GOALI: Catalysts for Copolymerization of Acrylate Monomers with Simple Olefins

宾夕法尼亚州立大学化学系的Ayusman Sen教授和Rohm&amp；Haas公司的Brian Goodall博士得到了化学部无机、生物无机和有机金属计划的资助，用于开发用于丙烯酸酯单体和单烯烃共聚合的高活性催化剂。在这项研究中，将以铜(I)、钯(II)和铑(III)络合物为基础的催化剂为目标。选择这些金属离子是因为它们的亲氧性相对较低，这将有助于最小化金属离子与丙烯酸酯基团之间的任何相互作用。具体地说，将评估一系列双(恶唑啉)铜配合物、单阴离子、名义上双齿配体的Pd(II)配合物，包括磺化膦和“NaC-NaC”；以及三氮杂环烷的三脚架Rh配合物的催化性能。将进行详细的机理研究，以确定催化活性物种的性质和链繁殖的步骤。结果将被用来调整催化剂以实现对共聚的控制。通过在非极性聚合物中加入官能团，可以控制重要的性能，如韧性、附着力、阻隔性、表面性能(可喷漆性、可印刷性、光泽度、硬度、耐损性)、耐溶剂性(或相反)、与其他聚合物的相容性以及流变性。该项目旨在开发高活性催化剂，使合成由极性丙烯酸酯和非极性烯烃组成的聚合物成为可能。由于没有有效的催化剂可用于将烯烃和丙烯酸酯快速共聚为高分子量聚合物，该项目的成功完成将填补聚合物科学中缺失的一环。Rohm and Haas是生产丙烯酸酯聚合物的行业领先者，Sen教授是共聚方面的学术专家。因此，两者之间的合作将为开发实用催化剂提供一个独特的环境。该项目将通过对结构和机械有机金属化学、聚合物化学和催化等重叠领域的本科生、研究生和博士后学者的教育，促进科学技术人力资源的发展。此外，与罗姆和哈斯的合作将为研究人员提供宝贵的工业经验。

Prof. Ayusman Sen, Chemistry Department, Pennsylvania State University, and Dr. Brian Goodall, Rohm & Haas Company, are supported by a GOALI grant from the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for the development of high activity catalysts for the copolymerization of acrylate monomers and simple olefins. In this study catalysts based on complexes of copper(I), palladium(II) and rhodium(III) will be targeted. The choice of these metal ions stems from their relatively low oxophilicity, which will serve to minimize any interactions between the metal ion and the acrylate ester group. Specifically, the catalytic properties of a series of bis(oxazoline) copper complexes, Pd(II) complexes of monoanionic, nominally bidentate ligands, including sulfonated phosphines and "nac-nac;" and tripodal Rh complexes of triazacyclononane will be evaluated. Detailed mechanistic studies will be undertaken to determine the nature of the catalytically active species and the steps in chain propagation. The results will be used to tune the catalysts to achieve control of the copolymerization. The incorporation of functional groups into an otherwise non-polar polymer allows the control of important properties, such as toughness, adhesion, barrier properties, surface properties (paintability, printability, gloss, hardness, mar resistance), solvent resistance (or its inverse), miscibility with other polymers, and rheological properties. This project aims to develop high activity catalysts that allow the synthesis of polymers that are composed of polar acrylates and nonpolar olefins. Because no efficient catalyst is available for rapidly copolymerizing olefins and acrylates to high molecular weight polymers, the successful completion of the project will fill a missing link in polymer science. Rohm and Haas is an industrial leader in the production of acrylate polymers and Prof. Sen is an academic expert in copolymerization. Hence, partnership between the two will provide a unique environment for the development of practical catalysts. The project will contribute to the development of human resources in science and technology through the education of undergraduates, graduate students, and post-doctoral scholars in the overlapping areas of structural and mechanistic organometallic chemistry, polymer chemistry, and catalysis. Additionally, the collaboration with Rohm and Haas will provide the researchers with valuable industrial experience.