ISSN: 2350-0328

International Journal of Advanced Research in Science,

Engineering and Technology
Vol. 5, Issue 3 , March 2018

Importance and Applications of Polyethylene

Terephthalate wastes in the
Coating Industry: A Review
Jomin Thomas

Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kerala

ABSTRACT: Plastics are found almost everywhere and are indispensable part of the modern era. In such a Polymer
centric era, the issues caused by its pollution are inevitable. Polyethylene Terephthalate, PET comprises of the most
commonly used polymer with its widespread application in the packaging industry for bottles. With growing
environmental awareness, its recycling has become a topic of mainstream research. This paper reviews all the major
research carried out in chemical recycling of PET waste across the globe which can be later used in the coating industry.
A meticulous study is done so as to describe, compare and discuss the various techniques like methanolysis, glycolysis,
and aminolysis etc. which were cured onto air drying systems with isocyanate and also for stoving application by using
amine derivatives as curing agent. The future prospective it provides, in reducing our carbon food print and stepping on
to closed loop sustainable economy are reviewed thoroughly.

KEYWORDS: Depolymerization, Hydrolysis, Glycolysis, Methanolysis, Aminolysis, Recycling, PU, PET

I. INTRODUCTION
Polyethylene Terephthalate is undoubtedly the most widespread polymer used in the world in terms of quantity. It is a
clear polyester which is both light, strong with enhanced performance and rigidity with relatively cheap cost. From its
evolution in the early 1970s, it has emerged into an indispensable part of modern life. It is a condensation polymer
synthesized from terephthalic acid (TPA) or dimethyl terephthalate (DMT) and ethylene glycol (EG) with removal of
water molecules and methanol respectively in presence of antimony catalysts [1]. Other than water bottles, few
technically demanding applications of Virgin PET includes paper coatings packaging for food and other items, films
for touch screens which are abrasion and chemical resistant. It is also used as a substrate in electronic applications such
as in spin coating and inkjet printing.
Currently, it also stays at the top of the list of polymers that are recycled. If disposed in landfills, if causes great
environment concerns as its non-biodegrade and takes up a lot of space. The major outlet for recovered PET is still the
fiber market. Thus, various techniques are used for its reuse, reclamation and recovery of the waste PET bottles.
Mechanical recycling involves process like flotation and solution process wherein the mixed polymers and
contaminants are separated by their density differences [1].

Fig 1: Scope of PET waste Recycling and Reuse

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 ISSN: 2350-0328
International Journal of Advanced Research in Science,
Engineering and Technology
Vol. 5, Issue 3 , March 2018

Chemical recycling are more common for PET recycling as it degrades the PET chain by chain scission process using
water, methanol, glycols, polyamines in hydrolysis, methanolysis, glycolysis and aminolysis respectively using catalysts
like zinc acetate and cobalt acetate etc. In addition to it, hydrolysis can be further divided into acidic, neutral or alkaline.
All these processes suffer the disadvantages of needing high temperature and pressure for processing. Even then, the
post-consumer PET bottles are recycled into carpet, textiles, sheets etc. Scope of using PET wastes for coatings are
increasing in demand and we already have companies using these for synthesizing hydroxyl terminated products of
depolymerization with acids forming polyester polyols for polyurethane foams [2]. This paper summarizes various
works done in PET waste usage in Coating industry in detail. A meticulous study on various research possibilities were
thus looked into.

II. CHEMICAL RECYCLING OF PET

Under chemical recycling, even when we have numerous techniques and new ones arising every year, there are four to
five notable ones among them.Glycolysis is the treatment of high molecular weight PET with an excess of Glycol in
presence of catalysts like zinc acetate at about 180 0C to produce hydroxyl-terminated short chain fragments. Here, the
ester linkages are broken by the glycols resulting in trans-esterification reaction forming oligomers or oligo ester diols
and polyol [1].

Fig 2: Glycolysis of PET waste (1)

Mainly, it yields bis (2-hydroxyethylene terephthalate) after the depolymerization which later finds it usage in curing
with isocyanate or amine systems. In Aminolysis or ammonolysis, polyamines or tri-ethanolamines are respectively
used forming bis (2-hydroxyethylene terephthalamide) which also finds similar use in coatings. By using methanol to
depolymerize PET waste under high pressure and temperature, it results in the formation of dimethylterephthlate DMT
which is in turn a monomer of PET manufacturing [2].

