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The substitution of fossil resources by alternatives derived from biomass is a reality that is taking on a growing relevance in the chemical and energy industries. In this sense, fats, oils, and their derived products have become indispensable inputs due to their broad functional attributes, stable price and sustainable character. Acrylated vegetable oils are considered to be very versatile materials for very broad applications (such as in adhesives, coatings or inks) since, in the presence of photoinitiators, they can be polymerized by means of UV-initiated free radical polymerizations. The usual process for the synthesis of acrylate vegetable oils consists in reacting epoxidized oils derivatives with acrylic acid. Here, the influence of different catalysts on the activity and selectivity of the process of acrylation of epoxidized soybean oil is studied. In addition, a novel one-step method for direct acrylation of vegetable oils is also explored. This new approach advantageously uses the original vegetable resource and eliminates intermediate reactions, thus being more environmentally efficient. This study offers a simple and low-cost option for synthesizing a biomass-derived monomer and studies the potential for the 3D printing of complex structures via digital light processing (DLP) 3D printing of the thus-obtained novel sustainable formulations.

A new opportunity has arisen to produce new biomaterials from agro-industrial organic waste, within a circular economy and bio-based strategy. IRODDI is an ambitious initiative that proposes the development of new, greener processes to obtain bio-based products with specific properties/ functionalities derived from the Free Fatty Acids (FFA) contained in deodorization distillates, by-products obtained in the refining processes of vegetable oils/fats. It consists in the development of new sustainable processes to produce new bio-based products with specific properties/functionalities using innovative technologies based on supercritical CO2 (scCO2) and to isolate valuable minor compounds in gentler and environmentally friendly operating conditions, preserving their original quality and developing gentler extraction technologies.

209 p. : il., gráf., [ES]El glicerol y CO2 son dos compuestos orgánicos que hoy en día revisten gran relevancia ya que pueden ser materias primas alternativas al petróleo para la síntesis de numerosos productos derivados, entre los que se encuentra el carbonato de glicerol. Este compuesto, ha suscitado gran interés debido, principalmente, a sus propiedades, y a la gran variedad de usos y aplicaciones derivadas. En TECNALIA se ha llevado a cabo una tesis doctoral en que la que se han estudiado diferentes rutas indirectas de producción de carbonato de glicerol a partir de intermedios derivados de glicerol (3-cloro-1,2-propanodiol) y CO2 (K2CO3 y KHCO3 y DMC) fácilmente sintetizables y mucho más reactivos que los primeros. Aplicación en la Industria química La síntesis directa de carbonato de glicerol a partir de glicerol y CO2 supondría un hito en la industria química ya que implicaría obtener un producto de elevado valor a partir de dos fuentes baratas y cuyo origen es distinto al fósil. Sin embargo, los rendimientos hasta ahora obtenidos son inferiores al 10% como consecuencia de la baja reactividad del dióxido de carbono. Se han desarrollado procesos técnica y medioambientalmente eficientes, primándose en consecuencia la aplicación de procesos catalíticos y exentos de disolventes. Tras un análisis comparativo de las rutas estudiadas (en el que se consideran aspectos técnicos, económicos y medioambientales), la más apropiada para la síntesis de carbonato de glicerol resulta la transesterificación de glicerol y DMC, aunque la ruta a partir de 3-cloro-1,2-propanodiol y CO2,que utiliza TEA como agente de fijación-activación de CO2, es también muy prometedora., [EN]Glycerol and CO2 are two organic materials quite relevant because they can be used in the synthesis of different derivative products (alternative to oil) among which, glycerol carbonate is one of the most profitable. This compound has a great interest, mainly due to its properties, and the wide variety of uses and applications. This doctoral thesis has been carried out in Tecnalia in which different routes were studied to produce glycerol carbonate from glycerol derivatives (as the intermediate 3-chloro-1 ,2-propanediol) and CO2 derivatives (K2CO3 , KHCO3 and DMC) in an indirect way which results quite more reactive than the original glycerol and CO2. Application to the chemical industry The direct synthesis of glycerol carbonate from glycerol and CO2 would be a milestone in thechemical industry as it would mean obtaining a valued product employing two cheap sources whose origin is different than the fossil one. However, the yields obtained until now are far below 10% because of the low reactivity of carbon dioxide. Different processes technically and environmentally efficient for producing glycerol carbonate were studied in this thesis. The application of catalytic techniques and solvent-free processes were considered as a priority. After a comparative analysis of the evaluated routes (considering technical, economic and environmental aspects), the most appropriate for the synthesis of glycerol carbonate was selected as the trans esterification of glycerol with DMC, but the route starting from 3-chloro-1,2-propanediol and CO2, using TEA as a fixing agent-activation of CO2, is also very promising.