ISSN 2070-0504, Catalysis in Industry, 2018, Vol. 10, No. 1, pp. 41–48. © Pleiades Publishing, Ltd., 2018.

CATALYSIS
AND ENVIRONMENTAL PROTECTION

Sodium Methoxide Catalyzed Depolymerization of Waste

Polyethylene Terephthalate Under Microwave Irradiation1
Mahmoud A. Mohsina, *, Mohamed A. Alnaqbib, **, Reneesh M. Busheerb, ***, and Yousef Haikc, ****
a
Department of Chemistry, University of Sharjah, Sharjah, United Arab Emirates
b
Department of Chemistry, United Arab Emirates University, Al Ain, United Arab Emirates
c
College of Science and Engineering, Hamad Bin Khalifa University, Doha, Qatar
*e-mail: [email protected]
**e-mail: [email protected]
***e-mail: [email protected]
****e-mail: [email protected]
Received February 20, 2017

AbstractChemical recycling of polyethylene terephthalate (PET) to produce terephthalic acid (TPA) was
studied using in situ hydrolysis with sodium methoxide in methanol and dimethyl sulfoxide (DMSO) as sol-
vent under microwave irradiation. The microwave-assisted reaction was carried out at different temperatures,
and reaction time between 5 to 30 min. High degrees of depolymerization were examined at temperature near
70°C at microwave power 300 W. The reaction was carried out in a sealed microwave reactor in which the time
and temperature were controlled and recorded. The products were mainly monomers such as TPA and eth-
ylene glycol (EG) which were isolated and purified for further analysis. Monomethyl terephthalate, dimethyl
terephthalate, and terephthalic acid were formed initially then converted to TPA as a single monomer prod-
uct. Purified, TPA was analyzed and identified by NMR, TGA, DSC and FTIR. It was observed that the
reaction greatly depends on the amount of sodium methoxide, the volume of methanol and DMSO used, the
reaction time, and temperature. Compared to conventional heating methods, the time needed to achieve
complete degradation of PET was significantly reduced to 5 min by using microwave irradiation and sodium
methoxide catalyst. This has led to substantial saving in energy and cost supporting the conclusion that this
proposed recycling process is very beneficial for the recycling of PET wastes.

Keywords: poly(ethylene terephthalate), PET waste, depolymerization, sodium methoxide, microwave irra-
diation, terephthalic acid
DOI: 10.1134/S2070050418010087

1. INTRODUCTION the polycondensation reaction of BHET [4]. Due to

Polyethylene terephthalate (PET) is one of the the extensive use and disposal of PET products, the
most widely used plastics as it shows an excellent ten- amount of PET waste increases in the land fields cre-
sile and impact strength, chemical resistance, clarity, ating a serious environmental problem. Therefore,
colorability, low permeability of gases (mainly CO2) recycling of PET should be adopted for the environ-
and thermal stability [1]. The overall world consump- mental sustainability. PET is the most successful and
tion of PET is estimated to reach 19.1 million tons in widespread example of polymer recycling [5].
2017, with a 5.2% increase per annum [2]. PET is con- The growing interest of PET recycling is due to the
sidered an excellent material for various types of appli- widespread usage of packaging for the food industry
cations and is used in the textile industry, the manu- because it does not have any known major side effects
facturing of audio and video tapes, X-ray films, and on human beings. PET does not create a direct hazard
various types of packaging mainly, bottles and jars [3]. to the environment, but due to its substantial volume
There are two steps involved in PET synthesis. The fraction in the waste stream and its high resistance to
first step is the esterification or transesterification the atmospheric and biological agents, it is seen as a
reaction between terephthalic acid (TPA) and ethylene toxic material when degradation takes place. Ecologi-
glycol and bis(2-hydroxyethyl terephthalate) (BHET) cal and economic considerations have increased the
isolated at the end of this reaction. The second step is research on large scale chemical recycling of polyeth-
ylene terephthalate, similar to the recycling of tradi-
1 The article is published in the original.
tional materials such as glass, paper, and metals [6–8].

41
42 MAHMOUD A. MOHSIN et al.

