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

© 2014 American Chemical Society 14185 dx.doi.org/10.1021/ie501995m | Ind. Eng. Chem. Res. 2014, 53, 14185−14198
Industrial & Engineering Chemistry Research
byproducts are ethylene glycol and acetaldehyde. SSP is
frequently applied with high contaminant PET loads after
melt polymerization for enhancing the mechanical and
rheological properties of PET before injection blow molding
or extruding.
Chemical recycling, on the other hand, is an accepted PET
recycling method that follows the principles of “sustainable
development”.6 The fact that chemically recycled PET is well
suited for food-contact applications has increasingly attracted
researchers to the various chemolysis possibilities. Chemical
recycling methods are opening newer pathways for using PET
waste as a precursor in generating pure value-added products
for various industrial and commercial applications.7 However,
chemically recycled PET is more expensive than virgin PET
because of its raw material cost, capital investment, and scale of
operation. It has been calculated that for PET chemolysis
facilities to be economically viable, they require a minimum
throughput of 1.5 × 104 tonnes per annum. The specific
minimum size may vary with the technology used.
This review discusses recent research done in the area of
PET chemical recycling with emphasis on glycolytic and
aminolytic depolymerization of PET wastes. Applications of the
glycolysis and aminolysis products are also discussed.
2. CHEMICAL RECYCLING OF PET
PET, a thermoplastic polyester, is formed by the condensation
reaction between terephthalic acid (TPA) and ethylene glycol
(EG) or through a transesterification reaction between
dimethyl terephthalate (DMT) and EG. Chemical recycling
of PET totally depolymerizes it into monomers such as TPA,
DMT, bis(hydroxylethylene) terephthalate (BHET), and EG or
partially depolymerises it to oligomers or other chemical
substances. Thus, depolymerization is the reverse reaction of
the polymer formation. There are different depolymerization
routes such as methanolysis, glycolysis, hydrolysis, ammonol-
ysis, aminolysis, and hydrogenation depending on the chemical
agent used for PET chain scission.2 Figure 1 summarizes the
different routes for PET chemolysis, as well as the type of
products derived thereafter. Other condensation polymers such
Figure 1. Different methods of PET chemolysis and the value-added
products derived therefrom.2
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as polyamides, polyacetals, and polycarbonates, too, can be
subjected to chemical depolymerization reactions.2,8
2.1. Methanolysis. PET methanolysis is based on the
treatment of PET with methanol at relatively high temperatures
(180−280 °C) and pressures (20−40 atm), which leads to the
formation of DMT and EG as the main products, which are the
raw materials necessary for the production of this polymer.9−12
The reaction is catalyzed by typical transesterification catalysts
such as zinc acetate, magnesium acetate, cobalt acetate, and lead
dioxide; however, zinc acetate is the most commonly used
catalyst. The reaction products of methanolysis of postcon-
sumer PET comprise an extensive mixture of glycols, alcohols,
and phthalate derivatives in addition to DMT. The separation
and refinement of these make methanolysis a rather costly
process. The methanolysis process can tolerate a wide range of
contaminants; however, water does perturb the process and
poisons the catalyst to form various azeotropes. Currently the
cost of methanolysis-derived DMT from postconsumer PET
bottles is approximately double that of virgin DMT.13
2.2. Hydrolysis. Reaction of PET with water under neutral,
acidic, or basic conditions at high temperature and pressure
breaks the polyester chains into TPA and EG. Acid hydrolysis is
performed most frequently using concentrated sulfuric acid
(minimum 87 wt %), although the application of other
concentrated mineral acids (e.g., phosphoric or nitric acid) is
permissible.14,15 Alkaline hydrolysis is usually carried out with
the use of an aqueous solution of NaOH of a concentration of
4−20 wt %.16,17 Neutral hydrolysis is carried out with the use of
water or steam in the presence of alkali metal acetates as
transesterification catalysts.18−20 Low purity of TPA is the
major drawback of this method. Hydrolysis is comparatively
slow because water is a weak nucleophile.
2.3. Glycolysis. Glycolysis is the simplest and oldest
method of PET depolymerization. It is a commercial PET
recycling method practiced by renowned companies worldwide
such as DuPont, Goodyear, Shell Polyester, Zimmer, Eastman
Kodak, etc.3,21 The first patents on PET glycolysis were filed
more than 40 years ago.22−28 Glycolysis is considered to be a
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
with an ester bond in the chain and degrades the PET into
lower fractions.2
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Industrial & Engineering Chemistry Research
Figure 2. Three different stages of PET depolymerization with EG.33
2.3.1. Kinetics of PET Glycolysis. The glycolysis of PET has
been found to depend on the reaction parameters such as
glycolysis time, glycolysis temperature, catalyst concentration,
and glycol concentration. The strength of the reaction
parameters over the course of the glycolysis reaction of PET
follows the order catalyst concentration > glycolysis temper-
ature > glycolysis time.34−36 Glycolysis products with
significantly different functionalities and molecular weights
could be prepared by changing the glycol concentration,
keeping the other parameters constant.37,38 Studies on the
glycolysis of PET waste powder with EG under variable
external pressure, temperature, particle size,39 reaction time,39
and catalyst type/concentration40 showed that the reaction is of
first order. The rate of the glycolysis reaction of PET was found
to be proportional to the polymer surface area. Thus, by
reducing the size of the PET waste to small particles by
grinding or cutting, the glycolysis rate can be substantially
increased. Optimum particle size was found to be 127.5 μm.
