Journal Pre-proof

Recycled Polymer: Green Roads for Polyester

Plastics

Rulin Yang, Guangqiang Xu, Wenjie Tao,

Qinggang Wang, Yong Tang

PII: S2950-1555(24)00010-7
DOI: https://doi.org/10.1016/j.greenca.2024.01.004
Reference: GREENC29

To appear in: Green Carbon

Received date: 7 October 2023
Revised date: 7 December 2023
Accepted date: 25 January 2024
Please cite this article as: Rulin Yang, Guangqiang Xu, Wenjie Tao, Qinggang
Wang and Yong Tang, Recycled Polymer: Green Roads for Polyester Plastics,
Green Carbon, (2024) doi:https://doi.org/10.1016/j.greenca.2024.01.004
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Review

Recycled Polymer: Green Roads for Polyester Plastics

Rulin Yang a,b,c,d, Guangqiang Xu a,b,c,d,* Wenjie Tao a,b,c,d, Qinggang Wang a,b,c,d,* and Yong Tang e
a Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sci-
ences, Qingdao, 266101, China.
b Shandong Energy Institute, Qingdao, China.
c Qingdao New Energy Shandong Laboratory, China.
d Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China.
e State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,

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Shanghai, China.

* Corresponding author. E-mail: [email protected] (G. Xu); [email protected] (Q. Wang)

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ORCID. Guangqiang Xu: 0000-0001-8557-1192; Qinggang Wang: 0000-0003-1851-7078

Received: Day Month Year; Accepted: Day Month Year; Available online: Day Month Year

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ABSTRACT: Plastics are integral to numerous significant social advancements. Nonetheless, their contribution to environmental
pollution and climate crises cannot be disregarded, as their negative impact on the environment increases with incremental produc-
tion capacity and demand. Concerted global action is urgently required to promote the green recycle of plastics to prevent their
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accumulation in the environment and mitigate carbon emissions. This review aims to reveal the paths of green development for
polyester plastics, incorporating the trends of the green revolution in mature commercial polyester plastics, newly emerging biode-
gradable polyester plastics, and future polyester plastics. A critical discussion was conducted on the current and potential future
research areas from multiple perspectives, including raw materials, processes, and recycling, to propel us into a future marked by
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sustainability.
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Keywords: recycled polymer; polyester plastics; recycling; bio-based; plastic economy

© 2023 The Authors. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
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(http://creativecommons.org/licenses/by-nc-nd/4.0/).
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1. Introduction

CO2

Resource extraction Production Consumption End-of-life plastics

Raw materials Process Products Post- treatment

toward green carbon toward green carbon toward green carbon toward green carbon

Fig. 1. Carbon emissions and green development in the life cycle of plastics.

Modern society relies heavily on plastic materials, the output of which increases annually with industrialization
and consumerism. The life cycle of plastics not only causes some environmental pollution problems, but also contributes
to the worsening issue of climate change [1-4]. The evaluation report revealed that the greenhouse gas emissions caused
by plastics in 2015 were roughly 1.7 billion tons of carbon-dioxide-equivalent. This number is anticipated to turn into
6.5 billion tons by 2050, accounting for 15% of the global carbon emissions budget [5-7]. In line with the current trend

https://doi.org/xxxx
Green Carbon. 2023, 1, x FOR PEER REVIEW 2 of 19

of energy conservation and emission reduction, countries and regions have introduced relevant policies to facilitate the
advancement of sustainable and low-carbon economic models. The Paris Agreement also sets a climate action goal of
controlling global temperature rise within 2°C by 2100 [8]. Therefore, it is crucial to consider carbon reduction from the
perspective of plastics to achieve green and low-carbon development in the plastics economy.
Carbon emissions exist throughout the life cycle of plastics from the extraction and transportation of raw materials
to the refining and manufacturing of plastics, and to the circulation and disposal of plastic products (Fig. 1) [9]. Cur-
rently, 90% of the world's plastics are derived from fossil fuels and their manufacturing processes are both energy- and
emission-intensive [10]. The consumption and release of large amounts of carbon resources contradict the global climate
goals. Owing to non-standard disposal and the lack of effective recycling technology, the long-term accumulation of
waste plastics has caused serious environmental pollution. At present, only about 14% of plastics can be recycled [11-
13]. Moreover, conventional incineration and landfilling methods also result in high carbon emissions. Each ton of
burned plastic waste produces two tons of diverse greenhouse gases including carbon dioxide. Improving the recycling

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rate of plastics and developing efficient and high-value plastic reuse methods are important for sustainable plastic de-
velopment. It is estimated that if the complete recycling of plastic waste is achieved by 2050, the reduction in carbon
dioxide emissions in the entire industry could be as much as 25% or 4.9 billion tons [14-16]. Therefore, to achieve green

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development of plastics, it is important to consider every aspect of plastic life cycle. This includes focusing on raw
materials up to post-treatment processes. The application of green raw materials, low-carbon processes, green electric-

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ity, and efficient plastic recycling can significantly alter the current situation [17-19].
This review aims to discuss new trends in green and sustainable paths for plastics, mainly from the raw materials
and post-treatment perspectives. Traditional polyolefin plastics are mostly derived from petroleum-based sources, and
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their main chains are stable carbon-carbon bonds, which necessitate harsh activation and degradation conditions [20-
23]. Their green development is relatively challenging; therefore, this review will not introduce them in detail. Instead,
we will concentrate on polyester plastics, which are currently gaining widespread use and have great potential for
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further development. We will discuss the green development direction of mature commercial polyester plastics, newly
emerging biodegradable polyester plastics, and future polyester plastics such as poly(ethylene terephthalate) (PET),
polylactide (PLA), and polyethylene furanoate (PEF) (Fig. 2).
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Fig. 2. Green roads for polyester plastics.

