Poli(metacrilato de metila) (PMMA) de massa molar controlada foi sintetizado, em solução de tolueno, utilizando peróxido de benzoíla como iniciador e 1-dodecanotiol (DDM) como agente de transferência de cadeia. O efeito da concentração de DDM sobre a massa molar do PMMA foi investigado. Copolímeros de metacrilato de metila e ácido metacrílico, P(MMA-MAA), foram sintetizados a partir da hidrólise parcial de homopolímeros de metacrilato de metila com variadas massas molares. Utilizando uma técnica inédita na literatura para a síntese de ésteres poliméricos, foi realizada a reação das unidades ácidas do P(MMA-MAA) com álcoois de cadeia longa, na presença de 1,3-diciclo-carbodiimida e 4-dimetilamino-piridina, que produziu copolímeros contendo longos segmentos hidrocarbônicos pendentes, tais como o poli(metacrilato de metila-co-metacrilato de hexadecila).
With the increase in global demand for biodiesel, first generation feedstock has drawn the attention of governmental institutions due to the correlation with large land farming areas. The second and third feedstock generations are greener feedstock sources, nevertheless, they require different catalytic conditions if compared with first generation feedstock. In this work, we present the synthesis and characterization of oligoesters matrices and their functionalization to act as a pseudo-homogeneous acid catalyst for biodiesel production, named Oligocat. The main advantage of Oligocat is given due to its reactional medium interaction. Initially, oligocat is a solid catalyst soluble in the alcoholic phase, acting as a homogeneous catalyst, providing better mass transfer of the catalytic groups to the reaction medium, and as the course of the reaction happens, Oligocat migrates to the glycerol phase, also providing the advantage of easy separation of the biodiesel. Oligocat was synthesized through polymerization of aromatic hydroxy acids, followed by a chemical functionalization applying the sulfonation technique. Characterization of the catalysts was carried out by infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). The synthesized oligomers presented 5357 g·mol−1 (Mw) and 3909 g·mol−1 (Mn), with a moderate thermal resistance of approximately 175 °C. By sulfonation reaction, it was possible to obtain a high content of sulphonic groups of nearly 70 mol%, which provided the catalytic activity to the oligomeric matrix. With the mentioned physical–chemical properties, Oligocat is chemically designed to convert second generation feedstock to biodiesel efficiently. Preliminary investigation using Oligocat for biodiesel production resulted in conversion rates higher than 96.5 wt.%.
Summary
Low molar mass homopolymers, synthesized through free radical polymerization of acrylic acid under solvent control were reported. The polymers were characterized by FTIR, NMR, TGA, and GPC. The behavior as pour point improvers in biodiesel and blends biodiesel/diesel, were evaluated. By using 1000 ppm of the poly(tetradecyl acrylate) (A14) it was possible to decrease the pour point (PP) of neat biodiesel to −10°C, blend B5 to −39°C and blend B20 to −28°C, values below those reported in the literature. These results indicated that it would be possible to use higher amount of biodiesel in blends with diesel in regions where their use would not be feasible, mainly because of their poor flow properties.
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