Polymer Degradation and Stability 91 (2006) 1850e1854

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Aminolysis of polyethylene terephthalate waste

S.R. Shukla*, Ajay M. Harad
Department of Fibres and Textile Processing Technology, Institute of Chemical Technology, University of Mumbai,
Natahlal Parikh Marg, Matunga, Mumbai 400 019, India
Received 16 September 2005; received in revised form 4 November 2005; accepted 9 November 2005
Available online 18 January 2006

Abstract

Polyethylene terephthalate in the form of waste fibres and disposable soft drink bottles was subjected to depolymerisation through aminolysis
using excess of ethanolamine in the presence of different simple chemicals, namely glacial acetic acid, sodium acetate and potassium sulphate,
as catalysts. The product bis(2-hydroxy ethylene)terephthalamide (BHETA) obtained was in its pure form with sufficiently high yields with all
the catalysts. The purified product was characterised by elemental analysis, melting point, IR spectroscopy, Nuclear Magnetic Resonance (NMR)
and Differential Scanning Calorimetry (DSC). The process of aminolysis reported here is economically viable since yields of BHETA are as high
as 91%, it has potential for further reactions to obtain useful products and the chemicals used as catalysts are common and cheaply available.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: PET waste; Recycling; Aminolysis; Catalysts; Bis(2-hydroxy ethylene)terephthalamide

1. Introduction consumer products, large amount of PET waste is also generated,

Difference between the natural and the synthetic polymers
lies primarily in the fact that the natural polymers are biode-
gradable, making them less durable, while the synthetics have
long life due to their almost complete resistance to biodegrada-
tion. This aspect has caused a major concern to the environmen-
talists from the point of view of polymer waste management.
Polyethylene Terephthalate (PET) is a semicrystalline ther-
moplastic polymer, which is used in the preparation of a variety
of products differing widely in their physical characteristics
and hence, the end uses. The varieties of prominence are fibres
and filaments, sheets and soft drink bottles.
The production of PET fibres started in the 1960s, and since
then the global demand has grown rapidly at the rate of 8.3%
per annum.
In the 1980s, PET began to be used popularly for the produc-
tion of disposable soft drink bottles and in 1987, more than 700
million pounds of PET were consumed in their production [1].
As a result of the diversity of its applications in a high volume of
* Corresponding author. Tel.: þ91 22 24145616; fax: þ91 22 24145614.
E-mail address: sanjeevrshukla@rediffmail.com (S.R. Shukla).
which includes polymer manufacturing waste as well as the
products after the end of their useful life. With the increasing
pressure of keeping the environment clean, recycling the PET
waste in an ecofriendly manner is the only solution.
The chemical recycling of PET has been the subject of keen
interest as a valuable feedstock for different chemical processes.
During chemical recycling, PET waste can be depolymerised
to base monomers or oligomers. With the use of solvents
for depolymerisation, generally called solvolysis of polymer,
methanolysis [2e4] and glycolysis [5,6] are the main possible
routes. Hydrolysis [7e11] of PET is also possible using water
under pressure.
Aminolysis is another method of chemical degradation of
PET, which has been little explored as compared to other tech-
niques. Depolymerisation of the PET waste using different
amines such as allylamine [12], morpholine and hydrazine
[13], and polyamines [14] has been investigated at the Polish
laboratories. PET waste when treated for 2 h with an excess
of allylamine at 170
C under pressure of 2 MPa gave the
product N, N#-bisallyl terephthalamide. This product with
high melting temperature 217e219
C may be considered as
a high-temperature solid cross linking agent for unsaturated
polyester compositions.

0141-3910/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2005.11.005
 S.R. Shukla, A.M. Harad / Polymer Degradation and Stability 91 (2006) 1850e1854 1851

The present communication deals with the use of ethanol-
amine for the aminolytic degradation of PET waste in the pres-
ence of different simple chemicals such as glacial acetic acid,
sodium acetate and potassium sulphate as catalysts. The
degradation product after purification was characterised by
a number of techniques. The mechanism of depolymerisation
has also been discussed.
2. Experimental
2.1. Materials
Polyester staple fibre waste was obtained from Reliance
Industries (Mumbai, India). The waste comprises short fibres
with 1.44 d and various lengths up to 5 mm. Clear polyester
soft drink bottles were procured from a local market. These
bottles were cut into small pieces of approximate size
5  5 mm after separating from the non-PET components
such as labels and caps.
2.2. Chemicals
Glacial acetic acid, sodium acetate, potassium sulphate and
sodium hydroxide were of Laboratory Reagent (LR) grade.
Ethanolamine and hydrochloric acid were of Guaranteed
Reagent (GR) grade. Lentol FBOL (ICI Uniqema, Mumbai,
India) was used as a non-ionic detergent for cleaning of poly-
ester waste materials.
2.3. Cleaning of polyester waste materials
Polyethylene terephthalate staple fibre waste was boiled
with a solution containing 2 g/L of Lentol FBOL for 1 h to
remove any surface finish and dirt present in the fibre mass.
It was then washed thoroughly with water and air dried.
The soft drink bottle pieces were washed with the detergent
solution, rinsed with hot water and air dried.
2.4. Aminolysis of polyester waste material
Ethanolamine was used for the aminolysis of PET waste
materials in the molar ratio 1:6 (PET:ethanolamine) under
reflux in the presence of different catalysts for time periods
varying up to 8 h. The catalysts, namely glacial acetic acid,
sodium acetate and potassium sulphate, were used in concen-
trations ranging between 0.3 and 1.5% by weight of polymer.
At the end of the reaction, distilled water was added in excess
to the reaction mixture with vigorous agitation to precipitate