Pardal and Tersac41 made an attempt to study the isothermal
kinetics of PET glycolysis by DEG, dipropylene glycol (DPG),
glycerol, and mixtures of these glycols by two experimental
procedures: uncatalyzed at 220 °C and catalyzed at 190 °C
using titanium(IV) n-butoxide (TBT) as catalyst. The effect of
the TBT catalyst on the chemical reactivity was far more
intense for DPG than for DEG. A synergic effect was found
with the mixture of DPG and glycerol in which the PET is
digested more quickly than in pure DPG or glycerol in the
presence of 0.5/100 w/w TBT catalyst. They also studied the
influence of various parameters such as temperature (from 190
to 220 °C), catalysis, and PET morphology on the kinetics of
PET glycolysis by DEG.42
2.3.2. Catalysts of Glycolysis. 2.3.2.1. Heavy Metal Salts.
Heavy metal acetates are the conventional transesterification
catalysts used for the glycolysis of PET. Troev et al.43
introduced titanium(IV) phosphate as a novel catalyst for the
glycolysis of PET. The depolymerization of PET fibers
proceeds at a faster rate in the presence of this catalyst in
comparison with traditional heavy metal acetate salts as
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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.
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
studies to develop catalysts for the chemical recycling of PET
via glycolysis. However, only a few have attempted to recover
and reuse the catalysts. Wang et al.47 used urea as a green, low-
priced, efficient, and reusable catalyst for the glycolysis of PET
wastes under mild conditions. Experimental and DFT studies
show that the hydrogen bonds (H-bonds) formed between
ethylene glycol and urea play a key role in enhancing the
glycolysis of PET.
Ionic liquids, being considered green solvents, have the
potential to substitute for traditional organic solvents in the
degradation of PET. The degradation of PET using ionic
liquids proceeds easily under relatively lower pressure and
temperature, with no emission of toxic substances. Another
attractive feature of this reaction is that the products are easily
separated from the ionic liquid by the addition of water
followed by filtration, enabling the ionic liquid to be reused.
The purification of the glycolysis products catalyzed by ionic
liquids was simpler than that catalyzed by traditional
compounds, such as metal acetates.
Wang et al.48 investigated the potential of acidic, basic, and
neutral ionic liquids as novel catalysts in depolymerizing PET
wastes using EG. Basic ionic liquids and neutral ionic liquids
accelerated the glycolysis process, but the synthesis of basic
ionic liquids was quite complex and expensive, whereas the
acidic ionic liquids were found to be unstable at temperatures
above 180 °C. Therefore, neutral ionic liquids having good
catalytic effects and appropriate price were preferred. Even
though a better yield of about 98.7% was obtained with 1-butyl-
3-methylimidazolium bromide as catalyst, 1-butyl-3-methylimi-
dazolium chloride ([bmim]Cl) was chosen as the ideal catalyst
due to its high stability.49 No chemical reaction occurs between
PET and the ionic liquid, but the process proceeds through the
breakage of the chemical bonds. The kinetic study indicates
that the degradation of PET in the neutral ionic liquid, 1-butyl-
3-methylimidazolium chloride, is a first-order reaction with an
activation energy of about 232.79 kJ mol−1.
Yue et al.50 conducted the glycolysis of PET using several
basic ionic liquids as catalysts. Among different basic ionic
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liquids, 1-butyl-3-methylimidazolium hydroxyl exhibited higher
catalytic activity with 100% conversion of PET. Yue et al.51
showed that the Lewis acidic ionic liquid ([bmim]ZnCl3)
possesses high catalytic activity as compared to the neutral ionic
liquid ([bmim]Cl) in the glycolysis of PET. Significantly, the
conversion of PET was achieved at 100% with low catalyst
([bmim]ZnCl3) loading (0.16 wt %). The mechanism of the
glycolysis of PET catalyzed by [bmim]ZnCl3 (Figure 3)
suggests that Lewis acidity of the ionic liquid affected its
catalytic activity in the PET glycolysis.
zeolite is more active because it has high Si/Al ratios and large
mesopore surface for solubilization of PET.
