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Doctoral Thesis
DOI
https://doi.org/10.11606/T.46.2019.tde-24102019-104652
Document
Author
Full name
John Alexander Alzate Castillo
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2019
Supervisor
Committee
Santos, Paulo Sergio (President)
Demets, Gregoire Jean Francois
Noda, Lucia Kiyomi
Seoud, Omar Abdel Moneim Abou El
Title in Portuguese
Estudo de espectroscopia raman da interação de dióxido de enxofre com dendrímeros de polipropilenoimina e polietilenoimina hiper-ramificadas
Keywords in Portuguese
Absorventes de SO2
Complexos poliaminas-SO2
Espectroscopia Raman
Abstract in Portuguese
O presente trabalho investiga a interação de dióxido de enxofre com poliaminas dendriméricas de primeira, segunda e terceira geração, visando o uso desses sistemas na captação do SO2. Dado que essas espécies são estruturalmente muito mais complexas que as aminas simples monoméricas cujos complexos moleculares com SO2 foram detalhadamente investigados por várias décadas, não é possível fazer previsões simples do comportamento das mesmas. De fato, a enorme viscosidade e baixa solubilidade desses dendrímeros é uma dificuldade para a incorporação do SO2 no meio de reação de onde se isolam os sólidos gelatinosos em cujo espectro Raman se detecta a presença de bandas características de espécies HSO3-/SO32- e nenhuma evidência do complexo molecular. Para entender melhor os detalhes dessa interação diversas estratégias foram adotadas: A metilação completa das poliaminas que resultou na interação com SO2 na presença do complexo molecular juntamente com HSO3-/SO32-. A fixação das poliaminas na rede polimérica de PAA que resultou na formação de polímeros mistos de PAA-poliaminas. Uso de HMTA na forma do polímero PAA-HMTA pois a molécula de HMTA simula a microestrutura das poliaminas e a interação do HMTA com SO2 é bem conhecida. A análise dos dados de espectroscopia Raman e da análise térmica indica a importância da presença de agua na interação do SO2 com as poliaminas e, a importância da fixação das mesmas em matrizes poliméricas para aumentar a eficiência de absorção do SO2.
Title in English
Raman spectroscopic study of the interaction of sulfur dioxide with hyper-branched polypropylenimine and polyethyleneimine dendrimers
Keywords in English
Polyamines-SO2 complexes
Raman spectroscopy
SO2 absorbers
Abstract in English
Polyamines of first, second and third generations, are supramolecular species much more complex than the simple amines whose molecular complexes with SO2 were investigated in great detail. A straightforward prediction of their interaction with SO2 can not be made. In fact, the very high viscosity and very low solubility of such species present one of the difficulties for the incorporation of SO2. The obtained material is a gelatinous solid whose Raman spectrum shows the unequivocal presence of HSO3-/SO32- and no evidence of the molecular complex. For better understand the details of the interaction several strategies were adopted: The complete methylation of the polyamines that results in the presence of the molecular complex, together with the HSO3-/SO32- species. The fixation of the polyamines in a polymeric network of PAA that resulted in mixed polymers PAA-Polyamine. The use of PAA-HMTA polymer, since HMTA simulates the local microstructure of the polyamine dendrimers, and the HMTA interaction with SO2 is well understood. The analysis of the data from Raman spectroscopy and thermal analysis indicates the important role of the presence of water in the interaction of SO2 with the dendrimeric polyamines. In addition the transformation of such species in mixed polymers with PAA leads to an increased efficiency in the fixation of SO2.
 
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Publishing Date
2019-11-14
 
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