Investigating organocatalytic routes to degradable polyacetals and polythioacetals

在这项由化学系高分子、超分子和纳米化学计划资助的项目中，石溪大学化学系的罗伯特·B·格拉布斯和苏丽塔·R·巴蒂亚教授正在为构建可持续和可生物降解的聚合物材料开发新的合成路线。由许多与碳-碳键相连的重复单元组成的聚合物或塑料在许多不同的方面造福了我们的社会。由于其重量轻、经久耐用、形状适形，在过去的50年里，塑料帮助航空航天技术向前迈进了一大步，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、包装和交通运输等行业都从塑料材料中受益匪浅。虽然化学家们已经创造了许多方法来将碳-碳单元组装成聚合物，但逐个拆解它们的方法仍然非常罕见。这种反向过程至关重要，因为它导致聚合物可回收，从而为原本会在环境中积累的塑料提供了一个绿色的生命周期。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回收问题。通过这项工作产生的新型聚合物有望保留现有塑料的物理性质，但增加了可回收利用的好处。这项工作为本科生和研究生提供合成聚合物化学方面的培训和教育，并让历史上黑人大学(Prairie View University)中代表性不足的群体的研究人员参与合作研究活动。这项研究的重点是设计和合成以现有的丙烯酸酯和甲基丙烯酸酯为骨架的聚合物，这些聚合物具有类似的物理和响应特性，但具有可编程降解性。研究活动集中于系统地研究引发剂(醇和端羟基聚合物)、催化剂(三乙胺和其他有机碱)和单体结构(乙醛和乙草胺单体)对聚合过程控制的影响。还研究了这些不同的聚缩醛和多硫缩醛嵌段与其他聚合物嵌段在嵌段共聚物中的结合情况。这项研究具有创新性，专注于一类具有很高工业重要性的聚合物的性能和降解。预计合成的聚合物具有可调的热响应性、亲水性和疏水性，并容易被酸引起的光致裂解/降解。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.