Bartolome et al.55 used superparamagnetic γ-Fe2O3 nano-
particles having an average size of 10.5 ± 1.4 nm and surface
area reaching 147 m2 g−1 as a reusable catalyst for PET
glycolysis. After glycolysis, γ-Fe2O3 nanoparticles were easily
recovered by simple magnetic decantation. The glycolysis
reaction carried out at 300 °C and 1.1 MPa pressure with a 0.05
catalyst/PET weight ratio required only an hour to achieve
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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Industrial & Engineering Chemistry Research
300 °C and 1.1 MPa) conditions with a PET:EG ratio of
1:16.67. Supercritical fluids in a reaction can replace the
catalysts, which are difficult to separate from the reaction
products. Compared to the subcritical process, the BHET−
dimer equilibrium was achieved much earlier for the super-
critical process: a maximum BHET yield of 93.5% was reached
in a mere 30 min, whereas the yield of the side products (DEG,
TEG, BHET dimer, oligomers) was suppressed.
2.3.4. Microwave-Assisted Glycolysis. Microwave heating is
a unique and valuable tool in the hands of organic chemists to
revolutionize organic syntheses. The use of microwave heating
offers many advantages over conventional heating such as
instantaneous and rapid heating with high specificity without
contact with the material to be heated.45 Thus, extremely short
reaction time coupled with substantial energy conservation can
be attained. The increased efficiency of the microwave-assisted
glycolysis has been attributed to the high microwave absorption
capacity of glycols, which results from their high loss factor.
PET could be glycolyzed in the presence of lower or higher
glycols; however, the reactivity of glycols was found to decrease
with increase in the molecular weight.61
Microwave-assisted glycolytic recycling of PET bottle waste
was conducted in ethylene glycol using zinc acetate, sodium
carbonate, and bicarbonate as catalysts.45 The reaction time
drastically reduced from 8 h to 35 min, and the yield of BHET
increased using microwaves as the heating source. The
comparative yields of BHET using different heating sources
are presented in Figure 4.
Figure 4. Comparative yield of BHET using different heating sources:
catalyst concentration, 0.5% w/w; PET:EG ratio, 1:6; time, 8 h for
conventional heating (black bars) and 35 min for microwave heating
(gray bars).45
Benes et al.62 used castor oil (CO) as a renewable alternative
to petrochemical-based reagents, for example, glycols for the
chemical depolymerization of waste PET under microwave
irradiation using zinc acetate as catalyst. The optimum
decomposition of PET was observed at a relatively narrow
temperature interval from 230 to 240 °C. A maximum number
of six repeating monomeric units of PET was found in the
product, which confirmed practically the complete depolyme-
rization of PET chain and good reactivity of the acyl ester
hydroxyl groups of CO. The expected polyol products have the
following formula: H−(E−T)x−TG, where H is hydrogen, E is
the ethylene glycol unit (−O−CH 2 CH 2 −), T is the
terephthalic unit (−O−CO−C6H4−CO−), and TG is the
triglyceride unit of CO. The index x indicates the number of
repeating PET units.
2.3.5. Applications of the PET Glycolyzed Products.
Recently, growing interest has been observed in the utilization
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of chemically recycled PET products as raw materials for the
preparation of a rather different class of polymers such as
unsaturated polyester resins, polyurethanes, epoxy resins, vinyl
esters, and alkyd resins. Major reported applications of the PET
glycolyzed products are briefly discussed below.
2.3.5.1. Unsaturated Polyester Resins. The products of PET
glycolysis can be utilized as a lower cost source of raw material
for the production of unsaturated polyester (UP) resins. For
the past two decades, this segment of recycling has seen vast
developments as awareness and concern for environmental
protection, preservation of petrochemical sources, and
conservation of energy have increased. Depending on the
type of glycol used for depolymerization, and the nature of
dicarboxylic acid used for subsequent polycondensation, the
polyester obtained may be saturated or unsaturated. PET-based
polyols and residual glycol are reacted with maleic anhydride at
a fixed ratio of 1:1 for the hydroxyl to carboxyl groups to form
the polyester. The reaction was stopped when the acid value
reached 29−34 mg KOH/g. The esterification step may also
include phthalic anhydride63/adipic acid.64 These were
subsequently mixed with styrene (35−45 wt %) and cured
using different initiator/catalyst systems such as benzoyl
peroxide (BPO)/amine,63 BPO/methyl ethyl ketone peroxide
(MEKP),65 MEKP/cobalt 2-ethylhexanoate,66 and MEKP/
cobalt octoate.67 In the preparation of UP resin, glycolysis
and polyesterification can proceed in the same reaction vessel
by a two-stage reaction. A scheme for the synthesis of UP resin
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
product.
