Elucidating Ring Opening Metathesis Copolymerization Thermodynamics of Monomers with Dissimilar Ring Strain Energies

阐明不同环应变能单体的开环复分解共聚热力学

• 批准号: 2305099
• 负责人: Justin Kennemur
• 金额: $ 45.98万
• 依托单位: Florida State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-05-01 至 2026-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2305099&HistoricalAwards=false
• 关键词: Elucidating; Ring; Opening; Metathesis; Copolymerization

With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Professor Justin G. Kennemur of Florida State University is studying copolymerization thermodynamics of cyclic monomers in ring opening metathesis polymerization (ROMP). Copolymerization of two or more individual monomers into one macromolecule or polymer offers a divergent means of producing societal plastics that contain distributed functionality for a myriad of applications. Specifically, ROMP affords a variety of industrially relevant polyolefin-based materials through chain growth of strained cycloolefin monomers using well-established catalysts. This Kennemur team will perform systematic synthetic, kinetic and mechanistic studies to gain understanding of how basic thermodynamic principles along with key conditions, such as catalyst and solvent, ultimately dictate the reactivity ratios of various cycloolefin comonomers and their sequencing within the macromolecular chains that are grown. The project will also introduce new biomass-based terpene cycloolefins to provide a thermodynamic spectrum of medium ring-strain not afforded by the commonly employed cycloolefin monomers in ROMP. The research team will continue engagement with the first ever American Chemical Society Division of Polymer Chemistry and Division of Polymer Materials Science and Engineering student chapter that is co-established between a historically black college/university of Florida Agricultural and Mechanical University (FAMU) and an R1 research university in Florida State University. This student chapter will bring together a highly diverse body of students and faculty aimed at polymer science research. This unique platform will additionally be utilized to promote the growth of graduate and undergraduate students towards the development of leadership, both governed by outreach and the development of a new Florida-based conference, centered on polymer science.This project will focus on elucidating ring opening metathesis copolymerization thermodynamics of monomers with dissimilar ring strain energies. In the first aim, reactivity ratios of low-strain cyclopentene monomers that are highly sensitive to slight variations in their ring strain energy (RSE) will be determined using modern integrated approaches. Determined parameters will then be correlated to monomer sequencing within the polymer microstructure as a function of thermodynamic principles (monomer concentration, stoichiometry, and temperature). The second aim will examine, delta-pinene, and its variant, apopinene , which have RSEs that are in-between the high strain and low strain monomers typically employed in ROMP. Fundamental thermodynamic investigations and copolymerizations of these terpene-based monomers with each other and with low/ high RSE monomers will also be explored. Finally, the last specific aim will push the limits of disparity between RSEs by investigating high strain and low strain monomers in combination. Such investigations have potential for both alternating and blocky sequencing strategies. Taken together, these studies have the potential to provide guiding principles for the rational design of copolymers from readily available cycloolefin monomers; there is the potential to uncover basic principles that will apply to ring-opening polymerization (ROMP), in general, and thereby have a significant long-term scientific impact on polymer chemistry.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.

在化学系中的大分子，超分子和纳米化学计划的支持下，佛罗里达州立大学的贾斯汀·G·肯尼姆教授正在研究环环分解过程中环状单体的共聚热力学热力学（ROMP）。 将两个或多个单个单体共聚在一个大分子或聚合物中提供了一种不同的方法，可以生产包含无数应用的分布功能的社会塑料。具体而言，ROMP使用良好的催化剂通过紧张的Cycloolefin单体的链生长提供了各种与工业相关的基于多烯烃的材料。这个Kennemur团队将执行系统的合成，动力学和机械研究，以了解基本的热力学原理以及关键条件如何以及诸如催化剂和溶剂等关键条件，最终决定了各种旋风的反应性比，在大分子内种植的各种旋风的反应性比。该项目还将引入新的基于生物量的萜烯环菌素，以提供romp中常用的cycloolefin单体所提供的中型环形晶体的热力学光谱。 研究小组将继续与有史以来第一个美国化学学会聚合物化学部和聚合物材料科学与工程学生分会的局部参与，该分会是历史悠久的黑人学院/佛罗里达大学农业和机械大学（FAMU）之间的共同建立的佛罗里达州立大学的R1研究大学。 该学生章节将汇集一个针对聚合物科学研究的高度多样化的学生和教师。 这个独特的平台还将被用来促进研究生和本科生的领导力发展，均由外展和开发基于佛罗里达的新会议，以聚合物科学为中心。单体与不同环应变能的单体共聚热力学。在第一个目的中，使用现代集成方法确定对略微变化（RSE）对略有变化（RSE）高度敏感的低压环烯单体的反应比。 然后，确定的参数将与聚合物微结构内的单体测序相关联，这是热力学原理（单体浓度，化学计量和温度）的函数。 第二个目的将检查三角洲及其变体的阿彭烯，它们的rsE位于高应变和低应变单体之间。还将探索这些基于萜烯的单体和低/高RSE单体的基本热力学研究和共聚。 最后，最后一个特定的目标将通过研究高应变和低应变单体组合来推动RSE之间的差异。这种研究具有交替的和块状测序策略的潜力。综上所述，这些研究有可能提供指导原理，以从容易获得的Cycloolefin单体中合理设计共聚物。有可能发现适用于开环聚合（ROMP）的基本原则，从而对聚合物化学产生了重大的长期科学影响。该奖项反映了NSF的法定任务，并被认为值得支持。通过使用基金会的智力优点和更广泛影响的评论标准进行评估。