Organic synthesis of 5-hydroxymethylfurfural and levulinic acid from starches and subsequent transformation to bio-based materials

点击翻译按钮获取中文摘要

The long term goal of my research program is to reach a sustainable bio-economy through the transformation of key Canadian bioresources (agricultural and food residues) into chemicals and materials. The short term objectives of my research program will focus on the transformation of starch into high value chemicals and polymers. The chemicals targeted are 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), which have an impressive market value. As such, the selling price of HMF was estimated around $1,228/metric tons and the production of fuel extenders and biodegradable herbicide from LA have potential market values of 4536-45360 million kg per year. Moreover, HMF and LA will further be processed to produce polyurethanes and polyesters; two of the most versatile polymers on the market. As such, these polymers are used in many industrial sectors such as the construction, the food (packaging) and the automotive industry. In order to produce high yields of HMF and LA, the first step of this program will involve the characterization of various starch sources found in Canada (e.g. pea, triticale, corn, etc.). These feedstocks will be characterized for their amylose and amylopectin content, their granular morphology, their molecular weight distribution and their thermal properties. This will provide information which will allow for an understanding of the influence of the starches’ structure (e.g. amylose/amylopectin content) on the yield of HMF and LA. Afterwards, microwave-assisted hydrothermal degradation of starch in sub-critical water, microwave-assisted catalytic dehydration of starch by ion-exchange resin in mixed-aqueous systems, or microwave-assisted one-pot synthesis of HMF and LA over a solid catalyst are a few of the synthetic pathways which will be considered for the production of HMF and LA. The choice of microwave technology is considered as it will speed up the reaction process. This technology is very attractive as the use of “safe solvents” and “energy efficient” methodologies are two key principles of green chemistry that microwave-assisted organic synthesis has been proven to respect due to high yields and selectivity. After optimization of the yield of HMF and LA, these bio-based chemicals will be transformed into different monomers such as dicarboxylic acids, diols, polyols and polyisocyanates. The monomers will then be polymerized into polyesters by polycondensation reaction and into polyurethanes by step growth polymerization reaction. All monomers and polymers will be characterized through state-of-the-art techniques namely, x-ray diffraction, differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, gas permeation chromatography, tensile analysis among others. Training HQP in the field of Bioresource Engineering is a highly valuable long term investment. The HQP will be considered as an integral component of the research program and work toward the success of the proposed program. The synthesis of HMF, LA and both polymers will require the enrollment of two PhD, two MSc and four summer students.This research program offers a tremendous potential in terms of increasing the value of Canadian agricultural feedstocks. It has been shown that the bio-based plastic and resin market has been increasing considerably and the government of Canada estimates this growth to reach 23.7% by 2015 which represents an estimated $3.6 US billion global market potential. This is also true for green chemicals which growth rate is estimated to attain 5.3% by 2015 representing an estimated $62.3 US billion global market potential.