Suh et al.68 studied the influence of glycol compositions on
the cure characteristics and the mechanical properties of the
cured UP resin based on glycolyzed PET using PG, DEG, and
their mixtures as depolymerization agents. The gelation time of
UP was delayed with increasing DEG content. The tensile
modulus decreased, and the toughness of the UP resins was
greatly enhanced on increasing the percentage of DEG. DEG
also imparts good flexural properties to the resin, because its
long chains with ether linkage improve flexibility.70 The cured
resin based on the glycolyzed PET has a tensile strength similar
to that of the typical hand lay-up mat laminate polyester resin.
Duque-Ingunza et al.66 conducted polyesterification of the
recovered monomer BHET- instead of PET-derived oligomers
with maleic anhydride to obtain UP resin.
Raheem and Uyigue71 converted PET wastes into a
thermosetting polyester resin employing two different
chemolysis routes: glycolysis (using DEG) and hydrolysis−
glycolysis (using DEG/water) with potassium acetate as
catalyst. They deduced 4 and 3 h, respectively, as the maximum
reaction times for the glycolysis and hydrolysis−glycolysis of
the PET waste.
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Industrial & Engineering Chemistry Research
Figure 5. PET glycolysis and synthesis of UP resin from the glycolyzed PET oligomers.32
Tahvildari et al.72 prepared several unsaturated polyester
resins through catalytic glycolysis of PET wastes with DEG and
triethylene glycol (TEG) in the presence of zinc acetate as a
catalyst. The products were then reacted with two different
anhydrides, namely, maleic anhydride (MA) and phthalic
anhydride (PA), along with EG and PG to obtain PET-based
UP resins. DEG and TEG imparted flexibility, whereas EG and
PG added at the polycondensation step increased the spacing
between the double bonds incorporated by MA and PA.
Synthesis of the UP resin using the longer chain glycolyzed
products led to higher molecular weight (Mn) and improved
flexibility of the UP resin.
Limpiti and Potiyaraj67 tried to improve the mechanical
properties of cured UP resin prepared from glycolyzed PET by
mixing it with a commercial UP resin at various ratios. The
hardness and cross-link density of UP resin prepared from
glycolyzed PET were slightly higher than those of the cured
commercial resin. The addition of commercial resin did not
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affect the hardness of mixed resins. The impact strength and
flexural strength increased as the amount of commercial resin
increased. However, at higher loading of the commercial resin
(>60 wt %), the improvement was leveled off. Abdelaal et al.29
glycolyzed waste PET bottles with different glycols, namely,
PG, DEG, TEG, and a mixture of DEG with PG or TEG in
equal amounts. Among all of the glycol-based matrices, PG-
based UP showed a higher overall rate of cross-linking.
Abdullah and Ahmad73 prepared a coconut fiber reinforced
composite by blending the synthesized UP resin from waste
PET with 0.3 vol % of coconut fiber via in situ interactive
polymerization. A phosphate type of flame retardant (Dricon)
was also incorporated into the matrix. Coconut fiber before
incorporation was first treated with 5% (w/v) sodium
hydroxide followed by washing and drying. The coconut fiber
was then soaked in a 0.5% silane solution for an hour and finally
dried at room temperature. The treated fiber composite showed
better mechanical and thermal properties as compared to the
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untreated fiber composite. The well-dispersed Dricon enhanced
the flame retardancy of coconut fiber/polyester composites
without sacrificing their mechanical properties.
2.3.5.2. Polyurethanes. The oligoesters derived from
glycolyzed PET can be further reacted with aliphatic diacids
to form polyester polyols used as a starting material in the
polyurethane industry for applications such as adhesives,
elastomers, and foams. Glycolyzed PET oligoesters can also
be reacted directly as a polyol component with diisocyanate
compounds to build up a urethane group.
Mercit and Akar74 synthesized new urethane oil varnishes
from glycolyzed PET waste. The glycolyzed products of PET
were transesterified with soybean oil and glycerin. The product
of this step was reacted with toluene diisocyanate to yield
urethane varnish oil that was diluted with white spirit to about
60% solid. Saravari et al.75 obtained urethane oils at hydroxyl to
isocyanate ratios from 1:1 to 1:0.7, with and without methanol
acting as a blocking agent. A lower diisocyanate content and the
presence of a blocking agent resulted in higher viscosity, higher
molecular weight, and shorter drying time. The properties of
urethane oil in both liquid and dry film were comparable to
those of commercial urethane oil. The films exhibited good
hardness and adhesion and excellent water and acid resistance
but only fair alkali resistance. However, the prepared urethane
oils showed lower flexibility and poor wear resistance compared
to those of the commercial urethane oil.
Desai et al.31 made an attempt to synthesize polyester polyols
using starch, PET waste, and vegetable oil based fatty acids. The
starch was glycolyzed with EG to synthesize a novel polyhydric
compound (glycol glycoside), and further depolymerization of
PET waste was conducted using this polyhydric compound.
