Polymer Degradation and Stability 211 (2023) 110320

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Polymer Degradation and Stability

journal homepage: www.journals.elsevier.com/polymer-degradation-and-stability

Review article

Recent advances in plastics waste degradation using ionic

liquid-based process
Megawati Zunita *, Haryo Pandu Winoto, M. Fikar Kamil Fauzan, Rahmat Haikal
Department of Chemical Engineering, Faculty of Industrial Technology, Institut Teknologi Bandung, Jalan Ganesha 10, Bandung, West Java 40132, Indonesia

A R T I C L E I N F O A B S T R A C T

Keywords: Plastics waste are increasing due to the increased production and consumption of plastics worldwide. Plastics
Ionic liquid those are difficult to decompose naturally complicate its recycle process. There are various methods for
Polymer degrading plastics waste, including mechanical and chemical. Many catalysts have been used to degrade plastics
Plastics recycling
waste, but they require high temperatures and pressures to operate. Plastics depolymerization efforts face
Depolymerization
numerous challenges, including operating conditions, product purification processes, corrosion, and pollution
issues. Ionic liquids (ILs) are being researched as solvents and catalysts, and both have grown exponentially over
the last decade. ILs are currently regarded as "green" solvents due to their unique properties that enable them to
degrade plastics under more benign conditions. ILs can also be easily separated from depolymerized product and
reused. Plastics waste conventional treatment; types of plastics; types of ILs used as solvents, catalysts, or both in
plastics degradation; plastics degradation mechanisms using ILs; and the potential use of ILs in plastics degra­
dation are covered in this review paper.

1. Introduction management, collection, and disposal of plastics waste also contribute to

Plastics are one of the primary materials that cannot be separated in
everyday life. Starting from its discovery in 1869 by John Wesley Hatt
[1], new materials in the form of synthetic polymers are now increas­
ingly diverse. Unlike other materials, plastics offer advantages such as
high flexibility, low maintenance requirements, lightweight, weather
resistance, low toxicity, and low price [2–4]. As a result of these ad­
vantages, the use of plastics is increasingly unlimited and endless [5].
Currently, plastics have been widely used in various industries such as
construction, healthcare, electronic components, automotive, and agri­
cultural packaging [6]. Research and development efforts in plastics
production technology continue to increase every year, which causes
global annual plastics production to jump from around 1.5 million
metric tons in 1950 to 359 million metric tons in 2018 [7]. Annual
global production is expected to double in the next two decades,
reaching 1,000 million metric tons by 2050 [8]. Annual worldwide
plastics production and forecast data for 2050 are presented in Fig. 1A.
The annual production of plastics and their ever-increasing use have
led to the rapid growth of plastic waste [9]. In addition, the widespread
use of single-use plastics, which quickly become waste in a short time,
has contributed to the growth of plastics waste [10]. Improper
increased plastics waste [11,12]. It is estimated that 91% of plastics
waste are from all plastics produced. If this increase continues, there will
be 12 million metric tons of plastics waste by 2050, which is not a small
amount. The cumulative plastics waste production (in a million metric
tons) is presented in Fig. 1B. Of the total plastics waste worldwide, 20%
of this waste enters the aquatic environment [10] and is a significant
contributor to marine waste [13], with a total of 80–85% of marine
waste [14]. If left unchecked, these plastics waste will harm marine
organisms and living things that consume it and damage activities such
as tourism, fisheries, and services [15].
Moreover, plastics also participate in air pollution and greenhouse
gas emissions problems. Greenhouse gas emissions are caused by carbon
dioxide gas emitted when producing plastics. In 2015, the carbon di­
oxide gas released in plastics production reached 1.78 CO2-eq, and it
was observed to increase to reach 6.5 Gt CO2-eq [16]. The problem is
further complicated because plastics are tough to decompose in nature
[17]. Naturally, recycling plastics waste can take up to 600 years [18].
Therefore, comprehensive and effective plastics waste management is
required to solve these problems.
Currently, there are two methods for degrading plastics waste: me­
chanical and chemical. Mechanical methods can convert plastics waste

* Corresponding author.
E-mail address: m.zunita@itb.ac.id (M. Zunita).

https://doi.org/10.1016/j.polymdegradstab.2023.110320
Received 12 February 2023; Received in revised form 3 March 2023; Accepted 4 March 2023
Available online 7 March 2023
0141-3910/© 2023 Elsevier Ltd. All rights reserved.
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

into products that can be reused as new plastics materials. There are
several stages in the mechanical method, such as milling, washing,
agglutination, extrusion, and cooling. This method can only be applied
to specific polymers because each type of polymer responds differently
depending on its mechanical and thermal characteristics [19,20].
Polymers that can be degraded using this method are PE and PET1 [21].
In addition, the mechanical method produces a poor-quality product
compared to the chemical method. [22]. Meanwhile, the chemical
method breaks down the polymer structure, which leads to the forma­
tion of monomers or raw materials that can be reused to produce
good-quality polymers or other advanced materials by the principles of
sustainable development [23,24]. Chemical methods can be carried out
using various techniques such as chemolysis, pyrolysis, fluid catalytic
cracking (FCC), gasification, and dissolving chemicals or catalysts.
There are several processes in chemical recycling methods, such as
methanolysis, hydrolysis, glycolysis, and other methods [25]. Several
such processes have been investigated but are generally slow without a
catalyst. Many studies have been carried out on catalysts to degrade
plastics waste, such as metal acetate [26], metal chloride [27], and other
catalysts. However, these catalysts require higher temperatures and
pressures than usual. In addition, the product is difficult to separate from
the catalyst [25]. Therefore, it would be better if a catalyst could be

Fig. 1. (A) Global plastics production and projection to 2050. (B) Cumulative plastics waste production (in a million metric tons) (reprinted with permission from
Ref. [8]). (C) The number of publications related to IL and plastics degradation indexed by Scopus. Queries (TITLE-ABS-KEY("ionic liquid") and TITLE-ABS-KEY
("polymer" or "plastic") and TITLE-ABS-KEY("chemical recycling" or "degradation" or "depolymerization")); Accessed on December 9rd, 2022.

operated under lower temperature conditions with a more straightfor­

ward separation process.
1
See List of Abbreviation
Nowadays, a new class of chemical compounds is being intensively

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M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

developed by world researchers, namely ionic liquids (ILs). ILs are salt in
their liquid phase at conditions below 100◦ C [28]. This chemical class is
widely used as solvent compounds, antistatic agents, catalysts, electro­
lytes, CO2 absorbers, and mechanical systems lubricants [29,30]. There
have been several studies that have tested the ability of ILs to process
polymers such as PET, PP, LDPE, and other polymers [31,32]. Even more
with ILs, PET waste can be processed into its monomer (BHET) and
re-polymerized into qualified PET so that an endless cycle can occur in
the recycling of this type of plastics [33,34]. ILs provide a new alter­
native, with ongoing research developments, in recycling plastics waste
into raw materials. Using ILs can reduce the pressure, temperature, and
amount of catalyst needed for the reaction [35]. The number of publi­
cations related to plastics degradation and IL indexed by Scopus is
presented in Fig. 1C. Accordingly, this paper reviews significant ad­
vances regarding the use of ILs in the degradation of plastics waste. The
first part of this review includes an introduction to the types of plastics.
The second part covers the conventional treatment of plastics waste
before the presence of ILs. The third and fourth include a description of
the IL and the applications. The last section covers the development of
ILs in degrading plastics waste or polymers, such as PET, PC, PA, PHB,
PLA, epoxy, and PE.
2. Plastics classification
According to the American Society for Testing and Materials [36],
plastics comprise one or more organic polymers with a high molecular
weight. In their final form, plastics are solid and may be molded at will
throughout different phases of production or processing. Despite
meeting this description, rubber, textiles, adhesives, and paints are not
considered plastics. Plastics are classified into two types based on their

Fig. 2. (A) Flow chart of plastics based on their physical properties (adapted from Ref. [46]). (B) Distribution of global polymer demand by type in 2016 (adapted
from Ref. [47]). (C) Several methods of recycling plastics waste (adapted from Ref. [48]).

3
M. Zunita et al.
physical properties: thermoplastics and thermosets. Thermoplastic is a
form of plastics that may be recycled by heating them. Examples of
thermoplastic polymers are PC, PE, PET, and PS. Meanwhile, thermoset
is a form of plastics that cannot be recycled by re-heating since
re-heating causes the thermoset polymer molecules to break down. Ex­
amples of thermoset polymers are bakelite, epoxy resin, melamine resin,
and phenolic [18]. Fig. 2A depicts the flowchart of plastics based on
their physical properties.
In addition, the Society of Plastic Industry (SPI) classifies plastics
based on their polymer type to simplify identifying the polymers used in
creating products and accelerating the recycling process [38]. These
polymers include PET, HDPE, PVC, LDPE, PP, PS, and other polymers
(PC) (see Table 1). According to the US Environmental Protection
Agency (EPA), these six types collectively represent the most significant
plastics garbage, with an 86% majority share [39]. PE is the most widely
produced polymer of these various polymers worldwide [40]. The dis­
tribution of global polymer demand by type in 2016 is presented in
Fig. 2B.
3. Plastics waste treatment
Currently, there are several conventional methods of recycling
plastics waste. It consists of primary recycling (closed-loop recycling),
secondary recycling (open-loop recycling), tertiary recycling (chemical
or thermochemical or feedstock recycling), and quaternary recycling
(energy recovery) [41] (see Fig. 2C). The processing method will be
explained in the following subsection.
3.1. Primary recycling
Primary plastics recycling is the process of producing similar plastics
items from recovered materials [42,43]. Because it turns the whole input
of plastics garbage into a comparable product, the primary recycling
process is known as closed-loop recycling. Plastics processing is not
limited to a particular kind of plastics. On the other hand, the plastics
type ideal for primary recycling has high purity and little mixing. Me­
chanical recycling and polymer dissolution with solvents are examples
of primary recycling. Plastics not combined with other materials or
polymers may be recycled by re-extruding them. The second process is
like supercritical solvent dissolution. Specific solvents dissolve the
polymer, clearing it of contaminants.
3.2. Secondary recycling
Secondary recycling, also known as open-loop recycling, is a me­
chanical process that employs recycled materials to create new items
with different purposes than the original materials [39,49,50]. Because
thermoplastic polymers may be melted and recycled, the plastics uti­
lized are of the thermoplastic polymer type. This procedure uses just
physical methods and does not include any polymer modifications. The
steps taken in the secondary recycling process are that plastics waste is
collected first and then cut, torn, or made into granules, flakes, or pel­
lets. Then it is melted and followed by extrusion to make a new product.
This process can also be done by mixing materials that have been
reprocessed with other virgin materials to get better results [51].
This strategy can reduce the quantity of plastics garbage collected
[51]. Furthermore, although this approach is affordable, well-known,
and influential, it does need a considerable initial investment [52,24].
As a result, the polymers employed in this approach are often utilized in
goods with lesser performance requirements than their original use. This
process has been used to make floor tiles from mixed polyolefins [45]
and to recycle polyurethane foam waste by crushing it into flakes and
then shaping it with a mold [54]. Because the final product has a loss in
quality or mechanical qualities, this procedure is sometimes referred to
as a downgrade or downcycling process [39,50,55]
Furthermore, there is a drop in molecular weight during the
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Polymer Degradation and Stability 211 (2023) 110320
secondary recycling process owing to the presence of water and the
quantity of acid, which causes the polymer chain to be severed [51]. The
occurrence of a polymer chain-cutting process reduces the polymer’s
mechanical characteristics. Various stable improvements, such as thor­
ough drying, chain-extending chemicals, and repeated vacuum degass­
ing, may counteract this problem [56]. In addition, mixed waste streams
generally contain many contaminants, and plastic products can have a
mixture of materials and polymers, which also causes a decrease in
mechanical properties and complicates the recycling process. For
example, contamination of the primary polymer (PVC) with the main
polymer (PET) causes solid formation in the PVC phase, resulting in
decreased mechanical properties [52]. The answer to this challenge is to
use various physical ways to separate distinct components and detect
and isolate undesired elements.
3.3. Tertiary recycling
The tertiary recycling approach involves the thermochemical
breakdown of polymers into smaller molecules (monomers) or conver­
sion into raw materials [35,57]. This process is often referred to as
feedstock or chemical recycling. This process produces liquids or gases
that may be utilized as raw materials to make fuels, new polymers, and
other compounds. The problem with this technology is that it is not
economically viable owing to the cheap cost of petrochemical raw ma­
terials compared to the facilities and procedures required to produce
monomers from plastics waste [58]. Furthermore, this process needs
significant energy and professional workers [59,60]. Hydrogenation,
glycolysis, gasification, hydrolysis, liquefaction, pyrolysis, meth­
anolysis, chemical depolymerization, thermal cracking, catalytic
cracking and reforming, photodegradation, ultrasonic degradation, and
microwave degradation are all examples of this approach [60–62].
3.4. Energy recovery
Direct combustion, sometimes known as incineration, is immediately
burning waste. Because incineration produces the most thermal energy,
this technique is an energy recovery-based plastics waste treatment.
Carbon dioxide and water vapor are the byproducts. However, owing to
combustion, incineration is likely to release additional pollutants.
Incineration may occur in high-temperature environments with an
abundance of oxygen. The release of pollutants such as NOx, SOx, di­
oxins, furans, mercury, and particulates is accompanied by the creation
of thermal energy from the combustion of plastic trash [63,64]. Plastics
garbage cannot be burnt recklessly due to these dangerous pollutants.
Because of the hazardous substance emitted into the air, burning do­
mestic garbage, often seen in the yards of residents’ houses, is consid­
ered a health danger. These noxious chemicals in the air may behave as
carcinogens and mutagens, raising the risk of additional health issues
such as heart disease and lung illness [63]. Incineration technology has
been extensively developed and implemented in the industrial sector.
Incineration may be better than gasification systems for small-scale
power-generating requirements. In a boiler furnace, biomass fuel or
plastics waste is burnt. The heat produced by the process is utilized to
heat the steam in turbines, which produces electricity [65].
4. Ionic liquids (ILs)
4.1. The IL in general
ILs are organic salts that are liquid at room temperature [66–70].
These liquids have a unique combination of non-volatile, non-flam­
mable, low viscosity, thermally and chemically stable properties, high
conductivity, and a wide working temperature range. As a result of their
unique properties, ILs are widely used as solvent media for various
chemical processes. They can dissolve many organic, inorganic, and
metalorganic compounds [71]. Therefore, ILs can replace the use of
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Table 1
Types of plastics based on the SPI number (adapted and modified from Ref. [38,39,44,45]).
SPI Symbol Polymer Uses Currently Repurpose to Make
Number Recyclable?

