CAS: Deconstructing Plastic and Agricultural Waste via Organosulfur Chemistry

CAS：通过有机硫化学解构塑料和农业废物

• 批准号: 2203669
• 负责人: Rhett Smith
• 金额: $ 34.49万
• 依托单位: Clemson University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2203669&HistoricalAwards=false
• 关键词: CAS; Deconstructing; Plastic; Agricultural; Waste

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Rhett Smith of Clemson University will research ways to recycle agricultural and plastic waste, two underutilized and environmentally detrimental waste streams that represent critical barriers to a sustainable economy. The proposed research aims to benefit society by (1) elucidating new, sustainable ways to recycle plastic waste, (2) allowing access to sustainable products made from plant-derived material instead of from petroleum, and (3) alleviating environmental damage of plastic waste in the environment. This work will also benefit society through sustainability education. Resources on green and sustainable chemistry will be made available online where they may be accessed for free worldwide. This project will also help to improve participation in science, technology, engineering and mathematics degrees by engaging students from historically underserved and underrepresented groups.This work seeks to establish thio-cracking as a mechanism for chemical recycling/upcycling of plastic and agricultural waste. The thio-cracking approach being pursued involves the reaction of waste materials with elemental sulfur to yield organics and organosulfur compounds. Mixtures so derived are expected to be amenable to desulfurization to give new organic feedstocks. One aim of the research is to establish reactivity pathways between sulfur and functionalities found in target waste compounds including polyethylene terephthalate, polycarbonates, and lignin. These studies will involve the study of reactions of authentic waste materials and of small molecular model compounds. The anticipated reactivity will facilitate the formation of C–S bonds as sulfur will react with radical/radical-reactive species formed in the course of the thermal decomposition of organics at temperatures below 350 °C. This work aims to unveil fundamentally important mechanisms and microstructures resulting from C–S bond-formation and yield new organosulfur polymers. This work further seeks to provide one-pot protocols to convert plastics and biomass into new polymers and small molecular derivatives at significantly lower energy cost than required for many current chemical recycling strategies. This research has the potential to contribute to society by enabling waste reservoirs to be reclaimed for value-added applications, with this approach to recycling drawing upon the thermal reversibility of S–S bond formation.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.

在化学系大分子，超分子和纳米化学计划的支持下，克莱姆森大学的Rhett Smith教授将研究回收农业和塑料废物的方法，这两种未充分利用和对环境有害的废物流是可持续经济的关键障碍。这项研究旨在通过以下方式造福社会：（1）阐明回收塑料废物的新的可持续方法，（2）允许使用植物源材料而不是石油制成的可持续产品，以及（3）减轻塑料废物对环境的破坏。这项工作还将通过可持续性教育造福社会。将在网上提供关于绿色和可持续化学的资源，全世界均可免费查阅。该项目还将通过吸引历史上服务不足和代表性不足的群体的学生，帮助提高科学、技术、工程和数学学位的参与度，这项工作旨在将硫裂解作为塑料和农业废物的化学回收/升级循环的机制。正在采用的硫裂解方法涉及废料与元素硫的反应，以产生有机物和有机硫化合物。这样得到的混合物预期可进行脱硫以得到新的有机原料。研究的一个目的是建立硫和目标废物化合物（包括聚对苯二甲酸乙二醇酯，聚碳酸酯和木质素）中发现的功能之间的反应途径。这些研究将涉及真实废料和小分子模型化合物的反应研究。预期的反应性将促进C-S键的形成，因为硫将与在低于350 °C的温度下有机物热分解过程中形成的自由基/自由基反应性物质反应。本工作旨在揭示C-S键形成的重要机理和微观结构，并产生新的有机硫聚合物。这项工作进一步寻求提供一锅协议，将塑料和生物质转化为新的聚合物和小分子衍生物，其能源成本比目前许多化学品回收策略所需的能源成本低得多。这项研究有可能为社会做出贡献，使废物库能够回收用于增值应用，这种回收方法利用了S-S键形成的热可逆性。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

Single‐stage chemical recycling of plastic waste to yield durable composites via a tandem transesterification‐thiocracking process

• DOI: 10.1002/pol.20220686
• 发表时间: 2023-02
• 期刊: Journal of Polymer Science
• 影响因子: 3.4
• 作者: Charini Maladeniya;Andrew G. Tennyson;Rhett C. Smith

Chemical recycling of poly(ethylene terephthalate) via sequential glycolysis, oleoyl chloride esterification and vulcanization to yield durable composites

• DOI: 10.1039/d2ma00986b
• 发表时间: 2023
• 期刊: Materials Advances
• 影响因子: 5
• 作者: Claudia V. Lopez;Rhett C. Smith

Detoxification of bisphenol A via sulfur-mediated carbon–carbon σ-bond scission

通过硫介导的碳-碳-键断裂对双酚A进行解毒

• DOI: 10.1039/d2su00138a
• 发表时间: 2023
• 期刊: RSC Sustainability
• 作者: Thiounn, Timmy;Karunarathna, Menisha S.;Lauer, Moira K.;Tennyson, Andrew G.;Smith, Rhett C.
• 通讯作者: Smith, Rhett C.

Thermal and Mechanical Properties of Recyclable Composites Prepared from Bio-Olefins and Industrial Waste

• DOI: 10.3390/jcs7060248
• 发表时间: 2023-06
• 期刊: Journal of Composites Science
• 影响因子: 3.3
• 作者: Perla Y. Sauceda-Oloño;A. Borbón-Almada;Martin Gaxiola;Ashlyn D. Smith;Andrew G. Tennyson;Rhett C. Smith

Influence of pozzolans on plant oil‐sulfur polymer cements: More sustainable and chemically‐resistant alternatives to Portland cement

• DOI: 10.1002/app.53684
• 发表时间: 2023-02
• 期刊: Journal of Applied Polymer Science
• 影响因子: 3
• 作者: M. J. Graham;Claudia V. Lopez;Charini Maladeniya;Andrew G. Tennyson;Rhett C. Smith