CAREER: Functional Polymer Surfaces and Networks via Thiol-Click Chemistry

职业：通过硫醇点击化学实现功能聚合物表面和网络

• 批准号: 1056817
• 负责人: Derek Patton
• 金额: $ 50万
• 依托单位: University of Southern Mississippi
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-05-01 至 2018-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1056817&HistoricalAwards=false
• 关键词: CAREER; Functional; Polymer; Surfaces; Networks

TECHNICAL SUMMARY: Recent advances in synthetic polymer chemistry have resulted in numerous fundamental scientific discoveries that have enabled the development of materials with unique and useful properties. Among notable discoveries, "click" chemistry and the ensuing "Robust, Efficient, Orthogonal" strategies are revolutionizing our ability to tailor-make polymeric materials with specific function. This CAREER proposal leverages a specific class of click reactions - "thiol-click" - to tackle unexplored areas in polymer surface engineering and hybrid polymer networks that will lead to unprecedented control of surface functionality and a novel set of functional glassy polymer networks. The research objectives of this CAREER proposal are three fold: 1) design "reactive inkjet" and scanning-near field lithography strategies that exploit high efficiency thiol-click reactions for multicomponent, precision engineered surfaces 2) synthesize and gain fundamental understanding of a new class of hybrid polymer networks via orthogonal thiol-click/benzoxazine chemistries, and 3) fundamentally investigate polybenzothiazines as a new class of thiol-containing thermosets. Towards achieving these objectives, the following specific research directives are proposed. 1) Surface Engineering via Thiol-Click Reactions: The PI will develop thiol-click reactions for the design and fabrication of patterned, multicomponent polymer surfaces. Orthogonal strategies involving radical-mediated thiol-yne and base-catalyzed thiol-isocyanate, thiol-epoxide and thiol-bromo enable advancements in surface engineering. Exploitation of high efficiency thiol-click reactions with "reactive inkjet" and "wet" near-field lithography will provide the ability to investigate nanoscale chemical reactions at surfaces under mild, biologically relevant conditions. 2) Dual-Crosslink Thiol-Click/Benzoxazine Hybrid Networks: Using thiol-click reactions, the PI will design and prepare a unique class of dual crosslinked polymer networks comprising a primary thiol-ene network which templates a sequential secondary polybenzoxazine network. Aside from unique network architectures, the sequential nature of network synthesis offers opportunities to provide fundamental knowledge of network formation and structure in glassy polymeric materials. 3) Synthesis of Novel Polybenzothiazine Networks: A new class of thiol-containing thermoset polymers derived from bis(1,3-benzothiazine) monomers will be synthesized. Sister to polybenzoxazines, these polymers comprise a thiophenol/Mannich-bridge backbone and exhibit properties substantially different from polybenzoxazines. The influence of hydrogen bonding on network structure and thermomechanical properties will be elucidated. NON-TECHNICAL SUMMARY: The proposed research offers a robust strategy for the fabrication of multifunctional polymer surfaces and hybrid polymer networks using highly efficient, orthogonal chemistries. Successful implementation of this research will provide access to functional surfaces and networks that will facilitate advancements in areas such as 1) sensors, microfluidics, and "smart" self-cleaning, antifouling surfaces and 2) polymer composite matrices, adhesives, and high temperature coatings. The educational objective of this CAREER is to implement an integrated, discovery-driven education platform that promotes polymer science and diversity from K - Graduates. A significant outreach program is proposed comprising 1) a teacher development workshop for a school district comprising 92% underrepresented minorities, 2) a high school job shadow/research experience program, and 3) an undergraduate engagement program that aims to attract/retain polymer science majors. Graduate students involved in each of the above outreach activities will be given frequent opportunities to integrate research activities to grow interest in polymer science for K - UG students. Graduate students will be trained and educated in technologically relevant areas via a comprehensive, multilevel approach involving synthesis-advanced characterization-modeling strategies. The ultimate outcome of this integrated K - Graduate education and research platform is to provide a large socio-economic impact by 1) encouraging a diverse population of students to pursue careers in scientific disciplines and 2) by providing the fundamental understanding of polymer surface engineering and networks necessary to establish the shortest paths between scientific discovery and exploratory applications.