1 Soda bottles, water Yes Fiber (clothing, carpet), film

bottles, medicine (balloons, packaging,
jars, and salad thermal sheets, and adhesive
dressing bottles backing), bottles (pop and
water), cosmetics packaging,
and food containers

PETE or PET
2 Soap bottles, Yes Nonfood containers (laundry
detergent, bleach detergent, shampoo,
containers, and conditioner, and motor oil
trash bags bottles), plastics lumber,
pipe, buckets, crates,
flowerpots, film, recycling
bins, and floor tiles

HDPE
3 Plumbing pipes, No Packaging, loose-leaf
cables, fencing, binders, decking, paneling,
garden furniture, gutters, mud flaps, film, floor
carpet backing tiles and mats, traffic cones,
electrical equipment, garden
hoses, and mobile home
skirting

PVC
4 Cling wrap, Mostly no Shipping envelopes, garbage
sandwich bags, can liners, floor tile, plastics
grocery bags, films, lumber, food wrapping film,
trays, and shopping bags, compost bins,
computer dry cleaning bags, and
components trashcans

LDPE
5 Reusable food Sometimes Automobile battery cases,
containers, signal lights, brooms, oil
prescription funnels, brushes, ice
bottles, bottle caps, scrapers, condiment bottles,
and car parts margarine containers, yogurt
containers, bicycle racks, and
rakes

PP
6 Plastics utensils, Sometimes Thermometers, light switch
packaging peanuts, plates, thermal insulation,
and styrofoam egg cartons, vents, rulers,
license plate frames, foam
packing, take-out food
containers, and disposable
cutlery

PS
7 Others * Multilayer barrier No Polycarbonate (refillable
films, toothbrushes, plastics bottles, baby bottles,
CDs, and DVDs metal food can liners,
consumer electronics, and
lenses); nylons (clothing,
carpets, and gears);
(continued on next page)

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M. Zunita et al.
Table 1 (continued )
SPI Symbol Polymer
Number
PC
*
Other plastics, such as polyester, PLA, PHB, polyether, nylon or PA, PC, polymethyl methacrylate (PMMA), and acrylonitrile butadiene styrene (ABS).
conventional solvents, which often exhibit toxic and dangerous prop­
erties, such as flammable and explosive [72], and often contain many
Volatile Organic Compounds (VOC) [73]. In addition, ILs can also be
recycled and hence are referred to as "green solvents" [74].
ILs comprise relatively large asymmetric organic cations and small
inorganic or organic anions (see Fig. 3A). The cations widely used in ILs
are generally imidazolium, pyridinium, pyrrolidinium, ammonium,
phosphonium, and sulfonium derivatives [75–79]. Imidazolium has
been named the most used cation in ILs because these cations are easy to
make, cheap, and easy to find [73]. Meanwhile, the anions that are
widely used are usually inorganic, such as bis(trifluoromethane)sul­
fonamide, tetrachloroaluminate, halides, tetrafluoroborate, and hexa­
fluorophosphate, or organic anions, such as tosylate and trifluoroacetate
[80]. A general classification of ILs is presented in Fig. 3B. The structures
of several cations and anions used in ILs are shown in Fig. 3C and
Fig. 3D.
Various cations and anions cause ILs which can be considered special
solvents because, with a proper selection of cations and anions, the
physical and chemical properties of ILs can be adapted to specific pro­
cesses [81–84]. The type of cation determines the density, viscosity, and
hydrophilic or lipophilic properties of ILs. An IL’s viscosity and hydro­
philic or lipophilic properties can be increased by lengthening the alkyl
chain [85]. Meanwhile, the type of anion in the ILs determines acid,
base, or neutral. Anions such as Cl–, PF–6, BF–4, and HSO–4 produce acidic
ILs, while anions such as acetate (C2H3O–2) produce alkaline ILs [86].
The number of ILs produced currently reaches more than 500 and
will continue to grow [87]. It is based on about ten simple anions, such
as BF–4 and PF–6 paired with one of the cations, such as 1-alkyl-3-methy­
limidazolium substituted with various alkyl groups will produce more
than 600 ILs [123]. It is estimated that the number of possible combi­
nations of cations and anions for ILs exceeds 106 [88]. The naming of ILs
uses square brackets for cations and complex compounds (without
charge). Naming begins with the name of the cation followed by the
anion. For cations, the name corresponds to the length of the alkyl chain,
followed by the type of cation, for example, 1-butyl-3-methyl imidazo­
lium. The naming abbreviation of the cation is [bmim]. As for anions,
the naming is adapted to the general name of the principle, for example,
Cl which is chloride, and Ac which means acetate [72]. As a result,
1-butyl-3-methylimidazolium can be reduced to [bmim]Cl.
The discovery of ILs has gone through a long history. Walden first
synthesized the ethylammonium nitrate IL in 1914 with a melting point
of 12◦ C [89]. Research on ILs was then continued by Hurley and Wier in
1951, who developed ILs with chloroaluminate ions for
low-temperature aluminum plating. According to the author, these ILs
can be applied to the electrochemical field [90]. Then, the development
of ILs continued until Fry and Pienta and Boon et al. investigated that ILs
can be used as solvents for organic synthesis. From these experiments,
the authors stated that ILs create a new unique medium for chemical
reactions with melting points below 100◦ C [91,92]. The impact of pre­
vious research led to an explosion of research on ILs from 2002 to the
present, as shown in Fig. 1C. The explosion made ILs more and more
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Polymer Degradation and Stability 211 (2023) 110320
Uses Currently Repurpose to Make
Recyclable?
biodegradable resins (food
and beverage packaging)
commercially available. However, the cost is still relatively high
compared to conventional organic solvents (about 2–100 times the
organic price). Therefore, commercial use must continue to be devel­
oped, and the manufacture of ILs on a large scale must be carried out to
reduce costsignificantly [71,93].
Along with the development of science, a new type of IL is currently
being developed, namely the deep eutectic solvent (DES). DES is
considered a new type of IL analog because it has similar characteristics
and properties to IL [94,95]. DES is a system formed from a eutectic
mixture of Lewis or Brønsted acid and base, which can contain a variety
of anionic, cationic, or both species. DES contains large and
non-symmetric ions with low lattice energy and melting points. DESs are
usually formed from the complexation of a quaternary ammonium salt
with a metal salt or hydrogen bond donor (HBD). This study also reviews
several uses of DESs to degrade plastics waste.
4.2. Properties
ILs have non-volatile properties, meaning the vapor pressure is
negligible at temperatures close to room temperature. This effect causes
the ILs not to pollute the environment [81,87]. This property occurs
because of the strong Coulomb force between anions and cations in ILs
[72]. However, Earle et al. and Wasserscheid found that some ILs can be
vaporized and then condensed under high vacuum conditions at
200–300◦ C [96,97]. The vapor pressure of the ILs remains constant so
that the ILs can be considered a non-volatile solvent under room
conditions.
Moreover, ILs also have a melting point below 100◦ C. This statement
was proved by Mars et al., who studied the melting point of the IL 1-pro­
pyl-3-methylimidazolium chloride ([pmim]Cl) [87]. Mars found that the
IL had a melting point of 60◦ C and was lower than the inorganic salt
NaCl which had a melting point of 803◦ C. Marsh stated that lowering the
point melting point in ILs caused replacing small inorganic cations with
large asymmetrical organic cations. In addition, Marsh also stated that
the main factors affecting ILs’ melting point are the distribution of
charge on the ion, the ability of H-bonds, ionic symmetry, and Van der
Waals bonds. Then, Vishwakarma, Holbrey and Seddon, Visser et al.,
and Chun et al. studied the influence of alkyl chains on the melting point
of ILs [72,98–100]. It was found that the melting point of the IL de­
creases with increasing alkyl chain length. Vishwakarma also found that
the melting point of ILs increases with an increasing degree of
symmetry.
ILs were found to have a greater density than water. Marsh et al.
stated that ILs have densities ranging from 1–1.6 g/cm3, and the density
decreases with increasing alkyl chain length [87]. In contrast, Plechkova
and Seddon stated that ILs have densities ranging from 0.8–3 g/cm3
[93]. Marsh found that most ILs are viscous liquids. The liquid is more
viscous than organic solvents because it has two to three times the vis­
cosity of organic solvents. Johnson stated that ILs generally have a vis­
cosity of less than 100 cP [101]. Then, Plechkova and Seddon clarified
that ILs have viscosities ranging from 22–44,000 cP. Like density,
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Fig. 3. (A) Schematic showing the structure of ILs (reprinted with permission from Ref. [102]). (B) The general classifications of ILs (adapted from Ref. [103,104]).
(C) The structure of various cations used in ILs (adapted from Ref. [73,105]). (D) The structure of various anions used in ILs (adapted from Ref. [66,73]).

