Development of More Active and More Selective Catalysts for ATRP

开发活性更高、选择性更高的 ATRP 催化剂

• 批准号: 2000391
• 负责人: Krzysztof Matyjaszewski
• 金额: $ 60万
• 依托单位: Carnegie-Mellon University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2000391&HistoricalAwards=false
• 关键词: Development; More; Active; Selective; Catalysts

With this award, the Macromolecular, Supramolecular, and Nanochemistry Program in the Chemistry Division is supporting Professor Krzysztof Matyjaszewski at Carnegie Mellon University to develop new Cu-based catalysts for atom transfer radical polymerization (ATRP). Radical polymerization is a chemical reaction that sequentially adds small molecules of monomers to form long polymer chains that consist of hundreds or thousands of repeating units. This powerful synthetic method is used to make nearly half of all plastics, about 100 million tons worldwide each year. ATRP is a special type of radical polymerization that can prepare advanced polymers with precisely controlled chain lengths and shapes. ATRP is also used to prepare various hybrid materials by chemically linking synthetic polymers to biomolecules and to surfaces of inorganic particles. Professor Matyjaszewski’s team develops new catalysts for such important ATRP processes with enhanced activity and selectivity. This study will contribute to the creation of more precise polymers and expansion of range of polymerizable monomers, while using diminished levels of catalyst. By employing “green” ATRP catalysts, this research provides environmentally improved polymerization conditions, relevant for the industrial production of polymers. The broader impacts include the training undergraduate and graduate students in polymer science and educating the public about controlled radical polymerization via instructional webpages and videos.Under this ward, Professor Matyjaszewski and his team will explore preparation of catalysts with much higher activity than the original ATRP catalysts and that retain selectivity for the ATRP pathway while suppressing Cu-induced termination and transfer reactions. ATRP is based on a reversible atom transfer process between dormant alkyl halides and growing radicals, catalyzed by redox active transition metal complexes. ATRP is used to prepare advanced polymers with well-defined architecture. They include uniform linear chains and also star, comb and cyclic polymers, as well as statistical, periodic, gradient and block copolymers. The new ATRP catalysts are based on ligands belonging to the tris(pyridylmetyl)amine, or tetra-aza-macrocycle families. Thermodynamic and kinetic properties of new complexes will be determined through electrochemical, spectroscopic and computational methods to establish the comprehensive structure/reactivity relationship. The new catalysts being developed will be employed for ATRP of (meth)acrylates and (meth)acrylamides and also for less ATRP-active monomers such as vinyl esters and N-vinylamides. The catalysts will be evaluated for their ability to activate alkyl (pseudo)halides with F-C, N3-C, SCN-C bonds, much less active species than the alkyl bromides or chlorides that are typically used in ATRP. The extremely reactive Cu-based catalysts react not only with alkyl halides but also with propagating radicals, forming transient organocuprate species. The latter paramagnetic compounds induce termination processes. Therefore, the mechanism of Cu-catalyzed termination will be studied in great detail to gain insight into the design of more selective catalysts and optimize polymerization conditions.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.

