Metathesis-derived Green Lubricants, Waxes, Polymers and Chemicals from Vegetable Oils

拟议的研究重点是使用一种绿色方法，复分解，化学改性植物油，以生产一系列环境友好的产品：热塑性聚合物，高价值的化学品，功能润滑剂和功能蜡。复分解是连接到两个碳-碳双键的原子彼此改变位置的过程。 这导致从不饱和原料如植物油形成全新的化学品。 当仅用单一原料（例如不饱和植物油）进行复分解时，该方法被称为自复分解。该过程导致植物油分子的基本结构单元（三酰甘油酯分子）的异构化、环化和连接。 如果控制起始原料和加工条件，则可以在结构上增强所得产物混合物以提供一系列功能特性，范围从液体润滑剂到具有不同粘度、熔融温度、硬度和粘附特性的固体蜡。将小的不饱和分子引入到用于复分解的起始混合物中导致发生自复分解和交叉复分解，并且在不饱和植物油的情况下，该方法可用于将官能团引入到自复分解产物中，通过增加诸如粘度和粘附性的性质来进一步增强最终产物混合物的物理性质。 在聚合物的情况下，可以利用交叉复分解，以便在植物油的基本结构单元上的特定位置引入大量官能团;这些官能团然后成为将基本结构单元缝合在一起成为长链聚合物的位点。 交叉复分解还产生更小的副产物分子，这些分子本身作为高价值平台化学品通常非常有用。 本研究集中于控制起始材料和加工条件，以在植物油的自-、交叉-和同时自-/交叉-复分解反应的最终产物中产生受控结构。 通过研究复分解产物的结构与其物理官能度的关系，可以通过明智地选择起始材料来靶向复分解反应，以生产高官能聚合物、化学品、润滑剂和蜡。 这些材料目前是由碳密集型石化工业的石化产品生产的。 这项研究有可能将这些无处不在的材料的来源从石油碳转变为可再生的农业碳。此外，所使用的工艺是绿色的，并且不是能源密集型的，并且产品本身是环境友好的。 在材料中使用可再生碳也有助于减缓气候变化。

The proposed research is focused on the use of a green method, metathesis, to chemically modify vegetable oils to produce a range of environmentally friendly products: thermoplastic polymers, high value chemicals, functional lubricants and functional waxes. Metathesis is a process whereby the atoms connected to two carbon-carbon double bonds change places with one another.  This results in totally new chemicals being formed from unsaturated feedstock such a vegetable oils.  When metathesis is conducted with only a single feedstock, such as an unsaturated vegetable oil, the process is referred to as self-metathesis. This process results in the isomerization, cyclization and concatenation of the basic building block of a vegetable oil molecule, the triacylglyceride molecule.  If the starting feedstock and the processing conditions are controlled, the resulting product mixture can be structurally enhanced to deliver a range of functional properties, ranging from liquid lubricants to solid waxes with varying viscosities, melting temperatures, hardness and adhesion properties. The introduction of a small unsaturated molecule into the starting mixture for metathesis results in both self- and cross- metathesis taking place, and in the case of an unsaturated vegetable oil, this approach can be used to introduce functional groups into the self-metathesis products, further enhancing the physical properties of the final product mixture by increasing properties such as viscosity and adhesion.  In the case of polymers, cross-metathesis can be utilized so as to introduce a large amount of functional groups at specific locations on the basic building block of a vegetable oil; these functional groups then become the sites for the stitching together of the basic building blocks into long chain polymers.  Cross-metathesis also creates smaller by-product molecules, which are often very functional in their own right as high value platform chemicals.  This research focusses on the control of the starting materials and processing conditions to produce controlled structures in the final products of self-, cross- and simultaneous self-/cross- metathesis reactions of vegetable oils.  By studying the relationship of the structure of the products of metathesis to their physical functionality, the metathesis reaction can be targeted with judicious selection of the starting materials to produce highly functional polymers, chemicals, lubricants and waxes.  These materials are currently produced from petrochemicals from carbon-intensive petrochemical industries.  This research has the potential to switch the source of these ubiquitous materials from petroleum carbon to renewable, agriculturally grown carbon. Furthermore, the process used is green and not energy intensive and the products themselves environmentally friendly.  Utilization of renewable carbon in materials also helps abate climate change.**