7
M. Zunita et al.
viscosity increases with increasing alkyl chain length [85]. However,
Marsh stated that increasing alkyl chain length does not always result in
a monotonous increase in viscosity.
Furthermore, Kubisa stated that ILs are highly polar [71]. Maia also
stated that ILs’ polarity was due to cations and anions in ILs [73]. A
solvent can be said to be polar or non-polar by measuring the dielectric
constant of the solvent. However, Kubisa stated that ILs are electrolytes,
so direct measurement of the dielectric constant is impossible. As an
alternative, Bonhte et al. and Davis studied the polarity of liquids by
measuring them using solvatochromic and fluorescence tests [106,107].
It was found that the polarity of the IL is close to the polarity of low
alcohol. Picquet et al. and Plechkova and Seddon stated that ILs are not
as polar as assumed. Hence, the polarity of ILs is still questionable [108].
Then, Wassercheid and Keim and Papovic et al. stated that an IL’s hy­
drophilic or lipophilic properties could be increased by lengthening the
alkyl chain [85,109]. The solubility of ILs in water depends on the an­
ions. It is known that the anions Cl–, Br–, and BF–4 can mix perfectly with
water. At the same time, bistriflimide is insoluble in water or separates
to form two phases [110]. The physical and chemical properties of ILs
are summarized in Table 2.
5. Applications of ILs
Due to its unique properties, IL is now used in various applications
such as electrochemical, additives, extraction and separation processes,
chemicals, industries, analytical, advanced material, environmental
protection, and polymer recycling [29]. The following is an explanation
of the various applications of ILs regarding their role and the benefits
which they provide.
5.1. Polymer recycling
Chemical recycling methods can degrade polymer waste into
monomers or raw materials. Chemical recycling methods, such as
glycolysis, aminolysis, alcoholysis, hydrolysis and many methods, have
been investigated to be more efficient and effective when using ILs. This
method is carried out in extreme conditions requiring high temperatures
and pressures. In addition, this method requires a sufficiently large
amount of acid or base catalyst. These catalysts are also non-reusable
and have negative impacts such as environmental problems and equip­
ment corrosion [111,112].
Until now, there have been many studies on the degradation of
plastics waste, especially for PET and PC, using ILs [113,114]. The most
studied ILs for use in plastics degradation are imidazolium cation based
ILs. IL has been proven to increase the solubility and activity of plastics
depolymerization reactions, especially on PET and PC plastics. Several
other types of plastics, such as PE, PA, PHB, and TER, have also been
studied to be degraded with the presence of ILs [108,115]. Discussion
regarding applying chemical recycling in degrading polymers using ILs
will be discussed further in Chapter 6.
Table 2
Physical and chemical properties of ILs (adapted from Ref. [29,93,101]).
Parameter Characteristics of ILs
Component Large enough cations and small anions
Vapour pressure Generally negligible vapor pressure at ambient
temperatures
Melting point Less than 100◦ C
Viscosity Generally high of order 20–97,000 cP
Density 0.8–3.3 g/cm3
Refractive index 1.3–2.2
Dielectric constant Less than 30
Electrical Conductivity up to 120 mS.cm− 1
conductivity
Polarity Moderate
Thermal stability High thermal stability
Flammability Non-flammable
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Polymer Degradation and Stability 211 (2023) 110320
5.2. Separation process
ILs are used as an alternative to traditional solvents, which have
disadvantages such as requiring a longer time, lower efficiency, and a lot
of organic solvents in the extraction and separation process [116]. In
biomass extraction, ILs can increase the efficiency and selectivity of the
dissolution process and the extraction of polysaccharides from natural
sources [117]. ILs also provide efficient extraction with high yields in
extracting phytochemicals to apply in flavonoid extraction [118].
Another research also found that ILs can improve the process efficiency
and selectivity of lignin from wood [119]. In water treatment technol­
ogy, an IL of [amim][PF6], for instance, can be an extracting agent and
adsorbent to clean up the arsenic substance from wastewater [120].
Another application of IL was also found to increase oil recovery and
many more [121].
5.3. Advanced materials
ILs are used in advanced materials such as artificial muscles, liquid
crystals, and thermal energy storage devices. In artificial muscle, IL roles
as a bioactive molecule [122]. Composite polymer mixed with IL can
provide an excellent bending performance of actuators without signifi­
cant back-relaxation, such as low actuation voltage, high durability,
large tip displacement, and response under AC and DC voltages. Cubic IL
crystals (CILCs) of POMs-based ILs can be used as anti-corrosion coatings
because of their ability to act as a barrier so that oxygen cannot diffuse
[123]. In thermal energy storage devices, IL was also utilized to increase
the working coefficient and enhance energy storage density [124]. In
addition, ILs are also being developed in nanoparticle synthesis, where
ILs role as solvents and stabilizers [125]. Nanoparticles utilizing ILs can
exhibit significant catalytic activity in hydrogenation processes.
6. Degradation of plastics using ILs
6.1. Degradation of PET
6.1.1. Glycolysis
Yue et al. studied the glycolysis of PET by using some lewis acidic ILs
as a catalyst [126]. The catalysts examined include [bmim]Cl, [bmim]
[ZnCl3], and [bmim][MnCl3]. The reaction conditions, including
[bmim][ZnCl3] (1.25 g) as a catalyst, the temperature of 190◦ C, for 2 h
reaction time in the study, resulted in 100% conversion of PET and
84.95% yield of BHET, the best performing conditions in the study. The
performance of [bmim][ZnCl3] as catalysts was also compared to ZnCl2
catalyst, resulting in better BHET yield in the same amount and condi­
tions. Yue et al. also studied the effects of reaction time and reusability
of [bmim][ZnCl3] catalyst in the glycolysis of PET. This study has
proven that reaction time affected the conversion of PET and the yield of
BHET. The optimum reaction time examined was 5 h (in conditions of
0.16 wt% of [bmim][ZnCl3] catalyst, the temperature of 190◦ C), with
PET conversion reaching 100% and BHET yield up to 83.8%. Yue found
that [bmim][ZnCl3] could be reused as a catalyst in the glycolysis of PET
up to 5 times without a significant change in results.
Wang et al. studied the glycolysis of PET using [amim]-
Halometallate ILs as catalysts [127]. The ILs examined as catalysts in
the study were [amim][MnCl3], [amim][FeCl4], [amim][CoCl3],
[amim][CuCl3], [amim][ZnCl3], [amim]Cl, [bmim]Cl, [bmim][FeCl4].
In addition, ZnCl2 was also examined as a catalyst in the study. The
catalytic activities among the [amim]+-containing ILs follow the order:
[amim][ZnCl3]>[amim][CoCl3]>[amim][MnCl3] > [amim][FeCl4] >
[amim][CuCl3] >[amim]Cl. Metal anions are essential in PET degra­
dation when the cation is the same [amim]+. While compared to
[bmim]+ cation, [amim]+ cation performs better. The [bmim]Cl catalyst
only reached up to 3.7% PET conversion while [amim]Cl up to 4.8%.
The study also found that [amim][ZnCl3] and [amim][CoCl3] has the
advantage of separating the BHET product and the high purity of the
M. Zunita et al.
BHET.
Yue et al. studied the glycolysis of PET using metal-containing ILs as
a catalyst [128]. The catalysts examined include [bmim][ZnCl3], and
[bmim][MnCl3], [bmim][PbCl3], [bmim][FeCl3], [bmim][NiCl3],
[bmim][AlCl3], [bmim][SnCl3], and [bmim][CuCl3]. The study found
that ILs containing Zn give the best results among other ILs tested in the
study. The reaction time affected the conversion of PET and the yield of
BHET. The maximum yield of BHET was reached for the reaction time of
5 h (1 wt% of [bmim][ZnCl3] catalyst, at a temperature of 180◦ C), while
the maximum yield of PET conversion reached 100% after 6 h reaction.
The yield of BHET was increased along with the increased reaction time
from 1 to 5 h, then decreased slightly when the reaction time increased
to 6 h. The authors also studied the effect of reaction temperature on the
yield of BHET and PET conversion. The optimum reaction temperature
examined in the research was 180◦ C. The reaction performance was
increased along with the temperature increase from 160 to 180◦ C. The
reusability performance of [bmim][ZnCl3] as a catalyst was examined,
resulting in the catalyst being reused six times without an obvious
change in the yield of BHET.
Al-Sabagh et al. studied PET glycolysis lewis base IL ([bmim][OAc])
as catalysts [129]. The ILs of [bmim]Br and [bmim]Cl were also used as
catalysts for comparison. At first, the glycolysis reactions were con­
ducted using no catalyst and using [bmim]Br, [bmim]Cl, and [bmim]
[OAc] as catalysts. The performance of each catalyst was observed,
resulting that under the same conditions, only [bmim][OAc] catalyst
carried out the reaction with PET conversion of 75.1%, BHET selectivity
of 61.9%, and a yield of 46.4%. It was observed that when the catalyst
increased from 0.125 to 1.0 g, the conversion of PET, selectivity of
BHET, and yield of BHET increased significantly. The conversion of PET
reached 100% when the catalyst was added in the amount of 1.0 g. The
reaction performance reached a maximum in the catalyst amount of 1.0
g, then decreased after further addition of the catalyst. At the same time,
the reaction performance increased along with the increase of reaction
temperature from 150 to 190◦ C. The PET conversion reached a
maximum value of 100%, and the BHET yield of 58.2%.
The effects of the reaction time on the reaction performance were
observed, resulting that after 2 h of reaction, the PET conversion reached
100%. The optimal reaction time was 3 h with the BHET selectivity and
yield both 53.5%. The selectivity and yield of BHET then decreased at
prolonged reaction times. The effect of EG amount was also studied in
the research, resulting in the constant 100% conversion of PET from 5 to
25 g of EG amount. BHET selectivity and mass fraction in the products
both have maximum values (53.5%, both) in the amount of 20 g of EG.
The amount of PET was examined in the range from 1 to 7 g, resulting in
PET completely degrading in the range of 1 to 6 g of PET amount, and
then the PET conversion decreased to 91%. While the selectivity and
yield of BHET had maximum values (58.21%, both) when the amount of
the PET was 3 g due to the mass ratio of PET, EG, and catalyst can in­
fluence the equilibrium shift between BHET and other reaction products.
The reusability performances of residual EG and [bmim][OAc] were
examined, resulting in the catalyst being reused up to 6 times without a
noticeable change in the reaction performances.
Alnaqbi et al. studied the glycolysis of PET using [bmim]Br as a
catalyst and MW irradiation as a heat source to get the desired reaction
temperature [130]. The increase in reaction time enhanced the reaction
results. The optimum reaction time that was examined in the research
was 2 h. At the same time, the increase in the reaction temperature (from
50 to 180◦ C) affected the increase of the glycolysis performances. This
study also found that MW irradiation as a heat source significantly re­
duces the glycolysis time compared to conventional heating (to get the
same performance, conventional heating could be reacted up to 8–10 h).
Al-Sabagh et al. studied glycolyze PET by using an IL-coordinated
ferrous acetate complex immobilized on bentonite ([bmim-Fe]
[(OAc)3]/bentonite) as a catalyst [131]. The study examined the cata­
lyst’s performance in various amounts, resulting in the optimum amount
of catalyst being 1.0 g in the conditions of PET (2.0 g), EG (20 g), 1 atm,
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Polymer Degradation and Stability 211 (2023) 110320
180◦ C, and 2 h. The effect of reaction temperature on the yield of BHET
and PET conversion. The optimum reaction temperature examined in
the research was 190◦ C. The reaction performance was increased along
with the increase in temperature from 150 to 180◦ C. The reaction time
affected the conversion of PET and the yield of BHET. The maximum
conversion of PET was reached for the reaction time of 3 h (1 g of
catalyst, at a temperature of 190◦ C). It must be noted that although the
conversion of PET was 100%, the yield of BHET was only 44%, which
means the PET was degraded to a mixture of the oligomer, dimer, and
monomer, not only BHET. The reaction performances are increased
along with the increase of reaction time from 1 to 3 h. Afterward, for the
reaction time of 4 h, the BHET yield was slightly decreased. The research
also studied the effect of EG amounts on reaction performance, resulting
in 20 g of EG (in conditions of 2.0 g PET, 1 g [bmim-Fe][(OAc)3]/ben­
tonite, 1 atm, 190◦ C, 3 h) gives the best performance. While the PET
amounts were also affected, the reaction with the best performance was
reached in the amount of 2.0 g (in conditions of 20 g EG, 1 g [bmim-Fe]
[(OAc)3]/bentonite, 1 atm, 190◦ C, 3 h). The reusability performance of
[bmim-Fe][(OAc)3]/bentonite as a catalyst. It was shown that the
catalyst could be reused 6 times without an apparent change in the re­
action performances.
Wang et al. studied PET glycolysis using first-row transition metal-
containing ILs as catalysts [132]. The catalysts used in the study were
[bmim][CrCl4], [bmim][MnCl3], [bmim][FeCl4], [bmim]2[CoCl4],
[bmim]2[NiCl4], [bmim]2[CuCl4], and [bmim]2[ZnCl4]. At first, the
researchers studied the catalyst’s performance to get the best catalyst for
further study. This preliminary study has resulted in [bmim][CoCl4] as
the best-performing catalyst with 100% PET conversion and 89.7% mass
fraction of BHET products. The study also found that smaller PET par­
ticle sizes give better reaction performance. It could happen due to the
bigger surface area, so the catalyst and EG can interact with PET more
easily. The effect of the catalyst amount on reaction performance shows
that when the catalyst was added, the conversion of PET, selectivity of
BHET, and mass fraction of BHET in products increased rapidly, much
higher than the values obtained without the catalyst. The conversion of
PET reached 100% when the catalyst was added in the amount of 1.0 g.
The effect of the reaction temperature on the reaction performance. The
reaction performance increased along with the increase of reaction
temperature from 130 to 175◦ C. Afterward, there decreased perfor­
mances slightly without obvious changes. The effect of the reaction time
on the reaction performance was examined, resulting in an increase in
reaction time from 0.5 to 3.0 h, and the PET conversion increased
significantly. The PET conversion reached 100%, with 77.8% of BHET
selectivity and 88.7% of BHET mass fraction in the products, after 3 h
reaction, at a temperature of 170◦ C. The effect of EG amount was also
studied in the research, resulting in the constant 100% conversion of
PET from 20 to 40 g of EG amount.
In comparison, the products’ BHET selectivity and mass fraction
have maximum values (79.6% and 93.6%, respectively) in 35 g of EG.
The amount of PET was examined in the range from 2 to 7 g, resulting in
complete degrading. While the selectivity and mass fraction of BHET in
the products had maximum values (81.1% and 95.7%, respectively)
when the amount of the PET was 3 g due to the mass ratio of PET, EG,
and catalyst can influence the equilibrium shift between BHET and other
reaction products. The reusability performances of residual EG and
[bmim]2[CoCl4] were observed, and the catalyst could be reused up to 6
times without a noticeable change in the reaction performances.
Sun et al. studied PET glycolysis using bifunctional-ILs as a catalyst
[133]. Some ILs: [Ch]3[PO4], [Ch][Lys], [emim][OAc], [dmim][OAc],
and [emim]Cl, resulted that they can solubilize PET pellet in a condition
of 100 g PET, 900 mg IL, atmospheric pressure at 120◦ C for 1–6 h.
However, some other ILs examined were unable to solubilize PET. ILs
that cannot solubilize PET include [dmim][MeSO4], [Ch][OAc], [eoa]
[OAc], [tea][HSO4], and [Ch][Asp]. Of the various ILs used, it was
found that [Ch]3[PO4] gave the best performance with a PET solubility
of 9.3%. Sun also found that the moisture content affects PET’s solubility
M. Zunita et al.
in IL. The glycolysis of PET degradation was conducted mainly using
[Ch]3[PO4] as a catalyst. The optimum reaction in the study was ob­
tained in conditions of 5 g PET, 2 g EG, 0.1 g [Ch]3[PO4], at 190◦ C for 4
h, resulting in 100% conversion of PET and 63.6% yield of BHET. The
reusability of [Ch]3[PO4] was also examined up to 3 times.
Silva et al. studied PET glycolysis using [bmim][ZnCl3] as a catalyst
[134]. The optimization of response surface methodology with the
Box-Behnken Design (BBD) model was carried out to optimize the
monomer yield response to three independent variables, including re­
action time, temperature, and mass ratio of EG:PET in 3 levels (-1, 0,
+1). The highest monomer yield was 38.28%, obtained in conditions of
10:1 of EG:PET mass ratio, at 180◦ C, after 120 min. The resulting graph
of the response surface shows a good region where yields more signifi­
cant than 50% are obtained in the conditions set by increasing the three
variables together.
Cano et al. studied the application of paramagnetic IL-coated
SiO2@Fe3O4 nanoparticles in the glycolysis of PET [135]. The reaction
performances varied in the 15 times cycle of ILCMNP reuse, reaching up
to 63% of PET conversion and 59% of BHET yield. Cano also examined
the reusability of ILCMNP at the temperature of 180◦ C (190◦ C outside of
the flask). It could be observed that the reaction performances increase
significantly compared to the reaction at 160◦ C. The recyclability and
reusability of ILCMNP were examined up to 12 times, in conditions of
ILCMNP (15 mg), PET (100 mg), and EG (1 mL), at a temperature of
180◦ C, for 24 h, without any significant loss in catalytic activity and
with only a slight decrease in the yield of BHET.
Najafi-Shoa et al. studied cobalt-based IL grafted on a graphene
surface (rGO\[tespmi]2CoCl4) to be used as a catalyst for PET glycolysis
[136]. The use of graphene as support is intended to facilitate the sep­
aration of the catalyst from the reaction medium. In recent years, the
usage of carbon allotropes like carbon nanotubes and graphene has been
noted in the heterogeneous systems of glycolysis research. Graphene
oxide (GO), a derivative of graphene, is a two-dimensional nanomaterial
whose structure resembles a honeycomb bound to a variety of
oxygen-functionalized groups [137–141]. GO is a promising material
that has attracted the interest of numerous researchers due to its po­
tential to improve separation performance. GO has a significant role in
assisting the process of gas separation, water treatment, electrochemical
energy, and other separation processes.
The effects of the amount of rGO\[tespmi]2CoCl4 catalyst, reaction
temperature, reaction time, EG amount, PET amount, type of catalyst,
and the number of times the catalyst was reused on PET glycolysis were
examined. This study found that the cobalt-based IL grafted on a gra­
phene surface performed better than the untreated cobalt-based IL
catalyst. The optimum conditions for PET glycolysis tested in this study
were PET (1 g), rGO\[tespmi]2CoCl4 catalyst (0.15 g), EG (14 g), 190◦ C,
1 atm, 3 h, resulting in 100% conversion of PET, and 95.22% yield of
BHET. The rGO\[tespmi]2CoCl4 also could be reused up to 5 times
without a significant decrease in performance.
Marullo et al. studied the glycolysis of PET by using some amino
acid-based cholinium ILs as a catalyst [142]. The catalysts examined
include [Ch][Gly], [Ch][Ala], [Ch][Lys], [Ch][OH], [Ch][Im], and
[Ch]3[PO]4. The optimum reaction in the study was obtained at 150◦ C
after 6 h, from PET deriving from a clear water bottle, using [Ch][Gly]
catalyst. The [Ch][Gly] catalyst was found to have the best performance
among other catalysts.
Shuangjun et al. studied the usage of lewis acidic ILs (LAILs) as
catalysts in PET glycolysis [143]. The effects of catalysts synthesized by
[hmim]Cl and ZnCl2 complex on the PET glycolysis using different
molar ratios was examined. In reaction conditions of PET (2.0 g), EG
(22.0 g), LAIL (1.0 wt%), 190◦ C, and for 2 h reaction, the PET conver­
sion and BHET yield are so low when only [hmim]Cl is used as a catalyst.
The optimal molar ratio between [hmim]Cl and ZnCl2 was 1:1, resulting
in a 100% conversion of PET and a 76.8% yield of BHET. In order to
improve the glycolysis performance, [hmim]ZnCl3 complexes were
paired with other LAILs with excellent catalytic performance. The PET
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Polymer Degradation and Stability 211 (2023) 110320
glycolysis performance using different mole ratios of [hmim][ZnCl3]
and [hmim][CoCl3] mixtures were examined. The BHET yield for the
glycolysis of PET using [hmim][ZnCl3] and [hmim][CoCl3] mole ratios
of 1:1 and 3:1 was higher (87.1% and 79.6%, respectively) than only
using the single catalyst for each LAILs. The effect of using different
ratios of LAILs on the PET glycolysis performance was examined. The
optimum catalyst was equimolar of [hmim][ZnCl3] and [hmim][CoCl3]
mixture. The PET conversion and BHET yield of PET glycolysis using
[hmim][ZnCl3] or [hmim] individually [CoCl3] as a catalyst for different
reaction times (from 1 to 4 h) was observed. The [hmim][ZnCl3] has an
optimal reaction time of 2 h, resulting in 100% and 76.8% of PET con­
version and BHET yield, respectively. At the same time, [hmim][CoCl3]
catalyst reached the maximum performance after 4 h reaction with
100% and 79.0% of PET conversion and BHET yield.
Wang et al. studied PET glycolysis using a series of 1,1,3,3,-tetrame­
thylguanidine (tmg) based ILs [33]. The catalysts used in the study were
[tmg]Cl/ZnCl2, [tmg]Cl/CoCl2, [tmg]Cl/FeCl3, [C2tmg]Cl/ZnCl2,
[C4tmg]Cl/ZnCl2, [C6tmg]Cl/ZnCl2, [C8tmg]Cl/ZnCl2, and [C6tmg]
Cl/2ZnCl2. The study observed the catalyst’s performance to get the best
catalyst for further study. At first, the performance of metal ions in the
ILs compared, resulting IL catalyst containing Zn2+ having an excellent
catalytic effect. The study then observed the effect of different cation
structures among [tmg]-based ILs. It could be observed that when using
[C2tmg]Cl/ZnCl2 as a catalyst, the yield of BHET is higher than that of
using [tmg]Cl/ZnCl2 as a catalyst. However, [C6tmg]Cl/ZnCl2 catalyst
resulted in a higher conversion of PET and yield of BHET. Moreover,
using [C6tmg]Cl/2ZnCl2 as a catalyst gave a better performance with a
92.7% BHET yield. It was found that [tmg]-based ILs have an excellent
catalytic effect and potential application.
The effect of reaction temperature was examined, resulting in the
reaction performance increasing along with the increase of reaction
temperature from 180 to 195◦ C. Afterward, there was decreasing BHET
yield slightly without apparent changes. Reaction time also examined
that with an increase in reaction time from 30 to 50 min, the PET con­
version increases from 77% to 100%. The BHET yield reached a
maximum value of 92.7% after 70 min reaction. Catalyst amount on
reaction performance was observed, resulting that the PET conversion
being kept at 100% when the catalyst was added from 0.1 to 0.6 g.
However, the BHET yield was increased along with the increases in
catalyst amount and reached the maximum value when the catalyst was
0.5 g. The effect of EG amount was also studied in the research, resulting
in the constant 100% conversion of PET from 10 to 35 g of EG amount,
while BHET yield reached maximum values at the EG amount of 25 g.
When the EG amount was more than 25 g, the change in BHET yields
was insignificant. The reusability performances of residual EG and
[C6tmg]Cl/2ZnCl2 were observed, resulting tha the catalyst being
reused 6 times without a noticeable change in the reaction
performances.
Wang et al. studied the upcycling of PET using protic ILs (PILs) as
catalysts [113]. The PILs examined in the study were synthesized by
mixing DBN with phenol or derivatives. The mixing of DBN with phenol,
4-chlorophenol, 4-methylphenol, 2-methylphenol, and 3-methylphenol,
resulting PIL1, PIL2, PIL3, PIL4, and PIL5, respectively. After the PILs
were synthesized, the performance of each PIL was examined to glyco­
lyze the PET. The study found that PIL3 is the best-performing catalyst
among other PILs examined, with 100% conversion of PET and 87.3%
yield of BHET. The study continued to examine the influence of tem­
perature, catalyst amount, reaction time, and cycle times in PET
glycolysis using PIL3 as a catalyst.
The effect of reaction temperature was examined, resulting in the
conversion of PET increasing along with the increase of reaction tem­
perature from 5 to 190◦ C. Afterward, there was a decreasing perfor­
mance in BHET yield and selectivity, slightly without noticeable
changes; thus, the optimal temperature was 190◦ C. The effect of the
catalyst amount on reaction performance was examined, resulting in
PET conversion reaching 100% when the catalyst was added in the
M. Zunita et al.
amount of 6 wt%. When the catalyst further increased, the yield and
selectivity of BHET were slightly decreased. The effect of the reaction
time on the reaction performance was observed, and the maximum
performance was reached when the reaction time was 30 min. The
reusability performances of PIL3 as a catalyst were also examined. It was
shown that the catalyst could be reused 8 times without a noticeable
change in the reaction performances.
Zhu et al. studied the waste PET recycling using the 1,5,7-triazabicy­
clo[4.4.0]decium acetate/ zinc acetate ([htbd][OAc]/Zn(OAc)2] deep
eutectic solvent (DES) [145]. The effect of the molar ratios of [htbd]
[OAc] and Zn(OAc)2 on PET glycolysis was examined. The performance
of PET glycolysis reached the maximum value of 72.8% yield of BHET
when the molar ratio is 1:1. The effect of catalyst dosage on PET
glycolysis was observed that the BHET yield reached a maximum
(82.3%) when the catalyst amount was 3 %-wt. While the reaction
performance increased significantly along with the increase of reaction
temperature from 150 to 190◦ C (PET, 2 g; [htbd][OAc]/Zn(OAc)2, 0.06
g; 1 atm; 60 min). Afterward, the BHET yield started to decrease. The
BHET yield reached the maximum value of 88.5% after heating to
190◦ C. The effect of reaction time on glycolysis performance was
examined. The BHET yield reached the maximum value of 88.5% when
the reaction time reached 40 min, in conditions of PET (2 g), [htbd]
[OAc]/Zn(OAc)2 (0.06 g), and atmospheric pressure. Therefore, the
optimum reaction conditions obtained were PET (2 g), [htbd][OAc]/Zn
(OAc)2 (3 %-wt), atmospheric pressure, at 190◦ C, for 40 min, with the
PET conversion of 100%, and BHET yield of 88.5%. The reusability
performances of the DES were observed in that the catalyst could be
reused 7 times and remained at 84.6% of BHET yield in the last cycle.
The following is a general mechanism of the glycolysis reaction
proposed in degrading PET using IL. When the IL is added, it is assumed
that there exists a synergic effect between the cation and anion of this
catalyst [129]. The cation of the IL interacts with the carbonyl oxygen
(C=O) in the ester of PET. The oxygen in the hydroxyl group of ethylene
glycol then attacks the carbon cation of the ester group, forming a
tetrahedral intermediate. Meanwhile, the anion (–) of the catalyst in­
teracts with the hydrogen in the hydroxyl group of ethylene glycol,
resulting in the oxygen of ethylene glycol becoming more hostile and
better able to attack the carbon cation of the ester group, breaking the
C=O bond in PET. Last, the hydrogen in ethylene glycol leaves and
combines with the IL’s anion to form weak acid as an intermediate. The
weak acid then partially dissociates to give H+ and a lewis base ion. In
this case, the EG molecule and carbon are connected, a new ester group
is formed, and the chain of PET is cleaved. The electrons on the oxygen
in –O(cat+) then transfer, forming C=O. The acyl oxygen cleaves, and
the –OCH2CH2– group leaves, combining with H+ to form HOCH2CH2–.
The suggested scheme of PET glycolysis mechanism is shown in Fig. 4A.
6.1.2. Hydrolysis
Liu et al. studied ILs as a solvent and catalyst in the hydrolysis re­
action of PET [146]. The study resulted that the solvent mixture of water
(4 g) and [bmim]Cl (6 g) could hydrolyze 3 g of PET at 170◦ C in the
presence of 0.6 g of [HSO3-pmim][HSO4] as a catalyst, with PET con­
version by 100% and TPA yield of 88.7%. Several other ILs, including
[bmim][BF4], [bymim]Cl, [bymim][BF4], [omim]Cl, and [omim][PF6],
were also examined as solvents in this study and resulted in the different
conversion of PET and TPA yield in lower values. This study found that
the PET pellet’s size affected the hydrolysis reaction’s performance. The
PET size of 0.15 mm, the smallest size tested in this study, gave the best
results among larger pellet sizes. Smaller PET particle size will accel­
erate the PET dissolution process in the hydrolysis reaction, thus
providing the best results. In addition, PET with smaller particle sizes
increases the surface area available for reaction. Therefore, the reaction
rate increases, and higher PET conversion and TPA yield can be ob­
tained. The solvent of [bmim]Cl and catalyst of [HSO3-pmim][HSO4]
could be recycled up to eight times and gave performances that were not
much different from using its fresh ILs.
11
Polymer Degradation and Stability 211 (2023) 110320
Hu et al. studied [toma]Br as a catalyst for PET alkaline-hydrolysis
(saponification-neutralization) [147]. The study was begun with a pre­
liminary experiment aiming to select the best-performing catalyst
among [toma]Br, [htbp]Br, [ctma]Br, and [tba]Br. The IL of [toma]Br
had the best performance as catalyst, among others. The primary reac­
tion began with PET hydrolyzed in NaOH to yield TPA-Na2 and EG.
TPA-Na2 salt was then acidified to yield TPA. The optimization of
response surface methodology with the Box-Behnken Design (BBD)
model was carried out to optimize the TPA yield response to four in­
dependent variables, including reaction time, temperature, alkali
amount, and catalyst amount in 3 levels (-1, 0, +1). The study resulted in
the optimal values of the process as follows: 100 g (PET), 2.7 g ([toma]
Br), 260 mL (15% NaOH), 85◦ C (temperature, using heat from MW
irradiation), after 2.2 h. The experiment results have shown that the four
parameters examined significantly affected the TPA yield with the R2
value of 0.9814.
The mechanism of PET alkaline-hydrolysis (saponification-neutrali­
zation) begins with the hydrolysis of PET in NaOH to yield TPA-Na2 and
EG. The TPA-Na2 salt was continuously acidified to yield TPA. The
scheme of the PET alkaline hydrolysis is shown in Fig. 4B.
6.1.3. Glycolysis-hydrolysis
Choi et al. studied the depolymerization of PET in the blend fabrics
by using bio-based DES under MW irradiation [148]. The DES used in
the study was [Ch]Cl/Glycerol, while the four types of fabrics were
studied 100% PET, blend PET:cotton fabric of 65:35 (PC63), blend PET:
cotton fabric of 50:50 (PC55), and 100% cotton fabric. The glycolysis
and hydrolysis reactions were expected to be involved due to glycerol
and 5% NaOH within the DES. The study found that the DES depoly­
merized the PET at or in less than 100 s of MW irradiation. At the same
time, the 100% cotton was dissolved in DES at around 5-6% at 100 s of
MW irradiation. When 65% PET and 35% Cotton blend were depoly­
merized, PET decomposed into TPA (3.5%) and BHET (0.1%).
Azeem et al. studied depolymerized PET through sequential
glycolysis-hydrolysis under microwave irradiation using cholinium
DESs as catalysts [149]. The DESs used in the study were [Ch]Cl/urea
(DES-1) and [Ch]Cl/thiourea (DES-2). The optimization of response
surface methodology with the Box-Behnken Design (BBD) model was
carried out to optimize the initial PET conversion and residual PET
characteristics that allow enhanced depolymerization in the
MW-assisted hydrolysis step, response to 3 independent variables,
including volume of DES, the volume of EG, and MW irradiation time, in
3 levels (-1, 0, +1). Additionally, enhanced PET hydrolytic depolymer­
ization can be achieved through low crystallinity and high carbonyl
index of residual PET. Therefore, the MW-assisted glycolysis conditions
were adjusted to achieve minimum crystallinity index, maximum
carbonyl index of residual PET, and maximum weight loss. The opti­
mized level for each independent value was obtained as DES-1 (X1 = 4
mL, X2 = 6 mL, and X3 = 0.5 min) and DES-2 (X1 = 4 mL, X2 = 5.5 mL,
and X3 = 0.5 min). Afterward, the residual PET was then depolymerized
through MW assisted hydrolysis technique. The virgin PET was also
depolymerized in this step to compare the result. The MW-assisted hy­
drolysis was conducted in conditions of PET samples (virgin, 1.0 g; re­
sidual from DES-1 glycolysis, 0.85; and residual from DES-2 glycolysis,
0.82 g), Na2CO3 10%(w/v), EG (20 mL), and stirred for 10 min. The MW
irradiation was then conducted at 350 W power for 3 min. The study
observed that when applying the untreated virgin PET in a hydrolysis
reaction, the conversion of PET was only 66.8%. At the same time, the
MW-assisted DES-1/glycolysis and the MW-assisted DES-2/glycolysis
resulted in 98.62% and 99.31% of PET conversion within 3.5 min of
total reaction time.
Attallah et al. studied depolymerizing PET through DES-based low-
energy microwave (MW) treatment and enzymatic hydrolysis [150]. The
monomer concentration after a 4-days incubation of LCCv enzyme with
the untreated and treated PET materials is summarized in Table 3. The
DES used in the study was [Ch]Cl/ glycerol/urea. The optimization of
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Fig. 4. (A) Suggested mechanism for glycolysis reaction of PET using ILs as catalysts (reprinted from Ref. [133]). (B) Suggested mechanism for production of
compounds during depolymerization of PET (reprinted from Ref. [149]). (C) Reaction scheme of PET hydrolysis using IL as catalyst (reprinted from Ref. [147]).

