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      Organocatalysed depolymerisation of PET in a fully sustainable cycle using thermally stable protic ionic salt

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          Abstract

          An innovative temperature-resistant organocatalyst allows the depolymerisation of PET through a solvent-free process, opening routes to green recycling of common plastics.

          Abstract

          The world's plastic production is continuously and exponentially increasing, creating millions of tons of short-lived items that end as waste and accumulate in the environment. Poly(ethylene terephthalate) (PET) provides one of the best examples as it is a non-biodegradable polymer that is mainly used as raw material for a wide range of packaging applications, making degradation of PET a subject of great interest for researchers. Herein we report a sustainable process for the chemical recycling of PET from waste to a new polymer using an innovative protic ionic salt. Using a simple solvent-free process, post-consumer PET bottles are degraded into bis(2-hydroxyethyl) terephthalate (BHET) monomer. The catalyst, formed by an equimolar quantity of triazabicyclodecene (TBD) and methanesulfonic acid (MSA), completely depolymerises PET in less than 2 h, producing 91% of highly pure BHET. Due to the unusual thermal stability of the TBD : MSA salt, the catalyst can be recycled at least 5 times to depolymerise more PET waste. In addition, we demonstrate that the monomer obtained from the degradation reaction can be used to synthesise new PET with similar thermal properties to that produced using a conventional polycondensation method. The protic ionic salt catalyst combines the excellent catalytic ability of organocatalysts with the thermal stability of metal catalysts, resisting degradation up to >400 °C, thus for the first time presenting an industrially-relevant organocatalyst for high-temperature polymer degradation and recycling.

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          Most cited references32

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          A review on pyrolysis of plastic wastes

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            Recycling and recovery routes of plastic solid waste (PSW): a review.

            Plastic solid waste (PSW) presents challenges and opportunities to societies regardless of their sustainability awareness and technological advances. In this paper, recent progress in the recycling and recovery of PSW is reviewed. A special emphasis is paid on waste generated from polyolefinic sources, which makes up a great percentage of our daily single-life cycle plastic products. The four routes of PSW treatment are detailed and discussed covering primary (re-extrusion), secondary (mechanical), tertiary (chemical) and quaternary (energy recovery) schemes and technologies. Primary recycling, which involves the re-introduction of clean scrap of single polymer to the extrusion cycle in order to produce products of the similar material, is commonly applied in the processing line itself but rarely applied among recyclers, as recycling materials rarely possess the required quality. The various waste products, consisting of either end-of-life or production (scrap) waste, are the feedstock of secondary techniques, thereby generally reduced in size to a more desirable shape and form, such as pellets, flakes or powders, depending on the source, shape and usability. Tertiary treatment schemes have contributed greatly to the recycling status of PSW in recent years. Advanced thermo-chemical treatment methods cover a wide range of technologies and produce either fuels or petrochemical feedstock. Nowadays, non-catalytic thermal cracking (thermolysis) is receiving renewed attention, due to the fact of added value on a crude oil barrel and its very valuable yielded products. But a fact remains that advanced thermo-chemical recycling of PSW (namely polyolefins) still lacks the proper design and kinetic background to target certain desired products and/or chemicals. Energy recovery was found to be an attainable solution to PSW in general and municipal solid waste (MSW) in particular. The amount of energy produced in kilns and reactors applied in this route is sufficiently investigated up to the point of operation, but not in terms of integration with either petrochemical or converting plants. Although primary and secondary recycling schemes are well established and widely applied, it is concluded that many of the PSW tertiary and quaternary treatment schemes appear to be robust and worthy of additional investigation.
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              Chemically recyclable polymers: a circular economy approach to sustainability

              Developing recyclable polymers provides a solution to materials' end-of-life issues and also an approach to establish a circular materials economy. The current practices in the generation and disposal of synthetic polymers are largely unsustainable. As part of the solution, the development of biodegradable polymers, which constitute a class of “green polymers” according to green chemistry principles, has been intensively pursued in the past two decades. However, the degradation of such polymers in Earth's landfills typically leads to no recovery of the materials’ value, and their degradation in the Oceans could create new or unintended environmental consequences. Industrial mechanical recycling always suffers from a significant quality loss. The proposed more sustainable solution is to develop chemically recyclable polymers that not only solve the end-of-life issue of polymers, but also provide a direct approach to establish a circular materials economy. Accordingly, this critical review article captures some selected highlights of the emerging area of recyclable “green polymers” by focusing on the major progress made and the technical and environmental benefits obtained in the development of repurposing and depolymerization processes for chemical recycling of polymers at the end of their useful life.
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                Author and article information

                Journal
                GRCHFJ
                Green Chemistry
                Green Chem.
                Royal Society of Chemistry (RSC)
                1463-9262
                1463-9270
                2018
                2018
                : 20
                : 6
                : 1205-1212
                Affiliations
                [1 ]POLYMAT
                [2 ]University of the Basque Country UPV/EHU
                [3 ]Joxe Mari Korta Center
                [4 ]20018 Donostia-San Sebastián
                [5 ]Spain
                [6 ]School of Chemistry
                [7 ]University of Birmingham
                [8 ]Edgbaston
                [9 ]UK
                Article
                10.1039/C7GC03396F
                872d5d29-6868-4956-aa15-44a3603ee698
                © 2018

                http://rsc.li/journals-terms-of-use

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