Review

pubs.acs.org/IECR

Recent Developments in the Chemical Recycling of Postconsumer

Poly(ethylene terephthalate) Waste
Neena George* and Thomas Kurian
Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi 22, Kerala, India

ABSTRACT: Global production and consumption of poly(ethylene terephthalate) (PET) products has increased dramatically
over the past few decades. World consumption of PET has exceeded 13 million tonnes, of which about 1.5 million tonnes is
exclusively consumed by the packaging sector itself. However, this tremendous increase in PET consumption has resulted in the
accumulation of an enormous quantity of waste, the disposal of which is complex day by day. Among different PET recycling
methods, chemical recycling (chemolysis) is the most successful method to convert PET into its monomers/oligomers. This
review presents in detail recent developments in the chemical recycling (glycolysis and aminolysis) of PET. The wide spectrum
of depolymerizing agents used, the reaction conditions, catalysts, products of depolymerization, and their potential applications
are described.

1. INTRODUCTION (v) PVC liners in bottle caps are problematic to the PET
Polyethylene terephthalate (PET) is one of the most recycling process. PVC and PET have almost the same
commonly used consumer plastics in the world by virtue of density and are difficult to separate from each other. PVC
its light weight, durability, excellent wear, and chemical releases hydrochloric acid during PET reprocessing,
resistance coupled with its low market price. Its widespread reducing the commercial value of recycled PET.
use, particularly in the textile and packaging sectors, generates (vi) The presence of colored PET wastes imparts an
tonnes of PET waste to the environment. PET accounts for 8% undesirable gray color to the recycled PET.
by weight and 12% by volume of the global solid waste.1 Thus, (vii) Trace metals such as antimony, cobalt, and manganese
the current scenario demands a simple, ecofriendly, and (from the catalyst residues and additives used for PET
economical route for recycling PET wastes that may otherwise production) present in postconsumer PET wastes
disrupt the balance of the ecosystem due to their non- promote transesterification and polycondensation reac-
biodegradable nature. PET can be recycled practically by tions in the recycled PET. This makes the recycled PET
mechanical, thermal, and chemical recycling methods and has chemically heterogeneous and may affect the melt
the number “1” as its recycling symbol. Nevertheless, post- rheology behavior from batch to batch.
consumer PET wastes and industrial plant scraps are commonly
recycled either mechanically or chemically. Thus, it is very difficult to recycle complex and contaminated
Mechanical recycling (material recycling) of PET involves a PET wastes mechanically. Recycled PET obtained from
number of treatments and operations: separation of PET from mechanical recycling plants exhibits relatively low and
other plastics, washing to remove dirt and other contaminants, heterogeneous intrinsic viscosity values. This characteristic
grinding and crushing to reduce the PET particle size, extrusion has prevented recycled PET from being directly used to
by heat, pelletizing, and reprocessing into new PET products.2 produce bottle-grade PET, films, and superior industrial fibers.
Compared to chemolysis recycling routes, mechanical recycling It is usually used for applications such as textile fibers, carpets,
of PET is relatively simple, requires low investments, utilizes non-food-contact containers, and injection-molded household
established equipment, is flexible in terms of feedstock volume, products, all of which do not always claim superiority in their
and has little adverse environmental impact. Despite the properties.4
positive incentives to recycle PET mechanically, there are a Solid state polymerization (SSP) processing can be done
number of barriers, and these include:3 with mechanically recycled PET pellets to convert them to a
desired high molecular weight polymer of uniform and
(i) Paper labels and label adhesives (based on polyvinyl consistent intrinsic viscosity.5 The undesirable side reactions
acetate/ethylene vinyl acetate) cause the PET to discolor and the levels of byproducts are also considerably reduced. SSP
and lose clarity. is usually done at a high temperature (below the melt
(ii) PET containing residual moisture degrades readily when temperature of the polymer) in the absence of oxygen and
reprocessed, if not dried. water, by means of either vacuum or purging with an inert gas
(iii) Thermal and oxidative degradation products cause to drive off the byproducts of reactions. For PET, the SSP
yellowing and diminish the mechanical properties of
PET. Received: May 17, 2014
(iv) Collection, sorting, and separation costs are high because Revised: August 18, 2014
of the low-bulk density of PET bottles and the stringent Accepted: August 28, 2014
requirement to have well-sorted feedstock. Published: August 28, 2014