Depolymerized oligomers were esterified with dehydrated
castor oil fatty acids to give polyester polyols. Polyurethane
adhesives were synthesized using these polyols for joining SBR
substrates. The amount of PET content in polyurethane
determines the properties such as adhesion, flexibility, and
chemical resistance. Adhesion and flexibility improved as the
amount of PET increased in the polyol. Synthesized polyur-
ethanes were found to possess good resistance against cold and
hot water but moderate resistance against acid and alkali.
Chaudhary et al.61 prepared polyurethane foams utilizing the
PET-derived polyester polyols with aromatic diphenylmethane
diisocyanate. The compressive strength of the polyurethane
foams was found to be inversely proportional to the molecular
weight of the glycolyzed polyol used for its preparation.
2.3.5.3. Polymer Concrete. Tawfik and Eskander64 synthe-
sized a fast-curing polymer concrete (PC) by mixing styrenated
polyester and marble wastes as fillers. UP was prepared from
the reaction of glycolyzed PET oligomers with maleic
anhydride and adipic acid. The UP was then mixed with the
styrene monomers at a ratio of 60:40% by weight to obtain the
styrenated polyester used for the synthesis of the PC. The
synthesized PC exhibited acceptable physical properties, good
mechanical integrity, enhanced chemical resistance, good heat,
and flame resistance. Kim et al.65 reacted PET waste flakes with
EG, DEG, and 2-methyl-1,3-propanediol mixtures at a PET/
glycol weight ratio of 250:142. The obtained PET oligomers
were then reacted with maleic anhydride and dicyclopentadiene
to synthesize UP resin that could be used for the synthesis of
polymer concrete upon mixing with styrene.
2.3.5.4. Epoxy Resin. Atta et al.76 formulated two-pack epoxy
coating systems using saturated polyester polyols as base
component and melamine formaldehyde resins as hardener
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component. Polyester polyols were obtained through a
transesterification reaction between castor oil/jatropha oil and
the glycolyzed oligoesters of PET wastes with poly(propylene
glycol) of molecular weight 2000. Their results clearly indicate
that the coating properties were influenced by the amount of
PET used for glycolysis and the type of oil used for
transesterification. Castor oil-based system formed a dense
coating with an excellent corrosion resistance.77
2.3.5.5. Vinyl Esters. Atta et al.1,78 prepared epoxy resin by
the reaction of glycolyzed products of PET with epichlorohy-
drin. New diacrylate and dimethacrylate vinyl esters were then
synthesized by the reaction of the terminal epoxy groups with
acrylic and methacrylic acid. These vinyl esters were used as
cross-linking agents for preparing UP resin-based coating on
steel.
2.3.5.6. Alkyd Resin. Atta et al.79 glycolyzed waste PET using
pentaerytheritol in the presence of manganese acetate as
catalyst and m-cresol as solvent at 220 °C to produce suitable
hydroxyl oligomers for alkyd resin application. Alkyd resins for
coating applications on steel were then prepared using phthalic
anhydride, glycerin, PET-derived oligomers, sunflower oil/
linseed oil, and ethylene glycol in the presence of
butylhydroxytin oxide as catalyst. The data reported indicated
that all cured alkyd resins based on sunflower oil have superior
adhesion and mechanical properties with steel. They showed
excellent chemical resistance, too, as organic coatings among
other cured resins. Torlakoğlu and Gücļ ü80 prepared two short
oil alkyd resins of high acid values (30−40 mg KOH/g)
utilizing the glycolyzed products of waste PET. Phthalic
anhydride (PA), glycerin, and coconut oil fatty acids were
mixed with glycolyzed products of waste PET to synthesize
PET-based alkyd resins.
2.3.5.7. Acrylic and Allylic Monomers. Aguilar et al.81
utilized BHET obtained by glycolysis of postconsumer PET
with boiling EG for synthesizing an acrylic and two novel allylic
bifunctional monomers, which find application as cross-linking
agents. The bifunctional acrylic monomer (bis(2-(acryloyloxy)-
ethyl) terephthalate) was obtained from acryloyl chloride,
whereas the allylic monomers (2-(((allyloxy)carbonyl)oxy)
ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxy)-
carbonyl)oxy)ethyl) terephthalate) were obtained from allyl-
chloroformate.
Karayannidis et al.70 methacrylated the oligoesters obtained
on glycolysis of PET waste flakes to synthesize a value-added
monomer for preparing a UV-curable acrylic copolymer with
styrene. Thermal polymerization of this monomer was carried
out at 80 °C in the presence of BPO as initiator. Nanoparticles
of silicon dioxide were dispersed into the copolymer matrix as
reinforcing agents, but their incorporation resulted in slightly
lower Young’s modulus, perhaps due to the presence of
nanoparticle agglomerates and their inefficient dispersion into
the copolymer matrix.
