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的方法-化合作用，对植物油进行化学修饰，以生产一系列环境友好产品：热塑性聚合物、高价值化学品、功能润滑剂和功能蜡。化合作用是指连接到两个碳-碳双键的原子相互交换位置的过程。这导致了从不饱和原料(如植物油)中形成全新的化学物质。当只用一种原料进行化合反应时，如不饱和植物油，这个过程被称为自化合作用。这一过程导致植物油分子的基本构件三酰甘油酯分子的异构化、环化和连接。如果对起始原料和加工条件进行控制，所得到的产品混合物可以在结构上得到改进，以提供一系列功能特性，从液体润滑剂到具有不同粘度、熔融温度、硬度和粘附性的固体蜡。将一个小的不饱和分子引入到初始混合物中进行化合会导致自和交叉化合作用的发生，在不饱和植物油的情况下，这种方法可以用来在自复分解产品中引入官能团，通过增加粘度和粘附性等性质进一步提高最终产品混合物的物理性质。对于聚合物，可以利用交叉化合作用，在植物油的基本组成块上的特定位置引入大量官能团；这些官能团然后成为基本组成块缝合在一起的位置，形成长链聚合物。交叉化合作用还会产生更小的副产品分子，作为高价值的平台化学品，这些分子本身往往具有非常高的功能。这项研究的重点是控制原料和工艺条件，以在植物油的自、交叉和同时自/交叉化合反应的最终产品中产生受控结构。通过研究复分解产物的结构与其物理功能的关系，复分解反应可以通过明智地选择起始材料来进行定向，以生产高功能聚合物、化学品、润滑剂和蜡。这些材料目前是从碳密集型石化行业的石化产品中生产的。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、农业种植的碳。此外，使用的工艺是绿色的，不是能源密集型的，而且产品本身是环保的。在材料中利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.