2. Green roads for mature commercial polyester plastics

Green development of mature commercial polyester plastics, which are extremely pervasive, should be considered
first, with poly(ethylene terephthalate) (PET) being the most representative [24,25]. As the most widespread and versa-
tile thermoplastic, polyethylene terephthalate (PET) has applications in many products, from food packaging and
Green Carbon. 2023, 1, x FOR PEER REVIEW 3 of 19

beverage bottles to synthetic fibers, accounting for approximately 13% of all plastic usage. Since 2003, the global PET
production capacity has continuously expanded at a rate of 9% [26,27]. Therefore, the green development of PET is
imperative, as it is not only necessary to break through the green source of raw materials but also to comprehensively
advance the recycling and reutilization of waste PET.

2.1 Developing bio-based raw material

Traditionally, the raw materials for PET production, terephthalic acid (PTA) and ethylene glycol (EG), are con-
verted from paraxylene and ethylene, respectively, which are derived from petroleum [28]. Recently, the development
of bio-based polymers has been identified as an important means of reducing carbon emissions (Fig. 3). Bio-based raw
materials are obtained by “carbon sequestration” technique during the plant growth process, which can substantially
mitigate the release of carbon dioxide during the fossil fuels refining. Life cycle assessment revealed that the manufac-
turing process of bio-PET can decrease greenhouse gas emissions by 82% compared with petroleum-based PET [29].

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Fig. 3. Different routes for bio-based PET synthesis from biomass.

Bio-based PET is mostly derived from only 30% biomass (Bio-PET30); that is, EG is a renewable biological source
[30]. The relatively mature production of bio-based EG has a long history, and can be derived from various pathways,
such as ethanol, glycerol, sorbitol, sugar, and cellulose biomass [31]. For example, as an important biomass-derived
chemical, ethanol can be dehydrated to prepare ethylene and subsequently obtain EG, which is currently the most
Green Carbon. 2023, 1, x FOR PEER REVIEW 4 of 19

advanced generation method for bioderived EG [32,33]. JBF has developed relevant processes to provide products to
Coca-Cola. Furthermore, glycerol-derived chemicals have also garnered special attention as a byproduct of biodiesel.
Glycerol hydrogenolysis produces propylene glycol, EG, and other chemicals, and catalyst optimization can improve
the selectivity for a single product. However, given the greater economic value of propylene glycol and the increased
difficulty in controlling the selectivity of EG, researchers are currently aligning their efforts toward converting propyl-
ene glycol [34-36]. Sorbitol is one of the 12 most important platform chemicals released by the U.S. Department of Energy
to produce fuel and chemicals from biomass. However, its conversion to EG has a low conversion and selectivity [37,38].
In contrast, the selectivity of the preparation of EG from cellulose reached 75%. However, because of the high crystal-
linity and low solubility of cellulose, the reaction efficiency must be improved [39,40]. Notably, biomass-derived EG
often coexists with other mixed alcohols, and if not fully purified, it affects the performance of the prepared PET [41].
Although 30% bio-based PET has already been commercialized, 100% bio-based PET is a long-term ambition, and
the bottleneck is the poor economy of bio-based terephthalic acid [42]. Numerous techniques have been developed for

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the direct synthesis of p-xylene or terephthalic acid from biomass. The procedures of using isobutanol as a raw material,
dehydrating into isobutylene, oligomerizing into diisobutylene, followed by dehydrogenating and cyclizing into p-xy-
lene, have been applied in actual production [43,44]. However, based on the economic calculations, the cost of this

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substance exceeds that of petroleum-based p-xylene. In addition, the yield of p-xylene synthesized with 5-hy-
droxymethylfurfural (HMF) can reach a maximum of 85% [45] although, the high cost significantly reduces the eco-
nomic feasibility of this process.
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Bio-based PET has entered the market with significant environmental benefits, but the issues of low conversion
efficiency and high economic cost cannot be overlooked. With the advancement of catalytic systems and production
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processes and the decline in production costs, it is believed that bio-based PET will occupy the main market in the near
future.
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2.2 Mechanical recycling

Mechanical recycling through melt extrusion is currently the mainstream method for PET recycling. As the main
material of beverage bottles, the recycling rate of PET bottles can reach 57% because of their ease of recycling [46,47].
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However, this recycling process is limited to food-grade transparent PET. Colored PET bottles are removed because
they contain colorants as well as other fiber PET materials that are difficult to recycle. Simultaneously, the polymer
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chains of PET break after several high-temperature melting processes, leading to a decline in performance [48,49].
Hence, mechanical recycling is a process of “downcycling,” which will eventually generate waste plastic. Therefore,
mechanical recycling should be prioritized for PET recycling, and chemical recycling should be considered for PET that
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cannot ultimately be mechanically recycled.

