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CAS: Harvesting Carbon Resources Locked in PVC and Polybutadiene Waste

CAS：收集 PVC 和聚丁二烯废物中锁定的碳资源

基本信息

批准号：
2203535
负责人：
Rebecca Braslau
金额：
$ 46.5万
依托单位：
University of California-Santa Cruz
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=2203535&HistoricalAwards=false
关键词：
CAS Harvesting Carbon Resources Locked

项目摘要

With the support of the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Professor Rebecca Braslau of the University of California – Santa Cruz (UCSC) will work to develop a chemical upcycling strategy for the commercial polymer, polyvinyl chloride (PVC). A series of chemical reactions will be used to transform this material from its non-recyclable form into value-added products using mild temperatures and ambient pressure. These transformations are aimed at producing 1,5-hexadiene, which can be collected or further transformed into other valuable alkane products. Use of waste plastic consisting of all-carbon backbones as a rich feedstock would provide a non-petrochemical source for useful organic chemicals, while mitigating part of the ecological catastrophe of persistent plastic waste in our environment and landfills. The impact of chemical upcycling of waste PVC would provide a significant environmental benefit. Utilizing PVC as a valued carbon-rich resource would give the carbon atoms in the polymer backbone new uses, and result in its diversion from landfills and reduce environmental contamination. The research experience will provide interdisciplinary training to graduate and undergraduate students in synthetic organic chemistry and materials science. UCSC is a Hispanic-Serving Institution; underrepresented undergraduates will experience meaningful, exciting research. Active outreach by presenting talks on plastics with hands-on experiments to local middle and high schools serving large, underrepresented populations will engage students from diverse backgrounds in science and provide role models for pursuing higher education. Polyvinyl chloride (PVC) is a commodity polymer that is notoriously difficult to reuse or recycle, hence the polymer often ends up in a landfill after use. This work will address this problem by developing an upcycling strategy for this commercial polymer. Elimination of HCl from the (CH2-CHCl) units of PVC to form polyenes followed by olefin metathesis with added small alkenes will form a variety of specific dienes as value-added products. Likewise, olefin metathesis to upcycle polybutadiene (and related polymers with olefin-containing repeat units) will allow the breakdown of synthetic rubbers and provide access to 1,5-hexadienes derived from polybutadiene fragments. These dienes, or their direct reduction products (devoid of E/Z isomers) have the long term potential of serving as feedstocks for the chemical industry with low supply chain energy investments and minimal greenhouse gas emissions. Development of reaction conditions that allow olefin formation in tandem with olefin metathesis will provide a powerful synthetic tool for targeted alkene harvesting from used/discarded polymer sources, but also for applications beyond plastics upcycling. Use of plastic waste as an untapped carbon resource provides an earth-friendly route to continued chemical innovation, without relying on petrochemical sources.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，加州大学圣克鲁斯分校(UCSC)的丽贝卡·布拉斯劳教授将致力于为商业聚合物聚氯乙烯(PVC)开发一种化学升级策略。利用温和的温度和环境压力，将通过一系列化学反应将这种材料从不可回收的形式转化为附加值产品。这些转化的目的是生产1，5-己二烯，这些己二烯可以被收集或进一步转化为其他有价值的烷烃产品。使用由全碳骨架组成的废塑料作为丰富的原料，将为有用的有机化学品提供一种非石化来源，同时减轻我们环境和垃圾填埋场中持久性塑料废物造成的部分生态灾难。废旧聚氯乙烯化学循环的影响将提供显著的环境效益。利用聚氯乙烯作为一种有价值的富碳资源，将给聚合物主干中的碳原子带来新的用途，并导致其从垃圾填埋场转移，减少环境污染。研究经验将为合成有机化学和材料科学的研究生和本科生提供跨学科培训。UCSC是一家为拉美裔服务的机构；未被充分代表的本科生将体验到有意义的、令人兴奋的研究。通过在当地初中和高中举办关于塑料的讲座并进行动手实验，积极开展活动，为人数众多、代表性不足的人口提供服务，将吸引来自不同科学背景的学生，并为追求高等教育提供榜样。聚氯乙烯(PVC)是一种商品聚合物，出了名的难以重复使用或回收，因此这种聚合物在使用后往往会被送到垃圾填埋场。这项工作将通过为这种商业聚合物开发升级循环策略来解决这个问题。从聚氯乙烯的(CH2-CHCl)单元中消除HCl形成多烯，然后与添加的小烯烃进行烯烃歧化反应，将形成各种特殊的双烯作为增值产品。同样，将烯烃歧化为上循环聚丁二烯(以及相关的含有烯烃重复单元的聚合物)将允许合成橡胶分解，并提供从聚丁二烯碎片衍生的1，5-己二烯的途径。这些二烯烃或其直接还原产物(不含E/Z异构体)具有长期潜力，可作为供应链能源投资较低、温室气体排放最少的化学工业的原料。随着烯烃化合反应条件的发展，将提供一种强大的合成工具，用于从旧的/废弃的聚合物来源中有针对性地收集烯烃，而且还可用于塑料回收以外的应用。使用塑料垃圾作为一种未开发的碳资源，为持续的化学创新提供了一条对地球友好的途径，而不依赖于石化资源。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。