Fig 3: Aminolysis of PET waste (3)

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 ISSN: 2350-0328
International Journal of Advanced Research in Science,
Engineering and Technology
Vol. 5, Issue 3 , March 2018

This process gives in an opportunity for a closed coop recycling of PET but the process is cumbersome with a lot of unit
operations combined like filtration, crystallization and distillation with an added danger of using highly explosive
methanol in excess. Hydrolysis are of three main types, using water, alkaline solutions and acidic solutions in Neutral,
Alkaline and acidic hydrolysis respectively. In all these cases, the monomer Terephthalic acid is effectively recovered
whereas ethylene glycol is not. Also, we use strong inorganic acids like nitric acid, sulfuric acid etc. which has to
purified using the formation of sodium salt can thus needs highly expensive materials which are corrosion resistant.
Same issues demerit the alkaline hydrolysis as well. Also, Solvolysis wherein solvolytic chain cleavage into low
molecular products are also explored in detail. In generic words, it can be stated that PET waste can be depolymerized
by using any of these methods at high pressures like 20-25 kg/cm3 and temperature ranging from 180-2300C using zinc
acetate , manganese acetate etc. [2]. We will look onto to the various literature works carried out in this field which goes
into practical application.

III. CURRENT DEVELOPMENTS

Various process of chemical recycling has been instated in the coating industry over the years which has found its
benefits and are being applied onto plant scale. Out of these, aminolysis and glycolysis are the most successful ones till
date.
Corrosion resistance was a major factor that was improved with the aminolysis process [3]. Using 3-amino- 1 propanol,
disposed Pet bottles were reacted in presence of catalyst like sodium acetate to facilitate aminolysis process where in
they were depolymerized into bis-(3-hydroxy propyl) terephthalamide (BHPTA) [3]. They were purified in the later
stage with e-caprolactone to get long chain saturated polyol. In this process dibutyl-tin-dilaurate (DBTDL) was used as
the catalyst. With the polyol derived as the base component and curing with isocyanate to form two pack polyurethane
coatings, performance properties observed were remarkable including mechanical and chemical resistance, enhanced
hardness and impact resistance. Most striking among them was the anti-corrosive performance as measured by the salt
spray test .Characterization of thermal properties using Differential scanning calorimetry (DSC) and Thermogravimetric
analysis (TGA) confirmed the findings. Not just amino derivatives, more modifications were seen to have done well
during and throughout the aminolysis process such as the formation of polyester amine resins. It includes the usage of
jatropha oil which was first treated with dicarboxylic acid like sebacic acid and thus, converted into its corresponding
fatty amide, i.e. hydroxyl ethyl jatropha oil fatty acid amide (HEJA) [4]. Later this was treated with the product so
obtained by the aminolysis of PET waste, bis(2-hydroxyethyl) terephthalamide (BHETA) and jatropha derivative
formed eventually curing it with isocyanates and finds use in coating applications. It had an added advantage of
balanced flexibility and hardness. It can be attributed to the structural difference in BHETA and HEJA. BHETA
increases hardness and retards degradation because of its aromatic structure. Whereas HEJA increases flexibility due to
its aliphatic nature. Adhesion is also seen to be increased greatly by this amine linkage resulting in better mechanical
properties and corrosion resistance [4].
Glycolysis is another well-established process in chemical recycling of PET. It has found its use in coating industry both
in stoving process for automotive finishes and also in air drying process with isocyanate curing. Automotive coatings
are ranked one among the topmost expensive coatings wherein the incorporation of a waste material would be perfect
example of a sustainable yet innovative solution. Stoving usually refers to the resin, usually the acrylic or polyester
polyols cured by amine derivatives and cooked in oven for specified time. Properties are bound to be immensely
heightened in such a process and are now commonly used in automotive coating applications. On carrying out the
glycolysis process by using propylene glycol of molecular weight 2000 and later reacting these depolymerized oligo
esters into trans-esterification with oils such as castor or jatropha, highly saturated hydroxyl functional polyester polyols
were obtained [5]. Melamine formaldehyde resins were used as the hardener component for two pack coating system
and stoving was carried out. Cured films, on testing, showed great improvement in hardness and chemical and corrosion
resistance. Glycolysis was also confirmed by FTIR characterizations [6].
This list of developing secondary value added resin like alkyds from glycolysis of PET waste us an area that has been
scrutinized well by many researchers over the century. It involves using Di-ethylene glycol with different molar ratios.
More meticulous work were done by synthesizing unsaturated polyester polyol from then by reacting them further with
maleic anhydride, phthalic anhydride and propylene glycol and even mixed with styrene before curing with amine
derivate in benzoyl peroxide systems in ambient condition itself, Comparable mechanical properties like tensile and
elongation at break were obtained with these cured films [6]. This in turn open up the scope for various modifications
that can be done to each sub group under glycolysis.