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byproducts are ethylene glycol and acetaldehyde. SSP is as polyamides, polyacetals, and polycarbonates, too, can be
frequently applied with high contaminant PET loads after subjected to chemical depolymerization reactions.2,8
melt polymerization for enhancing the mechanical and 2.1. Methanolysis. PET methanolysis is based on the
rheological properties of PET before injection blow molding treatment of PET with methanol at relatively high temperatures
or extruding. (180−280 °C) and pressures (20−40 atm), which leads to the
Chemical recycling, on the other hand, is an accepted PET formation of DMT and EG as the main products, which are the
recycling method that follows the principles of “sustainable raw materials necessary for the production of this polymer.9−12
development”.6 The fact that chemically recycled PET is well The reaction is catalyzed by typical transesterification catalysts
suited for food-contact applications has increasingly attracted such as zinc acetate, magnesium acetate, cobalt acetate, and lead
researchers to the various chemolysis possibilities. Chemical dioxide; however, zinc acetate is the most commonly used
recycling methods are opening newer pathways for using PET catalyst. The reaction products of methanolysis of postcon-
waste as a precursor in generating pure value-added products sumer PET comprise an extensive mixture of glycols, alcohols,
for various industrial and commercial applications.7 However, and phthalate derivatives in addition to DMT. The separation
chemically recycled PET is more expensive than virgin PET and refinement of these make methanolysis a rather costly
because of its raw material cost, capital investment, and scale of process. The methanolysis process can tolerate a wide range of
operation. It has been calculated that for PET chemolysis contaminants; however, water does perturb the process and
facilities to be economically viable, they require a minimum poisons the catalyst to form various azeotropes. Currently the
throughput of 1.5 × 104 tonnes per annum. The specific cost of methanolysis-derived DMT from postconsumer PET
minimum size may vary with the technology used. bottles is approximately double that of virgin DMT.13
This review discusses recent research done in the area of 2.2. Hydrolysis. Reaction of PET with water under neutral,
PET chemical recycling with emphasis on glycolytic and acidic, or basic conditions at high temperature and pressure
aminolytic depolymerization of PET wastes. Applications of the breaks the polyester chains into TPA and EG. Acid hydrolysis is
glycolysis and aminolysis products are also discussed. performed most frequently using concentrated sulfuric acid
(minimum 87 wt %), although the application of other
2. CHEMICAL RECYCLING OF PET concentrated mineral acids (e.g., phosphoric or nitric acid) is
permissible.14,15 Alkaline hydrolysis is usually carried out with
PET, a thermoplastic polyester, is formed by the condensation
reaction between terephthalic acid (TPA) and ethylene glycol the use of an aqueous solution of NaOH of a concentration of
(EG) or through a transesterification reaction between 4−20 wt %.16,17 Neutral hydrolysis is carried out with the use of
dimethyl terephthalate (DMT) and EG. Chemical recycling water or steam in the presence of alkali metal acetates as
of PET totally depolymerizes it into monomers such as TPA, transesterification catalysts.18−20 Low purity of TPA is the
DMT, bis(hydroxylethylene) terephthalate (BHET), and EG or major drawback of this method. Hydrolysis is comparatively
partially depolymerises it to oligomers or other chemical slow because water is a weak nucleophile.
substances. Thus, depolymerization is the reverse reaction of 2.3. Glycolysis. Glycolysis is the simplest and oldest
the polymer formation. There are different depolymerization method of PET depolymerization. It is a commercial PET
routes such as methanolysis, glycolysis, hydrolysis, ammonol- recycling method practiced by renowned companies worldwide
ysis, aminolysis, and hydrogenation depending on the chemical such as DuPont, Goodyear, Shell Polyester, Zimmer, Eastman
agent used for PET chain scission.2 Figure 1 summarizes the Kodak, etc.3,21 The first patents on PET glycolysis were filed
different routes for PET chemolysis, as well as the type of more than 40 years ago.22−28 Glycolysis is considered to be a
products derived thereafter. Other condensation polymers such versatile chemical recycling method in view of the fact that
besides monomer formation specialized oligomeric products
such as α,ω-dihydroxy materials (polyols) are also produced,
which can be further utilized for the synthesis of polymers such
as unsaturated polyesters, polyurethanes, vinyl esters, epoxy
resins, and polymer concretes.29,30 Glycolysis is a preferred
recycling option when the incoming PET feed source is of
known history and high quality. It is not suited to remove low
levels of copolymers, colorants, or dyes. It is best suited to the
recovery of postindustrial scrap.3
The method involves a transesterification reaction of PET
with an excess of glycol at temperatures in the range of 180−
240 °C, promoting the formation of BHET (a substrate for
PET synthesis). Different glycols, such as EG, diethylene glycol
(DEG), propylene glycol (PG), polyethylene glycol (PEG),
1,4-butanediol, and hexylene glycol, are used for the glycolysis
of PET.31,32 Because the process is sluggish in the absence of
any catalyst, transesterification catalysts are usually employed.32
Glycolysis of waste PET proceeds through at least three
stages: oligomers, dimer, and monomer (Figure 2). The glycol
diffuses into the polymer, causing the polymer to swell up, thus
increasing the diffusion rate. The glycol subsequently reacts
Figure 1. Different methods of PET chemolysis and the value-added with an ester bond in the chain and degrades the PET into
products derived therefrom.2 lower fractions.2
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catalysts. Pingale et al.44 showed that chlorides of different

