Collaborative Research: Synthesis and Rigidity Quantification of Ladder Polymers with Controlled Structural Defects

合作研究：具有受控结构缺陷的梯形聚合物的合成和刚性定量

• 批准号: 2003733
• 负责人: Lei Fang
• 金额: $ 37.7万
• 依托单位: Texas A&M 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 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2003733&HistoricalAwards=false
• 关键词: Collaborative; Research; Synthesis; Rigidity; Quantification

With funding from the Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division, Professors Lei Fang of Texas A&M University and Xiaodan Gu of University of Southern Mississippi are investigating how chain flexibility influences the physical properties of conjugated ladder polymers. Conjugated polymers are a unique class of non-metallic polymers with semiconducting properties resembling that of the chemical element silicon. These long chain carbon-based molecules can become conductive when external voltage is applied (like in transistors) or light shines on them (like in photovoltaic cells). Conjugated polymers are extensively used in solar cells, LED screens and other applications that utilize the conversion of electricity to light. Ladder polymers, on the other hand, are a type of double stranded polymers with the connectivity of a ladder. This is achieved by interconnecting repeating units along the main polymer chain by four chemical bonds, instead of the two bonds typically seen in conventional plastics. In this research, conjugated ladder polymers with varied structural features are synthesized. Control polymers are prepared with deliberately introduced backbone defects that consist of small molecules. Detailed studies are then conducted to correlate backbone composition and length with the flexibility of the polymer chains. These studies are enabled by employing neutron and light scattering techniques which provide accuracy at lengths ranging from sub 1 nanometer (1/100,000 of human hair diameter) to well beyond 10 micrometers (the width of cotton fiber). Correlations established as a result of this work may provide knowledge that could lead to the development of materials with better optical and electronic performance. Educational innovation tackles the problems associated with outdated contents in undergraduate organic chemistry laboratory courses. The newly designed “Nobel Prize Reactions” are first implemented at both universities and then disseminated at national and international scales. Outreach activities expose undergraduate and high school students to modern chemical research. This work is specifically designed to benefit a large number of underrepresented minorities and economically disadvantaged students in Mississippi.The primary goal of this research is to establish the fundamental correlations between backbone constitution and the chain rigidity for rigid ladder conjugated polymers. The research is conducted through the design and synthesis of model ladder polymers with varied structural features, and controls with deliberately introduced backbone defects, followed by quantitative evaluation of their chain persistence length and correlation with structural features. Chain rigidity of the ladder polymer models and controls is quantified using combined modern characterization tools with an emphasis on neutron and light scattering. Studies are also performed to understand the influence of chain bending energy on persistent length for ladder polymers. Comprehensive structural-rigidity correlation through iterative design-synthesis-measurement-design cycles is established. Results associated with this award have the potential to advance knowledge on how the chain rigidity (or flexibility) determines the fundamental properties and practical applications of a wide range of polymers.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.

在化学系大分子、超分子和纳米化学项目的资助下，德克萨斯A M大学的方磊教授和南密西西比大学的顾晓丹教授正在研究链柔性如何影响共轭梯形聚合物的物理性质。 共轭聚合物是一类独特的非金属聚合物，具有类似于化学元素硅的半导体性质。 这些长链碳基分子可以在施加外部电压（如晶体管）或光线照射时（如光伏电池）变得导电。 共轭聚合物广泛用于太阳能电池、LED屏幕和利用电转化为光的其他应用。 另一方面，梯形聚合物是一种具有梯形连接性的双链聚合物。 这是通过沿着主聚合物链通过四个化学键而不是传统塑料中通常看到的两个键将重复单元沿着互连来实现的。 本研究合成了具有不同结构特征的共轭梯形聚合物。 对照聚合物是用故意引入的由小分子组成的主链缺陷制备的。 然后进行详细的研究，将主链的组成和长度与聚合物链的柔性相关联。 这些研究是通过采用中子和光散射技术实现的，这些技术提供了从1纳米（人类头发直径的1/100，000）到远远超过10微米（棉纤维的宽度）的精确度。 作为这项工作的结果建立的相关性可能会提供知识，可能导致更好的光学和电子性能的材料的发展。 针对本科有机化学实验教学内容陈旧的问题，进行教学改革。 新设计的“诺贝尔奖反应”首先在两所大学实施，然后在国家和国际范围内传播。 外联活动使本科生和高中生接触到现代化学研究。 这项工作是专门为受益于大量代表性不足的少数民族和经济上处于不利地位的学生在密西西比。本研究的主要目标是建立刚性梯形共轭聚合物的主链构成和链刚性之间的基本关系。 该研究通过设计和合成具有不同结构特征的模型梯形聚合物，并控制故意引入主链缺陷，然后定量评估其链持久性长度和与结构特征的相关性。 链刚性的梯形聚合物模型和控制量化使用组合现代表征工具，重点是中子和光散射。 研究还进行了了解链弯曲能对梯形聚合物的持久长度的影响。 通过迭代设计-综合-测量-设计循环建立了全面的结构刚度相关性。 与该奖项相关的结果有可能促进对链刚性（或柔性）如何决定广泛聚合物的基本性质和实际应用的认识。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

Probing conformational properties of conjugated polymers in dilute solutions under variable solvent quality via coarse‐grained modeling

• DOI: 10.1002/pol.20230689
• 发表时间: 2023-11
• 期刊: Journal of Polymer Science
• 影响因子: 3.4
• 作者: Zhaofan Li;Yang Wang;Guorong Ma;Yangchao Liao;X. Gu;Wenjie Xia

How rigid are conjugated non‐ladder and ladder polymers?

• DOI: 10.1002/pol.20210550
• 发表时间: 2021-08
• 期刊: Journal of Polymer Science
• 影响因子: 3.4
• 作者: Zhiqiang Cao;Mingwan Leng;Yirui Cao;X. Gu;Lei Fang

Robust chain aggregation of low-entropy rigid ladder polymers in solution

溶液中低熵刚性梯形聚合物的稳健链聚集

• DOI: 10.1039/d2tc00761d
• 发表时间: 2022
• 期刊: Journal of Materials Chemistry C
• 影响因子: 6.4
• 作者: Ma, Guorong;Leng, Mingwan;Li, Shi;Cao, Zhiqiang;Cao, Yirui;Tabor, Daniel P.;Fang, Lei;Gu, Xiaodan
• 通讯作者: Gu, Xiaodan

Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers

• DOI: 10.1021/acsapm.1c01511
• 发表时间: 2022-05-13
• 期刊: ACS APPLIED POLYMER MATERIALS
• 影响因子: 5
• 作者: Cao, Zhiqiang;Ma, Guorong;Gu, Xiaodan
• 通讯作者: Gu, Xiaodan