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

GOALI：美国制造：用于连续金属介导的伪均相催化的弹性体微粒填充床反应器

• 批准号: 1803428
• 负责人: Milad Abolhasani
• 金额: $ 36万
• 依托单位: North Carolina State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1803428&HistoricalAwards=false
• 关键词: GOALI; Manufacturing; USA; Elastomeric; Microparticle

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.

来自北卡罗来纳州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，天然产物和药物。 微粒将作为聚合物微反应器与嵌入金属催化剂中心。一个高度灵活的弹性微粒填充床反应器将被设计，可以同时表现出均相和多相催化的好处。研究工作将集中在揭示设计原则，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种的化学结构和反应环境。 建议的催化体系是基于交联聚（羟甲基硅氧烷）与官能化的二烯和嵌入钯（Pd）催化剂在这样的球形弹性体支架。一种新型的催化反应器系统将被开发，是模块化的和高度可调的。这些属性通过改变交联剂的化学性质、交联度、Pd催化剂的类型、负载和可及性以及Pd催化剂周围的化学微环境来实现。弹性体微粒将负载有Pd纳米催化剂并提供受控的反应环境。Pd催化剂将是无配体的，因此非常具有反应性;它牢固地存在于非常柔性的弹性体微粒内，这使得Pd催化剂中心局部移动的，同时保护微反应容器免受外部环境的影响。化学可调性与机械和结构灵活性、可变形性和在各种溶剂中的可溶胀性相结合是关键属性，其可以使所提出的催化系统高效、稳健和可扩展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，该项目还将用于培训一名研究生和两名本科生。研究团队计划通过北卡罗来纳州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。该奖项反映了NSF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。

项目成果

Network-Supported, Metal-Mediated Catalysis: Progress and Perspective

网络支持的金属介导的催化：进展与前景

• DOI: 10.1039/d0re00229a
• 发表时间: 2020
• 期刊: Reaction Chemistry & Engineering
• 影响因子: 3.9
• 作者: Bennett, Jeffrey A;Davis, Bradley;Efimenko, Kirill;Genzer, Jan;Abolhasani, Milad
• 通讯作者: Abolhasani, Milad

Microfluidic Synthesis of Elastomeric Microparticles: A Case Study in Catalysis of Palladium-Mediated Cross-Coupling

• DOI: 10.1002/aic.16119
• 发表时间: 2018-08-01
• 期刊: AICHE JOURNAL
• 影响因子: 3.7
• 作者: Bennett, Jeffrey A.;Kristof, Andrew J.;Abolhasani, Milad
• 通讯作者: Abolhasani, Milad

Continuous synthesis of elastomeric macroporous microbeads

• DOI: 10.1039/c8re00189h
• 发表时间: 2019-02-01
• 期刊: REACTION CHEMISTRY & ENGINEERING
• 影响因子: 3.9
• 作者: Bennett, Jeffrey A.;Campbell, Zachary S.;Abolhasani, Milad
• 通讯作者: Abolhasani, Milad