12
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Table 3
Monomer concentration after a 4-days incubation of LCCv enzyme with the
untreated and treated PET materials (adapted from Ref. [150]).
Material Yield (µM)
TPA MHET
Untreated (virgin): control 0.55 ± 0.04 0.00 ± 0.00
Untreated (virgin): LCCv 521.13 ± 23.22 287.04 ± 7.63
MW-Treated: control 0.83 ± 0.04 0.20 ± 0.00
MW-Treated: LCCv 384.79 ± 4.91 158.83 ± 4.52
response surface methodology with the Box-Behnken Design (BBD)
model was carried out to optimize the initial PET conversion and re­
sidual PET characteristics that allow enhanced depolymerization in the
enzymatic hydrolysis step, response to 3 independent variables,
including MW time, MW power, and DES volume, in 3 levels (-1, 0, +1).
Therefore, the MW-assisted glycolysis conditions were adjusted to ach­
ieve minimum crystallinity index, maximum carbonyl index of residual
PET, and maximum weight loss. The optimized level for each indepen­
dent value was obtained: X1 = 3.0 min, X2 = 260 W, and X3 = 20.0 mL.
Afterward, the MW-treated PET was then depolymerized through the
enzymatic hydrolysis technique. The virgin PET was also depolymerized
in this step to compare the result. The enzymatic hydrolysis was con­
ducted in 10 mL of 100 mM potassium phosphate buffer, pH 8, con­
taining 100 mg of PET residue and 4 µM of the enzyme (LCC variant
ICCG, LCCv), at 55◦ C incubation, under shaking for four days. Control
reactions without the addition of enzymes were also conducted. More­
over, the total PET weight loss of multistep depolymerization was 22 ±
1.7%, and the total monomer conversion was ≈16%-wt.
6.1.4. Butanolysis
Liu et al. studied the butanol alcoholysis reaction of PET using acidic
IL as a catalyst [151]. The catalysts used in the study were ZnCl2, Zn
(CH3COO)2, Ti(CH3CH2CH2CH2O)4, H2SO4, [HO3S-(CH2)3-NEt3]Cl,
[HO3S-(CH2)3-NEt3]Cl-ZnCl2 (x=0.67), [HO3S-(CH2)3-NEt3]Cl-FeCl3
(x=0.67), [HO3S-(CH2)3-NEt3]Cl-FeCl2 (x=0.67), [HO3S-(CH2)3-NEt3]
Cl-CuCl2 (x=0.67), and [C4mim]Cl-ZnCl2 (x=0.67). The effect of
different catalysts in the alcoholysis reaction of PET was observed that
[HO3S-(CH2)3-NEt3]Cl-ZnCl2 (x=0.67) catalyst gives the best perfor­
mance with 100% of PET conversion, 95.3% DBTP yield, and 95.7% EG
yield. The effect of reaction conditions was examined, resulting that the
reaction performance significantly increasing along with the tempera­
ture increase from 195 to 205◦ C. Afterward, the reaction performance
increased slightly along the increasing temperature to 215◦ C. The in­
crease in the IL amount (from 1.5 to 2.5 g) affected the increase in re­
action performance. The yield of DBTP and EG increased significantly
due to the increase of IL from 1.5 to 2.0 g. Afterward, the performance
BHET
only increases slightly. The decreasing of n-butanol from 13.5 to 9.7 g,
PET conversion decreased from 100% to 91.4%. DBTP and EG yield also
0.00 ± 0.00
decreased from 95.3% to 87.1% and 95.7% to 87.2%.
7.07 ± 0.36
0.00 ± 0.00
4.21 ± 0.06 6.1.5. Aminolysis
Palekar et al. studied IL-catalyzed aminolysis of PET [152]. The
amines utilized for the reaction were sourced from ethanolamine
(resulting BHETA) and hydrazine hydrate (resulting TH). The IL catalyst
examined in the study include [bmim][PF6], [bmim][HSO4], [hmim]
[TfO], [bmim]Cl, [bmim][BF4], and [hmim][TfO]. From all ILs used,
[hmim][TfO] was found that result in the best performance, as shown in
Table 4 (entries 1 to 6). At the same time, the optimization [hmim][TfO]
catalyst concentration indicates that 10 wt% of catalyst (w.r.t. PET)
gives the maximum yield of both BHETA and TH with 1:6 molar ratio
(PET:amine source) for 60 min reaction. The product yield increased
significantly with the amount of catalyst up to 0.2 g, increasing only
marginally. The effect of reaction time was also studied (from 15 to 120
min), resulting in the yield of BHETA and TH increasing with time. The
PET:amines ratio also affected the yield of BHETA and TH. It was found
that the increase in PET:EA ratio from 1:3 to 1:12 increased the yield of
the BHETA from 81 to 93% (using [hmim][TfO] for 60 min reaction). In
the case of PET:hydrazine hydrate, the ratio of 1:6 is sufficient to give a
high yield of TH (up to 84%). The mechanism of reactions is shown in
Fig. 5A.
Musale et al. studied the aminolysis of PET using DESs as a catalyst
[153]. The DES used in the study were [Ch]Cl/(ZnCl2), [Ch]Cl/2
(ZnCl2), [Ch]Cl/3(ZnCl2), and [Ch]Cl/2(urea). The urea and ZnCl2
were also examined as catalysts in the study to get the comparison. The
aminolysis of PET is divided into three reaction types, resulting in the
specific product each: THETA, TPA, and BHETA. The THETA product
was obtained in conditions of PET (3 g), DEA (9.85 g), and DES catalyst
(1–8 % w/w) for a time-varying up to 30 min. Afterwards, the excess
methanol was added at the end of the reaction and stirred until a ho­
mogeneous solution was formed. Ethyl acetate was then added to pre­
cipitate out the product. The TPA product was obtained in conditions of
PET (3 g), DEA (9.85 g), and DES catalyst (1–8 % w/w) for a
time-varying up to 30 min. Afterwards, the excess distilled water was
added at the end of the reaction and stirred until a homogeneous