2.3.5.8. Textile Dyes. Shukla et al.82 converted PET fiber
waste into useful products, such as hydrophobic disperse dyes
for synthetic textiles. For this, the glycolyzed product (BHET)
was converted partly to p-amino benzoic ester and partly to a
benzothiazole derivative, the latter when coupled with N,N-
diethylaniline produced a bright yellow disperse dye. Similarly,
coupling of p-amino benzoic ester with N,N-diethylaniline
yielded an orange-colored disperse dye. These dyes when
applied onto polyester fabric by conventional method gave
promising results.
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Industrial & Engineering Chemistry Research
2.3.5.9. Plasticizers. Thavornsetawat et al.83 directly
esterified the TPA obtained from glycolysis of PET with 2-
ethyl-1-hexanol at 160 °C for 6 h to yield a clear, slightly
yellowish liquid plasticizer, dioctyl terephthalate (DOTP), with
a specific gravity of 0.936, a refractive index of 1.472, and an
acid value of 0.0044 mg KOH/g. Their investigations on the
possibility of using DOTP as a plasticizer in PVC found that
the tensile strength of DOTP-plasticized PVC was comparable
to that of DOP-plasticized PVC, but the DOTP-plasticized
PVC possessed a higher modulus than DOP-plasticized PVC.
On the other hand, Dutt and Soni84 obtained a polyester
polymeric plasticizer with an average molecular weight in the
range of 450−900 g/mol on depolymerizing PET waste directly
with 2-ethyl-1-hexanol. Nitrile rubber and nitrile−PVC blend
sheets were prepared using the synthesized polymeric
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
recycling. Chemical depolymerization of postconsumer PET
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
solutions such as methylamine, ethylamine, ethanolamine, and
anhydrous n-butylamine in the temperature range of 20−100
°C.2
2.4.1. Kinetics of Aminolysis. Goje et al. have made
significant contributions in the studies on the kinetics and
thermodynamics of aminolytic recycling of waste PET. PET
waste powder on reaction with boiling EG at 470 K followed by
treatment with hydrazine monohydrate (HMH) and hydroxyl-
amine hydrochloride gives terephthalic dihydrazide (TDH)4,85
and terephthalohydroxamic acid,4,86 respectively. A one-step
aminolysis of PET waste with HMH at 339 K also recovered
TDH with significant yields.87 Depolymerization of PET waste
was found to be proportional to the reaction time (3 h) and
inversely proportional to the particle size of PET waste
(optimal reactant size ∼ 127.5 μm). The activation energy (Ea)
was recorded as 62.4 kJ/mol, and the Arrhenius constant (A)
was recorded as 12,173 L mol−1 min−1.
2.4.2. Uncatalyzed Aminolysis. Soni et al. have contributed
much in the area of aminolysis of PET and developed an
ecological and economical methodology for the recycling of
PET waste at ambient temperature and pressure. They studied
the degradation reaction of PET waste with various amines.
namely. methylamine, ethylamine, and n-butyl amine. at
ambient temperature and pressure so as to obtain N,N′-
dialkylterephthalamide.88 The complete degradation of PET
waste was achieved after 45 days in the case of a 1:10 weight/
volume ratio of PET to amine, but with a 1:2 weight/volume
ratio of PET to HMH, the degradation time was considerably
reduced to 24 h at ambient conditions.89
Hoang and Dang90 obtained bis(2-aminoethyl) terephthala-
mide (BAET, or trimer) and α,ω-aminoligo(ethylene tereph-
thalamide) (AOET, or oligomers) through the reaction of PET
waste with an excess amount of ethylenediamine (EDA).
2.4.3. Catalyzed Aminolysis. Shukla and Harad91 amino-
lyzed PET fiber waste with excess ethanolamine (EA) so as to
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obtain bis(2-hydroxyethylene) terephthalamide (BHETA) with
91% yield. The catalytic activities of glacial acetic acid, sodium
acetate, and potassium sulfate were compared. Tawfik and
Eskander92 investigated the catalytic activity of dibutyl tin oxide
for the aminolytic degradation of PET waste with EA at 190 °C
and under atmospheric pressure. The next year, Tawfik et al.93
came up with an environmentally friendly degradation route for
aminolyzing PET flakes with EA utilizing sunlight as a
renewable source of energy. The catalysts used were dibutyl
tin oxide, sodium acetate, and cetyltrimethylammonium
bromide. The complete degradation of PET was achieved
after 60 days of exposure to sunlight.
Fukushima et al.94 have reported an organocatalyzed
aminolytic depolymerization of waste PET using 1,5,7-
triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst (Figure 6),
Figure 6. Organocatalysis of the aminolytic depolymerization of waste
PET using TBD as catalyst.94
producing a broad range of crystalline terephthalamides having
great potential as building blocks for high-performance
applications with attractive thermal and mechanical properties.
Their computational study established insight into self-
catalyzed and organocatalyzed aminolysis of terephthalic esters,
suggesting that the bifunctionality of TBD is capable of
activating the carbonyl group of PET. This differentiates TBD
from other organic bases.