Mechanism
O O

HO C C O CH2 CH2 O H
n
PET

H / Na, K
+ + + H2N CH2 CH2 OH
Ethanolamine (excess)

O OH / ONa, OK

HO C C O CH2 CH2 O H
n

H2N CH2 CH2 OH

O O H/ Na, K

HO C C O CH2 CH2 O
n
H N CH2 CH2 OH
H

O O

HO CH2 CH2 NH C C NH CH2 CH2 OH

BHETA

Fig. 1. Mechanism of depolymerisation of bis(2-hydroxy ethylene)terephthalamide.

1852 S.R. Shukla, A.M. Harad / Polymer Degradation and Stability 91 (2006) 1850e1854

out the product, bis(2-hydroxy ethylene)terephthalamide Table 2

(BHETA). The filtrate contained mainly unreacted ethanol- Effect of depolymerisation time on yield of BHETA
amine and little quantities of a few water soluble PET degra- Time (h) Yield % in the presence of
dation products. The precipitate obtained was filtered and Acetic acid Sodium acetate Potassium sulphate
dissolved in distilled water by boiling for about 30 min. White Fibre Bottle Fibre Bottle Fibre Bottle
crystalline powder of BHETA was obtained by first concentrat- waste waste waste waste waste waste
ing the filtrate by boiling and then chilling it. It was further 4 52.4 42.0 60.5 58.04 58.5 41.25
purified by recrystallisation in water. It was then dried in an 6 61.5 54.0 75.0 65.9 71.05 59.00
oven at 80
C and weighed for estimating the yield. Different 7 69.3 62.0 87.05 77.8 80.3 68.05
techniques of analysis were used for its characterisation. 8 76.4 68.2 91.1 83.2 87.2 74.05
9 63.3 60.05 83.3 75.2 75.2 65.3

2.5. Characterisation of the product

Melting point of the purified monomer, BHETA was deter-
mined in an open capillary. Elemental analysis was carried out
by using Heraus combustion apparatus. For Nuclear Magnetic
Resonance (NMR), the product after aminolysis reaction was
dissolved in solvent DMSO. Trimethyl Silane (TMS) was
used as an internal standard and the spectrograph was re-
corded on JEOL, FT-NMR (60 MHz). Differential Scanning
Calorimetry (DSC) was performed with DSC 2100 (TA in-
struments, USA), using 100e240
C scanning window under
nitrogen atmosphere. Infrared spectrum was recorded using
KBr disc technique on PerkineElmer IR spectrophotometer
(Buck Scientific, Model 500).
3. Results and discussion
As the PET polymer consumption is very high, the waste gen-
eration is also large due to its nonbiodegradability. PET as such
does not create a direct hazard to the environment, but its high
inertness to the atmospheric and biological agents is the cause
of environmental problems. Recycling is feasible when the pro-
cess and the product of recycling are ecofriendly and cost effec-
tive. In chemical recycling, PET is depolymerised with various
solvents to get different products such as terephthalic acid, their
ester and bis(2-hydroxy ethylene)terephthalate [6]. The tereph-
thalic acid as well as its ester is conventionally used during
repolymerisation. Bis(2-hydroxy ethylene)terephthalate shows
the potential for further chemical reactions, which has been
explored at our laboratory and a few useful textile wet process-
ing related chemicals have been synthesised. These findings
form part of further communication.
Table 1
Effect of different catalysts on yield of BHETA
Catalyst Yield % in the presence of
concentration
Acetic acid Sodium acetate Potassium sulphate
(w/w)
Fibre Bottle Fibre Bottle Fibre Bottle
waste waste waste waste waste waste
Zahn and Pfeifer [15] carried out aminolysis of PET with
solutions of hydrazine, benzyl amine, ethylene diamine,
hexamethylene diamine, piperidine and aniline. They obtained
different reaction products as the diamides of terephthalic acid,
which do not possess any potential for further chemical
reactions.
According to Popoola [16], the basicity of an amine relative
to water as well as its steric hindrance due to size decides the
rate of degradation of PET. During aminolysis of PET with
methylamine, the methyl terephthalamide is obtained, which
is not enough reactive for its recycling into any useful product
through further reactions.
The present work attempts aminolysis as a route to depoly-
merisation of PET using ethanolamine in the presence of dif-
ferent catalysts, which are essentially simple chemicals. The
reaction has been shown to yield bis(2-hydroxy ethylene)ter-
ephthalamide (BHETA).
In this reaction, ethanolamine has two nucleophilic centres.
Nitrogen is more electronegative than oxygen. The amine
group of ethanolamine attacks on the ester linkage of PET.
The catalysts used are glacial acetic acid, sodium acetate
and potassium sulphate, which form complexes with the car-
bonyl group [17,18] and increase its polarity. Amino group
of ethanolamine attacks PET and BHETA is obtained as shown
in Fig. 1.
Table 1 gives the results of the optimisation of concentra-
tion of different catalysts during depolymerisation of PET
wastes to obtain BHETA. For all the catalysts used namely,
acetic acid, sodium acetate and potassium sulphate the
maximum yield of BHETA was achieved at 1% (w/w)
concentration.
Similarly, Table 2 indicates that 8 h reaction was optimum
to produce the maximum amount of BHETA. Beyond 8 h and
1% (w/w) catalyst concentration the yield decreased, probably
due to further degradation of the amide formed.
Table 3
Elemental analysis of BHETA (formula, C12H16N2O4; molecular weight, 252;
melting point, 227
C)