metals such as zinc, lithium, didymium, magnesium, and iron
can catalyze the glycolytic depolymerization of PET bottle
waste with EG to obtain the pure monomer BHET with an
equivalent performance as the acetate salts.
2.3.2.2. Nontoxic Metal Salts. Even though heavy metal salts
are the common catalysts used in the glycolysis of PET wastes
with high conversion of PET and selectivity of BHET, there are
some drawbacks, such as severe reaction conditions, slow
reaction rates, and difficult recycling of the catalyst. Many
sincere efforts have been put forward by researchers to find an
efficient and green catalyst for the glycolytic depolymerization
of PET. In this regard, glycolysis of PET bottle waste with EG
was conducted using ecofriendly salts such as sodium carbonate
and sodium bicarbonate as catalysts to substitute for the
conventional zinc acetate catalyst.45 It was observed that under
identical conditions of catalyst concentration and PET:EG
ratio, the yield of BHET (61%) was nearly the same as that
obtained earlier by conventional catalyst (63%). Lopez-Fonseca
et al.46 also examined several ecofriendly simple salts, namely,
sodium carbonate, sodium bicarbonate, sodium sulfate, and
potassium sulfate, for the glycolytic degradation of PET.
Figure 2. Three different stages of PET depolymerization with EG.33
Among these salts sodium carbonate and sodium bicarbonate
depolymerized PET wastes almost as efficiently as zinc acetate.
2.3.2.3. Recoverable Catalysts. There have been numerous
2.3.1. Kinetics of PET Glycolysis. The glycolysis of PET has studies to develop catalysts for the chemical recycling of PET
been found to depend on the reaction parameters such as via glycolysis. However, only a few have attempted to recover
glycolysis time, glycolysis temperature, catalyst concentration, and reuse the catalysts. Wang et al.47 used urea as a green, low-
and glycol concentration. The strength of the reaction priced, efficient, and reusable catalyst for the glycolysis of PET
parameters over the course of the glycolysis reaction of PET wastes under mild conditions. Experimental and DFT studies
follows the order catalyst concentration > glycolysis temper- show that the hydrogen bonds (H-bonds) formed between
ature > glycolysis time.34−36 Glycolysis products with ethylene glycol and urea play a key role in enhancing the
significantly different functionalities and molecular weights glycolysis of PET.
could be prepared by changing the glycol concentration, Ionic liquids, being considered green solvents, have the
keeping the other parameters constant.37,38 Studies on the potential to substitute for traditional organic solvents in the
glycolysis of PET waste powder with EG under variable degradation of PET. The degradation of PET using ionic
external pressure, temperature, particle size,39 reaction time,39 liquids proceeds easily under relatively lower pressure and
and catalyst type/concentration40 showed that the reaction is of temperature, with no emission of toxic substances. Another
first order. The rate of the glycolysis reaction of PET was found attractive feature of this reaction is that the products are easily
to be proportional to the polymer surface area. Thus, by separated from the ionic liquid by the addition of water
reducing the size of the PET waste to small particles by followed by filtration, enabling the ionic liquid to be reused.
grinding or cutting, the glycolysis rate can be substantially The purification of the glycolysis products catalyzed by ionic
increased. Optimum particle size was found to be 127.5 μm. liquids was simpler than that catalyzed by traditional
Pardal and Tersac41 made an attempt to study the isothermal compounds, such as metal acetates.
kinetics of PET glycolysis by DEG, dipropylene glycol (DPG), Wang et al.48 investigated the potential of acidic, basic, and
glycerol, and mixtures of these glycols by two experimental neutral ionic liquids as novel catalysts in depolymerizing PET
procedures: uncatalyzed at 220 °C and catalyzed at 190 °C wastes using EG. Basic ionic liquids and neutral ionic liquids
using titanium(IV) n-butoxide (TBT) as catalyst. The effect of accelerated the glycolysis process, but the synthesis of basic
the TBT catalyst on the chemical reactivity was far more ionic liquids was quite complex and expensive, whereas the
intense for DPG than for DEG. A synergic effect was found acidic ionic liquids were found to be unstable at temperatures
with the mixture of DPG and glycerol in which the PET is above 180 °C. Therefore, neutral ionic liquids having good
digested more quickly than in pure DPG or glycerol in the catalytic effects and appropriate price were preferred. Even
presence of 0.5/100 w/w TBT catalyst. They also studied the though a better yield of about 98.7% was obtained with 1-butyl-
influence of various parameters such as temperature (from 190 3-methylimidazolium bromide as catalyst, 1-butyl-3-methylimi-
to 220 °C), catalysis, and PET morphology on the kinetics of dazolium chloride ([bmim]Cl) was chosen as the ideal catalyst
PET glycolysis by DEG.42 due to its high stability.49 No chemical reaction occurs between
2.3.2. Catalysts of Glycolysis. 2.3.2.1. Heavy Metal Salts. PET and the ionic liquid, but the process proceeds through the
Heavy metal acetates are the conventional transesterification breakage of the chemical bonds. The kinetic study indicates
catalysts used for the glycolysis of PET. Troev et al.43 that the degradation of PET in the neutral ionic liquid, 1-butyl-
introduced titanium(IV) phosphate as a novel catalyst for the 3-methylimidazolium chloride, is a first-order reaction with an
glycolysis of PET. The depolymerization of PET fibers activation energy of about 232.79 kJ mol−1.
proceeds at a faster rate in the presence of this catalyst in Yue et al.50 conducted the glycolysis of PET using several
comparison with traditional heavy metal acetate salts as basic ionic liquids as catalysts. Among different basic ionic
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liquids, 1-butyl-3-methylimidazolium hydroxyl exhibited higher zeolite is more active because it has high Si/Al ratios and large
catalytic activity with 100% conversion of PET. Yue et al.51 mesopore surface for solubilization of PET.
showed that the Lewis acidic ionic liquid ([bmim]ZnCl3) Bartolome et al.55 used superparamagnetic γ-Fe2O3 nano-
possesses high catalytic activity as compared to the neutral ionic particles having an average size of 10.5 ± 1.4 nm and surface
liquid ([bmim]Cl) in the glycolysis of PET. Significantly, the area reaching 147 m2 g−1 as a reusable catalyst for PET
conversion of PET was achieved at 100% with low catalyst glycolysis. After glycolysis, γ-Fe2O3 nanoparticles were easily
([bmim]ZnCl3) loading (0.16 wt %). The mechanism of the recovered by simple magnetic decantation. The glycolysis
glycolysis of PET catalyzed by [bmim]ZnCl3 (Figure 3) reaction carried out at 300 °C and 1.1 MPa pressure with a 0.05
suggests that Lewis acidity of the ionic liquid affected its catalyst/PET weight ratio required only an hour to achieve
catalytic activity in the PET glycolysis. BHET yield >90%. The high catalytic activity of the
superparamagnetic γ-Fe2O3 nanoparticles may be attributed
to its ability to catalyze the glycolysis through redox reactions,
high surface area rendering more active sites, thermal stability,
and good crystallinity.
Metal oxide-doped silica nanoparticles were recently used as
a recoverable transesterification catalyst for the glycolysis of
PET to obtain BHET at 300 °C and 1.1 MPa with an EG:PET
molar ratio of 11 and a PET:catalyst weight ratio of 0.01. The
oxides of zinc, manganese, and cerium were deposited on silica
nanospheres with diameters ranging from 60 to 750 nm
employing ultrasonic irradiation.56,57 The reaction reached
equilibrium after 80 min, and the highest BHET yield reached
>90% for a manganese oxide-doped silica nanoparticle based
system. The distribution of the catalysts on the support
becomes better as the size of the support becomes smaller. This
could be due to the higher chances of contact between the
catalyst and the support because of the higher surface area to
volume ratio for smaller supports. The better distribution of the
catalysts resulted in higher catalytic activity.
The optimum glycolysis conditions of PET with EG in the
presence of various catalysts under ambient pressure conditions
are summarized in Table 1.