The surface morphology of the aminolyzed PET waste flakes
with HMH95 and aqueous methyl amine96 at different intervals
of time during the aminolysis reaction, both in the presence and
in the absence of catalyst, was investigated. PET degraded more
quickly in the presence of catalyst; the long polymeric chains in
the semicrystalline PET were reduced to monodisperse rods
before full degradation into the end products, and the fissures
on the surface of PET were found to deepen with time. The
amorphous portion was removed at a faster rate, and there was
a marked increase in the crystallinity of the residue toward the
completion of the reaction. SEM photographs of PET flakes
subjected to aminolytic degradation with aqueous methyl amine
in the presence of quaternary ammonium salt as catalyst are
given in Figure 7.
2.4.4. Microwave-Assisted Aminolysis. In the field of PET
aminolysis also, microwave irradiation offers an economical and
convenient technology for producing degradation products
with little compromise in the yield in comparison to the
conventional heating method. In this regard, Pingale and
Shukla97 tried to depolymerize PET with excess EA to
synthesize BHETA under microwave irradiation in the presence
of cheap and nontoxic catalysts such as sodium acetate, sodium
bicarbonate, and sodium sulfate. The use of microwave energy
gave >90% yield of BHETA in a considerably shortened
reaction time of 4 min.
Parab et al.98 carried out aminolytic depolymerization of PET
bottle waste with HMH under microwave irradiation using
sodium acetate and sodium sulfate as catalysts. TDH with a
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Industrial & Engineering Chemistry Research
Figure 7. SEM photographs of (a) PET flakes before degradation, (b)
PET flakes after 7 days of degradation, (c) PET flakes after 21 days of
degradation, and (d) product obtained after degradation with aqueous
methyl amine in the presence of quaternary ammonium salt as
catalyst.96
yield of about 86% was obtained with a PET:HMH molar ratio
of 1:6 with a 1% w/w concentration of either of the two
catalysts. The reaction time was reduced significantly from 4 h
to 10 min with microwave irradiation as heating source. The
mechanism of aminolytic depolymerization of PET with HMH
in the presence of sodium salt as catalyst is given in Figure 8.
Figure 8. Mechanism of aminolytic depolymerization of PET with
HMH in the presence of sodium salt as catalyst.98
Parab and Shukla99 conducted microwave-assisted expedi-
tious synthesis of medicinally important 2,5-disubstituted-1,3,4-
oxadiazoles possessing antibacterial properties in a single step
from TDH in a very short reaction time of 20 min. Later they
explored the catalytic activity of heterogeneous and recyclable
β-zeolite acid catalyst and montmorillonite KSF clay catalyst in
the aminolytic depolymerization of PET waste with ethanol
amine.100 The product, BHETA (85−88% yield), undergoes a
cyclization reaction on refluxing with polyphosphoric acid to
give the product, 2,2′-(1,4-phenylene)-bis(2-oxazoline) (PBO),
which finds applications in polymer synthesis as a chain
extender/chain coupling agent or a cross-linker. Shah et al.101
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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
PVC sheets also improved by 5−15%, and the stability
increased as the dosage of TDH was increased in the
formulations.
2.4.5.2. Acrylic Oligomer. Soni et al.102 synthesized a novel
acrylic aromatic amide oligomer (N,N′-bis(2-propenamido)
benzene-1,4-dicarboxamide) with the reaction of acryloyl
chloride with TDH (depolymerized end product of PET
waste with HMH). This oligomer can be used as an adhesion
promoter on metal/glass surface along with other acrylate
monomers in UV-curable formulations. The oligomer with
excellent hydrogen bonding capacity also finds application as an
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.
2.4.5.5. Corrosion Inhibitors. The suitability of BHETA
obtained from the aminolyzed PET waste was assessed for use
as an ingredient in the anticorrosive paint formulations for the
protection of steel structures.93 The synthesized BHETA
possessed high hardness and stiffness, good resistance to
weathering, creep strength, and high dimensional stability. The
addition of organic BHETA into the paint formulation barely
affected the physical and mechanical properties of the paint
films. The platelet-shaped BHETA provided a reinforcing effect
and reduced the water and gas permeability, imparting good
anticorrosive properties and a special appearance to the paint
film. The paint film with a pigment/binder ratio of 2.233
containing 10% BHETA exhibited the best adherence to the
steel substrate and corrosion resistance, and the results were
comparable to that of the high-built control.
