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.

来自北卡罗来纳州立大学和伊士曼化学公司的研究团队将设计和制造催化微粒，用于使用环保溶剂节能合成精细化学品、天然产物和药物。 微粒将充当具有嵌入金属催化剂中心的聚合物微反应器。将设计一种高度灵活的弹性体微粒填充床反应器，可以同时展现均相和非均相催化的优点。研究工作将集中于揭示设计原理，以促进具有高合成灵活性的高效模块化微反应容器的开发。金属介导的化学转化的效率关键取决于反应物质的化学结构和反应环境。 所提出的催化系统基于聚（羟甲基硅氧烷）与官能化二烯的交联以及在此类球形弹性体支架中嵌入钯（Pd）催化剂。将开发一种模块化且高度可调的新型催化反应器系统。这些属性是通过改变交联剂的化学性质、交联程度、类型、负载量和钯催化剂的可及性以及钯催化剂周围的化学微环境来实现的。弹性体微粒将负载钯纳米催化剂并提供受控的反应环境。 Pd 催化剂不含配体，因此反应活性很高；它牢固地驻留在非常柔韧的弹性体微粒内，这使得钯催化剂中心可以局部移动，同时保护微反应容器免受外部环境的影响。化学可调节性与机械和结构灵活性、可变形性和在各种溶剂中的可膨胀性相结合是关键属性，可以使所提出的催化系统在精细化学品和药物的连续有机合成中高效、稳健和可扩展。 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立大学的 Science House 项目开展外展活动，旨在吸引当地 K-12 学生在 STEM 领域追求职业生涯。还有一项计划招募 STEM 领域的女性和代表性不足群体的成员来参与拟议的研究和推广计划。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优点和更广泛的影响审查进行评估，被认为值得支持标准。

项目成果

Continuous synthesis of elastomeric macroporous microbeads

弹性体大孔微珠的连续合成

• DOI: 10.1039/c8re00189h
• 发表时间: 2019-02-04
• 期刊: Reaction Chemistry & Engineering
• 影响因子: 3.9
• 作者: Jeffrey A. Bennett;Zachary S. Campbell;M. Abolhasani
• 通讯作者: M. Abolhasani

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

弹性体微粒的微流控合成：钯介导的交叉偶联催化案例研究

• 发表时间: 2018-10
• 期刊: 2018 AIChE Annual Meeting
• 作者: Bennett, Jeffrey A;Genzer, Jan;Abolhasani, Milad
• 通讯作者: Abolhasani, Milad

Continuous flow synthesis of phase transition-resistant titania microparticles with tunable morphologies

连续流动合成具有可调形貌的抗相变二氧化钛微粒

• DOI: 10.1039/d0ra01442g
• 发表时间: 2020-02-24
• 期刊: RSC Advances
• 影响因子: 3.9
• 作者: Zachary S. Campbell;Daniel Jackson;J. Lustik;Amur K. Al;Jeffrey A. Bennett;Fanxing Li;M. Abolh
• 通讯作者: M. Abolh

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: 2020-01
• 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

Role of continuous flow processes in green manufacturing of pharmaceuticals and specialty chemicals

连续流工艺在药品和特种化学品绿色制造中的作用

• DOI: 10.1016/j.coche.2019.07.007
• 发表时间: 2019-12
• 期刊: Current Opinion in Chemical Engineering
• 影响因子: 6.6
• 作者: Bennett, Jeffrey A;Campbell, Zachary S;Abolhasani, Milad
• 通讯作者: Abolhasani, Milad