CAREER: SusChEM: Develop Unprecedented Chain-growth Polymerization Method to Access Structurally Defined Hyperbranched Polymers

聚合物是一种具有高分子质量的大分子，存在于日常生活的许多方面，使用塑料、橡胶、树脂和泡沫。为了提供坚固耐用、价格适中的聚合物材料，聚合物化学的一个主要目标是开发高效、廉价的聚合方法，以制备结构、组成和尺寸精确控制的定义明确的聚合物。这些聚合物可以转化为特定用途的功能材料，如自愈合材料、纳米复合材料、涂层、润滑剂、微电子和纳米医学。在化学系高分子、超分子和纳米化学项目的资助下，圣母大学高海峰教授开发了一种简便的一锅一批聚合方法，可以制备具有高度支化结构和非常窄的尺寸分布的功能聚合物。这项研究计划与一项教育计划相结合，以发展本科水平的聚合物课程和推广活动(包括一年一度的圣母大学软材料研讨会和科学博览会)，以促进学术和产业合作，并吸引当地高中学生和教师的参与。本研究试图开发一种全新的聚合方法，将铜(铜)催化的叠氮烷-炔环加成(CuAAC)聚合应用于ABM(m大于或等于2)单体的聚合，在一锅中形成聚三唑基超支化聚合物。这种方法的一个重要特点是将铜催化剂限制在每个超支化聚合物分子中，导致聚合机理为链增长聚合，聚合物相对分子质量线性增加，多分散性随着反应转化率的降低而降低。此外，线型单元中悬挂的B基团有望表现出比末端单元中更高的反应性，从而在超支化聚合物中实现线型单元到树枝单元的快速转化，最终实现高度支化。研究活动为巴黎圣母院的研究生和本科生提供有机合成、聚合物化学和各种表征技术的动手实验室培训。学生们正在培养针对专家和非专家受众的演示技能。更广泛的教育和外展影响通过以下方式放大：1)改善当前和新的聚合物化学主题在本科和研究生课程中的影响，2)在当地高中讲课，以提高公众对先进聚合物材料和纳米技术的认识，以及3)组织每年一次的圣母大学聚合物材料研讨会，以促进学术和产业合作，并让高中学生和教师参加当地的科学博览会。

Polymers, a type of giant molecules with high molecular weights, are found in many facets of everyday life that utilize plastics, rubbers, resins, and foams. To provide robust and affordable polymer materials, one thrust in polymer chemistry is to develop efficient and inexpensive polymerization method that can prepare well-defined polymers with precisely controlled structures, compositions and dimensions. These polymers could be translated into functional materials for specific applications, such as self-healing materials, nanocomposites, coatings, lubricants, microelectronics and nanomedicines. In this project, funded by the Macromolecular, Supramolecular and Nanochemistry Program of the Division of Chemistry, Professor Haifeng Gao at the University of Notre Dame develops a facile one-pot one-batch polymerization method that can prepare functional polymers with highly branched structures and very narrow size distribution. The research program is integrated with an education plan to develop undergraduate-level polymer courses and outreach activities (which including an annual Notre Dame Soft Materials Symposium and Science Fair) to stimulate academic-industrial collaboration and to engage the participation of local high school students and teachers.This research seeks to develop a conceptually new polymerization method that applies the copper (Cu)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization of ABm (m is greater than or equal to 2) monomers to form polytriazole-based hyperbranched polymers in one pot. An important feature of this method is the confinement of the Cu catalyst within each hyperbranched polymer molecule, resulting in a chain-growth polymerization mechanism with a linear increase of polymer molecular weight and decreased polydispersity with reaction conversion. In addition, the dangling B group in the linear unit is expected to demonstrate higher reactivity than those in the terminal unit, resulting in a fast conversion of linear unit to dendritic unit in hyperbranched polymers and ultimately achieving a high degree of branching. The research activities provide hands-on laboratory training to the graduate and undergraduate students at Notre Dame in organic synthesis, polymer chemistry, and various characterization techniques. The students are developing presentation skills targeting both expert and non-expert audiences. The broader education and outreach impacts are magnified by: 1) improving the impact of current and new polymer chemistry topics in the undergraduate and graduate curriculum, 2) lecturing at local high schools to raise the public awareness of advanced polymer materials and nanotechnologies, and 3) organizing an annual Notre Dame Polymer Materials Symposium to stimulate academic-industrial collaborations and engaging the participation of high school students and teachers in a local science fair.