0.3 41 40.7 48.0 58.8 40.5 44.05 Elemental Calculated Observed

0.5 61.5 52.7 77.0 63.5 61.8 59.0 analysis (%)
0.7 65.0 61.2 89.5 78.2 72.6 64.0 C 57.14 57.10
1.0 76.4 68.2 91.1 83.2 87.2 74.05 H 6.34 6.25
1.5 68.2 60.3 65.0 71.02 55.0 68.02 N 11.11 11.05
 S.R. Shukla, A.M. Harad / Polymer Degradation and Stability 91 (2006) 1850e1854 1853

Fig. 2. IR spectrum of bis(2-hydroxy ethylene)terephthalamide.

Ethanolamine used for the aminolysis of PET was in excess
(PET:ethanolamineT1:6) to that required by the stoichiometric
proportion for the reaction.
It may be observed from the data obtained that by using any
catalyst under optimised conditions, the yield of BHETA was
higher for PET fibre waste than for the bottle waste. Thus,
the maximum yields of BHETA under optimised conditions
were 91.1% from PET fibrous waste and 83.2% from bottle
waste. In the absence of any catalyst, the yield was only 52%.
Similar were the results of depolymerisation of PET through
glycolysis to obtain bis(2-hydroxy ethylene)terephthalate [6].
This difference in the yields was attributed to the molecular
weight and its distribution in PET fibrous waste and the bottle
waste. For the fibre grade PET, the molecular weight is lower
and the molecular weight distribution is narrower than that for
the bottle grade PET in order to attain higher viscosity for the
latter, necessary for the blow-molding process. This is
achieved through modification using certain co-monomers
and chain terminating agents [19e21].
The purified BHETA was characterised by elemental anal-
ysis, and melting point. These results are given in Table 3,
which confirm that the product of PET depolymerisation is
BHETA. This was further confirmed through instrumental
characterisation.
The IR spectrograph of the purified compound has been
shown in Fig. 2. It may be clearly seen that the spectrograph

Fig. 3. NMR spectrum of bis(2-hydroxy ethylene)terephthalamide.

1854 S.R. Shukla, A.M. Harad / Polymer Degradation and Stability 91 (2006) 1850e1854
Fig. 4. DSC spectrum of bis(2-hydroxy ethylene)terephthalamide.
contains peaks at 1053 and 3289 cm1 indicating the presence
of primary alcohol. The peaks for secondary amide stretching
are observed at 1314, 1553 and 3368 cm1.
Fig. 3 gives 1H NMR for the same compound wherein
it may be observed that the peaks at d 8.59 corresponds to
eNHCO groups, d 3.25e3.65 corresponds to aliphatic
CH2eCH2 proton, d 7.98 corresponds to aromatic ring protons
and d 4.70 corresponds to eOH groups.
Fig. 4 gives DSC scan, which indicates that the melting
point of the compound is 227
C. This is in close agreement
with the melting of BHETA, as reported by Lu and coworkers,
who had obtained it by degradation of 1,1#-(terephthaloyl)bis-
benztriazole (PBBT) in the presence of dimethyl formamide as
a solvent [22].
From all these observations it was concluded that the struc-
ture of the purified monomer is that of BHETA. The highest
yield was obtained using 1% (w/w) sodium acetate from the
PET fibrous waste.
4. Conclusion
The simple chemicals like glacial acetic acid or simple salts
are found to be capable of depolymerising PET fibre waste
through aminolysis. With this process, the yield and purity
of the chemically reactive product BHETA are of high order
with much less reaction time. The product of depolymerisation
has the potential of recycling it into useful products through
various chemical reactions, which is being explored.
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