Precisely Functionalized Alternating Copolymers Based on Substituted Stilbene Monomers

基于取代二苯乙烯单体的精确官能化交替共聚物

• 批准号: 0905231
• 负责人: Richard Turner
• 金额: $ 37.2万
• 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: 2009
• 资助国家: 美国
• 起止时间: 2009-07-01 至 2012-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0905231&HistoricalAwards=false
• 关键词: Precisely; Functionalized; Alternating; Copolymers; Based

ARRA STATEMENT:This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5).TECHNICAL SUMMARY:The ability to control functional group placement and polymer backbone structure in synthetic polymers is important for understanding fundamental structure property relationships as well as designing polymeric materials with important performance characteristics. The alternating copolymerization of substituted stilbenes and maleic anhydride or N-substituted maleimides will be studied as a new route to synthesize macromolecules with precise control of the placement and density of functional groups along the polymer backbone. The incorporation of the sterically crowded 1,2-diphenylethane units, in conjunction with the five member cyclic imide or anhydride units, results in structures that are anticipated to be considerably stiffened when compared to less constrained polymer chains. Synthetic targets of this research will include new sterically crowded polyanions and polycations with a regular variation of charge densities along the chain enabled by the alternating copolymerization of specifically designed and prepared functional stilbenes and maleimide comonomers. The consequences of the sterically constrained backbones and placement of functional groups on fundamental properties such as persistence length and solution rheological properties will be studied. Solid state NMR will be used to study the enchainment stereochemistry of the maleic anhydride and maleimide comonomers. The stiffened polyanions and polycations will be compared to polyzwitterionic structures with similar chain backbones. These new polyelectrolytes and polyzwitterions will be enchained into double hydrophilic block copolymers (DHBC) by controlled free radical polymerization techniques. These DHBC structures will be used to assist in establishing structure property relationships that govern the ?like-charge? attraction observed in DNA and more recently reported from the PI?s laboratory in a synthetic DHBC derived from a substituted stilbene-alt-maleic anhydride zwitterionic copolymer.NON-TECHNICAL SUMMARY:New precisely functionalized polymeric materials, based on easily scaleable and industrially practiced free radical polymerization chemistries have significant potential to have practical impact across a broad range of advanced technology frontiers. The fundamental research described in this proposal could foster a new polymer platform which has the potential to be used to produce new porous and high surface area network materials for hydrogen storage, new rigid polyelectrolytes for control of flow in aqueous fluids, new polyelectrolyte gels which could be applied in membranes, and new nano-particle stabilization agents. In addition the synthesis and study of new rod-coil aqueous block copolymers, derived from the new polymers of this study, will provide fundamental biomimetic information that can have impact in various biomedical applications such as therapeutic delivery. Active participation in the research project will require graduate students to master modern polymerization and synthetic chemistries and to interact with other scientists and engineers in a strong interdisciplinary mode in order to fully characterize and understand the properties of these new polymeric materials. The graduate students involved with this research will interact with industrial researchers in Virginia Tech polymer short courses and will mentor summer undergraduate students in the Macromolecules and Interfaces Institute?s NSF REU program. This specific training will be valuable for initiating viable careers for these researchers in a variety of industrial and academic areas important for sustaining and growing the nation?s science and technology enterprise.

ARRA声明：该奖项是根据2009年的《美国回收与再投资法》资助的（公法111-5）。技术摘要：控制功能组放置和聚合物骨架结构合成聚合物中的能力对于理解基本结构的财产关系很重要以及设计具有重要性能特征的聚合物材料。 将研究取代的高苯甲酸酯和甲基酸酐或N-取代的马来酰亚胺的交替共聚，作为合成大分子的新途径，以精确控制沿聚合物骨架的官能团的位置和密度。与五个构件的环状酰亚胺或酸酐单元结合，将静置拥挤的1,2-二苯基乙烷单元掺入，与较不受限制的聚合物链相比，预期的结构会相当僵硬。这项研究的合成目标将包括新的空间拥挤的多元和多阳离子，其沿链条定期变化，沿链条沿链条定期变化，这是由专门设计和准备好的功能性stim型和马来酰亚胺共聚物的交替共聚。 将研究在持久性长度和解决方案的流变特性等基本特性上的空间骨架和官能团的位置的后果。固态NMR将用于研究甲基酸酐和马来酰亚胺联合体的凹痕立体化学。 将僵硬的聚体和多阳离子与具有相似链条骨架的多元屈服结构进行比较。这些新的聚电解质和多氮化器将通过受控的自由基聚合技术将其掺入双重亲水块共聚物（DHBC）中。 这些DHBC结构将用于协助建立结构的财产关系，以控制？在DNA中观察到的吸引力，最近在PI的实验室中观察到的合成DHBC中报道了源自替代的Stilbene-Alt-Maleic赤铁藻Zwitterionic共聚物。非技术摘要：新的精确功能性的聚合物材料，基于易于缩放和工业型的易于缩小的型号和工业化的材料。激进的聚合化学具有在广泛的先进技术边界上产生实际影响的巨大潜力。 该提案中描述的基础研究可以促进一个新的聚合物平台，该平台有可能用于生产新的多孔和高表面积网络材料，用于氢存储，新的刚性多电解质，用于控制水性流体中的流量，新的聚电解质凝胶，这可能可以应用于膜和新的纳米粒子稳定剂。 此外，从本研究的新聚合物中得出的新杆芯水块共聚物的合成和研究将提供基本的仿生信息，这些信息可能会影响各种生物医学应用，例如治疗性递送。 积极参与研究项目将要求研究生掌握现代聚合和综合化学，并以强大的跨学科模式与其他科学家和工程师进行互动，以充分表征和了解这些新聚合物材料的特性。参与这项研究的研究生将与弗吉尼亚技术聚合物短期课程的工业研究人员进行互动，并将指导大分子和接口研究所的NSF REU计划中的夏季本科生。 这项特定的培训对于在各种工业和学术领域的这些研究人员开始对维持和发展国家的科学技术企业至关重要的工业和学术领域的可行职业将是有价值的。