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

从淀粉有机合成 5-羟甲基糠醛和乙酰丙酸并随后转化为生物基材料

• 批准号: RGPIN-2014-06321
• 负责人: Dumont, MarieJosée
• 金额: $ 1.82万
• 依托单位: McGill University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2015
• 资助国家: 加拿大
• 起止时间: 2015-01-01 至 2016-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=588940
• 关键词: Organic; synthesis; hydroxymethylfurfural; levulinic; acid

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.

我的研究计划的长期目标是通过将加拿大主要生物资源（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于将淀粉转化为高价值化学品和聚合物。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 的售价估计约为 1,228 美元/吨，洛杉矶生产的燃油增量剂和可生物降解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；市场上两种最通用的聚合物。因此，这些聚合物用于许多工业领域，例如建筑、食品（包装）和汽车工业。 为了生产高产的 HMF 和 LA，该计划的第一步将涉及加拿大发现的各种淀粉来源（例如豌豆、黑小麦、玉米等）的特性。这些原料的特征包括直链淀粉和支链淀粉含量、颗粒形态、分子量分布和热性能。这将提供有助于了解淀粉结构（例如直链淀粉/支链淀粉含量）对 HMF 和 LA 产量影响的信息。随后，在亚临界水中微波辅助淀粉水热降解、混合水体系中离子交换树脂微波辅助淀粉催化脱水、或在固体催化剂上微波辅助一锅法合成 HMF 和 LA 是生产 HMF 和 LA 时考虑的几种合成途径。考虑选择微波技术，因为它将加速反应过程。这项技术非常有吸引力，因为使用“安全溶剂”和“节能”方法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已被证明遵守这两个原则。 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。 然后单体将通过缩聚反应聚合成聚酯，并通过逐步生长聚合反应聚合成聚氨酯。所有单体和聚合物都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，并致力于使拟议计划取得成功。 HMF、LA 和两种聚合物的合成需要招收两名博士生、两名硕士生和四名暑期学生。 该研究计划在增加加拿大农业原料的价值方面具有巨大的潜力。研究表明，生物基塑料和树脂市场一直在大幅增长，加拿大政府预计到 2015 年这一增长率将达到 23.7%，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。