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Conducting Cyclic Polymers

导电环状聚合物

基本信息

批准号：
1808234
负责人：
Adam Veige
金额：
$ 46.5万
依托单位：
University of Florida
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 2021-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1808234&HistoricalAwards=false
关键词：
Conducting Cyclic Polymers

项目摘要

Professors Adam S Veige and Brent S Sumerlin of the University of Florida are supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the Division of Chemistry to synthesize cyclic polymers. Most plastics are composed of linear polymers (chains of relatively small molecular fragments known as monomers that are joined together). This project aims to develop a new and improved class of plastics by eliminating the polymer chain ends and creating cyclic polymers. The cyclic polymers are characterized and their properties are compared with their linear analogs. The ability to manipulate the composition and structure of polymers to yield a desired set of properties, such as strength, heat resistance and electrical conductivity, has significantly expanded the many roles plastics play in our modern industrial economy. Cyclic polymers have dramatically different properties compared to their equivalent linear counterparts. Catalyst technology developed at the University of Florida enables the efficient production of cyclic polymers. Some plastics are able to conduct electricity and are used in organic light emitting diodes (OLEDs). This project aims to create the first electrically conducting cyclic polymers. The project provides the students involved with hands-on training in modern inorganic and organometallic chemistry. Demonstrations that illustrate the principles of cyclic polymers are developed and presented to the general public during an annual Chemistry Day at the Mall event. In this project, a key catalyst which was discovered at the University of Florida will be employed for the synthesis of macrocyclic polyene polymers. The main thrusts are: 1) to maximize the conductivity of cyclic poly (acetylene-co-1-alkyne) polymers while retaining their solubility; 2) to improve conjugation by forcing the alignment of the polymer via side-chain ligation of substituted polyalkynes; and 3) to synthesize cyclic poly[n]carbon, which represents a new carbon allotrope. Conducting cyclic polymers are scarce, and the consequence of their cyclic topology on conductivity have yet to be explored. The project employs a tungsten catalyst that is capable of inserting acetylenes into a growing metallacycle. Cyclic polyacetylenes are then obtained by termination of the polymerization reaction via reductive elimination. Copolymerization of acetylene and substituted acetylenes produce free standing lustrous films that are interrogated for electrical conductivity upon doping. Substituted acetylenes are essential for creating soluble polyacetylenes; however, their incorporation into the polymer chain inherently reduces conjugation by twisting the polymer backbone. This project aims to produce conducting cyclic polymers through linking the substituents by post-polymerization functionalization to constrain the geometry of the polymer backbone. Finally, the project also aims to synthesize cyclic poly[n]carbon, which represents a new carbon allotrope. Linear poly[n]carbon is unstable unless the chain ends are functionalized. By having no chain ends it is expected that the cyclic polymer will be more stable and therefore, potentially isolable.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.

佛罗里达大学的Adam S Veige和布伦特S Sumerlin教授得到化学系大分子、超分子和纳米化学（MSN）计划的支持，合成环状聚合物。大多数塑料是由线性聚合物（链相对较小的分子片段称为单体连接在一起）。该项目旨在通过消除聚合物链端并创建环状聚合物来开发新的和改进的塑料类别。环状聚合物的特点和他们的性能进行了比较，与他们的线性类似物。操纵聚合物的组成和结构以产生所需的一组特性（例如强度、耐热性和导电性）的能力显著扩展了塑料在现代工业经济中发挥的许多作用。环状聚合物与其等价的线性对应物相比具有显著不同的性质。佛罗里达大学开发的催化剂技术能够高效生产环状聚合物。一些塑料能够导电，并用于有机发光二极管（OLED）。该项目旨在创造第一个导电的环状聚合物。该项目为参与现代无机和有机金属化学的学生提供实践培训。演示，说明环状聚合物的原则开发和呈现给公众在一年一度的化学日在商场活动。在这个项目中，在佛罗里达大学发现的一种关键催化剂将用于合成大环多烯聚合物。主要目标是：1）使环状聚（乙炔-共-1-炔）聚合物的导电性最大化，同时保持它们的溶解性; 2）通过经由取代的聚炔的侧链连接迫使聚合物对齐来改善共轭;和3）合成环状聚[n]碳，其代表新的碳同素异形体。导电的环状聚合物是稀缺的，其环状拓扑结构对导电性的影响还有待探索。该项目采用钨催化剂，能够将乙炔插入到不断增长的金属乳糖中。然后通过还原消除终止聚合反应获得环状聚乙炔。乙炔和取代的乙炔的共聚产生独立的荧光膜，其在掺杂时被询问电导率。取代的乙炔对于产生可溶性聚乙炔是必不可少的;然而，它们并入聚合物链中固有地通过扭曲聚合物主链而减少共轭。本项目旨在通过聚合后官能化连接取代基来限制聚合物主链的几何形状，从而制备导电环状聚合物。最后，该项目还旨在合成环状聚[n]碳，这是一种新的碳同素异形体。线性聚[n]碳是不稳定的，除非链端被官能化。由于没有链端，预期环状聚合物将更稳定，因此可能是可分离的。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

期刊论文数量（7）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Author Correction: Cyclic polyacetylene

作者更正：环状聚乙炔

DOI：
10.1038/s41557-021-00809-9
发表时间：
2021
期刊：
Nature Chemistry
影响因子：
21.8
作者：
Miao, Zhihui;Gonsales, Stella A.;Ehm, Christian;Mentink-Vigier, Frederic;Bowers, Clifford R.;Sumerlin, Brent S.;Veige, Adam S.
通讯作者：
Veige, Adam S.

Cyclic Poly(4-methyl-1-pentene): Efficient Catalytic Synthesis of a Transparent Cyclic Polymer