Otimização da modificação de cadeia do PHB com anidrido maleico e estudo de comportamento térmico
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Data
2007-01-19
Autores
Souza, Josiane de Lima [UNESP]
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Editor
Universidade Estadual Paulista (Unesp)
Resumo
O polímero PHB poli(3-hidroxibutirato) tem despertado interesse comercial, principalmente pelas suas propriedades de biodegradabilidade e biocompatibilidade. Desta forma este trabalho estudou a interação de anidrido maleico com PHB tendo trietilamina como catalisador. As variáveis avaliadas neste estudo foram: a concentração de catalisador, temperatura e tempo de reação. O acompanhamento das modificações obtidas no novo material foi realizado através do comportamento térmico dos filmes formados, determinando-se a temperatura de transição vítrea (Tg), temperatura de cristalização (Tc), temperatura de fusão cristalina (Tm) e porcentagem de cristalização por DSC e estabilidade térmica por TG-DTA, definindo a condição mais adequada para promoção da reação de cadeia por meio de estudo de planejamento e otimização de experimentos. Avaliou-se inicialmente o comportamento térmico dos filmes promovendo a reação na proporção fixa PHB/AM 90/10, definindo as melhores condições de reação em 110 °C, tempo de reação de 1 hora e concentração de catalisador em 5 % (v/v), a partir do planejamento e otimização de experimentos. Estas condições otimizadas foram utilizadas para a promoção da reação da modificação com diferentes proporções de anidrido maleico, entre 0 a 20 % (m/m) em relação ao PHB. Para avaliar a proporção de anidrido maleico presente nos filmes de PHB, foram otimizadas as condições experimentais e determinados os principais parâmetros de validação para a análise simultânea de derivados de PHB e AM, utilizando-se cromatografia em fase gasosa (GC). Os resultados demonstram que o procedimento analítico pode ser aplicado com confiabilidade. Os filmes de PHB/AM analisados por GC-FID e o índice de acidez do PHB homopolímero forneceram resultados da interação de PHB com AM. Estes dados juntamente com os de TG-DTA,...
PHB poly(3-hydroxybutyrate) homopolymer shows biodegradability and biocompatibility properties, therefore the PHB has been extensively studied. PHB was structurally modified by maleic anhydride (AM). The transesterification reaction PHB/AM with 90/10% w/w was carried out with several concentrations of a proposed catalyst based on a tertiary amine, time and temperature to obtain films by solvent casting. Glass transition temperature (Tg), melting point (Tm), crystallization temperature (Tc) obtained by DSC and thermal degradation studied by TGA were parameters employed to evaluate the optimum conditions of PHB/AM structural modification according to factorial design. According to the results, the most indicated conditions to carried out the PHB modification reaction with AM could be at 110 °C during 1 hour with 5 % v/v triethylamine concentration. These optimized conditions were used to modify the PHB chain, however with different mass proportions of AM (from 0 to 20 %). A gas chromatography (GC) method has been optimized and validated for simultaneous determination of monomeric proportions in PHB/MA films. The results demonstrated that the analytical procedure is a consistent chromatographic method to identification and quantification from PHB and MA isoamilic esters derivatives. PHB/AM films analyzed by GC-FID and the acid value of the PHB homopolymer presented results about the PHB/AM interactions. Additionally, from the DTA, The intermediary step where mass change was detected may due to a new polymeric chain structure that could be formed by the incorporation through transesterification of maleate units, and DSC, that compared to the PHB homopolymer, the PHB/MA film has a lower Tg value and much more pronounced crystallization peak and a similar melting point, result a possible mechanism reaction involving PHB and AM was present. According to the results obtained, the PHB/AM 80/20 was the suitable proportion.
PHB poly(3-hydroxybutyrate) homopolymer shows biodegradability and biocompatibility properties, therefore the PHB has been extensively studied. PHB was structurally modified by maleic anhydride (AM). The transesterification reaction PHB/AM with 90/10% w/w was carried out with several concentrations of a proposed catalyst based on a tertiary amine, time and temperature to obtain films by solvent casting. Glass transition temperature (Tg), melting point (Tm), crystallization temperature (Tc) obtained by DSC and thermal degradation studied by TGA were parameters employed to evaluate the optimum conditions of PHB/AM structural modification according to factorial design. According to the results, the most indicated conditions to carried out the PHB modification reaction with AM could be at 110 °C during 1 hour with 5 % v/v triethylamine concentration. These optimized conditions were used to modify the PHB chain, however with different mass proportions of AM (from 0 to 20 %). A gas chromatography (GC) method has been optimized and validated for simultaneous determination of monomeric proportions in PHB/MA films. The results demonstrated that the analytical procedure is a consistent chromatographic method to identification and quantification from PHB and MA isoamilic esters derivatives. PHB/AM films analyzed by GC-FID and the acid value of the PHB homopolymer presented results about the PHB/AM interactions. Additionally, from the DTA, The intermediary step where mass change was detected may due to a new polymeric chain structure that could be formed by the incorporation through transesterification of maleate units, and DSC, that compared to the PHB homopolymer, the PHB/MA film has a lower Tg value and much more pronounced crystallization peak and a similar melting point, result a possible mechanism reaction involving PHB and AM was present. According to the results obtained, the PHB/AM 80/20 was the suitable proportion.
Descrição
Palavras-chave
Polimeros - Biodegradação - Dissertação, Anidridos - Dissertação
Como citar
SOUZA, Josiane de Lima. Otimização da modificação de cadeia do PHB com anidrido maleico e estudo de comportamento térmico. 2007. 88 f. Dissertação (mestrado) - Universidade Estadual Paulista, Instituto de Química, 2007.