S?ntese, caracteriza??o e aplica??o de catalisadores heterog?neos para produ??o de biocombust?veis. Universidade Federal do Cear?. Fortaleza. 2008. ANGELESCU, E. et al. Solid base catalysts obtained from hydrotalcite precursors, for Knoevenagel synthesis of cinamic acid and coumarin derivatives. Applied Catalysis, v. 308, p. 13-18, maio 2006. ATKINS, P.; JONES, L. Princ?pios de Qu?mica - Questionando a Vida Moderna e o Meio Ambiente. [S.l.]: Bookman, 2006. BANDYOPADHYAY, M.; TSUNOJI, N.; SANO, T. Mesoporous MCM-48 immobilized with aminoporpyltriethoxysilane: a potential catalyst for trasesterification of triacetin. Catalysis Letters, v. 147, p. 1040-1050, Abril 2017. BAO, Y. et al. Application of amine-functionalized MCM-41 modified ultrafiltration membrane to remove chromium (VI) and copper (II). Chemical Engineering Journal, 281, 1 dezembro 2015. 460-467. BASTOS, D. S. et al. S?ntese de Peneiras Moleculares Mesoporosas MCM-41 Apresentando Diferentes Di?metros de Poros. XII Congresso Brasileiro de Cat?lise. [S.l.]: Sociedade Brasileira de Cat?lise. 2003. p. 28-32. BECK, J. S. et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates. American Chemical Society, Junho 1992. 10834-10843. BRANDON, D.; KAPLAN, W. D. Microstructural Characterization of Materials. 2?. ed. [S.l.]: John Wiley & Sons, 2008. BROEKHOFF, J.; DEBOER, J. Studies on pore system in catalysts IX. Calculation of pore distribution from the adsorption branch of nitrogen sorption isotherm in the case of open cylindrical pores a fundamental equations. Journal of Catalysis, 9, 1967. 8-14. BROEKHOFF, J.; DEBOER, J. Studies on pore system in catalysts X. Calculation of pore distribution from the adsorption branch of nitrogen adorption isotherm in the case of open cylindrical pores. b. applications. Journal of Catalysis, 9, 1967. 15-27. BROEKHOFF, J.; DEBOER, J. Studies on pore system in catalysts. XI. Calculation of pore distribution from the adsorption branch of a nitrogen sorption isotherm in the case of "inkbottle" pores. Journal of Catalysis, 10, 1968. 153-165. CAKIRYILMAZ, N. et al. Effect of W incorporation on the product distribution in steam reforming of bio-oil derived acetic acid over Ni based Zr-SBA-15 catalyst. International Journal os Hydrogen Energy, 43, 2018. 3629-3642. CHEN, H.; WANG, Y. Preparation os MCM-41 with high thermal stability and complementary textural porosity. Ceramics International, 2002. 541-547. CHOUDARY, B. M. et al. Knoevenagel and aldol condensations catalysed by a new diaminofunctionalised mesoporous material. Journal of Molecular Catalysis, p. 361-365, 1999. CLIMENT, M. J. et al. Base catalysis for fine chemicals production: Claisen-Schmidt condensation on Zeolites and Hydrotalcites for the production of Chalcones and Flavonones of pharmaceutical interest. Journal of Catalysis, 1995. 60-66. 67 CORMA, A. et al. Synthesis of MCM-41 with Different Pore Diameters without Addition of Auxiliary Organics. Chemistry of Materials, 9 (10), 1997. 2123-2126. CORMA, A.; KAN, Q.; REY, F. Synthesis of Si and Ti-Si-MCM-48 mesoporous materials with controlled pore sizes in the absence of polar organic additives and alkali metal ions. Chem. Commun., 1998. 579-580. EL-NAHHAL, I. M. et al. Synthesis and structural characterization of ZnO and CuO nanoparticles supported mesoporous silica SBA-15. Chemical Physics Letters, 2017. 165- 171. FERREIRA, J. M. G. D. O. Otimiza??o da rea??o de Knoevenagel em sistema bin?rio etanol:?gua. UFPB. Jo?o Pessoa, p. 135. 