CAS: Recycling Sulfur Petroleum Waste to Fabricate Metal Capture and Adhesive Polysulfides

CAS：回收含硫石油废料来制造金属捕获和粘合性多硫化物

• 批准号: 2004257
• 负责人: Courtney Jenkins
• 金额: $ 30.83万
• 依托单位: Idaho State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2004257&HistoricalAwards=false
• 关键词: CAS; Recycling; Sulfur; Petroleum; Waste

NON-TECHNICAL SUMMARYThis project is focused on creating functional materials from elemental sulfur and is jointly funded by the Division of Materials Research (DMR) and the Established Program to Stimulate Competitive Research (EPSCoR). Each year ~70 billion kilograms of sulfur are removed from crude oil to prevent the release of small molecules that form acid rain. Inverse vulcanization is an efficient, solvent-free synthetic method that repurposes sulfur waste into functional polymers. This technique will be used to create a series of water-soluble, electrically charged polymers that can selectively capture heavy metal contaminants from water. Using petroleum waste to create polymers to remediate industrial waste helps manage two waste streams with one material. Straightforward, rapid synthesis and inexpensive reagents could make these materials practical and cost-effective for large-scale water treatment applications. The work will also combine reclaimed sulfur with renewable monomers including essential oils from native Idaho plants and mussel-mimetic components to develop adhesive polymers. These renewable adhesives would be solvent-free from synthesis to application, thus limiting the release of volatile organic compounds and reducing further waste production. The presence of sulfur may likely impart solvent resistance, which would improve the adhesive’s functionality and durability under harsh environmental conditions. Incorporating mussel-mimetic chemistry into this system would improve adhesion and enable mild cure conditions. Mussel-mimetic molecules have demonstrated strong adhesion on a variety of surfaces even in wet conditions. However, they are sensitive to oxygen, which can limit the material’s utility. Fundamental analysis would determine the impact of sulfur on polymer stability over time. These projects will also provide high-school, undergraduate and MS students with training in polymer science, which is not available in many primarily undergraduate departments. This hands-on experience helps students develop the skills necessary to attend graduate school or obtain a career in STEM.TECHNICAL SUMMARYThis proposal aims to create functional polysulfides from elemental sulfur (S8). Each year ~70 billion kg of S8 are removed from crude oil to prevent SO2 formation upon combustion, which produces acid rain. Inverse vulcanization (IV) repurposes this waste into functional materials. Ring opening of S8 at high temperatures forms thiyl radicals that bind to olefins, forming polysulfides. Here, IV will be employed to produce metal capture materials and renewable adhesives. Prior work has developed sulfur-containing polymers to bind a variety of heavy metals, offering substantial improvements by increasing the surface area. Charged polysulfides will be synthesized by IV to create water-soluble polymers (Aim 1). The enhanced water solubility will increase polymer-metal interactions and maximize metal capture. The charged monomers, S content, and cross-linking will be varied to examine the impacts on solubility and heavy metal binding. Copolymers will be tailored to undergo a phase change upon metal binding, enabling precipitation of metal-bound polymers and removal by simple filtration. Recycled S8 will also be used to initiate polymerization with renewable monomers including essential oils from native Idaho plants and mussel-mimetic components to develop adhesive polysulfides (Aim 2). The low Tg allows these polymers to be spread onto surfaces eliminating the need for solvents. Upon high temperature curing, materials transition into flexible solids. The incorporation of catecholic moieties should improve adhesive interactions and provide alternative curing methods including cross-linking by oxidation and metal chelation. The polysulfide composition will be systematically varied and subjected to both adhesive and toughness analysis. To better mimic mussel-foot proteins, controlled reduction will convert a subset of S-S bonds in polysulfides to thiols to determine the impact on adhesion strength and polymer stability. Successful adhesives will be exposed to various solvents to examine the influence of polymer composition and cross-linking on solubility and swelling. Creating swell-resistant materials would be useful in developing and maintaining strong, durable adhesives that could be relevant for industrial use.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.

