GOALI: CAS: Targeted Design of Blocky Poly(Ether Ether Ketone) Copolymers for Enhanced Interfacial Interactions in Blends and Composites

目标：CAS：用于增强共混物和复合材料中界面相互作用的嵌段聚醚醚酮共聚物的针对性设计

• 批准号: 2104856
• 负责人: Robert Moore
• 金额: $ 43万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2104856&HistoricalAwards=false
• 关键词: GOALI; CAS; Targeted; Design; Blocky

NON-TECHNICAL SUMMARY:The current demand for enhanced material properties has often followed a bottom-up approach to synthesize new polymers using complex chemical procedures that generally just expands that vast array of long-lasting plastics in the environment. A more sustainable approach is to use existing materials in new ways. For example, the high cost of poly(ether ether ketone) (PEEK) and its inherent stability strongly favor end-of-use recycling and/or upcycling as opposed to landfilling. In this project, the widely valued approach of compatibilizing polymers in blends to address the critical economic and environmental sustainability needs of our society will be accomplished by performing simple chemical modifications on existing feedstocks of PEEK. Specifically, a new physical approach will be used to create blocky copolymers that are known to be beneficial in polymer blends by selectively modifying specific sequences of units along the chains of commercially available polymers. The blocky PEEK polymers will be targeted toward new blends of PEEK with other valuable polymers as a means to eliminate waste and upcycle PEEK to new materials with synergistic enhancements in properties. These same polymers will also be used to facilitate strong bonds between PEEK and solid fillers in the formation of new composites with enhanced mechanical properties. With respect to the grand challenges facing our society, this project will provide cost-effective, environmentally friendly, readily available materials alternatives needed to meet critical demands for advanced materials in a wide range of commercially relevant technologies. The nature of research activities in this project, involving close collaboration between academic and industrial laboratories, will provide broadly interdisciplinary training to a diverse community of researchers and students, including underrepresented groups.TECHNICAL SUMMARYThe widespread commercial application of block copolymers as blend compatibilizers and fiber sizings is limited by the expensive and rigorous polymerization methods needed to control the sequence of comonomers in the form of discrete blocks. As a transformative approach, the PIs propose a facile, physical polymer chemistry alternative to yield controlled blocky microstructures in poly(ether ether ketone) (PEEK) via post-polymerization functionalizations in a heterogeneous, semi-crystalline, gel state. The fundamental focus of this project will be on pushing the limits of blockiness that is achievable with this new process, expanding the synthetic toolbox of functionalization chemistries for targeted interfacial interactions/reactions, and understanding the molecular-level impact of blocky functionalization on phase behavior and interfacial interactions in high-performance polymer blends and composites. This academic-industrial collaboration is poised to address the grand challenge of forming interfacially active copolymers for PEEK-based blends and composites, with compatibilization efficiencies rivaling that observed with conventional segmented block copolymers. The overall fundamental goal of this project is to understand the role of the compatibilizer microstructure (blocky vs. random) on interfacial properties in multiphase systems. The interdisciplinary nature of research activities in this project, ranging from pure chemistry, materials recyclability, to macromolecular engineering, will provide a plethora of educational opportunities to a diverse community of citizens and researchers eager to contribute to our nation’s leadership in ensuring a healthier, more sustainable global society.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.

目前对增强材料性能的需求通常遵循自下而上的方法，使用复杂的化学过程合成新的聚合物，通常只是扩大了环境中大量持久的塑料。 更可持续的方法是以新的方式使用现有材料。 例如，聚醚醚酮（PEEK）的高成本及其固有的稳定性强烈支持最终使用回收和/或升级循环，而不是填埋。在这个项目中，广泛重视的方法相容性聚合物的共混物，以满足我们社会的关键经济和环境可持续性的需求将通过对现有的PEEK原料进行简单的化学改性来实现。 具体地，将使用新的物理方法来产生嵌段共聚物，已知嵌段共聚物通过选择性地改性沿着市售聚合物的链的单元沿着的特定序列在聚合物共混物中是有益的。 块状PEEK聚合物将针对PEEK与其他有价值聚合物的新混合物，作为消除浪费和将PEEK升级为具有协同增强性能的新材料的手段。这些相同的聚合物也将用于促进PEEK和固体填料之间的牢固结合，以形成具有增强机械性能的新复合材料。关于我们社会面临的巨大挑战，该项目将提供具有成本效益，环境友好，易于获得的材料替代品，以满足广泛的商业相关技术对先进材料的关键需求。 本项目研究活动的性质涉及学术和工业实验室之间的密切合作，将为不同的研究人员和学生社区提供广泛的跨学科培训，嵌段共聚物作为共混物增容剂和纤维施胶剂的广泛商业应用受到控制共聚单体的序列所需的昂贵和严格的聚合方法的限制。离散块的形式。 作为一种变革性方法，PI提出了一种简便的物理聚合物化学替代方案，通过在非均相、半结晶、凝胶状态下的聚合后官能化，在聚醚醚酮（PEEK）中产生受控的块状微结构。该项目的基本重点将是推动这种新工艺可实现的嵌段性的极限，扩展针对目标界面相互作用/反应的功能化化学的合成工具箱，并了解嵌段功能化对高性能聚合物共混物和复合材料中的相行为和界面相互作用的分子水平影响。这一学术-工业合作旨在解决为PEEK基共混物和复合材料形成界面活性共聚物的巨大挑战，其增容效率可与传统的嵌段共聚物相媲美。 本项目的总体基本目标是了解相容剂微观结构（块状与随机）对多相系统界面性能的作用。该项目研究活动的跨学科性质，从纯化学，材料可回收性到大分子工程，将为渴望为我们国家的领导做出贡献的多元化公民和研究人员社区提供过多的教育机会。该奖项反映了NSF的法定使命，并通过使用基金会的知识产权进行评估，被认为值得支持。优点和更广泛的影响审查标准。

项目成果

Crystallization kinetics and equilibrium melting temperature of poly(ether ketone ketone) with high terephthalate content utilizing fast scanning calorimetry

利用快速扫描量热法研究高对苯二甲酸酯含量聚醚酮酮的结晶动力学和平衡熔融温度

• DOI: 10.1016/j.polymer.2023.125810
• 发表时间: 2023
• 期刊: Polymer
• 影响因子: 4.6
• 作者: Pomatto, Michelle E.;Moore, Robert B.
• 通讯作者: Moore, Robert B.

Tailored sequencing of highly brominated Poly(ether ether ketone) as a means to preserve crystallizability and enhance Tg

高度溴化聚醚醚酮的定制测序作为保持结晶性和提高 Tg 的手段

• DOI: 10.1016/j.polymer.2022.124918
• 发表时间: 2022
• 期刊: Polymer
• 影响因子: 4.6
• 作者: Kasprzak, Christopher R.;Anderson, Lindsey J.;Moore, Robert B.
• 通讯作者: Moore, Robert B.