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2.3 Chemical recycling

PET and other polyester materials have highly polarized ester groups in the polymeric main chain that are suscep-
tible to nucleophilic attack, providing favorable conditions for their chemical recycling (Fig. 4) [50]. The chemical recy-
cling of PET is a relatively booming field, and many review papers have provided detailed summaries [13,26-28,47,49].
In this review, we focus on achieving sustainable and green development of PET depolymerization to avoid redun-
dancy, mainly expressing insights into the field and highlighting promising research ideas.
Green Carbon. 2023, 1, x FOR PEER REVIEW 5 of 19

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Fig. 4. Chemical recycling of waste PET. (a) Depolymerization through nucleophilic attack. (b) Depolymerization
through hydrogenolytic deconstruction. (c) Novel catalytic methods including photocatalysis, photothermal catalysis,
and electrocatalysis.
Green Carbon. 2023, 1, x FOR PEER REVIEW 6 of 19

Compared with mechanical recycling, chemical recycling usually requires intricate processes and relatively ele-
vated production costs; therefore, large-scale production is necessary to achieve economic efficiency. Nevertheless,
chemical recycling can resolve the issues of the degraded performance of recycled plastics and the high-purity require-
ments of waste raw materials. The ester bonds in PET can be broken chemically to degrade it to its initial monomer, and
chemically regenerated PET can then be obtained by polycondensation (Fig. 4a). Currently, degradation strategies in-
clude glycolysis, alcoholysis, and alkaline hydrolysis [51,52]. Ethylene terephthalate (BHET) is produced by the glycol-
ysis of EG, which is subsequently filtered for impurity removal and decolorized, before use in the production of PET
[53-55]. Goodyear, DuPont, Hoechst, and other enterprises have industrialized this technology. In addition, PET can be
converted into crude dimethyl terephthalate (DMT) by pressure alcoholysis with methanol, and high-purity DMT is
obtained by distillation or sublimation [56]. Considering the potential dangers of pressurization, Teijin developed a new
process to obtain crude BHET by depolymerizing at the boiling temperature of EG. After filtration and separation to
remove impurities, BHET was transesterified with methanol and converted to DMT [57].

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Although remarkable progress has been made in the field of industrialization, the main challenge of PET chemical
recycling is that PET shows high solvent resistance and stability; therefore, its depolymerization conditions are usually
harsh, involving high temperatures and energy consumption [58,59]. Developing depolymerization methods under

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mild conditions has been a long-standing research direction for scientists. Niu et al. designed a binuclear Zn catalyst
based on a biomimetic catalytic strategy. The “bimetallic site” active center assisted in transforming the intermolecular

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nucleophilic reaction into an intramolecular reaction, thus leading to a significant rate enhancement under mild condi-
tions. The catalyst can facilitate the continuous hydrolysis of PET in a real seawater environment (pH 7.9), which pro-
vides the possibility of environmental remediation [60]. Wang et al. developed a THF-promoted selective nonaqueous
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hydrolysis method. The THF solvent improved the compatibility between PET and the solution through etching the
surface of PET to enhance the contact between the substrate and solution. Therefore, PET degradation occurs even at
30°C [61].
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In addition to recycling PET back to the initial monomer, upcycling PET into a high-value-added product is also a
significant direction (Fig. 4a). An intriguing example is the commonly used plasticizer, dioctyl terephthalate (DOTP),
in the polymer industry, which is typically manufactured using phthalic acid as the fundamental raw material. Inter-
estingly, Zhang et al. developed a new method to directly convert PET to DOTP by alcoholysis using efficient choline
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chloride-based deep eutectic solvents as the catalytic system and 2-ethyl-1-hexanol (2-EH) as the solvent [62]. Fu et al.
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reported a novel and efficient method for PET acetolysis. In addition to terephthalic acid, another product is EG diace-
tate, a third-generation environmentally friendly solvent [63]. Life cycle assessment (LCA) showed that this method
had the lowest environmental impact among all PET chemical recycling methods. In addition, using bis(2-hydroxyethyl)
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terephthalamide, a product obtained after the amino-alcoholysis of PET, Chatterjee et al. synthesized a series of poly(es-
ter amides) (PEAs) as new polymer materials [64,65]. These polymers exhibit excellent biocompatibility, which makes
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them ideal candidates for bone-tissue regeneration. These examples demonstrate the feasibility of PET upcycling and
have inspired researchers to explore additional high-value applications.
The successful implementation of the above cases utilized the ester bonds in PET because they are susceptible to
nucleophilic attack, aided by catalysts or solvents to further activate the carbonyls or enhance the nucleophilicity of the
nucleophilic reagents. In addition, the existence of ester bonds facilitates hydrogenolytic deconstruction, in which the
C–O bonds are cleaved under the action of hydrogen and catalysts [66,67]. With the development of green hydrogen
technology, H2 can be considered as a green reagent. Therefore, catalytic hydrogenolysis is important for sustainable
development (Fig. 4b). Depending on the degree of hydrogenation, the final degradation products are diverse, thus
enriching PET recycling pathways. An early catalytic process involved the use of a homogeneous Ru-ester hydrogena-
tion catalyst to directly depolymerize PET into 1,4-phenylenedimethanol and EG [66]. However, the reaction usually
required a high H2 pressure (> 50 Pa) and temperature (> 120°C), as well as the involvement of noble metal catalysts,
the safety and economy of this process require further consideration. These constraints have prompted researchers to
focus on the hydrogenolysis using inexpensive catalysts under mild conditions. For example, Marks et al. developed a
carbon-supported single-site Mo-dioxo catalyst that can depolymerize PET into terephthalic acid (TPA) and ethylene
under 1 atm H2 [67]. Alternatively, using a tandem catalytic approach, Hf(OTf)4 and Pd/C could be employed to decon-
struct PET into TPA and ethane [68]. Despite the above progress, it cannot be ignored that the direct hydrogenation of
PET has an inherently low efficiency, requiring a prolonged reaction time. To address this challenge, a combination of
alcoholysis and hydrogenation reactions has been proposed [69]. In this situation, the main focus will shift to further
Green Carbon. 2023, 1, x FOR PEER REVIEW 7 of 19

