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

提议的研究重点是使用一种绿色方法，即转化，对植物油进行化学改性，以生产一系列环保产品：热塑性聚合物、高价值化学品、功能性润滑剂和功能性蜡。复合是连接两个碳-碳双键的原子相互改变位置的过程。这导致从不饱和原料如植物油中形成全新的化学物质。当仅用单一原料（如不饱和植物油）进行复分解时，该过程称为自复分解。这个过程导致植物油分子的基本组成部分——三酰甘油分子的异构化、环化和串联。如果起始原料和加工条件得到控制，所得到的产品混合物可以在结构上得到增强，以提供一系列功能特性，从液体润滑剂到具有不同粘度、熔化温度、硬度和附着力的固体蜡。在起始混合物中引入一个小的不饱和分子进行复分解会导致自我和交叉复分解的发生，在不饱和植物油的情况下，这种方法可以用来将官能团引入到自我复分解产品中，通过增加粘度和附着力等特性进一步增强最终产品混合物的物理特性。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构建块上的特定位置引入大量的官能团；这些官能团随后成为将基本构建块拼接成长链聚合物的位点。交叉分解还会产生更小的副产物分子，这些分子通常作为高价值的平台化学品具有很强的功能。本研究的重点是控制起始原料和加工条件，以在植物油的自、交叉和同时自/交叉反应的最终产物中产生可控的结构。通过研究复分解产物的结构与其物理功能的关系，可以有针对性地进行复分解反应，合理选择原料，生产高功能的聚合物、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，所使用的过程是绿色的，不消耗能源，产品本身是环保的。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.