An official website of the United States government
Abstract Chlorinated plastics are part of the everyday lives of consumers and producers alike. They can be found in buildings, automobiles, fashion, packaging, and many other places. This prevalence makes them a considerable part of the plastic waste crisis. Interest in “upcycling” (as opposed to recycling) has grown recently to augment the possibilities of managing plastic waste. The advances made in plastic upcycling have focused on polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET) and polystyrene (PS) while chlorinated plastics, chiefly polyvinyl chloride (PVC), have received much less attention. The release of chlorine‐containing molecules during treatment of chlorinated plastic greatly complicates cross‐method upcycling, or even the treatment of plastic mixes containing chlorinated plastics. This review presents a case for extracting value from chlorinated plastics by highlighting appealing upcycling products made owing to, or despite, the C‐Cl bond via depolymerization, carbonization and modification. This article is protected by copyright. All rights reserved.
more »
« less
Plastic Composites from Repurposed Poly(ethylene terephthalate) Wasted Functionalized Graphene Oxide through Dynamic Depolymerization
Plastic upcycling, which involves making plastic-derived products with unique or improved properties from discarded plastic materials, is a promising alternative to recycling and disposal to help reduce the overall production of waste. However, recycled and reused materials typically have inferior mechanical, thermal, optical, and barrier properties compared with virgin plastics. Upcycled plastic materials could improve these properties while addressing future waste accumulation. In this study, we use waste poly(ethylene terephthalate) (PET) collected from disposable food packaging to create a repurposed plastic graphene oxide (GO) composite with a goal of upcycling. We developed a one-pot “dynamic depolymerization” to break down PET in the presence of GO and successfully enabled transesterification of the polymer onto GO. Covalent attachment of PET onto GO and tailorable plastic content was confirmed by thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. These covalent composites (PET-GO) were found to be relatively impermeable to water vapor, showing promise for applications in packaging materials. Aqueous degradation experiments on the composite materials demonstrated that, in bulk conditions, PET-GOs remain mechanically robust while in contact with water over appropriate time scales for packaging applications, while beginning to break down in accelerated conditions. The use of depolymerization methods to promote polymer grafting concurrently with polymer deconstruction could provide a more general method for grafting waste polymers onto oxidized carbonaceous substrates with further study.
more »
« less
- Award ID(s):
- 2318652
- PAR ID:
- 10534394
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- ACS Applied Nano Materials
- Volume:
- 7
- Issue:
- 4
- ISSN:
- 2574-0970
- Page Range / eLocation ID:
- 3691 to 3701
- Subject(s) / Keyword(s):
- Graphene Oxide Upcycling Depolymerization Poly(Ethylene Terephthalate) Composite
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Management of polyethylene terephthalate (PET) plastic waste remains a challenge. PET-hydrolyzing enzymes (PHEs) such as IsPETase and variants like FAST-PETase demonstrate promising PET depolymerization capabilities at ambient temperatures and can be utilized to recycle and upcycle plastic waste. Whole-cell biocatalysts displaying PHEs on their surface offer high efficiency, reusability, and stability for PET depolymerization. However, their efficacy in fully breaking down PET is hindered by the necessity of two enzymes: PETase and MHETase. Current whole-cell systems either display only one enzyme or struggle with performance when displaying larger enzymes such as the MHETase–PETase chimera. We developed a Saccharomyces cerevisiae-based whole-cell biocatalyst for complete depolymerization of PET into its constituent monomers with no accumulation of intermediate products. Leveraging a cellulosome-inspired trifunctional protein scaffoldin displayed on the yeast surface, we co-immobilized FAST-PETase and MHETase, forming a multi-enzyme cluster. This whole-cell biocatalyst achieved complete PET depolymerization at 30 °C, yielding 4.95 mM terephthalic acid (TPA) when tested on a PET film. Furthermore, we showed improved PET depolymerization ability by binding FAST-PETase at multiple sites on the scaffoldin. The whole cells had the added advantage of retained activity over multiple reusability cycles. This breakthrough in complete PET depolymerization marks a step toward a circular plastic economy.more » « less
-
Abstract While various plastic waste management practices are demonstrated to result in materials with similar properties, morphological features of plastic waste are often lost after recycling/upcycling. Particularly, synthetic textiles are a severely underutilized waste stream that contains built‐in value stemming from their woven architectures. This work demonstrates a simple upcycling strategy to convert polypropylene‐based (PP) woven fabrics to carbon fiber mats through direct pyrolysis for direct use in various end applications without need of additional processing steps, distinct from prior works converting plastic waste to carbon‐based additives. The retention of material properties and architectures, taking advantage of the inherent value with initial product manufacturing, is investigated, with optimal conditions resulting in consistent high carbon yields. Moreover, the textile‐derived carbon shows exceptional Joule heating performance, which can be employed in various heating applications, resulting in reduced energy consumption compared to conventional heating. Furthermore, decoration of fabric‐derived carbon with metal nanoparticles is demonstrated through electroplating, leading to altered surface functionality and further enhanced Joule heating performance. This work introduces a scalable method for upcycling of plastic waste to functional carbons that can completely retain initial material architectures with controlled shrinkage, providing a viable strategy for generating value‐added products toward electrification of heating processes.more » « less
-
Abstract Herein, we report a selective photooxidation of commodity postconsumer polyolefins to produce polymers with in‐chain ketones. The reaction does not involve the use of catalyst, metals, or expensive oxidants, and selectively introduces ketone functional groups. Under mild and operationally simple conditions, yields up to 1.23 mol % of in‐chain ketones were achieved. Installation of in‐chain ketones resulted in materials with improved adhesion of the materials and miscibility of mixed plastics relative to the unfunctionalized plastics. The introduction of ketone groups into the polymer backbone allows these materials to react with diamines, forming dynamic covalent polyolefin networks. This strategy allows for the upcycling of mixed plastic waste into reprocessable materials with enhanced performance properties compared to polyolefin blends. Mechanistic studies support the involvement of photoexcited nitroaromatics in consecutive hydrogen and oxygen atom transfer reactions.more » « less
-
Epoxy-based polymer networks from step-growth polymerizations are ubiquitous in coatings, adhesives, and as matrices in composite materials. Dynamic covalent bonds in the network allow its degradation into small molecules and thus, enable chemical recycling; however, such degradation often requires elevated temperatures and costly chemicals, resulting in various small molecules. Here, we design crosslinked polyesters from structurally similar epoxy and anhydride monomers derived from phthalic acid. We achieve selective degradation of the polyesters through transesterification reactions at near-ambient conditions using an alkali carbonate catalyst, resulting in a singular phthalic ester. We also demonstrate upcycling the network polyesters to photopolymers by one-step depolymerization using a functional alcohol.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/acsanm.3c05131