hydrogenation upcycling of alcoholysis products, such as DMT or oligomers. Xie et al. designed a new class of qui-
naldine-based Ru(II)-pincer catalysts that could catalyze the conversion of PET into DMT through an initial transester-
ification, followed by hydrogenolysis to obtain the final products 1,4-phenylenedimethanol and EG [70]. The reaction
conditions could be as mild as 80°C and 1 bar H2. The hydrogenation of DMT to prepare dimethyl cyclohexanedicar-
boxylates (DMCD) or p-xylene (PX) also has significant value, as the former can be used to manufacture coating resins,
while the latter is the major component of gasoline fuels [71,72]. It is worth noting that in recent years, some advanced
hydrogenation technologies can avoid the use of additional H2 and instead utilize in situ generation. For example, Zhao
et al. used modified Cu/SiO2 as a catalyst to design a reaction system that integrates PET methanolysis, methanol dehy-
drogenation, in situ H2 production, and DMT hydrodeoxygenation to PX [73].
In view of the significance of PET chemical recycling, in addition to the above chemical or thermal catalysis, some
cutting-edge catalytic methods, including photocatalysis, photothermal catalysis, and electrocatalysis, have attracted
considerable attention from the scientific community (Fig. 4c). As a green, clean, and sustainable energy source, solar

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energy provides more opportunities for the green development of plastics when applied to their chemical recycling
[74]. Solar-driven catalytic plastic recycling can be classified as photocatalytic or photothermal catalytic. Photocatalysis
utilizes photo-generated electron/hole pairs (e- - h+) to drive various chemical reactions under mild conditions, achieving

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the conversion and storage of solar energy into chemical energy [75]. In this process, a photocatalyst is usually neces-
sary, which promotes the absorption of solar energy to generate energetic electron-hole pairs. Electrons migrate to the

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catalyst surface to induce oxidation, reduction, or tandem reactions [76]. Reisner et al. implemented a CdS/CdOx quan-
tum dot (QD) photocatalyst in an alkaline aqueous solution [77]. Under simulated solar light, PET and other plastic
materials were converted into H2 fuel, accompanied by some organic products such as formate, glycolate, ethanol, and
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acetate. Most research on photocatalysis has focused on low-energy reaction systems, which inevitably exhibit low ef-
ficiency [78]. In contrast, the use of photothermal catalysis to improve depolymerization activity and selectivity has also
been confirmed recently. With the help of photothermal materials, the process of converting solar energy into thermal
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energy is realized to enhance the thermal vibration and transportation of reactants [79,80]. A representative study was
conducted by Chen et al. They developed a series of photothermal catalysts, such as multiwalled carbon nanotubes pre-
modified by polydopamine (CNT-PDA), integrated cobalt single-site catalysts (Co SSCs), and c-ZIF-8@SiO2 nanostruc-
tures, to convert solar energy into thermal energy, thus promoting the glycolysis of PET [81-83]. Benefiting from the
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unique localized solar heating effect, lower depolymerization temperatures and higher recovery rates could be
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achieved.
Electrocatalysis is another sustainable strategy because electrical energy can be obtained from renewable sources
(such as solar and wind). This field has great potential for development, but is still in its infancy. The seminal study was
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conducted by Duan [84]. In this study, a bifunctional CoNi0.25P electrocatalyst was employed, and the reaction was
carried out in a membrane-electrode assembly reactor using a KOH electrolyte. PET waste is converted into potassium
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diformate (KDF), TPA, and H2 at a commercially relevant current density. This work will shed light on the electrocata-
lytic depolymerization of plastics.