Table 4
Aminolysis of PET degradation catalyzed by various catalysts and conditions, resulting in BHETA and TH (adapted from Ref. [152]).
No. ILs Amount of IL (g) t (min) PET:EA BHETA yield (%) PET:hydrazine hydrate TH yield (%)

1 No catalyst 0.2 60 1:6 No reaction 1:6 Trace

2 [bmim][PF6] 0.2 60 1:6 60 1:6 44
3 [bmim][HSO4] 0.2 60 1:6 84 1:6 79
4 [hmim][TfO] 0.2 60 1:6 89 1:6 84
5 [bmim]Cl 0.2 60 1:6 66 1:6 54
6 [bmim][BF4] 0.2 60 1:6 53 1:6 46
7 [hmim][TfO] 0.1 60 1:6 71 1:6 68
8 [hmim][TfO] 0.15 60 1:6 82 1:6 73
9 [hmim][TfO] 0.25 60 1:6 90 1:6 86
10 [hmim][TfO] 0.3 60 1:6 91 1:6 87
11 [hmim][TfO] 0.2 15 1:6 84 1:6 64
12 [hmim][TfO] 0.2 25 1:6 86 1:6 72
13 [hmim][TfO] 0.2 30 1:6 87 1:6 77
14 [hmim][TfO] 0.2 40 1:6 89 1:6 82
15 [hmim][TfO] 0.2 90 1:6 90 1:6 86
16 [hmim][TfO] 0.2 120 1:6 91 1:6 87
17 [hmim][TfO] 0.2 60 1:3 79 1:3 52
18 [hmim][TfO] 0.2 60 1:4 84 1:4 63
19 [hmim][TfO] 0.2 60 1:5 87 1:5 75
20 [hmim][TfO] 0.2 60 1:8 91 1:8 88
21 [hmim][TfO] 0.2 60 1:10 92 1:10 89
22 [hmim][TfO] 0.2 60 1:12 93 1:12 91

13
M. Zunita et al.
Fig. 5. (A) Reaction scheme of PET aminolysis producing BHETA and TH using IL catalyst (reprinted from Ref. [152]), (B) Reaction scheme of PET aminolysis using
alkanolamine and IL as catalyst (reprinted from Ref. [153]).
solution was formed. HCl solution (25 %) was then added to precipitate
the product. While the BHETA was obtained in conditions of PET (3 g),
EA (5.73 g), and DES catalyst (1–8 % w/w) for a time-varying up to 30
min. The excess distilled water was added at the end of the reaction with
vigorous agitation to precipitate BHETA. The effect of different catalysts
on the yield of each aminolysis product of PET was observed that [Ch]
Cl/2(ZnCl2) has the best performance among all aminolysis catalysts,
with the yield of THETA, TPA, and BHETA being 82%, 83%, and 95%,
respectively.
The effect of the reaction time on the reaction performance was
14
Polymer Degradation and Stability 211 (2023) 110320
observed, resulting in an increase in reaction time from 10 to 120 min,
and the yield of monomers also increased. However, increasing the
monomers yield after 30 min was only marginal. The optimum results
were reached in the catalyst amount of 5%-wt. The yield of products
increased rapidly in the catalyst amount up to 5%-wt. Afterward, it
increased slightly. The molar ratio effects of PET:DEA (for THETA and
TPA products) and PET:EA (for BHETA products) were also studied in
the research. It could be observed that the molar ratios of 1:6, for PET:
DEA and PET:EA, were the best-performing molar ratios between PET
and amines. The mechanism of reactions is shown in Fig. 5B.
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