2016. FIGUEIREDO, J. L.; RIBEIRO, F. R. Cat?ise Heterog?nea. Lisboa: Funda??o Calouste Gulbenkian, 1989. GALV?O, L. P. et al. Iodeto de Pot?ssio suportado em peneiras moleculares mesoporosas (SBA-15 e MCM-41) como catalisador b?sico para a s?ntese do biodiesel. Qu?mica Nova, 35, 2012. 41-44. GRECCO, D. T.; RANGEL, M. D. C.; URQUETA-GONZ?LEZ, E. A. Ze?litas hierarquicamente estruturadas. Qu?mica Nova, v. 36, 2013. GR?N, M. et al. Novel pathways for the preparationn of mesoporous MCM-41 materials: control of porosity and morphology. Microporous and Mesoporous Materials, 1999. 207- 216. HATTORI, H. Solid base catalysts: generation of basic sites and application to organic synthesis. Applied Catalysis A, 222, 2001. 247-259. KAUFMANN, E. N. Characterization of Materials. [S.l.]: John Wiley & Sons, v. 1, 2003. KOH, M. H. et al. Surface morphology and physicochemical properties of ordered mesoporous silica SBA-15 synthesized at low temperature. 29th Symposium of Malaysian Chemical Engineers. [S.l.]: [s.n.]. 2016. KUBOTA, Y. et al. Organic?silicate hybrid catalysts based on various defined structures for Knoevenagel condensation. Microporous and Mesoporous Materials, p. 135-149, 2004. LEOFANTI, G. et al. Surface area and pore texture of catalysts. Catalysis Today, p. 207-219, 1998. LIN, X.; CHUAH, G. K.; JAENICKE, S. Base-functionalized MCM-41 as catalysts for the synthesis of monoglycerides. Journal of Molecular Catalysis A: Chemical, Singapore, 150, 6 maio 1999. 287-294. MAGALH?ES, J. B. T. S?ntese de Peneiras Moleculares MCM-41 Ativas em Cat?lise B?sica para a Produ??o de Chalconas. UFRRJ. Serop?dica, p. 67. 2006. MAIA, D. S?ntese e caracteriza??o de complexos de Base de Schiff com n?quel (II) ancorados no material mesoporoso SBA-15. Universidade Federal do Rio Grande do Norte. Natal, Rio Grande do Norte. 2015. 68 MARTINS, L.; CARDOSO, D. Aplica??o catal?tica de peneiras moleculares b?sicas micro e mesoporosas. Qu?mica Nova, S?o Paulo, 29, 2006. Disponivel em: <www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422006000200028>. Acesso em: 30 abr. 2018. MOUSSAOUI, Y.; SALEM, R. B. Catalyzed Knoevenagel reactions on inorganic solids supports: Application to the synthesis of coumarine compounds. Compters Rendus Chimie, 2007. 1162-1169. ONO, Y. Solid base catalysts for the synthesis of fine chemicals. Journal of Catalysis, 216, 2003. 406-415. PARIDA, K. M. et al. A facile method for synthesis of amine-functionalized mesoporous zirconia and its catalytic evaluation in Knoevenagel condensation. Applied Catalysis A: General, 2010. 226-232. PARIDA, K. M.; RATH, D. Amine functionalized MCM-41: An active and reusable catalyst for Knoevenagel condensation reaction. Journal of Molecular Catalysis A: Chemical, Junho 2009. 93-100. PEREIRA, M. G. A. et al. Aplica??o do catalisador KI-MCM-41 na rea??o de esterifica??o do ?leo de oiticica (licania rigida benth). 5? Encontro Regional de Qu?mica & 4? Encontro Nacional de Qu?mica. [S.l.]: Blucher Chemistry Proceedings. 2015. POSTNOVA, I. V.; HA, C.-S.; SHCHIPUNOV, Y. A. Dependence of SBA-15 formation on the block copolymer concentration in the course of synthesis with precursor containing ethylene glycol residues. Colloid Journal, 2017. 378-385. QUEVEDO, G. P. et al. SBA-type mesoporous materials with cylindrical and spherical structures for the controlled loading and release of ibuprofen. Journal Sol-Gel, Hybrids and Solution Chemistries, 85, 2017. 