3. Green roads for new emerging biodegradable polyester plastics

The design of conventional plastics prioritizes high performance and durability over degradability. For example,
PET can exist for 100 years under environmental conditions without degradation [85,86]. In recent years, there has been
a global consensus on the comprehensive control of “white pollution.” Countries and regions actively promote manda-
tory regulations and policies such as plastic restrictions and vigorously develop biodegradable plastics as alternatives.
Biodegradable plastic refers to the biodegradability to carbon dioxide, water, and biomass (standard CEN/TR
15351:2006), thus avoiding continuous harm to the environment [87]. Therefore, developing biodegradable plastics is
regarded as a promising option for reducing and ultimately eradicating global plastic pollution.
Biodegradable plastics can be divided into bio-based and petroleum-based plastics based on the source of the raw
materials. Among these, polylactide (PLA), which is prepared from lactic acid fermented by biomass, is the most ma-
ture, and its industrial scale accounts for approximately 30% of all biodegradable plastics [88,89]. However, how they
really contribute to environmental benefits and how to maximize their eco-friendliness have become the focus of dis-
cussion (Fig. 5).
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Fig. 5. Recycling pathways of biodegradable PLA.
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3.1 Biological cycle
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Under the action of microorganisms, end-of-life biodegradable plastics are degraded into carbon dioxide and wa-
ter, which can be fixed through plant photosynthesis to obtain organic matter such as starch. Therefore, “Biodegrada-
tion” is the process that enables the biological recycling of carbon resources [90].
Despite being biodegradable, the degradation efficiencies of these materials in natural environments have not with-
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stood practical testing. The rate of biodegradation depends heavily on various conditions, such as the concentration of
degrading enzymes, microorganisms, temperature, pH, humidity, oxygen supply, and light. Hence, it is imperative to
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compare the biodegradation rates of the same polymer in various environments to assess its sustainability. For example,
PLLA is a hydrophobic semi-crystalline polymer with a glass transition temperature (Tg) of about 60°C [91]. Therefore,
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when the ambient temperature is lower than this temperature, degradation is usually difficult because the crystalline
segments are difficult to move. Agarwal et al. investigated the degradation rate with the simulated seawater condition
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at 25°C. After one year, there was almost no mass change in PLA [92]. Under industrial composting conditions, degra-
dation was allowed to proceed because of the guaranteed temperature and humidity (temperature > 58°C and humidity
> 60%). However, at present, back-end facilities such as composting plants are incomplete, limiting their popularization
and application.
Generally, with the powerful promotion of biodegradable polyester plastics, environmental pressure can be alle-
viated to a certain extent. However, the long-term biological cycle in the natural environment also urges us to consider
more perfect recycling methods. Meanwhile, the further development of more promising new materials is also worthy
of attention by gaining an in-depth understanding of microorganisms and their degradation patterns in different envi-
ronments.

3.2 Chemical recycling

Although biodegradable plastics can be biorecycled, recycling and utilization are also good choices considering
the long biological cycles and poor economic efficiency. The easy degradation characteristics of biodegradable plastics,
such as PET, make them unsuitable for mechanical recycling. To address these challenges, several studies have focused
on chemical recycling. Hence, for biodegradable plastics that can be recycled, priority should be given to chemical re-
cycling, whereas biodegradation should be adopted for those that are not easy to recycle to maximize the value of
biodegradable plastics.
Green Carbon. 2023, 1, x FOR PEER REVIEW 9 of 19

As PLA is the most widely used biodegradable material, its chemical recycling has received extensive attention in
recent years. In previous reviews, the chemical recycling of PLA was systematically summarized based on the reaction
type [26,89], including pyrolysis, hydrolysis, and alcoholysis. In this study, efforts were made to emphasize a direction
that is conducive to the green development of plastics from the perspective of product application. Various chemical
recycling strategies have been intensively studied to facilitate the conversion of PLA into its initial monomers, high-
value-added chemicals, and new polymer materials [93,94].
(1) PLA to monomer
PLA materials are typically prepared by the ring-opening polymerization of lactide, a six-membered ring mono-
mer; thus, the transformation of PLA to lactide monomers can enable a complete closed-loop recycling process. Accord-
ing to the calculation formula of Gibbs free energy ΔG = ΔH - TΔS. When ΔG is less than 0, polymerization occurs
smoothly. For typical polymerizations, owing to the release of ring tension and the reduction in monomer molecular
freedom after polymerization, the enthalpy and entropy changes are less than 0, thereby leading to a ceiling temperature

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(Tc) for polymerization [95]. Polymerization occurs only when the temperature is lower than Tc, whereas depolymeri-
zation occurs.
However, the Tc of lactide polymerization is as high as 640°C (in bulk) [96]; therefore, in the early exploration of

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high-temperature pyrolysis of PLA, only a small amount of lactide was produced, accompanied by low selectivity
[97,98]. Currently, this process is mostly conducted under heating and low-pressure conditions. Under reduced pres-

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sure, lactide is continuously removed, which promotes a shift in equilibrium to depolymerization so that lactide can be
obtained in high yield at relatively low temperatures [99]. Optimization of the catalytic system is crucial for the activity
and selectivity of the reaction. For example, Zhang et al. designed chlorostannate(II) ionic liquids prepared by 1-butyl-
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3-methylimidazolium chloride and tin(II) chloride [100]. When used for the depolymerization of PLA, the reaction pro-
ceeded smoothly at 200°C and 10 Torr. The imidazolium cation forms a tight bond with the carbonyl oxygen of PLA,
enhancing the electrophilicity of the carbonyl carbon and facilitating the backbiting of the hydroxyl chain end to gener-
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ate lactide. Moreover, owing to the large steric hindrance of the imidazole group, the interaction with the terminal
carbonyl group of the carboxylic chain end inhibited backbiting of the carboxylic group, thereby preventing the for-
mation of meso-lactide.
High Tc is a bottleneck in the depolymerization of PLA to lactide. To overcome this problem, in 2022, Odelius et al.
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reported a method utilizing solvation to regulate the balance between PLA polymerization and depolymerization [101].
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Due to the interaction between solvent, monomer, and polymer, the ceiling temperature of lactide could be lowered to
119°C using the high-polar solvent DMF. Therefore, PLLA can accomplish rapid depolymerization at a milder temper-
ature of 140°C, generating a yield of 95% lactide and a selectivity of 98-99%. However, the high boiling point of DMF
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makes purification of the lactide difficult.

