Monomers and Functional Biopolymers from Renewable Lipid Resources

现代生活依赖于广泛用于工业应用的聚合物，包括包装、汽车、建筑、体育、医药、诊断和电子产品。合成这些聚合物的单体主要来自石油。由于对石油可持续性的担忧和温室气体(GHG)人为排放的增加，将可再生原料转化为单体和生物聚合物是非常可取的。因此，利用烯烃歧化化学将可再生脂肪/油转化为单体已引起人们的兴趣。我在艾伯塔大学的研究小组正在使用化合方法从可再生的脂类资源中开发基于生物的单体和聚合物。最近，我的实验室获得了3项专利，开发了一种利用均相催化将可再生脂肪转化为单体和随后的生物聚合物的无溶剂微波辅助歧化工艺。基于这些发现，一家新的副产品生物炼油厂被纳入其中。然而，为了克服催化剂成本高、湿度敏感、催化剂失活等导致复分解产物金属污染的关键技术障碍，需要开发可回收、可重复使用、水分稳定和低成本的多相催化剂，以实现大规模向油脂生物精制的过渡。与定义明确的均相催化相比，由于有效固定化以保持催化活性的挑战以及对可再生原料中催化剂失活过程的了解，可再生能源的多相歧化催化研究进展有限。在本文中，我们将致力于开发水分稳定、可回收和可重复使用的聚合物固定化均相催化剂和纳米负载多相催化剂，用于可再生油脂原料的微波歧化反应。这项研究的另一个目标将是利用二氧化碳(CO2)和由歧化脂肪产生的内部烯烃单体来制备可再生聚碳酸酯。拟议的研究计划将有助于在多相载体的设计和合成、催化剂的固定化、脂肪转化中的催化剂回收以及使用生产的单体和二氧化碳合成生物聚合物方面的基础知识发现。这些领域的研究是高度多学科的，将导致绿色催化技术的进步，将可再生资源转化为单体和聚合物材料。这项研究将减少我们对化石燃料的依赖，减少温室气体排放，并促进向生物经济的过渡。这项拟议研究的预期成果将是开发经济上可行的多相催化工艺，这将导致快速的潜在商业化。拟议的研究方案将为培训高素质人员提供独特的环境。

Modern life relies on polymers which are used in wide range of industrial applications including packaging, automotive, construction, sporting, medicine, diagnostics and electronic. The monomers for synthesis of these polymers are primarily sourced from petroleum. Due to concerns over the sustainability of petroleum and the increasing anthropogenic emissions of greenhouse gases (GHG), the conversion of renewable feedstocks into monomers and biopolymers is highly desirable. Therefore, the conversion of renewable fats/oils into monomers using olefin metathesis chemistry has gained interest. My research group at the University of Alberta is developing biobased monomers and polymers from renewable lipid resources using metathesis approach. Recently, with 3 patents awarded, my laboratory developed a solvent free microwave assisted metathesis process using homogeneous catalysis to convert renewable lipids into monomers and subsequent biopolymers. Based on these finding, a new spin off biorefinery has been incorporated. However, to overcome the critical technical barriers such as high catalyst cost, moisture sensitivity, and deactivation of catalyst leading to metal contamination of metathesis products, the development of recyclable, reusable, moisture stable and cost effective heterogeneous catalysis is required for large scale transition to lipid biorefining. In contrast to the well-defined homogeneous catalysis, the progress on heterogeneous metathesis catalysis of renewables has been limited due to the challenges in effective immobilization to maintain catalytic activity and poor understanding of the process of the catalyst deactivation in renewable feedstocks. In this DG, we will focus on the development of moisture stable, recyclable and reusable polymer immobilized homogeneous and nano-supported heterogeneous catalysts for microwave-assisted metathesis of renewable lipidic feedstocks. Another goal of the research will be to prepare renewable polycarbonates using carbon dioxide (CO2) and internal olefinic monomers produced from metathesized lipids. The proposed research program will contribute to fundamental knowledge discovery in the areas of design and synthesis of heterogeneous supports, catalysts immobilizations, catalyst recycling in lipid conversions and biopolymers synthesis using produced monomers and CO2. Research in these areas is highly multidisciplinary and will lead to advances in green catalysis techniques for conversion of renewable resources into monomers and polymeric materials. The research will reduce our dependency on fossil fuels, reduce GHG emissions and facilitate the transition to a bioeconomy. The anticipated output of this proposed research would be development of economically viable heterogeneous catalytic processes which can lead to rapid potential commercialization. The proposed research program will provide a unique environment towards the training of highly qualified personnel