GOALI: Manufacturing USA: Elastomeric Microparticle-Packed Bed Reactor for Continuous Metal-Mediated Pseudo-Homogeneous Catalysis

来自北卡罗莱纳州立大学和伊士曼化学公司的一组研究人员将设计和制造催化微粒，用于使用环保溶剂高效合成精细化学品、天然产品和药品。微粒将作为嵌入金属催化剂中心的聚合物微反应器。将设计一种高度柔性的弹性体微颗粒填充床反应器，可以同时显示均相和非均相催化的好处。研究工作将集中于揭示设计原则，这将有助于开发具有高合成灵活性的高效模块化微反应容器。金属介导的化学转化的效率主要取决于反应物质的化学结构和反应环境。所提出的催化体系是基于聚氢甲基硅氧烷与功能化二烯的交联，并在这种球形弹性支架中嵌入钯（Pd）催化剂。将开发一种新型的模块化、高可调催化反应器系统。这些特性是通过改变交联剂的化学性质、交联程度、钯催化剂的类型、负载和可及性以及钯催化剂周围的化学微环境来实现的。弹性体微粒将装载钯纳米催化剂，并提供一个可控的反应环境。钯催化剂是无配体的，因此反应性很强；它牢牢地驻留在一个非常灵活的弹性体微粒中，这使得钯催化剂中心在局部移动，同时保护微反应容器不受外界环境的影响。化学可调节性结合机械和结构的灵活性、可变形性和在各种溶剂中的溶胀性是使所提出的催化系统高效、稳健和可扩展的关键属性，可用于精细化学品和药物的连续有机合成。除了拟议研究的科学和技术影响外，该项目还将用于培养一名研究生和两名本科生。研究小组计划通过北卡罗来纳州立大学的科学之家项目开展外展活动，旨在吸引当地K-12学生在STEM领域从事职业。还有一项计划是招募女性和STEM领域代表性不足群体的成员参与拟议的研究和外展项目。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

A team of researchers from North Carolina State University and Eastman Chemical Company will design and fabricate catalytic microparticles for applications in energy-efficient synthesis of fine chemicals, natural products, and pharmaceuticals using environmentally friendly solvents. The microparticles will act as polymer microreactors with an embedded metal catalyst center. A highly flexible elastomeric microparticle-packed bed reactor will be designed that can simultaneously exhibit the benefits of both homogeneous and heterogeneous catalysis. The research efforts will focus on uncovering design principles that will facilitate the development of highly efficient modular microreaction vessels with high synthetic flexibility.The efficiency of metal-mediated chemical transformations depends critically on the chemical structure of the reacting species and the reaction environment. The proposed catalytic system is based on crosslinking poly(hydromethyl siloxane)s with functionalized dienes and embedding palladium (Pd) catalysts in such spherical elastomeric scaffolds. A novel catalytic reactor system will be developed that is modular and highly tunable. These attributes are achieved by varying the chemistry of the crosslinker, degree of crosslinking, type, loading, and accessibility of the Pd catalyst, and chemical microenvironment surrounding the Pd catalyst. The elastomeric microparticles will be loaded with Pd nanocatalysts and provide a controlled reaction environment. The Pd catalyst will be ligand-free and thus very reactive; it resides firmly inside a very flexible elastomeric microparticle, which makes the Pd catalyst center mobile locally while simultaneously protecting the microreaction vessel from the outside environment. Chemical adjustability in conjunction with mechanical and structural flexibility, deformability, and swellability in various solvents are key attributes that can make the proposed catalytic system efficient, robust, and scalable for the continuous organic synthesis of fine chemicals and pharmaceuticals. In addition to the scientific and technological impact of the proposed research, the project will be used to train one graduate and two undergraduate students. The research team plans to pursue outreach activities through the Science House program at North Carolina State University aimed at attracting local K-12 students to pursue careers in STEM fields. There is also a plan to recruit women and members of underrepresented groups in STEM fields to participate in the proposed research and outreach programs.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.