Despite some academic advances, in actual production, only the application of PLA oligomers to lactides has been
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demonstrated, and there have been a few successful cases of the application of high-molecular-weight PLA. This was
mainly due to an increase in the viscosity of the system as the molecular weight of the PLA increased while the high
viscosity of the reaction system affected the uniformity of agitation and heat transfer. Furthermore, this also makes it
difficult to quickly separate the product, leading to racemization and even carbonization of the lactide. Developing a
mild and efficient PLA pyrolysis system to obtain lactides with high yield and purity and implementing this process in
actual production are the next research focuses in this field.
(2) PLA to high-value-added chemical
Another approach for effectively utilizing the waste carbon resources of PLA is to convert it into high-value-added
chemicals. For example, lactic acid can be obtained by the hydrolysis of PLA and subsequently utilized to prepare lac-
tides [102,103]. However, harsh reaction conditions such as strong acids, strong bases, high temperatures, and low deg-
radation rates render hydrolysis less environmentally safe and economical.
Currently, the primary focus is on the depolymerization of PLA to alkyl lactate by alcoholysis, taking advantage
of transesterification [104,105]. Alkyl lactate can serve as not only a green solvent, but has also been successfully used
to directly prepare lactide monomer [106,107]. In recent years, catalytic systems including organic catalysts, ionic liq-
uids, metal compounds, and organometallic complexes have been developed to achieve efficient alcoholysis under mild
conditions [26,108]. For example, in a study by Leibfarth, TBD demonstrated exceptional catalytic alcoholysis activity,
and the yield of ethyl lactate reached > 90% within 3 min at room temperature [109]. Moreover, some inexpensive and
Green Carbon. 2023, 1, x FOR PEER REVIEW 10 of 19

readily available metal salts, such as zinc acetate and stannous octanoate, can also be used to catalyze alcoholysis, mak-
ing practical production possible [110,111].
In addition to the depolymerization method for breaking the ester bond of PLA using nucleophiles, high-value
products have been effectively constructed in recent years by selectively introducing additional chemical functional
groups. In 2022, Ma et al. introduced an amino group to convert PLA to alanine [112]. PLA is first hydrolyzed to am-
monium lactate under alkaline conditions produced by ammonia and water. Subsequently, dehydrogenation occurs
under the catalysis of Ru to produce the reaction intermediate, which is finally converted to alanine through hydro-
genation and amination. More recently, PLA was successfully converted to methyl methacrylate using a two-step pro-
cess, in which methyl propionate was first obtained and then reacted with formaldehyde [113]. These methods will
inspire more diversification and upcycling of PLA.
(3) PLA to new polymer materials
One research objective in this field is to further improve the recycling efficiency of PLA. Recently, Wang et al.

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reported a strategy of “depolymerization - repolymerization” [114]. In this strategy, waste PLA is first degraded into a
short-chain polymer to regain its polymerization activity, followed by chain growth to obtain high-performance poly-
mer materials. This strategy directly converts waste PLA into new polymer materials, thereby shortening the recycling

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process.

4. Green roads for future polyester plastics

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With the development of polymer science, various plastic materials suitable for various applications have been
developed. Novel materials that differ from traditional materials and have unique functions or uses are emerging. Based
re
on their current status, researchers are more oriented toward biodegradable polyester materials from biological sources
to achieve the green development of plastics [115,116]. Sustainable bio-based sources can circumvent the use of tradi-
tional nonrenewable fossil fuels. Moreover, its degradable properties prevent it from becoming trapped in plastic pol-
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lution. For future polyester plastics, it is necessary to fully consider their recycling routes, including biodegradation,
mechanical recycling, and chemical recycling. In recent years, with the continuous progress in science and technology,
several promising biodegradable polyester materials have been developed, which are expected to become the next gen-
a

eration of large-scale application materials (Fig. 6).

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Fig. 6. Representatives of future polyester plastics.