Table 1. Optimum Conditions of PET Glycolysis Reactions

Figure 3. Mechanism of glycolysis of PET catalyzed by Lewis acidic with EG in the Presence of Various Catalysts
ionic liquid, ([bmim]ZnCl3).51
PET:EG reflux reaction yield of
ratio time temp BHET
(w/w) (h) (°C) catalyst (w/w of PET) (%) ref
Zhu et al.52 synthesized three series of recyclable solid acid 1:5 3 196 1% zinc acetate 85.6 33
catalysts including sulfated oxides of zinc/titanium (SO42−/
ZnO, SO42−/TiO2), and their binary oxide (SO42−/ZnO− 1:6 8 196 0.5% zinc acetate 63 45
TiO2) by precipitation/coprecipitation method. The glycolysis 0.5% sodium carbonate 61
of PET into the monomer BHET was conducted over these 0.5% sodium 61
solid catalysts. Relationships between the catalyst’s textural bicarbonate
properties, the surface acidity, and the catalytic activity have
been investigated. SO42−/ZnO−TiO2 presented the highest 1:18 6 190 1% zinc acetate 87.0 58
catalytic activity due to its high surface area and predominance 1:14 8 197 0.5% zinc chloride 74.0 44
of Lewis acid sites. However, the corrosive nature of these 1:7.6 8 196 1% sodium carbonate 70.0 59
catalysts resulting in severe pollution cannot be ruled out. 1:4 3 180 10% urea 78.0 47
Fukushima et al.53 conducted organocatalytic glycolysis of 1:6 8 196 1% Y-zeolite/ 65.0 54
1% β-zeolite
PET with EG using 1.0 mol % of a commercially available
1:10 2 190 5% [bmim]OH 71.2 50
guanidine catalyst, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD).
1:4 8 180 80% [bmim]Cl 78.0 48
Their computational and experimental studies revealed that
1:11 2 190 1.25% [bmim]ZnCl3 84.9 51
TBD and EG activate PET through hydrogen bond formation/
0.96:5 3.5 190 0.7% TBD 78 53
activation to facilitate its glycolytic depolymerization reaction.
TBD exhibited catalytic efficiency comparable to that of the
common metal acetates/alkoxide catalysts used for the 2.3.3. Supercritical Glycolysis. Supercritical glycolysis has a
glycolytic depolymerization of PET. considerably shorter reaction time with high throughput due to
2.3.2.4. High Surface Area Catalysts. Natural and environ- the high solvent density, solubility, high kinetic energy, and
mentally safe large-pore aluminosilicates having considerably high diffusion and reaction rates of the supercritical ethylene
large void spaces (β-zeolite and Y-zeolite) were found to glycol. Imran et al.60 investigated the glycolysis of PET with EG
substitute effectively for the conventional heavy metal catalysts (Tc = 446.70 °C, Pc = 7.7 MPa) under supercritical (at 450 °C
for the glycolysis of PET bottle waste.54 Of the two zeolites, Y- and 15.3 MPa) and subcritical (at 350 °C and 2.49 MPa; and
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300 °C and 1.1 MPa) conditions with a PET:EG ratio of of chemically recycled PET products as raw materials for the
1:16.67. Supercritical fluids in a reaction can replace the preparation of a rather different class of polymers such as
catalysts, which are difficult to separate from the reaction unsaturated polyester resins, polyurethanes, epoxy resins, vinyl
products. Compared to the subcritical process, the BHET− esters, and alkyd resins. Major reported applications of the PET
dimer equilibrium was achieved much earlier for the super- glycolyzed products are briefly discussed below.
critical process: a maximum BHET yield of 93.5% was reached 2.3.5.1. Unsaturated Polyester Resins. The products of PET
in a mere 30 min, whereas the yield of the side products (DEG, glycolysis can be utilized as a lower cost source of raw material
TEG, BHET dimer, oligomers) was suppressed. for the production of unsaturated polyester (UP) resins. For
2.3.4. Microwave-Assisted Glycolysis. Microwave heating is the past two decades, this segment of recycling has seen vast
a unique and valuable tool in the hands of organic chemists to developments as awareness and concern for environmental
revolutionize organic syntheses. The use of microwave heating protection, preservation of petrochemical sources, and
offers many advantages over conventional heating such as conservation of energy have increased. Depending on the
instantaneous and rapid heating with high specificity without type of glycol used for depolymerization, and the nature of
contact with the material to be heated.45 Thus, extremely short dicarboxylic acid used for subsequent polycondensation, the
reaction time coupled with substantial energy conservation can polyester obtained may be saturated or unsaturated. PET-based
be attained. The increased efficiency of the microwave-assisted polyols and residual glycol are reacted with maleic anhydride at
