Investigating organocatalytic routes to degradable polyacetals and polythioacetals

研究可降解聚缩醛和聚硫缩醛的有机催化路线

基本信息

批准号：
1904932
负责人：
Robert Grubbs
金额：
$ 41.21万
依托单位：
SUNY at Stony Brook
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-09-01 至 2024-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904932&HistoricalAwards=false
关键词：
Investigating organocatalytic routes degradable polyacetals

项目摘要

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.

在这个由化学系高分子、超分子和纳米化学项目资助的项目中，石溪大学化学系教授 Robert B. Grubbs 和 Surita R. 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。由许多通过碳-碳键连接的重复单元组成的聚合物或塑料以多种不同的方式使我们的社会受益。由于其重量轻、耐用且能够适应形状，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、电子、包装和运输行业都从塑料材料中受益匪浅。尽管化学家已经创造了多种将碳-碳单元组装成聚合物的方法，但将它们一一分解的方法仍然非常罕见。这种逆向过程至关重要，因为它可以提高聚合物的可回收性，从而为塑料提供绿色生命周期，否则这些塑料将在环境中积累。该项目通过提供新的合成路线来制备具有可编程降解性的聚合物材料，从而解决聚合物的分子回收问题。这项工作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。这项工作为本科生和研究生提供合成高分子化学方面的培训和教育，以及涉及历史悠久的黑人大学（草原景观大学）代表性不足群体的研究人员的合作研究活动。这项研究的重点是设计和合成以现有丙烯酸酯和甲基丙烯酸酯主链为模型的聚合物，这些聚合物具有相似的物理和响应特性，但具有可编程的降解性。研究活动重点是系统研究引发剂（醇和羟基封端聚合物）、催化剂（三乙胺和其他有机碱）和单体结构（乙醛酸酯和乙二酰胺单体）对聚合过程控制的影响。还研究了将这些不同的聚缩醛和聚硫缩醛嵌段与其他聚合物嵌段并入嵌段共聚物中。该研究具有创新性，重点关注一类具有高度工业重要性潜力的聚合物的特性和降解。合成的聚合物预计具有可调节的热响应性、亲水性、疏水性，并且易于受到酸的光诱导裂解/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点和更广泛的影响审查标准进行评估，被认为值得支持。