Chemical recycling of PET is one of the most [34]. Consequently, it is a widely used method for
attractive recycling processes as it leads to complete heating and drying materials, and it is utilized in many
depolymerization of PET to terephthalic acid, eth- household and industrial applications [35]. The main
ylene glycol and other useful substances. Several advantage of using microwave heating over conven-
chemical processes have been employed. The main tional heating is that the microwave energy is directly
five techniques for chemical recycling of waste PET coupled with the molecules present in the reaction
are: glycolysis, methanolysis, hydrolysis, aminolysis, mixture, leading to rapid but controllable rise in the
and ammonolysis [6, 9–11]. Nevertheless, most of temperature. Dipole rotation and ionic conduction
these techniques necessitate severe reaction condi- are the two basic mechanisms behind the transferring
tions, such as prolonged reaction time, high tempera- of energy from microwave irradiation to the reacted
ture and pressure, or even the presence of large molecules. Dipole rotation is an interaction between
amounts of concentrated acids or bases [12, 13]. polar molecules and electric field component of
During the chemical recycling processes the polymer microwave radiation; polar molecules align with the
can be depolymerized into monomers or partial depo-
rapidly changing electric field of the microwave,
lymerized into oligomers [14–16]. The glycolysis pro-
cess proceeds with the insertion of ethylene glycol into resulting in transfer of energy. Polar solvents like
the polymer chain to produce BHET as monomer, but water, methanol, ethanol, acetone, and dimethyl for-
this process has several disadvantages. It requires the mamide are able to directly absorb microwave energy
use of large amount of solvent, expensive catalyst ionic and that rapidly increases the reaction rate of the dis-
liquid, inert reaction conditions, high temperature, solved reagent. On the other hand, ionic conduction
and long reaction time. The glycolysis and hydrolysis results if there are free ions or ionic species present in
of PET using ionic liquid as solvent and catalyst have the reaction mixture. The free ions move through the
attracted a lot of attention in recent years [17–19]. solution under the influence of an electric field, result-
However, the high cost and the complex synthetic pro- ing in an expenditure of energy due to an increased col-
cedure limited its expansive use. Alcoholysis to lision rate, converting the kinetic energy to heat. The
dimethyl terephthalate with super critical methanol conductivity mechanism is a much stronger interaction
has the obvious disadvantage of volatilization of meth- than the dipolar mechanism with regards to the heat
anol [20, 21]. generating capacity [36].
Hydrolysis of PET waste into TPA and ethylene In this research article, we used strong base sodium
glycol can be performed as acid hydrolysis, alkaline
methoxide and microwave energy for the in-situ
hydrolysis, and neutral hydrolysis [6, 7, 22–26]. The
growing interest of this method is linked with the syn- hydrolysis of PET waste, which was taken from com-
thesis of PET directly from TPA and ethylene glycol mon soft drink bottles. A combination of polar sol-
[27]. Researchers mainly used nitric acid and sulfuric vents, methanol, and dimethyl sulfoxide (DMSO) was
acid as catalyst for acid hydrolysis of PET, but large used in this process to give high advantages such as sol-
scale handling of these acids requires extreme safety ubility of sodium methoxide and high dielectric con-
precautions and also results in corrosion of the reactor stant [37]. The influences of process parameters like
[28–30]. Alkaline hydrolysis always assisted with the time and temperature on the degradation of PET and
presence of phase transfer catalyst such as tributyl hexa- TPA recovery were investigated. The main goal was to
decyl phosphonium bromide, benzalkonium chloride, examine if the microwave energy applied during depo-
and tetrabutyl ammonium iodide [22, 31, 32]. lymerization of PET could result in either shorter
Most organic reactions have been carried out using reaction time or lower reaction temperature with sig-
traditional heat transfer equipment such as oil baths, nificant energy saving. The innovative parts of this
sand baths, and heating jackets. These heating tech- research include the use of microwave reactor in place
niques are rather slow and a temperature gradient can of conventional heating methods and avoided phase
develop within the sample. Moreover, local overheat- transfer catalyst. The main products obtained in this
ing or hotspots can lead to products and reagents process are terephthalic acid and ethylene glycol,
decomposition. In the present study, some of these which were analyzed and identified.
difficulties were overcome using microwave irradia-
tion and sodium methoxide (strong nucleop-
hile/strong base) as catalyst for the in situ hydrolysis of 2. EXPERIMENTAL
PET waste. The time required for the depolymeriza-
tion could be significantly reduced in this method to 2.1. Materials
approximately 5 min by using microwave as the energy
source, compared to the conventional heating meth- PET bottles were collected, washed, dried, and cut
ods, which requires 2 to 3 h [33]. Microwave irradia- into small chips approximately 2 × 2 × 2 mm in size.
tion as heating technique offers many advantages over Sodium methoxide obtained from Sigma Aldrich
conventional heating methods, such as noncontact, (USA) was used as received. The solvent DMSO and
instantaneous, and rapid heating with high specificity methanol used were LR grade.

CATALYSIS IN INDUSTRY Vol. 10 No. 1 2018