Self-Assembly of Multinuclear Catalysts for the Direct Synthesis of Functionalized Polyolefins

用于直接合成功能化聚烯烃的多核催化剂自组装

• 批准号: 1709159
• 负责人: Richard Jordan
• 金额: $ 62万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-06-15 至 2021-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1709159&HistoricalAwards=false
• 关键词: Self; Assembly; Multinuclear; Catalysts; Direct

Polyethylene, a plastic that is ubiquitous in everyday life, is used in innumerable applications ranging from packaging films and milk jugs to machine parts and artificial joints. Polyethylene is made by linking small 2-carbon-unit gas molecules (ethylene) together into long chains with the aid of metal catalysts in a process known as polymerization. The research group of Professor Richard Jordan is developing a new generation of metal catalysts that can incorporate other kinds of small molecules into the polyethylene chains, to produce plastics with improved properties, including increased toughness, superior resistance to penetration by gases and chemicals, and enhanced biodegradability. This project is contributing to the development of human resources in science, technology, engineering and mathematics through the education of postdoctoral fellows, graduate students, undergraduates and high school students. This project is also providing summer research opportunities to high school students from the Chicago Public Schools (CPS) system through the University of Chicago Collegiate Scholars Program and mentoring and other support to CPS high school students through the Neighborhood Schools Program.This project is focused on the chemistry of palladium alkyl complexes with phosphine-bis-arenesulfonate ligands (OPO2-) that self-assemble into tetrameric structures in which four (OPO-Li)PdR units are arranged around the periphery of a cubic Li-sulfonate cage. "Pd cage" catalysts polymerize ethylene to ultra-high-molecular-weight linear polyethylene (MW 10^6 Da) and copolymerize ethylene with vinyl fluoride with tenfold-higher comonomer incorporation than can be achieved with mononuclear catalysts. This research is harnessing the power of programmed molecular self-assembly to synthesize exceptionally robust Pd cage structures that maintain their integrity at high temperature and function as single-site polymerization catalysts. The targets include assemblies based on OPO2- ligands that contain sulfonate groups with enhanced basicity to strengthen the Li─O interactions in the cage, "expanded" cages that incorporate additional ions to provide supplementary bonding interactions, "strapped" cages in which covalent links between OPO2- ligands provide high stability, and catalysts based on Zn-phosphonate cages that are inherently more robust than Li-sulfonate cages. The research team is establishing the factors that control the self-assembly of cage catalysts and the key mechanistic features of ethylene polymerization by these catalysts, and is exploiting this knowledge to develop high-performance catalysts for ethylene/vinyl-fluoride copolymerization.

聚乙烯是一种在日常生活中无处不在的塑料，用于从包装膜和牛奶罐到机器零件和人造关节的无数应用。聚乙烯是通过将金属催化剂的帮助在称为聚合的过程中借助金属催化剂将小链连接到长链中来制成的。理查德·乔丹（Richard Jordan）教授的研究小组正在开发新一代的金属催化剂，可以将其他类型的小分子融入聚乙烯链中，以产生具有改善特性的塑料，包括提高韧性，对气体和化学物质对渗透性的优势抗性，以及增强的生物降解性。该项目通过教育博士后研究员，研究生，本科生和高中生的教育来为科学，技术，工程和数学的人力资源发展做出贡献。该项目还通过芝加哥大学大学学者计划和通过邻里学校计划向CPS高中学生提供指导和其他支持为芝加哥公立学校（CPS）系统的高中生提供夏季研究机会。该项目的重点是与磷酸 - 甲磺酸盐构造Ligoders（Opemeren）的钯烷基化学有关，该项目是该项目的四个人（OPOPORECT） （OPO-LI）PDR单元被布置在立方李 - 磺酸盐笼的外围。 “ PD笼”催化剂将乙烯聚合到超高分子量线性聚乙烯（MW 10^6 DA），并与乙烯基氟化物与乙烯基氟化物与十倍高的共生仪合并相结合，而不是与单核催化剂可实现的。这项研究正在利用编程的分子自组装的力量，以合成异常可靠的PD笼结构，这些PD CAGE结构将其保持在高温和功能作为单位聚合催化剂的功能下。 The targets include assemblies based on OPO2- ligands that contain sulfonate groups with enhanced basicity to strengthen the Li─O interactions in the cage, "expanded" cages that incorporate additional ions to provide supplementary bonding interactions, "strapped" cages in which covalent links between OPO2- ligands provide high stability, and catalysts based on Zn-phosphonate cages that are本质上比硫酸盐笼更健壮。研究团队正在建立控制笼催化剂自组装的因素，以及这些催化剂的乙烯聚合的关键机理特征，并利用这些知识来开发用于乙烯/乙烯基 - 氟化物共聚的高性能催化剂。

项目成果

Copolymerization of Ethylene and Vinyl Fluoride by Self-Assembled Multinuclear Palladium Catalysts

自组装多核钯催化剂乙烯与氟乙烯的共聚

• DOI: 10.3390/polym12071609
• 发表时间: 2020
• 期刊: Polymers
• 影响因子: 5
• 作者: Liu, Q

Ethylene Oligomerization and Polymerization by Palladium(II) Methyl Complexes Supported by Phosphines Bearing a Perchlorinated 10-Vertex closo -Carborane Anion Substituent

带有全氯 10 顶点近碳硼烷阴离子取代基的膦负载的钯 (II) 甲基配合物的乙烯齐聚和聚合

• DOI: 10.1021/acs.organomet.8b00772
• 发表时间: 2018
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Kleinsasser, Jack F.;Reinhart, Erik D.;Estrada, Jess;Jordan, Richard F.;Lavallo, Vincent
• 通讯作者: Lavallo, Vincent

Complexation of an indole-based α-aminoimine ligand to Pd(II)

基于吲哚的 α-氨基亚胺配体与 Pd(II) 的络合

• DOI: 10.1016/j.ica.2018.06.030
• 发表时间: 2018
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Zhai, Feng;Jordan, Richard F.
• 通讯作者: Jordan, Richard F.

Multinuclear Palladium Olefin Polymerization Catalysts Based on Self-Assembled Zinc Phosphonate Cages

• DOI: 10.1021/acs.organomet.8b00683
• 发表时间: 2018-11
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Qian Liu;R. F. Jordan

Synthesis and reactivity of phosphine-arenesulfonate palladium(II) alkyl complexes that contain methoxy substituents

• DOI: 10.1016/j.jorganchem.2019.06.012
• 发表时间: 2019-09
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Qian Liu;R. F. Jordan