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 ISSN: 2350-0328
International Journal of Advanced Research in Science,
Engineering and Technology
Vol. 5, Issue 3 , March 2018

Fig 4: Alkyd resins from PET waste and Bio-derived fatty acids of oils (6)

On increasing PET percentage from 5 % to 10 %, MEK double rub resistance, solvent and chemical resistance and
corrosion resistance all were seen to increase. Also, lower corrosion current densities were clearly shown by the
potentiodyamic polarization study, i.e. reduced corrosion rate, there confirming dense coating formation with castor oil
and PET waste based system [6].
More generic form of glycolysis involved the isocyanate curing systems. Further starch derived glycol glycosides were
used for depolymerization and later the oligomers so formed were further reacted with Soya oil fatty acid SOFA to
obtain urethane coatings. These were used in industrial maintenance finishes and found to be giving tremendous
improvement in properties [7]. More versatile alkyds were also formed with the same process of glycolysis of PET
waste and bio resources such as linseed oil and sunflower oil fatty acids. From the so cured films, it had enhanced
properties in terms of adhesion, bending, impact and ductility coupled with good gloss and hardness which were seen to
be dependent on the degree of branching and the molecular weight of resin in the backbone of the polymer. Usage of
these polyol based on PET waste, i.e., BHET, better thermal stability and film properties were obtained. Initial
decomposition temperature of all these cured films mentioned above were seen to be more than 200 0C with the help of
TGA curve, thereby showing its wide acceptance in coating industry. Few researchers also evaluated the changes in
properties on using potassium acetate (1% w/w of the total raw materials) as catalyst and the ratios chosen to understand
trend in yield increment [8].

IV. CONCLUSION

By recycling PET waste, we are not only giving a partial solution to the solid waste problem but also giving a vast
scope for a new raw material to many industries including paint and coating Industry. Even now, fiber industry still
remains as the highest consumer of PET waste to be used polyester textiles. PET recycling reduces our dependence on
petroleum derived p products and energy. As it’s a replenishable resource, any step towards reducing our dependence on
such resources are worth looking into by dedicating our time, energy and money. We saw above the various techniques
used around the world by scientist to come out with value added product from PET waste. It has a huge scope of further

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 ISSN: 2350-0328
International Journal of Advanced Research in Science,
Engineering and Technology
Vol. 5, Issue 3 , March 2018

research and of implementation in companies. The processing constraints like the high temperature, high pressure and
explosive chemical usage needs to be accommodated by proper process control measures, advanced reactor designing
and taking up all necessary precautions. With the rate of advancements going on in the plastic industry right now, it’s
just a matter of time when at least one such process is carried out in huge scale effectively. Amongst the varied options,
BHET from Glycolysis seems to be better for air drying isocyanate curing systems and aminolysis could be preferred
for stoving applications with amine derivatives.
Many improvements are being ferociously carried out in the sustainability of materials used in the coatings industry.
This can be attributed to the growing environmental, safety and health concerns which is gaining interests as people get
more awareness about it by various programs put forward by governments of different countries. The concept of a
circular economy by stewarding better global resources throughout are just the part of a larger movement towards
recycling. More concentration is given by the researchers on a non-petroleum dependent, bio-resources like natural oils
etc. to add properties to the recycled PET and to come up with economical yet efficient high performance Industrial
coatings. Reclamation, Recycling and reuse of materials are undoubtedly the key to the progress of any country into a
profitable and sustainable economy.

REFERENCES
[1]. F.LaMantia, Handbook of plastics technology, Rapra Technology, Shropshine, united kingdom, 2002
[2]. V.Sinha, M.R Patel,J.V Patel, PET waste management by chemical recycling: a review, J.Polymer Environ, 18, (2010),8-25
[3]. Aarti P. More, Ravindra Abhimanyu Kute and Shashank T. Mhaske , Polyesteramide resin from PET waste and fatty amide, Pigment &
Resin Technology ,43 ,2014 · 285–292
[4]. P. U. Kapadi, S. R. Shukla1, S. T. Mhaske, A. More, M. N. Mali, Development of corrosion resistant polyurethane coating from aminolytic
depolymerization of pet bottle waste, J. Mater. Environ. Sci. 6 (1) (2015) 119-128
[5]. J Purohit, G Chawada, B Choubisa, M Patel, B Dholakiya, Polyester Polyol Derived From Waste Poly (Ethylene Terephthalate) for Coating
Application on Mild Steel , Chemical Sciences Journal, Vol. 2012: CSJ-76
[6]. N.E. Ikladious et al. Alkyd resins based on hyperbranced polyesters and PET waste for coating applications. Progress in Organic Coatings,
102 (2017) 217–224
[7]. G.P. Karayannidis et al. Alkyd resins derived from glycolised waste polyethylene terephthalate , European Polymer Journal , 41 (2005) 201–
210
[8]. Jigar V. Patel , Paresh K. Soni&Vijaykumar Sinha (2001): Two Pack Polyurethane Coatings from PET Waste and Biological Materials,
International Journal of Polymeric Materials and Polymeric Biomaterials, 49:2, 205-215

AUTHOR’S BIOGRAPHY

Jomin Thomas, M.Tech Polymer Technology from CUSAT,Kerala and Chemical Engineering
from Visvesvaraya National Institute of Technology, India. Received summer industrial training
from Astra Polymers Compounding limited in B.Tech and in Asian Paints Research and
Technology Centre, Mumbai. Got highly interested in polymers, coatings and materials science
field even more from then and looking for more opportunities for gaining more knowledge.
Closed loop polymer recycling is my dream and my passion both.

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