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Produção enzimática de Poli(E-caprolactona) em fluidos pressurizados

  • Comim, Sibele Recco Rosso
Publication Date
Jan 01, 2012
Repositório Institucional da UFSC
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Abstract : Lipase catalyzed polymerizations in pressurized fluids are becoming more attractive due to the need for development of cleaner processes able to yield products free of residues for pharmaceutical and food applications. Polycaprolactone is a biocompatible, biodegradable and bioresorbable polymer, is applied in a wide variety of structures for use in biomedical, food and pharmaceutical industries. Therefore, this thesis aims to study the enzymatic production of polycaprolactone using pressurized fluids as solvents in order to define the best conditions for the polymerization reaction. For this purpose, experiments were performed to evaluate the influence of the operating pressure (120-280 bar), the solvent/monomer mass ratio (2:1-1:2) and the percentage of enzyme related to monomer (5-15%) over the reaction yield, numberaverage molecular weight (Mn), weight-average molecular weight (Mw) and polydispersity index (PI) using liquefied petroleum gas (LPG) and carbon dioxide (CO2)as solvents. The use of a variable-volume reactor allowed an independent evaluation of pressure and solvent/monomer ratio. Results from these experiments defined the conditions for carrying out the polymerization kinetics. The kinetics assays were performed by assessing the influence of the percentage of enzyme (1%, 3%, 5% and 15%) and temperature (50 ° C and 60 ° C) in the CO2 reactions, and the influence of the percentage of enzyme (3 % and 5%) and pressure (25 bar, 50 bar and 120 bar) in the LPG reactions. Kinetic samples were evaluated by means of reaction yield, Mn, Mw, PI, productivity, melting temperature and crystallinity degree. In order to reduce the impact of enzyme cost over overall process cost, the possibility of enzyme reuse was also studied. The results for ANOVA analysis showed that pressure is not a significant variable for any of the selected parameters. Regarding solvent/monomer ratio, best results for yield, Mn and Mw for CO2 reactions were obtained for the solvent/monomer ratio of 1:2, whereas for LPG the solvent/monomer ratio of 2:1 provided the optimum results. Increasing the percentage of enzyme resulted in yield increase, higher molecular mass and higher polydispersity indexes. Reaction kinetics was performed using different percentages of enzyme and temperatures. Reaction yields up to 90%, Mn up to 13,700 Da and Mw of up to 22,200 Da were obtained for CO2 using 15 wt% enzyme. Reaction yields up to 81%, Mn up to 5,000 Da and Mw of up to 23,000 Da were obtained for LPG using 5 wt% of enzyme. The polydispersity index varied from 1.2 to 1.7. Taking into account the productivity calculations, the conditions chosen to perform the reuse assays were 120 bar, solvent/monomer ratio of 1:2, 3 wt% of enzyme, 65°C and 12 hours of reaction for CO2 assays and 25 bar, solvent/monomer ratio of 2:1, 3 wt% of enzyme, 65°C and 8 hours of reaction for LPG assays. When the enzyme was applied in reuse cycles, it showed a sharp decrease in reaction yields for CO2 assays probably due to its deleterious effect on the enzyme activity. For LPG the reaction yield decrease was progressive. The molecular masses obtained decreased with each cycle for both solvents. Comparing the results of yield, productivity and molecular mass of polymers obtained with the use of CO2, LPG and without the use of solvent, LPG is the option that stands out because of the good results obtained. Moreover, it has lower cost and milder operating pressure when compared to the use of CO2. The use of LPG, a solvent not previously reported in the production of polyesters and the innovative aspect of using a variable-volume reactor which allows independent analysis of the influence of pressure, temperature and the solvent/ monomer ratio are the highlights of this work.


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