Polyhydroxyalkanoates (PHA) are natural polymer materials synthesized by microorganisms [117]. Its excellent
degradation and physical properties as well as its increasingly mature technology provide a strong driving force for the
growth of PHA, rendering it the most promising biodegradable material. The most prominent advantage of PHA is that
it can exhibit a wide range of physical properties by adjusting its composition. In addition, the biodegradability of PHA
Green Carbon. 2023, 1, x FOR PEER REVIEW 11 of 19

has been verified to be the best of all plastics at present, which can be degraded in various scenarios such as soil, sea-
water, and lake water [118,119]. Therefore, biodegradation should be prioritized when considering the disposal of PHA
waste. Chemical recycling is another noteworthy option because waste PHA can be used as a bio-based carbon source
to synthesize chemicals [120,121]. However, the application of PHA as a new material is still in its infancy, and there
are only a few examples of its chemical recycling research. Wang et al. studied the chemical recycling of poly(3-hy-
droxybutyrate) (PHB), one of the most important members of PHA, using chemical catalysis to convert it into alkyl 3-
hydroxybutanoate through alcoholysis or crotonic acid through pyrolysis. [122,123] In recent years, the PHA industry
has progressed quickly. Kaneka, RWDC, and Bluepha have accomplished kiloton production while its high cost renders
it more suitable for high-end medical applications. In the future, with the progress in synthetic biology technology, it
will gradually move toward commercial maturity.
Polyethylene furanoate (PEF) is a 100% biodegradable polymer material. During its production, hydroxymethyl
furfural is initially obtained from fructose and glucose; subsequently, the furan dicarboxylic acid monomer can be de-

of
rived [124]. PEF combines environmentally friendly properties with superior functionality and is regarded as an ideal
alternative material to PET, with higher mechanical strength and gas barrier properties. The data show that if it replaces
PET, carbon emissions can be reduced by 57% [125]. However, there is a problem with the actual production of PEF;

ro
that is, using the conventional polycondensation method, high-temperature conditions can easily lead to product deg-
radation and unwanted discoloration. This necessitates more stringent requirements for the production of PEF. Mor-

-p
bidelli et al. proposed that the discoloration problem could be resolved by ring-opening polymerization of cyclic oligo-
mers, but it is still in the laboratory research stage [126]. Since PEF and PET have similar chemical structures, the recy-
cling methods applied to PET can also be applied to PEF [127]. For example, glycolysis can be used in the chemical
re
recycling of PEF to obtain bis(2-hydroxyethyl)-furan-2,5-dicarboxylate (BHEF), which can act as a raw material for re-
polymerization by polycondensation [128]. We believe that PEF have room for future growth.
It is well known that the linear hydrocarbon chains of polyethylene enable crystal accumulation and provide ex-
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cellent material properties [129]. Because of the difficulty in degrading inert carbon-carbon bonds, it is important to
develop degradable materials similar to polyethylene. Studies have shown that the properties of polyethylene are al-
most unaffected by the introduction of small amounts of polyester or polycarbonate groups, which provide opportuni-
ties for polyester materials with long alkyl chains. Such materials can be prepared by condensation polymerization of
a

diols or diacids with long carbon chains, which are derived from unsaturated fatty acids in vegetable oil [130]. Unsatu-
rn

rated fatty acids make up 20-60 wt% of vegetable oils; thus, their production is substantial [19]. Mecking et al. studied
the properties of polyester-18,18 (PE-18,18) and polycarbonate-18 (PC-18) prepared from long-chain C18 dimethyl ester
and C18 diol [131]. The elastic moduli and ductilities of the two materials were comparable to those of polyolefins.
u

Simultaneously, it can be degraded to its initial monomer by alcoholysis or hydrolysis because of the existence of key
breakable sites in the ester bonds. Although this material is excellent in terms of performance, its cost is also an issue to
Jo

consider.
As a common cyclic lactone monomer, δ-valerolactone can be widely obtained from bio-base derived furfural.
However, the application of poly(δ-valerolactone) (PVL) has been neglected before. The main reason for this is that the
physical properties of PVL, such as its toughness, are traditionally considered poor. For example, its elongation at break
is only 3-6% [132,133]. Interestingly, in a recent study by Xu et al., the primary factor affecting the performance of PVL
was the polymer molecular weight [134]. If the molecular weight exceeds the critical entanglement molecular weight,
the properties of PVL can surpass those of polyolefin materials, such as polyethylene and polypropylene. Similar to
PLA, PVL can achieve a closed-loop recycling process to monomer by utilizing backbiting reactions and regulating the
chemical equilibrium between polymerization and depolymerization. It is believed that PVL will occupy a place in the
plastic market in the near future.

5. Conclusion and outlook

In general, the current green development of polyester plastics considers source green and post-treatment green. It
is necessary to curb the use of nonrenewable resources, avoid the generation of non-green factors, address existing
threats to the sustainable development of plastics, and plan for potential problems in the future.
Current countermeasures include the renewability of plastic sources, recycling of plastics, and the design of new
biodegradable plastic materials. Traditional mature commercial plastics such as PET have a long history of development
Green Carbon. 2023, 1, x FOR PEER REVIEW 12 of 19

and are widely used. However, these types of plastics are generally derived from petroleum-based raw materials due
to the lack of consideration for their potential environmental threats at the beginning of their design. In addition, their
biodegradability has been neglected due to the focus on their performance. Facing up to this situation, reforming the
sources of synthetic monomers to biomass-derived monomers will address the reliance on fossil fuels for plastic syn-
thesis. Second, the poor environmental degradation of these plastics causes loads of plastic waste, which can be consid-
ered for mechanical recycling owing to their durability. However, attention should be paid to the issue of decreased
performance after mechanical recycling. Alternatively, chemical recycling can achieve multidimensional reutilization
of waste plastics, although the process is also more complex. Although emerging biodegradable polyester plastics, such
as PLA, are widely claimed to be biodegradable, their low degradation efficiency in the natural environment also re-
quires considerations of the recycling process after their lifespan ends. It is necessary to increase the construction of
back-end facilities such as composting plants. In addition, their degradability makes them difficult to recycle mechani-
cally; therefore, chemical recycling is particularly important to ensure the effective utilization of this type of waste car-

of
bon resource. Furthermore, the development of new recyclable monomers and polymers from renewable sources has
important application value and is expected to revolutionize the plastic market in the future.
The following issues need to be addressed for green plastic sources: (1) The conversion efficiency and selectivity of

ro
renewable resources to polymeric monomers or polymers need to be improved. Although many monomers or precur-
sors can be obtained from green raw materials, they still face general problems, such as complex steps and low yields.

