CAREER: Olefin Polymerization Catalysts with Ligands Featuring Weakly Coordinating Carborane Anions

职业：具有弱配位碳硼烷阴离子配体的烯烃聚合催化剂

• 批准号: 1455348
• 负责人: Vincent Lavallo
• 金额: $ 67.5万
• 依托单位: University of California-Riverside
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-04-01 至 2020-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1455348&HistoricalAwards=false
• 关键词: CAREER; Olefin; Polymerization; Catalysts; Ligands

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor Vincent Lavallo of the University of California at Riverside is developing new catalysts capable of converting olefin feedstocks into polymers with distinct and desirable properties. Polymers are long chain organic molecules and are found in many facets of everyday life that utilize plastics, including food packaging, structural materials for automotive and aerospace transportation, and lightweight electronic devices. The preparation of useful polymers, such as plastics, requires the utilization of a catalyst to facilitate the chain building process and control the physical properties of the ensuing material. Professor Lavallo is developing catalysts that contain a novel collection of boron and carbon atoms called a carborane anion, which is predicted to bestow unique properties upon the catalysts. Undergraduate and graduate students in the Chemistry Department at the University of California Riverside are being mentored in this program and are participating in the research. Professor Lavallo is also developing a mentorship program for high school students from economically disadvantaged backgrounds. In the summer months, these high school students will participate in the proposed research at UCR, and during the academic year, a novel curriculum will be implemented at the high school, allowing a large number of students to directly engage in the project. In this project, Professor Lavallo is synthesizing and studying phosphine and N-heterocyclic carbene ligands containing icosahedral carborane anion substituents. Icosahedral carborane anions are far more weakly coordinating, less basic, and larger than sulfonates (palladium complexes of phosphine-sulfonates are an unusual family of olefin polymerization catalysts that produce mostly linear polyethylene copolymers), and these properties should favor the formation of the trans-pi-complexes necessary for catalysis and also inhibit beta-elimination. The objective is to produce olefin polymerization catalysts that display enhanced activity, functional group tolerance, and produce polymers with greater uniformity and molecular weight compared to state-of-the-art systems. The broader impacts of the project pertain to the potential uses of phosphine and N-heterocyclic carbene ligands containing icosahedral carborane anion substituents and the planned educational activities targeted towards high school students from economically disadvantaged backgrounds.

在这个由化学部化学催化项目资助的项目中，加州大学河滨分校的 Vincent Lavallo 教授正在开发能够将烯烃原料转化为具有独特且理想性能的聚合物的新型催化剂。 聚合物是长链有机分子，存在于日常生活中使用塑料的许多方面，包括食品包装、汽车和航空航天运输的结构材料以及轻型电子设备。 有用聚合物（例如塑料）的制备需要利用催化剂来促进链构建过程并控制所得材料的物理性质。 拉瓦洛教授正在开发含有一种新型硼和碳原子集合（称为碳硼烷阴离子）的催化剂，预计它将赋予催化剂独特的性能。 加州大学河滨分校化学系的本科生和研究生正在接受该项目的指导并参与研究。拉瓦洛教授还正在为经济困难的高中生制定一个导师计划。在夏季，这些高中生将参与加州大学河滨分校的拟议研究，在学年期间，高中将实施新颖的课程，让大量学生直接参与该项目。 在这个项目中，Lavallo教授正在合成和研究含有二十面体碳硼烷阴离子取代基的膦和N-杂环卡宾配体。 二十面体碳硼烷阴离子的配位性更弱，碱性更弱，并且比磺酸盐更大（膦-磺酸盐的钯配合物是一种不寻常的烯烃聚合催化剂家族，主要生产线性聚乙烯共聚物），这些特性应该有利于反式-催化所需的 pi 配合物，也抑制 β 消除。 目标是生产具有增强活性、官能团耐受性的烯烃聚合催化剂，并生产出与最先进的系统相比具有更高均匀性和分子量的聚合物。 该项目更广泛的影响涉及磷化氢和含有二十面体碳硼烷阴离子取代基的N-杂环卡宾配体的潜在用途以及针对经济困难背景的高中生的计划教育活动。