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Resumo: Neste trabalho foi realizado um estudo cinético da redução da massa molar do poli(3-hidroxibutirato-co-3-hidroxivalerato) (PHBHV) em três diferentes metodologias: hidrólise ácida com ácido clorídrico, transesterificação com hexilenoglicol ou etilenoglicol e redução na presença do borohidreto de sódio (NaBH 4 ). Foram investigados os parâmetros de processo: tempo, temperatura, tipo e concentração de catalisadores. Os resultados de redução de massa molar foram analisados pelo modelo cinético de ordem n. A redução com NaBH 4 foi mais eficiente do ponto de vista cinético, tendo em vista os parâmetros: constante de reação k e energia de ativação (E a ), uma vez que os valores observados foram significativamente maiores em comparação com os calculados para os demais métodos. Palavras-chave: Polihidroxialcanoatos, PHBHV, redução da massa molar, análise cinética. Kinetic Study of the Molecular Weight Reduction of Poly (3-Hydroxybutirate-co-3-Hydroxyvalerate) (PHBHV)Abstract: In this work a kinetic study was carried out of the molecular weight reduction of poly(3-hydroxybutirate-co-3-hydroxyvalerate) (PHBHV) in three different methodologies: acid hydrolysis using hydrochloric acid, transesterification with ethylene glycol or hexylene glycol and reduction in the presence of sodium borohydride (NaBH 4 ). The following process parameters were investigated: time, temperature, type and concentration of catalysts. The results of molecular weight reduction were fitted with a n-order kinetic model. The kinetics analysis has shown that the NaBH 4 reduction was the most efficient in terms of reaction rate in comparison with the other methods.

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We report first results on the controlled radical polymerization of 2,3‐epithiopropyl methacrylate (ETMA) also known as thiiran‐2‐ylmethyl methacrylate. Reversible addition‐fragmentation chain transfer (RAFT) of ETMA was carried out in bulk and in solution, using AIBN as initiator and the chain transfer agents: cyanopropyl dithiobenzoate (CPDB) and cumyl dithiobenzoate (CDB). A linear increase of the number‐average molecular weight and decrease of the polydispersity with monomer conversion were observed using CPDB as transfer agent, indicating a controlled process. Atom transfer radical polymerization (ATRP) of ETMA was performed under different reaction conditions using copper bromide complexed by tertiary amine ligands and ethyl 2‐bromoisobutyrate (EBiB) or 2‐bromopropionitrile (BPN) as initiator. All experiments lead to a crosslinked polymer. Preliminary studies in the absence of initiator showed that the CuBr/ligand complex alone initiates the ring‐opening polymerization of thiirane leading to a poly(propylene sulfide) with pendant methacrylate groups.magnified image