技术概要：合成聚合物化学的最新进展导致了许多基础科学发现，这些发现使得能够开发具有独特和有用特性的材料。在这些值得注意的发现中，“点击”化学和随之而来的“稳健、高效、正交”策略正在彻底改变我们定制具有特定功能的聚合物材料的能力。该CAREER提案利用特定类别的点击反应-"硫醇点击"-来解决聚合物表面工程和混合聚合物网络中未探索的领域，这将导致对表面功能的前所未有的控制和一组新的功能性玻璃状聚合物网络。本职业计划的研究目标有三个方面：1）设计"反应性喷墨"和扫描近场光刻策略，其利用高效的硫醇点击反应用于多组分、精密工程表面2）通过正交硫醇点击/苯并恶嗪化学合成并获得对一类新的混合聚合物网络的基本理解，和3）从根本上研究聚苯并噻嗪作为一类新的含硫醇热固性材料。为了实现这些目标，提出了以下具体的研究方向。1)通过硫醇点击反应进行表面工程：PI将开发硫醇点击反应，用于图案化多组分聚合物表面的设计和制造。 涉及自由基介导的硫醇-炔和碱催化的硫醇-异氰酸酯、硫醇-环氧化物和硫醇-溴的正交策略使得表面工程能够进步。利用"反应性喷墨"和"湿"近场光刻的高效巯基点击反应将提供在温和的生物相关条件下研究表面处的纳米级化学反应的能力。2)双交联巯基点击/苯并恶嗪混合网络：使用巯基点击反应，PI将设计和制备一类独特的双交联聚合物网络，包括一个初级硫醇-烯网络，其模板是连续的二级聚苯并恶嗪网络。除了独特的网络结构，网络合成的顺序性质提供了机会，提供在玻璃态聚合物材料的网络形成和结构的基础知识。 3)新型聚苯并噻嗪网络的合成：将合成一类新的衍生自双（1，3-苯并噻嗪）单体的含硫醇热固性聚合物。 与聚苯并恶嗪类似，这些聚合物包含苯硫酚/曼尼希桥骨架，并表现出与聚苯并恶嗪显著不同的性质。氢键对网络结构和热机械性能的影响将被阐明。非技术性总结：拟议的研究提供了一个强大的策略，多功能聚合物表面和混合聚合物网络的制造使用高效，正交化学。 这项研究的成功实施将提供对功能表面和网络的访问，这些功能表面和网络将促进以下领域的进步：1）传感器，微流体和“智能”自清洁，可再生表面和2）聚合物复合材料基质，粘合剂和高温涂层。这个职业的教育目标是实施一个综合的，发现驱动的教育平台，促进聚合物科学和K-毕业生的多样性。提出了一个重要的外展计划，包括1）一个学区教师发展研讨会，其中包括92%的代表性不足的少数民族，2）高中工作阴影/研究经验计划，和3）本科参与计划，旨在吸引/留住聚合物科学专业。参与上述每一项推广活动的研究生将经常有机会整合研究活动，以提高K-UG学生对聚合物科学的兴趣。研究生将通过涉及综合先进表征建模策略的全面，多层次方法在技术相关领域接受培训和教育。 这个综合K-研究生教育和研究平台的最终结果是通过以下方式提供巨大的社会经济影响：1）鼓励不同的学生群体从事科学学科的职业生涯，2）提供对聚合物表面工程和网络的基本理解，以建立科学发现和探索性应用之间的最短路径。

项目成果

Post-polymerization modification of styrene–maleic anhydride copolymer brushes

苯乙烯—马来酸酐共聚物刷的后聚合改性

• DOI: 10.1039/c7py01659j
• 发表时间: 2017
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: Guo, Wei;Xiong, Li;Reese, Cassandra M.;Amato, Douglas V.;Thompson, Brittany J.;Logan, Phillip K.;Patton, Derek L.
• 通讯作者: Patton, Derek L.