化学部的大分子、超分子和纳米化学项目正在支持卡内基梅隆大学的Krzysztof Matyjaszewski教授开发用于原子转移自由基聚合（ATRP）的新型cu基催化剂。自由基聚合是一种化学反应，它依次添加小分子单体，形成由数百或数千个重复单元组成的长聚合物链。这种强大的合成方法用于制造近一半的塑料，全球每年约1亿吨。ATRP是一种特殊类型的自由基聚合，可以制备具有精确控制链长和形状的高级聚合物。ATRP还用于通过化学连接合成聚合物与生物分子和无机颗粒表面来制备各种杂化材料。Matyjaszewski教授的团队为这种重要的ATRP过程开发了新的催化剂，具有更高的活性和选择性。这项研究将有助于创造更精确的聚合物和扩大可聚合单体的范围，而使用较少的催化剂水平。通过采用“绿色”ATRP催化剂，本研究为聚合物的工业生产提供了环境改善的聚合条件。更广泛的影响包括培养高分子科学的本科生和研究生，并通过教学网页和视频教育公众有关受控自由基聚合的知识。在这个方向下，Matyjaszewski教授和他的团队将探索制备比原始ATRP催化剂活性高得多的催化剂，并在抑制cu诱导的终止和转移反应的同时保留ATRP途径的选择性。ATRP是基于休眠的烷基卤化物和生长的自由基之间的可逆原子转移过程，由氧化还原活性过渡金属配合物催化。ATRP用于制备结构明确的高级聚合物。它们包括均匀线性链和星形、梳状和环状聚合物，以及统计、周期、梯度和嵌段共聚物。新的ATRP催化剂是基于属于三（吡啶基）胺或四氮杂环家族的配体。通过电化学、光谱学和计算方法确定新配合物的热力学和动力学性质，建立全面的结构/反应性关系。正在开发的新型催化剂将用于（甲基）丙烯酸酯和（甲基）丙烯酰胺的ATRP，以及乙烯酯和n -乙烯酰胺等ATRP活性较低的单体。该催化剂将被评估其激活具有F-C， N3-C， SCN-C键的烷基（伪）卤化物的能力，这些活性物质远低于ATRP中通常使用的烷基溴或氯化物。cu基催化剂不仅能与烷基卤化物反应，还能与增殖自由基反应，形成瞬态有机酸盐。后一种顺磁性化合物诱导终止过程。因此，我们将对cu催化的终止机理进行详细的研究，以帮助设计更具选择性的催化剂和优化聚合条件。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。

项目成果

Synthesis of Tris[2‐(dimethylamino)ethyl]amine with Regiospecific Deuterium Labels

具有区域特异性氘标记的三[2-(二甲氨基)乙基]胺的合成

• DOI: 10.1002/slct.202300053
• 发表时间: 2023
• 期刊: ChemistrySelect
• 影响因子: 2.1
• 作者: Sobieski, Julian;Ruzhylo, Illia;Szczepaniak, Grzegorz;Gorczyński, Adam;Matyjaszewski, Krzysztof;Manoury, Eric;Poli, Rinaldo
• 通讯作者: Poli, Rinaldo

Biocompatible photoinduced CuAAC using sodium pyruvate

使用丙酮酸钠的生物相容性光诱导 CuAAC

• DOI: 10.1039/d1cc05566f
• 发表时间: 2021
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Jeong, Jaepil;Szczepaniak, Grzegorz;Yerneni, Saigopalakrishna S.;Lorandi, Francesca;Jafari, Hossein;Lathwal, Sushil;Das, Subha R.;Matyjaszewski, Krzysztof
• 通讯作者: Matyjaszewski, Krzysztof

Under pressure: electrochemically-mediated atom transfer radical polymerization of vinyl chloride

• DOI: 10.1039/d0py00995d
• 发表时间: 2020-11-14
• 期刊: POLYMER CHEMISTRY
• 影响因子: 4.6
• 作者: De Bon, Francesco;Ribeiro, Diana C. M.;Coelho, Jorge F. J.
• 通讯作者: Coelho, Jorge F. J.

PET-RAFT Increases Uniformity in Polymer Networks

PET-RAFT 提高聚合物网络的均匀性

• DOI: 10.1021/acsmacrolett.2c00448
• 发表时间: 2022
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Wanasinghe, Shiwanka V.;Sun, Mingkang;Yehl, Kevin;Cuthbert, Julia;Matyjaszewski, Krzysztof;Konkolewicz, Dominik
• 通讯作者: Konkolewicz, Dominik

Conjugated Cross-linked Phenothiazines as Green or Red Light Heterogeneous Photocatalysts for Copper-Catalyzed Atom Transfer Radical Polymerization

• DOI: 10.1021/jacs.1c04428
• 发表时间: 2021-06-21
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Dadashi-Silab, Sajjad;Lorandi, Francesca;Matyjaszewski, Krzysztof
• 通讯作者: Matyjaszewski, Krzysztof