SusChEM: Stereoselective Polymerization Catalysis of Biomass Monomers by Chiral Transition-Metal and Organic Catalysts

SusChEM：手性过渡金属和有机催化剂对生物质单体的立体选择性聚合催化

• 批准号: 1664915
• 负责人: Eugene Chen
• 金额: $ 45万
• 依托单位: Colorado State 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=1664915&HistoricalAwards=false
• 关键词: SusChEM; Stereoselective; Polymerization; Catalysis; Biomass

The Chemical Catalysis Program and the Macromolecular, Supramolecular, and Nanochemistry Program of the Chemistry Division support the project by Professor Eugene Chen. Professor Chen is a faculty member in the Department of Chemistry at Colorado State University. He is developing new methods of chemical catalysis for the synthesis of new types of plastics (polymers). These new plastics are renewable, meaning that they are prepared from grown feedstocks, and thus are sustainable. The second feature of these new polymers is that they have regular and well-controlled (stereoregular) chemical structures. Plastics with these characteristics have better physical properties for many applications. These two properties, stereoregularity and renewability, are important for new applications of plastics in the modern economy. The proposed research encompasses diverse areas of chemistry, materials science, and sustainability, thereby providing an excellent opportunity for training and teaching of students, including underrepresented minorities and undergraduate students.The proposed study addresses three currently unmet challenges still facing both the metal catalyzed and organocatalyzed polymerizations of acrylic monomers. First, existing chiral metal catalysts show high stereoselectivity in the polymerization of linear, petroleum-based acrylics but lack of stereochemical control over the polymerization of biomass-derived compact cyclic acrylics. Hence, the first specific objective of the work is to design advanced chiral transition-metal catalysts, assisted by theory, to enable stereoselective polymerization of such challenging bio-derived cyclic acrylic monomers. Second, the recently developed organocatalyzed proton-transfer polymerization can convert diacrylics uniquely into biodegradable unsaturated polyesters, but the current polyester product is an amorphous non-crystalline material, thus limiting its application. Accordingly, the second specific objective of the work is to develop the stereoselective proton-transfer polymerization for the synthesis of stereoregular crystalline unsaturated polyesters. Third, the current organocatalytic conjugate-addition polymerization of acrylic monomers produces only achiral acrylic polymers. Thus, the third specific objective of the work is to establish asymmetric organopolymerization of acrylic monomers to produce optically active chiral polymers. The education plan includes training and teaching of a diverse study body with complementary experimental and computational methods employed in this catalytic chemistry research, as well as for educating students and the general public about the central role of chemistry in addressing the global sustainability challenges.

化学学部的化学催化项目和大分子、超分子和纳米化学项目支持Eugene Chen教授的项目。陈教授是科罗拉多州立大学化学系的教员。他正在开发合成新型塑料（聚合物）的化学催化新方法。这些新塑料是可再生的，这意味着它们是由种植的原料制备的，因此是可持续的。这些新聚合物的第二个特点是它们具有规则和良好控制的（立体规则）化学结构。具有这些特性的塑料在许多应用中具有更好的物理性能。这两种特性，即立体规整性和可再生性，对塑料在现代经济中的新应用具有重要意义。拟议的研究涵盖化学，材料科学和可持续发展的不同领域，从而为学生提供培训和教学的绝佳机会，包括代表性不足的少数民族和本科生。提出的研究解决了目前仍面临的金属催化和有机催化丙烯酸单体聚合的三个未解决的挑战。首先，现有的手性金属催化剂在聚合线性石油基丙烯酸方面表现出较高的立体选择性，但在聚合生物质衍生的致密环丙烯酸方面缺乏立体化学控制。因此，这项工作的第一个具体目标是设计先进的手性过渡金属催化剂，在理论的帮助下，使这种具有挑战性的生物衍生环丙烯酸单体的立体选择性聚合成为可能。其次，近年来发展起来的有机催化质子转移聚合技术可以独特地将二丙烯酸酯转化为可生物降解的不饱和聚酯，但目前的聚酯产品是无定形的非晶体材料，限制了其应用。因此，本工作的第二个具体目标是开发用于合成立体规则结晶不饱和聚酯的立体选择性质子转移聚合。第三，目前丙烯酸单体的有机催化共轭加成聚合只能产生非手性丙烯酸聚合物。因此，本研究的第三个具体目标是建立丙烯酸单体的不对称有机聚合，以生产旋光性手性聚合物。该教育计划包括培训和教学一个多元化的研究机构，在催化化学研究中采用互补的实验和计算方法，以及教育学生和公众化学在解决全球可持续性挑战中的核心作用。

项目成果

Selective or living organopolymerization of a six-five bicyclic lactone to produce fully recyclable polyesters

• DOI: 10.1039/c9py00190e
• 发表时间: 2019-06-21
• 期刊: POLYMER CHEMISTRY
• 影响因子: 4.6
• 作者: Cywar, Robin M.;Zhu, Jian-Bo;Chen, Eugene Y. -X.
• 通讯作者: Chen, Eugene Y. -X.

A synthetic polymer system with repeatable chemical recyclability

• DOI: 10.1126/science.aar5498
• 发表时间: 2018-04-27
• 期刊: SCIENCE
• 影响因子: 56.9
• 作者: Zhu, Jian-Bo;Watson, Eli M.;Chen, Eugene Y. -X.
• 通讯作者: Chen, Eugene Y. -X.

Toward Infinitely Recyclable Plastics Derived from Renewable Cyclic Esters

• DOI: 10.1016/j.chempr.2018.10.011
• 发表时间: 2019-02
• 期刊: Chem
• 影响因子: 23.5
• 作者: Xiaoyan Tang;E. Chen

Stereosequenced crystalline polyhydroxyalkanoates from diastereomeric monomer mixtures

• DOI: 10.1126/science.aax8466
• 发表时间: 2019-11-08
• 期刊: SCIENCE
• 影响因子: 56.9
• 作者: Tang, Xiaoyan;Westlie, Andrea H.;Chen, Eugene Y. -X.
• 通讯作者: Chen, Eugene Y. -X.

Closed-Loop Polymer Upcycling by Installing Property-Enhancing Comonomer Sequences and Recyclability

• DOI: 10.1021/acs.macromol.9b00817
• 发表时间: 2019-06
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Xia Liu;Miao Hong;L. Falivene;L. Cavallo;E. Chen