glycolysis has been attributed to the high microwave absorption a fixed ratio of 1:1 for the hydroxyl to carboxyl groups to form
capacity of glycols, which results from their high loss factor. the polyester. The reaction was stopped when the acid value
PET could be glycolyzed in the presence of lower or higher reached 29−34 mg KOH/g. The esterification step may also
glycols; however, the reactivity of glycols was found to decrease include phthalic anhydride63/adipic acid.64 These were
with increase in the molecular weight.61 subsequently mixed with styrene (35−45 wt %) and cured
Microwave-assisted glycolytic recycling of PET bottle waste using different initiator/catalyst systems such as benzoyl
was conducted in ethylene glycol using zinc acetate, sodium peroxide (BPO)/amine,63 BPO/methyl ethyl ketone peroxide
carbonate, and bicarbonate as catalysts.45 The reaction time (MEKP),65 MEKP/cobalt 2-ethylhexanoate,66 and MEKP/
drastically reduced from 8 h to 35 min, and the yield of BHET cobalt octoate.67 In the preparation of UP resin, glycolysis
increased using microwaves as the heating source. The and polyesterification can proceed in the same reaction vessel
comparative yields of BHET using different heating sources by a two-stage reaction. A scheme for the synthesis of UP resin
are presented in Figure 4. from glycolyzed PET oligomers is shown in Figure 5.
UP resins obtained from recycled PET would be applicable
as matrices in fiber-reinforced plastics, sheet molding
compounds, bulk molding compounds, gel coats, polymer
concretes, and mortars as they offer versatility in processing and
enhanced properties.68 For UP resins, propylene glycol (PG) is
preferred over EG or DEG as a glycolytic agent. The reason is
that PET/PG-derived UP resins are compatible with styrene
and increase the activity of the anhydrides before starting the
reaction, whereas PET/EG- or PET/DEG-derived resin
glycolysis products are not fully compatible with styrene.69
PG is of low cost and possesses good hydrolytic resistance,
which imparts excellent physical and chemical properties to the
Figure 4. Comparative yield of BHET using different heating sources: product.
catalyst concentration, 0.5% w/w; PET:EG ratio, 1:6; time, 8 h for Suh et al.68 studied the influence of glycol compositions on
conventional heating (black bars) and 35 min for microwave heating the cure characteristics and the mechanical properties of the
(gray bars).45
cured UP resin based on glycolyzed PET using PG, DEG, and
their mixtures as depolymerization agents. The gelation time of
Benes et al.62 used castor oil (CO) as a renewable alternative UP was delayed with increasing DEG content. The tensile
to petrochemical-based reagents, for example, glycols for the modulus decreased, and the toughness of the UP resins was
chemical depolymerization of waste PET under microwave greatly enhanced on increasing the percentage of DEG. DEG
irradiation using zinc acetate as catalyst. The optimum also imparts good flexural properties to the resin, because its
decomposition of PET was observed at a relatively narrow long chains with ether linkage improve flexibility.70 The cured
temperature interval from 230 to 240 °C. A maximum number resin based on the glycolyzed PET has a tensile strength similar
of six repeating monomeric units of PET was found in the to that of the typical hand lay-up mat laminate polyester resin.
product, which confirmed practically the complete depolyme- Duque-Ingunza et al.66 conducted polyesterification of the
rization of PET chain and good reactivity of the acyl ester recovered monomer BHET- instead of PET-derived oligomers
hydroxyl groups of CO. The expected polyol products have the with maleic anhydride to obtain UP resin.
following formula: H−(E−T)x−TG, where H is hydrogen, E is Raheem and Uyigue71 converted PET wastes into a
the ethylene glycol unit (−O−CH 2 CH 2 −), T is the thermosetting polyester resin employing two different
terephthalic unit (−O−CO−C6H4−CO−), and TG is the chemolysis routes: glycolysis (using DEG) and hydrolysis−
triglyceride unit of CO. The index x indicates the number of glycolysis (using DEG/water) with potassium acetate as
repeating PET units. catalyst. They deduced 4 and 3 h, respectively, as the maximum
2.3.5. Applications of the PET Glycolyzed Products. reaction times for the glycolysis and hydrolysis−glycolysis of
Recently, growing interest has been observed in the utilization the PET waste.
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Figure 5. PET glycolysis and synthesis of UP resin from the glycolyzed PET oligomers.32

