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

我的研究计划的长期目标是通过加拿大生物资源（农业和食品残留物）转化为化学品和材料来实现可持续的生物经济。我的研究计划的短期目标将集中在淀粉转化为高价值的化学品和聚合物。目标化学品是5-羟甲基糠醛（HMF）和乙酰丙酸（LA），它们具有令人印象深刻的市场价值。因此，HMF的销售价格估计约为1，228美元/公吨，从LA生产的燃料填充剂和可生物降解的除草剂的潜在市场价值为每年4536-45360百万公斤。此外，HMF和LA将进一步加工生产聚氨酯和聚酯，这是市场上最通用的两种聚合物。因此，这些聚合物用于许多工业部门，如建筑，食品（包装）和汽车工业。 为了生产高产量的HMF和LA，该计划的第一步将涉及在加拿大发现的各种淀粉来源的表征（例如豌豆，黑小麦，玉米等）。这些原料将表征其直链淀粉和支链淀粉含量、颗粒形态、分子量分布和热性能。这将提供允许理解淀粉的结构（例如直链淀粉/支链淀粉含量）对HMF和LA的产率的影响的信息。之后，微波辅助淀粉在亚临界水中的水热降解，微波辅助淀粉在混合水体系中通过离子交换树脂的催化脱水，或微波辅助HMF和LA在固体催化剂上的一锅法合成是将被考虑用于生产HMF和LA的几种合成途径。微波技术的选择被认为是因为它将加快反应过程。该技术是非常有吸引力的，因为“安全溶剂”和“节能”方法的使用是绿色化学的两个关键原则，微波辅助有机合成由于高产率和选择性而被证明是尊重的。 在优化HMF和LA的产率后，这些生物基化学品将转化为不同的单体，如二羧酸、二醇、多元醇和多异氰酸酯。然后，单体通过缩聚反应聚合成聚酯，并通过逐步增长聚合反应聚合成聚氨酯。所有单体和聚合物将通过最先进的技术进行表征，即X射线衍射、差示扫描量热法、动态力学分析、热重分析、傅里叶变换红外光谱、气体渗透色谱、拉伸分析等。 在生物资源工程领域培训HQP是一项非常有价值的长期投资。HQP将被视为研究计划的一个组成部分，并为拟议计划的成功而努力。HMF，LA和两种聚合物的合成将需要两名博士，两名硕士和四名暑期学生的入学。 该研究项目在增加加拿大农业原料价值方面具有巨大潜力。据显示，生物基塑料和树脂市场一直在大幅增长，加拿大政府估计，到2015年，这一增长将达到23.7%，这意味着全球市场潜力估计为36亿美元。绿色化学品也是如此，预计到2015年增长率将达到5.3%，全球市场潜力估计为623亿美元。

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.