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Industrial & Engineering Chemistry Research
Figure 9. Aminolysis reactions of PET.86−91
Abd El-Hameed105 evaluated the performance of BHETA
prepared from waste PET as corrosion inhibitors for carbon
steel (in HCl corrosive medium) by checking weight loss, open
circuit potential, and potentiodynamic polarization. The
polarization curves indicate that these compounds can act as
mixed-type initiators. The inhibition efficiency imparted by the
adsorbed BHETA on carbon steel increased with increase in
the concentration of inhibitors and decreased with increase in
the temperature. The values of activation energy (Ea) and free
energy of adsorption (ΔGads) indicate adsorption by both
physical and chemical process, whereas the decrease in
inhibition efficiency with increase in temperature indicated
predominate physisorption of the inhibitor. The adsorption
followed a Langmuir adsorption isotherm without modifying
the mechanism of corrosion process.
2.4.5.6. Epoxy Emulsion Hardener and Polyol Component
for Polyurethane Foams. Spychaj et al.106 aminolyzed PET
waste flakes by diethylenetriamine, triethylenetetramine, and
their mixtures, as well as mixtures of triethylenetetramine
(TETA) and p-phenylenediamine/triethanol amine (TEA) at
200−210 °C with a molar ratio of the recurrent polymer unit to
amine of 1:2. The reaction products were tested as water-borne
self-emulsifying epoxy resin hardener and a polyol component
for rigid polyurethane foams. The glass transition temperature
(Tg) of the resin hardened using PET recycled product was
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higher than the Tg of the resin hardened with a conventional
cross-linker (TETA). The compression strength and thermal
conductivity of the polyurethane foams made with the polyol
component derived from PET were similar to those of the
foams made with a commercial polyol.
2.5. Ammonolysis. The ammonolysis of PET waste flakes
is usually carried out with liquor ammonia either in the
presence or in the absence of catalyst at temperatures between
70 and 180 °C, under pressure.2 Usually, zinc acetate is used as
the catalyst for the process. The main degradation product
obtained is 1,4-benzene dicarboxamide, commonly known as
terephthalamide. Ammonolysis has not been studied exten-
sively for PET chemical recycling.
2.6. Hydrogenation. Most of the methods to chemically
depolymerize PET convert the polymer to the corresponding
terephthalates. Ruthenium(II) PNN pincer complexes have
recently been used as an effective catalyst for hydrogenative
depolymerization of postconsumer PET bottles to furnish
value-added chemicals such as EG and 1,4-benzene dimethanol
(BDM) rather than a phthalate.107 To increase the PET
solubility a 50:50 mixture of anisole and THF was used as the
solvent, and the reaction system was exposed to 13.6 atm of
hydrogen gas for 48 h at 120 °C. Moreover, an equivalent of
the catalyst (1 mol %) was activated with 2 equiv of potassium
tert-butoxide (KOtBu) to ensure complete PET depolymeriza-
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Industrial & Engineering Chemistry Research
tion. The catalyst system was found to be tolerant to impurities
such as pigments and additives in postconsumer PET bottles.
Typical ruthenium(II) PNN pincer complexes used for
hydrogenation of PET are shown in Figure 10.
Figure 10. Ruthenium(II) PNN pincer complexes used for hydro-
genation of PET.107
3. CONCLUSION
The review of the reaction process, kinetics, and broad range of
catalysts employed in the glycolytic and aminolytic degradation
of postconsumer PET waste shows that the reaction parameters
such as reaction time, temperature, catalyst concentration, and
PET:reagent ratio have great significance on the efficient
depolymerization of PET. The strength of the reaction
parameters follows the order catalyst concentration > reaction
temperature > reaction time. The degradation products of PET
after glycolysis and aminolysis find potential application as
plasticizers, cross-linking agents, chain extenders, corrosion
inhibitors, and precursors in the generation of value-added
products such as UP resins, polyurethanes, textile dyes,
antibacterial drugs, epoxy resins, and vinyl esters. A microwave
heating method considerably reduces the reaction time from
several hours to a few minutes. The rapidly growing
nanotechnology provides efficient, ecofriendly, and reusable
catalysts to increase the yield of PET degradation products.
Thus chemica recycling of PET, besides providing a partial
solution to the solid waste problem, contributes to the
conservation of raw petrochemical products and energy.
■ AUTHOR INFORMATION
Corresponding Author
*(N.G.) E-mail: neenapattamana@gmail.com. Tel: +91-484-
2575723.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We are grateful to the University Grants Commission (UGC),
India, for the research fellowship.
■
ABBREVIATIONS
AIBN = azobis(isobutyronitrile)
BHET = bis (hydroxyethylene) terephthalate
BHETA = bis(2-hydroxyethylene) terephthalamide
BPO = benzoyl peroxide
CO = castor oil
DEG = diethylene glycol
DMT = dimethyl terephthalate
DOTP = dioctyl terephthalate
DPG = dipropylene glycol
EG = ethylene glycol
HMH = hydrazine monohydrate
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Review
MA = maleic anhydride
MEKP = methyl ethyl ketone peroxide
PA = phthalic anhydride
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
TPA = terephthalic acid
UP = unsaturated polyester
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