非技术总结该项目的重点是从元素硫中创造功能材料，并由材料研究部（DMR）和刺激竞争研究的既定计划（EPSCoR）共同资助。每年约有700亿公斤的硫被从原油中去除，以防止形成酸雨的小分子的释放。反相硫化是一种高效、无溶剂的合成方法，可将硫废料再利用为功能聚合物。这项技术将被用来制造一系列水溶性的带电聚合物，可以选择性地从水中捕获重金属污染物。利用石油废料制造聚合物来修复工业废物，有助于用一种材料管理两种废物流。简单，快速的合成和廉价的试剂可以使这些材料在大规模水处理应用中具有实用性和成本效益。这项工作还将结合联合收割机再生硫与可再生单体，包括从本土爱达荷州植物精油和贻贝模拟成分开发粘合剂聚合物。这些可再生粘合剂从合成到应用都是无溶剂的，从而限制了挥发性有机化合物的释放，并进一步减少了废物的产生。 硫的存在可能赋予耐溶剂性，这将改善粘合剂在恶劣环境条件下的功能性和耐久性。在该体系中加入仿贻贝化学物质将改善粘合性并实现温和的固化条件。模拟贻贝的分子已经显示出即使在潮湿条件下在各种表面上的强粘附性。然而，它们对氧气敏感，这会限制材料的实用性。基本分析将确定硫随时间对聚合物稳定性的影响。 这些项目还将为高中，本科和MS学生提供聚合物科学的培训，这在许多主要的本科部门是不可用的。这种实践经验有助于学生发展必要的技能，以参加研究生院或获得STEM职业生涯。技术概述该提案旨在从元素硫（S8）中产生功能性多硫化物。每年从原油中去除约700亿公斤的S8，以防止燃烧时形成SO2，从而产生酸雨。 反硫化（IV）将这些废物再利用为功能材料。S8在高温下开环形成与烯烃结合的硫代自由基，形成多硫化物。在这里，IV将用于生产金属捕获材料和可再生粘合剂。先前的工作已经开发了含硫聚合物来结合各种重金属，通过增加表面积来提供实质性的改进。带电多硫化物将通过IV合成以产生水溶性聚合物（目标1）。增强的水溶性将增加聚合物-金属相互作用并使金属捕获最大化。将改变带电单体、S含量和交联，以检查对溶解度和重金属结合的影响。共聚物将被定制为在金属结合时经历相变，从而使金属结合的聚合物沉淀并通过简单的过滤去除。 S8也将用于引发与可再生单体的聚合，包括来自本土爱达荷州植物的精油和贻贝模拟成分，以开发粘合剂聚硫化物（目标2）。低Tg允许这些聚合物铺展到表面上，从而消除了对溶剂的需求。在高温固化时，材料转变成柔性固体。儿茶酚部分的掺入应改善粘合剂相互作用，并提供替代的固化方法，包括通过氧化和金属螯合交联。将系统地改变多硫化物的组成，并进行粘合性和韧性分析。为了更好地模拟贻贝足蛋白，受控还原将多硫化物中的S-S键的子集转化为硫醇，以确定对粘附强度和聚合物稳定性的影响。成功的粘合剂将暴露于各种溶剂中，以检查聚合物成分和交联对溶解度和溶胀的影响。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Allyl Sulfides in Garlic Oil Initiate the Formation of Renewable Adhesives

大蒜油中的烯丙基硫引发可再生粘合剂的形成

• DOI: 10.1039/d3py00390f
• 发表时间: 2023
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: Sayer, Kyler B.;Miller, Veronica L.;Merrill, Zackery;Davis, Anthony E.;Jenkins, Courtney L.
• 通讯作者: Jenkins, Courtney L.

Utilizing Reclaimed Petroleum Waste to Synthesize Water-Soluble Polysulfides for Selective Heavy Metal Binding and Detection

• DOI: 10.1021/acsapm.1c01536
• 发表时间: 2022-01-15
• 期刊: ACS APPLIED POLYMER MATERIALS
• 影响因子: 5
• 作者: Eder, M. Logan;Call, Cameron B.;Jenkins, Courtney L.
• 通讯作者: Jenkins, Courtney L.