Atom Transfer Radical Polymerization of Acidic Monomers

酸性单体的原子转移自由基聚合

• 批准号: 1707490
• 负责人: Krzysztof Matyjaszewski
• 金额: $ 43.2万
• 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: 2017
• 资助国家: 美国
• 起止时间: 2017-08-01 至 2020-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1707490&HistoricalAwards=false
• 关键词: Atom; Transfer; Radical; Polymerization; Acidic

Radical polymerization is a chemical reaction that sequentially adds together small molecules (called monomers) to form long polymer chains that consist of hundreds or thousands of repeating units. Radical polymerization is a powerful synthetic method. It is used to make nearly half of all polymers (plastics), about 100 million tons worldwide each year. Atom transfer radical polymerization (ATRP) is a special type of radical polymerization that can prepare polymers with precisely controlled chain lengths. In addition, depending on the chemical structure of the monomer, it can produce a variety of shapes, such as stars, combs, brushes or rings and each of these has specialty applications. While ATRP is a common technique, some monomers, especially those with acidic functionalities, are difficult to polymerize using ATRP. Polymers formed from acidic monomers are desirable because they have unique properties that make them useful in a variety of applications. With the support of the Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division, Professor Matyjaszewski at Carnegie Mellon University is developing ATRP methods for the controlled polymerization of acidic monomers. The project, which could enable the creation of new commercially-scaled plastics that benefit society, trains undergraduate and graduate students in polymer science. The research team also works with members of the Controlled Radical Polymerization (CRP) Consortium at Carnegie Mellon University to develop new materials for use in a range of industrial markets. The intellectual challenge of this research comprises understanding, improving, and expanding direct ATRP of acidic monomers without neutralization or protection. Controlled ATRP of acidic monomers requires a fundamental understanding of the kinetics and thermodynamics of ATRP and the associated side reactions. New copper catalyst complexes are developed to achieve higher selectivity and stability under acidic conditions. Iron catalysts and metal-free organic photoredox catalysts are studied to further reduce an environmental impact of ATRP. New synthetic pathways are explored to economically produce acidic polymers by direct ATRP of unprotected monomers. The new polymers with well-controlled complex architectures, including organic-inorganic hybrids such as nanocomposites, functionalized surfaces, and bioconjugates are of both academic and commercial importance. The process saves time and energy and reduces cost in academic and industrial laboratories. The results of this research are disseminated through Professor Matyjaszewski's website, timely publications, student presentations at (inter)national conferences, and through the industrial CRP Consortium at Carnegie Mellon University.

自由基聚合是一种化学反应，它将小分子（称为单体）按顺序加在一起，形成由数百或数千个重复单元组成的长聚合物链。自由基聚合是一种强大的合成方法。它被用来制造近一半的聚合物（塑料），全世界每年约有1亿吨。原子转移自由基聚合（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的聚合物。此外，根据单体的化学结构，它可以产生各种形状，如星形、梳子形、刷子形或环状状，每种形状都有特殊的用途。虽然ATRP是一种常用的技术，但一些单体，特别是那些具有酸性官能团的单体，很难用ATRP进行聚合。由酸性单体形成的聚合物是理想的，因为它们具有独特的性质，使它们在各种应用中都很有用。在化学部大分子、超分子和纳米化学项目的支持下，卡内基梅隆大学的Matyjaszewski教授正在开发用于酸性单体控制聚合的ATRP方法。该项目可以创造新的商业规模的塑料，造福社会，培养高分子科学的本科生和研究生。该研究小组还与卡内基梅隆大学的控制自由基聚合（CRP）联盟的成员合作，开发用于一系列工业市场的新材料。本研究的智力挑战包括理解、改进和扩大酸性单体在没有中和或保护的情况下的直接ATRP。控制酸性单体的ATRP需要对ATRP及其相关副反应的动力学和热力学有基本的了解。开发了新的铜催化剂配合物，在酸性条件下具有更高的选择性和稳定性。为了进一步减少ATRP对环境的影响，研究了铁催化剂和无金属有机光氧化还原催化剂。探索了用无保护单体直接ATRP法经济生产酸性聚合物的新合成途径。具有良好控制的复杂结构的新型聚合物，包括有机-无机杂化物，如纳米复合材料，功能化表面和生物偶联物，具有学术和商业重要性。该工艺节省了时间和能源，降低了学术和工业实验室的成本。这项研究的结果通过Matyjaszewski教授的网站、及时的出版物、学生在（国际）国家会议上的报告以及卡内基梅隆大学的工业CRP联盟传播。

项目成果

Investigating Temporal Control in Photoinduced Atom Transfer Radical Polymerization

• DOI: 10.1021/acs.macromol.0c00888
• 发表时间: 2020-07-14
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Dadashi-Silab, Sajjad;Lee, In-Hwan;Matyjaszewski, Krzysztof
• 通讯作者: Matyjaszewski, Krzysztof

Mechanistically Guided Predictive Models for Ligand and Initiator Effects in Copper-Catalyzed Atom Transfer Radical Polymerization (Cu-ATRP)

• DOI: 10.1021/jacs.9b02158
• 发表时间: 2019-05-08
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Fang, Cheng;Fantin, Marco;Liu, Peng
• 通讯作者: Liu, Peng

Enzyme-Deoxygenated Low Parts per Million Atom Transfer Radical Polymerization in Miniemulsion and Ab Initio Emulsion.

• DOI: 10.1021/acsmacrolett.8b00711
• 发表时间: 2018-10
• 期刊: ACS macro letters
• 影响因子: 5.8
• 作者: Yi Wang;Liye Fu;K. Matyjaszewski

Disproportionation or Combination? The Termination of Acrylate Radicals in ATRP

• DOI: 10.1021/acs.macromol.7b01552
• 发表时间: 2017-10
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Thomas G Ribelli;Kyle F. Augustine;Marco Fantin;Pawel Krys;R. Poli;K. Matyjaszewski

Preparation of Well-Defined Polymers and DNA–Polymer Bioconjugates via Small-Volume eATRP in the Presence of Air

在空气存在下通过小体积 eATRP 制备结构明确的聚合物和 DNA 聚合物生物缀合物

• DOI: 10.1021/acsmacrolett.9b00159
• 发表时间: 2019
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Sun, Yue;Lathwal, Sushil;Wang, Yi;Fu, Liye;Olszewski, Mateusz;Fantin, Marco;Enciso, Alan E.;Szczepaniak, Grzegorz;Das, Subha;Matyjaszewski, Krzysztof
• 通讯作者: Matyjaszewski, Krzysztof