Tahvildari et al.72 prepared several unsaturated polyester affect the hardness of mixed resins. The impact strength and
resins through catalytic glycolysis of PET wastes with DEG and flexural strength increased as the amount of commercial resin
triethylene glycol (TEG) in the presence of zinc acetate as a increased. However, at higher loading of the commercial resin
catalyst. The products were then reacted with two different (>60 wt %), the improvement was leveled off. Abdelaal et al.29
anhydrides, namely, maleic anhydride (MA) and phthalic glycolyzed waste PET bottles with different glycols, namely,
anhydride (PA), along with EG and PG to obtain PET-based PG, DEG, TEG, and a mixture of DEG with PG or TEG in
UP resins. DEG and TEG imparted flexibility, whereas EG and equal amounts. Among all of the glycol-based matrices, PG-
PG added at the polycondensation step increased the spacing based UP showed a higher overall rate of cross-linking.
between the double bonds incorporated by MA and PA. Abdullah and Ahmad73 prepared a coconut fiber reinforced
Synthesis of the UP resin using the longer chain glycolyzed composite by blending the synthesized UP resin from waste
products led to higher molecular weight (Mn) and improved PET with 0.3 vol % of coconut fiber via in situ interactive
flexibility of the UP resin. polymerization. A phosphate type of flame retardant (Dricon)
Limpiti and Potiyaraj67 tried to improve the mechanical was also incorporated into the matrix. Coconut fiber before
properties of cured UP resin prepared from glycolyzed PET by incorporation was first treated with 5% (w/v) sodium
mixing it with a commercial UP resin at various ratios. The hydroxide followed by washing and drying. The coconut fiber
hardness and cross-link density of UP resin prepared from was then soaked in a 0.5% silane solution for an hour and finally
glycolyzed PET were slightly higher than those of the cured dried at room temperature. The treated fiber composite showed
commercial resin. The addition of commercial resin did not better mechanical and thermal properties as compared to the
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untreated fiber composite. The well-dispersed Dricon enhanced component. Polyester polyols were obtained through a
the flame retardancy of coconut fiber/polyester composites transesterification reaction between castor oil/jatropha oil and
without sacrificing their mechanical properties. the glycolyzed oligoesters of PET wastes with poly(propylene
2.3.5.2. Polyurethanes. The oligoesters derived from glycol) of molecular weight 2000. Their results clearly indicate
glycolyzed PET can be further reacted with aliphatic diacids that the coating properties were influenced by the amount of
to form polyester polyols used as a starting material in the PET used for glycolysis and the type of oil used for
polyurethane industry for applications such as adhesives, transesterification. Castor oil-based system formed a dense
elastomers, and foams. Glycolyzed PET oligoesters can also coating with an excellent corrosion resistance.77
be reacted directly as a polyol component with diisocyanate 2.3.5.5. Vinyl Esters. Atta et al.1,78 prepared epoxy resin by
compounds to build up a urethane group. the reaction of glycolyzed products of PET with epichlorohy-
Mercit and Akar74 synthesized new urethane oil varnishes drin. New diacrylate and dimethacrylate vinyl esters were then
from glycolyzed PET waste. The glycolyzed products of PET synthesized by the reaction of the terminal epoxy groups with
were transesterified with soybean oil and glycerin. The product acrylic and methacrylic acid. These vinyl esters were used as
of this step was reacted with toluene diisocyanate to yield cross-linking agents for preparing UP resin-based coating on
urethane varnish oil that was diluted with white spirit to about steel.
60% solid. Saravari et al.75 obtained urethane oils at hydroxyl to 2.3.5.6. Alkyd Resin. Atta et al.79 glycolyzed waste PET using
isocyanate ratios from 1:1 to 1:0.7, with and without methanol pentaerytheritol in the presence of manganese acetate as
acting as a blocking agent. A lower diisocyanate content and the catalyst and m-cresol as solvent at 220 °C to produce suitable
presence of a blocking agent resulted in higher viscosity, higher hydroxyl oligomers for alkyd resin application. Alkyd resins for
molecular weight, and shorter drying time. The properties of coating applications on steel were then prepared using phthalic
urethane oil in both liquid and dry film were comparable to anhydride, glycerin, PET-derived oligomers, sunflower oil/
those of commercial urethane oil. The films exhibited good linseed oil, and ethylene glycol in the presence of
hardness and adhesion and excellent water and acid resistance butylhydroxytin oxide as catalyst. The data reported indicated
but only fair alkali resistance. However, the prepared urethane that all cured alkyd resins based on sunflower oil have superior
oils showed lower flexibility and poor wear resistance compared adhesion and mechanical properties with steel. They showed
to those of the commercial urethane oil. excellent chemical resistance, too, as organic coatings among
Desai et al.31 made an attempt to synthesize polyester polyols other cured resins. Torlakoğlu and Gücļ ü80 prepared two short
using starch, PET waste, and vegetable oil based fatty acids. The oil alkyd resins of high acid values (30−40 mg KOH/g)
starch was glycolyzed with EG to synthesize a novel polyhydric
utilizing the glycolyzed products of waste PET. Phthalic
compound (glycol glycoside), and further depolymerization of
anhydride (PA), glycerin, and coconut oil fatty acids were
PET waste was conducted using this polyhydric compound.
mixed with glycolyzed products of waste PET to synthesize
Depolymerized oligomers were esterified with dehydrated
PET-based alkyd resins.
castor oil fatty acids to give polyester polyols. Polyurethane
2.3.5.7. Acrylic and Allylic Monomers. Aguilar et al.81
adhesives were synthesized using these polyols for joining SBR
utilized BHET obtained by glycolysis of postconsumer PET
substrates. The amount of PET content in polyurethane
determines the properties such as adhesion, flexibility, and with boiling EG for synthesizing an acrylic and two novel allylic
chemical resistance. Adhesion and flexibility improved as the bifunctional monomers, which find application as cross-linking
amount of PET increased in the polyol. Synthesized polyur- agents. The bifunctional acrylic monomer (bis(2-(acryloyloxy)-
ethanes were found to possess good resistance against cold and ethyl) terephthalate) was obtained from acryloyl chloride,
hot water but moderate resistance against acid and alkali. whereas the allylic monomers (2-(((allyloxy)carbonyl)oxy)
Chaudhary et al.61 prepared polyurethane foams utilizing the ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxy)-
PET-derived polyester polyols with aromatic diphenylmethane carbonyl)oxy)ethyl) terephthalate) were obtained from allyl-
diisocyanate. The compressive strength of the polyurethane chloroformate.
foams was found to be inversely proportional to the molecular Karayannidis et al.70 methacrylated the oligoesters obtained
weight of the glycolyzed polyol used for its preparation. on glycolysis of PET waste flakes to synthesize a value-added
2.3.5.3. Polymer Concrete. Tawfik and Eskander64 synthe- monomer for preparing a UV-curable acrylic copolymer with
sized a fast-curing polymer concrete (PC) by mixing styrenated styrene. Thermal polymerization of this monomer was carried
polyester and marble wastes as fillers. UP was prepared from out at 80 °C in the presence of BPO as initiator. Nanoparticles
the reaction of glycolyzed PET oligomers with maleic of silicon dioxide were dispersed into the copolymer matrix as
anhydride and adipic acid. The UP was then mixed with the reinforcing agents, but their incorporation resulted in slightly
styrene monomers at a ratio of 60:40% by weight to obtain the lower Young’s modulus, perhaps due to the presence of