-p
Moreover, compared to chemical synthesis, the monomer prepared by a biological method is usually mixed with im-
purities that are difficult to remove, which affects the properties and color of the polymer obtained, limiting the appli-
cation of these materials. In addition, the overall cost of monomers from bio-based sources is relatively high, restricting
re
the economy and large-scale production. To solve these problems, chemists and biologists must work together to im-
prove the scientific and technological levels of synthetic biology and biomass conversion. (2) The choice of renewable
resources should avoid conflicts with grain, and use non-grain biomass as much as possible, such as corn straw, forestry
lP

waste, etc. For example, lactic acid, monomer of the most mature PLA bioplastic, is mostly fermented from starch, which
is generally obtained from corn. Although there is currently no threat to food security, in the long run, it is inevitable to
reduce its dependence on food in the face of increasing demand. Some new production processes have recently
emerged, such as using straw to produce lactic acid, which has the benefit of high-value utilization of agricultural waste.
a

However, the maturity of these processes remains low, and further development of iterative techniques is required for
rn

large-scale promotion and application. (3) Compatibility between the performance and degradability of new polymers
and cost issues should be prioritized, and an LCA needs to be conducted to determine whether carbon reduction is
achieved. The creation of new sustainable materials is currently a hot research field, especially for polyester materials
u

that can be closed-loop recycled into monomers. However, owing to the mutual exclusion between performance and
degradability, many new materials are now being developed in pursuit of degradability, ignoring the exploration of
Jo

performance, making actual application scenarios unclear. To obtain excellent comprehensive properties, copolymeri-
zation or blending modification of different materials may be the key to solving this problem. (4) Obtain monomers that
are compatible with existing polymerization industries and promote their large-scale production and application. The
construction of a new production line is costly and time-consuming and carries risks. With existing production facilities,
production and popularization can be quickly realized. For example, PEF can take advantage of the currently widely
available PET production units. If the raw material cost can be further reduced, there will be great market competitive-
ness.
Additionally, the following issues need to be considered from the perspective of plastic post-treatment green: (1)
Whether waste plastics can be recycled instead of being released into the environment. This requires joint efforts from
everyone around the world. It is imperative to enhance citizens’ awareness of waste recycling and sorting. Existing
plastic recycling support for public equipment needs to be improved, and the government should bolster the garbage
collection system. Biodegradable plastic composting plants must be equipped. (2) Post-treatment processes such as
plastic sorting and cleaning must be further developed. This is because plastic composition in an actual application
scenario is typically complex. Several plastic-sorting methods have been developed, including water flotation and elec-
trostatic separation. The separation of composite materials, additives, and plasticizers is challenging. For mechanical
recycling, the mixing of plastics and impurities leads to dark-colored products with low added value. The only solution
is to improve the separation efficiency at the front end. Chemical recycling offers a greater potential for the reuse of
mixed plastics, allowing the separation of subsequent products. (3) It is necessary to evaluate the economy and green
Green Carbon. 2023, 1, x FOR PEER REVIEW 13 of 19

nature of the plastic recycling process, especially the energy consumption to establish a cheap, mild, and pollution-free
degradation system. Appropriate treatment methods should be selected for different materials according to their prop-
erties to minimize damage to the environment and consumption of resources and manpower. For polymer materials
that are easy to sort and have good thermal stability, melting and reformation are preferred, while composting should
be prioritized for materials with good biodegradability. When considering chemical recycling, the specific treatment
method should also be determined based on the availability of the process, economic value, etc.
Green and sustainable development of plastics is a long and arduous task, but we must do it for our humanity's
future. It is believed that through our joint efforts, we can solve the plastic crisis and give the Earth a green tomorrow.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could
have appeared to influence the work reported in this paper.

of
Acknowledgments

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This work was support by the National Natural Science Foundation of China (21901249) and the Taishan Scholars
Program of Shandong Province (tsqn201812112) and the Scientific Research and Innovation Fund Project of the Shan-
dong Energy Research Institute (SEI I202004).

Author Contributions
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re
Rulin Yang: Data curation; Formal analysis; Investigation; Methodology; Resources; Roles/Writing - original draft.
Guangqiang Xu: Investigation; Project administration; Supervision; Roles/Writing - original draft. Wenjie Tao: Supervi-
sion; Writing- Reviewing and Editing. Qinggang Wang: Conceptualization; Project administration; Supervision; Vali-
lP

dation; Visualization; Writing - review & editing. Yong Tang: Conceptualization; Project administration; Writing - re-
view & editing.

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Declaration of competing interest
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The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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