Investigating organocatalytic routes to degradable polyacetals and polythioacetals

在这个由化学系大分子、超分子和纳米化学项目资助的项目中，Robert B. Grubbs和Surita R.斯托尼布鲁克大学化学系的Bhatia正在开发新的合成路线，用于构建可持续和可生物降解的聚合物基材料。 聚合物或塑料由许多碳碳键连接的重复单元组成，以许多不同的方式造福于我们的社会。 由于其重量轻，耐用性和符合形状的能力，塑料在过去50年中帮助航空航天技术取得了巨大进步，包括卫星，航天飞机，飞机和导弹的进步。 此外，建筑和建筑，电子，包装和运输行业都从塑料材料中受益匪浅。 虽然化学家已经创造了许多方法来将碳-碳单元组装成聚合物，但将它们逐一拆解的方法仍然非常罕见。 这种逆向过程至关重要，因为它导致聚合物可回收性，从而为塑料提供绿色生命周期，否则塑料将在环境中积累。 该项目通过为制备具有可编程降解性的聚合物材料提供新的合成路线来解决聚合物的分子再循环问题。 从这项工作中产生的新型聚合物预计将保留现有塑料的物理特性，但具有可回收的额外好处。 这项工作提供了培训和教育，本科生和研究生在合成聚合物化学，以及合作研究活动，涉及研究人员从代表性不足的群体在历史上的黑人大学（草原视图大学）。这项研究的重点是设计和合成的聚合物建模现有的丙烯酸酯和甲基丙烯酸酯主链具有类似的物理和响应性能的潜力，但可编程的降解性。 研究活动集中在引发剂（醇和羟基封端的聚合物），催化剂（三乙胺和其他有机碱）和单体结构（乙醛酸酯和乙二醛酰胺单体）对聚合过程控制的影响的系统调查。 还研究了这些不同的聚缩醛和聚硫缩醛嵌段与其它聚合物嵌段结合成嵌段共聚物的情况。 该研究具有创新性，重点关注一类具有高度工业重要性的聚合物的性质和降解。 合成的聚合物预计具有可调的热响应性，亲水性，疏水性和易受光诱导的裂解/降解的酸。这个奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professors Robert B. Grubbs and Surita R. Bhatia of the Department of Chemistry at Stony Brook University are developing new synthetic routes for the construction of sustainable and biodegradable polymer-based materials. Polymers or plastics consisting of many repeating units linked with carbon-carbon bonds have benefited our society in many different ways. Due to its light weight, durability and ability to conform to shape, plastic has helped aerospace technologies take giant steps forward over the past 50 years, including advancements in satellites, shuttles, aircraft, and missiles. In addition, the building and construction, electronics, packaging, and transportation industries have all benefited greatly from plastic materials. While chemists have created numerous ways to assemble carbon-carbon units into polymers, methodologies to disassemble them one-by-one are still very rare. This reverse process is crucial because it leads to polymer recyclability, therefore providing a green life-cycle for plastics that would otherwise accumulate in the environment. This project addresses the molecular recycling of polymers by providing new synthetic routes for the preparation of polymeric materials with programmable degradability. New classes of polymers that result from this work are expected to retain the physical properties of current plastics but with the added benefit of being recyclable. This work provides training and education to undergraduate and graduate students in synthetic polymer chemistry, and collaborative research activities involving researchers from underrepresented groups at a historically Black university (Prairie View University). This research is focused on the design and synthesis of polymers modeled on existing acrylate and methacrylate backbones with the potential for similar physical and responsive properties but with programmable degradability. The research activities focus on the systematic investigation of the effects of initiators (alcohols and hydroxyl-terminated polymers), catalysts (triethylamines and other organic bases), and monomer structure (glyoxylate and glyoxamide monomers) on the control of the polymerization process. The incorporation of these different polyacetal and polythioacetal blocks with other polymer blocks into block copolymers is also investigated. The research is innovative and focuses on the properties and degradation of a class of polymers with high potential for industrial importance. The synthesized polymers are expected to have tunable thermoresponsivity, hydrophilicity, hydrophobicity and to be susceptible to photoinduced cleavage/degradation by acid.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.