6.2. Degradation of PC ILs could overcome the limitation of the previous experiment [154,155],
which needed a very large amount of IL. In addition, it has been shown
6.2.1. Methanolysis that DBU-based ILs exhibit the most outstanding and desirable perfor­
Liu et al. studied the first experiment in degrading PC by the meth­ mance in IL synthesis simplicity, operation ease, and environmental
anolysis method to recover BPA and DMC using IL as solvent and cata­ friendliness. Liu examined and optimized the structure, reaction con­
lyst without an acid or base catalyst under moderate conditions [154]. ditions, kind of alcohol used, and reuse of ILs in these studies. Among the
Liu experimented by reacting PC, methanol, and IL at a predetermined various catalysts or ILs used, [bmim][OAc], [hmp][LAc], [htea][LAc],
temperature and time. After completing the reaction, Liu determined the [hmim][LAc], [hdbu][LAc], [hdbu][OAc], [hdbu][PAc], [htea][LAc],
PC’s value conversion by weighing the unreacted PC. In addition, the and [hmim][LAc], [hdbu][LAc] exhibited the best performance with
weights of BPA and DMC were examined and computed using HP 5890 100% PC conversion and 99% BPA yield under the following optimum
gas chromatography using a 50 m long DB-5 glass capillary column to reaction conditions: n(PC) = 15.7 mmol; n(CH3OH):n(PC) = 5:1; cata­
determine BPA and DMC yield. lyst 0.80 mol% (of reactants); T = 120◦ C; and t = 1 h. [hdbu][LAc]
The best-performing IL was [bmim]Cl, outperforming [emim]Br, demonstrated the highest performance owing to its strong basicity. Ac­
[amim]Cl, [omim]Cl, [epydin]Br, [bmim][BF4], [omim][PF6], [cemim] cording to prior research [155], PC methanolysis is a transesterification
Cl, and [bymim]Cl, with a PC conversion rate of 100% and a BPA and reaction. Thus, it is logical that ILs with high basicity perform the best
DMC yield of over 95%. Liu hypothesized that this is because PC is more since the reaction needs an alkaline medium to facilitate catalysis. Liu
soluble in [bmim]Cl than other types of ILs. Liu found that PC meth­ stated that the basicity of ILs might attract protons in methanol to
anolysis did not occur in the absence of IL. Liu also stated that the produce oxyanion intermediates, making methanol more active and able
optimal reaction conditions for enhanced performance and efficiency to carry out nucleophilic attacks on ester groups in PC with greater ease.
were 105◦ C, 2.5 hours, and m(PC):m(CH3OH):m([bmim]Cl) = 2:3:2. Based on a study of alcohol types, it was determined that methanol had
Temperatures below 105◦ C significantly reduced PC conversion (95◦ C: the highest performance compared to ethanol, n-propanol, iso-propanol,
30.5%; 85◦ C: 10.4%). In addition, raising the dosage of methanol from 2 n-butyl alcohol, and isobutyl alcohol. Liu elaborated on PC meth­
to 4 g lowered PC conversion from 100 % to 90.6%. Meanwhile, anolysis, explaining that PC was originally activated by being dissolved
decreasing the IL dosage from 2 to 0.5 g lowered PC conversion from or swelled in the reaction system. The basic anions in the IL undergo
100% to 96%. Liu stated that the PC conversion achieved 100% after a electrostatic interactions with the hydrogen protons in methanol after
2.5-hour reaction at 105◦ C. PC conversion did not reach 100% for the dissolution of PC. According to the conjugated acid-base hypothesis,
almost 2.5 hours at 95◦ C. this interaction activates methanol molecules to form oxyanion in­
After successfully depolymerizing the PC, Liu discovered that the IL termediates. Additionally, activated methanol molecules (oxyanion in­
could be reused eight times without a noticeable decrease in PC con­ termediates) may attach to PC ester groups by the nucleophilic attack to
version and yields of BPA and DMC. According to Liu, this results from produce soluble oligomers. After reacting with methanol, the oligomer
the exceptional thermal stability of ILs due to their unique features. Liu produces BPA and DMC monomers.
further identified the methanolysis product as BPA by examining its IR Recently, Liu et al. studied succinimide-based ILs (SIILs) as envi­
spectra using a Nicolet 510P FT-IR spectrometer in the range of ronmentally benign solvents and catalysts for the methanolysis-based
4000–400 cm− 1 and KBr powder comprising about 1% of the sample. degradation of PC to BPA [157]. Liu examined the influence of SIIL
The collected IR spectra data are as follows: (cm− 1) 3362, 2964, 1612, structure, the effects of reaction parameters, the reusability of SIIL, and
1598, 1510, 1446, 1362, 1239, 1221, 1178, and 829. The spectrum data the interaction of SIIL with methanol on the reaction’s catalytic activity
values are equivalent to the BPA standard. In addition, Liu proved that in this research. Liu discovered that among the many ILs utilized, [hdbu]
PC could be entirely depolymerized to BPA and DMC without forming [Suc] displayed excellent efficacy and was able to depolymerize PC with
oligomers. This experiment was the foundation for additional research a BPA yield of 96% under moderate circumstances of 70◦ C in less than
to identify an IL capable of degrading PC under less severe two hours (see Table 5). In addition, according to Liu, [hbdu][Suc]
circumstances. displayed superior catalytic activity and reaction conditions compared
Then, Liu et al. studied ILs [bmim][OAc] as catalysts for PC meth­ to earlier research. Liu analyzed the BPA obtained by FT-IR and 1H NMR
anolysis under favorable circumstances and without an acid or base (see Fig. 6A and Fig. 6B) and discovered that the produced BPA samples
catalyst [155]. The studies found that ILs [bmim][OAc] performed were identical to commercial BPA samples, with no contaminants or
better than ILs [bmim]Cl. PC was effectively converted to 100% IL oligomers created. Liu also discovered the ideal circumstances for the
[bmim][OAc] when degraded at 90◦ C in the presence of IL [bmim] methanolysis technique by varying the values of the reaction parame­
[OAc]. In contrast, PC methanolysis did not occur in IL [bmim]Cl. Liu ters, obtaining the following optimal conditions: ratio n(cat.):n(PC) =
stated that this is because [bmim][OAc] is a more basic catalyst than 0.3:1; n(CH3OH):n(PC) = 6:1; reaction temperature of 70◦ C and a total
[bmim][Cl]. Liu stated that the more a catalyst’s basicity, the greater its duration of 2 hours (see Fig. 6C). Liu found that after the
activity. Liu also examined the effects of temperature, time, and the
amount of IL and methanol on PC methanolysis outcomes. Liu
concluded, based on these experiments, that the optimal reaction con­ Table 5
ditions were as follows: m([bmim][OAc]):m(PC) = 0.75:1; m(CH3OH): Methanolysis of PC using various ILs (adapted from Ref. [157]). a
m(PC) = 0.75:1; reaction temperature 90◦ C and a total time of 2.5 hours. Entry ILs T (◦ C) t (h) PC conversion (%) BPA yield (%)
In addition, Liu observed that the IL [bmim][OAc] could be reused six
1 Blank 70 2.0 0 0
times without a noticeable decrease in catalytic activity. Upon 2 [hdbn][Suc] 70 2.0 100 65
completion of the reaction, Liu examined the kinetics of the process and 3 [htmg][Suc] 90 2.0 100 77
determined that the methanolysis of PC in [bmim][OAc] was a 4 [P444][Suc] 70 2.0 11 –b
5 [hdbu][Suc] 70 2.0 100 96
first-order reaction with an activation energy of 167 kJ/mol. Liu proved
6 [hdbu][BHS] 70 2.0 trace –
that PC was entirely depolymerized into BPA and DMC monomers, with 7c [hdbu][LAc] 90 2.5 100 98
no oligomer intermediates in the resulting product. This concept, ac­ 8d [bmim][OAc] 90 2.5 100 95
cording to Liu, may eliminate the drawbacks of conventional techniques, 9e [bmim][FeCl4] 120 3.0 100 97
such as the impossibility of recycling catalysts, equipment corrosion, a
PC 15.7 mmol, n(cat.):n(PC) = 0.3:1, n(CH3OH):n(PC) = 6:1.
laborious processing processes, and environmental problems. b
Soluble oligomers.
Liu et al. studied PC alcoholysis using DBU-based ILs in metal and c
See Ref. [114].
solvent-free settings [156]. Liu found in this experiment that DBU-based d
See Ref. [159].

15
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Fig. 6. (A) FT-IR spectra of commercial and obtained BPA samples (reprinted with permission from Ref. [157]). (B) 1H NMR spectrum of obtained BPA product
(reprinted with permission from Ref. [157]). (C) Effects of various reaction parameters: (a) reaction temperature, (b) n(cat.):n(PC), (c) n(CH3OH):n(PC), (d) reaction
time. Standard conditions: n(cat.):n(PC) = 0.3:1, n(CH3OH):n(PC) = 6:1,70◦ C, 2 h (reprinted with permission from Ref. [157]). (D) (a) Reusability of [hdbu][Suc]
catalyst, black: degree of PC degradation (%), grey: BPA yields (%), and (b) FT-IR spectra of fresh and reused [hdbu][Suc]. Conditions: n(cat.):n(PC) = 0.3:1, n
(CH3OH):n(PC) = 6:1,70◦ C, 2 h (reprinted with permission from Ref. [157]).

16
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

depolymerization procedure, [hdbu][Suc] could be reused six times

without any loss of catalytic activity.
Moreover, Liu investigated the structure of the re-used IL using FT-IR
and discovered commonalities with new ILs (see Fig. 6D). Liu found an
additional new peak that appeared at 1767 cm− 1. According to Liu, this
occurred because the remaining oligomer was soluble in [hdbu][Suc]. In
addition, Liu reported that there was no discernible impact on the cat­
alytic activity and that [hbdu][Suc] exhibited excellent structural sta­
bility. Liu discovered that SIIL could activate PC and CH3OH through
electrostatic and hydrogen interactions. According to Liu, the previously
activated CH3OH then conducted a nucleophilic attack on the carbonyl
carbon of the PC macromolecule. The nucleophilic attack leads to the
fragmentation of PC macromolecules into different soluble oligomers.
The oligomer is then similarly targeted by CH3OH to generate BPA and Fig. 8. Depolymerization of PA 6 to caprolactam in [emim][BF4] (modified
DMC (see Fig. 7A). According to our knowledge, this is the last study on from Ref. [115]).
the utilization of IL in the methanolysis of PC.

6.3. Degradation of PA Table 6

Depolymerization of PA 6 in [emim][BF4] (adapted from Ref. [115]).

Recently, Kamimura et al. studied the depolymerization of PA 6 to Entry DMAP Time Temp Caprolactam Recovery of
(wt%) (min) (◦ C) yield (%)a [emim][BF4]
caprolactam using hydrophilic IL [emim][BF4] (see Fig. 8) [115]. Under
(%)b
various reaction conditions, the depolymerization experiment was
conducted by heating PA 6 in IL [emim][BF4] utilizing microwave 1 0 60 280 0 95
2 0 60 300 36 94
irradiation. Table 6 demonstrates that the depolymerization process did 3 10 60 300 55 85
not proceed when the reaction mixture was heated to 280◦ C (entry 1). 4 10 30 300 24 85
Meanwhile, when heated to 300◦ C, a depolymerization process occurred 5 10 60 290 6 83
with a 36% caprolactam yield (entry 2). According to prior research by 6 10 60 310 54 85
7 10 60 320 38 81
Kamimura, PA 6 did not depolymerize at a temperature of 270◦ C [160].
In addition, the authors determined that the addition of 10 wt% N, a
Determined by isolation and GC analysis.
b
N-dimethylaminopyridine (DMAP) catalyst improved the PA 6 depoly­ Determined by isolation.
merization process with a caprolactam yield of 55% at 300◦ C (entry 3).
Compared to temperatures of 290, 310, and 320◦ C, the prior capro­ Kamimura discovered trace quantities of various products, but no olig­
lactam yield (entry 3) was the greatest, with 6, 54, and 38% yields, omers were created.
respectively. In addition, the yield decreased by 24% when the response In addition, the procedure of separating the product from the IL is
time was shortened to 30 minutes (entry 4). After the experiment,

Fig. 7. (A) The mechanism for the methanolysis of PC (reprinted with permission from Ref. [157]). (B) The mechanism for the hydrolysis of PC (reprinted with
permission from Ref. [114].

17
M. Zunita et al.
conducted. The separation was accomplished using liquid-liquid
extraction with water as the solvent. Based on the separation findings,
Kamimura determined that the liquid-liquid extraction technique is
more cost-effective than the distillation approach, which needs a tem­
perature of more than 300◦ C to generate caprolactam. In addition,
Kamimura discovered that the IL acquired after separation increased by
about 80%. By studying its 13C NMR spectra, Kamimura further vali­
dated the IL product and yield. The product’s characterization revealed
that it included caprolactam and a minor impurity [emim][BF4], as
evidenced by a little peak. In contrast, the characterization of the IL
revealed that essentially little change occurred in the IL during the
response. Finally, Kamimura studied the usage of recycled ILs in this
procedure and determined that ILs could be recovered three times with
less discernible modifications.
6.4. Degradation of PLA
6.4.1. Methanolysis
Under favorable circumstances, Song et al. studied the depolymer­
ization of PLA into methyl lactate monomer through the methanolysis
technique utilizing IL as a catalyst (see Fig. 9B) [161]. In this experi­
ment, Song studied the influence of factors such as IL type, reaction
duration, reaction temperature, IL dosage, and methanol dosage on PLA
conversion and methyl lactate production. Of the several ILs used,
including [bmim]Cl, [bmim][PF6], [bmim][OAc], and [bmim][HSO4],
[bmim][OAc] was shown to have the highest catalytic activity, as
measured by the conversion of PLA and yield of methyl lactate, which
were 97.2% and 92.5%, respectively, under the following optimum
conditions: n(CH3OH):n(PLA) = 5:1; m(IL):m(PLA) = 0.02:1; t = 3 h; T
= 115◦ C. It was also discovered that PLA does not depolymerize without
an IL. According to Song, the methanolysis of PLA is a transesterification
process that requires an acid or basic catalyst. Therefore, [bmim][OAc]
can function optimally. In addition, Song examined the influence of
reaction parameters on PLA conversion and methyl lactate production. It
was discovered that increasing temperature and time might enhance
PLA conversion. The greater the temperature, the more easily PLA will
dissolve or expand. In contrast, a drop in IL dosage or increased meth­
anol dosage led to decreased PLA conversion.
Then, Song used FTIR to evaluate PLA residue and product samples
(see Fig. 9B). A modest hydroxyl signal was seen at 3.500 cm− 1 when the
PLA residue was investigated, and the peak got stronger as PLA con­
version increased. According to Song, this suggests that the ester group’s
C-O bond is broken during methanolysis. In addition, the IR spectra of
the final samples were identical to that of pure methyl lactate samples,
demonstrating that PLA may be depolymerized into methyl lactate. After
depolymerization, Song discovered that [bmim][OAc] could be reused
six times without a noticeable decrease in its catalytic activity. Song also
discovered that PLA methanolysis is a first-order kinetic process with an
activation energy of 38.29 kJ/mol.
6.4.2. Hydrolysis
Besides methanolysis, Song et al. also studied the depolymerization
of PLA into calcium lactate monomers by hydrolysis utilizing ILs as
catalysts under favorable circumstances (see Fig. 9A) [162]. Song
examined the influence of variables such as reaction duration, temper­
ature, [bmim][OAc], and water dosage. Of the several ILs used, such as
[bmim]Cl, [emim][OAc], [HSO3-pmim][HSO4], [bmim][OAc], and
[emim][NTf2], [bmim][OAc] exhibited the highest catalytic activity
concerning the conversion of PLA and the production of calcium lactate,
93.93% and 76.08%, respectively, under the following optimal condi­
tions: n(H2O):n(PLA) = 6:1; m(IL):m(PLA) = 0.5:1; t = 2 h; T = 130◦ C.
After depolymerization, Song discovered that [bmim][OAc] could be
reused seven times without a noticeable decrease in its catalytic activity.
Song discovered that PLA hydrolysis is a first-order kinetic process with
an activation energy of 133.9 kJ/mol.
18
Polymer Degradation and Stability 211 (2023) 110320
6.5. Degradation of PHB
6.5.1. Methanolysis
Xiuyan et al. studied the methanolysis of PHB waste utilizing an
imidazolium-based Fe-containing IL as a catalyst to produce an M3HB
monomer [163]. Under this experiment, IL [bmim][FeCl4] was used,
and it was found that this IL demonstrated superior catalytic activity
when compared to FeCl3 and [bmim]Cl. In addition, it was also found
that the optimal conditions for obtaining the best performance in terms
of catalytic activity were as follows: X(cat.) = 0.67; n(cat.):n(PHB) =
0.05:1; t = 3 hours; T = 140◦ C; n(CH3OH):n(PHB) = 5:1 resulting in PHB
conversion and M3HB yield of 94.1% and 85.0%, respectively. The
product of this reaction was further characterized using GC, IR, and 1H
NMR to establish that it was M3HB. The retention period was around
1.48 minutes, and the product purity was more than 98%, as determined
by GC. IR examination (see Fig. 10A) demonstrated that the product
spectra produced from the various conversions were almost similar,
suggesting that they represent the same substance. The spectrum also
reveals the existence of the following functional groups and compounds:
3435 cm− 1 includes the –OH band, 1740 cm− 1 contains the stretched
C=O band, and 1132 cm− 1 has the C–O bend. These three wave numbers
indicate the presence of an ester group; 2990 cm− 1 contains C–H alkyl
bonds, and 1380 cm− 1 has the –CH3 bend. Analysis by 1H NMR (see
Fig. 10B) revealed the following chemical structure: the methyl proton
of –CH3 is indicated by a double signal at the delta of 1.00–1.19 ppm; the
methylene proton of –CH2– is shown by the multiple at the delta of
2.32–2.48 ppm; the methyl proton of –OCH3 is indicated by a single
signal at the delta of 3.595 ppm; and the methenyl proton of CH– is
shown by the multiple at delta 4.15 ppm. Based on these three charac­
terizations, it can be confirmed that the structure of the product is
M3HB.
Furthermore, the influence of parameters such as temperature, time,
methanol dosage, and IL dosage on PHB conversion and M3HB yield was
investigated. The effect of temperature is that as the reaction tempera­
ture rises, so does the PHB conversion and M3HB yield. The impact of
time is that the PHB conversion and M3HB yield to rise as time passes.
However, when the reaction was continued for up to 4 hours, there was
no significant increase in PHB conversion or M3HB yield because the
methanolysis reaction is a transesterification reaction, which is revers­
ible. ILs have the effect of increasing PHB conversion as the quantity of
ILs rises. The increased number of active sites on the substrate inter­
acting with cations and anions in ILs created it.
Meanwhile, increasing the amount of methanol enhanced PHB con­
version and M3HB production, but only marginally. However, when the
methanol ratio was gradually raised until it reached 6:1, the conversion
and reaction gain decreased. The authors indicated this was due to the
mixture’s lower IL concentration, resulting in a significant drop in cat­
alytic activity. Under optimal circumstances, ILs may be reused six times
without substantially declining PHB conversion. Product acquisitions,
on the other hand, have fallen somewhat. The IL utilized was charac­
terized by comparing fresh with IL that had been used six times using IR
and TGA (see Fig. 10C and Fig. 10D). The findings of the IR study
demonstrate that the two ILs have identical spectra, indicating that they
have the same structure.
Meanwhile, the TGA analysis revealed no change in the stability of
the two ILs. The presence of evaporating water is responsible for the
minor difference in mass. The mass change that occurs at temperatures
over 425◦ C is due to the breakdown of ILs. However, this is not a sig­
nificant issue since methanolysis occurs at 140◦ C. As a result, the IL
employed is an excellent catalyst that may be reused for PHB meth­
anolysis. The residual PHB was characterized using IR at various con­
versions to determine the mechanism of PHB methanolysis. According to
the IR characterization results, the hydroxyl and carbonyl groups
became more robust with increasing PHB conversion. The IR analysis of
the primary product also shows the existence of M3HB. The authors
describe the mechanism of PHB degradation in ILs (see Fig. 10E). When
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Fig. 9. (A) Depolymerization of PLA using ILs: (a) hydrolysis and (b) methanolysis. (B) The IR spectrum of the residue and methyl lactate was obtained at different
conversions of PLA (a, 41.5%; b, 77.3%) (reprinted with permission from Ref. [161]). (C) The mechanism for the methanolysis of PLA (reprinted with permission
from Ref. [161]). (D) The mechanism for the hydrolysis of PLA (reprinted with permission from Ref. [162]).