486-494. RANA, S.; JONNALAGADDA, S. B. Synthesis and characterization of amine functionalized graphene oxide and scope as catalyst for Knoevenagel condensation reaction. Catalysis Communications, n. 92, p. 31-34, 2017. REIS, M. et al. Produ??o de biodiesel a partir de ?cidos graxos provenientes do refino de ?leos vegetais via cat?lise ?cida heterog?nea e micro-ondas. Qu?mica Nova, 38, Outubro 2015. 1307-1312. RESENDE FILHO, J. B. Condensa??o de knoevenagel e s?ntese de n-acilidrazonas catalisadas por nanopart?culas magn?ticas funcionalizadas. Universidade Federal da Para?ba. Jo?o Pessoa. 2016. ROCHA, A. S.; NUNES, R. M.; HIRSCH, T. K. Compara??o entre difra??o de raios X e "m?todo do furo cego" para medi??o de tens?es residuais em barras cil?ndricas. Mat?ria, Rio de Janeiro, v. 14, 2009. Disponivel em: <www.materia.coppe.ufrj.br/sarra/artigos/artigo11078/>. Acesso em: 21 dez. 2017. RODRIGUEZ, I. et al. Heterogeneized Br?nsted base catalysts for fine chemicals production: grafted quaternary organic ammonium hydroxides as catalyst for the production of chromenes and coumarins. Applied Catalysis A: General, 2000. 241-252. 69 SCARAMUZZI, et al. Uma hist?ria contada no futuro: complexo imunog?nico constitu?do por ant?genos vacinais adsorvidos/encapsulados em s?lica mesoporosa nanoestruturada. Cadernos de Hist?ria da Ci?ncia, S?o Paulo, 5, 2009. SKOOG, D. A. et al. Fundamentos de Qu?mica Anal?tica. 8?. ed. [S.l.]: THOMSON, 2005. SKOOG, D. A.; HOLLER, F. J.; NIEMAN, T. A. Princ?pios de an?lise instrumental. 5?. ed. Porto Alegre: Bookman, 2002. SOLOMONS, T. W. G.; FRYHLE, C. B. Qu?mica Org?nica. Tradu??o de Robson Mendes Matos. 8?. ed. Rio de Janeiro: LTC Editora, v. 1, 2005. SUGINO, K. et al. A simple modification creates a great difference: new solid-base catalyst using methylated N-substituted SBA-15. Journal of the American Chemical Society, novembro 2011. 20030-20032. TERASAKI, O. Mesoporous crystals and related nano-structured materials. [S.l.]: Elsevier, 2004. TSENG, H.-H. et al. Structure-controlled mesoporous SBA-15-derived mixed matrix membranes for H2 purification and CO2 capture. International Journal of Hydrogen Energy Publications LLC, v. 42, p. 11379 - 11391, 2017. VARADWAJ, G. B. B.; RANA, S.; PARIDA, K. M. Amine functionalized K10 montmorillonite: a solid acid?base catalyst for the Knoevenagel condensation reaction. Dalton Transactions, Fevereiro 2013. 5122-5129. VOEGTLIN, A. C. et al. Room-temperatura synthesis of silicate mesoporous MCM-41-type materials: influence of the synthesis pH on the porosity of the materials obtained. Microporous Materials, p. 137-147, 1997. VRBKOV?, E. et al. Heterogeneous basic catalysts in 2- butylcinnamylaldehyde synthesis, 2015. WANG, J.; GE, H.; BAO, W. Synthesis andcharacteristics ofSBA-15 with thick pore wall and high hydrotermal stability. Materials Latters, p. 4, 2015. ZENDEHDEL, M.; ZAMANI, F. MCM-41-supported NNO type Schiff base complexes: a highly selective heterogeneous nanocatalyst for esterification, Diels?Alder and aldol condensation. Journal J Porous Mater, 16 Fevereiro 2017. ZHANG, X. et al. An investigation of Knoevenagel condensation reaction in microreactors using a new zeolite catalyst. Applied Catalyst A: General, 2004. 109-118. ZHAO, D. et al. Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores. SCIENCE, 279, Janeiro 1998. 548-552. |
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