Síntese e caracterização de misturas poliméricas contendo acetato de celulose: aproveitamento de resíduos da cana-de-açúcar

Abstract

Brazil is the world s major sugarcane producer and this production has been increasing continuously in the last years, chiefly due to the production of ethanol, one of the main biofuels until the moment. Besides, sugarcane is also used for producing sugar. Among the residues of these two activities, the production of sugar and ethanol, is sugarcane bagasse, which is composed mainly by cellulose, lignin and hemicellulose. The Group of Polymer Recycling of the Federal University of Uberlândia has been studying the use of sugarcane bagasse in the last years, specially for producing cellulose acetate, a derivative obtained from the acetylation of the hydroxyl groups on the cellulosic chain. This cellulose acetate produced from sugarcane bagasse cellulose has been used for producing membranes. However, the membranes initially produced were fragile, indicating a low molecular weight of the produced cellulose acetate. An alternative for solving this problem was producing a polymeric blend of cellulose acetate with polystyrene from plastic cups, what resulted in more resistant membranes, although these produced membranes could not resist to high pressure. As a way to solve this problem, the process of acetylation of sugarcane bagasse cellulose was optimized in order to obtain a polymer with higher molecular weight, using the simplex methodology. Intrinsic viscosity of solutions of the obtained cellulose acetate in dichloromethane was used as comparison parameter, since it is proportional to the molecular weight. The optimized variables were the volume of acetic acid, acetic anhydride and catalyst (sulfuric acid), as well as the activation and reaction times. At the end of the optimization process, the viscometric average molecular weight increased from 5,0 Kg mol-1 to 55,0 Kg mol-1. In order to test the quality of the produced cellulose acetate, obtained from the optimized methodology of acetylation of sugarcane bagasse cellulose, membranes produced with this cellulose acetate were produced and characterized. Besides solutions of cellulose acetate and dichloromethane, solutions containing different contents of poly (ethylene glycol) with molecular weight 600 g mol-1 (PEG600) were also used. PEG600 is used as pore former agent in the production of cellulose acetate membranes, which can be used in matrices for controlled release of drugs. The Group of Polymer Recycling of the Federal University of Uberlândia has been studying this system, but the membranes produced using PEG600 were very brittle. The characterization was carried out in the Department de Physics and Chemistry of the University of Caxias do Sul. The characterization of the membranes showed the absence of PEG600 in the membranes, which was probably released in the water bath at the phase inversion step. Although PEG600 has been removed from the system, it led to alterations in the membrane morphologies, as shown by Differential Scanning Calorimetry and Scanning Electron Microscopy. These changes in the morphology resulted in alterations in the properties of pure water flow and ion diffusion through the membranes. It was observed that membranes prepared with solutions containing 0% and 2.5% PEG600 have not shown pure water flow, although they have resisted well to the used pressures (up to 7 atm). Membranes produced with solutions containing 5% and 10% PEG600 also resisted well to the highest pressure of the equipment and allowed pure water flow, which was higher for the membrane produced with the solution containing 10%PEG. Ion diffusion also increased with the increase of PEG600 content in the solutions used for preparing the membranes. Since the membranes obtained with cellulose acetate produced from the optimized methodology of acetylation of sugarcane bagasse cellulose had been characterized, the last step of this thesis was produce and characterize membranes of cellulose acetate and polyaniline (PANi). This step was carried out in the Department of Chemistry of the University of Coimbra as part of the Sandwich Doctorate project CAPES BEX 0368/07-5. It was also studied the effect of the degree of substitution of cellulose acetate on the properties of the blends, using cellulose diacetate and cellulose triacetate. The used techniques showed structural changes caused by PANi on cellulose acetate matrix. It was also observed an increase (200 times) on the electrical conductibility of the membrane composed by the cellulose diacetate/PANi blend in relation to the membrane of cellulose diacetate without PANi.