styrenated polyester used for the synthesis of the PC. The nanoparticle agglomerates and their inefficient dispersion into
synthesized PC exhibited acceptable physical properties, good the copolymer matrix.
mechanical integrity, enhanced chemical resistance, good heat, 2.3.5.8. Textile Dyes. Shukla et al.82 converted PET fiber
and flame resistance. Kim et al.65 reacted PET waste flakes with waste into useful products, such as hydrophobic disperse dyes
EG, DEG, and 2-methyl-1,3-propanediol mixtures at a PET/ for synthetic textiles. For this, the glycolyzed product (BHET)
glycol weight ratio of 250:142. The obtained PET oligomers was converted partly to p-amino benzoic ester and partly to a
were then reacted with maleic anhydride and dicyclopentadiene benzothiazole derivative, the latter when coupled with N,N-
to synthesize UP resin that could be used for the synthesis of diethylaniline produced a bright yellow disperse dye. Similarly,
polymer concrete upon mixing with styrene. coupling of p-amino benzoic ester with N,N-diethylaniline
2.3.5.4. Epoxy Resin. Atta et al.76 formulated two-pack epoxy yielded an orange-colored disperse dye. These dyes when
coating systems using saturated polyester polyols as base applied onto polyester fabric by conventional method gave
component and melamine formaldehyde resins as hardener promising results.
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2.3.5.9. Plasticizers. Thavornsetawat et al.83 directly obtain bis(2-hydroxyethylene) terephthalamide (BHETA) with
esterified the TPA obtained from glycolysis of PET with 2- 91% yield. The catalytic activities of glacial acetic acid, sodium
ethyl-1-hexanol at 160 °C for 6 h to yield a clear, slightly acetate, and potassium sulfate were compared. Tawfik and
yellowish liquid plasticizer, dioctyl terephthalate (DOTP), with Eskander92 investigated the catalytic activity of dibutyl tin oxide
a specific gravity of 0.936, a refractive index of 1.472, and an for the aminolytic degradation of PET waste with EA at 190 °C
acid value of 0.0044 mg KOH/g. Their investigations on the and under atmospheric pressure. The next year, Tawfik et al.93
possibility of using DOTP as a plasticizer in PVC found that came up with an environmentally friendly degradation route for
the tensile strength of DOTP-plasticized PVC was comparable aminolyzing PET flakes with EA utilizing sunlight as a
to that of DOP-plasticized PVC, but the DOTP-plasticized renewable source of energy. The catalysts used were dibutyl
PVC possessed a higher modulus than DOP-plasticized PVC. tin oxide, sodium acetate, and cetyltrimethylammonium
On the other hand, Dutt and Soni84 obtained a polyester bromide. The complete degradation of PET was achieved
polymeric plasticizer with an average molecular weight in the after 60 days of exposure to sunlight.
range of 450−900 g/mol on depolymerizing PET waste directly Fukushima et al.94 have reported an organocatalyzed
with 2-ethyl-1-hexanol. Nitrile rubber and nitrile−PVC blend aminolytic depolymerization of waste PET using 1,5,7-
sheets were prepared using the synthesized polymeric triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst (Figure 6),
plasticizer, and a comparative study was conducted with the
conventionally used dioctyl phthalate plasticizer. The sheets
prepared by incorporating the synthesized polymeric plasticizer
provided excellent tensile properties and aging resistance for
high-performance applications as compared to sheets prepared
using dioctyl phthalate.
2.4. Aminolysis. Aminolysis of PET waste has been scarcely
studied so far. There are no known papers concerning the
utilization of this process on a commercial scale for PET Figure 6. Organocatalysis of the aminolytic depolymerization of waste
recycling. Chemical depolymerization of postconsumer PET PET using TBD as catalyst.94
through an aminolytic chain cleavage yields corresponding
diamides of terephthalic acid (TPA) and ethylene glycol. The
reaction is usually carried out using primary amine aqueous producing a broad range of crystalline terephthalamides having
solutions such as methylamine, ethylamine, ethanolamine, and great potential as building blocks for high-performance
anhydrous n-butylamine in the temperature range of 20−100 applications with attractive thermal and mechanical properties.
°C.2 Their computational study established insight into self-
2.4.1. Kinetics of Aminolysis. Goje et al. have made catalyzed and organocatalyzed aminolysis of terephthalic esters,
significant contributions in the studies on the kinetics and suggesting that the bifunctionality of TBD is capable of
thermodynamics of aminolytic recycling of waste PET. PET activating the carbonyl group of PET. This differentiates TBD
waste powder on reaction with boiling EG at 470 K followed by from other organic bases.
treatment with hydrazine monohydrate (HMH) and hydroxyl- The surface morphology of the aminolyzed PET waste flakes
amine hydrochloride gives terephthalic dihydrazide (TDH)4,85 with HMH95 and aqueous methyl amine96 at different intervals
and terephthalohydroxamic acid,4,86 respectively. A one-step of time during the aminolysis reaction, both in the presence and
aminolysis of PET waste with HMH at 339 K also recovered in the absence of catalyst, was investigated. PET degraded more
TDH with significant yields.87 Depolymerization of PET waste quickly in the presence of catalyst; the long polymeric chains in
was found to be proportional to the reaction time (3 h) and the semicrystalline PET were reduced to monodisperse rods
inversely proportional to the particle size of PET waste before full degradation into the end products, and the fissures
(optimal reactant size ∼ 127.5 μm). The activation energy (Ea) on the surface of PET were found to deepen with time. The
was recorded as 62.4 kJ/mol, and the Arrhenius constant (A) amorphous portion was removed at a faster rate, and there was
was recorded as 12,173 L mol−1 min−1. a marked increase in the crystallinity of the residue toward the
2.4.2. Uncatalyzed Aminolysis. Soni et al. have contributed completion of the reaction. SEM photographs of PET flakes
much in the area of aminolysis of PET and developed an subjected to aminolytic degradation with aqueous methyl amine
ecological and economical methodology for the recycling of in the presence of quaternary ammonium salt as catalyst are
PET waste at ambient temperature and pressure. They studied given in Figure 7.
the degradation reaction of PET waste with various amines. 2.4.4. Microwave-Assisted Aminolysis. In the field of PET
namely. methylamine, ethylamine, and n-butyl amine. at aminolysis also, microwave irradiation offers an economical and
ambient temperature and pressure so as to obtain N,N′- convenient technology for producing degradation products
dialkylterephthalamide.88 The complete degradation of PET with little compromise in the yield in comparison to the
waste was achieved after 45 days in the case of a 1:10 weight/ conventional heating method. In this regard, Pingale and
volume ratio of PET to amine, but with a 1:2 weight/volume Shukla97 tried to depolymerize PET with excess EA to
ratio of PET to HMH, the degradation time was considerably synthesize BHETA under microwave irradiation in the presence
reduced to 24 h at ambient conditions.89 of cheap and nontoxic catalysts such as sodium acetate, sodium
Hoang and Dang90 obtained bis(2-aminoethyl) terephthala- bicarbonate, and sodium sulfate. The use of microwave energy
mide (BAET, or trimer) and α,ω-aminoligo(ethylene tereph- gave >90% yield of BHETA in a considerably shortened
thalamide) (AOET, or oligomers) through the reaction of PET reaction time of 4 min.
waste with an excess amount of ethylenediamine (EDA). Parab et al.98 carried out aminolytic depolymerization of PET
2.4.3. Catalyzed Aminolysis. Shukla and Harad91 amino- bottle waste with HMH under microwave irradiation using
lyzed PET fiber waste with excess ethanolamine (EA) so as to sodium acetate and sodium sulfate as catalysts. TDH with a
14192 dx.doi.org/10.1021/ie501995m | Ind. Eng. Chem. Res. 2014, 53, 14185−14198
Industrial & Engineering Chemistry Research Review