19
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Fig. 10. (A) IR spectra of M3HB at the different conversion of PHB (a: 39.6%; b: 73.0%; c: 94.1%). (B) 1H NMR of M3HB. (C) IR spectra of [bmim][FeCl4] (x=0.67)
used in the methanolysis of PHB (a: fresh; b: reused six times). (D) TGA curves of fresh and reused [Bmim]FeCl4 (a: before reused; b: after reused. (E) The mechanism
for the methanolysis of PHB (all figures were reprinted with permission from Ref. [163]).

PHB is dissolved in IL, the [bmim]+ cation combines with –C=O in the
PHB ester group, increasing the electropositivity of the carbonyl group’s
carbon atom. In addition, the [FeCl4]– anion reacts with the hydrogen
atom on the hydroxyl group in methanol to generate a six-membered
ring transition state. It causes the oxygen atom in the hydroxyl group
of methanol to become more electronegative, making it extremely easy
to attack the carbonyl carbon atom in the ester group. Following
removing the hydrogen atoms from the methanol and [bmim]+ from the
six-membered ring, the oxygen atoms’ electrons return to create the
C=O double bond. Both the acyl oxygen and alkoxy groups are cleaved.
When this transformation was repeated, the M3HB monomer was
produced.
6.6. Degradation of epoxy
Pérez et al. studied the swelling and dissolution of TERs using ILs,
alcohol, or both as solvents under moderate conditions [164]. In the first
experiment, the swelling and dissolution of TER samples were evaluated
by Pérez using EG and Gly at different temperatures of 70, 100, and
150◦ C. At that temperature, the epoxy’s most significant swelling and
dissolution of the epoxy occurred at 150◦ C as shown below: mass
swelling of 25% using EG; mass dissolution of 9.35% using Gly (see

20
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Fig. 11. (A) Normalized mass of TER over time at different temperatures in the presence of: (a) EG and (b) Gly. (c) Normalized mass of TER over time in the presence
of pure ILs (reprinted with permission from Ref. [157]). (B) Normalized mass of epoxy thermoset over time in the presence of mixtures of 20% ILs plus (a) EG and (b)
Gly (reprinted with permission from Ref. [157]). (C) (a) Normalized mass of TER over time in the presence of mixtures of 20:80 of [bmim]-based ILs and EG mixtures.
(b) Normalized mass and length of the TER sample at different times when subjected to dissolution conditions with 20:80 [bmim][OAc]:EG. (c) TER sample size and
appearance at different times in the presence of 20:80 [bmim][OAc]:EG solution at 150◦ C (reprinted with permission from Ref. [157]). (D) Normalized mass of TER
over time in the presence of 20:80 [bmim][OAc]:EG solvent mixtures at different recycling cycles (reprinted with permission from Ref. [157]).

Fig. 11A). The experimental results show that both alcohols used are
more effective in interacting with the epoxy at a high temperature, in
this case, 150◦ C. The previous experiment became the basis for the au­
thors to determine the temperature to evaluate TER samples’ swelling
using ILs. In this case, Pérez used alkyl-methyl imidazolium ILs with
different alkyl lengths, such as [bmim]Cl, [hmim]Br, and [omim]Br, and
all these ILs were reported to be able to penetrate the covalently
cross-linked matrix of the epoxy. As can be seen in Fig. 11B, the most
significant swelling occurs when using [bmim]Cl. [bmim]Cl can swell
epoxy up to 50% of its original mass compared to [hmim]Br and [omim]
Br, which only swell by 30% and 22.5%, respectively. Pérez stated that
the results were consistent with the increase in the length of the alkyl
chain, where the IL with shorter chains penetrated the polymer matrix in
large numbers.
After evaluating using an IL, the authors evaluated the swelling and
dissolution of the epoxy using a 20% IL in combination with alcohol (EG

21
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

and Gly). As can be seen in Fig. 11B, the most significant swelling Table 7
occurred when using IL [bmim]Cl with swelling values as follows: The reaction of PE in several ILs (adapted from Ref. [108]).
44.6% in combination with EG; 12% in combination with Gly. This Entry Polymer IL T t Yield Low-volatility to
result agrees with the results of previous experiments when using pure (◦ C) (h) (%) volatile product
ILs and pure alcohol. Pérez also uses ILs with a weight of 40 and 60%. ratio
The results have the same pattern when using 20% by weight of IL, so 1 HDPE [emim]Cl- 120b 72 95 1.2
Pérez used 20% by weight of IL and 80% by weight of EG in his sub­ AlCl3 (X =
sequent evaluations. 0.67)a
2 HDPE [emim]Cl- 200 72 90 0.8
Previous experiments have shown that the IL [bmim]Cl performs AlCl3 (X =
well in swelling high percent epoxy. However, the IL can only swell the 0.67)a
epoxy and cannot dissolve. Therefore, the authors evaluated the 3 LDPE [emim]Cl- 120b 72 68 0.8
[bmim]-based IL using a different anion. The anions evaluated in this AlCl3 (X =
0.67)a
experiment were acetate ([OAc− ]), propionate ([prop− ]), hexanoate
4 LDPE [C4py]Cl- 120b 72 62 1.0
([hex− ]), tetrafluoroborate ([BF4− ]), and hexafluorophosphate AlCl3 (X =
([PF6− ]). As can be seen in Fig. 11C, the anions that can completely 0.67)a
dissolve TER are as follows: [bmim][OAc] takes 150 minutes; [bmim] 5 LDPE [bmim]Cl- 120b 72 60 1.0
[prop] takes 210 minutes. These results have the same pattern as ex­ AlCl3 (X =
0.67)a
periments using ILs with different alkyl lengths. Pérez stated that TER 6 LDPE [bmim]Cl- 200 48 85 0.9
could be dissolved in a mixture of 20% [bmim][OAc] and 80% EG AlCl3 (X =
combinations due to oxygen in the acetate anion. The presence of such 0.67)c
oxygen promotes the attack of the polymeric ester bond. In addition, 7 LDPE LiCl-AlCl3 (X 250 24 95 0.6d
= 0.67)c
Pérez also stated that the presence of alcohol helped form the alcohol
derivative of the DGBA molecule. a
1 mol% of [emim][HCl2] used as co-catalyst.
b
After the successful dissolving process, Pérez evaluated the monomer Reaction heated to 90◦ C for 72 h before being heated to 120◦ C.
c
resulting from the previous experiment. The epoxy monomer was 2 mol% of concentrated sulfuric acid used as co-catalyst.
d
depolymerized in a precipitated solution using water as a solvent. Pérez Some decomposition of carbon was observed due to the high reaction
then reused the monomer to synthesize a new TER. Pérez found that the temperature.
newly synthesized TER retained the mechanical properties of the TER
before depolymerization. However, there was a slight reduction of about GCMS and found to be highly susceptible to polycyclic aliphatics (see
8% in both Young’s modulus and compressive strength. Lastly, Pérez Fig. 12). In this catalytic cracking reaction, the formation of alkene or
evaluated the recycling of the solvent mixture used in this process and aromatic compounds was not found. However, at temperatures above
found that the solvent mixture could be reused without needing new ILs 200◦ C, non-alkane products were found in black solids with high carbon
or new alcohol (see Fig. 11D). However, reusing the solvent mixture content. Adam stated that the rate of this cracking reaction depends on
adds a reaction time of 30 minutes on the first use, and so on. the surface area of the PE in contact with the IL, so the PE form must be a
fine powder for the reaction to occur. The overview of the chapter 6 and
6.7. Degradation of PE

Adams et al. studied the catalytic cracking reaction of PE (LDPE or

HDPE) into light alkanes using chloroaluminate (III) IL [108]. Several
varieties of ILs were employed in this experiment, including [emim]
Cl-AlCl3, [C4py]Cl-AlCl3, [bmim]Cl-AlCl3, and LiCl-AlCl3. In addition,
acid co-catalysts such as [emim][HCl2] (1 mol%) or concentrated sul­
furic acid (2 mol%) are introduced. The inclusion of the co-catalyst
contributes to the acid’s Brønsted super acidity. Experiments were
conducted by combining these substances and heating them at
90–250◦ C for 1–6 days. Adams achieved the maximum yield in HDPE,
95% (see Table 7). The experiment produces two products: gaseous al­
kanes (volatile alkanes) and low-volatile cyclic alkanes. In this experi­
ment, Adam discovered two products; the first is a gas that developed
from the surface of PE, while the second floats on the surface of IL.
The two products were collected and analyzed by gas chromatog­
raphy (first product only), 1H and 13C NMR spectroscopy, and GCMS
(second product only). According to the first product analysis results, the
isolated gas was an alkane with the formula CnH2n+2. As seen in Table 7,
the reaction temperature affects the composition of the gas formed. The
higher the reaction temperature, the higher the proportion of propane
and butane, and the lower the pentane formed. Adam stated that this
cracking reaction involved the formation of a carbocation species. Adam
also stated that the formation of secondary cations (leading to the for­
mation of propane and butane) has a high activation energy barrier.
When the temperature increases, the barrier is easily overcome so that
more secondary carbocations are formed. The results of the second
product analysis show that the composition consists of alkanes with a
cyclic structure and branches in several products. As seen in
Table 8, the temperature has little effect on the composition of low- Fig. 12. The typical structures of low-volatility alkanes proposed were ob­
volatility products. The low-volatile alkanes were further analyzed by tained (adapted from Ref. [108]).

