Supercritical fluid processing of natural based polymers doped with ionic liquids

Some approaches have been developed in our group to investigate the role of ionic liquids as process and property modifiers of natural-based polymers. In our previous work, we proposed the use of ionic liquids as plasticizing agents for the creation of porous structures from a semi-crystalline natural-based polymer. The current work intended to complement the previous studies, evaluating the ability of ionic liquid (IL) to plasticize blends of starch with poly (lactic) acid, with different ratios of starch and PLA of 50:50 and 30:70, and its effect on supercritical fluid foaming process (SCF) and providing more insights on the mechanisms involved. For this purpose, SPLA blends were modified and processed using 1-butyl-3-methylimidazolium chloride ([bmim]Cl). Supercritical fluid foaming was studied at different soaking times (1, 3 and 6 h) using carbon dioxide at 20.0 MPa and 40 oC. The blends were characterized by different techniques, such as infra-red spectroscopy, differential scanning calorimetry and compression and tensile mechanical analysis. The morphology of the foamed structures was analyzed by scanning electron microscopy and micro-computed tomography. The results suggest that after 3h of soaking time an equilibrium state of carbon dioxide into the bulk samples is attained, yielding structures with 6% and 15% of porosity, for SPLA70 and SPLA50 respectively. The solubility of carbon dioxide withinthe matrices was studied for the same conditions and the results demonstrate a higher sorption degree in the samples doped with ionic liquid. Sorption and desorption diffusion coefficients of supercritical CO2 in the SPLA matrix were determined for the raw polymer and for the SPLA doped with [bmim]Cl. It was found that the lower desorption diffusion coefficients are related with the higher porosity obtained by the foaming process.The research leading to these results has received funding from Fundacao da Ciencia e Tecnologia (FCT) through the project ENIG-MA - PTDC/EQU-EPR/121491/2010 and from the European Union's Seventh Framework Programme (FP7/2007-2013) under Grant Agreement No. REGPOT-CT2012-316331-POLARIS. Marta Martins and Rita Craveiro are grateful for financial support from Fundacao da Ciencia e Tecnologia (FCT) through the Grants BIM/PTDC/EQUEPR/121491/2010/ENIGMA and PTDC/EQUEPR/12191/2010/ENIGMA