aminolyzed PET bottle waste flakes using 3-amino-1-propanol

under conventional (5 h) and microwave heating (7 min)
methods in the presence of sodium acetate/potassium sulfate as
catalyst. The product, bis(3-hydroxy propyl) terephthalamide,
was converted into bis-oxazin by cyclization with thionyl
chloride. Bis-oxazin is useful in polymer syntheses as a chain
extender or a cross-linking agent. Some reported aminolysis
reactions of PET are shown in Figure 9.
2.4.5. Applications of PET Aminolyzed Products.
2.4.5.1. Secondary Plasticizer in PVC Formulations. TDH
obtained on PET aminolysis with HMH finds application as a
secondary plasticizer in PVC compounding.89 The mechanical
properties PVC sheets were improved with the incorporation of
TDH as secondary plasticizer as compared with DOP
(conventional plasticizer) alone. The thermal stability of the
Figure 7. SEM photographs of (a) PET flakes before degradation, (b) PVC sheets also improved by 5−15%, and the stability
PET flakes after 7 days of degradation, (c) PET flakes after 21 days of increased as the dosage of TDH was increased in the
degradation, and (d) product obtained after degradation with aqueous formulations.
methyl amine in the presence of quaternary ammonium salt as 2.4.5.2. Acrylic Oligomer. Soni et al.102 synthesized a novel
catalyst.96 acrylic aromatic amide oligomer (N,N′-bis(2-propenamido)
benzene-1,4-dicarboxamide) with the reaction of acryloyl
yield of about 86% was obtained with a PET:HMH molar ratio chloride with TDH (depolymerized end product of PET
of 1:6 with a 1% w/w concentration of either of the two waste with HMH). This oligomer can be used as an adhesion
catalysts. The reaction time was reduced significantly from 4 h promoter on metal/glass surface along with other acrylate
to 10 min with microwave irradiation as heating source. The monomers in UV-curable formulations. The oligomer with
mechanism of aminolytic depolymerization of PET with HMH excellent hydrogen bonding capacity also finds application as an
in the presence of sodium salt as catalyst is given in Figure 8. alternative to urethane acrylates in radiation curable for-
mulations.
2.4.5.3. Antibacterial Drugs. Palekar et al.103 synthesized a
novel series of bis-substituted thiadiazoles and thiazolidinone
derivatives from TDH derived from PET. Bis-substituted
oxadiazoles and terephthalohydrazides were also synthesized
from TDH by cyclization with various aromatic acids and
aldehydes. All of the synthesized compounds were screened for
their antibacterial activities against various bacterium and
fungus strains. Most of these compounds showed antibacterial
activity comparable to those of commercial drugs.
2.4.5.4. Textile Dyes. Palekar et al.104 reacted TDH with 4-
aminobenzoic acid in the presence of polyphosphoric acid to
obtain a cyclic compound (4,4′-[5,5′-(1,4)-phenylene] bis-
(1,3,4-oxadiazole-5,2-diyl) dianiline) having a heterocyclic
moiety. Diazotization of this compound followed by coupling
with various N,N-disubstituted anilines resulted in a series of
novel disazo disperse dyes. Application of these dyes on
polyester and nylon fabrics using high-temperature dyeing
methods gave brilliant yellowish red hues with fair to moderate
light fastness and very good to excellent wash fastness and
sublimation fastness.
Figure 8. Mechanism of aminolytic depolymerization of PET with 2.4.5.5. Corrosion Inhibitors. The suitability of BHETA
HMH in the presence of sodium salt as catalyst.98 obtained from the aminolyzed PET waste was assessed for use
as an ingredient in the anticorrosive paint formulations for the
Parab and Shukla99 conducted microwave-assisted expedi- protection of steel structures.93 The synthesized BHETA
tious synthesis of medicinally important 2,5-disubstituted-1,3,4- possessed high hardness and stiffness, good resistance to
oxadiazoles possessing antibacterial properties in a single step weathering, creep strength, and high dimensional stability. The
from TDH in a very short reaction time of 20 min. Later they addition of organic BHETA into the paint formulation barely
explored the catalytic activity of heterogeneous and recyclable affected the physical and mechanical properties of the paint
β-zeolite acid catalyst and montmorillonite KSF clay catalyst in films. The platelet-shaped BHETA provided a reinforcing effect
the aminolytic depolymerization of PET waste with ethanol and reduced the water and gas permeability, imparting good
amine.100 The product, BHETA (85−88% yield), undergoes a anticorrosive properties and a special appearance to the paint
cyclization reaction on refluxing with polyphosphoric acid to film. The paint film with a pigment/binder ratio of 2.233
give the product, 2,2′-(1,4-phenylene)-bis(2-oxazoline) (PBO), containing 10% BHETA exhibited the best adherence to the
which finds applications in polymer synthesis as a chain steel substrate and corrosion resistance, and the results were
extender/chain coupling agent or a cross-linker. Shah et al.101 comparable to that of the high-built control.
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Industrial & Engineering Chemistry Research Review

Figure 9. Aminolysis reactions of PET.86−91

Abd El-Hameed105 evaluated the performance of BHETA higher than the Tg of the resin hardened with a conventional
prepared from waste PET as corrosion inhibitors for carbon cross-linker (TETA). The compression strength and thermal
steel (in HCl corrosive medium) by checking weight loss, open conductivity of the polyurethane foams made with the polyol
circuit potential, and potentiodynamic polarization. The component derived from PET were similar to those of the
polarization curves indicate that these compounds can act as foams made with a commercial polyol.
mixed-type initiators. The inhibition efficiency imparted by the 2.5. Ammonolysis. The ammonolysis of PET waste flakes
adsorbed BHETA on carbon steel increased with increase in is usually carried out with liquor ammonia either in the
the concentration of inhibitors and decreased with increase in presence or in the absence of catalyst at temperatures between
the temperature. The values of activation energy (Ea) and free 70 and 180 °C, under pressure.2 Usually, zinc acetate is used as
energy of adsorption (ΔGads) indicate adsorption by both the catalyst for the process. The main degradation product
physical and chemical process, whereas the decrease in obtained is 1,4-benzene dicarboxamide, commonly known as
inhibition efficiency with increase in temperature indicated terephthalamide. Ammonolysis has not been studied exten-
predominate physisorption of the inhibitor. The adsorption sively for PET chemical recycling.
followed a Langmuir adsorption isotherm without modifying 2.6. Hydrogenation. Most of the methods to chemically
the mechanism of corrosion process. depolymerize PET convert the polymer to the corresponding
2.4.5.6. Epoxy Emulsion Hardener and Polyol Component terephthalates. Ruthenium(II) PNN pincer complexes have
for Polyurethane Foams. Spychaj et al.106 aminolyzed PET recently been used as an effective catalyst for hydrogenative
waste flakes by diethylenetriamine, triethylenetetramine, and depolymerization of postconsumer PET bottles to furnish
their mixtures, as well as mixtures of triethylenetetramine value-added chemicals such as EG and 1,4-benzene dimethanol
(TETA) and p-phenylenediamine/triethanol amine (TEA) at (BDM) rather than a phthalate.107 To increase the PET
200−210 °C with a molar ratio of the recurrent polymer unit to solubility a 50:50 mixture of anisole and THF was used as the
amine of 1:2. The reaction products were tested as water-borne solvent, and the reaction system was exposed to 13.6 atm of
self-emulsifying epoxy resin hardener and a polyol component hydrogen gas for 48 h at 120 °C. Moreover, an equivalent of
for rigid polyurethane foams. The glass transition temperature the catalyst (1 mol %) was activated with 2 equiv of potassium
(Tg) of the resin hardened using PET recycled product was tert-butoxide (KOtBu) to ensure complete PET depolymeriza-
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Industrial & Engineering Chemistry Research Review

tion. The catalyst system was found to be tolerant to impurities MA = maleic anhydride
such as pigments and additives in postconsumer PET bottles. MEKP = methyl ethyl ketone peroxide
Typical ruthenium(II) PNN pincer complexes used for PA = phthalic anhydride
hydrogenation of PET are shown in Figure 10. PC = polymer concrete
PET = poly(ethylene terephthalate)
PG = propylene glycol
PVC = poly(vinyl chloride)
SBR = styrene butadiene rubber
TBD = 1,5,7-triazabicyclo[4.4.0]dec-5-ene
TBT = titanium(IV) n-butoxide
TDH = terephthalic dihydrazide
TEG = triethylene glycol
TETA = triethylenetetramine
TEA = triethanol amine
Figure 10. Ruthenium(II) PNN pincer complexes used for hydro-
genation of PET.107 TPA = terephthalic acid
UP = unsaturated polyester

3. CONCLUSION
The review of the reaction process, kinetics, and broad range of
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