22
M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

the most effective ILs for polymer degradation is shown in Table 9. (continued )
Abbreviations Definition
7. Challenges and prospective outcomes [amim][CuCl3] 1-Allyl-3-methylimidazolium trichlorocuprate
[amim][FeCl4] 1-Allyl-3-methylimidazolium tetrachloroferrate
ILs have been investigated and found to have a significant role in [amim][MnCl3] 1-Allyl-3-methylimidazolium trichloromanganate
degrading plastics, especially PET, PC, PA, PE, PLA, PHB, and TER [amim][ZnCl3] 1-Allyl-3-methylimidazolium trichlorozincate
[amim]Cl 1-Allyl-3-methylimidazolium chloride
plastics. Until now, the studies have been carried out on a laboratory
[bmim][AlCl4] 1-Butyl-3-methylimidazolium tetrachloroaluminate
scale. Increasing the scale of research is a challenge that must be [bmim][BF4] 1-Butyl-3-methylimidazolium tetrafluoroborate
resolved in order to obtain more in-depth and practical information [bmim][CrCl4] 1-Butyl-3-methylimidazolium tetrachlorochromate
regarding the potential for developing ILs for solving the problem of [bmim][CuCl3] 1-Butyl-3-methylimidazolium trichlorocuprate
[bmim][FeCl3] 1-Butyl-3-methylimidazolium trichloroferrate
plastics waste. Research on the types of ILs that can be used in plastics
[bmim][FeCl4] 1-Butyl-3-methylimidazolium tetrachloroferrate
degradation must also be developed. The use of appropriate ILs has the [bmim][hex] 1-Butyl-3-methylimidazolium hexanoate
potential to reduce costs associated with plastics degradation as a result [bmim][HSO4] 1-Butyl-3-methylimidazolium hydrogen sulfate
of easier and less expensive operating conditions. The use of appropriate [bmim][MnCl3] 1-Butyl-3-methylimidazolium trichloromanganate
ILs can help reduce the amount of energy required to degrade plastics. [bmim][NiCl3] 1-Butyl-3-methylimidazolium trichloronickelate
[bmim][NTf2] 1-Butyl-3-methylimidazolium bis
On the other hand, the reusability of ILs has been widely tested and has
(trifluoromethylsulfonyl)imide
yielded good conversion values due to their stable nature. This plastics [bmim][OAc] 1-Butyl-3-methylimidazolium acetate
degradation technology could provide an opportunity for the future [bmim][PbCl3] 1-Butyl-3-methylimidazolium trcihloroleadate
plastics waste treatment. More research is needed to obtain process [bmim][PF6] 1-Butyl-3-methylimidazolium hexafluorophosphate
[bmim][prop] 1-Butyl-3-methylimidazolium propanoate
conditions and technologies that are cheap, easy, and safe for the
[bmim][SnCl3] 1-Butyl-3-methylimidazolium trichlorostannate
environment. [bmim][ZnCl3] 1-Butyl-3-methylimidazolium trichlorozincate
[bmim]2[CoCl4] 1-Butyl-3-methylimidazolium tetrachlorocobaltate
Conclusion [bmim]2[CuCl4] 1-Butyl-3-methylimidazolium tetrachlorocuprate
[bmim]2[NiCl4] 1-Butyl-3-methylimidazolium tetrachloronickelate
[bmim]2[ZnCl4] 1-Butyl-3-methylimidazolium tetrachlorozincate
Whether acting as catalysts, solvents, or both, ILs can degrade [bmim]Br 1-Butyl-3-methylimidazolium bromide
polymers such as PET, PC, PHB, PA, epoxy, PE, and PLA into their [bmim]Cl 1-Butyl-3-methylimidazolium chloride
monomers or more useful raw materials with conversions and yields [bmim]Cl/ZnCl2 1-Butyl-3-methylimidazolium chloride/zinc acetate
exceeding 90%. In addition, ILs can invalidate conventional recycling [bmim-Fe][(OAc)3] 1-Butyl-3-methylimidazolium acetate coordinated
ferrous acetate
methods under extreme conditions. Moreover, ILs offer unique features
[bymim][BF4] 1-Benzyl-3-methylimidazolium tetrafluoroborate
such as recyclability, so that the utilization of ILs in plastics waste [bymim]Cl 1-Benzyl-3-methylimidazolium chloride
recycling is a promising area of research. However, it should be noted [C2tmg]Cl/ZnCl2 1,1,3,3-tetramethylguanidine (TMG)-based IL with C2
that using ILs in degrading polymers is expensive compared to tradi­ branch, trichlorozincate anion
tional uses. There are many more unanswered questions. Is the use of ILs [C4tmg]Cl/ZnCl2 1,1,3,3-tetramethylguanidine (TMG)-based IL with C4
branch, trichlorozincate anion
on a factory scale profitable, and can it be applied in the future? Can the [C6tmg]Cl/2ZnCl2 1,1,3,3-tetramethylguanidine (TMG)-based IL with C6
free movement of plastics waste affect the use of ILs in dissolving plastics branch, trichlorozincate anion (a doubled molar ZnCl2
waste? Therefore, these facts may open new avenues for ILs to be used as preparation)
solvents, catalysts, or both in degrading plastics waste. [C6tmg]Cl/ZnCl2 1,1,3,3-tetramethylguanidine (TMG)-based IL with C6
branch, trichlorozincate anion
[C8tmg]Cl/ZnCl2 1,1,3,3-tetramethylguanidine (TMG)-based IL with C8
List of abbreviations branch, trichlorozincate anion
[cemim]Cl 1-Chloroethyl-3-methyl chloride
Abbreviations Definition [Ch][Ala] Cholinium alaninate
[Ch][Asp] Cholinium aspartate
IL Ionic liquid
[Ch][Gly] Cholinium glycinate
HDPE High-density polyethylene
[Ch][Im] Cholinium imidazolate
LDPE Low-density polyethylene
[Ch][Lys] Cholinium lysinate
M3HB Methyl 3-hydroxybutyrate
[Ch][OAc] Cholinium acetate
PA Polyamide
[Ch][OH] Cholinium hydroxide
PC Polycarbonate
[Ch]3[PO4] Cholinium phosphate
PE Polyethylene
[deme][NTf2] N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium
PET Polyethylene terephthalate
bis(trifluoromethylsulfonyl)imide
PHB Poly(3-hydroxybutyrate)
[dmeim][OAc] 1,2-Dimethyl-3-ethyl imidazolium acetate
PLA Polylactic acid
[emim][BF4] 1-Ethyl-3-methylimidazolium tetrafluoroborate
PP Polypropylene
[emim][OAc] 1-Ethyl-3-methylimidazolium acetate
PS Polystyrene
[emim]Br 1-Ethyl-3-methylimidazolium bromide
PVC Polyvinyl chloride
[emim]Cl 1-Ethyl-3-methylimidazolium chloride
TER Thermoset epoxy resin
[eoa][OAc] Ethanolamine acetate
[aeim][NTf2] 3-Aminoethylimidazolium bis(trifluoromethylsulfonyl)
[hdbu][LAc] 1,8-Diazabicyclo[5.4.0]undecium lactide
imide
[hmim][CoCl3] 1-Hexyl-3-methylimidazolium trichlorocobaltate
[amim][CoCl3] 1-Allyl-3-methylimidazolium trichlorocobaltate
(continued on next page)
(continued on next column)

Table 8
Composition of the volatile hydrocarbons in the cracking of PE in Table 7 (adapted from Ref. [108]).
Volatile Alkane Product Composition at 120◦ C for Entry 1 (%) Composition at 200◦ C for Entry 2 (%) Composition at 200◦ C for Entry 6 (%)

Propane 10 35 30
2-Methylpropane 55 50 45
2-Methylbutane 20 5 5
Butane 5 10 15
Others 10 5 5

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M. Zunita et al. Polymer Degradation and Stability 211 (2023) 110320

Table 9
Overview of chapter 6 and the most effective ILs for polymer degradation.
Polymer IL Reaction Reaction Condition Products Conv. Yield (%) Reusability Ref.
(%) (times)

PET [amim][ZnCl3] Glycolysis T = 175◦ C; t = 1.25 h; m(IL):m(PET) = 1:10; BHET 100 80.1 6 [127]
m(EG):m(PET) = 4:1.
[htbd][OAc]/ Glycolysis T = 190◦ C; t = 0.5 h; m(IL):m(PET) = 0.03:1; BHET 100 88.0 7 [145]
Zn(OAc)2 m(EG):m(PET) = 5:1
(DES)
[toma]Br Hydrolysis T = 85◦ C (MW); t = 2.2 h; m(IL):m(PET) = TPA and EG N/A 98.59 (TPA, N/A [147]
2.7:100; m(NaOH):m(PET) = 39:100 pred.), 97.53
(TPA, act.)
[Ch]Cl/ Glycolysis- tg = 0.5 min; Glycolysis under MW irradiation BHET, MHET, and 99.31 0.54 (BHET), N/A [149]
thiourea (DES) Hydrolysis (P = 350 W) th = 3 min; m(IL)g:m(PET)g = TPA. 17.22 (MHET),
4:1; m(EG)g:m(PET)g = 5.5:1; Na2CO3 = 10% 80.66 (TPA)
(w/v); m(EG)h:m(PET)h = 22.3:0.82
[hmim][TfO] Aminolysis T = 196◦ C; t = 1 h; m(IL):m(PET) = 1:1; n BHETA N/A 89 N/A [152]
(EA):n(PET) = 6:1
T = 110◦ C; t = 1 h; m(IL):m(PET) = 1:1; n TH N/A 84 N/A
(Hydrazine Hydrate):n(PET) = 6:1
[Ch]Cl/2ZnCl2 Aminolysis t = 0.5 h; IL conc. = 5 %(w/w); n(DEA):n THETA and TPA N/A 82 (THETA), 83 N/A [153]
(DES) (PET) = 6:1 (TPA)
t = 0.5 h; IL conc. = 5 %(w/w); n(EA):n(PET) BHETA N/A 95 N/A
= 6:1
[HO3S-(CH2)3- Butanolysis T = 205◦ C; t = 8 h; m(IL):m(PET) = 2:10; m DBTP and EG 100 95.3 (DBTP), 7 [151]
NEt3]Cl-ZnCl2 (n-butanol):m(PET) = 11.6:10 95.7 (EG)
(X = 0.67)
PC [hdbu][Suc] Methanolysis T = 70◦ C; t = 2 h; n(IL):n(PC) = 0.3:1; n BPA and DMC 100 96 6 [157]
(CH3OH):n(PC) = 6:1
[hdbu][LAc] Hydrolysis T = 140◦ C; t = 3 h; n(IL):n(PC) = 0.1:1; n BPA 100 97 6 [114]
(H2O):n(PC) = 3:1
PA [emim][BF4] N/A T = 300◦ C; t = 60 min; DMAP Caprolactam N/A 55 3 [115]
PLA [hdbu][AA] Methanolysis T = 100◦ C; t = 5 h; PLA 27.8 mmol (2 g); n Methyl lactate 100 91 6 [165]
(IL):n(PLA) = 0.05:1; n(CH3OH):n(PLA) =
5:1
[bmim][OAc] Hydrolysis T = 130◦ C; t = 2 h; m(IL):m(PLA) = 0.5:1; n Calcium lactate 93.93 76.08 7 [162]
(H2O):n(PLA) = 6:1
PHB [mimps] Methanolysis T = 140◦ C; t = 4 h; n(IL):n(PHB) = 0.05:1; n M3HB 98.5 87.4 6 [167]
[FeCl4] (CH3OH):n(PHB) = 5:1
[HSO3-pmim] Hydrolysis T = 140◦ C; t = 4 h; m(IL):m(PHB) = 0.06:1; n 3-hydroxybutyric acid 98 N/A 6 [168]
[HSO4] (H2O):n(PHB) = 7:1
TER [bmim][OAc]d Alcoholysis T = 150◦ C; t = 2.5 h Epoxy monomer 100 5 3 [164]
HDPE [emim]Cl- Catalytic T = 120◦ Cb; t = 72 h Gaseous alkanes and N/A 95 N/A [108]
AlCl3 (X = cracking low-volatile cyclic
0.67)a alkanes
LDPE LiCl-AlCl3 (X = T = 250◦ C; t = 24 h N/A 95
0.67)c
a
1 mol% of [emim][HCl2] used as co-catalyst.
b
Reaction heated to 90◦ C for 72 h before being heated to 120◦ C.
c
2 mol% of concentrated sulfuric acid used as co-catalyst.
d
a mixture of 20% IL and 80% EG

(continued ) (continued )
Abbreviations Definition Abbreviations Definition

[hmim][CuCl3] 1-Hexyl-3-methylimidazolium trichlorocuprate [omim]Cl 1-Octyl-3-methylimidazolium chloride

[hmim][FeCl4] 1-Hexyl-3-methylimidazolium tetrachloroferrate [p13][NTf2] N-Propyl-N-methylpyrrolidinium bis
[hmim][TfO] 1-Hexyl-3-methylimidazolium (trifluoromethylsulfonyl)imide
trifluoromethanesulfonate [p14][NTf2] N-Butyl-1-methylpyrrolidinium bis
[hmim][ZnCl3] 1-Hexyl-3-methylimidazolium trichlorozincate (trifluoromethylsulfonyl)imide
[hmim]Br 1-Hexyl-3-methylimidazolium bromide [pga][TFSA] Protected glycerammonium bis
[HO3S-(CH2)3-NEt3]Cl (3-Sulfonic acid)-propyl-triethylammonium chloride (trifluoromethanesulfonyl)amide
[HO3S-(CH2)3-NEt3]Cl- (3-Sulfonic acid)-propyl-triethylammonium [pp13][NTf2] N-Methyl-N-propylpiperidinium bis
CuCl2 trichlorocuprate (trifluoromethylsulfonyl)imide
[HO3S-(CH2)3-NEt3]Cl- (3-Sulfonic acid)-propyl-triethylammonium [tea]Br Tetraethylammonium bromide
FeCl2 trichloroferrate [tea]Cl Tetraethylammonium chloride
[HO3S-(CH2)3-NEt3]Cl- (3-Sulfonic acid)-propyl-triethylammonium [tea]F Tetraethylammonium fluoride
FeCl3 tetrachloroferrate [tea]I Tetraethylammonium iodide
[HO3S-(CH2)3-NEt3]Cl- (3-Sulfonic acid)-propyl-triethylammonium [tespmi]2[CoCl4] 1-(Triethoxysilylpropyl)-3-methylimidazolium
ZnCl2 trichlorozincate tetrachlorocobaltate
[HSO3-pmim][HSO4] 1-Methyl-3-(3-sulfopropyl)-imidazolium hydrogen [tespmi]Cl 1-(Triethoxysilylpropyl)-3-methylimidazolium
sulfate chloride
[mmim][MeSO4] 1,3-Dimethylimidazolium methylsulfate [tma][HSO4] Tetramethylammonium bisulfate
[mmim][OAc] 1,3-Dimethylimidazolium acetate [tma]Br Tetramethylammonium bromide
[omim][PF6] 1-Octyl-3-methylimidazolium hexafluorophosphate [tma]Cl Tetramethylammonium chloride
[omim]Br 1-Octyl-3-methylimidazolium bromide [tma]F Tetramethylammonium fluoride
(continued on next column) (continued on next page)

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